catena-Poly[1,10-phenanthrolin-1-ium [[dichloridoanti­monate(III)]-di-μ-chlorido] methanol solvate]

The asymmetric unit of the title compound, {(C₁₂H₉N₂)[SbCl₄]·CH₃OH}_n, comprises a 1,10-phenanthrolinium cation, a tetra­chloridoanti­monate anion and a methanol solvent mol­ecule. Centrosymmetrically-related anions are linked by short Sb...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...Cl and N—H...O hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](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

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S1. Comment

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).

Related literature

For the corresponding complex of SbF₃ with 1,10-phenanthroline, see: Bertazzi et al. (1983).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2 U_eq(C, O) or 1.5 U_eq(C) for the methyl group.

Computing details

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.

Figures

	Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids. H atoms are omitted for clarity.
	Fig. 2. Crystal packing of the title compound, showing a one-dimensional polymeric chain formed by O—H···Cl, N—H···O hydrogen bonds and intermolecular Sb···Cl contacts (dashed lines). H atoms are omitted for clarity.

catena-Poly[1,10-phenanthrolin-1-ium [[dichloridoantimonate(III)]-di- µ-chlorido] methanol solvate]

Crystal data

(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) Å^3

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 0.4963P] where P = (Fo^2 + 2Fc^2)/3
2947 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.74 e Å^−3
1 restraint	Δρmin = −0.64 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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, º)

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—Cl2^i	3.0184 (12)	C5—C6	1.425 (5)
Sb1—Cl1^ii	3.2492 (12)	C6—C7	1.411 (5)
Cl1—Sb1^ii	3.2492 (12)	C7—C8	1.402 (5)
Cl2—Sb1^i	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—Cl2^i	86.39 (4)	N2—C6—C5	118.2 (3)
Cl4—Sb1—Cl2^i	173.22 (4)	C7—C6—C5	118.3 (3)
Cl1—Sb1—Cl2^i	94.84 (3)	C8—C7—C6	117.3 (3)
Cl2—Sb1—Cl2^i	84.62 (3)	C8—C7—C12	123.4 (4)
Cl3—Sb1—Cl1^ii	171.36 (4)	C6—C7—C12	119.3 (3)
Cl4—Sb1—Cl1^ii	89.92 (4)	C9—C8—C7	119.4 (4)
Cl1—Sb1—Cl1^ii	81.90 (3)	C9—C8—H8	120.3
Cl2—Sb1—Cl1^ii	99.14 (3)	C7—C8—H8	120.3
Cl2^i—Sb1—Cl1^ii	91.41 (3)	C8—C9—C10	118.9 (4)
Sb1—Cl1—Sb1^ii	98.10 (3)	C8—C9—H9	120.6
Sb1—Cl2—Sb1^i	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, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^iii	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.