supplementary materials
catena-Poly[1,10-phenanthrolin-1-ium [[dichloridoantimonate(III)]-di-![[mu]](/logos/entities/mu_rmgif.gif)
-chlorido] methanol solvate]
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.
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.
catena-Poly[1,10-phenanthrolin-1-ium [[dichloridoantimonate(III)]-di-
µ-chlorido] methanol solvate]
top
Crystal data top
| (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 | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 2947 independent reflections |
| Radiation source: fine-focus sealed tube | 2584 reflections with I > 2σ(I) |
| graphite | 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 top
| 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 = −0.63 e Å−3 |
Crystal data top
| (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)° | |
Data collection top
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 | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.077 | Δρmax = 0.74 e Å−3 |
| S = 1.01 | Δρmin = −0.63 e Å−3 |
| 2947 reflections | Absolute structure: ? |
| 184 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | 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* | |
Atomic displacement parameters (Å2) top| | 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) |
Geometric parameters (Å, °) top
| 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. |
Hydrogen-bond geometry (Å, °) top
| 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 codes: (iii) x+1, y, z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.86 | 1.88 | 2.685 (4) | 155 |
| O1—H1···Cl2 | 0.82 | 2.34 | 3.143 (4) | 166 |
| Symmetry codes: (i) x+1, y, z. |
We acknowledge the financial support of the Shandong Province Science Foundation
and the State Key Laboratory of Crystalline Materials, Shandong University,
People's Republic of China.
Bertazzi, N., Alonzo, G. & Gibb, T. C. (1983). Inorg. Chim. Acta, 73, 121–124.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Cl intermolecular contacts into [Sb2Cl8]2- dimeric units to form one-dimensional polymeric chains running parallel to the a axis. The crystal structure is stabilized by O-H![[Figure 1]](./rz2155fig1thm.gif)
![[Figure 2]](./rz2155fig2thm.gif)
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).