N-Methyl­piperazinediium penta­chloridoanti­monate(III) monohydrate

Abstract

The asymmetric unit of the title compound, (C₅H₁₄N₂)[SbCl₅]·H₂O, consists of an N-methyl­piperazinediium cation, a penta­chloridoanti­monate anion with the Sb^III ion in a slightly distorted square-pyramidal coordination environment, and one solvent water mol­ecule. The crystal structure is stabilized by inter­molecular N—H⋯Cl, O—H⋯Cl and N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Baker & Williams (1978 ▶); Bujak & Zaleski (1999 ▶); Clemente & Marzotto (2003 ▶); Feng et al. (2007 ▶); Knodler et al. (1988 ▶); Linden et al. (1999 ▶); Marsh (1995 ▶).

Experimental

Crystal data

• (C₅H₁₄N₂)[SbCl₅]·H₂O

• M _r = 419.20

• Monoclinic,

• a = 9.600 (4) Å

• b = 7.934 (3) Å

• c = 19.966 (6) Å

• β = 106.765 (16)°

• V = 1456.1 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 2.79 mm⁻¹

• T = 273 (2) K

• 0.33 × 0.18 × 0.14 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.460, T _max = 0.696

• 7167 measured reflections

• 2577 independent reflections

• 2400 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.024

• wR(F ²) = 0.054

• S = 1.07

• 2577 reflections

• 129 parameters

• H-atom parameters constrained

• Δρ_max = 0.35 e Å⁻³

• Δρ_min = −0.48 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected geometric parameters (Å, °).

Sb1—Cl2	2.4110 (10)
Sb1—Cl3	2.4623 (10)
Sb1—Cl1	2.5538 (11)
Sb1—Cl4	2.7446 (11)
Sb1—Cl5	2.9112 (11)

Cl2—Sb1—Cl3	89.29 (4)
Cl2—Sb1—Cl1	90.76 (4)
Cl3—Sb1—Cl1	93.67 (4)
Cl2—Sb1—Cl4	91.71 (4)
Cl3—Sb1—Cl4	90.95 (4)
Cl1—Sb1—Cl4	174.79 (3)
Cl5—Sb1—Cl1	92.15(4)
Cl5—Sb1—Cl2	84.50(4)
Cl5—Sb1—Cl3	171.54(4)
Cl5—Sb1—Cl4	83.52(4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1F⋯Cl1i	0.82	2.57	3.346 (4)	159
O1—H1G⋯Cl4	0.82	2.51	3.223 (5)	147
N1—H1A⋯Cl5ii	0.90	2.43	3.179 (4)	141
N1—H1B⋯O1iii	0.90	1.91	2.801 (5)	168
N2—H2⋯Cl5	0.91	2.28	3.133 (5)	157

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

supplementary crystallographic information

Comment

Halogenoantimonates constitute a group of salts in which a number of compounds have been reported (e.g. Feng et al., 2007; Bujak & Zaleski, 1999; Knodler et al., 1988; Baker & Williams, 1978 and see: Clemente & Marzotto (2003); Marsh et al. (1995) for corrected space groups of some of these types of compounds). In our laboratory, a compound containing pentachloridoantimonate has been synthesized, its crystal structure is reported herein.

As shown in Fig. 1, an ion pair consisting of N-methylpiperazinium and (SbCl₅)²⁺, and one water molecule comprise the formula unit. In the selected asymmetric unit The SbCl₅ anion is linked to N-methylpiperazinium and the water molecule by N—H···Cl and O—H···Cl hydrogen bonds.

The Sb atom is coordinated by five Cl atoms, with Sb—Cl distances ranging from 2.4110 (10) to 2.9112 (11) Å. The Sb—Cl distances are slightly different to the values of 2.499 (4)–2.768 (4)Å reported by Bujak & Zaleski (1999). In the title compound the difference between the longest bond (Sb1—Cl5) and shortest bond (Sb1—Cl2) is ca 0.50 Å. The slight deformation of the square-pyramidal coordination environment may be attributed to the presence of relatively strong N—H···Cl hydrogen bonds. The atoms Cl1/Cl3/Cl4/Cl5 form the basal plane, while atom Cl2 is the apical atom. The structure of the anion is similar to that of the (TiCl₅)^2- anion (Linden et al., 1999).

The six-membered piperazine ring is in chair conformation. The crystal structure is stabilized by N—H···Cl, O—H···Cl and N—H···O hydrogen bonds, and by weak C—H···Cl and C—H···O hydrogen bonds (Fig. 2).

Experimental

SbCl₃, N-methylpiperazine and 30% aqueous HCl in a molar ratio of 1:1:1 were mixed and dissolved in sufficient ethanol by heating to 373 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were fromed, collected and washed with dilute aqueous HCl.

Refinement

H atoms were included in calculated positions with O—H = 0.82, N—H = 0.90 - 0.91 and C—H = 0.96–0.97 Å and included in the riding-model approximation with U_iso(H) = 1.2U_eq(C,N,O) or 1.5U_eq(C) for methyl H atoms.

Figures

Fig. 1.

The asymmetric unit of the title compound with atom labels, and 30% probability displacement ellipsoids. Hydrogen bonds are illustrated as dashed lines.

Fig. 2.

The packing viewed approximately along the b axis. Hydrogen bonds are drawn as dashed lines.

Crystal data

(C5H14N2)[SbCl5]·H2O	F000 = 816
Mr = 419.20	Dx = 1.912 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3256 reflections
a = 9.600 (4) Å	θ = 2.1–25.0º
b = 7.934 (3) Å	µ = 2.79 mm−1
c = 19.966 (6) Å	T = 273 (2) K
β = 106.765 (16)º	Block, brown
V = 1456.1 (9) Å3	0.33 × 0.18 × 0.14 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2577 independent reflections
Radiation source: fine-focus sealed tube	2400 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.021
T = 273(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.460, Tmax = 0.696	k = −9→9
7167 measured reflections	l = −16→23

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024	w = 1/[σ2(Fo2) + (0.0213P)2 + 0.8984P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054	(Δ/σ)max = 0.002
S = 1.07	Δρmax = 0.35 e Å−3
2577 reflections	Δρmin = −0.48 e Å−3
129 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0050 (3)
Secondary atom site location: difference Fourier map

Special details

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.6846 (3)	1.0018 (3)	0.96651 (12)	0.0597 (6)
H1F	0.6811	1.0770	0.9378	0.072*
H1G	0.7246	0.9149	0.9607	0.072*
N1	0.8129 (3)	0.3813 (3)	0.60274 (12)	0.0430 (6)
H1A	0.8580	0.2814	0.6042	0.052*
H1B	0.7664	0.4045	0.5577	0.052*
N2	0.7418 (2)	0.6714 (3)	0.67442 (12)	0.0386 (5)
H2	0.7903	0.6427	0.7192	0.046*
C1	0.6710 (4)	0.8384 (4)	0.67596 (18)	0.0546 (8)
H1C	0.7433	0.9196	0.6988	0.082*
H1D	0.5999	0.8284	0.7011	0.082*
H1E	0.6242	0.8747	0.6290	0.082*
C2	0.9227 (3)	0.5143 (4)	0.63140 (17)	0.0432 (7)
H2A	0.9879	0.5239	0.6024	0.052*
H2B	0.9800	0.4835	0.6783	0.052*
C3	0.8497 (3)	0.6806 (4)	0.63348 (16)	0.0434 (7)
H3A	0.9230	0.7645	0.6544	0.052*
H3B	0.8006	0.7163	0.5861	0.052*
C4	0.6329 (3)	0.5373 (4)	0.64511 (18)	0.0490 (8)
H4A	0.5765	0.5684	0.5981	0.059*
H4B	0.5665	0.5278	0.6735	0.059*
C5	0.7048 (3)	0.3696 (4)	0.64308 (18)	0.0524 (8)
H5A	0.7533	0.3331	0.6904	0.063*
H5B	0.6315	0.2864	0.6216	0.063*
Sb1	0.82184 (2)	0.48123 (2)	0.906548 (10)	0.03847 (9)
Cl1	0.71738 (9)	0.22687 (12)	0.83017 (4)	0.0586 (2)
Cl2	0.63328 (9)	0.65958 (12)	0.83543 (5)	0.0628 (2)
Cl3	0.67147 (9)	0.43460 (13)	0.98606 (5)	0.0607 (2)
Cl4	0.95679 (9)	0.75059 (10)	0.98509 (4)	0.0497 (2)
Cl5	0.98660 (8)	0.58815 (10)	0.81238 (4)	0.04343 (18)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0592 (15)	0.0667 (16)	0.0495 (14)	0.0137 (11)	0.0096 (12)	0.0028 (11)
N1	0.0458 (14)	0.0450 (14)	0.0374 (13)	0.0000 (11)	0.0106 (11)	−0.0041 (11)
N2	0.0367 (13)	0.0475 (14)	0.0324 (13)	0.0034 (11)	0.0114 (10)	0.0027 (11)
C1	0.053 (2)	0.0537 (19)	0.061 (2)	0.0157 (16)	0.0214 (17)	0.0051 (17)
C2	0.0366 (16)	0.0524 (18)	0.0428 (18)	−0.0024 (13)	0.0150 (14)	−0.0043 (14)
C3	0.0448 (17)	0.0477 (17)	0.0432 (17)	−0.0071 (14)	0.0213 (14)	−0.0033 (14)
C4	0.0324 (15)	0.063 (2)	0.052 (2)	−0.0043 (14)	0.0140 (14)	−0.0037 (16)
C5	0.0505 (19)	0.0527 (19)	0.059 (2)	−0.0117 (15)	0.0233 (16)	−0.0005 (17)
Sb1	0.03744 (13)	0.04726 (14)	0.03172 (13)	0.00487 (8)	0.01155 (9)	0.00274 (8)
Cl1	0.0575 (5)	0.0664 (5)	0.0521 (5)	−0.0089 (4)	0.0163 (4)	−0.0123 (4)
Cl2	0.0541 (5)	0.0779 (6)	0.0553 (5)	0.0234 (4)	0.0140 (4)	0.0178 (4)
Cl3	0.0572 (5)	0.0802 (6)	0.0548 (5)	0.0108 (4)	0.0323 (4)	0.0108 (5)
Cl4	0.0565 (5)	0.0523 (4)	0.0457 (4)	0.0030 (4)	0.0232 (4)	−0.0021 (4)
Cl5	0.0432 (4)	0.0520 (4)	0.0346 (4)	0.0007 (3)	0.0104 (3)	−0.0005 (3)

Geometric parameters (Å, °)

O1—H1F	0.8219	C2—H2A	0.9700
O1—H1G	0.8128	C2—H2B	0.9700
N1—C2	1.485 (4)	C3—H3A	0.9700
N1—C5	1.488 (4)	C3—H3B	0.9700
N1—H1A	0.9000	C4—C5	1.505 (4)
N1—H1B	0.9000	C4—H4A	0.9700
N2—C4	1.488 (4)	C4—H4B	0.9700
N2—C1	1.493 (4)	C5—H5A	0.9700
N2—C3	1.496 (3)	C5—H5B	0.9700
N2—H2	0.9100	Sb1—Cl2	2.4110 (10)
C1—H1C	0.9600	Sb1—Cl3	2.4623 (10)
C1—H1D	0.9600	Sb1—Cl1	2.5538 (11)
C1—H1E	0.9600	Sb1—Cl4	2.7446 (11)
C2—C3	1.500 (4)	Sb1—Cl5	2.9112 (11)
H1F—O1—H1G	116.3	C2—C3—H3A	109.2
C2—N1—C5	111.3 (2)	N2—C3—H3B	109.2
C2—N1—H1A	109.4	C2—C3—H3B	109.2
C5—N1—H1A	109.4	H3A—C3—H3B	107.9
C2—N1—H1B	109.4	N2—C4—C5	111.5 (2)
C5—N1—H1B	109.4	N2—C4—H4A	109.3
H1A—N1—H1B	108.0	C5—C4—H4A	109.3
C4—N2—C1	111.7 (2)	N2—C4—H4B	109.3
C4—N2—C3	109.8 (2)	C5—C4—H4B	109.3
C1—N2—C3	111.1 (2)	H4A—C4—H4B	108.0
C4—N2—H2	108.0	N1—C5—C4	110.9 (3)
C1—N2—H2	108.0	N1—C5—H5A	109.5
C3—N2—H2	108.0	C4—C5—H5A	109.5
N2—C1—H1C	109.5	N1—C5—H5B	109.5
N2—C1—H1D	109.5	C4—C5—H5B	109.5
H1C—C1—H1D	109.5	H5A—C5—H5B	108.0
N2—C1—H1E	109.5	Cl2—Sb1—Cl3	89.29 (4)
H1C—C1—H1E	109.5	Cl2—Sb1—Cl1	90.76 (4)
H1D—C1—H1E	109.5	Cl3—Sb1—Cl1	93.67 (4)
N1—C2—C3	110.5 (2)	Cl2—Sb1—Cl4	91.71 (4)
N1—C2—H2A	109.5	Cl3—Sb1—Cl4	90.95 (4)
C3—C2—H2A	109.5	Cl1—Sb1—Cl4	174.79 (3)
N1—C2—H2B	109.5	Cl5—Sb1—Cl1	92.15 (4)
C3—C2—H2B	109.5	Cl5—Sb1—Cl2	84.50 (4)
H2A—C2—H2B	108.1	Cl5—Sb1—Cl3	171.54 (4)
N2—C3—C2	112.0 (2)	Cl5—Sb1—Cl4	83.52 (4)
N2—C3—H3A	109.2
C5—N1—C2—C3	−55.7 (3)	C1—N2—C4—C5	179.5 (3)
C4—N2—C3—C2	−56.1 (3)	C3—N2—C4—C5	55.8 (3)
C1—N2—C3—C2	179.8 (3)	C2—N1—C5—C4	55.9 (3)
N1—C2—C3—N2	56.2 (3)	N2—C4—C5—N1	−56.3 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1F···Cl1i	0.82	2.57	3.346 (4)	159
O1—H1G···Cl4	0.82	2.51	3.223 (5)	147
N1—H1A···Cl5ii	0.90	2.43	3.179 (4)	141
N1—H1B···O1iii	0.90	1.91	2.801 (5)	168
N2—H2···Cl5	0.91	2.28	3.133 (5)	157

Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+3/2, z−1/2.