Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034344/rz2155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034344/rz2155Isup2.hkl |
CCDC reference: 657594
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.028
- wR factor = 0.077
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Sb1 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.19 Ratio
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Sb1 (3) 2.77 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the corresponding complex of SbF3 with 1,10-phenanthroline, see: Bertazzi et al. (1983).
Antimony trichloride (0.5 mmol) was dissolved in methanol (20 ml) and 1,10-phenanthroline (0.5 mmol) was added with stirring at room temperature. The resulting orange-red solution was allowed to react for five hours and was then filtered. Orange crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol/dichloromethane (1:2 v/v) solution over a period of two weeks (yield 85%. m.p. 400k). Anal. Calcd (%) for C13H13Cl4N2OSb (Mr = 476.80): C, 32.75; H, 2.75; N, 5.88. Found (%): C, 32.81; H, 2.71; N, 5.81.
The H atom bound to N1 was located in a difference map and refined with a distance restraint (N—H = 0.86 (2) Å). All other H atoms were placed in calculated positions, with C—H = 0.93–0.96 Å, O—H = 0.82 Å, and treated as riding on their parent atoms, with Uiso(H) = 1.2 Ueq(C, O) or 1.5 Ueq(C) for the methyl group.
The acceptor ability of SbF3 towards neutral ligands has been previously investigated. Adducts with bi- and tri-dentate nitrogen donor atoms such as 1,10-phenanthroline have been obtainted (Bertazzi et al., 1983), but the corresponding complex of SbCl3 has not yet been reported. As a contribution to the chemistry of antimony complexes with neutral ligands, we report here the synthesis and crystal structure of the title compound.
The title compound, {C12H9N2+.SbCl4-.CH3OH}n (Fig.1), consists of tetrachloroantimonate(III) anions, 1,10-phenanthrolinium cations and methanol solvent molecules. In the crystal, centrosymmetrically related anions are linked by short intermolecular Sb1···Cl2i and Cl1···Sb1ii contacts [symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z] into [Sb2Cl8]2- dianions made up from two octahedra sharing a common edge, forming one-dimensional polymeric chains running parallel to the a axis. The cis and trans Cl—Sb—Cl bond angles within the distorted octahedral coordination geometry about Sb are in the range 81.90 (3)–99.14 (3)° and 171.36 (4)–178.83 (3)°, respectively. The Sb—Cl distances also vary with the role they play in the structure, the terminal Sb1—Cl3 [2.3970 (11) Å] and Sb1—Cl4 [2.4248 (11) Å] bonds being shorter than those involving the bridging Cl atoms which range from 2.5375 (11) Å to 2.7890 (12) Å. The crystal structure is further stabilized by O—H···Cl and N—H···O hydrogen bonds (Fig. 2, Table 1).
For the corresponding complex of SbF3 with 1,10-phenanthroline, see: Bertazzi et al. (1983).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
(C12H9N2)[SbCl4]·CH4O | Z = 2 |
Mr = 476.80 | F(000) = 464 |
Triclinic, P1 | Dx = 1.858 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5228 (10) Å | Cell parameters from 3120 reflections |
b = 10.0340 (14) Å | θ = 2.6–27.8° |
c = 12.3933 (19) Å | µ = 2.24 mm−1 |
α = 78.242 (3)° | T = 298 K |
β = 73.266 (2)° | Block, orange |
γ = 73.751 (2)° | 0.43 × 0.18 × 0.16 mm |
V = 852.3 (2) Å3 |
Bruker SMART CCD area-detector diffractometer | 2947 independent reflections |
Radiation source: fine-focus sealed tube | 2584 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.436, Tmax = 0.701 | k = −11→11 |
4451 measured reflections | l = −11→14 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.043P)2 + 0.4963P] where P = (Fo2 + 2Fc2)/3 |
2947 reflections | (Δ/σ)max = 0.001 |
184 parameters | Δρmax = 0.74 e Å−3 |
1 restraint | Δρmin = −0.64 e Å−3 |
(C12H9N2)[SbCl4]·CH4O | γ = 73.751 (2)° |
Mr = 476.80 | V = 852.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5228 (10) Å | Mo Kα radiation |
b = 10.0340 (14) Å | µ = 2.24 mm−1 |
c = 12.3933 (19) Å | T = 298 K |
α = 78.242 (3)° | 0.43 × 0.18 × 0.16 mm |
β = 73.266 (2)° |
Bruker SMART CCD area-detector diffractometer | 2947 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2584 reflections with I > 2σ(I) |
Tmin = 0.436, Tmax = 0.701 | Rint = 0.017 |
4451 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 1 restraint |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.74 e Å−3 |
2947 reflections | Δρmin = −0.64 e Å−3 |
184 parameters |
x | y | z | Uiso*/Ueq | ||
Sb1 | 0.68935 (3) | 0.57643 (2) | 0.559783 (19) | 0.03694 (11) | |
Cl1 | 0.95856 (16) | 0.69961 (11) | 0.46610 (9) | 0.0530 (3) | |
Cl2 | 0.38832 (17) | 0.44568 (12) | 0.66090 (9) | 0.0555 (3) | |
Cl3 | 0.46181 (17) | 0.79796 (12) | 0.55715 (10) | 0.0607 (3) | |
Cl4 | 0.71999 (18) | 0.58182 (13) | 0.74824 (9) | 0.0602 (3) | |
N1 | 0.9207 (4) | 0.8500 (3) | 0.8227 (3) | 0.0417 (7) | |
H1A | 0.9810 | 0.7763 | 0.8582 | 0.050* | |
N2 | 0.8913 (5) | 0.8228 (3) | 1.0520 (3) | 0.0415 (7) | |
O1 | 0.1745 (6) | 0.6117 (4) | 0.8691 (3) | 0.0868 (10) | |
H1 | 0.2104 | 0.5678 | 0.8146 | 0.130* | |
C1 | 0.9356 (6) | 0.8526 (5) | 0.7135 (4) | 0.0513 (10) | |
H1B | 1.0100 | 0.7761 | 0.6767 | 0.062* | |
C2 | 0.8398 (6) | 0.9697 (5) | 0.6539 (4) | 0.0528 (11) | |
H2 | 0.8466 | 0.9710 | 0.5776 | 0.063* | |
C3 | 0.7359 (6) | 1.0829 (5) | 0.7076 (4) | 0.0495 (10) | |
H3 | 0.6746 | 1.1624 | 0.6670 | 0.059* | |
C4 | 0.7203 (5) | 1.0806 (4) | 0.8233 (3) | 0.0394 (8) | |
C5 | 0.8147 (5) | 0.9581 (4) | 0.8822 (3) | 0.0350 (8) | |
C6 | 0.8008 (5) | 0.9454 (4) | 1.0008 (3) | 0.0339 (8) | |
C7 | 0.6897 (5) | 1.0596 (4) | 1.0593 (3) | 0.0392 (9) | |
C8 | 0.6761 (6) | 1.0441 (4) | 1.1762 (3) | 0.0468 (10) | |
H8 | 0.6064 | 1.1172 | 1.2180 | 0.056* | |
C9 | 0.7660 (6) | 0.9209 (5) | 1.2281 (4) | 0.0532 (11) | |
H9 | 0.7571 | 0.9083 | 1.3058 | 0.064* | |
C10 | 0.8719 (6) | 0.8133 (4) | 1.1624 (3) | 0.0478 (10) | |
H10 | 0.9325 | 0.7298 | 1.1990 | 0.057* | |
C11 | 0.6112 (6) | 1.1946 (4) | 0.8862 (4) | 0.0469 (10) | |
H11 | 0.5492 | 1.2769 | 0.8489 | 0.056* | |
C12 | 0.5970 (6) | 1.1848 (4) | 0.9975 (4) | 0.0463 (10) | |
H12 | 0.5256 | 1.2605 | 1.0359 | 0.056* | |
C13 | 0.2317 (9) | 0.5266 (5) | 0.9613 (4) | 0.0868 (10) | |
H13A | 0.3662 | 0.5159 | 0.9511 | 0.130* | |
H13B | 0.2060 | 0.4364 | 0.9678 | 0.130* | |
H13C | 0.1628 | 0.5681 | 1.0292 | 0.130* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sb1 | 0.03766 (17) | 0.04080 (16) | 0.03077 (16) | −0.00679 (11) | −0.00700 (11) | −0.00671 (10) |
Cl1 | 0.0555 (7) | 0.0497 (6) | 0.0502 (6) | −0.0168 (5) | −0.0071 (5) | −0.0011 (5) |
Cl2 | 0.0637 (7) | 0.0637 (7) | 0.0374 (5) | −0.0188 (5) | −0.0062 (5) | −0.0066 (5) |
Cl3 | 0.0650 (7) | 0.0510 (6) | 0.0553 (7) | 0.0096 (5) | −0.0156 (5) | −0.0148 (5) |
Cl4 | 0.0736 (8) | 0.0784 (8) | 0.0364 (6) | −0.0285 (6) | −0.0178 (5) | −0.0041 (5) |
N1 | 0.0424 (19) | 0.0375 (17) | 0.0427 (19) | −0.0106 (14) | −0.0055 (15) | −0.0053 (14) |
N2 | 0.0410 (19) | 0.0375 (17) | 0.0441 (19) | −0.0092 (14) | −0.0100 (15) | −0.0018 (14) |
O1 | 0.100 (2) | 0.0662 (18) | 0.0658 (19) | 0.0277 (16) | −0.0156 (17) | −0.0179 (15) |
C1 | 0.051 (3) | 0.059 (3) | 0.043 (2) | −0.016 (2) | −0.0009 (19) | −0.016 (2) |
C2 | 0.056 (3) | 0.067 (3) | 0.039 (2) | −0.021 (2) | −0.008 (2) | −0.010 (2) |
C3 | 0.048 (2) | 0.055 (2) | 0.045 (2) | −0.018 (2) | −0.0137 (19) | 0.006 (2) |
C4 | 0.032 (2) | 0.042 (2) | 0.041 (2) | −0.0125 (16) | −0.0052 (16) | −0.0007 (17) |
C5 | 0.0283 (19) | 0.0358 (19) | 0.041 (2) | −0.0110 (15) | −0.0042 (15) | −0.0060 (16) |
C6 | 0.0317 (19) | 0.0330 (18) | 0.037 (2) | −0.0116 (15) | −0.0051 (15) | −0.0049 (15) |
C7 | 0.031 (2) | 0.041 (2) | 0.044 (2) | −0.0099 (16) | −0.0040 (17) | −0.0081 (17) |
C8 | 0.046 (2) | 0.055 (2) | 0.040 (2) | −0.0126 (19) | −0.0055 (18) | −0.0148 (19) |
C9 | 0.055 (3) | 0.071 (3) | 0.037 (2) | −0.024 (2) | −0.0076 (19) | −0.006 (2) |
C10 | 0.047 (2) | 0.050 (2) | 0.043 (2) | −0.0146 (19) | −0.0115 (19) | 0.0056 (19) |
C11 | 0.041 (2) | 0.039 (2) | 0.056 (3) | −0.0044 (17) | −0.0129 (19) | 0.0009 (18) |
C12 | 0.041 (2) | 0.038 (2) | 0.055 (3) | −0.0020 (17) | −0.0085 (19) | −0.0127 (18) |
C13 | 0.100 (2) | 0.0662 (18) | 0.0658 (19) | 0.0277 (16) | −0.0156 (17) | −0.0179 (15) |
Sb1—Cl3 | 2.3970 (11) | C3—C4 | 1.402 (6) |
Sb1—Cl4 | 2.4248 (11) | C3—H3 | 0.9300 |
Sb1—Cl1 | 2.5375 (11) | C4—C5 | 1.411 (5) |
Sb1—Cl2 | 2.7890 (12) | C4—C11 | 1.435 (5) |
Sb1—Cl2i | 3.0184 (12) | C5—C6 | 1.425 (5) |
Sb1—Cl1ii | 3.2492 (12) | C6—C7 | 1.411 (5) |
Cl1—Sb1ii | 3.2492 (12) | C7—C8 | 1.402 (5) |
Cl2—Sb1i | 3.0184 (12) | C7—C12 | 1.441 (5) |
N1—C1 | 1.322 (5) | C8—C9 | 1.363 (6) |
N1—C5 | 1.363 (5) | C8—H8 | 0.9300 |
N1—H1A | 0.8600 | C9—C10 | 1.402 (6) |
N2—C10 | 1.320 (5) | C9—H9 | 0.9300 |
N2—C6 | 1.357 (5) | C10—H10 | 0.9300 |
O1—C13 | 1.378 (6) | C11—C12 | 1.338 (6) |
O1—H1 | 0.8200 | C11—H11 | 0.9300 |
C1—C2 | 1.388 (6) | C12—H12 | 0.9300 |
C1—H1B | 0.9300 | C13—H13A | 0.9600 |
C2—C3 | 1.362 (6) | C13—H13B | 0.9600 |
C2—H2 | 0.9300 | C13—H13C | 0.9600 |
Cl3—Sb1—Cl4 | 93.24 (4) | C3—C4—C11 | 123.9 (4) |
Cl3—Sb1—Cl1 | 89.95 (4) | C5—C4—C11 | 118.0 (3) |
Cl4—Sb1—Cl1 | 91.93 (4) | N1—C5—C4 | 118.4 (3) |
Cl3—Sb1—Cl2 | 88.98 (4) | N1—C5—C6 | 120.0 (3) |
Cl4—Sb1—Cl2 | 88.61 (4) | C4—C5—C6 | 121.7 (3) |
Cl1—Sb1—Cl2 | 178.83 (3) | N2—C6—C7 | 123.5 (3) |
Cl3—Sb1—Cl2i | 86.39 (4) | N2—C6—C5 | 118.2 (3) |
Cl4—Sb1—Cl2i | 173.22 (4) | C7—C6—C5 | 118.3 (3) |
Cl1—Sb1—Cl2i | 94.84 (3) | C8—C7—C6 | 117.3 (3) |
Cl2—Sb1—Cl2i | 84.62 (3) | C8—C7—C12 | 123.4 (4) |
Cl3—Sb1—Cl1ii | 171.36 (4) | C6—C7—C12 | 119.3 (3) |
Cl4—Sb1—Cl1ii | 89.92 (4) | C9—C8—C7 | 119.4 (4) |
Cl1—Sb1—Cl1ii | 81.90 (3) | C9—C8—H8 | 120.3 |
Cl2—Sb1—Cl1ii | 99.14 (3) | C7—C8—H8 | 120.3 |
Cl2i—Sb1—Cl1ii | 91.41 (3) | C8—C9—C10 | 118.9 (4) |
Sb1—Cl1—Sb1ii | 98.10 (3) | C8—C9—H9 | 120.6 |
Sb1—Cl2—Sb1i | 95.38 (3) | C10—C9—H9 | 120.6 |
C1—N1—C5 | 123.4 (3) | N2—C10—C9 | 124.2 (4) |
C1—N1—H1A | 118.3 | N2—C10—H10 | 117.9 |
C5—N1—H1A | 118.3 | C9—C10—H10 | 117.9 |
C10—N2—C6 | 116.7 (3) | C12—C11—C4 | 121.2 (4) |
C13—O1—H1 | 109.5 | C12—C11—H11 | 119.4 |
N1—C1—C2 | 119.7 (4) | C4—C11—H11 | 119.4 |
N1—C1—H1B | 120.1 | C11—C12—C7 | 121.6 (4) |
C2—C1—H1B | 120.1 | C11—C12—H12 | 119.2 |
C3—C2—C1 | 119.7 (4) | C7—C12—H12 | 119.2 |
C3—C2—H2 | 120.1 | O1—C13—H13A | 109.5 |
C1—C2—H2 | 120.1 | O1—C13—H13B | 109.5 |
C2—C3—C4 | 120.6 (4) | H13A—C13—H13B | 109.5 |
C2—C3—H3 | 119.7 | O1—C13—H13C | 109.5 |
C4—C3—H3 | 119.7 | H13A—C13—H13C | 109.5 |
C3—C4—C5 | 118.1 (4) | H13B—C13—H13C | 109.5 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1iii | 0.86 | 1.88 | 2.685 (4) | 155 |
O1—H1···Cl2 | 0.82 | 2.34 | 3.143 (4) | 166 |
Symmetry code: (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (C12H9N2)[SbCl4]·CH4O |
Mr | 476.80 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.5228 (10), 10.0340 (14), 12.3933 (19) |
α, β, γ (°) | 78.242 (3), 73.266 (2), 73.751 (2) |
V (Å3) | 852.3 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.24 |
Crystal size (mm) | 0.43 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.436, 0.701 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4451, 2947, 2584 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.077, 1.01 |
No. of reflections | 2947 |
No. of parameters | 184 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.64 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 1.88 | 2.685 (4) | 154.7 |
O1—H1···Cl2 | 0.82 | 2.34 | 3.143 (4) | 165.6 |
Symmetry code: (i) x+1, y, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The acceptor ability of SbF3 towards neutral ligands has been previously investigated. Adducts with bi- and tri-dentate nitrogen donor atoms such as 1,10-phenanthroline have been obtainted (Bertazzi et al., 1983), but the corresponding complex of SbCl3 has not yet been reported. As a contribution to the chemistry of antimony complexes with neutral ligands, we report here the synthesis and crystal structure of the title compound.
The title compound, {C12H9N2+.SbCl4-.CH3OH}n (Fig.1), consists of tetrachloroantimonate(III) anions, 1,10-phenanthrolinium cations and methanol solvent molecules. In the crystal, centrosymmetrically related anions are linked by short intermolecular Sb1···Cl2i and Cl1···Sb1ii contacts [symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z] into [Sb2Cl8]2- dianions made up from two octahedra sharing a common edge, forming one-dimensional polymeric chains running parallel to the a axis. The cis and trans Cl—Sb—Cl bond angles within the distorted octahedral coordination geometry about Sb are in the range 81.90 (3)–99.14 (3)° and 171.36 (4)–178.83 (3)°, respectively. The Sb—Cl distances also vary with the role they play in the structure, the terminal Sb1—Cl3 [2.3970 (11) Å] and Sb1—Cl4 [2.4248 (11) Å] bonds being shorter than those involving the bridging Cl atoms which range from 2.5375 (11) Å to 2.7890 (12) Å. The crystal structure is further stabilized by O—H···Cl and N—H···O hydrogen bonds (Fig. 2, Table 1).