Tetrameric indium trichloride, a new modification of a widely used compound

The title compound, hexa-μ-chloro-1:2κ⁴Cl;2:3κ⁴Cl;3:4κ⁴Cl-hexachloro-1κ²Cl,2κCl,3κCl,4κ²Cl-hexakis­(diethyl­amine)-1κ²N,2κN,3κN,4κ²N-tetraindium(III), [(InCl₃)₄(Et₂NH)₆] or [In₄Cl₁₂(C₄H₁₁N)₆], lies about an inversion centre and consists of four octahedrally coordinated In centres linked by bridging Cl atoms to form three four-membered In₂Cl₂ rings.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

[In4Cl12(C4H11N)6]	Z = 1
Mr = 1323.64	F(000) = 652
Triclinic, P1	Dx = 1.820 Mg m^−3
a = 10.962 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.407 (2) Å	Cell parameters from 8192 reflections
c = 11.674 (2) Å	θ = 1.9–25.0°
α = 95.46 (3)°	µ = 2.57 mm^−1
β = 109.57 (3)°	T = 133 K
γ = 114.20 (3)°	Block, colourless
V = 1207.8 (4) Å^3	0.3 × 0.3 × 0.1 mm

Data collection

Stoe-Siemens-Huber four-circle diffractometer	5291 independent reflections
Radiation source: fine-focus sealed tube	4871 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 8.192 pixels/mm pixels mm^-1	θmax = 27.1°, θmin = 1.9°
φ and ω scans	h = −14→12
Absorption correction: semi-empirical (using intensity measurements) (SADABS; Sheldrick, 1999)	k = −14→14
Tmin = 0.512, Tmax = 0.783	l = 0→14
45298 measured reflections

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0293P)^2 + 0.4598P] where P = (Fo^2 + 2Fc^2)/3
5291 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 0.58 e Å^−3
3 restraints	Δρmin = −1.08 e Å^−3

Special details

Experimental. Intensities were measured with a Siemens CCD area detector

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.

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

	x	y	z	Uiso*/Ueq
In1	−0.16254 (2)	0.17520 (2)	0.26727 (1)	0.01588 (5)
In2	0.09422 (2)	0.42290 (1)	0.12313 (1)	0.01431 (5)
Cl1	−0.15375 (6)	0.21661 (5)	0.03551 (5)	0.0180 (1)
Cl2	0.09098 (6)	0.41004 (5)	0.33569 (5)	0.0180 (1)
Cl3	−0.37922 (7)	−0.03459 (6)	0.15741 (6)	0.0279 (1)
Cl4	−0.12865 (7)	0.19437 (6)	0.48348 (5)	0.0271 (1)
Cl5	0.22419 (7)	0.29472 (6)	0.13154 (6)	0.0227 (1)
Cl6	0.05579 (6)	0.44214 (5)	−0.10137 (5)	0.0169 (1)
N1	−0.2675 (2)	0.3108 (2)	0.2337 (2)	0.0178 (4)
H1	−0.232 (3)	0.350 (2)	0.182 (2)	0.021*
C1	−0.2138 (3)	0.4232 (2)	0.3454 (2)	0.0266 (5)
H11	−0.1053	0.4726	0.3810	0.032*
H12	−0.2422	0.3858	0.4111	0.032*
C2	−0.2742 (3)	0.5203 (3)	0.3138 (3)	0.0320 (6)
H21	−0.2561	0.5503	0.2424	0.048*
H22	−0.2254	0.5975	0.3873	0.048*
H23	−0.3800	0.4757	0.2913	0.048*
C3	−0.4310 (3)	0.2349 (2)	0.1691 (2)	0.0245 (5)
H31	−0.4597	0.1613	0.0972	0.029*
H32	−0.4691	0.2950	0.1348	0.029*
C4	−0.5005 (3)	0.1773 (3)	0.2570 (3)	0.0382 (7)
H41	−0.4486	0.1333	0.3048	0.057*
H42	−0.6039	0.1120	0.2072	0.057*
H43	−0.4939	0.2493	0.3156	0.057*
N2	0.0003 (2)	0.1031 (2)	0.2658 (2)	0.0181 (4)
H2	0.054 (3)	0.163 (2)	0.237 (2)	0.022*
C5	0.1007 (3)	0.1161 (2)	0.3956 (2)	0.0225 (5)
H51	0.0477	0.0417	0.4264	0.027*
H52	0.1265	0.2005	0.4528	0.027*
C6	0.2404 (3)	0.1151 (3)	0.4029 (3)	0.0387 (7)
H61	0.2162	0.0307	0.3487	0.058*
H62	0.3009	0.1245	0.4903	0.058*
H63	0.2949	0.1896	0.3743	0.058*
C7	−0.0581 (3)	−0.0279 (2)	0.1726 (2)	0.0259 (5)
H71	0.0221	−0.0284	0.1517	0.031*
H72	−0.1358	−0.0351	0.0938	0.031*
C8	−0.1206 (3)	−0.1487 (3)	0.2196 (3)	0.0339 (6)
H81	−0.0406	−0.1528	0.2862	0.051*
H82	−0.1731	−0.2298	0.1496	0.051*
H83	−0.1886	−0.1416	0.2536	0.051*
N3	0.2885 (2)	0.6302 (2)	0.2043 (2)	0.0164 (4)
H3	0.270 (3)	0.675 (2)	0.148 (2)	0.020*
C9	0.3011 (3)	0.7068 (2)	0.3231 (2)	0.0200 (5)
H91	0.3580	0.6859	0.3963	0.024*
H92	0.2017	0.6776	0.3209	0.024*
C10	0.3748 (3)	0.8562 (2)	0.3411 (2)	0.0281 (5)
H101	0.4747	0.8864	0.3466	0.042*
H102	0.3789	0.9012	0.4191	0.042*
H103	0.3186	0.8777	0.2693	0.042*
C11	0.4325 (3)	0.6367 (2)	0.2198 (2)	0.0217 (5)
H111	0.4472	0.5719	0.2661	0.026*
H112	0.5126	0.7270	0.2713	0.026*
C12	0.4415 (3)	0.6067 (2)	0.0953 (2)	0.0252 (5)
H121	0.3676	0.5147	0.0468	0.038*
H122	0.5395	0.6173	0.1105	0.038*
H123	0.4234	0.6684	0.0477	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
In1	0.01848 (9)	0.01507 (8)	0.01782 (9)	0.00917 (7)	0.00935 (7)	0.00713 (6)
In2	0.01696 (8)	0.01360 (8)	0.01490 (8)	0.00792 (6)	0.00782 (6)	0.00637 (6)
Cl1	0.0198 (3)	0.0152 (2)	0.0162 (2)	0.0060 (2)	0.0069 (2)	0.0049 (2)
Cl2	0.0213 (3)	0.0169 (2)	0.0144 (2)	0.0071 (2)	0.0078 (2)	0.0057 (2)
Cl3	0.0241 (3)	0.0175 (3)	0.0363 (3)	0.0054 (2)	0.0118 (3)	0.0056 (2)
Cl4	0.0361 (3)	0.0374 (3)	0.0221 (3)	0.0239 (3)	0.0175 (3)	0.0163 (3)
Cl5	0.0279 (3)	0.0219 (3)	0.0297 (3)	0.0173 (2)	0.0165 (2)	0.0125 (2)
Cl6	0.0219 (3)	0.0187 (2)	0.0162 (2)	0.0125 (2)	0.0102 (2)	0.0073 (2)
N1	0.020 (1)	0.0195 (9)	0.0186 (9)	0.0111 (8)	0.0103 (8)	0.0071 (8)
C1	0.034 (1)	0.027 (1)	0.023 (1)	0.021 (1)	0.009 (1)	0.003 (1)
C2	0.042 (2)	0.028 (1)	0.032 (1)	0.024 (1)	0.014 (1)	0.006 (1)
C3	0.021 (1)	0.024 (1)	0.029 (1)	0.012 (1)	0.008 (1)	0.009 (1)
C4	0.033 (2)	0.038 (2)	0.061 (2)	0.020 (1)	0.032 (2)	0.025 (1)
N2	0.025 (1)	0.0164 (9)	0.0194 (9)	0.0124 (8)	0.0125 (8)	0.0094 (8)
C5	0.024 (1)	0.025 (1)	0.021 (1)	0.015 (1)	0.007 (1)	0.0081 (9)
C6	0.033 (2)	0.055 (2)	0.042 (2)	0.030 (2)	0.017 (1)	0.025 (2)
C7	0.037 (1)	0.023 (1)	0.025 (1)	0.019 (1)	0.015 (1)	0.006 (1)
C8	0.042 (2)	0.022 (1)	0.037 (2)	0.018 (1)	0.012 (1)	0.008 (1)
N3	0.0169 (9)	0.0163 (9)	0.0172 (9)	0.0078 (8)	0.0078 (8)	0.0064 (7)
C9	0.024 (1)	0.017 (1)	0.018 (1)	0.0079 (9)	0.0105 (9)	0.0024 (9)
C10	0.033 (1)	0.017 (1)	0.032 (1)	0.008 (1)	0.016 (1)	0.003 (1)
C11	0.0179 (1)	0.024 (1)	0.023 (1)	0.011 (1)	0.007 (1)	0.0053 (9)
C12	0.0229 (1)	0.026 (1)	0.031 (1)	0.012 (1)	0.016 (1)	0.009 (1)

Geometric parameters (Å, º)

In1—N2	2.256 (2)	N1—C3	1.493 (3)
In1—N1	2.267 (2)	N1—C1	1.498 (3)
In1—Cl3	2.394 (2)	C1—C2	1.522 (3)
In1—Cl4	2.3994 (8)	C3—C4	1.519 (4)
In1—Cl2	2.746 (2)	N2—C5	1.496 (3)
In1—Cl1	2.8165 (8)	N2—C7	1.505 (3)
In2—N3	2.263 (2)	C5—C6	1.510 (3)
In2—Cl5	2.4122 (8)	C7—C8	1.514 (4)
In2—Cl2	2.5109 (7)	N3—C11	1.497 (3)
In2—Cl1	2.531 (2)	N3—C9	1.499 (3)
In2—Cl6	2.5573 (8)	C9—C10	1.513 (3)
In2—Cl6^i	2.6474 (8)	C11—C12	1.506 (3)
Cl6—In2^i	2.6474 (8)
N2—In1—N1	155.12 (7)	Cl1—In2—Cl6	89.54 (5)
N2—In1—Cl3	96.92 (6)	N3—In2—Cl6^i	82.61 (5)
N1—In1—Cl3	98.42 (6)	Cl5—In2—Cl6^i	177.08 (2)
N2—In1—Cl4	99.63 (6)	Cl2—In2—Cl6^i	88.95 (3)
N1—In1—Cl4	95.84 (6)	Cl1—In2—Cl6^i	85.42 (3)
Cl3—In1—Cl4	103.04 (5)	Cl6—In2—Cl6^i	81.33 (3)
N2—In1—Cl2	77.64 (5)	In2—Cl1—In1	97.88 (4)
N1—In1—Cl2	82.72 (5)	In2—Cl2—In1	100.24 (5)
Cl3—In1—Cl2	165.53 (2)	In2—Cl6—In2^i	98.67 (3)
Cl4—In1—Cl2	91.14 (5)	C3—N1—C1	112.8 (2)
N2—In1—Cl1	81.63 (5)	C3—N1—In1	112.6 (1)
N1—In1—Cl1	78.90 (5)	C1—N1—In1	115.5 (1)
Cl3—In1—Cl1	90.04 (4)	N1—C1—C2	113.3 (2)
Cl4—In1—Cl1	166.54 (2)	N1—C3—C4	112.5 (2)
Cl2—In1—Cl1	75.97 (4)	C5—N2—C7	113.7 (2)
N3—In2—Cl5	98.95 (5)	C5—N2—In1	112.6 (1)
N3—In2—Cl2	92.15 (6)	C7—N2—In1	117.0 (2)
Cl5—In2—Cl2	93.45 (3)	N2—C5—C6	113.9 (2)
N3—In2—Cl1	167.85 (5)	N2—C7—C8	113.9 (2)
Cl5—In2—Cl1	93.10 (3)	C11—N3—C9	110.9 (2)
Cl2—In2—Cl1	85.54 (4)	C11—N3—In2	115.1 (1)
N3—In2—Cl6	90.70 (6)	C9—N3—In2	113.5 (1)
Cl5—In2—Cl6	96.15 (3)	N3—C9—C10	112.8 (2)
Cl2—In2—Cl6	169.43 (2)	N3—C11—C12	112.6 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.88 (2)	2.75 (2)	3.258 (2)	118 (2)
N2—H2···Cl5	0.88 (2)	2.62 (2)	3.476 (2)	167 (2)
N2—H2···Cl2	0.88 (2)	2.76 (2)	3.158 (2)	110 (2)
N1—H1···Cl6^i	0.88 (2)	2.85 (2)	3.685 (2)	158 (2)
N3—H3···Cl1^i	0.89 (2)	2.78 (2)	3.653 (2)	168 (2)

Symmetry code: (i) −x, −y+1, −z.