Crystal-structure studies of 4-phenyl­piperazin-1-ium 4-eth­oxy­benzoate monohydrate, 4-phenyl­piperazin-1-ium 4-meth­oxy­benzoate monohydrate, 4-phenyl­piperazin-1-ium 4-methyl­benzoate monohydrate and 4-phenyl­piperazin-1-ium tri­fluoro­acetate 0.12-hydrate

Four novel piperazinium salts are reported, and based on 1-phenyl­piperazinium as a common cation in the asymmetric units that include additionally water mol­ecules, and different P-substituent benzoate anions or a tri­fluoro­acetate anion. They are hydrated and there are three crystallized as 1:1 salts while the fourth is a 2:2 salt. Their crystal packing depends on strong ribbons or sheets stabilized by hydrogen bonds of type N—H⋯O and O—H⋯O and other inter­actions as C—H⋯O, C—H⋯π and C—H⋯F in the tri­fluoro­acetate-based one.

Abstract

In this study, four new piperazinium salts, namely, 4-phenyl­piperazin-1-ium 4-eth­oxy­benzoate monohydrate, C₉H₉O₃·C₁₀H₁₅N₂·H₂O (I); 4-phenyl­piperazin-1-ium 4-meth­oxy­benzoate monohydrate, C₁₀H₁₅N₂·C₈H₇O₃·H₂O (II); 4-phenyl­piperazin-1-ium 4-methyl­benzoate monohydrate, C₁₀H₁₅N₂·C₈H₇O₂·H₂O (III); and 4-phenyl­piperazin-1-ium tri­fluoro­acetate 0.12 hydrate, C₁₀H₁₅N₂·C₂F₃O₂·0.12H₂O (IV), have been synthesized. The single-crystal structures of these compounds reveal that all of them crystallize in the triclinic P space group and the crystal packing of (I)–(III) is built up of ribbons formed by a combination of hydrogen bonds of type N—H⋯O, O—H⋯O and other weak inter­actions of type C—H⋯O and C—H⋯π, leading to a three-dimensional network. In the crystal of (IV), the cations and the anions are connected by C—H⋯O, N—H⋯O and C—H⋯F hydrogen bonds and by C—H⋯π inter­actions, forming sheets which in turn inter­act to maintain the crystal structure by linking through the oxygen atoms of water mol­ecules and van der Waals inter­actions, giving the whole structure.

1. Chemical context

Piperazines are among the most important building blocks in today’s drug discovery efforts and are found in biologically active compounds across a number of different therapeutic areas (Brockunier et al., 2004 ▸; Bogatcheva et al., 2006 ▸). For a review on the current pharmacological and toxicological information for piperazine derivative, see Elliott (2011 ▸). Various pharmacological properties of phenyl­piperazines and their derivatives have been discussed by several authors (Cohen et al., 1982 ▸; Conrado et al., 2010 ▸; Neves et al., 2003 ▸; Hanano et al., 2000 ▸). The design and synthesis of phenyl­piperazine derivatives as potent anti­cancer agents for prostate cancer have been described (Demirci et al., 2019 ▸). Many pharmaceutical compounds are derived from 1-phenyl­piperazine, viz., oxypertine, trazodone, nefazodone, etc.

The crystal structures of 2-(4-methyl-2-phenyl­piperazin-4-ium-1-yl)pyridine-3-carboxyl­ate dehydrate (Li et al., 2008 ▸), 1-chloro-2-(4-phenyl­piperazin-1-yl)-ethanone (Xu & Jing, 2009 ▸), 4-phenyl­piperazin-1-ium di­hydrogen phosphate (Essid et al., 2010 ▸) and 1-phenyl­piperazine-1,4-diium bis­(hydrogen sulfate) (Marouani et al., 2010 ▸) have been reported, as have those of 4-phenyl­piperazin-1-ium 6-chloro-5-ethyl-2,4-dioxopyrimidin-1-ide and 4-phenyl­piperazin-1-ium 6-chloro-5-isopropyl-2,4-dioxopyrimidin-1-ide (Al-Alshaikh et al., 2015 ▸). We have reported the crystal structures of some salts of 4-meth­oxy­phenyl­piperazine (Kiran Kumar et al., 2019a ▸), six 1-aroyl-4-(4-meth­oxy­phen­yl)piperazines (Kiran Kumar et al., 2019b ▸), 2-meth­oxy­phenyl­piperazine (Harish Chinthal et al., 2020 ▸) and the recreational drug N-(4-meth­oxy­phen­yl)piperazine (MeOPP) and three of its salts (Kiran Kumar et al., 2020a ▸).

In view of the importance of piperazines in general and the use of 1-phenyl­piperazine in particular, the present paper reports the crystal structure studies of some salts of 1-phenyl­piperazine with organic acids viz., 4-phenyl­piperazin-1-ium 4-eth­oxy­benzoate monohydrate, C₉H₉O₃·C₁₀H₁₅N₂·H₂O (I); 4-phenyl­piperazin-1-ium 4-meth­oxy­benzoate monohydrate, C₁₀H₁₅N₂·C₈H₇O₃·H₂O (II); 4-phenyl­piperazin-1-ium 4-methyl­benzoate monohydrate, C₁₀H₁₅N₂·C₈H₇O₂·H₂O (III); and 4-phenyl­piperazin-1-ium tri­fluoro­acetate 0.12 hydrate C₁₀H₁₅N₂·C₂F₃O₂·0.12H₂O (IV).

2. Structural commentary

The asymmetric unit of the compound (I), (Fig. 1 ▸), consists of a 4-phenyl­piperazin-1-ium cation, a 4-eth­oxy­benzoate anion and one water mol­ecule. The aromatic ring of the cation is essentially planar while the protonated piperazine ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975 ▸) Q _T = 0.553 (2) Å, θ = 175.0 (2)° and φ = 15 (3)°. In compound (II) the asymmetric unit (Fig. 2 ▸) comprises a 4-phenyl­piperazin-1-ium cation, a 4-meth­oxy­benzoate anion and one water mol­ecule. The aromatic ring of the cation is essentially planar while the protonated piperazine ring adopts a chair conformation, with puckering parameters Q _T = 0.5614 (18) Å, θ = 175.89 (17)° and φ = 346 (3)°. Compound (III) presents an asymmetric unit (Fig. 3 ▸) composed of a 4-phenyl­piperazin-1-ium cation, a 4-methyl­benzoate anion and one water mol­ecule. The aromatic ring of the cation is essentially planar but the protonated piperazine ring adopts a distorted chair conformation, with puckering parameters Q _T = 0.5486 (19) Å, θ = 9.38 (19)° and φ = 167.9 (13)°. On the other hand, the asymmetric unit of (IV) (Fig. 4 ▸) contains two 4-phenyl­piperazin-1-ium cations (A1 with N1, A2 with N3) and two tri­fluoro­acetate anions (B1 with F1, B2 with F4) and a 0.12 occupancy water molecule. The aromatic rings of the cations (A1, A2) are essentially planar while the protonated piperazine rings adopt a chair conformation for cation A1, with puckering parameters (Cremer & Pople, 1975 ▸) Q _T = 0.552 (4) Å, θ = 0.0 (4)° and φ = 207 (14)°, and a distorted chair conformation for the cation A2, with puckering parameters Q _T = 0.559 (5) Å, θ = 6.6 (4)° and φ = 168 (4)°.

Figure 1.

The independent components of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2.

The independent components of compound (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3.

The independent components of compound (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4.

The independent components of compound (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. (Atom splitting is omitted for clarity.)

3. Supra­molecular features

In the crystal structure of (I), the cation pairs are connected across two water mol­ecules by C—H⋯O and N—H⋯O hydrogen bonds, forming an (10) ring motif in which the anions and cations are linked through the water mol­ecules by O—H⋯O and N—H⋯O hydrogen bonds, forming ribbons along the a-axis direction (Table 1 ▸, Fig. 5 ▸ a). In addition, a set of C—H⋯π inter­actions, through the benzene rings of the anions and the cations, connect the mol­ecules together in ribbons along the a-axis direction (Table 1 ▸, Fig. 5 ▸ b). The C—H⋯O, N—H⋯O, O—H⋯O hydrogen bonds and C—H⋯π inter­actions together form a three-dimensional network, contributing to the stabilization of the crystal structure.

Table 1. Hydrogen-bond geometry (Å, °) for (I) .

Cg1 and Cg3 are the centroids of the C12–C17 and C1–C6 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN1⋯OW1i	0.89 (2)	1.94 (2)	2.817 (3)	167 (2)
N2—HN2⋯O1	0.93 (2)	1.80 (2)	2.724 (3)	174 (2)
OW1—HW1⋯O2	0.88 (3)	1.75 (3)	2.630 (3)	178 (4)
OW1—HW2⋯O1ii	0.91 (3)	1.89 (3)	2.789 (3)	167 (3)
C9—H9A⋯OW1	0.97	2.52	3.308 (3)	138
C1—H1⋯Cg1iii	0.93	2.91	3.607 (3)	133
C5—H5⋯Cg1iv	0.93	2.79	3.570 (3)	142
C18—H18B⋯Cg3v	0.97	2.88	3.737 (4)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 5.

Parts of the crystal structure of compound (I) showing (a) the formation of a cyclic hydrogen-bonded (10) aggregate and (b) a general view of C—H⋯π inter­actions parallel to [100]. Hydrogen bonds and C—H⋯π inter­actions are drawn as dashed lines.

In the crystal structure of (II), the cations, the anions and the water mol­ecules are connected by C—H⋯O, N—H⋯O and O—H⋯O hydrogen bonds, forming ribbons along the a-axis direction (Table 2 ▸, Fig. 6 ▸ a). Furthermore, the cations inter­act via C—-H⋯π inter­actions through the benzene ring of the anion, forming ribbons along the b-axis direction (Table 2 ▸, Fig. 6 ▸ b). The C—H⋯O, N—H⋯O, O—H⋯O hydrogen bonds and C—H⋯π inter­actions together form a three-dimensional network, contributing to the stabilization of the crystal structure.

Table 2. Hydrogen-bond geometry (Å, °) for (II) .

Cg3 is the centroid of the C12–C17 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN1⋯OW1i	0.93 (2)	1.91 (2)	2.815 (2)	166 (2)
OW1—HW1⋯O1ii	0.84 (2)	1.80 (2)	2.633 (2)	175 (2)
N2—HN2⋯O2	0.93 (2)	1.81 (2)	2.7350 (19)	176 (2)
OW1—HW2⋯O2iii	0.85 (2)	1.96 (2)	2.7876 (19)	168 (2)
C8—H8B⋯OW1ii	0.97	2.53	3.331 (2)	140
C1—H1⋯Cg3ii	0.93	2.76	3.549 (2)	144
C5—H5⋯Cg3iv	0.93	2.86	3.625 (2)	140

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 6.

Parts of the crystal structure of compound (II) showing (a) the formation of hydrogen-bonded ribbons parallel to [010] and (b) a general view of the C—H⋯π inter­actions parallel to [010]. Hydrogen bonds and C—H⋯π inter­actions are drawn as dashed lines.

In the crystal structure of (III), the cations, the anions and the water mol­ecules are connected by C—H⋯O, N—H⋯O and O—H⋯O hydrogen bonds, forming ribbons along the a-axis direction (Table 3 ▸, Fig. 7 ▸). There are no C—H⋯π inter­actions or π-π stacking inter­actions. The crystal structure is stabilized by C—H⋯O, N—H⋯O, O—H⋯O hydrogen bonds and van der Waals inter­actions between the ribbons, which run along the a-axis direction.

Table 3. Hydrogen-bond geometry (Å, °) for (III) .

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—HW1⋯O2i	0.89 (3)	1.90 (3)	2.782 (2)	171 (4)
OW1—HW2⋯O1	0.84 (2)	1.92 (3)	2.751 (2)	172 (3)
N2—HN1⋯O1ii	0.90 (2)	1.94 (2)	2.819 (2)	164 (2)
N2—HN2⋯O2	0.92 (2)	1.80 (2)	2.7207 (19)	176 (2)
C8—H8A⋯OW1	0.97	2.33	3.116 (3)	138

Symmetry codes: (i) ; (ii) .

Figure 7.

Part of the crystal structure of compound (III) showing the formation of a hydrogen-bonded chain of rings parallel to [001]. Hydrogen bonds are drawn as dashed lines.

In the crystal structure of (IV), the cations and the anions are connected by C—H⋯O, N—H⋯O and C—H⋯F hydrogen bonds (Table 4 ▸, Fig. 8 ▸ a) and C—H⋯π inter­actions, generating sheets parallel to the (100) plane (Table 4 ▸, Fig. 8 ▸). These sheets further inter­act to maintain the crystal structure by linking through the oxygen atoms of water mol­ecules and by van der Waals inter­actions. As shown in Table 4 ▸, the main interactions in the structure of (IV) involve the oxygen atoms of carboxylate groups, while the 0.12 fraction of the water molecule contributes with one interaction of the type C—H⋯O and it is weak in comparison to the other oxygen-based ones.

Table 4. Hydrogen-bond geometry (Å, °) for (IV) .

Cg2 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1i	0.88	1.91	2.790 (4)	174
N2—H22⋯O3	0.87	2.04	2.860 (4)	157
N2—H22⋯O4	0.87	2.47	3.164 (5)	137
N4—H41⋯O4ii	0.86	1.95	2.759 (6)	156
N4—H42⋯O2iii	0.89	1.90	2.758 (4)	164
C18—H18A⋯F5′iii	0.97	2.53	3.273 (18)	134
C18—H18B⋯Ow1	0.97	2.08	2.929 (15)	145
C19—H19B⋯O3iv	0.97	2.59	3.420 (5)	144
C20—H20A⋯F5iv	0.97	2.64	3.468 (8)	144
C16—H16⋯Cg2v	0.93	2.99	3.745 (4)	140

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 8.

Parts of the crystal structure of compound (IV) showing (a) a general view of the C—H⋯O, N—H⋯O and C—H⋯F hydrogen bonds and C—H⋯π inter­actions and (b) the mol­ecular packing of (IV) down the a-axis. Hydrogen bonds and C—H⋯π inter­actions are drawn as dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 2020.3, last update February 2022; Groom et al., 2016 ▸) for an unsubstituted 4-phenyl­piperazin-1-ium cation and para-substituted benzoate anion involved in the reported salts (I)–(III) gave no hits. However, searching for a branched phenyl piperazinium cation and para-substituted benzoate anion gave comparable hits, namely; 4-(4-meth­oxy­phen­yl)piperazin-1-ium 4-fluoro­benzoate monohydrate, 4-(4-meth­oxy­phen­yl)piperazin-1-ium 4-chloro­benzoate monohydrate, 4-(4-meth­oxy­phen­yl)piperazin-1-ium 4-bromo­benzoate monohydrate (FOVPOY, FOVPUE, FOVQAL; Kiran Kumar et al., 2019a ▸), 4-(4-meth­oxy­phen­yl)piperazin-1-ium 4-iodo­benzoate monohydrate (KUJPUD; Kiran Kumar et al., 2020b ▸). They exhibit a meth­oxy group as a substituent in the 4-phenyl­piperazin-1-ium cation while the reported compounds (I)–(IV) have no substituent. They also crystallize as monohydrates, and their crystal structures are based on differently sized chains of rings formed via a combination of hydrogen bonds of the type N–H⋯O and O–H⋯O and other weak inter­actions of types C—H⋯O and C—H⋯π to form sheets. In 4-(4-meth­oxy­phen­yl)piperazin-1-ium 4-amino­benzoate monohydrate (IHIMEU; Kiran Kumar et al., 2020a ▸) the presence of the amino substituent in the anion, which acts as both a donor and as an acceptor of hydrogen bonds, makes the supra­molecular assembly of this compound more complex than those reported here. A search for 4-phenyl­piperazin-1-ium and acetate derivatives involved in the reported compound (IV) gave no hits.

5. Synthesis and crystallization

For the synthesis of salts (I)–(IV), a solution of commercially available (from Sigma–Aldrich) 1-phenyl­piperazine (100 mg, 0.62 mol) in methanol (10 ml) was mixed with equimolar solutions of the appropriate organic acids in methanol (10 ml) viz., 4-eth­oxy­benzoic acid (103 mg, 0.62 mol) for (I), 4-meth­oxy­benzoic acid (94 mg, 0.62 mol) for (II), 4-methyl­benzoic acid (84 mg, 0.62 mol) for (III) and tri­fluoro­acetic acid (71 mg, 0.62 mol) for (IV). The corresponding solutions were stirred for 15 min at room temperature and allowed to stand at the same temperature. X-ray quality crystals were formed on slow evaporation in a week for all compounds, where ethanol:ethyl­acetate (1:1) was used for crystallization. The corresponding melting points were 353–355 K for (I), 368–370 K for (II), 338–340 K for (III) and 385–387 K for (IV).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5 ▸. All H atoms bonded to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), C—H = 0.96 Å (meth­yl) or 0.97 Å (methyl­ene), with U _iso(H) = 1.2U _eq(C) or 1.5U _eq(C). For the H atoms bonded to the N and O atoms, the atomic coordinates were refined with U _iso(H) = 1.2U _eq(N) and 1.5U _eq(O), [for (I), N2—HN2 = 0.931 (19), N2—HN1 = 0.888 (17) Å and OW1—HW2 = 0.91 (3), OW1—HW1 = 0.88 (3) Å; for (II), N2—HN1 = 0.927 (16), N2—HN2 = 0.931 (18) Å and OW—HW1 = 0.840 (19), OW1—HW2 = 0.85 (2) Å; for (III), N2—HN1 = 0.900 (16), N2—HN2 = 0.918 (17) Å and OW1—HW1 = 0.89 (3), OW1—HW2 = 0.84 (2) Å and for (IV), N2—H22 = 0.87 (2) and N2—H21 = 0.88 (3) Å]. In (IV), the atoms of the CF₃ groups of two tri­fluoro­acetate anions (B1, B2) are disordered over two sets of sites with site occupancies of 0.737 (3) and 0.263 (3). The corresponding bond distances in the disordered groups were restrained to be equal. The U ^ij components of these atoms were restrained to be equal and were restrained to approximate isotropic behaviour. The OW1 water molecule was refined with a resulting occupation factor of 0.245 (10) and the H atoms of the water molecule were placed geometrically.

Table 5. Experimental details.

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	C10H15N2 +·C9H9O3 −·H2O	C10H15N2 +·C8H7O3 −·H2O	C10H15N2 +·C8H7O2 −·H2O	C10H15N2 +·C2F3O2 −·0.123H2O
M r	346.42	332.39	316.39	278.47
Crystal system, space group	Triclinic, P	Triclinic, P	Triclinic, P	Triclinic, P
Temperature (K)	293	293	293	293
a, b, c (Å)	6.1635 (5), 7.5946 (6), 20.458 (2)	6.2039 (4), 7.5565 (7), 18.614 (1)	6.1175 (5), 7.6225 (7), 18.452 (1)	9.6544 (6), 9.9029 (6), 15.2090 (9)
α, β, γ (°)	79.545 (7), 86.521 (7), 83.791 (7)	81.799 (7), 87.020 (7), 84.852 (7)	97.421 (9), 90.403 (8), 92.405 (8)	79.621 (6), 86.579 (6), 70.603 (6)
V (Å3)	935.38 (14)	859.53 (11)	852.40 (12)	1349.10 (15)
Z	2	2	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	0.09	0.09	0.08	0.12
Crystal size (mm)	0.48 × 0.42 × 0.1	0.48 × 0.48 × 0.32	0.5 × 0.4 × 0.08	0.48 × 0.48 × 0.36
Data collection
Diffractometer	Oxford Diffraction Xcalibur	Oxford Diffraction Xcalibur	Oxford Diffraction Xcalibur	Oxford Diffraction Xcalibur
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▸)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▸)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▸)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▸)
T min, T max	0.623, 1.000	0.520, 1.000	0.837, 1.000	0.724, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5989, 3429, 2159	5360, 3142, 2322	5354, 3126, 2248	9220, 4940, 2777
R int	0.022	0.016	0.013	0.014
(sin θ/λ)max (Å−1)	0.602	0.602	0.602	0.602
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.054, 0.124, 1.08	0.045, 0.125, 1.06	0.046, 0.128, 1.03	0.070, 0.235, 1.07
No. of reflections	3424	3139	3118	4927
No. of parameters	244	230	226	375
No. of restraints	2	4	4	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.15, −0.15	0.2, −0.17	0.16, −0.16	0.42, −0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009 ▸), CrysAlis RED (Oxford Diffraction, 2009 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), Mercury (Macrae et al., 2020 ▸), PLATON (Spek, 2020 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

CCDC references: 2177037, 2177036, 2177035, 2177034

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Crystal data

C10H15N2+·C9H9O3−·H2O	Z = 2
Mr = 346.42	F(000) = 372
Triclinic, P1	Dx = 1.23 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1635 (5) Å	Cell parameters from 2352 reflections
b = 7.5946 (6) Å	θ = 3.0–27.8°
c = 20.458 (2) Å	µ = 0.09 mm−1
α = 79.545 (7)°	T = 293 K
β = 86.521 (7)°	Plate, colourless
γ = 83.791 (7)°	0.48 × 0.42 × 0.1 mm
V = 935.38 (14) Å3

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Data collection

Oxford Diffraction Xcalibur diffractometer	2159 reflections with I > 2σ(I)
ω scans	Rint = 0.022
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	θmax = 25.4°, θmin = 3.0°
Tmin = 0.623, Tmax = 1.000	h = −7→7
5989 measured reflections	k = −9→9
3429 independent reflections	l = −24→14

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Refinement

Refinement on F2	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.124	w = 1/[σ2(Fo2) + (0.0392P)2 + 0.2859P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3424 reflections	Δρmax = 0.15 e Å−3
244 parameters	Δρmin = −0.15 e Å−3
2 restraints	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.0058 (17)
Primary atom site location: structure-invariant direct methods

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1990 (4)	0.7508 (4)	0.79338 (12)	0.0626 (7)
H1	0.069252	0.809989	0.776125	0.075*
C2	0.2437 (5)	0.7539 (4)	0.85869 (13)	0.0782 (9)
H2	0.142853	0.814295	0.884641	0.094*
C3	0.4331 (5)	0.6699 (4)	0.88559 (14)	0.0759 (9)
H3	0.462163	0.672073	0.929504	0.091*
C4	0.5786 (5)	0.5827 (4)	0.84658 (14)	0.0753 (8)
H4	0.709095	0.525999	0.864083	0.09*
C5	0.5363 (4)	0.5771 (3)	0.78183 (12)	0.0579 (7)
H5	0.638106	0.515837	0.756445	0.069*
C6	0.3432 (3)	0.6615 (3)	0.75355 (10)	0.0407 (5)
C7	0.1046 (3)	0.7635 (3)	0.66062 (11)	0.0484 (6)
H7A	0.130663	0.888733	0.656771	0.058*
H7B	−0.01969	0.742138	0.691398	0.058*
C8	0.0502 (3)	0.7292 (3)	0.59343 (11)	0.0496 (6)
H8A	0.005085	0.609001	0.59798	0.059*
H8B	−0.07032	0.814458	0.576145	0.059*
C9	0.4290 (3)	0.6216 (3)	0.57366 (10)	0.0480 (6)
H9A	0.555062	0.634835	0.543053	0.058*
H9B	0.392361	0.498713	0.578625	0.058*
C10	0.4839 (3)	0.6594 (3)	0.64012 (10)	0.0447 (6)
H10A	0.602615	0.572985	0.657958	0.054*
H10B	0.5333	0.778458	0.634186	0.054*
C11	0.2356 (4)	0.7988 (3)	0.37750 (13)	0.0504 (6)
C12	0.1740 (3)	0.8093 (3)	0.30715 (11)	0.0409 (5)
C13	−0.0108 (3)	0.7381 (3)	0.29259 (11)	0.0462 (6)
H13	−0.09987	0.685018	0.327326	0.055*
C14	−0.0669 (4)	0.7436 (3)	0.22762 (11)	0.0496 (6)
H14	−0.191724	0.694349	0.218988	0.06*
C15	0.0633 (4)	0.8223 (3)	0.17610 (11)	0.0480 (6)
C16	0.2462 (4)	0.8988 (3)	0.18948 (12)	0.0547 (6)
H16	0.332264	0.955074	0.154649	0.066*
C17	0.3005 (4)	0.8916 (3)	0.25403 (12)	0.0521 (6)
H17	0.424178	0.942678	0.262421	0.063*
C18	−0.1614 (5)	0.7562 (5)	0.09410 (14)	0.0931 (10)
H18A	−0.293805	0.818359	0.110377	0.112*
H18B	−0.155291	0.63023	0.114607	0.112*
C19	−0.1605 (8)	0.7747 (7)	0.02032 (17)	0.178 (2)
H19A	−0.195823	0.898767	0.00101	0.268*
H19B	−0.266871	0.703796	0.008494	0.268*
H19C	−0.018288	0.73364	0.003915	0.268*
N1	0.2969 (3)	0.6493 (2)	0.68767 (8)	0.0382 (4)
N2	0.2420 (3)	0.7474 (3)	0.54621 (10)	0.0452 (5)
O1	0.1211 (3)	0.7133 (2)	0.42359 (8)	0.0622 (5)
O2	0.3970 (3)	0.8727 (3)	0.38724 (10)	0.0885 (7)
O3	0.0253 (3)	0.8330 (2)	0.11014 (8)	0.0681 (5)
OW1	0.7230 (4)	0.8819 (2)	0.46338 (9)	0.0591 (5)
HN1	0.275 (4)	0.860 (2)	0.5421 (11)	0.056 (7)*
HN2	0.208 (4)	0.729 (3)	0.5044 (9)	0.067 (8)*
HW1	0.612 (5)	0.879 (4)	0.4385 (15)	0.102 (11)*
HW2	0.842 (5)	0.825 (4)	0.4445 (15)	0.102 (12)*

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0719 (17)	0.0673 (18)	0.0465 (15)	0.0151 (14)	−0.0066 (13)	−0.0156 (13)
C2	0.103 (2)	0.079 (2)	0.0522 (17)	0.0150 (18)	−0.0020 (16)	−0.0248 (15)
C3	0.106 (2)	0.076 (2)	0.0510 (17)	−0.0055 (18)	−0.0223 (17)	−0.0207 (15)
C4	0.0735 (18)	0.090 (2)	0.0636 (18)	0.0027 (16)	−0.0267 (15)	−0.0145 (17)
C5	0.0561 (15)	0.0696 (18)	0.0486 (15)	0.0031 (13)	−0.0116 (12)	−0.0147 (13)
C6	0.0467 (12)	0.0353 (13)	0.0414 (13)	−0.0092 (10)	−0.0045 (10)	−0.0067 (10)
C7	0.0399 (12)	0.0595 (16)	0.0441 (13)	0.0007 (11)	−0.0025 (10)	−0.0078 (11)
C8	0.0407 (12)	0.0622 (16)	0.0445 (14)	−0.0045 (11)	−0.0053 (10)	−0.0053 (11)
C9	0.0480 (13)	0.0512 (15)	0.0423 (13)	−0.0011 (11)	0.0026 (10)	−0.0057 (11)
C10	0.0396 (12)	0.0496 (14)	0.0435 (13)	−0.0024 (10)	−0.0018 (10)	−0.0062 (11)
C11	0.0524 (14)	0.0427 (14)	0.0593 (17)	0.0050 (12)	−0.0162 (13)	−0.0190 (12)
C12	0.0398 (12)	0.0373 (13)	0.0475 (13)	−0.0007 (10)	−0.0072 (10)	−0.0121 (10)
C13	0.0494 (13)	0.0462 (14)	0.0432 (13)	−0.0111 (11)	−0.0024 (11)	−0.0048 (11)
C14	0.0502 (13)	0.0519 (15)	0.0490 (14)	−0.0163 (11)	−0.0091 (11)	−0.0063 (12)
C15	0.0556 (14)	0.0469 (15)	0.0412 (14)	−0.0042 (11)	−0.0052 (11)	−0.0065 (11)
C16	0.0534 (14)	0.0566 (16)	0.0533 (16)	−0.0136 (12)	0.0088 (12)	−0.0063 (12)
C17	0.0409 (12)	0.0533 (16)	0.0659 (17)	−0.0098 (11)	−0.0026 (12)	−0.0174 (13)
C18	0.111 (2)	0.121 (3)	0.0572 (18)	−0.046 (2)	−0.0218 (17)	−0.0148 (18)
C19	0.242 (6)	0.251 (6)	0.063 (2)	−0.137 (5)	−0.039 (3)	−0.007 (3)
N1	0.0374 (9)	0.0419 (11)	0.0350 (10)	−0.0028 (8)	−0.0021 (8)	−0.0062 (8)
N2	0.0548 (12)	0.0428 (13)	0.0390 (11)	−0.0088 (10)	−0.0079 (9)	−0.0058 (9)
O1	0.0706 (11)	0.0703 (12)	0.0465 (10)	−0.0048 (10)	−0.0127 (9)	−0.0108 (9)
O2	0.0835 (13)	0.1109 (17)	0.0825 (14)	−0.0368 (12)	−0.0321 (11)	−0.0215 (12)
O3	0.0816 (12)	0.0792 (13)	0.0450 (10)	−0.0182 (10)	−0.0052 (9)	−0.0080 (9)
OW1	0.0593 (11)	0.0598 (12)	0.0604 (12)	−0.0122 (10)	−0.0135 (10)	−0.0092 (9)

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Geometric parameters (Å, º)

C1—C6	1.377 (3)	C11—O2	1.237 (3)
C1—C2	1.385 (3)	C11—O1	1.267 (3)
C1—H1	0.93	C11—C12	1.497 (3)
C2—C3	1.365 (4)	C12—C13	1.383 (3)
C2—H2	0.93	C12—C17	1.391 (3)
C3—C4	1.362 (4)	C13—C14	1.386 (3)
C3—H3	0.93	C13—H13	0.93
C4—C5	1.375 (3)	C14—C15	1.373 (3)
C4—H4	0.93	C14—H14	0.93
C5—C6	1.395 (3)	C15—O3	1.370 (3)
C5—H5	0.93	C15—C16	1.386 (3)
C6—N1	1.416 (3)	C16—C17	1.372 (3)
C7—N1	1.465 (2)	C16—H16	0.93
C7—C8	1.508 (3)	C17—H17	0.93
C7—H7A	0.97	C18—O3	1.425 (3)
C7—H7B	0.97	C18—C19	1.490 (4)
C8—N2	1.482 (3)	C18—H18A	0.97
C8—H8A	0.97	C18—H18B	0.97
C8—H8B	0.97	C19—H19A	0.96
C9—N2	1.484 (3)	C19—H19B	0.96
C9—C10	1.504 (3)	C19—H19C	0.96
C9—H9A	0.97	N2—HN1	0.887 (16)
C9—H9B	0.97	N2—HN2	0.930 (16)
C10—N1	1.462 (3)	OW1—HW1	0.88 (3)
C10—H10A	0.97	OW1—HW2	0.91 (3)
C10—H10B	0.97
C6—C1—C2	121.2 (2)	O2—C11—C12	118.0 (2)
C6—C1—H1	119.4	O1—C11—C12	118.2 (2)
C2—C1—H1	119.4	C13—C12—C17	117.6 (2)
C3—C2—C1	121.1 (3)	C13—C12—C11	121.3 (2)
C3—C2—H2	119.4	C17—C12—C11	121.1 (2)
C1—C2—H2	119.4	C12—C13—C14	121.8 (2)
C4—C3—C2	118.4 (3)	C12—C13—H13	119.1
C4—C3—H3	120.8	C14—C13—H13	119.1
C2—C3—H3	120.8	C15—C14—C13	119.4 (2)
C3—C4—C5	121.3 (3)	C15—C14—H14	120.3
C3—C4—H4	119.4	C13—C14—H14	120.3
C5—C4—H4	119.4	O3—C15—C14	124.4 (2)
C4—C5—C6	121.1 (2)	O3—C15—C16	115.8 (2)
C4—C5—H5	119.4	C14—C15—C16	119.8 (2)
C6—C5—H5	119.4	C17—C16—C15	120.1 (2)
C1—C6—C5	116.9 (2)	C17—C16—H16	119.9
C1—C6—N1	122.23 (19)	C15—C16—H16	119.9
C5—C6—N1	120.8 (2)	C16—C17—C12	121.2 (2)
N1—C7—C8	112.74 (18)	C16—C17—H17	119.4
N1—C7—H7A	109	C12—C17—H17	119.4
C8—C7—H7A	109	O3—C18—C19	107.7 (3)
N1—C7—H7B	109	O3—C18—H18A	110.2
C8—C7—H7B	109	C19—C18—H18A	110.2
H7A—C7—H7B	107.8	O3—C18—H18B	110.2
N2—C8—C7	110.70 (17)	C19—C18—H18B	110.2
N2—C8—H8A	109.5	H18A—C18—H18B	108.5
C7—C8—H8A	109.5	C18—C19—H19A	109.5
N2—C8—H8B	109.5	C18—C19—H19B	109.5
C7—C8—H8B	109.5	H19A—C19—H19B	109.5
H8A—C8—H8B	108.1	C18—C19—H19C	109.5
N2—C9—C10	110.47 (18)	H19A—C19—H19C	109.5
N2—C9—H9A	109.6	H19B—C19—H19C	109.5
C10—C9—H9A	109.6	C6—N1—C10	115.21 (16)
N2—C9—H9B	109.6	C6—N1—C7	115.50 (17)
C10—C9—H9B	109.6	C10—N1—C7	111.72 (16)
H9A—C9—H9B	108.1	C8—N2—C9	109.60 (17)
N1—C10—C9	112.16 (17)	C8—N2—HN1	106.9 (15)
N1—C10—H10A	109.2	C9—N2—HN1	109.4 (15)
C9—C10—H10A	109.2	C8—N2—HN2	110.8 (15)
N1—C10—H10B	109.2	C9—N2—HN2	112.2 (15)
C9—C10—H10B	109.2	HN1—N2—HN2	108 (2)
H10A—C10—H10B	107.9	C15—O3—C18	117.7 (2)
O2—C11—O1	123.7 (2)	HW1—OW1—HW2	107 (3)
C6—C1—C2—C3	0.6 (4)	O3—C15—C16—C17	−178.7 (2)
C1—C2—C3—C4	0.2 (5)	C14—C15—C16—C17	1.8 (4)
C2—C3—C4—C5	−0.7 (5)	C15—C16—C17—C12	−0.4 (4)
C3—C4—C5—C6	0.5 (4)	C13—C12—C17—C16	−1.2 (3)
C2—C1—C6—C5	−0.8 (4)	C11—C12—C17—C16	178.9 (2)
C2—C1—C6—N1	177.0 (2)	C1—C6—N1—C10	143.0 (2)
C4—C5—C6—C1	0.3 (4)	C5—C6—N1—C10	−39.3 (3)
C4—C5—C6—N1	−177.6 (2)	C1—C6—N1—C7	10.3 (3)
N1—C7—C8—N2	−54.6 (3)	C5—C6—N1—C7	−171.9 (2)
N2—C9—C10—N1	56.7 (2)	C9—C10—N1—C6	172.59 (17)
O2—C11—C12—C13	−176.6 (2)	C9—C10—N1—C7	−53.0 (2)
O1—C11—C12—C13	4.1 (3)	C8—C7—N1—C6	−173.71 (18)
O2—C11—C12—C17	3.3 (3)	C8—C7—N1—C10	52.0 (2)
O1—C11—C12—C17	−176.0 (2)	C7—C8—N2—C9	57.2 (2)
C17—C12—C13—C14	1.6 (3)	C10—C9—N2—C8	−58.4 (2)
C11—C12—C13—C14	−178.6 (2)	C14—C15—O3—C18	−0.4 (4)
C12—C13—C14—C15	−0.3 (3)	C16—C15—O3—C18	−179.9 (2)
C13—C14—C15—O3	179.1 (2)	C19—C18—O3—C15	−176.7 (3)
C13—C14—C15—C16	−1.4 (3)

4-Phenylpiperazin-1-ium 4-ethoxybenzoate monohydrate (I). Hydrogen-bond geometry (Å, º)

Cg1 and Cg3 are the centroids of the C12–C17 and C1–C6 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN1···OW1i	0.89 (2)	1.94 (2)	2.817 (3)	167 (2)
N2—HN2···O1	0.93 (2)	1.80 (2)	2.724 (3)	174 (2)
OW1—HW1···O2	0.88 (3)	1.75 (3)	2.630 (3)	178 (4)
OW1—HW2···O1ii	0.91 (3)	1.89 (3)	2.789 (3)	167 (3)
C9—H9A···OW1	0.97	2.52	3.308 (3)	138
C1—H1···Cg1iii	0.93	2.91	3.607 (3)	133
C5—H5···Cg1iv	0.93	2.79	3.570 (3)	142
C18—H18B···Cg3v	0.97	2.88	3.737 (4)	148

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1, y, z; (iii) −x, −y+2, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1.

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Crystal data

C10H15N2+·C8H7O3−·H2O	Z = 2
Mr = 332.39	F(000) = 356
Triclinic, P1	Dx = 1.284 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2039 (4) Å	Cell parameters from 2855 reflections
b = 7.5565 (7) Å	θ = 3.1–27.8°
c = 18.614 (1) Å	µ = 0.09 mm−1
α = 81.799 (7)°	T = 293 K
β = 87.020 (7)°	Prism, colourless
γ = 84.852 (7)°	0.48 × 0.48 × 0.32 mm
V = 859.53 (11) Å3

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Data collection

Oxford Diffraction Xcalibur diffractometer	2322 reflections with I > 2σ(I)
ω scans	Rint = 0.016
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	θmax = 25.3°, θmin = 3.1°
Tmin = 0.520, Tmax = 1.000	h = −7→5
5360 measured reflections	k = −9→9
3142 independent reflections	l = −22→22

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Refinement

Refinement on F2	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.125	w = 1/[σ2(Fo2) + (0.0613P)2 + 0.1503P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3139 reflections	Δρmax = 0.2 e Å−3
230 parameters	Δρmin = −0.16 e Å−3
4 restraints	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.032 (4)
Primary atom site location: structure-invariant direct methods

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.0254 (3)	0.4086 (3)	0.19209 (10)	0.0516 (5)
H1	−0.120858	0.476382	0.219629	0.062*
C2	−0.0695 (3)	0.3996 (3)	0.12102 (11)	0.0625 (6)
H2	−0.194898	0.46027	0.101533	0.075*
C3	0.0686 (3)	0.3024 (3)	0.07854 (10)	0.0597 (6)
H3	0.039957	0.298402	0.030279	0.072*
C4	0.2497 (3)	0.2117 (3)	0.10901 (10)	0.0593 (6)
H4	0.343702	0.143909	0.08102	0.071*
C5	0.2964 (3)	0.2181 (3)	0.18024 (9)	0.0512 (5)
H5	0.420732	0.154912	0.199433	0.061*
C6	0.1594 (2)	0.3180 (2)	0.22353 (8)	0.0361 (4)
C7	0.0222 (3)	0.3258 (2)	0.34797 (8)	0.0419 (4)
H7A	−0.026461	0.205915	0.354319	0.05*
H7B	−0.096084	0.40906	0.32889	0.05*
C8	0.0795 (3)	0.3708 (2)	0.42029 (9)	0.0456 (4)
H8A	0.116889	0.494094	0.414858	0.055*
H8B	−0.044531	0.359357	0.454053	0.055*
C9	0.4547 (3)	0.2652 (3)	0.39777 (9)	0.0485 (5)
H9A	0.574598	0.182967	0.416336	0.058*
H9B	0.499661	0.386146	0.392734	0.058*
C10	0.3979 (3)	0.2229 (3)	0.32457 (9)	0.0445 (4)
H10A	0.520581	0.241283	0.29068	0.053*
H10B	0.36928	0.097655	0.328948	0.053*
C11	0.2655 (3)	0.2146 (2)	0.63263 (10)	0.0474 (5)
C12	0.3208 (3)	0.2073 (2)	0.71052 (9)	0.0389 (4)
C13	0.1897 (3)	0.1251 (2)	0.76647 (10)	0.0479 (5)
H13	0.067829	0.072733	0.755273	0.057*
C14	0.2386 (3)	0.1207 (3)	0.83782 (10)	0.0496 (5)
H14	0.149875	0.065178	0.874461	0.06*
C15	0.4186 (3)	0.1982 (2)	0.85567 (9)	0.0442 (4)
C16	0.5528 (3)	0.2784 (2)	0.80102 (9)	0.0453 (4)
H16	0.675183	0.329713	0.812349	0.054*
C17	0.5021 (3)	0.2808 (2)	0.72949 (9)	0.0424 (4)
H17	0.592994	0.333766	0.6929	0.051*
C18	0.6395 (4)	0.2628 (4)	0.94845 (12)	0.0858 (8)
H13A	0.643815	0.248303	1.000449	0.129*
H13B	0.76663	0.201465	0.928951	0.129*
H13C	0.63455	0.388125	0.929616	0.129*
N1	0.2079 (2)	0.33487 (18)	0.29565 (7)	0.0359 (3)
N2	0.2652 (2)	0.2489 (2)	0.44963 (8)	0.0434 (4)
O1	0.1058 (3)	0.1395 (3)	0.61995 (9)	0.0873 (6)
O2	0.3847 (2)	0.29717 (19)	0.58441 (7)	0.0598 (4)
O3	0.4517 (2)	0.1895 (2)	0.92816 (7)	0.0620 (4)
OW1	0.2271 (2)	0.8777 (2)	0.46022 (8)	0.0579 (4)
HN1	0.230 (3)	0.131 (2)	0.4565 (11)	0.07*
HW1	0.120 (3)	0.865 (3)	0.4356 (11)	0.07*
HN2	0.303 (3)	0.270 (3)	0.4956 (9)	0.07*
HW2	0.336 (3)	0.822 (3)	0.4413 (12)	0.07*

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0534 (11)	0.0579 (12)	0.0441 (10)	0.0127 (9)	−0.0106 (8)	−0.0169 (9)
C2	0.0654 (13)	0.0739 (14)	0.0491 (11)	0.0143 (11)	−0.0228 (10)	−0.0166 (10)
C3	0.0820 (14)	0.0654 (13)	0.0347 (10)	−0.0036 (11)	−0.0147 (10)	−0.0145 (9)
C4	0.0717 (13)	0.0660 (13)	0.0411 (10)	0.0070 (11)	0.0022 (9)	−0.0202 (9)
C5	0.0535 (11)	0.0597 (12)	0.0399 (10)	0.0105 (9)	−0.0032 (8)	−0.0137 (8)
C6	0.0405 (9)	0.0344 (9)	0.0346 (8)	−0.0042 (7)	−0.0035 (7)	−0.0071 (7)
C7	0.0388 (9)	0.0515 (11)	0.0352 (9)	0.0009 (8)	−0.0006 (7)	−0.0083 (7)
C8	0.0518 (10)	0.0495 (11)	0.0354 (9)	0.0016 (8)	0.0004 (8)	−0.0104 (8)
C9	0.0425 (10)	0.0619 (12)	0.0419 (10)	−0.0015 (8)	−0.0105 (8)	−0.0090 (8)
C10	0.0385 (9)	0.0569 (11)	0.0381 (9)	0.0049 (8)	−0.0053 (7)	−0.0113 (8)
C11	0.0484 (11)	0.0464 (11)	0.0508 (11)	0.0051 (8)	−0.0161 (9)	−0.0190 (9)
C12	0.0387 (9)	0.0356 (9)	0.0443 (9)	0.0023 (7)	−0.0086 (7)	−0.0131 (7)
C13	0.0366 (9)	0.0485 (11)	0.0617 (12)	−0.0058 (8)	−0.0057 (8)	−0.0157 (9)
C14	0.0437 (10)	0.0551 (12)	0.0500 (11)	−0.0060 (8)	0.0047 (8)	−0.0079 (9)
C15	0.0450 (10)	0.0485 (10)	0.0398 (9)	0.0020 (8)	−0.0042 (8)	−0.0110 (8)
C16	0.0461 (10)	0.0501 (11)	0.0430 (10)	−0.0103 (8)	−0.0101 (8)	−0.0112 (8)
C17	0.0447 (10)	0.0437 (10)	0.0400 (9)	−0.0072 (8)	−0.0036 (7)	−0.0075 (7)
C18	0.0785 (16)	0.136 (2)	0.0509 (13)	−0.0228 (16)	−0.0171 (11)	−0.0274 (14)
N1	0.0347 (7)	0.0416 (8)	0.0320 (7)	0.0006 (6)	−0.0034 (5)	−0.0091 (6)
N2	0.0553 (9)	0.0450 (8)	0.0319 (7)	−0.0061 (7)	−0.0089 (6)	−0.0082 (6)
O1	0.0815 (11)	0.1184 (15)	0.0727 (11)	−0.0352 (10)	−0.0327 (9)	−0.0230 (10)
O2	0.0721 (9)	0.0700 (10)	0.0402 (7)	−0.0038 (7)	−0.0139 (7)	−0.0144 (7)
O3	0.0641 (9)	0.0866 (11)	0.0365 (7)	−0.0067 (8)	−0.0047 (6)	−0.0117 (7)
OW1	0.0595 (9)	0.0631 (9)	0.0544 (8)	−0.0097 (7)	−0.0177 (7)	−0.0108 (7)

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Geometric parameters (Å, º)

C1—C2	1.377 (3)	C10—H10A	0.97
C1—C6	1.393 (2)	C10—H10B	0.97
C1—H1	0.93	C11—O1	1.234 (2)
C2—C3	1.371 (3)	C11—O2	1.263 (2)
C2—H2	0.93	C11—C12	1.499 (2)
C3—C4	1.368 (3)	C12—C17	1.381 (2)
C3—H3	0.93	C12—C13	1.396 (3)
C4—C5	1.380 (3)	C13—C14	1.373 (3)
C4—H4	0.93	C13—H13	0.93
C5—C6	1.388 (2)	C14—C15	1.383 (3)
C5—H5	0.93	C14—H14	0.93
C6—N1	1.4165 (19)	C15—O3	1.367 (2)
C7—N1	1.469 (2)	C15—C16	1.386 (2)
C7—C8	1.502 (2)	C16—C17	1.381 (2)
C7—H7A	0.97	C16—H16	0.93
C7—H7B	0.97	C17—H17	0.93
C8—N2	1.485 (2)	C18—O3	1.424 (3)
C8—H8A	0.97	C18—H13A	0.96
C8—H8B	0.97	C18—H13B	0.96
C9—N2	1.484 (2)	C18—H13C	0.96
C9—C10	1.509 (2)	N2—HN1	0.924 (15)
C9—H9A	0.97	N2—HN2	0.938 (16)
C9—H9B	0.97	OW1—HW1	0.847 (16)
C10—N1	1.467 (2)	OW1—HW2	0.850 (16)
C2—C1—C6	121.26 (16)	C9—C10—H10B	109.1
C2—C1—H1	119.4	H10A—C10—H10B	107.9
C6—C1—H1	119.4	O1—C11—O2	124.33 (18)
C3—C2—C1	121.01 (18)	O1—C11—C12	117.62 (19)
C3—C2—H2	119.5	O2—C11—C12	118.06 (16)
C1—C2—H2	119.5	C17—C12—C13	117.75 (16)
C4—C3—C2	118.25 (17)	C17—C12—C11	121.49 (16)
C4—C3—H3	120.9	C13—C12—C11	120.77 (16)
C2—C3—H3	120.9	C14—C13—C12	120.75 (16)
C3—C4—C5	121.67 (17)	C14—C13—H13	119.6
C3—C4—H4	119.2	C12—C13—H13	119.6
C5—C4—H4	119.2	C13—C14—C15	120.56 (17)
C4—C5—C6	120.65 (17)	C13—C14—H14	119.7
C4—C5—H5	119.7	C15—C14—H14	119.7
C6—C5—H5	119.7	O3—C15—C14	116.20 (16)
C5—C6—C1	117.15 (15)	O3—C15—C16	124.10 (16)
C5—C6—N1	122.11 (14)	C14—C15—C16	119.69 (16)
C1—C6—N1	120.68 (14)	C17—C16—C15	119.06 (16)
N1—C7—C8	111.59 (14)	C17—C16—H16	120.5
N1—C7—H7A	109.3	C15—C16—H16	120.5
C8—C7—H7A	109.3	C16—C17—C12	122.16 (16)
N1—C7—H7B	109.3	C16—C17—H17	118.9
C8—C7—H7B	109.3	C12—C17—H17	118.9
H7A—C7—H7B	108	O3—C18—H13A	109.5
N2—C8—C7	110.40 (13)	O3—C18—H13B	109.5
N2—C8—H8A	109.6	H13A—C18—H13B	109.5
C7—C8—H8A	109.6	O3—C18—H13C	109.5
N2—C8—H8B	109.6	H13A—C18—H13C	109.5
C7—C8—H8B	109.6	H13B—C18—H13C	109.5
H8A—C8—H8B	108.1	C6—N1—C10	115.62 (12)
N2—C9—C10	110.34 (14)	C6—N1—C7	114.90 (12)
N2—C9—H9A	109.6	C10—N1—C7	111.53 (12)
C10—C9—H9A	109.6	C9—N2—C8	109.67 (13)
N2—C9—H9B	109.6	C9—N2—HN1	108.7 (13)
C10—C9—H9B	109.6	C8—N2—HN1	110.6 (13)
H9A—C9—H9B	108.1	C9—N2—HN2	110.0 (13)
N1—C10—C9	112.30 (13)	C8—N2—HN2	113.2 (13)
N1—C10—H10A	109.1	HN1—N2—HN2	104.5 (18)
C9—C10—H10A	109.1	C15—O3—C18	117.68 (16)
N1—C10—H10B	109.1	HW1—OW1—HW2	106 (2)
C6—C1—C2—C3	−0.7 (3)	C13—C14—C15—C16	−1.1 (3)
C1—C2—C3—C4	1.2 (3)	O3—C15—C16—C17	−179.35 (16)
C2—C3—C4—C5	−0.9 (3)	C14—C15—C16—C17	0.7 (3)
C3—C4—C5—C6	0.0 (3)	C15—C16—C17—C12	0.5 (3)
C4—C5—C6—C1	0.6 (3)	C13—C12—C17—C16	−1.4 (2)
C4—C5—C6—N1	−176.76 (18)	C11—C12—C17—C16	178.68 (15)
C2—C1—C6—C5	−0.2 (3)	C5—C6—N1—C10	−7.1 (2)
C2—C1—C6—N1	177.14 (18)	C1—C6—N1—C10	175.65 (16)
N1—C7—C8—N2	−57.13 (19)	C5—C6—N1—C7	−139.28 (17)
N2—C9—C10—N1	55.4 (2)	C1—C6—N1—C7	43.5 (2)
O1—C11—C12—C17	177.14 (17)	C9—C10—N1—C6	172.93 (14)
O2—C11—C12—C17	−3.0 (2)	C9—C10—N1—C7	−53.34 (19)
O1—C11—C12—C13	−2.8 (2)	C8—C7—N1—C6	−171.86 (13)
O2—C11—C12—C13	177.07 (16)	C8—C7—N1—C10	54.06 (18)
C17—C12—C13—C14	1.0 (2)	C10—C9—N2—C8	−57.61 (19)
C11—C12—C13—C14	−179.05 (15)	C7—C8—N2—C9	58.76 (19)
C12—C13—C14—C15	0.2 (3)	C14—C15—O3—C18	178.00 (19)
C13—C14—C15—O3	178.99 (15)	C16—C15—O3—C18	−1.9 (3)

4-Phenylpiperazin-1-ium 4-methoxybenzoate monohydrate (II). Hydrogen-bond geometry (Å, º)

Cg3 is the centroid of the C12–C17 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN1···OW1i	0.93 (2)	1.91 (2)	2.815 (2)	166 (2)
OW1—HW1···O1ii	0.84 (2)	1.80 (2)	2.633 (2)	175 (2)
N2—HN2···O2	0.93 (2)	1.81 (2)	2.7350 (19)	176 (2)
OW1—HW2···O2iii	0.85 (2)	1.96 (2)	2.7876 (19)	168 (2)
C8—H8B···OW1ii	0.97	2.53	3.331 (2)	140
C1—H1···Cg3ii	0.93	2.76	3.549 (2)	144
C5—H5···Cg3iv	0.93	2.86	3.625 (2)	140

Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1.

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Crystal data

C10H15N2+·C8H7O2−·H2O	Z = 2
Mr = 316.39	F(000) = 340
Triclinic, P1	Dx = 1.233 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1175 (5) Å	Cell parameters from 2877 reflections
b = 7.6225 (7) Å	θ = 3.0–27.8°
c = 18.452 (1) Å	µ = 0.08 mm−1
α = 97.421 (9)°	T = 293 K
β = 90.403 (8)°	Plate, colourless
γ = 92.405 (8)°	0.5 × 0.4 × 0.08 mm
V = 852.40 (12) Å3

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Data collection

Oxford Diffraction Xcalibur diffractometer	2248 reflections with I > 2σ(I)
ω scans	Rint = 0.013
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	θmax = 25.4°, θmin = 3.1°
Tmin = 0.837, Tmax = 1.000	h = −7→7
5354 measured reflections	k = −7→9
3126 independent reflections	l = −22→22

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Refinement

Refinement on F2	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128	w = 1/[σ2(Fo2) + (0.0582P)2 + 0.2086P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3118 reflections	Δρmax = 0.16 e Å−3
226 parameters	Δρmin = −0.16 e Å−3
4 restraints	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.011 (3)
Primary atom site location: structure-invariant direct methods

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5691 (4)	0.8192 (4)	0.17484 (12)	0.0759 (7)
H1	0.680156	0.871649	0.206032	0.091*
C2	0.5967 (5)	0.8079 (4)	0.10029 (13)	0.0979 (9)
H2	0.725499	0.854112	0.082348	0.117*
C3	0.4416 (5)	0.7314 (4)	0.05273 (13)	0.0932 (8)
H3	0.462879	0.722711	0.002561	0.112*
C4	0.2536 (5)	0.6676 (4)	0.08016 (13)	0.0966 (9)
H4	0.144014	0.6157	0.048248	0.116*
C5	0.2219 (4)	0.6782 (3)	0.15497 (11)	0.0776 (7)
H5	0.091389	0.633226	0.172178	0.093*
C6	0.3793 (3)	0.7539 (2)	0.20421 (9)	0.0472 (4)
C7	0.5393 (3)	0.8071 (3)	0.32686 (9)	0.0497 (4)
H7A	0.626347	0.904686	0.31147	0.06*
H7B	0.626834	0.703106	0.320724	0.06*
C8	0.4853 (3)	0.8506 (3)	0.40599 (10)	0.0534 (5)
H8A	0.619196	0.865746	0.435007	0.064*
H8B	0.410139	0.960943	0.413335	0.064*
C9	0.1390 (3)	0.6889 (3)	0.38632 (10)	0.0554 (5)
H9A	0.062182	0.798326	0.394853	0.067*
H9B	0.04531	0.594989	0.401599	0.067*
C10	0.1858 (3)	0.6476 (3)	0.30616 (9)	0.0502 (5)
H10A	0.241603	0.529612	0.296889	0.06*
H10B	0.050244	0.647749	0.278608	0.06*
C11	0.3129 (3)	0.7088 (2)	0.62385 (9)	0.0445 (4)
C12	0.2060 (3)	0.7367 (2)	0.69737 (9)	0.0413 (4)
C13	0.2989 (3)	0.6749 (3)	0.75734 (10)	0.0535 (5)
H13	0.428845	0.615675	0.752062	0.064*
C14	0.2008 (4)	0.7003 (3)	0.82503 (11)	0.0656 (6)
H14	0.265661	0.657329	0.864556	0.079*
C15	0.0081 (4)	0.7885 (3)	0.83492 (11)	0.0611 (5)
C16	−0.0837 (3)	0.8490 (3)	0.77515 (11)	0.0583 (5)
H16	−0.214079	0.907628	0.780509	0.07*
C17	0.0129 (3)	0.8250 (2)	0.70719 (10)	0.0484 (4)
H17	−0.052163	0.868519	0.667839	0.058*
C18	−0.0996 (5)	0.8177 (4)	0.90877 (13)	0.0968 (9)
H18A	−0.171921	0.927853	0.913714	0.145*
H18B	0.009588	0.821099	0.946613	0.145*
H18C	−0.204829	0.722525	0.912877	0.145*
N1	0.3441 (2)	0.77371 (19)	0.28025 (7)	0.0434 (4)
N2	0.3444 (2)	0.7069 (2)	0.43010 (8)	0.0487 (4)
O1	0.4844 (2)	0.62506 (19)	0.61816 (7)	0.0632 (4)
O2	0.2244 (2)	0.77468 (19)	0.57233 (7)	0.0601 (4)
OW1	0.7937 (3)	0.7241 (4)	0.52207 (11)	0.1232 (9)
HW1	0.926 (4)	0.748 (5)	0.542 (2)	0.177 (17)*
HW2	0.702 (4)	0.704 (4)	0.5539 (13)	0.119 (11)*
HN1	0.415 (3)	0.605 (2)	0.4225 (11)	0.061 (6)*
HN2	0.310 (3)	0.731 (3)	0.4786 (9)	0.065 (6)*

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0620 (13)	0.114 (2)	0.0494 (12)	−0.0113 (13)	0.0106 (10)	0.0080 (12)
C2	0.0883 (18)	0.148 (3)	0.0556 (15)	−0.0138 (18)	0.0233 (13)	0.0120 (15)
C3	0.123 (2)	0.109 (2)	0.0456 (13)	−0.0055 (18)	0.0201 (15)	0.0043 (13)
C4	0.130 (2)	0.106 (2)	0.0480 (13)	−0.0340 (18)	−0.0161 (14)	0.0036 (13)
C5	0.0895 (16)	0.0936 (17)	0.0466 (12)	−0.0337 (13)	−0.0042 (11)	0.0105 (11)
C6	0.0561 (11)	0.0456 (10)	0.0397 (9)	0.0045 (8)	0.0038 (8)	0.0042 (7)
C7	0.0473 (10)	0.0550 (11)	0.0456 (10)	−0.0123 (8)	0.0008 (8)	0.0070 (8)
C8	0.0581 (11)	0.0569 (12)	0.0440 (10)	−0.0065 (9)	−0.0031 (8)	0.0045 (8)
C9	0.0439 (10)	0.0734 (13)	0.0494 (11)	−0.0025 (9)	0.0087 (8)	0.0105 (9)
C10	0.0383 (9)	0.0668 (12)	0.0446 (10)	−0.0056 (8)	0.0005 (7)	0.0064 (8)
C11	0.0429 (10)	0.0454 (10)	0.0432 (10)	−0.0062 (8)	0.0042 (7)	0.0012 (7)
C12	0.0413 (9)	0.0376 (9)	0.0439 (9)	−0.0047 (7)	0.0046 (7)	0.0025 (7)
C13	0.0525 (11)	0.0601 (12)	0.0479 (11)	0.0081 (9)	0.0012 (8)	0.0054 (9)
C14	0.0798 (15)	0.0739 (14)	0.0439 (11)	0.0046 (11)	−0.0013 (10)	0.0111 (9)
C15	0.0742 (14)	0.0597 (12)	0.0479 (11)	−0.0009 (10)	0.0167 (10)	0.0012 (9)
C16	0.0577 (12)	0.0554 (12)	0.0614 (12)	0.0098 (9)	0.0173 (9)	0.0025 (9)
C17	0.0525 (10)	0.0458 (10)	0.0476 (10)	0.0047 (8)	0.0056 (8)	0.0072 (8)
C18	0.125 (2)	0.108 (2)	0.0567 (14)	0.0110 (17)	0.0378 (15)	0.0048 (13)
N1	0.0436 (8)	0.0487 (8)	0.0379 (8)	−0.0025 (6)	0.0016 (6)	0.0068 (6)
N2	0.0519 (9)	0.0577 (10)	0.0371 (8)	0.0057 (8)	0.0054 (7)	0.0068 (7)
O1	0.0546 (8)	0.0720 (9)	0.0633 (9)	0.0149 (7)	0.0170 (6)	0.0047 (7)
O2	0.0557 (8)	0.0833 (10)	0.0426 (7)	0.0032 (7)	0.0096 (6)	0.0120 (7)
OW1	0.0607 (12)	0.250 (3)	0.0691 (12)	0.0102 (15)	0.0088 (10)	0.0577 (15)

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Geometric parameters (Å, º)

C1—C2	1.379 (3)	C10—H10A	0.97
C1—C6	1.385 (3)	C10—H10B	0.97
C1—H1	0.93	C11—O1	1.249 (2)
C2—C3	1.349 (4)	C11—O2	1.260 (2)
C2—H2	0.93	C11—C12	1.504 (2)
C3—C4	1.356 (4)	C12—C13	1.385 (2)
C3—H3	0.93	C12—C17	1.386 (2)
C4—C5	1.388 (3)	C13—C14	1.384 (3)
C4—H4	0.93	C13—H13	0.93
C5—C6	1.375 (3)	C14—C15	1.383 (3)
C5—H5	0.93	C14—H14	0.93
C6—N1	1.411 (2)	C15—C16	1.374 (3)
C7—N1	1.461 (2)	C15—C18	1.512 (3)
C7—C8	1.497 (2)	C16—C17	1.384 (2)
C7—H7A	0.97	C16—H16	0.93
C7—H7B	0.97	C17—H17	0.93
C8—N2	1.481 (2)	C18—H18A	0.96
C8—H8A	0.97	C18—H18B	0.96
C8—H8B	0.97	C18—H18C	0.96
C9—N2	1.481 (2)	N2—HN1	0.900 (15)
C9—C10	1.504 (2)	N2—HN2	0.918 (15)
C9—H9A	0.97	OW1—HW1	0.886 (19)
C9—H9B	0.97	OW1—HW2	0.839 (18)
C10—N1	1.462 (2)
C2—C1—C6	121.3 (2)	C9—C10—H10B	109
C2—C1—H1	119.3	H10A—C10—H10B	107.8
C6—C1—H1	119.3	O1—C11—O2	124.44 (16)
C3—C2—C1	121.6 (2)	O1—C11—C12	118.17 (16)
C3—C2—H2	119.2	O2—C11—C12	117.37 (15)
C1—C2—H2	119.2	C13—C12—C17	118.11 (16)
C2—C3—C4	118.1 (2)	C13—C12—C11	120.69 (15)
C2—C3—H3	120.9	C17—C12—C11	121.19 (15)
C4—C3—H3	120.9	C14—C13—C12	120.81 (17)
C3—C4—C5	121.2 (2)	C14—C13—H13	119.6
C3—C4—H4	119.4	C12—C13—H13	119.6
C5—C4—H4	119.4	C15—C14—C13	121.14 (19)
C6—C5—C4	121.4 (2)	C15—C14—H14	119.4
C6—C5—H5	119.3	C13—C14—H14	119.4
C4—C5—H5	119.3	C16—C15—C14	117.78 (17)
C5—C6—C1	116.25 (18)	C16—C15—C18	120.7 (2)
C5—C6—N1	121.84 (18)	C14—C15—C18	121.5 (2)
C1—C6—N1	121.81 (17)	C15—C16—C17	121.68 (18)
N1—C7—C8	112.51 (14)	C15—C16—H16	119.2
N1—C7—H7A	109.1	C17—C16—H16	119.2
C8—C7—H7A	109.1	C16—C17—C12	120.47 (17)
N1—C7—H7B	109.1	C16—C17—H17	119.8
C8—C7—H7B	109.1	C12—C17—H17	119.8
H7A—C7—H7B	107.8	C15—C18—H18A	109.5
N2—C8—C7	110.19 (15)	C15—C18—H18B	109.5
N2—C8—H8A	109.6	H18A—C18—H18B	109.5
C7—C8—H8A	109.6	C15—C18—H18C	109.5
N2—C8—H8B	109.6	H18A—C18—H18C	109.5
C7—C8—H8B	109.6	H18B—C18—H18C	109.5
H8A—C8—H8B	108.1	C6—N1—C7	116.19 (14)
N2—C9—C10	110.84 (14)	C6—N1—C10	116.09 (14)
N2—C9—H9A	109.5	C7—N1—C10	113.11 (13)
C10—C9—H9A	109.5	C8—N2—C9	108.70 (15)
N2—C9—H9B	109.5	C8—N2—HN1	108.9 (13)
C10—C9—H9B	109.5	C9—N2—HN1	109.5 (13)
H9A—C9—H9B	108.1	C8—N2—HN2	111.2 (13)
N1—C10—C9	112.96 (15)	C9—N2—HN2	108.7 (13)
N1—C10—H10A	109	HN1—N2—HN2	109.8 (18)
C9—C10—H10A	109	HW1—OW1—HW2	111 (3)
N1—C10—H10B	109
C6—C1—C2—C3	−0.7 (5)	C13—C14—C15—C16	0.4 (3)
C1—C2—C3—C4	1.1 (5)	C13—C14—C15—C18	−179.7 (2)
C2—C3—C4—C5	−0.8 (5)	C14—C15—C16—C17	−0.6 (3)
C3—C4—C5—C6	0.1 (4)	C18—C15—C16—C17	179.5 (2)
C4—C5—C6—C1	0.4 (4)	C15—C16—C17—C12	0.7 (3)
C4—C5—C6—N1	176.6 (2)	C13—C12—C17—C16	−0.5 (3)
C2—C1—C6—C5	−0.1 (4)	C11—C12—C17—C16	179.76 (17)
C2—C1—C6—N1	−176.3 (2)	C5—C6—N1—C7	162.90 (19)
N1—C7—C8—N2	56.4 (2)	C1—C6—N1—C7	−21.0 (3)
N2—C9—C10—N1	−53.3 (2)	C5—C6—N1—C10	26.2 (3)
O1—C11—C12—C13	1.6 (2)	C1—C6—N1—C10	−157.72 (19)
O2—C11—C12—C13	−177.16 (17)	C8—C7—N1—C6	172.21 (15)
O1—C11—C12—C17	−178.61 (16)	C8—C7—N1—C10	−49.8 (2)
O2—C11—C12—C17	2.6 (2)	C9—C10—N1—C6	−173.76 (14)
C17—C12—C13—C14	0.3 (3)	C9—C10—N1—C7	48.2 (2)
C11—C12—C13—C14	−179.94 (18)	C7—C8—N2—C9	−60.59 (19)
C12—C13—C14—C15	−0.3 (3)	C10—C9—N2—C8	59.1 (2)

4-Phenylpiperazin-1-ium 4-methylbenzoate monohydrate (III). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1···O2i	0.89 (3)	1.90 (3)	2.782 (2)	171 (4)
OW1—HW2···O1	0.84 (2)	1.92 (3)	2.751 (2)	172 (3)
N2—HN1···O1ii	0.90 (2)	1.94 (2)	2.819 (2)	164 (2)
N2—HN2···O2	0.92 (2)	1.80 (2)	2.7207 (19)	176 (2)
C8—H8A···OW1	0.97	2.33	3.116 (3)	138

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1.

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Crystal data

C10H15N2+·C2F3O2−·0.123H2O	Z = 4
Mr = 278.47	F(000) = 580.9
Triclinic, P1	Dx = 1.371 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6544 (6) Å	Cell parameters from 3827 reflections
b = 9.9029 (6) Å	θ = 2.6–27.7°
c = 15.2090 (9) Å	µ = 0.12 mm−1
α = 79.621 (6)°	T = 293 K
β = 86.579 (6)°	Prism, colourless
γ = 70.603 (6)°	0.48 × 0.48 × 0.36 mm
V = 1349.10 (15) Å3

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Data collection

Oxford Diffraction Xcalibur diffractometer	2777 reflections with I > 2σ(I)
ω scans	Rint = 0.014
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	θmax = 25.3°, θmin = 2.6°
Tmin = 0.724, Tmax = 1.000	h = −11→11
9220 measured reflections	k = −11→11
4940 independent reflections	l = −18→18

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.070	Hydrogen site location: mixed
wR(F2) = 0.235	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1128P)2 + 0.3819P] where P = (Fo2 + 2Fc2)/3
4927 reflections	(Δ/σ)max < 0.001
375 parameters	Δρmax = 0.42 e Å−3
4 restraints	Δρmin = −0.28 e Å−3
0 constraints

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.2559 (3)	0.7294 (3)	0.51366 (18)	0.0565 (7)
C2	0.1392 (4)	0.7473 (3)	0.5737 (2)	0.0733 (9)
H2	0.043765	0.775704	0.552306	0.088*
C3	0.1634 (5)	0.7235 (4)	0.6648 (3)	0.0913 (12)
H3	0.083976	0.737161	0.703837	0.11*
C4	0.3019 (6)	0.6803 (4)	0.6979 (2)	0.0945 (12)
H4	0.317436	0.664341	0.759246	0.113*
C5	0.4172 (5)	0.6606 (4)	0.6405 (3)	0.0939 (11)
H5	0.512209	0.630205	0.66299	0.113*
C6	0.3958 (4)	0.6850 (4)	0.5497 (2)	0.0746 (9)
H6	0.476639	0.671553	0.511724	0.089*
C7	0.3582 (4)	0.7522 (4)	0.3646 (2)	0.0748 (9)
H7A	0.439678	0.665346	0.385364	0.09*
H7B	0.386552	0.835603	0.369838	0.09*
C8	0.3289 (5)	0.7565 (4)	0.2686 (2)	0.0924 (11)
H8A	0.41407	0.762586	0.232966	0.111*
H8B	0.311597	0.667892	0.261853	0.111*
C9	0.0709 (5)	0.8815 (5)	0.2926 (3)	0.1078 (14)
H9A	0.044836	0.796648	0.287542	0.129*
H9B	−0.01211	0.967225	0.272441	0.129*
C10	0.1038 (4)	0.8774 (5)	0.3876 (2)	0.0933 (12)
H10A	0.121556	0.966325	0.393067	0.112*
H10B	0.019188	0.872467	0.424128	0.112*
C11	0.7162 (3)	0.7837 (3)	0.34093 (18)	0.0568 (7)
C12	0.6756 (3)	0.9091 (3)	0.3787 (2)	0.0682 (8)
H12	0.637995	0.999179	0.342289	0.082*
C13	0.6902 (4)	0.9023 (4)	0.4692 (2)	0.0777 (9)
H13	0.660653	0.987687	0.492938	0.093*
C14	0.7475 (4)	0.7719 (5)	0.5247 (2)	0.0786 (10)
H14	0.758672	0.767891	0.585529	0.094*
C15	0.7878 (4)	0.6476 (4)	0.4884 (2)	0.0856 (10)
H15	0.826468	0.558096	0.525259	0.103*
C16	0.7723 (4)	0.6527 (4)	0.3984 (2)	0.0760 (9)
H16	0.799969	0.566471	0.375625	0.091*
C17	0.8021 (5)	0.6701 (4)	0.2099 (2)	0.0988 (13)
H17A	0.807268	0.577457	0.246337	0.119*
H17B	0.898326	0.680875	0.21027	0.119*
C18	0.7624 (6)	0.6706 (5)	0.1152 (3)	0.1280 (18)
H18A	0.837937	0.594874	0.090434	0.154*
H18B	0.670336	0.65126	0.114843	0.154*
C19	0.6330 (5)	0.9270 (5)	0.0978 (2)	0.0940 (11)
H19A	0.540215	0.909315	0.096567	0.113*
H19B	0.622668	1.021169	0.061705	0.113*
C20	0.6691 (4)	0.9279 (4)	0.1919 (2)	0.0773 (9)
H20A	0.756179	0.95605	0.191813	0.093*
H20B	0.58882	0.999996	0.216184	0.093*
C21	0.2670 (4)	0.2041 (4)	0.1833 (2)	0.0776 (9)
C22	0.2420 (8)	0.3636 (6)	0.1772 (3)	0.1240 (19)	0.736 (3)
C22'	0.2420 (8)	0.3636 (6)	0.1772 (3)	0.1240 (19)	0.264 (3)
C23	0.1345 (7)	0.8145 (4)	0.0390 (2)	0.0940 (13)
C24	0.1356 (7)	0.7597 (5)	−0.0474 (3)	0.1064 (14)	0.736 (3)
C24'	0.1356 (7)	0.7597 (5)	−0.0474 (3)	0.1064 (14)	0.264 (3)
N1	0.2321 (3)	0.7528 (2)	0.42089 (15)	0.0596 (6)
N2	0.1985 (4)	0.8842 (3)	0.23622 (18)	0.0888 (9)
N3	0.6944 (3)	0.7878 (3)	0.24907 (15)	0.0687 (7)
N4	0.7485 (4)	0.8143 (4)	0.05995 (19)	0.1087 (12)
O1	0.2367 (4)	0.1448 (3)	0.25394 (17)	0.1168 (10)
O2	0.3178 (4)	0.1492 (4)	0.11854 (18)	0.1323 (12)
O3	0.2462 (4)	0.8383 (4)	0.05509 (19)	0.1252 (11)
O4	0.0222 (4)	0.8316 (3)	0.08423 (17)	0.1113 (10)
F1	0.3669 (7)	0.3949 (7)	0.1721 (5)	0.202 (3)	0.736 (3)
F2	0.1775 (9)	0.4242 (5)	0.2477 (4)	0.184 (3)	0.736 (3)
F3	0.1706 (8)	0.4421 (5)	0.1039 (4)	0.179 (3)	0.736 (3)
F1'	0.302 (2)	0.407 (2)	0.0998 (15)	0.202 (3)	0.264 (3)
F2'	0.282 (3)	0.3950 (17)	0.2311 (15)	0.184 (3)	0.264 (3)
F3'	0.102 (2)	0.4303 (16)	0.1642 (11)	0.179 (3)	0.264 (3)
F4	0.2609 (7)	0.6549 (8)	−0.0615 (4)	0.175 (2)	0.736 (3)
F5	0.1187 (10)	0.8524 (4)	−0.1159 (2)	0.181 (3)	0.736 (3)
F6	0.0480 (7)	0.6817 (8)	−0.0460 (4)	0.153 (2)	0.736 (3)
F4'	0.238 (2)	0.789 (2)	−0.1015 (13)	0.175 (2)	0.264 (3)
F5'	0.157 (4)	0.6370 (19)	−0.0412 (9)	0.181 (3)	0.264 (3)
F6'	−0.0072 (19)	0.8256 (19)	−0.0913 (10)	0.153 (2)	0.264 (3)
OW1	0.5122 (12)	0.6320 (14)	0.0361 (10)	0.150 (8)	0.245 (10)
H21	0.207318	0.969376	0.238227	0.18*
H22	0.187596	0.886717	0.179696	0.18*
H41	0.826598	0.838953	0.053835	0.18*
H42	0.722096	0.810784	0.005806	0.18*
HW1A	0.572085	0.618747	−0.007306	0.225*	0.245 (10)
HW1B	0.441675	0.707638	0.015874	0.225*	0.245 (10)

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.065 (2)	0.0490 (15)	0.0531 (16)	−0.0184 (13)	0.0022 (14)	−0.0040 (12)
C2	0.075 (2)	0.069 (2)	0.068 (2)	−0.0195 (16)	0.0111 (17)	−0.0051 (15)
C3	0.116 (3)	0.074 (2)	0.075 (2)	−0.025 (2)	0.033 (2)	−0.0120 (18)
C4	0.141 (4)	0.079 (2)	0.056 (2)	−0.028 (2)	−0.001 (2)	−0.0089 (17)
C5	0.107 (3)	0.098 (3)	0.072 (2)	−0.025 (2)	−0.026 (2)	−0.0087 (19)
C6	0.064 (2)	0.089 (2)	0.066 (2)	−0.0204 (17)	−0.0069 (16)	−0.0074 (16)
C7	0.073 (2)	0.086 (2)	0.0618 (18)	−0.0228 (17)	0.0105 (16)	−0.0132 (16)
C8	0.122 (3)	0.098 (3)	0.062 (2)	−0.039 (2)	0.010 (2)	−0.0215 (19)
C9	0.099 (3)	0.139 (4)	0.079 (3)	−0.044 (3)	−0.030 (2)	0.017 (2)
C10	0.065 (2)	0.128 (3)	0.063 (2)	−0.010 (2)	−0.0084 (17)	0.0067 (19)
C11	0.0597 (18)	0.0649 (18)	0.0512 (15)	−0.0254 (14)	0.0087 (13)	−0.0168 (13)
C12	0.086 (2)	0.0636 (18)	0.0605 (17)	−0.0280 (16)	0.0031 (15)	−0.0183 (14)
C13	0.089 (2)	0.093 (2)	0.066 (2)	−0.0390 (19)	0.0122 (18)	−0.0374 (19)
C14	0.076 (2)	0.119 (3)	0.0513 (17)	−0.044 (2)	0.0031 (16)	−0.019 (2)
C15	0.092 (3)	0.093 (3)	0.063 (2)	−0.024 (2)	−0.0075 (18)	−0.0006 (18)
C16	0.091 (2)	0.065 (2)	0.066 (2)	−0.0172 (16)	0.0037 (17)	−0.0140 (15)
C17	0.167 (4)	0.071 (2)	0.064 (2)	−0.042 (2)	0.028 (2)	−0.0283 (17)
C18	0.221 (6)	0.115 (4)	0.074 (3)	−0.078 (4)	0.039 (3)	−0.050 (2)
C19	0.118 (3)	0.118 (3)	0.0538 (19)	−0.051 (2)	0.0026 (19)	−0.0131 (19)
C20	0.094 (3)	0.076 (2)	0.0602 (18)	−0.0257 (18)	−0.0026 (17)	−0.0121 (16)
C21	0.102 (3)	0.086 (2)	0.0458 (17)	−0.0309 (19)	−0.0063 (17)	−0.0135 (16)
C22	0.194 (6)	0.122 (4)	0.068 (3)	−0.074 (4)	−0.044 (3)	0.011 (3)
C22'	0.194 (6)	0.122 (4)	0.068 (3)	−0.074 (4)	−0.044 (3)	0.011 (3)
C23	0.159 (4)	0.066 (2)	0.052 (2)	−0.032 (2)	0.011 (3)	−0.0113 (16)
C24	0.172 (5)	0.084 (3)	0.070 (2)	−0.047 (3)	0.028 (3)	−0.028 (2)
C24'	0.172 (5)	0.084 (3)	0.070 (2)	−0.047 (3)	0.028 (3)	−0.028 (2)
N1	0.0591 (15)	0.0674 (15)	0.0519 (13)	−0.0234 (12)	−0.0030 (11)	−0.0028 (11)
N2	0.136 (3)	0.082 (2)	0.0530 (15)	−0.0447 (19)	−0.0139 (17)	−0.0015 (13)
N3	0.094 (2)	0.0709 (16)	0.0501 (13)	−0.0357 (14)	0.0087 (12)	−0.0184 (12)
N4	0.162 (3)	0.127 (3)	0.0538 (16)	−0.066 (2)	0.0207 (19)	−0.0303 (18)
O1	0.205 (3)	0.0908 (18)	0.0635 (16)	−0.0618 (19)	0.0128 (17)	−0.0133 (13)
O2	0.163 (3)	0.164 (3)	0.0675 (16)	−0.038 (2)	0.0098 (17)	−0.0474 (18)
O3	0.161 (3)	0.157 (3)	0.0719 (18)	−0.062 (3)	0.0133 (19)	−0.0395 (18)
O4	0.154 (3)	0.121 (2)	0.0633 (15)	−0.0477 (19)	0.0290 (17)	−0.0313 (14)
F1	0.249 (6)	0.248 (6)	0.198 (6)	−0.196 (5)	−0.015 (4)	−0.040 (4)
F2	0.289 (8)	0.078 (3)	0.159 (4)	−0.016 (4)	0.037 (5)	−0.053 (2)
F3	0.278 (7)	0.117 (3)	0.142 (4)	−0.095 (3)	−0.104 (5)	0.068 (3)
F1'	0.249 (6)	0.248 (6)	0.198 (6)	−0.196 (5)	−0.015 (4)	−0.040 (4)
F2'	0.289 (8)	0.078 (3)	0.159 (4)	−0.016 (4)	0.037 (5)	−0.053 (2)
F3'	0.278 (7)	0.117 (3)	0.142 (4)	−0.095 (3)	−0.104 (5)	0.068 (3)
F4	0.227 (5)	0.149 (4)	0.137 (4)	−0.024 (4)	0.046 (3)	−0.082 (4)
F5	0.411 (11)	0.084 (2)	0.0504 (17)	−0.087 (4)	−0.014 (3)	0.0007 (16)
F6	0.226 (5)	0.152 (4)	0.118 (3)	−0.092 (4)	0.009 (3)	−0.061 (3)
F4'	0.227 (5)	0.149 (4)	0.137 (4)	−0.024 (4)	0.046 (3)	−0.082 (4)
F5'	0.411 (11)	0.084 (2)	0.0504 (17)	−0.087 (4)	−0.014 (3)	0.0007 (16)
F6'	0.226 (5)	0.152 (4)	0.118 (3)	−0.092 (4)	0.009 (3)	−0.061 (3)
OW1	0.082 (10)	0.146 (13)	0.219 (18)	−0.019 (8)	−0.031 (9)	−0.048 (11)

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Geometric parameters (Å, º)

C1—C6	1.388 (4)	C17—C18	1.512 (5)
C1—C2	1.392 (4)	C17—H17A	0.97
C1—N1	1.408 (3)	C17—H17B	0.97
C2—C3	1.384 (5)	C18—N4	1.485 (6)
C2—H2	0.93	C18—H18A	0.97
C3—C4	1.359 (6)	C18—H18B	0.97
C3—H3	0.93	C19—N4	1.465 (5)
C4—C5	1.357 (5)	C19—C20	1.495 (4)
C4—H4	0.93	C19—H19A	0.97
C5—C6	1.375 (5)	C19—H19B	0.97
C5—H5	0.93	C20—N3	1.451 (4)
C6—H6	0.93	C20—H20A	0.97
C7—N1	1.445 (4)	C20—H20B	0.97
C7—C8	1.494 (5)	C21—O1	1.197 (4)
C7—H7A	0.97	C21—O2	1.211 (4)
C7—H7B	0.97	C21—C22'	1.502 (7)
C8—N2	1.489 (5)	C21—C22	1.502 (7)
C8—H8A	0.97	C22—F3	1.321 (6)
C8—H8B	0.97	C22—F1	1.337 (7)
C9—N2	1.464 (5)	C22—F2	1.343 (7)
C9—C10	1.488 (5)	C22'—F2'	1.06 (2)
C9—H9A	0.97	C22'—F3'	1.306 (19)
C9—H9B	0.97	C22'—F1'	1.346 (19)
C10—N1	1.466 (4)	C23—O3	1.224 (5)
C10—H10A	0.97	C23—O4	1.228 (5)
C10—H10B	0.97	C23—C24'	1.506 (6)
C11—C16	1.386 (4)	C23—C24	1.506 (6)
C11—C12	1.390 (4)	C24—F5	1.238 (5)
C11—N3	1.417 (3)	C24—F6	1.319 (7)
C12—C13	1.379 (4)	C24—F4	1.342 (7)
C12—H12	0.93	C24'—F5'	1.151 (17)
C13—C14	1.369 (5)	C24'—F4'	1.32 (2)
C13—H13	0.93	C24'—F6'	1.459 (17)
C14—C15	1.368 (5)	N2—H21	0.8818
C14—H14	0.93	N2—H22	0.8672
C15—C16	1.377 (5)	N4—H41	0.8621
C15—H15	0.93	N4—H42	0.8861
C16—H16	0.93	OW1—HW1A	0.8501
C17—N3	1.471 (4)	OW1—HW1B	0.8501
C6—C1—C2	116.9 (3)	N4—C18—H18B	109.8
C6—C1—N1	122.0 (3)	C17—C18—H18B	109.8
C2—C1—N1	121.1 (3)	H18A—C18—H18B	108.2
C3—C2—C1	120.8 (3)	N4—C19—C20	110.7 (3)
C3—C2—H2	119.6	N4—C19—H19A	109.5
C1—C2—H2	119.6	C20—C19—H19A	109.5
C4—C3—C2	120.8 (3)	N4—C19—H19B	109.5
C4—C3—H3	119.6	C20—C19—H19B	109.5
C2—C3—H3	119.6	H19A—C19—H19B	108.1
C5—C4—C3	119.2 (4)	N3—C20—C19	112.8 (3)
C5—C4—H4	120.4	N3—C20—H20A	109
C3—C4—H4	120.4	C19—C20—H20A	109
C4—C5—C6	121.0 (4)	N3—C20—H20B	109
C4—C5—H5	119.5	C19—C20—H20B	109
C6—C5—H5	119.5	H20A—C20—H20B	107.8
C5—C6—C1	121.2 (3)	O1—C21—O2	127.2 (4)
C5—C6—H6	119.4	O1—C21—C22'	115.1 (4)
C1—C6—H6	119.4	O2—C21—C22'	117.7 (4)
N1—C7—C8	112.5 (3)	O1—C21—C22	115.1 (4)
N1—C7—H7A	109.1	O2—C21—C22	117.7 (4)
C8—C7—H7A	109.1	F3—C22—F1	103.5 (5)
N1—C7—H7B	109.1	F3—C22—F2	108.8 (6)
C8—C7—H7B	109.1	F1—C22—F2	100.9 (6)
H7A—C7—H7B	107.8	F3—C22—C21	112.7 (4)
N2—C8—C7	110.4 (3)	F1—C22—C21	112.9 (6)
N2—C8—H8A	109.6	F2—C22—C21	116.7 (4)
C7—C8—H8A	109.6	F2'—C22'—F3'	112.1 (15)
N2—C8—H8B	109.6	F2'—C22'—F1'	110.0 (16)
C7—C8—H8B	109.6	F3'—C22'—F1'	103.4 (13)
H8A—C8—H8B	108.1	F2'—C22'—C21	116.5 (11)
N2—C9—C10	110.4 (3)	F3'—C22'—C21	106.9 (7)
N2—C9—H9A	109.6	F1'—C22'—C21	107.0 (10)
C10—C9—H9A	109.6	O3—C23—O4	127.7 (4)
N2—C9—H9B	109.6	O3—C23—C24'	115.5 (5)
C10—C9—H9B	109.6	O4—C23—C24'	116.8 (5)
H9A—C9—H9B	108.1	O3—C23—C24	115.5 (5)
N1—C10—C9	112.1 (3)	O4—C23—C24	116.8 (5)
N1—C10—H10A	109.2	F5—C24—F6	111.9 (6)
C9—C10—H10A	109.2	F5—C24—F4	104.5 (6)
N1—C10—H10B	109.2	F6—C24—F4	96.7 (5)
C9—C10—H10B	109.2	F5—C24—C23	115.4 (4)
H10A—C10—H10B	107.9	F6—C24—C23	113.1 (4)
C16—C11—C12	116.8 (3)	F4—C24—C23	113.6 (5)
C16—C11—N3	121.0 (2)	F5'—C24'—F4'	106.2 (16)
C12—C11—N3	122.0 (3)	F5'—C24'—F6'	103.6 (18)
C13—C12—C11	121.1 (3)	F4'—C24'—F6'	109.6 (11)
C13—C12—H12	119.4	F5'—C24'—C23	116.0 (8)
C11—C12—H12	119.4	F4'—C24'—C23	110.3 (9)
C14—C13—C12	121.1 (3)	F6'—C24'—C23	110.7 (6)
C14—C13—H13	119.4	C1—N1—C7	116.1 (2)
C12—C13—H13	119.4	C1—N1—C10	115.0 (2)
C15—C14—C13	118.3 (3)	C7—N1—C10	110.5 (2)
C15—C14—H14	120.8	C9—N2—C8	110.4 (3)
C13—C14—H14	120.8	C9—N2—H21	104.1
C14—C15—C16	121.2 (3)	C8—N2—H21	115
C14—C15—H15	119.4	C9—N2—H22	115.8
C16—C15—H15	119.4	C8—N2—H22	108.2
C15—C16—C11	121.4 (3)	H21—N2—H22	103.4
C15—C16—H16	119.3	C11—N3—C20	115.9 (2)
C11—C16—H16	119.3	C11—N3—C17	114.7 (3)
N3—C17—C18	111.9 (4)	C20—N3—C17	111.7 (2)
N3—C17—H17A	109.2	C19—N4—C18	109.0 (3)
C18—C17—H17A	109.2	C19—N4—H41	108.2
N3—C17—H17B	109.2	C18—N4—H41	116.5
C18—C17—H17B	109.2	C19—N4—H42	109.5
H17A—C17—H17B	107.9	C18—N4—H42	106.4
N4—C18—C17	109.5 (3)	H41—N4—H42	107.1
N4—C18—H18A	109.8	HW1A—OW1—HW1B	104.5
C17—C18—H18A	109.8
C6—C1—C2—C3	0.8 (4)	O3—C23—C24—F5	−75.6 (8)
N1—C1—C2—C3	179.7 (3)	O4—C23—C24—F5	103.6 (7)
C1—C2—C3—C4	−0.8 (5)	O3—C23—C24—F6	153.8 (6)
C2—C3—C4—C5	0.1 (6)	O4—C23—C24—F6	−26.9 (7)
C3—C4—C5—C6	0.6 (6)	O3—C23—C24—F4	44.9 (7)
C4—C5—C6—C1	−0.5 (6)	O4—C23—C24—F4	−135.8 (6)
C2—C1—C6—C5	−0.2 (5)	O3—C23—C24'—F5'	102 (2)
N1—C1—C6—C5	−179.0 (3)	O4—C23—C24'—F5'	−79 (2)
N1—C7—C8—N2	55.4 (4)	O3—C23—C24'—F4'	−18.9 (12)
N2—C9—C10—N1	−57.1 (5)	O4—C23—C24'—F4'	160.3 (11)
C16—C11—C12—C13	−0.3 (5)	O3—C23—C24'—F6'	−140.4 (8)
N3—C11—C12—C13	176.4 (3)	O4—C23—C24'—F6'	38.8 (9)
C11—C12—C13—C14	1.1 (5)	C6—C1—N1—C7	−10.1 (4)
C12—C13—C14—C15	−1.1 (5)	C2—C1—N1—C7	171.1 (3)
C13—C14—C15—C16	0.3 (5)	C6—C1—N1—C10	−141.4 (3)
C14—C15—C16—C11	0.5 (6)	C2—C1—N1—C10	39.8 (4)
C12—C11—C16—C15	−0.5 (5)	C8—C7—N1—C1	171.8 (3)
N3—C11—C16—C15	−177.2 (3)	C8—C7—N1—C10	−54.8 (4)
N3—C17—C18—N4	56.6 (5)	C9—C10—N1—C1	−170.6 (3)
N4—C19—C20—N3	−55.9 (4)	C9—C10—N1—C7	55.5 (4)
O1—C21—C22—F3	−132.4 (6)	C10—C9—N2—C8	56.8 (4)
O2—C21—C22—F3	49.2 (8)	C7—C8—N2—C9	−55.8 (4)
O1—C21—C22—F1	110.7 (6)	C16—C11—N3—C20	−165.9 (3)
O2—C21—C22—F1	−67.7 (6)	C12—C11—N3—C20	17.6 (4)
O1—C21—C22—F2	−5.5 (8)	C16—C11—N3—C17	−33.3 (4)
O2—C21—C22—F2	176.1 (6)	C12—C11—N3—C17	150.2 (3)
O1—C21—C22'—F2'	47.1 (18)	C19—C20—N3—C11	−174.6 (3)
O2—C21—C22'—F2'	−131.3 (17)	C19—C20—N3—C17	51.5 (4)
O1—C21—C22'—F3'	−79.2 (9)	C18—C17—N3—C11	173.3 (3)
O2—C21—C22'—F3'	102.4 (10)	C18—C17—N3—C20	−52.1 (4)
O1—C21—C22'—F1'	170.6 (10)	C20—C19—N4—C18	59.6 (4)
O2—C21—C22'—F1'	−7.8 (12)	C17—C18—N4—C19	−60.0 (5)

4-Phenylpiperazin-1-ium trifluoroacetate 0.123-hydrate (IV). Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1i	0.88	1.91	2.790 (4)	174
N2—H22···O3	0.87	2.04	2.860 (4)	157
N2—H22···O4	0.87	2.47	3.164 (5)	137
N4—H41···O4ii	0.86	1.95	2.759 (6)	156
N4—H42···O2iii	0.89	1.90	2.758 (4)	164
C18—H18A···F5′iii	0.97	2.53	3.273 (18)	134
C18—H18B···Ow1	0.97	2.08	2.929 (15)	145
C19—H19B···O3iv	0.97	2.59	3.420 (5)	144
C20—H20A···F5iv	0.97	2.64	3.468 (8)	144
C16—H16···Cg2v	0.93	2.99	3.745 (4)	140

Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+2, −z; (v) −x+1, −y+1, −z+1.

Funding Statement

Funding for this research was provided by: Ministerio de Ciencia e Innovación (grant No. PID2020-113558RB-C41 to S. Garcia-Granda, M. S. M. Abdelbaky); Gobierno del Principado de Asturias (grant No. AYUD/2021/50997 to S. Garcia-Granda, M. S. M. Abdelbaky).