Bis(3-carboxy­anilinum) bis­(perchlorate) monohydrate

Lamia Bendjeddou; Aouatef Cherouana; Nasreddine Hadjadj; Slimane Dahaoui; Claude Lecomte

doi:10.1107/S1600536809025173

. 2009 Jul 4;65(Pt 8):o1770–o1771. doi: 10.1107/S1600536809025173

Bis(3-carboxyanilinum) bis(perchlorate) monohydrate

Lamia Bendjeddou ^a,^*, Aouatef Cherouana ^a, Nasreddine Hadjadj ^a, Slimane Dahaoui ^b, Claude Lecomte ^b

PMCID: PMC2977409 PMID: 21583479

Abstract

In the structure of the title compound, 2C₇H₈NO₂ ⁺·2ClO₄ ⁻·H₂O, the ions are connected via N—H⋯O, N—H⋯(O,O), O—H⋯O, O—H⋯(O,O) and C—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

Hydrogen bonds play a crucial role in supramolecular organization (Jeffrey, 1997 ▶; Nangia & Desiraju, 1998 ▶). Knowledge of hydrogen-bond geometries (Taylor & Kennard, 1984 ▶; Murray-Rust & Glusker, 1984 ▶) and motif formation is vital in the modeling of protein–ligand interactions (Tintelnot & Andrews, 1989 ▶; Böhm & Klebe, 1996 ▶). For hydriogen-bond motifs, see: Bernstein et al. (1995 ▶). For the structures of organic salts of carboxylic acids, see: Bendjeddou et al. (2003 ▶); Cherouana et al. (2003 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶);

Experimental

Crystal data

2C₇H₈NO₂ ⁺·2ClO₄ ⁻·H₂O
M _r = 493.20
Triclinic,
a = 4.9170 (3) Å
b = 12.4030 (2) Å
c = 17.1030 (4) Å
α = 70.520 (2)°
β = 88.697 (3)°
γ = 86.166 (4)°
V = 981.13 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 120 K
0.3 × 0.03 × 0.02 mm

Data collection

Enraf–Nonius KappaCCD diffractometer
Absorption correction: none
45183 measured reflections
7071 independent reflections
4775 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.102
S = 0.99
7071 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST97 (Nardelli, 1995 ▶), Mercury (Macrae et al., 2006 ▶) and POV-RAY (Persistence of Vision Team, 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025173/bq2150sup1.cif

e-65-o1770-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025173/bq2150Isup2.hkl

e-65-o1770-Isup2.hkl^{(339KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bonding geometry (Å, °) and unitary motifs.

D—H⋯A	D—A	H⋯A	D⋯A	D—H⋯A	Motifs
N1—H1A⋯O1Wⁱ	0.89	1.98	2.8664 (18)	171	D
N1—H1B⋯O6ⁱⁱ	0.89	2.11	2.9421 (19)	156	D
N1—H1B⋯O8	0.89	2.57	3.0343 (18)	114	D
N1—H1C⋯O1Wⁱⁱⁱ	0.89	1.98	2.8636 (18)	174	D
O1W—H1W⋯O1ⁱ	0.840 (14)	2.534 (19)	2.9435 (14)	111.2 (15)	D
O1W—H1W⋯O3ⁱⁱⁱ	0.840 (14)	2.258 (14)	3.0356 (16)	153.9 (16)	D
O1W—H2W⋯O1	0.863 (14)	2.019 (15)	2.8504 (17)	161.4 (18)	D
N2—H2A⋯O6	0.89	2.10	2.9336 (19)	155	D
N2—H2A⋯O7	0.89	2.57	2.9584 (18)	107	D
N2—H2B⋯O4^iv	0.89	2.06	2.9382 (18)	168	D
N2—H2C⋯O3^v	0.89	2.55	3.1176 (19)	122	D
N2—H2C⋯O4^v	0.89	1.98	2.8683 (18)	175	D
O12—H12⋯O11^vi	0.82	1.82	2.6425 (14)	178	(8)
O22—H22⋯O21^vii	0.82	1.82	2.6428 (17)	178	(8)
C13—H13⋯O8	0.93	2.31	3.1193 (19)	145	D
C15—H15⋯O2ⁱ	0.93	2.43	3.3058 (19)	156	D
C23—H23⋯O4^iv	0.93	2.55	3.2529 (19)	133	D
C25—H25⋯O8^viii	0.93	2.49	3.384 (2)	162	D
C27—H27⋯O11^vi	0.93	2.60	3.136 (2)	117	D

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) . Motifs: R = ring; D = finite patterns.

Acknowledgments

Technical support (X-ray measurements at SCDRX) from Université Henry Poincaré, Nancy 1, is gratefully acknowledged.

supplementary crystallographic information

Comment

Hydrogen bonds play a crucial role in supramolecular organization (Jeffrey, 1997; Nangia & Desiraju, 1998). Knowledge of hydrogen-bond geometries (Taylor & Kennard, 1984; Murray-Rust & Glusker, 1984) and motif formation is vital in the modeling of protein-ligand interactions (Tintelnot & Andrews, 1989; Böhm & Klebe, 1996). The supramolecular networks become especially interesting when the cation and anion can participate in hydrogen-bonding. In this regard previous studies have been concerned with organic salts of carboxylic acids (Bendjeddou et al., 2003), Cherouana et al., 2003). The asymmetric unit of (I) (Fig. 1) contains two carboxyanilinium cations (A and B), two perchlorate anion and one water molecule. A proton transfer from the perchloric acid to atom N1 and N2 of m-carboxyalinine resulted in the formation of salts.

1- Supramolecular organization:

The structure is formed by double anionic and cationic chains that extend along the b axis, giving rise to layers parallel to the plane (b, c). Chains of water molecules are sandwiched between the anionic double chains (Fig2.).

1–1- Overview.

The supramolecular architecture is generated by the nineteen independent interactions of the Table 1. Three types of intermolecular interactions are present in the structure, including O—H···O, N—H···O and C—H···O hydrogen bonds. The presence of water molecule in the structure results in the presence of additional hydrogen bonds. The construction of graphs-set of the twenty hydrogen bonds in this compound has led to a first-level graph set noted: N1 = R²₂(8)R²₂(8) (Bernstein et al., 1995) (Table 1.).

1–2- The O—H···O hydrogen-bonded network

The carboxylic acid groups at the opposite end of the carboxyanilinium cations forms a centrosymmetric hydrogen-bonded dimers with its counterpart in a cation from an adjacent ribbon and are centered at (0 1/2 0) and (1/2 0 0) respectively for cation A and cation B (Fig. 3). These interactions lead to the graph-set motif R²₂(8), which is a characteristic feature found in most salts of 3- and 4-aminobenzoic acid (Cambridge Structural Database; Allen, 2002).

The water molecule, bridges the anionic perchlorate via the O—H···O hydrogen bonds. The centrosymmetric hydrogen-bonded rings formed by two water molecules and two Cl(1)O4- anions can be described by the graph-set R⁴₄(12) and R²₄(8). The aggregation of this two ring motifs results in an overall one-dimensional hydrogen-bonded chain structure along the [100] direction (Fig. 4).

1–3- The N—H···O hydrogen-bonded network

In the first cationic (A) entity, all ammonium H atoms are involved in hydrogen bonds with the perchlorate (Cl(2) O₄^-) anion and water molecule. Two of these interactions link the anions and cations in an alternating fashion into extended chains along the [100] direction, which can be described by the graph-set C²₂(4). The two other interactions are in a crosslink from an adjacent chain C²₂(4). The combination of these two chain motifs generates noncentrosymmetric fused rings which can be described by the graph-set motif R³₄(10).

In the second cationic (B) entitie, all ammonium H atoms are involved in hydrogen bonds, with the two different perchlorate ion, so forming an alternating noncentrosymmetric rings a long [100] direction which can be described by the graph-set R³₄(10). Only one H atom (H2C) is involved in bifurcated hydrogen bonds with O(3) and O(4) perchlorate atoms, to form a four-membered hydrogen bonded ring R²₁(4). The junction betwen this two different cations (A and B) entities are assured by the perchlorate (Cl(2) O₄^-) anion via N1—H1B···O6, N1—H1B···O8, N2—H2A···O6, N2—H2A···O7 hydrogen bonds, so generete R³₂(6) rings along [100] direction (Fig. 5)

1–4- The C—H···O hydrogen-bonded network:

The junction between the cationic entity is consolidated by five weak independent C—H···O hydrogen bonds via the perchlorate anions, forming an alternating of R⁴₆(22) and R⁵₆(30)centrosymmetric Rings a long b axis (Fig. 6).

Experimental

m-carboxyanilinium acid and perchloric acid were mixed in a 2:2 stoichiometric ratio and dissolved in water. Crystal were obtained by slow evaporation.