Bis(trimethyl­phenyl­ammonium) hexa­[bromido/chlorido(0.792/0.208)]stannate(IV)

In the title mol­ecular salt, [C₆H₅(CH₃)₃N]₂[SnBr_4.75Cl_1.25], the Sn^IV atom (site symmetry ) adopts an octa­hedral coordination geometry. The Br and Cl atoms are disordered over three sites in 0.7415 (13):0.2585 (14), 0.8514 (14):0.1486 (14) and 0.7821 (14):0.2179 (14) ratios.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.021
• wR factor = 0.052
• Data-to-parameter ratio = 22.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Sn1
PLAT331_ALERT_2_C Small Average Phenyl   C-C Dist. C1     -C6            1.37 Ang.
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      27.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 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
   2 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


checkCIF publication errors

Alert level G
PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is
            missing. This is required for a full paper submission (but is
            optional for an electronic paper).

   0 ALERT level A = Data missing that is essential or data in wrong format
   1 ALERT level G = General alerts. Data that may be required is missing

---

Related literature

For the crystal structures of other ammonium hexabromidostannates(IV): see: Al-Far & Ali (2007); Al-Far, Haddad & Ali (2009); Ali et al. (2007); Howie et al. (2009).

S1. Experimental

Tribenzyltin chloride (0.34 g, 1 mmol) and trimethylphenylammonium tribromide (0.38 g, 1 mmol) were heated in ethanol (50 ml) for 1 hour. After filtering of the reaction mixture, yellow blocks of (I) were obtained upon slow evaporation of the filtrate. The crystal structure indicated that all the organic groups bonded to tin in the reactant were cleaved by the tribromide anion.

S2. Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.93–0.96 Å) and were treated as riding on their parent atoms, with U(H) set to 1.2–1.5 times U_eq(C). The initial refinement that assumed the halogens were only bromine atoms led to a difference Fourier with a large peak near Sn1 and a deep hole near Br1. The R-index was 0.0367.

The three halogen atoms were then refined as a mixture of chlorine and bromine. For each site, the displacement factor of the bromine and chlorine occupants were restrained to be identical. The refinement gave nearly 2.375 bromine and 0.625 chlorine atoms, and the difference Fourier was diffuse.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

Fig. 1. The molecular structure of (I) at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The bromine atoms are disordered with respect to the chlorine atoms.

Bis(trimethylphenylammonium) hexa[bromido/chlorido(0.792/0.208)]stannate(IV)

Crystal data

(C9H14N)2[SnBr4.75Cl1.25]	F(000) = 775
Mr = 815.00	Dx = 2.090 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4823 reflections
a = 8.8003 (1) Å	θ = 2.4–28.2°
b = 10.6362 (2) Å	µ = 8.45 mm^−1
c = 14.2869 (2) Å	T = 293 K
β = 104.433 (1)°	Block, yellow
V = 1295.07 (3) Å^3	0.30 × 0.30 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	2974 independent reflections
Radiation source: fine-focus sealed tube	2507 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.186, Tmax = 0.283	k = −13→13
12094 measured reflections	l = −18→18

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.052	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0273P)^2 + 0.3311P] where P = (Fo^2 + 2Fc^2)/3
2974 reflections	(Δ/σ)max = 0.001
133 parameters	Δρmax = 0.38 e Å^−3
5 restraints	Δρmin = −0.58 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sn1	0.5000	0.5000	0.5000	0.02940 (7)
Br1	0.79909 (3)	0.50477 (3)	0.52754 (2)	0.04523 (11)	0.7415 (13)
Br2	0.50568 (4)	0.71415 (3)	0.58689 (2)	0.04665 (11)	0.8514 (14)
Br3	0.53087 (4)	0.38474 (3)	0.66315 (2)	0.04326 (11)	0.7821 (14)
Cl1	0.79909 (3)	0.50477 (3)	0.52754 (2)	0.04523 (11)	0.2585 (14)
Cl2	0.50568 (4)	0.71415 (3)	0.58689 (2)	0.04665 (11)	0.1486 (14)
Cl3	0.53087 (4)	0.38474 (3)	0.66315 (2)	0.04326 (11)	0.2179 (14)
N1	0.8193 (2)	0.0359 (2)	0.70182 (15)	0.0404 (5)
C1	0.9413 (3)	0.0799 (2)	0.65257 (17)	0.0354 (5)
C2	0.8999 (3)	0.1456 (3)	0.5678 (2)	0.0586 (8)
H2	0.7949	0.1610	0.5382	0.070*
C3	1.0162 (4)	0.1887 (3)	0.5271 (3)	0.0689 (10)
H3	0.9879	0.2330	0.4692	0.083*
C4	1.1700 (4)	0.1687 (3)	0.5682 (2)	0.0564 (8)
H4	1.2466	0.1978	0.5390	0.068*
C5	1.2101 (4)	0.1053 (3)	0.6533 (2)	0.0636 (9)
H5	1.3155	0.0919	0.6831	0.076*
C6	1.0965 (3)	0.0603 (3)	0.6963 (2)	0.0566 (8)
H6	1.1253	0.0170	0.7546	0.068*
C7	0.8529 (4)	−0.0962 (3)	0.7393 (3)	0.0619 (9)
H7A	0.8527	−0.1518	0.6864	0.093*
H7B	0.7735	−0.1221	0.7708	0.093*
H7C	0.9537	−0.0988	0.7847	0.093*
C8	0.8202 (4)	0.1222 (3)	0.7851 (2)	0.0636 (9)
H8A	0.9203	0.1176	0.8310	0.095*
H8B	0.7393	0.0973	0.8156	0.095*
H8C	0.8015	0.2069	0.7618	0.095*
C9	0.6576 (3)	0.0366 (3)	0.6359 (2)	0.0567 (8)
H9A	0.6272	0.1215	0.6175	0.085*
H9B	0.5852	0.0008	0.6689	0.085*
H9C	0.6569	−0.0122	0.5793	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.02718 (11)	0.02958 (12)	0.03066 (12)	−0.00216 (9)	0.00577 (8)	−0.00056 (9)
Br1	0.02788 (16)	0.0596 (2)	0.04703 (19)	−0.00311 (13)	0.00721 (13)	0.00024 (14)
Br2	0.05446 (19)	0.03536 (16)	0.04899 (19)	−0.00321 (13)	0.01072 (14)	−0.00974 (12)
Br3	0.04800 (18)	0.04521 (18)	0.03699 (17)	0.00217 (13)	0.01141 (13)	0.00745 (13)
Cl1	0.02788 (16)	0.0596 (2)	0.04703 (19)	−0.00311 (13)	0.00721 (13)	0.00024 (14)
Cl2	0.05446 (19)	0.03536 (16)	0.04899 (19)	−0.00321 (13)	0.01072 (14)	−0.00974 (12)
Cl3	0.04800 (18)	0.04521 (18)	0.03699 (17)	0.00217 (13)	0.01141 (13)	0.00745 (13)
N1	0.0381 (11)	0.0413 (12)	0.0425 (12)	0.0010 (9)	0.0116 (9)	0.0063 (10)
C1	0.0365 (13)	0.0337 (12)	0.0367 (13)	−0.0019 (10)	0.0107 (10)	−0.0008 (10)
C2	0.0461 (16)	0.064 (2)	0.0621 (19)	0.0077 (15)	0.0071 (14)	0.0280 (16)
C3	0.075 (2)	0.071 (2)	0.064 (2)	−0.0009 (18)	0.0238 (18)	0.0325 (18)
C4	0.0603 (19)	0.0526 (18)	0.064 (2)	−0.0082 (15)	0.0306 (16)	0.0018 (15)
C5	0.0394 (15)	0.086 (2)	0.068 (2)	0.0031 (16)	0.0184 (15)	0.0090 (18)
C6	0.0422 (15)	0.081 (2)	0.0456 (16)	0.0065 (15)	0.0101 (13)	0.0173 (16)
C7	0.0571 (18)	0.0496 (18)	0.082 (2)	0.0043 (14)	0.0235 (17)	0.0281 (16)
C8	0.069 (2)	0.077 (2)	0.0519 (18)	0.0022 (17)	0.0294 (16)	−0.0079 (16)
C9	0.0356 (14)	0.0623 (19)	0.068 (2)	−0.0023 (13)	0.0049 (14)	0.0087 (16)

Geometric parameters (Å, º)

Sn1—Cl1^i	2.5630 (3)	C3—C4	1.352 (4)
Sn1—Br1^i	2.5630 (3)	C3—H3	0.9300
Sn1—Br1	2.5630 (3)	C4—C5	1.357 (5)
Sn1—Cl3^i	2.5874 (3)	C4—H4	0.9300
Sn1—Br3^i	2.5874 (3)	C5—C6	1.383 (4)
Sn1—Br2	2.5886 (3)	C5—H5	0.9300
Sn1—Br3	2.5874 (3)	C6—H6	0.9300
Sn1—Br2^i	2.5886 (3)	C7—H7A	0.9600
Sn1—Cl2^i	2.5886 (3)	C7—H7B	0.9600
N1—C8	1.501 (4)	C7—H7C	0.9600
N1—C1	1.498 (3)	C8—H8A	0.9600
N1—C9	1.498 (3)	C8—H8B	0.9600
N1—C7	1.506 (4)	C8—H8C	0.9600
C1—C6	1.368 (4)	C9—H9A	0.9600
C1—C2	1.367 (4)	C9—H9B	0.9600
C2—C3	1.375 (4)	C9—H9C	0.9600
C2—H2	0.9300
Cl1^i—Sn1—Br1^i	0.00 (2)	C8—N1—C7	109.1 (2)
Cl1^i—Sn1—Br1	180.000 (15)	C1—N1—C7	111.0 (2)
Br1^i—Sn1—Br1	180.000 (15)	C9—N1—C7	107.4 (2)
Cl1^i—Sn1—Cl3^i	89.879 (10)	C6—C1—C2	119.8 (2)
Br1^i—Sn1—Cl3^i	89.879 (10)	C6—C1—N1	119.2 (2)
Br1—Sn1—Cl3^i	90.121 (10)	C2—C1—N1	120.8 (2)
Cl1^i—Sn1—Br3^i	89.879 (10)	C1—C2—C3	118.9 (3)
Br1^i—Sn1—Br3^i	89.879 (10)	C1—C2—H2	120.6
Br1—Sn1—Br3^i	90.121 (10)	C3—C2—H2	120.6
Cl3^i—Sn1—Br3^i	0.000 (6)	C4—C3—C2	122.3 (3)
Cl1^i—Sn1—Br3	90.121 (10)	C4—C3—H3	118.9
Br1^i—Sn1—Br3	90.121 (10)	C2—C3—H3	118.9
Br1—Sn1—Br3	89.879 (10)	C3—C4—C5	118.4 (3)
Cl3^i—Sn1—Br3	180.0	C3—C4—H4	120.8
Br3^i—Sn1—Br3	180.0	C5—C4—H4	120.8
Cl1^i—Sn1—Br2	89.277 (10)	C4—C5—C6	121.0 (3)
Br1^i—Sn1—Br2	89.277 (10)	C4—C5—H5	119.5
Br1—Sn1—Br2	90.723 (10)	C6—C5—H5	119.5
Cl3^i—Sn1—Br2	90.014 (10)	C1—C6—C5	119.6 (3)
Br3^i—Sn1—Br2	90.014 (10)	C1—C6—H6	120.2
Br3—Sn1—Br2	89.986 (10)	C5—C6—H6	120.2
Cl1^i—Sn1—Br2^i	90.723 (10)	N1—C7—H7A	109.5
Br1^i—Sn1—Br2^i	90.723 (10)	N1—C7—H7B	109.5
Br1—Sn1—Br2^i	89.277 (10)	H7A—C7—H7B	109.5
Cl3^i—Sn1—Br2^i	89.986 (10)	N1—C7—H7C	109.5
Br3^i—Sn1—Br2^i	89.986 (10)	H7A—C7—H7C	109.5
Br3—Sn1—Br2^i	90.014 (10)	H7B—C7—H7C	109.5
Br2—Sn1—Br2^i	180.0	N1—C8—H8A	109.5
Cl1^i—Sn1—Cl2^i	90.723 (10)	N1—C8—H8B	109.5
Br1^i—Sn1—Cl2^i	90.723 (10)	H8A—C8—H8B	109.5
Br1—Sn1—Cl2^i	89.277 (10)	N1—C8—H8C	109.5
Cl3^i—Sn1—Cl2^i	89.986 (10)	H8A—C8—H8C	109.5
Br3^i—Sn1—Cl2^i	89.986 (10)	H8B—C8—H8C	109.5
Br3—Sn1—Cl2^i	90.014 (10)	N1—C9—H9A	109.5
Br2—Sn1—Cl2^i	180.0	N1—C9—H9B	109.5
Br2^i—Sn1—Cl2^i	0.000 (6)	H9A—C9—H9B	109.5
C8—N1—C1	108.6 (2)	N1—C9—H9C	109.5
C8—N1—C9	108.1 (2)	H9A—C9—H9C	109.5
C1—N1—C9	112.5 (2)	H9B—C9—H9C	109.5
C8—N1—C1—C6	73.7 (3)	N1—C1—C2—C3	177.3 (3)
C9—N1—C1—C6	−166.6 (3)	C1—C2—C3—C4	−0.3 (6)
C7—N1—C1—C6	−46.2 (4)	C2—C3—C4—C5	−0.8 (6)
C8—N1—C1—C2	−102.3 (3)	C3—C4—C5—C6	1.0 (5)
C9—N1—C1—C2	17.4 (4)	C2—C1—C6—C5	−1.2 (5)
C7—N1—C1—C2	137.8 (3)	N1—C1—C6—C5	−177.3 (3)
C6—C1—C2—C3	1.4 (5)	C4—C5—C6—C1	0.0 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.