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Acta Cryst. (2007). E63, m2375    [ doi:10.1107/S1600536807040196 ]

Bis(4-methylpyridinium) pentachloridoantimonate(III)

W.-J. Feng, X.-J. Ma, F. Zhang, Y.-C. Yuan and Z.-M. Jin

Abstract top

The asymmetric unit of the title compound, (C6H8N)2[SbCl5], consists of an SbCl5 anion linked to two 4-methylpyridinium cations by two N-H...Cl hydrogen bonds. The bond lengths and angles around the SbIII ion describe a disorted square-pyramidal coordination geometry. In the crystal structure, weak [pi]-[pi] stacking interactions occur between inversion-related pyridine rings [Cg1...Cg1 = 3.788 (2) Å and Cg2...Cg2 = 3.522 (2) Å, where Cg1 and Cg2 are the centroids of the two pyridine rings].

Comment top

The crystal structure of 4-methylpyridine has already been reported (Ohms et al., 1985). It is an important solvent and intermediate in organic synthesis and it is present in many complexes (Leonard et al., 1999; Biradha & Zaworotko, 1998; Jin et al., 2000). It can be coordinated to a metal ions (Battaglia et al., 1983; Johnson et al., 1984; Andras et al., 1993; Goher & Mautner 1999; James et al., 1999; Mayr et al., 1993; Clegg et al., 2000). Herein present here the crystal structure of the title compound.

As shown in Fig. 1, there are two 4-methylpyridinium (HMP) cations and one (SbCl5)2− anion in the formula unit. The anion is linked to one HMP cation (N1/C1–C6) by an N1—H1···Cl3 hydrogen bond, and to the other HMP cation (N2/C7–C12) by an N2—H2···Cl5 hydrogen bond. The dihedral angle between the two pyridine rings in the formula unit is 17.18 (3)°. The geometry of SbCl5 anion is a distorted square pyramid. The four atoms Cl1, Cl3, Cl4 and Cl5 form the basal plane, while Cl2 is the apex of the pyramid.

Symmetry related SbCl5 anions are linked into dimers via weak coordinated bonds of the type Sb1···Cl4(−x + 1, −y + 1, −z + 1) [3.271 (10) Å] (Fig. 2), which play a role in the stabilization of the crystal structure. In addtion, there are weak π···π stacking between symmetry related pyridine rings with a centroid to centroid distance of 3.522 (2) and 3.788 (2) Å and a interplanar distances of 3.434 and 3.431 Å resulting in offset angles of 25.1° and 12.8 (Fig. 3). These interactions further stablize the crystal structure.

Related literature top

For related literature, see: Andras et al. (1993); Battaglia et al. (1983); Biradha & Zaworotko (1998); Clegg et al. (2000); Goher & Mautner (1999); James et al. (1999); Jin et al. (2000); Johnson et al. (1984); Leonard et al. (1999); Mayr et al. (1993); Ohms et al. (1985).

Experimental top

Antimony trichloride, hydrochloride acid and 4-methylpyridine in a 1:2:2 molar ratio were mixed and dissolved in sufficient acetone to heat to a temperature at which a clear solution resulted. Crystals of the title compound were formed by gradual evaporation of acetone over a period of three days at 298 K.

Refinement top

All H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.86 Å for (N—H), 0.93 Å for aromatic groups and 0.96 Å for methyl, with Uiso(H) = 1.2–1.5 Ueq(C).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure shown with 30% probability displacement ellipsoids. Hydrogen bonds are illustrated as dashed lines.
[Figure 2] Fig. 2. A dimer unit of SbCl5 in the crystal structure. Atoms which are not labeled are obtained by symmetry operation of (−x + 1, −y + 1, −z + 1). Weak coordinated Sb1···Cl4 bonds are illustrated by dashed lines.
[Figure 3] Fig. 3. The packing of the title compound viewed down along the a axis. Hydrogen bonds and weak Sb1···Cl4 interactions are illustrated by dashed lines.
Bis(4-methylpyridinium) pentachloridoantimonate(III) top
Crystal data top
(C6H8N)2[SbCl5]V = 918.9 (2) Å3
Mr = 487.29Z = 2
Triclinic, P1F000 = 476
Hall symbol: -P 1Dx = 1.761 Mg m−3
a = 8.9815 (13) ÅMo Kα radiation
λ = 0.71073 Å
b = 10.4501 (16) ŵ = 2.22 mm−1
c = 10.7488 (16) ÅT = 273 (2) K
α = 97.639 (2)ºBlock, colourless
β = 110.180 (3)º0.39 × 0.29 × 0.17 mm
γ = 98.242 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3246 independent reflections
Radiation source: fine-focus sealed tube2966 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.012
T = 273(2) Kθmax = 25.0º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −10→10
Tmin = 0.467, Tmax = 0.686k = −11→12
4810 measured reflectionsl = −12→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027?
wR(F2) = 0.071  w = 1/[σ2(Fo2) + (0.0397P)2 + 0.2418P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3246 reflectionsΔρmax = 0.61 e Å−3
183 parametersΔρmin = −0.62 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C6H8N)2[SbCl5]γ = 98.242 (2)º
Mr = 487.29V = 918.9 (2) Å3
Triclinic, P1Z = 2
a = 8.9815 (13) ÅMo Kα
b = 10.4501 (16) ŵ = 2.22 mm−1
c = 10.7488 (16) ÅT = 273 (2) K
α = 97.639 (2)º0.39 × 0.29 × 0.17 mm
β = 110.180 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3246 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2966 reflections with I > 2σ(I)
Tmin = 0.467, Tmax = 0.686Rint = 0.012
4810 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027183 parameters
wR(F2) = 0.071?
S = 1.06Δρmax = 0.61 e Å−3
3246 reflectionsΔρmin = −0.62 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 > 2sigma(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
N10.2694 (4)0.1629 (3)0.6001 (3)0.0670 (8)
H10.33300.20020.56530.080*
C1−0.0441 (7)−0.0211 (4)0.7670 (5)0.111 (2)
H1A−0.14560.00690.73460.167*
H1B0.00220.00250.86390.167*
H1C−0.0618−0.11500.73950.167*
C20.0697 (5)0.0451 (3)0.7094 (4)0.0599 (9)
C30.0245 (4)0.1371 (3)0.6302 (4)0.0573 (8)
H3−0.07670.15880.61260.069*
C40.1285 (4)0.1961 (3)0.5777 (3)0.0582 (8)
H40.09940.25970.52610.070*
C50.3177 (5)0.0745 (5)0.6741 (5)0.0774 (11)
H50.41830.05310.68730.093*
C60.2201 (6)0.0152 (4)0.7305 (4)0.0742 (11)
H60.2547−0.04600.78380.089*
N20.8711 (4)0.5762 (3)0.1493 (3)0.0655 (8)
H20.79730.53950.17460.079*
C71.2405 (6)0.7603 (5)0.0351 (5)0.0882 (13)
H7A1.33590.72540.07280.132*
H7B1.26380.85350.06980.132*
H7C1.20690.7446−0.06150.132*
C81.1073 (4)0.6939 (3)0.0731 (3)0.0546 (8)
C91.1411 (4)0.6212 (3)0.1731 (3)0.0565 (8)
H91.24710.61170.21620.068*
C101.0231 (4)0.5636 (3)0.2096 (4)0.0575 (8)
H101.04800.51460.27750.069*
C110.8306 (4)0.6439 (4)0.0511 (4)0.0626 (9)
H110.72320.65060.00950.075*
C120.9468 (5)0.7039 (4)0.0112 (4)0.0647 (9)
H120.91860.7516−0.05770.078*
Sb10.56843 (2)0.360071 (18)0.368247 (19)0.04399 (9)
Cl10.83975 (11)0.34203 (10)0.35602 (11)0.0707 (3)
Cl20.43481 (12)0.18074 (9)0.17427 (10)0.0691 (2)
Cl30.59349 (11)0.18528 (10)0.52378 (10)0.0643 (2)
Cl40.27301 (11)0.38111 (10)0.38662 (10)0.0670 (2)
Cl50.53816 (10)0.52942 (9)0.20178 (10)0.0613 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0599 (19)0.0698 (19)0.0691 (19)−0.0025 (16)0.0302 (16)0.0061 (16)
C10.165 (5)0.072 (3)0.121 (4)−0.015 (3)0.102 (4)0.009 (3)
C20.083 (3)0.0412 (16)0.062 (2)0.0044 (16)0.041 (2)0.0033 (15)
C30.0500 (19)0.0549 (19)0.066 (2)0.0136 (15)0.0217 (16)0.0028 (16)
C40.067 (2)0.0500 (18)0.0543 (19)0.0111 (16)0.0174 (17)0.0149 (15)
C50.059 (2)0.085 (3)0.085 (3)0.025 (2)0.022 (2)0.006 (2)
C60.094 (3)0.065 (2)0.072 (2)0.037 (2)0.030 (2)0.023 (2)
N20.0598 (19)0.0619 (18)0.077 (2)0.0050 (15)0.0344 (17)0.0043 (16)
C70.082 (3)0.087 (3)0.105 (3)0.002 (2)0.050 (3)0.025 (3)
C80.056 (2)0.0495 (17)0.0576 (19)0.0065 (15)0.0235 (16)0.0058 (15)
C90.0467 (18)0.0585 (19)0.059 (2)0.0160 (15)0.0127 (16)0.0076 (16)
C100.060 (2)0.0580 (19)0.060 (2)0.0198 (16)0.0229 (17)0.0190 (16)
C110.047 (2)0.064 (2)0.065 (2)0.0127 (17)0.0095 (17)0.0005 (18)
C120.070 (3)0.062 (2)0.055 (2)0.0154 (19)0.0125 (18)0.0158 (17)
Sb10.03552 (13)0.04786 (14)0.05226 (15)0.01193 (9)0.01773 (10)0.01444 (10)
Cl10.0467 (5)0.0858 (6)0.0981 (7)0.0261 (4)0.0359 (5)0.0417 (6)
Cl20.0676 (6)0.0604 (5)0.0681 (5)0.0170 (4)0.0123 (4)0.0064 (4)
Cl30.0558 (5)0.0732 (5)0.0761 (6)0.0246 (4)0.0290 (4)0.0306 (5)
Cl40.0491 (5)0.0798 (6)0.0834 (6)0.0194 (4)0.0276 (4)0.0396 (5)
Cl50.0471 (5)0.0627 (5)0.0748 (6)0.0161 (4)0.0181 (4)0.0233 (4)
Geometric parameters (Å, °) top
N1—C41.311 (5)C7—C81.501 (5)
N1—C51.322 (5)C7—H7A0.9600
N1—H10.8600C7—H7B0.9600
C1—C21.502 (5)C7—H7C0.9600
C1—H1A0.9600C8—C91.372 (5)
C1—H1B0.9600C8—C121.389 (5)
C1—H1C0.9600C9—C101.344 (5)
C2—C61.379 (6)C9—H90.9300
C2—C31.380 (5)C10—H100.9300
C3—C41.365 (5)C11—C121.364 (5)
C3—H30.9300C11—H110.9300
C4—H40.9300C12—H120.9300
C5—C61.352 (6)Sb1—Cl22.4268 (10)
C5—H50.9300Sb1—Cl12.5173 (9)
C6—H60.9300Sb1—Cl32.6177 (9)
N2—C111.325 (5)Sb1—Cl52.6555 (9)
N2—C101.329 (5)Sb1—Cl42.7649 (10)
N2—H20.8600
C4—N1—C5122.6 (3)H7A—C7—H7B109.5
C4—N1—H1118.7C8—C7—H7C109.5
C5—N1—H1118.7H7A—C7—H7C109.5
C2—C1—H1A109.5H7B—C7—H7C109.5
C2—C1—H1B109.5C9—C8—C12117.2 (3)
H1A—C1—H1B109.5C9—C8—C7120.4 (3)
C2—C1—H1C109.5C12—C8—C7122.3 (3)
H1A—C1—H1C109.5C10—C9—C8120.8 (3)
H1B—C1—H1C109.5C10—C9—H9119.6
C6—C2—C3117.6 (3)C8—C9—H9119.6
C6—C2—C1122.0 (4)N2—C10—C9120.5 (3)
C3—C2—C1120.3 (4)N2—C10—H10119.8
C4—C3—C2119.9 (3)C9—C10—H10119.8
C4—C3—H3120.1N2—C11—C12119.8 (3)
C2—C3—H3120.1N2—C11—H11120.1
N1—C4—C3119.8 (3)C12—C11—H11120.1
N1—C4—H4120.1C11—C12—C8120.2 (3)
C3—C4—H4120.1C11—C12—H12119.9
N1—C5—C6119.7 (4)C8—C12—H12119.9
N1—C5—H5120.1Cl2—Sb1—Cl190.58 (4)
C6—C5—H5120.1Cl2—Sb1—Cl388.40 (3)
C5—C6—C2120.3 (4)Cl1—Sb1—Cl390.59 (3)
C5—C6—H6119.8Cl2—Sb1—Cl589.28 (3)
C2—C6—H6119.8Cl1—Sb1—Cl589.22 (3)
C11—N2—C10121.5 (3)Cl3—Sb1—Cl5177.67 (3)
C11—N2—H2119.2Cl2—Sb1—Cl490.26 (3)
C10—N2—H2119.2Cl1—Sb1—Cl4178.98 (3)
C8—C7—H7A109.5Cl3—Sb1—Cl488.86 (3)
C8—C7—H7B109.5Cl5—Sb1—Cl491.36 (3)
C6—C2—C3—C4−0.9 (5)C12—C8—C9—C10−0.6 (5)
C1—C2—C3—C4−179.6 (3)C7—C8—C9—C10178.7 (4)
C5—N1—C4—C3−0.9 (5)C11—N2—C10—C90.8 (5)
C2—C3—C4—N11.6 (5)C8—C9—C10—N2−0.1 (5)
C4—N1—C5—C6−0.4 (6)C10—N2—C11—C12−0.8 (5)
N1—C5—C6—C21.0 (6)N2—C11—C12—C80.1 (5)
C3—C2—C6—C5−0.4 (6)C9—C8—C12—C110.6 (5)
C1—C2—C6—C5178.3 (4)C7—C8—C12—C11−178.7 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl30.862.553.272 (5)142
N2—H2···Cl50.862.433.212 (6)151
Selected geometric parameters (Å, °) top
Sb1—Cl22.4268 (10)Sb1—Cl52.6555 (9)
Sb1—Cl12.5173 (9)Sb1—Cl42.7649 (10)
Sb1—Cl32.6177 (9)
Cl2—Sb1—Cl190.58 (4)Cl3—Sb1—Cl5177.67 (3)
Cl2—Sb1—Cl388.40 (3)Cl2—Sb1—Cl490.26 (3)
Cl1—Sb1—Cl390.59 (3)Cl1—Sb1—Cl4178.98 (3)
Cl2—Sb1—Cl589.28 (3)Cl3—Sb1—Cl488.86 (3)
Cl1—Sb1—Cl589.22 (3)Cl5—Sb1—Cl491.36 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl30.862.553.272 (5)142
N2—H2···Cl50.862.433.212 (6)151
references
References top

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