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Acta Cryst. (2009). E65, m683    [ doi:10.1107/S1600536809019072 ]

Diisonicotinium pentachloridoantimonate(III) monohydrate

L.-Z. Chen

Abstract top

In the title compound, (C6H6NO2)2[SbCl5]·H2O, the SbIII atom exhibits a distorted square-pyramidal coordination geometry. The crystal structure is stabilized by intermolecular N-H...Cl, N-H...O, O-H...Cl and O-H...O hydrogen bonds, forming an extended three-dimensional network.

Comment top

Recently, the crystal structure of some halogenoantimonate salts has been reported (Feng et al.,2007; Bujak & Zaleski, 1999; Shen-Tu et al. 2008). As a contribution to this field, the synthesis and crystal structure of the title compound is reported herein.

The asymmetric unit of the title compound (Fig. 1) contains two protonated isonicotinic acid cations, a pentachloridoantimonate anion and a water molecule. The antimony(III) ion is in a distorted square-pyramidal coordination geometry, with the Sb—Cl distances ranging from 2.3642 (12) to 2.9002 (14) Å. This range of values is in agreement with that observed in N-methylpiperazinediium pentachloridoantimonate(III) monohydrate (2.4110 (10)–2.9112 (11) Å; Shen-Tu et al., 2008) and slightly larger than that reported for bis(ethyldimethylammonium) pentachloroantimonate(III) (2.499 (4)–2.768 (4) Å; Bujak & Zaleski, 1999). The crystal structure is stabilized by intermolecular N—H···Cl, N—H···O, O—H···Cl and O—H···O hydrogen bonds (Table 1), forming an extended three-dimensional network (Fig. 2).

Related literature top

For related structures, see: Bujak & Zaleski (1999); Feng et al. (2007); Shen-Tu et al. (2008).

Experimental top

SbCl3, isonicotinic acid and 20% aqueous HCl in a molar ratio of 1:1:3 were mixed and dissolved in water by heating to 373 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed, collected and washed with dilute aqueous HCl.

Refinement top

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å, O—H = 0.85 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O). The deepest residual electron density hole is located 1.47 Å from atom H5A.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed approximately along the b axis. Hydrogen bonds are drawn as dashed lines.
Diisonicotinium pentachloridoantimonate(III) monohydrate top
Crystal data top
(C6H6NO2)2[SbCl5]·H2OF000 = 1104
Mr = 565.25Dx = 1.842 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4071 reflections
a = 10.334 (2) Åθ = 3.1–27.5º
b = 8.7319 (17) ŵ = 2.03 mm−1
c = 23.615 (7) ÅT = 291 K
β = 106.98 (3)ºBlock, colourless
V = 2038.0 (9) Å30.25 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer		4675 independent reflections
Radiation source: fine-focus sealed tube4071 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.061
Detector resolution: 13.6612 pixels mm-1θmax = 27.5º
T = 291 Kθmin = 3.1º
ω scansh = −13→12
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −11→11
Tmin = 0.61, Tmax = 0.67l = −30→30
19258 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.057  w = 1/[σ2(Fo2) + (0.0112P)2 + 1.8681P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max < 0.001
S = 1.19Δρmax = 0.76 e Å−3
4675 reflectionsΔρmin = −1.76 e Å−3
227 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0094 (3)
Secondary atom site location: difference Fourier map
Crystal data top
(C6H6NO2)2[SbCl5]·H2OV = 2038.0 (9) Å3
Mr = 565.25Z = 4
Monoclinic, P21/cMo Kα
a = 10.334 (2) ŵ = 2.03 mm−1
b = 8.7319 (17) ÅT = 291 K
c = 23.615 (7) Å0.25 × 0.20 × 0.20 mm
β = 106.98 (3)º
Data collection top
Rigaku SCXmini
diffractometer		4675 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		4071 reflections with I > 2σ(I)
Tmin = 0.61, Tmax = 0.67Rint = 0.061
19258 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057227 parameters
wR(F2) = 0.085H-atom parameters constrained
S = 1.19Δρmax = 0.76 e Å−3
4675 reflectionsΔρmin = −1.76 e Å−3
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.7498 (3)0.9688 (4)0.04677 (14)0.0569 (9)
H1C0.82141.02220.05830.085*
O20.8222 (3)0.8846 (4)0.14010 (14)0.0583 (10)
N10.4007 (4)0.6022 (5)0.0507 (2)0.0561 (11)
H1B0.33080.54360.04270.067*
C10.4199 (5)0.6891 (5)0.0081 (2)0.0527 (13)
H1A0.35860.6866−0.02960.063*
C60.7409 (5)0.8855 (5)0.0914 (2)0.0419 (11)
C20.5301 (5)0.7820 (5)0.01973 (19)0.0425 (11)
H2B0.54510.8430−0.01000.051*
C50.4841 (6)0.6009 (6)0.1054 (2)0.0586 (14)
H5A0.46680.53720.13380.070*
C40.5956 (5)0.6935 (6)0.1197 (2)0.0489 (12)
H4A0.65410.69470.15800.059*
C30.6198 (4)0.7850 (5)0.07631 (18)0.0376 (10)
Cl50.21814 (12)0.35116 (14)0.08488 (5)0.0501 (3)
O1W0.9650 (5)0.1234 (6)0.0754 (3)0.195 (4)
H1WA1.02850.07150.09840.292*
H1WB0.99820.20070.06270.292*
Sb10.38449 (3)0.14611 (3)0.173118 (11)0.03103 (11)
Cl10.51635 (14)−0.04608 (16)0.24298 (6)0.0646 (4)
Cl30.18317 (14)0.09286 (16)0.21279 (7)0.0642 (4)
Cl20.60393 (12)0.19468 (15)0.13735 (5)0.0521 (3)
Cl40.30831 (13)−0.04201 (14)0.09880 (6)0.0554 (3)
O3−0.0419 (4)0.6811 (4)0.04218 (15)0.0734 (12)
H3A−0.09440.67700.00700.110*
O4−0.1684 (4)0.4904 (5)0.05540 (16)0.0797 (13)
N20.1577 (4)0.5697 (5)0.25122 (17)0.0513 (11)
H2A0.20570.56700.28770.062*
C12−0.0780 (5)0.5765 (6)0.0741 (2)0.0474 (12)
C90.0065 (4)0.5778 (5)0.13730 (19)0.0388 (10)
C8−0.0139 (5)0.4684 (6)0.1746 (2)0.0497 (12)
H8A−0.08160.39580.16100.060*
C110.1813 (5)0.6798 (6)0.2169 (2)0.0565 (14)
H11A0.24900.75160.23210.068*
C100.1047 (5)0.6868 (5)0.1585 (2)0.0528 (13)
H10A0.11900.76390.13390.063*
C70.0648 (5)0.4649 (6)0.2321 (2)0.0533 (13)
H7A0.05250.38860.25760.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.051 (2)0.072 (3)0.046 (2)−0.0181 (18)0.0115 (17)0.0049 (18)
O20.052 (2)0.071 (3)0.0415 (19)0.0017 (18)−0.0026 (17)−0.0019 (17)
N10.060 (3)0.047 (3)0.062 (3)−0.012 (2)0.019 (2)−0.002 (2)
C10.058 (3)0.051 (3)0.044 (3)−0.010 (3)0.007 (3)−0.004 (2)
C60.039 (3)0.050 (3)0.036 (2)0.003 (2)0.009 (2)−0.006 (2)
C20.048 (3)0.047 (3)0.031 (2)−0.007 (2)0.009 (2)0.000 (2)
C50.077 (4)0.050 (3)0.058 (3)0.001 (3)0.033 (3)0.014 (3)
C40.055 (3)0.058 (3)0.036 (3)0.006 (3)0.016 (2)0.007 (2)
C30.040 (3)0.044 (3)0.032 (2)0.004 (2)0.015 (2)−0.002 (2)
Cl50.0542 (7)0.0498 (7)0.0434 (6)0.0001 (6)0.0096 (6)0.0118 (6)
O1W0.074 (4)0.146 (5)0.316 (9)−0.059 (4)−0.017 (5)0.112 (6)
Sb10.03618 (18)0.02999 (17)0.02550 (15)0.00013 (12)0.00678 (12)0.00076 (12)
Cl10.0674 (9)0.0654 (9)0.0561 (8)0.0156 (7)0.0105 (7)0.0324 (7)
Cl30.0663 (9)0.0638 (9)0.0750 (10)−0.0064 (7)0.0401 (8)−0.0022 (7)
Cl20.0472 (7)0.0707 (9)0.0378 (6)0.0062 (6)0.0115 (6)0.0107 (6)
Cl40.0676 (9)0.0479 (7)0.0506 (7)−0.0077 (6)0.0169 (7)−0.0207 (6)
O30.094 (3)0.070 (3)0.041 (2)−0.026 (2)−0.005 (2)0.0129 (18)
O40.079 (3)0.102 (3)0.043 (2)−0.046 (3)−0.006 (2)0.007 (2)
N20.053 (3)0.058 (3)0.034 (2)0.012 (2)−0.0022 (19)−0.002 (2)
C120.051 (3)0.049 (3)0.037 (3)−0.002 (2)0.006 (2)−0.002 (2)
C90.039 (3)0.039 (3)0.035 (2)0.004 (2)0.005 (2)−0.005 (2)
C80.053 (3)0.053 (3)0.039 (3)−0.008 (2)0.008 (2)−0.003 (2)
C110.049 (3)0.049 (3)0.057 (3)−0.004 (2)−0.006 (3)−0.006 (3)
C100.055 (3)0.046 (3)0.050 (3)−0.005 (2)0.002 (3)0.007 (2)
C70.060 (3)0.057 (3)0.039 (3)−0.001 (3)0.008 (3)0.007 (2)
Geometric parameters (Å, °) top
O1—C61.306 (5)Sb1—Cl12.4661 (13)
O1—H1C0.8500Sb1—Cl32.5613 (15)
O2—C61.210 (5)Sb1—Cl22.6748 (14)
N1—C11.322 (6)O3—C121.306 (6)
N1—C51.325 (6)O3—H3A0.8500
N1—H1B0.8600O4—C121.180 (5)
C1—C21.359 (6)N2—C71.307 (6)
C1—H1A0.9300N2—C111.326 (6)
C6—C31.484 (6)N2—H2A0.8600
C2—C31.386 (6)C12—C91.493 (6)
C2—H2B0.9300C9—C81.357 (6)
C5—C41.366 (7)C9—C101.375 (6)
C5—H5A0.9300C8—C71.365 (6)
C4—C31.379 (6)C8—H8A0.9300
C4—H4A0.9300C11—C101.375 (6)
O1W—H1WA0.8500C11—H11A0.9300
O1W—H1WB0.8499C10—H10A0.9300
Sb1—Cl52.9002 (14)C7—H7A0.9300
Sb1—Cl42.3646 (12)
C6—O1—H1C107.9Cl4—Sb1—Cl390.89 (5)
C1—N1—C5123.2 (5)Cl1—Sb1—Cl388.91 (5)
C1—N1—H1B118.4Cl4—Sb1—Cl290.28 (5)
C5—N1—H1B118.4Cl1—Sb1—Cl288.01 (5)
N1—C1—C2119.4 (5)Cl3—Sb1—Cl2176.73 (4)
N1—C1—H1A120.3C12—O3—H3A109.1
C2—C1—H1A120.3C7—N2—C11123.0 (4)
O2—C6—O1125.3 (5)C7—N2—H2A118.5
O2—C6—C3121.8 (4)C11—N2—H2A118.5
O1—C6—C3112.8 (4)O4—C12—O3123.9 (5)
C1—C2—C3119.4 (5)O4—C12—C9123.2 (5)
C1—C2—H2B120.3O3—C12—C9112.9 (4)
C3—C2—H2B120.3C8—C9—C10119.2 (4)
N1—C5—C4119.9 (5)C8—C9—C12119.2 (4)
N1—C5—H5A120.1C10—C9—C12121.6 (4)
C4—C5—H5A120.1C9—C8—C7120.1 (5)
C5—C4—C3118.7 (5)C9—C8—H8A119.9
C5—C4—H4A120.6C7—C8—H8A119.9
C3—C4—H4A120.6N2—C11—C10119.3 (5)
C4—C3—C2119.3 (4)N2—C11—H11A120.3
C4—C3—C6119.2 (4)C10—C11—H11A120.3
C2—C3—C6121.5 (4)C9—C10—C11118.8 (5)
H1WA—O1W—H1WB109.5C9—C10—H10A120.6
Cl5—Sb1—Cl1175.24 (4)C11—C10—H10A120.6
Cl5—Sb1—Cl390.03 (4)N2—C7—C8119.4 (5)
Cl5—Sb1—Cl293.12 (4)N2—C7—H7A120.3
Cl5—Sb1—Cl484.06 (4)C8—C7—H7A120.3
Cl4—Sb1—Cl191.32 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1C···O1Wi0.851.672.520 (5)175
N1—H1B···O4ii0.862.453.031 (6)126
O1W—H1WA···Cl3iii0.852.713.378 (7)136
O1W—H1WB···Cl5iii0.852.543.241 (4)140
O3—H3A···Cl5ii0.852.193.034 (4)175
N2—H2A···O2iv0.862.412.988 (5)125
N2—H2A···Cl2v0.862.493.224 (4)144
N1—H1B···Cl50.862.423.147 (4)143
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1C···O1Wi0.851.672.520 (5)175
N1—H1B···O4ii0.862.453.031 (6)126
O1W—H1WA···Cl3iii0.852.713.378 (7)136
O1W—H1WB···Cl5iii0.852.543.241 (4)140
O3—H3A···Cl5ii0.852.193.034 (4)175
N2—H2A···O2iv0.862.412.988 (5)125
N2—H2A···Cl2v0.862.493.224 (4)144
N1—H1B···Cl50.862.423.147 (4)143
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2.
Acknowledgements top

# left intentionally blank; no acknowledgements required

references
References top

Bujak, M. & Zaleski, J. (1999). Acta Cryst. C55, 1775–1778.

Feng, W.-J., Wang, H.-B., Ma, X.-J., Li, H.-Y. & Jin, Z.-M. (2007). Acta Cryst. E63, m1786–m1787.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shen-Tu, C., Li, H. Y., Ma, X. J., Huang, W. & Jin, Z. M. (2008). Acta Cryst. E64, m146.