Substitutional disorder in a hypervalent diorganotin(IV) dihalide.

The structure of bromidochloridobis[2-(dimethyl-amino-meth-yl)phen-yl]tin(IV), [SnBr(0.65)Cl(1.35)(C(9)H(12)N)(2)], contains two 2-(Me(2)NCH(2))C(6)H(4) units bonded to a Sn atom which lies on a twofold axis. The compound exhibits substitutional disorder of the halide atoms bonded to the Sn, with 1.35 occupancy for Cl and 0.65 for Br; it is isomorphous with the corresponding dichloride. The Sn atom is hexa-coordinated with a (C,N)(2)SnX(2) (X = Cl/Br) distorted octa-hedral core as a result of the strong intra-molecular N→Sn coordination trans to the Sn-X bonds (N1-Sn1-X1 = 165.8°). As a result of the inter-molecular contacts, viz. H⋯X and H⋯benzene inter-actions, the mol-ecules are arranged in a three-dimensional supra-molecular manner in the crystal structure.

Related literature

For related literature see Varga et al. (2001 ▶, 2005 ▶, 2006 ▶, 2007 ▶); Rotar et al. (2007 ▶); Emsley (1994 ▶); IUPAC (1979 ▶).

Experimental

Crystal data

[SnBr0.65Cl1.35(C9H12N)2]

M = 486.89

Monoclinic,

a = 17.0221 (15) Å

b = 8.2387 (7) Å

c = 14.7510 (13) Å

β = 106.1050 (10)°

V = 1987.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.78 mm−1

T = 297 (2) K

0.32 × 0.25 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SAINT-Plus; Bruker, 2000 ▶) T min = 0.452, T max = 0.738

6916 measured reflections

1746 independent reflections

1693 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.060

S = 1.24

1746 reflections

108 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.47 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2001 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2007 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807063386/gd2029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063386/gd2029Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[SnBr0.65Cl1.35(C9H12N)2]	F000 = 966.8
Mr = 486.89	Dx = 1.627 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3754 reflections
a = 17.0221 (15) Å	θ = 2.5–26.9º
b = 8.2387 (7) Å	µ = 2.78 mm−1
c = 14.7510 (13) Å	T = 297 (2) K
β = 106.1050 (10)º	Block, colourless
V = 1987.5 (3) Å3	0.32 × 0.25 × 0.11 mm
Z = 4

Bruker Smart APEX CCD area-detector diffractometer	1746 independent reflections
Radiation source: fine-focus sealed tube	1693 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.035
T = 297(2) K	θmax = 25.0º
phi and ω scans	θmin = 2.5º
Absorption correction: multi-scan(SAINT-Plus; Bruker, 2000)	h = −19→20
Tmin = 0.452, Tmax = 0.738	k = −9→9
6916 measured reflections	l = −17→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H-atom parameters constrained
wR(F2) = 0.060	w = 1/[σ2(Fo2) + (0.P)2 + 3.2594P] where P = (Fo2 + 2Fc2)/3
S = 1.24	(Δ/σ)max = 0.001
1746 reflections	Δρmax = 0.36 e Å−3
108 parameters	Δρmin = −0.46 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	Occ. (<1)
Br1	1.04832 (5)	0.42622 (9)	0.36987 (5)	0.0721 (3)	0.325 (3)
Cl1	1.04832 (5)	0.42622 (9)	0.36987 (5)	0.0721 (3)	0.675 (3)
Sn1	1.0000	0.64336 (4)	0.2500	0.03453 (12)
C1	0.89182 (18)	0.7072 (4)	0.2862 (2)	0.0386 (7)
C6	0.8831 (2)	0.6785 (4)	0.3757 (2)	0.0455 (8)
H6	0.9254	0.6293	0.4212	0.055*
C2	0.8274 (2)	0.7761 (5)	0.2181 (3)	0.0517 (9)
C5	0.8125 (2)	0.7221 (5)	0.3982 (3)	0.0589 (10)
H5	0.8072	0.7022	0.4583	0.071*
C4	0.7506 (3)	0.7942 (6)	0.3318 (3)	0.0714 (12)
H4	0.7035	0.8260	0.3472	0.086*
C3	0.7572 (2)	0.8206 (6)	0.2424 (3)	0.0707 (12)
H3	0.7141	0.8688	0.1975	0.085*
N1	0.91474 (19)	0.8322 (4)	0.1136 (2)	0.0547 (8)
C7	0.8321 (2)	0.7923 (6)	0.1177 (3)	0.0653 (11)
H7A	0.8150	0.6911	0.0845	0.078*
H7B	0.7947	0.8766	0.0860	0.078*
C8	0.9324 (3)	1.0031 (5)	0.1373 (3)	0.0785 (13)
H8A	0.8954	1.0700	0.0915	0.118*
H8B	0.9876	1.0269	0.1371	0.118*
H8C	0.9259	1.0246	0.1987	0.118*
C9	0.9204 (3)	0.8054 (7)	0.0157 (3)	0.0838 (15)
H9A	0.8810	0.8724	−0.0273	0.126*
H9B	0.9096	0.6934	−0.0012	0.126*
H9C	0.9744	0.8331	0.0124	0.126*

	U11	U22	U33	U12	U13	U23
Br1	0.0787 (5)	0.0714 (5)	0.0805 (6)	0.0373 (4)	0.0458 (4)	0.0378 (4)
Cl1	0.0787 (5)	0.0714 (5)	0.0805 (6)	0.0373 (4)	0.0458 (4)	0.0378 (4)
Sn1	0.03419 (18)	0.03473 (18)	0.04017 (19)	0.000	0.01949 (13)	0.000
C1	0.0344 (16)	0.0371 (17)	0.0486 (19)	0.0027 (13)	0.0187 (15)	−0.0014 (14)
C6	0.0446 (19)	0.048 (2)	0.050 (2)	0.0021 (15)	0.0240 (16)	−0.0028 (16)
C2	0.0413 (19)	0.061 (2)	0.056 (2)	0.0070 (17)	0.0187 (17)	0.0090 (18)
C5	0.058 (2)	0.068 (3)	0.063 (2)	0.003 (2)	0.036 (2)	−0.002 (2)
C4	0.052 (2)	0.084 (3)	0.093 (3)	0.015 (2)	0.045 (2)	0.002 (3)
C3	0.044 (2)	0.082 (3)	0.089 (3)	0.018 (2)	0.023 (2)	0.013 (2)
N1	0.0518 (18)	0.068 (2)	0.0470 (17)	0.0091 (15)	0.0181 (14)	0.0161 (15)
C7	0.045 (2)	0.088 (3)	0.059 (2)	0.009 (2)	0.0076 (18)	0.019 (2)
C8	0.090 (3)	0.062 (3)	0.085 (3)	0.004 (2)	0.026 (3)	0.022 (2)
C9	0.084 (3)	0.121 (4)	0.050 (2)	0.019 (3)	0.024 (2)	0.030 (3)

Br1—Sn1	2.4893 (7)	C4—H4	0.9300
Sn1—C1	2.121 (3)	C3—H3	0.9300
Sn1—C1i	2.121 (3)	N1—C7	1.462 (5)
Sn1—Cl1i	2.4893 (7)	N1—C8	1.462 (5)
Sn1—Br1i	2.4893 (7)	N1—C9	1.491 (5)
C1—C2	1.387 (5)	C7—H7A	0.9700
C1—C6	1.389 (5)	C7—H7B	0.9700
C6—C5	1.380 (5)	C8—H8A	0.9600
C6—H6	0.9300	C8—H8B	0.9600
C2—C3	1.389 (5)	C8—H8C	0.9600
C2—C7	1.510 (5)	C9—H9A	0.9600
C5—C4	1.360 (6)	C9—H9B	0.9600
C5—H5	0.9300	C9—H9C	0.9600
C4—C3	1.372 (6)
C1—Sn1—C1i	151.30 (17)	C4—C3—C2	120.8 (4)
C1—Sn1—Cl1i	102.61 (9)	C4—C3—H3	119.6
C1i—Sn1—Cl1i	97.93 (9)	C2—C3—H3	119.6
C1—Sn1—Br1i	102.61 (9)	C7—N1—C8	110.1 (3)
C1i—Sn1—Br1i	97.93 (9)	C7—N1—C9	109.2 (3)
Cl1i—Sn1—Br1i	0.00 (4)	C8—N1—C9	108.0 (3)
C1—Sn1—Br1	97.93 (9)	N1—C7—C2	112.0 (3)
C1i—Sn1—Br1	102.61 (9)	N1—C7—H7A	109.2
Cl1i—Sn1—Br1	88.11 (4)	C2—C7—H7A	109.2
Br1i—Sn1—Br1	88.11 (4)	N1—C7—H7B	109.2
C2—C1—C6	119.2 (3)	C2—C7—H7B	109.2
C2—C1—Sn1	119.1 (2)	H7A—C7—H7B	107.9
C6—C1—Sn1	121.8 (2)	N1—C8—H8A	109.5
C5—C6—C1	120.9 (3)	N1—C8—H8B	109.5
C5—C6—H6	119.6	H8A—C8—H8B	109.5
C1—C6—H6	119.6	N1—C8—H8C	109.5
C1—C2—C3	119.0 (4)	H8A—C8—H8C	109.5
C1—C2—C7	120.0 (3)	H8B—C8—H8C	109.5
C3—C2—C7	120.9 (3)	N1—C9—H9A	109.5
C4—C5—C6	119.6 (4)	N1—C9—H9B	109.5
C4—C5—H5	120.2	H9A—C9—H9B	109.5
C6—C5—H5	120.2	N1—C9—H9C	109.5
C5—C4—C3	120.5 (4)	H9A—C9—H9C	109.5
C5—C4—H4	119.7	H9B—C9—H9C	109.5
C3—C4—H4	119.7
C1i—Sn1—C1—C2	70.1 (3)	C6—C1—C2—C7	−173.7 (4)
Cl1i—Sn1—C1—C2	−64.6 (3)	Sn1—C1—C2—C7	4.9 (5)
Br1i—Sn1—C1—C2	−64.6 (3)	C1—C6—C5—C4	−0.1 (6)
Br1—Sn1—C1—C2	−154.4 (3)	C6—C5—C4—C3	1.5 (7)
C1i—Sn1—C1—C6	−111.4 (3)	C5—C4—C3—C2	−0.8 (7)
Cl1i—Sn1—C1—C6	113.9 (3)	C1—C2—C3—C4	−1.3 (7)
Br1i—Sn1—C1—C6	113.9 (3)	C7—C2—C3—C4	175.0 (4)
Br1—Sn1—C1—C6	24.1 (3)	C8—N1—C7—C2	−75.8 (4)
C2—C1—C6—C5	−2.0 (5)	C9—N1—C7—C2	165.8 (4)
Sn1—C1—C6—C5	179.5 (3)	C1—C2—C7—N1	−37.0 (5)
C6—C1—C2—C3	2.6 (6)	C3—C2—C7—N1	146.8 (4)
Sn1—C1—C2—C3	−178.8 (3)

Y—H···Cg	Y—H	H···Cg	Y···Cg	Y—H···Cg
C3—H3···Cg1ii	0.93	3.19	3.78 (1)	123

D-H···A	D-H	H···A	D···A	D-H···A
C4-H4···Cl1ii/Br1ii	0.93	2.87	3.798 (5)	173
C6-H6···Cl1iii/Br1iii	0.93	3.02	3.710 (3)	132

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg1ii	0.93	3.19	3.78 (1)	123
C4—H4⋯Cl1ii/Br1ii	0.93	2.87	3.798 (5)	173
C6—H6⋯Cl1iii/Br1iii	0.93	3.02	3.710 (3)	132

Symmetry code: (ii) , , , (iii) , , . Cg1 is the centroid of the benzene ring C1–C6.