Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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 π–π 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].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040196/lh2475sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040196/lh2475Isup2.hkl
Contains datablock I

CCDC reference: 660133

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.027
  • wR factor = 0.071
  • Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for N2 - C10 .. 5.43 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Sb1
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Sb1 (3) 2.70
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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.

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).

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, P1F(000) = 476
Hall symbol: -P 1Dx = 1.761 Mg m3
a = 8.9815 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.4501 (16) ŵ = 2.22 mm1
c = 10.7488 (16) ÅT = 273 K
α = 97.639 (2)°Block, colourless
β = 110.180 (3)°0.39 × 0.29 × 0.17 mm
γ = 98.242 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3246 independent reflections
Radiation source: fine-focus sealed tube2966 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.012
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.467, Tmax = 0.686k = 1112
4810 measured reflectionsl = 1211
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
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 Å3
183 parametersΔρmin = 0.62 e Å3
0 restraints
Crystal data top
(C6H8N)2[SbCl5]γ = 98.242 (2)°
Mr = 487.29V = 918.9 (2) Å3
Triclinic, P1Z = 2
a = 8.9815 (13) ÅMo Kα radiation
b = 10.4501 (16) ŵ = 2.22 mm1
c = 10.7488 (16) ÅT = 273 K
α = 97.639 (2)°0.39 × 0.29 × 0.17 mm
β = 110.180 (3)°
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) = 0.0710 restraints
S = 1.06Δρmax = 0.61 e Å3
3246 reflectionsΔρmin = 0.62 e Å3
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
N10.2694 (4)0.1629 (3)0.6001 (3)0.0670 (8)
H10.33300.20020.56530.080*
C10.0441 (7)0.0211 (4)0.7670 (5)0.111 (2)
H1A0.14560.00690.73460.167*
H1B0.00220.00250.86390.167*
H1C0.06180.11500.73950.167*
C20.0697 (5)0.0451 (3)0.7094 (4)0.0599 (9)
C30.0245 (4)0.1371 (3)0.6302 (4)0.0573 (8)
H30.07670.15880.61260.069*
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)
H60.25470.04600.78380.089*
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*
H7C1.20690.74460.06150.132*
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)
H120.91860.75160.05770.078*
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, º) 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—C40.9 (5)C12—C8—C9—C100.6 (5)
C1—C2—C3—C4179.6 (3)C7—C8—C9—C10178.7 (4)
C5—N1—C4—C30.9 (5)C11—N2—C10—C90.8 (5)
C2—C3—C4—N11.6 (5)C8—C9—C10—N20.1 (5)
C4—N1—C5—C60.4 (6)C10—N2—C11—C120.8 (5)
N1—C5—C6—C21.0 (6)N2—C11—C12—C80.1 (5)
C3—C2—C6—C50.4 (6)C9—C8—C12—C110.6 (5)
C1—C2—C6—C5178.3 (4)C7—C8—C12—C11178.7 (4)
Hydrogen-bond geometry (Å, º) 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

Experimental details

Crystal data
Chemical formula(C6H8N)2[SbCl5]
Mr487.29
Crystal system, space groupTriclinic, P1
Temperature (K)273
a, b, c (Å)8.9815 (13), 10.4501 (16), 10.7488 (16)
α, β, γ (°)97.639 (2), 110.180 (3), 98.242 (2)
V3)918.9 (2)
Z2
Radiation typeMo Kα
µ (mm1)2.22
Crystal size (mm)0.39 × 0.29 × 0.17
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.467, 0.686
No. of measured, independent and
observed [I > 2σ(I)] reflections
4810, 3246, 2966
Rint0.012
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.071, 1.06
No. of reflections3246
No. of parameters183
Δρmax, Δρmin (e Å3)0.61, 0.62

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) 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, º) 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
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds