Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040196/lh2475sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040196/lh2475Isup2.hkl |
CCDC reference: 660133
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (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
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).
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.
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).
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).
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.
(C6H8N)2[SbCl5] | V = 918.9 (2) Å3 |
Mr = 487.29 | Z = 2 |
Triclinic, P1 | F(000) = 476 |
Hall symbol: -P 1 | Dx = 1.761 Mg m−3 |
a = 8.9815 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.4501 (16) Å | µ = 2.22 mm−1 |
c = 10.7488 (16) Å | T = 273 K |
α = 97.639 (2)° | Block, colourless |
β = 110.180 (3)° | 0.39 × 0.29 × 0.17 mm |
γ = 98.242 (2)° |
Bruker SMART CCD area-detector diffractometer | 3246 independent reflections |
Radiation source: fine-focus sealed tube | 2966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
Tmin = 0.467, Tmax = 0.686 | k = −11→12 |
4810 measured reflections | l = −12→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.027 | Hydrogen 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 reflections | Δρmax = 0.61 e Å−3 |
183 parameters | Δρmin = −0.62 e Å−3 |
0 restraints |
(C6H8N)2[SbCl5] | γ = 98.242 (2)° |
Mr = 487.29 | V = 918.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9815 (13) Å | Mo Kα radiation |
b = 10.4501 (16) Å | µ = 2.22 mm−1 |
c = 10.7488 (16) Å | T = 273 K |
α = 97.639 (2)° | 0.39 × 0.29 × 0.17 mm |
β = 110.180 (3)° |
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 = 0.686 | Rint = 0.012 |
4810 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 183 parameters |
wR(F2) = 0.071 | 0 restraints |
S = 1.06 | Δρmax = 0.61 e Å−3 |
3246 reflections | Δρmin = −0.62 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2694 (4) | 0.1629 (3) | 0.6001 (3) | 0.0670 (8) | |
H1 | 0.3330 | 0.2002 | 0.5653 | 0.080* | |
C1 | −0.0441 (7) | −0.0211 (4) | 0.7670 (5) | 0.111 (2) | |
H1A | −0.1456 | 0.0069 | 0.7346 | 0.167* | |
H1B | 0.0022 | 0.0025 | 0.8639 | 0.167* | |
H1C | −0.0618 | −0.1150 | 0.7395 | 0.167* | |
C2 | 0.0697 (5) | 0.0451 (3) | 0.7094 (4) | 0.0599 (9) | |
C3 | 0.0245 (4) | 0.1371 (3) | 0.6302 (4) | 0.0573 (8) | |
H3 | −0.0767 | 0.1588 | 0.6126 | 0.069* | |
C4 | 0.1285 (4) | 0.1961 (3) | 0.5777 (3) | 0.0582 (8) | |
H4 | 0.0994 | 0.2597 | 0.5261 | 0.070* | |
C5 | 0.3177 (5) | 0.0745 (5) | 0.6741 (5) | 0.0774 (11) | |
H5 | 0.4183 | 0.0531 | 0.6873 | 0.093* | |
C6 | 0.2201 (6) | 0.0152 (4) | 0.7305 (4) | 0.0742 (11) | |
H6 | 0.2547 | −0.0460 | 0.7838 | 0.089* | |
N2 | 0.8711 (4) | 0.5762 (3) | 0.1493 (3) | 0.0655 (8) | |
H2 | 0.7973 | 0.5395 | 0.1746 | 0.079* | |
C7 | 1.2405 (6) | 0.7603 (5) | 0.0351 (5) | 0.0882 (13) | |
H7A | 1.3359 | 0.7254 | 0.0728 | 0.132* | |
H7B | 1.2638 | 0.8535 | 0.0698 | 0.132* | |
H7C | 1.2069 | 0.7446 | −0.0615 | 0.132* | |
C8 | 1.1073 (4) | 0.6939 (3) | 0.0731 (3) | 0.0546 (8) | |
C9 | 1.1411 (4) | 0.6212 (3) | 0.1731 (3) | 0.0565 (8) | |
H9 | 1.2471 | 0.6117 | 0.2162 | 0.068* | |
C10 | 1.0231 (4) | 0.5636 (3) | 0.2096 (4) | 0.0575 (8) | |
H10 | 1.0480 | 0.5146 | 0.2775 | 0.069* | |
C11 | 0.8306 (4) | 0.6439 (4) | 0.0511 (4) | 0.0626 (9) | |
H11 | 0.7232 | 0.6506 | 0.0095 | 0.075* | |
C12 | 0.9468 (5) | 0.7039 (4) | 0.0112 (4) | 0.0647 (9) | |
H12 | 0.9186 | 0.7516 | −0.0577 | 0.078* | |
Sb1 | 0.56843 (2) | 0.360071 (18) | 0.368247 (19) | 0.04399 (9) | |
Cl1 | 0.83975 (11) | 0.34203 (10) | 0.35602 (11) | 0.0707 (3) | |
Cl2 | 0.43481 (12) | 0.18074 (9) | 0.17427 (10) | 0.0691 (2) | |
Cl3 | 0.59349 (11) | 0.18528 (10) | 0.52378 (10) | 0.0643 (2) | |
Cl4 | 0.27301 (11) | 0.38111 (10) | 0.38662 (10) | 0.0670 (2) | |
Cl5 | 0.53816 (10) | 0.52942 (9) | 0.20178 (10) | 0.0613 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0599 (19) | 0.0698 (19) | 0.0691 (19) | −0.0025 (16) | 0.0302 (16) | 0.0061 (16) |
C1 | 0.165 (5) | 0.072 (3) | 0.121 (4) | −0.015 (3) | 0.102 (4) | 0.009 (3) |
C2 | 0.083 (3) | 0.0412 (16) | 0.062 (2) | 0.0044 (16) | 0.041 (2) | 0.0033 (15) |
C3 | 0.0500 (19) | 0.0549 (19) | 0.066 (2) | 0.0136 (15) | 0.0217 (16) | 0.0028 (16) |
C4 | 0.067 (2) | 0.0500 (18) | 0.0543 (19) | 0.0111 (16) | 0.0174 (17) | 0.0149 (15) |
C5 | 0.059 (2) | 0.085 (3) | 0.085 (3) | 0.025 (2) | 0.022 (2) | 0.006 (2) |
C6 | 0.094 (3) | 0.065 (2) | 0.072 (2) | 0.037 (2) | 0.030 (2) | 0.023 (2) |
N2 | 0.0598 (19) | 0.0619 (18) | 0.077 (2) | 0.0050 (15) | 0.0344 (17) | 0.0043 (16) |
C7 | 0.082 (3) | 0.087 (3) | 0.105 (3) | 0.002 (2) | 0.050 (3) | 0.025 (3) |
C8 | 0.056 (2) | 0.0495 (17) | 0.0576 (19) | 0.0065 (15) | 0.0235 (16) | 0.0058 (15) |
C9 | 0.0467 (18) | 0.0585 (19) | 0.059 (2) | 0.0160 (15) | 0.0127 (16) | 0.0076 (16) |
C10 | 0.060 (2) | 0.0580 (19) | 0.060 (2) | 0.0198 (16) | 0.0229 (17) | 0.0190 (16) |
C11 | 0.047 (2) | 0.064 (2) | 0.065 (2) | 0.0127 (17) | 0.0095 (17) | 0.0005 (18) |
C12 | 0.070 (3) | 0.062 (2) | 0.055 (2) | 0.0154 (19) | 0.0125 (18) | 0.0158 (17) |
Sb1 | 0.03552 (13) | 0.04786 (14) | 0.05226 (15) | 0.01193 (9) | 0.01773 (10) | 0.01444 (10) |
Cl1 | 0.0467 (5) | 0.0858 (6) | 0.0981 (7) | 0.0261 (4) | 0.0359 (5) | 0.0417 (6) |
Cl2 | 0.0676 (6) | 0.0604 (5) | 0.0681 (5) | 0.0170 (4) | 0.0123 (4) | 0.0064 (4) |
Cl3 | 0.0558 (5) | 0.0732 (5) | 0.0761 (6) | 0.0246 (4) | 0.0290 (4) | 0.0306 (5) |
Cl4 | 0.0491 (5) | 0.0798 (6) | 0.0834 (6) | 0.0194 (4) | 0.0276 (4) | 0.0396 (5) |
Cl5 | 0.0471 (5) | 0.0627 (5) | 0.0748 (6) | 0.0161 (4) | 0.0181 (4) | 0.0233 (4) |
N1—C4 | 1.311 (5) | C7—C8 | 1.501 (5) |
N1—C5 | 1.322 (5) | C7—H7A | 0.9600 |
N1—H1 | 0.8600 | C7—H7B | 0.9600 |
C1—C2 | 1.502 (5) | C7—H7C | 0.9600 |
C1—H1A | 0.9600 | C8—C9 | 1.372 (5) |
C1—H1B | 0.9600 | C8—C12 | 1.389 (5) |
C1—H1C | 0.9600 | C9—C10 | 1.344 (5) |
C2—C6 | 1.379 (6) | C9—H9 | 0.9300 |
C2—C3 | 1.380 (5) | C10—H10 | 0.9300 |
C3—C4 | 1.365 (5) | C11—C12 | 1.364 (5) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | C12—H12 | 0.9300 |
C5—C6 | 1.352 (6) | Sb1—Cl2 | 2.4268 (10) |
C5—H5 | 0.9300 | Sb1—Cl1 | 2.5173 (9) |
C6—H6 | 0.9300 | Sb1—Cl3 | 2.6177 (9) |
N2—C11 | 1.325 (5) | Sb1—Cl5 | 2.6555 (9) |
N2—C10 | 1.329 (5) | Sb1—Cl4 | 2.7649 (10) |
N2—H2 | 0.8600 | ||
C4—N1—C5 | 122.6 (3) | H7A—C7—H7B | 109.5 |
C4—N1—H1 | 118.7 | C8—C7—H7C | 109.5 |
C5—N1—H1 | 118.7 | H7A—C7—H7C | 109.5 |
C2—C1—H1A | 109.5 | H7B—C7—H7C | 109.5 |
C2—C1—H1B | 109.5 | C9—C8—C12 | 117.2 (3) |
H1A—C1—H1B | 109.5 | C9—C8—C7 | 120.4 (3) |
C2—C1—H1C | 109.5 | C12—C8—C7 | 122.3 (3) |
H1A—C1—H1C | 109.5 | C10—C9—C8 | 120.8 (3) |
H1B—C1—H1C | 109.5 | C10—C9—H9 | 119.6 |
C6—C2—C3 | 117.6 (3) | C8—C9—H9 | 119.6 |
C6—C2—C1 | 122.0 (4) | N2—C10—C9 | 120.5 (3) |
C3—C2—C1 | 120.3 (4) | N2—C10—H10 | 119.8 |
C4—C3—C2 | 119.9 (3) | C9—C10—H10 | 119.8 |
C4—C3—H3 | 120.1 | N2—C11—C12 | 119.8 (3) |
C2—C3—H3 | 120.1 | N2—C11—H11 | 120.1 |
N1—C4—C3 | 119.8 (3) | C12—C11—H11 | 120.1 |
N1—C4—H4 | 120.1 | C11—C12—C8 | 120.2 (3) |
C3—C4—H4 | 120.1 | C11—C12—H12 | 119.9 |
N1—C5—C6 | 119.7 (4) | C8—C12—H12 | 119.9 |
N1—C5—H5 | 120.1 | Cl2—Sb1—Cl1 | 90.58 (4) |
C6—C5—H5 | 120.1 | Cl2—Sb1—Cl3 | 88.40 (3) |
C5—C6—C2 | 120.3 (4) | Cl1—Sb1—Cl3 | 90.59 (3) |
C5—C6—H6 | 119.8 | Cl2—Sb1—Cl5 | 89.28 (3) |
C2—C6—H6 | 119.8 | Cl1—Sb1—Cl5 | 89.22 (3) |
C11—N2—C10 | 121.5 (3) | Cl3—Sb1—Cl5 | 177.67 (3) |
C11—N2—H2 | 119.2 | Cl2—Sb1—Cl4 | 90.26 (3) |
C10—N2—H2 | 119.2 | Cl1—Sb1—Cl4 | 178.98 (3) |
C8—C7—H7A | 109.5 | Cl3—Sb1—Cl4 | 88.86 (3) |
C8—C7—H7B | 109.5 | Cl5—Sb1—Cl4 | 91.36 (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—C10 | 178.7 (4) |
C5—N1—C4—C3 | −0.9 (5) | C11—N2—C10—C9 | 0.8 (5) |
C2—C3—C4—N1 | 1.6 (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—C2 | 1.0 (6) | N2—C11—C12—C8 | 0.1 (5) |
C3—C2—C6—C5 | −0.4 (6) | C9—C8—C12—C11 | 0.6 (5) |
C1—C2—C6—C5 | 178.3 (4) | C7—C8—C12—C11 | −178.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl3 | 0.86 | 2.55 | 3.272 (5) | 142 |
N2—H2···Cl5 | 0.86 | 2.43 | 3.212 (6) | 151 |
Experimental details
Crystal data | |
Chemical formula | (C6H8N)2[SbCl5] |
Mr | 487.29 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 918.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.22 |
Crystal size (mm) | 0.39 × 0.29 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.467, 0.686 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4810, 3246, 2966 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.071, 1.06 |
No. of reflections | 3246 |
No. of parameters | 183 |
Δρmax, Δρmin (e Å−3) | 0.61, −0.62 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL.
Sb1—Cl2 | 2.4268 (10) | Sb1—Cl5 | 2.6555 (9) |
Sb1—Cl1 | 2.5173 (9) | Sb1—Cl4 | 2.7649 (10) |
Sb1—Cl3 | 2.6177 (9) | ||
Cl2—Sb1—Cl1 | 90.58 (4) | Cl3—Sb1—Cl5 | 177.67 (3) |
Cl2—Sb1—Cl3 | 88.40 (3) | Cl2—Sb1—Cl4 | 90.26 (3) |
Cl1—Sb1—Cl3 | 90.59 (3) | Cl1—Sb1—Cl4 | 178.98 (3) |
Cl2—Sb1—Cl5 | 89.28 (3) | Cl3—Sb1—Cl4 | 88.86 (3) |
Cl1—Sb1—Cl5 | 89.22 (3) | Cl5—Sb1—Cl4 | 91.36 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl3 | 0.86 | 2.55 | 3.272 (5) | 142 |
N2—H2···Cl5 | 0.86 | 2.43 | 3.212 (6) | 151 |
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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.