N,N,N′,N′,N′′,N′′-Hexa­methyl­guanidinium di-μ3-chlorido-tetra-μ2-chlorido-deca­chlorido­tetra­bis­muthate aceto­nitrile disolvate

Tiritiris, I.; Knobloch, G.; Saur, S.; Kantlehner, W.

doi:10.1107/S2414314616003175

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160317

https://doi.org/10.1107/S2414314616003175

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N,N,N′,N′,N′′,N′′-Hexamethylguanidinium di-μ₃-chlorido-tetra-μ₂-chlorido-decachloridotetrabismuthate acetonitrile disolvate

Ioannis Tiritiris,^a Georg Knobloch,^a Stefan Saur ^a and Willi Kantlehner ^a ^*

^aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
^*Correspondence e-mail: willi.kantlehner@hs-aalen.de

Edited by M. Zeller, Youngstown State University, USA (Received 20 February 2016; accepted 24 February 2016; online 27 February 2016)

The asymmetric unit of the solvated title compound, (C₇H₁₈N₃)₄[Bi₄Cl₁₆]·2CH₃CN, comprises two cations, one half [Bi₄Cl₁₆]⁴⁻ ion and one acetonitrile molecule. One N,N,N′,N′,N′′,N′′-hexamethylguanidinium ion shows orientational disorder and two sets of N- and C-atom positions were found, with an occupancy ratio of 0.941 (2):0.059 (2). The second cation is not disordered. The C—N bond lengths in the two guanidinium ions range from 1.334 (17) to 1.341 (17) Å, indicating double-bond character and pointing towards charge delocalization within the NCN planes. The four Bi^III ions are coordinated by six chloride ions in distorted octahedral manner. Two [Bi₂Cl₈]²⁻ dimers are fused together, forming a centrosymmetric tetranuclear [Bi₄Cl₁₆]⁴⁻ cluster. The bond lengths of bismuth to the terminal chlorides [2.4982 (7)–2.5509 (6) Å] are shorter than those of the double and triply bridging ones [2.7052 (6)–3.0320 (6) Å]. The acetonitrile solvent molecule is disordered over two positions, with an occupancy ratio of 0.818 (4):0.182 (4) for the two orientations. The crystal structure is stabilized by a three-dimensional network of C—H⋯Cl hydrogen bonds.

Keywords: crystal structure; hexamethylguanidinium salt; chlorobismuthate; C—H⋯Cl hydrogen bonds.

CCDC reference: 1455405

Structure description

Peralkylated guanidinium ions with complex inorganic anions are considered to be organic–inorganic hybrid compounds. Their physical behaviour makes them interesting for application in scanning electron microscopy (SEM), where the contrast and the brightness of the obtained pictures depend on the heaviest atom present in the anions. By testing various guanidinium salts with different inorganic complex anions, we found out that guanidinium chloridobismuthates and iodidobismuthates are very promising candidates for this purpose (Knobloch et al., 2016 ). One of them is the here presented title compound. The asymmetric unit comprises two N,N,N′,N′,N′′,N′′-hexamethylguanidinium ions, one half [Bi₄Cl₁₆]⁴⁻ ion and one acetonitrile molecule (Fig. 1). One cation (cation I) shows orientational disorder and two sets of N and C positions were found, with an occupancy ratio of 0.941 (2):0.059 (2) (Fig. 2). The second cation (cation II) is not disordered. The C—N bond lengths in the two guanidinium ions range from 1.334 (17) to 1.341 (17) Å, indicating partial double-bond character. The N—C—N angles range from 116 (2) to 120.8 (2)°, indicating nearly ideal trigonal-planar surroundings for the carbon centres C1 and C8 by the nitrogen atoms. The positive charge is completely delocalized on the CN₃ planes. The C—N bond lengths in both cations are in very good agreement with the data from the crystal structure analysis of known N,N,N′,N′,N′′,N′′-hexamethylguanidinium salts [see, for example: the tetraphenylborate (Frey et al., 1998 ), chloride (Oelkers & Sundermeyer, 2011 ) and cyanate (Tiritiris & Kantlehner, 2015 )].

Figure 1
The structure of the solvated title compound with displacement ellipsoids at the 50% probability level. All H atoms have been omitted for clarity. Only the major orientation of the disordered cation I and the acetonitrile molecule is shown.

Figure 2
The structure of the orientationally disordered N,N,N′,N′,N′′,N′′-hexamethylguanidinium ion (cation I). The N and C atoms are disordered between the opaque and dark positions. All H atoms have been omitted for clarity.

The four Bi^III ions are coordinated in a distorted octahedral manner by six chloride ions, with Bi—Cl bond lengths ranging from 2.4982 (7) to 3.0320 (6) Å. Two [Bi₂Cl₈]²⁻ dimers are fused together, forming a centrosymmetric tetranuclear [Bi₄Cl₁₆]⁴⁻ cluster (Fig. 3). The bond lengths of bismuth to the terminal chlorides [2.4982 (7)–2.5509 (6) Å] are shorter than those of the double and triply bridging ones [2.7052 (6)–3.0320 (6) Å]. The same anionic arrangement was observed in the crystal structure of the compound [(PPh)₄][Bi₄Cl₁₆]·3CH₃CN, where the Bi—Cl bond lengths range from 2.499 (5) to 3.071 (6) Å (Ahmed et al., 2001 ).

Figure 3
Two [Bi₂Cl₈]²⁻ dimers forming a centrosymmetric tetranuclear [Bi₄Cl₁₆]⁴⁻ cluster in the structure of the title compound. The other half of the anion is generated by the symmetry operator (−x, −y + 1, −z).

The crystal structure of the title compound is stabilized by C—H⋯Cl hydrogen bonds, forming a three-dimensional network (Fig. 4, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2B—H2E⋯Cl2	0.98	2.48	3.382 (3)	153
C3B—H3F⋯Cl8ⁱ	0.98	2.81	3.464 (3)	125
C4B—H4F⋯Cl4	0.98	2.80	3.632 (3)	143
C6A—H6B⋯Cl1ⁱⁱ	0.98	2.82	3.577 (3)	134
C6B—H6F⋯Cl6ⁱⁱⁱ	0.98	2.67	3.193 (3)	113
C7B—H7E⋯Cl5ⁱⁱ	0.98	2.71	3.594 (3)	151
C11—H11A⋯Cl2^iv	0.98	2.59	3.488 (3)	153
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 4
The molecular packing of the title compound (view along ab), showing the C—H⋯Cl hydrogen bonds (brown dashed lines). Both orientations (major: dark; minor: opaque) of the disordered N,N,N′,N′,N′′,N′′-hexamethylguanidinium ion (cation I) are depicted.

Synthesis and crystallization

The title compound was obtained by mixing an acetonitrile solution of N,N,N′,N′,N′′,N′′-hexamethylguanidinium chloride with BiCl₃ dissolved in acetonitrile at room temperature. The colorless precipitate was removed by filtration and it was recrystallized from an acetonitrile solution. After evaporation of the solvent at ambient temperature, colorless single crystals suitable for X-ray analysis emerged.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The atoms C1–C7 and N1–N3 of one cation (cation I) are disordered over two sets of sites (C1A/C1B–C7A/C7B and N1A/N1B–N3A/N3B) with refined occupancies of 0.941 (2):0.059 (2). The atoms C15, C16 and N7 of the acetonitrile molecule are disordered over two sets of sites (C15A/C15B, C16A/C16B and N7A/N7B) with refined occupancies of 0.818 (4):0.182 (4). The major and minor disordered components were each restrained to have similar geometries. The anisotropic displacement parameters of equivalent guanidinium carbon atoms were constrained to be identical, and the U^ij components of all disordered atoms were restrained to be similar if closer than 1.7 Å.

Table 2
Experimental details

Crystal data
Chemical formula	(C₇H₁₈N₃)₄[Bi₄Cl₁₆]·2C₂H₃N
M_r	2062.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.6427 (6), 18.8486 (11), 15.1377 (9)
β (°)	112.782 (2)
V (Å³)	3325.9 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	11.23
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII DUO
Absorption correction	Multi-scan Blessing, 1995
T_min, T_max	0.430, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	70365, 10188, 8598
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.038, 1.01
No. of reflections	10188
No. of parameters	395
No. of restraints	360
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −1.16
Computer programs: APEX2 (Bruker, 2008 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg & Putz, 2005 ).

Structural data

CCDC reference: 1455405

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616003175/zl4006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616003175/zl4006Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

N,N,N',N',N'',N''-Hexamethylguanidinium di-µ₃-chlorido-tetra-µ₂-chlorido-decachloridotetrabismuthate acetonitrile disolvate top

Crystal data top

(C₇H₁₈N₃)₄[Bi₄Cl₁₆]·2C₂H₃N	F(000) = 1944
M_r = 2062.20	D_x = 2.059 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.6427 (6) Å	Cell parameters from 70365 reflections
b = 18.8486 (11) Å	θ = 1.8–30.6°
c = 15.1377 (9) Å	µ = 11.23 mm⁻¹
β = 112.782 (2)°	T = 100 K
V = 3325.9 (3) Å³	Block, colorless
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker Kappa APEXII DUO diffractometer	10188 independent reflections
Radiation source: fine-focus sealed tube	8598 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.047
φ scans, and ω scans	θ_max = 30.6°, θ_min = 1.8°
Absorption correction: multi-scan Blessing, 1995	h = −16→18
T_min = 0.430, T_max = 0.746	k = −26→26
70365 measured reflections	l = −21→21

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.038	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0113P)² + 0.8846P] where P = (F_o² + 2F_c²)/3
10188 reflections	(Δ/σ)_max < 0.001
395 parameters	Δρ_max = 0.82 e Å⁻³
360 restraints	Δρ_min = −1.16 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Bi1	−0.10623 (2)	0.40160 (2)	−0.01456 (2)	0.00889 (2)
Bi2	0.24769 (2)	0.41496 (2)	0.19916 (2)	0.01052 (2)
Cl1	0.01311 (5)	0.37148 (3)	0.17264 (4)	0.01466 (12)
Cl2	0.28556 (6)	0.39319 (4)	0.37157 (5)	0.02219 (14)
Cl3	−0.19069 (5)	0.43227 (3)	−0.20501 (4)	0.01665 (13)
Cl4	0.29154 (6)	0.28873 (3)	0.16379 (5)	0.02239 (14)
Cl5	−0.29685 (5)	0.39552 (3)	0.00622 (5)	0.01453 (12)
Cl6	0.45474 (5)	0.45094 (4)	0.24316 (5)	0.02436 (15)
Cl7	−0.11342 (5)	0.27054 (3)	−0.05307 (5)	0.01789 (13)
Cl8	0.11940 (5)	0.44264 (3)	−0.01312 (4)	0.01272 (12)
C1A	0.2366 (2)	0.11935 (15)	0.3368 (3)	0.0121 (5)	0.941 (2)
N1A	0.33230 (18)	0.13654 (12)	0.41131 (17)	0.0159 (5)	0.941 (2)
C2A	0.3957 (5)	0.0846 (3)	0.4848 (2)	0.0194 (9)	0.941 (2)
H2A	0.3502	0.0411	0.4758	0.029*	0.941 (2)
H2B	0.4108	0.1043	0.5484	0.029*	0.941 (2)
H2C	0.4687	0.0736	0.4793	0.029*	0.941 (2)
C3A	0.3775 (3)	0.2088 (2)	0.4288 (3)	0.0208 (8)	0.941 (2)
H3A	0.3390	0.2378	0.3715	0.031*	0.941 (2)
H3B	0.4601	0.2080	0.4438	0.031*	0.941 (2)
H3C	0.3636	0.2292	0.4829	0.031*	0.941 (2)
N2A	0.15245 (19)	0.16682 (11)	0.29975 (16)	0.0153 (5)	0.941 (2)
C4A	0.1233 (3)	0.21768 (17)	0.3592 (2)	0.0208 (7)	0.941 (2)
H4A	0.1672	0.2069	0.4269	0.031*	0.941 (2)
H4B	0.0411	0.2147	0.3455	0.031*	0.941 (2)
H4C	0.1420	0.2657	0.3451	0.031*	0.941 (2)
C5A	0.0805 (3)	0.16864 (19)	0.1982 (2)	0.0222 (7)	0.941 (2)
H5A	0.1161	0.1403	0.1628	0.033*	0.941 (2)
H5B	0.0721	0.2178	0.1754	0.033*	0.941 (2)
H5C	0.0048	0.1491	0.1878	0.033*	0.941 (2)
N3A	0.22668 (19)	0.05542 (11)	0.29608 (16)	0.0155 (5)	0.941 (2)
C6A	0.1168 (5)	0.01769 (17)	0.2567 (4)	0.0219 (8)	0.941 (2)
H6A	0.0606	0.0421	0.2760	0.033*	0.941 (2)
H6B	0.1272	−0.0310	0.2812	0.033*	0.941 (2)
H6C	0.0891	0.0168	0.1866	0.033*	0.941 (2)
C7A	0.3259 (3)	0.01705 (15)	0.2938 (2)	0.0230 (7)	0.941 (2)
H7A	0.3916	0.0494	0.3109	0.035*	0.941 (2)
H7B	0.3080	−0.0017	0.2292	0.035*	0.941 (2)
H7C	0.3448	−0.0223	0.3397	0.035*	0.941 (2)
C1B	0.256 (3)	0.1261 (19)	0.347 (3)	0.0121 (5)	0.059 (2)
N1B	0.257 (2)	0.1880 (13)	0.391 (2)	0.013 (3)	0.059 (2)
C2B	0.366 (3)	0.225 (4)	0.442 (6)	0.0208 (8)	0.059 (2)
H2D	0.4028	0.2054	0.5066	0.031*	0.059 (2)
H2E	0.3522	0.2754	0.4448	0.031*	0.059 (2)
H2F	0.4171	0.2172	0.4071	0.031*	0.059 (2)
C3B	0.157 (3)	0.221 (3)	0.398 (4)	0.0208 (7)	0.059 (2)
H3D	0.1292	0.2592	0.3510	0.031*	0.059 (2)
H3E	0.1766	0.2399	0.4626	0.031*	0.059 (2)
H3F	0.0959	0.1850	0.3850	0.031*	0.059 (2)
N2B	0.161 (2)	0.1065 (15)	0.273 (2)	0.013 (3)	0.059 (2)
C4B	0.103 (5)	0.152 (3)	0.190 (3)	0.0222 (7)	0.059 (2)
H4D	0.0670	0.1921	0.2082	0.033*	0.059 (2)
H4E	0.0446	0.1245	0.1394	0.033*	0.059 (2)
H4F	0.1598	0.1697	0.1655	0.033*	0.059 (2)
C5B	0.124 (8)	0.032 (2)	0.258 (6)	0.0219 (8)	0.059 (2)
H5D	0.0428	0.0288	0.2473	0.033*	0.059 (2)
H5E	0.1697	0.0043	0.3147	0.033*	0.059 (2)
H5F	0.1358	0.0137	0.2019	0.033*	0.059 (2)
N3B	0.336 (2)	0.0776 (14)	0.391 (2)	0.013 (3)	0.059 (2)
C6B	0.376 (4)	0.025 (2)	0.340 (3)	0.0230 (7)	0.059 (2)
H6D	0.3406	0.0339	0.2713	0.035*	0.059 (2)
H6E	0.3557	−0.0227	0.3541	0.035*	0.059 (2)
H6F	0.4599	0.0285	0.3617	0.035*	0.059 (2)
C7B	0.394 (8)	0.075 (5)	0.496 (2)	0.0194 (9)	0.059 (2)
H7D	0.4734	0.0907	0.5146	0.029*	0.059 (2)
H7E	0.3924	0.0263	0.5178	0.029*	0.059 (2)
H7F	0.3540	0.1063	0.5246	0.029*	0.059 (2)
N4	0.67317 (17)	0.24075 (11)	0.16986 (15)	0.0154 (4)
C8	0.6079 (2)	0.18307 (12)	0.13462 (18)	0.0123 (5)
N5	0.53427 (17)	0.16194 (11)	0.17368 (15)	0.0142 (4)
C9	0.6330 (2)	0.30192 (13)	0.2072 (2)	0.0202 (6)
H9A	0.5504	0.2974	0.1913	0.030*
H9B	0.6478	0.3454	0.1785	0.030*
H9C	0.6737	0.3040	0.2770	0.030*
N6	0.61635 (18)	0.14779 (11)	0.06119 (15)	0.0163 (5)
C10	0.7919 (2)	0.24393 (14)	0.1767 (2)	0.0225 (6)
H10A	0.8151	0.1972	0.1622	0.034*
H10B	0.8425	0.2580	0.2417	0.034*
H10C	0.7977	0.2788	0.1307	0.034*
C11	0.4263 (2)	0.12587 (14)	0.11906 (19)	0.0166 (5)
H11A	0.4094	0.1303	0.0504	0.025*
H11B	0.3643	0.1476	0.1333	0.025*
H11C	0.4329	0.0756	0.1368	0.025*
C12	0.5605 (2)	0.16910 (14)	0.27610 (18)	0.0189 (6)
H12A	0.6383	0.1881	0.3083	0.028*
H12B	0.5556	0.1225	0.3030	0.028*
H12C	0.5053	0.2015	0.2857	0.028*
C13	0.6450 (2)	0.18217 (14)	−0.01299 (19)	0.0204 (6)
H13A	0.6432	0.2338	−0.0058	0.031*
H13B	0.5890	0.1683	−0.0762	0.031*
H13C	0.7219	0.1675	−0.0067	0.031*
C14	0.6018 (2)	0.07078 (13)	0.0509 (2)	0.0213 (6)
H14A	0.5938	0.0511	0.1079	0.032*
H14B	0.6691	0.0498	0.0437	0.032*
H14C	0.5329	0.0599	−0.0059	0.032*
C15A	0.0485 (7)	0.3900 (7)	0.4428 (8)	0.031 (2)	0.818 (4)
H15A	−0.0311	0.3952	0.4368	0.046*	0.818 (4)
H15B	0.0817	0.3471	0.4796	0.046*	0.818 (4)
H15C	0.0504	0.3863	0.3788	0.046*	0.818 (4)
C16A	0.1136 (3)	0.4506 (2)	0.4911 (3)	0.0300 (10)	0.818 (4)
N7A	0.1642 (3)	0.4984 (2)	0.5316 (3)	0.0486 (12)	0.818 (4)
C15B	0.028 (4)	0.389 (3)	0.430 (4)	0.025 (6)	0.182 (4)
H15D	0.0039	0.3927	0.3608	0.038*	0.182 (4)
H15E	0.0436	0.3391	0.4497	0.038*	0.182 (4)
H15F	0.0978	0.4170	0.4621	0.038*	0.182 (4)
C16B	−0.0609 (14)	0.4149 (8)	0.4577 (13)	0.028 (4)	0.182 (4)
N7B	−0.1330 (12)	0.4384 (7)	0.4757 (11)	0.031 (4)	0.182 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.00813 (4)	0.00989 (4)	0.00844 (5)	−0.00030 (3)	0.00299 (3)	0.00070 (3)
Bi2	0.00962 (4)	0.01166 (5)	0.00897 (5)	−0.00038 (3)	0.00217 (3)	0.00118 (3)
Cl1	0.0127 (3)	0.0191 (3)	0.0114 (3)	−0.0001 (2)	0.0038 (2)	0.0026 (2)
Cl2	0.0260 (3)	0.0270 (4)	0.0106 (3)	−0.0074 (3)	0.0038 (3)	0.0024 (3)
Cl3	0.0211 (3)	0.0158 (3)	0.0104 (3)	0.0001 (2)	0.0032 (2)	0.0000 (2)
Cl4	0.0219 (3)	0.0158 (3)	0.0304 (4)	0.0034 (2)	0.0111 (3)	−0.0015 (3)
Cl5	0.0112 (3)	0.0175 (3)	0.0162 (3)	−0.0001 (2)	0.0066 (2)	−0.0009 (2)
Cl6	0.0145 (3)	0.0301 (4)	0.0303 (4)	−0.0076 (3)	0.0107 (3)	−0.0059 (3)
Cl7	0.0217 (3)	0.0123 (3)	0.0219 (4)	−0.0003 (2)	0.0109 (3)	−0.0024 (3)
Cl8	0.0129 (3)	0.0142 (3)	0.0121 (3)	−0.0004 (2)	0.0060 (2)	0.0000 (2)
C1A	0.0115 (13)	0.0105 (12)	0.0168 (14)	−0.0011 (10)	0.0082 (10)	0.0014 (10)
N1A	0.0134 (11)	0.0163 (12)	0.0178 (13)	−0.0009 (9)	0.0060 (9)	0.0025 (10)
C2A	0.0116 (13)	0.023 (2)	0.0214 (17)	0.0007 (14)	0.0040 (13)	0.0068 (14)
C3A	0.0209 (14)	0.018 (2)	0.0250 (19)	−0.0077 (13)	0.0109 (13)	−0.0028 (14)
N2A	0.0165 (11)	0.0156 (12)	0.0146 (12)	0.0032 (9)	0.0069 (10)	0.0026 (9)
C4A	0.0226 (16)	0.0193 (15)	0.0252 (19)	0.0067 (13)	0.0146 (13)	0.0032 (15)
C5A	0.0192 (16)	0.0258 (19)	0.0192 (16)	0.0059 (12)	0.0049 (12)	0.0045 (13)
N3A	0.0171 (11)	0.0136 (11)	0.0192 (13)	−0.0019 (9)	0.0108 (10)	−0.0014 (10)
C6A	0.0256 (15)	0.0218 (18)	0.0206 (16)	−0.0134 (18)	0.0116 (13)	−0.0067 (18)
C7A	0.0273 (17)	0.0192 (15)	0.032 (2)	0.0037 (13)	0.0213 (15)	−0.0004 (14)
C1B	0.0115 (13)	0.0105 (12)	0.0168 (14)	−0.0011 (10)	0.0082 (10)	0.0014 (10)
N1B	0.013 (4)	0.011 (4)	0.017 (4)	0.001 (4)	0.007 (4)	0.000 (4)
C2B	0.0209 (14)	0.018 (2)	0.0250 (19)	−0.0077 (13)	0.0109 (13)	−0.0028 (14)
C3B	0.0226 (16)	0.0193 (15)	0.0252 (19)	0.0067 (13)	0.0146 (13)	0.0032 (15)
N2B	0.014 (4)	0.013 (4)	0.015 (4)	−0.004 (4)	0.009 (4)	0.005 (4)
C4B	0.0192 (16)	0.0258 (19)	0.0192 (16)	0.0059 (12)	0.0049 (12)	0.0045 (13)
C5B	0.0256 (15)	0.0218 (18)	0.0206 (16)	−0.0134 (18)	0.0116 (13)	−0.0067 (18)
N3B	0.013 (4)	0.013 (4)	0.018 (4)	0.001 (4)	0.012 (4)	0.002 (4)
C6B	0.0273 (17)	0.0192 (15)	0.032 (2)	0.0037 (13)	0.0213 (15)	−0.0004 (14)
C7B	0.0116 (13)	0.023 (2)	0.0214 (17)	0.0007 (14)	0.0040 (13)	0.0068 (14)
N4	0.0149 (10)	0.0134 (11)	0.0178 (12)	−0.0010 (8)	0.0063 (9)	0.0012 (9)
C8	0.0135 (12)	0.0107 (12)	0.0123 (13)	0.0018 (9)	0.0046 (10)	0.0025 (10)
N5	0.0138 (10)	0.0174 (11)	0.0110 (11)	−0.0001 (8)	0.0042 (9)	0.0001 (9)
C9	0.0270 (15)	0.0119 (13)	0.0220 (16)	0.0006 (10)	0.0099 (12)	0.0000 (11)
N6	0.0222 (11)	0.0134 (11)	0.0157 (12)	0.0017 (8)	0.0100 (10)	0.0024 (9)
C10	0.0150 (13)	0.0257 (15)	0.0267 (16)	−0.0029 (11)	0.0078 (12)	0.0070 (12)
C11	0.0107 (12)	0.0210 (14)	0.0156 (14)	−0.0031 (10)	0.0025 (10)	−0.0003 (11)
C12	0.0191 (13)	0.0281 (15)	0.0094 (14)	0.0002 (11)	0.0055 (11)	0.0027 (11)
C13	0.0287 (15)	0.0215 (14)	0.0159 (15)	0.0032 (11)	0.0139 (12)	0.0029 (11)
C14	0.0280 (15)	0.0155 (14)	0.0205 (16)	0.0017 (11)	0.0095 (12)	−0.0016 (12)
C15A	0.036 (4)	0.030 (3)	0.028 (4)	0.000 (3)	0.015 (3)	−0.002 (3)
C16A	0.031 (2)	0.040 (2)	0.026 (2)	0.0026 (17)	0.0187 (18)	−0.0040 (18)
N7A	0.044 (2)	0.062 (3)	0.048 (3)	−0.014 (2)	0.027 (2)	−0.026 (2)
C15B	0.033 (10)	0.019 (9)	0.028 (10)	−0.008 (8)	0.015 (9)	−0.008 (8)
C16B	0.041 (8)	0.019 (7)	0.032 (8)	−0.012 (6)	0.021 (6)	−0.008 (6)
N7B	0.040 (8)	0.013 (7)	0.048 (9)	−0.011 (6)	0.027 (7)	−0.014 (6)

Geometric parameters (Å, º) top

Bi1—Cl7	2.5317 (6)	N2B—C4B	1.467 (19)
Bi1—Cl5	2.5509 (6)	C4B—H4D	0.9800
Bi1—Cl1	2.7052 (6)	C4B—H4E	0.9800
Bi1—Cl3	2.7206 (6)	C4B—H4F	0.9800
Bi1—Cl8	2.9475 (6)	C5B—H5D	0.9800
Bi1—Cl8ⁱ	2.9794 (6)	C5B—H5E	0.9800
Bi2—Cl2	2.4982 (7)	C5B—H5F	0.9800
Bi2—Cl6	2.5309 (6)	N3B—C6B	1.465 (18)
Bi2—Cl4	2.5465 (6)	N3B—C7B	1.465 (19)
Bi2—Cl1	2.9507 (6)	C6B—H6D	0.9800
Bi2—Cl3ⁱ	2.9780 (6)	C6B—H6E	0.9800
Bi2—Cl8	3.0320 (6)	C6B—H6F	0.9800
Cl3—Bi2ⁱ	2.9780 (6)	C7B—H7D	0.9800
Cl8—Bi1ⁱ	2.9794 (6)	C7B—H7E	0.9800
C1A—N1A	1.336 (3)	C7B—H7F	0.9800
C1A—N2A	1.336 (3)	N4—C8	1.344 (3)
C1A—N3A	1.337 (3)	N4—C9	1.459 (3)
N1A—C3A	1.461 (4)	N4—C10	1.466 (3)
N1A—C2A	1.466 (4)	C8—N6	1.335 (3)
C2A—H2A	0.9800	C8—N5	1.342 (3)
C2A—H2B	0.9800	N5—C12	1.461 (3)
C2A—H2C	0.9800	N5—C11	1.461 (3)
C3A—H3A	0.9800	C9—H9A	0.9800
C3A—H3B	0.9800	C9—H9B	0.9800
C3A—H3C	0.9800	C9—H9C	0.9800
N2A—C5A	1.452 (4)	N6—C13	1.458 (3)
N2A—C4A	1.456 (3)	N6—C14	1.464 (3)
C4A—H4A	0.9800	C10—H10A	0.9800
C4A—H4B	0.9800	C10—H10B	0.9800
C4A—H4C	0.9800	C10—H10C	0.9800
C5A—H5A	0.9800	C11—H11A	0.9800
C5A—H5B	0.9800	C11—H11B	0.9800
C5A—H5C	0.9800	C11—H11C	0.9800
N3A—C6A	1.466 (5)	C12—H12A	0.9800
N3A—C7A	1.460 (3)	C12—H12B	0.9800
C6A—H6A	0.9800	C12—H12C	0.9800
C6A—H6B	0.9800	C13—H13A	0.9800
C6A—H6C	0.9800	C13—H13B	0.9800
C7A—H7A	0.9800	C13—H13C	0.9800
C7A—H7B	0.9800	C14—H14A	0.9800
C7A—H7C	0.9800	C14—H14B	0.9800
C1B—N2B	1.334 (17)	C14—H14C	0.9800
C1B—N3B	1.336 (17)	C15A—C16A	1.432 (12)
C1B—N1B	1.341 (17)	C15A—H15A	0.9800
N1B—C3B	1.457 (18)	C15A—H15B	0.9800
N1B—C2B	1.463 (19)	C15A—H15C	0.9800
C2B—H2D	0.9800	C16A—N7A	1.138 (5)
C2B—H2E	0.9800	C15B—C16B	1.43 (2)
C2B—H2F	0.9800	C15B—H15D	0.9800
C3B—H3D	0.9800	C15B—H15E	0.9800
C3B—H3E	0.9800	C15B—H15F	0.9800
C3B—H3F	0.9800	C16B—N7B	1.138 (14)
N2B—C5B	1.46 (2)

Cl7—Bi1—Cl5	91.899 (19)	H3D—C3B—H3E	109.5
Cl7—Bi1—Cl1	89.55 (2)	N1B—C3B—H3F	109.6
Cl5—Bi1—Cl1	91.813 (19)	H3D—C3B—H3F	109.5
Cl7—Bi1—Cl3	89.94 (2)	H3E—C3B—H3F	109.5
Cl5—Bi1—Cl3	97.95 (2)	C1B—N2B—C5B	121 (3)
Cl1—Bi1—Cl3	170.233 (18)	C1B—N2B—C4B	123 (3)
Cl7—Bi1—Cl8	101.898 (18)	C5B—N2B—C4B	114 (3)
Cl5—Bi1—Cl8	165.626 (18)	N2B—C4B—H4D	109.3
Cl1—Bi1—Cl8	84.364 (17)	N2B—C4B—H4E	109.9
Cl3—Bi1—Cl8	86.198 (18)	H4D—C4B—H4E	109.5
Cl7—Bi1—Cl8ⁱ	174.218 (19)	N2B—C4B—H4F	109.2
Cl5—Bi1—Cl8ⁱ	85.409 (17)	H4D—C4B—H4F	109.5
Cl1—Bi1—Cl8ⁱ	95.641 (18)	H4E—C4B—H4F	109.5
Cl3—Bi1—Cl8ⁱ	85.371 (17)	N2B—C5B—H5D	105.9
Cl8—Bi1—Cl8ⁱ	81.200 (17)	N2B—C5B—H5E	110.4
Cl2—Bi2—Cl6	90.51 (2)	H5D—C5B—H5E	109.5
Cl2—Bi2—Cl4	95.56 (2)	N2B—C5B—H5F	112.0
Cl6—Bi2—Cl4	91.06 (2)	H5D—C5B—H5F	109.4
Cl2—Bi2—Cl1	82.673 (19)	H5E—C5B—H5F	109.5
Cl6—Bi2—Cl1	173.16 (2)	C1B—N3B—C6B	123 (2)
Cl4—Bi2—Cl1	90.063 (19)	C1B—N3B—C7B	122 (3)
Cl2—Bi2—Cl3ⁱ	94.50 (2)	C6B—N3B—C7B	114 (2)
Cl6—Bi2—Cl3ⁱ	88.31 (2)	N3B—C6B—H6D	109.4
Cl4—Bi2—Cl3ⁱ	169.92 (2)	N3B—C6B—H6E	109.5
Cl1—Bi2—Cl3ⁱ	91.750 (17)	H6D—C6B—H6E	109.5
Cl2—Bi2—Cl8	160.554 (19)	N3B—C6B—H6F	109.4
Cl6—Bi2—Cl8	107.88 (2)	H6D—C6B—H6F	109.5
Cl4—Bi2—Cl8	90.49 (2)	H6E—C6B—H6F	109.5
Cl1—Bi2—Cl8	78.850 (16)	N3B—C7B—H7D	109.4
Cl3ⁱ—Bi2—Cl8	80.142 (16)	N3B—C7B—H7E	109.4
Bi1—Cl1—Bi2	101.987 (19)	H7D—C7B—H7E	109.5
Bi1—Cl3—Bi2ⁱ	100.032 (19)	N3B—C7B—H7F	109.7
Bi1—Cl8—Bi1ⁱ	98.801 (17)	H7D—C7B—H7F	109.5
Bi1—Cl8—Bi2	94.683 (17)	H7E—C7B—H7F	109.5
Bi1ⁱ—Cl8—Bi2	93.245 (17)	C8—N4—C9	122.7 (2)
N1A—C1A—N2A	120.4 (2)	C8—N4—C10	121.1 (2)
N1A—C1A—N3A	120.0 (2)	C9—N4—C10	116.2 (2)
N2A—C1A—N3A	119.5 (2)	N6—C8—N5	120.8 (2)
C1A—N1A—C3A	122.8 (3)	N6—C8—N4	119.9 (2)
C1A—N1A—C2A	122.0 (3)	N5—C8—N4	119.3 (2)
C3A—N1A—C2A	115.1 (3)	C8—N5—C12	121.9 (2)
N1A—C2A—H2A	109.5	C8—N5—C11	122.9 (2)
N1A—C2A—H2B	109.5	C12—N5—C11	115.0 (2)
H2A—C2A—H2B	109.5	N4—C9—H9A	109.5
N1A—C2A—H2C	109.5	N4—C9—H9B	109.5
H2A—C2A—H2C	109.5	H9A—C9—H9B	109.5
H2B—C2A—H2C	109.5	N4—C9—H9C	109.5
N1A—C3A—H3A	109.5	H9A—C9—H9C	109.5
N1A—C3A—H3B	109.5	H9B—C9—H9C	109.5
H3A—C3A—H3B	109.5	C8—N6—C13	122.9 (2)
N1A—C3A—H3C	109.5	C8—N6—C14	122.4 (2)
H3A—C3A—H3C	109.5	C13—N6—C14	114.6 (2)
H3B—C3A—H3C	109.5	N4—C10—H10A	109.5
C1A—N2A—C5A	122.0 (3)	N4—C10—H10B	109.5
C1A—N2A—C4A	122.2 (3)	H10A—C10—H10B	109.5
C5A—N2A—C4A	115.7 (2)	N4—C10—H10C	109.5
N2A—C4A—H4A	109.5	H10A—C10—H10C	109.5
N2A—C4A—H4B	109.5	H10B—C10—H10C	109.5
H4A—C4A—H4B	109.5	N5—C11—H11A	109.5
N2A—C4A—H4C	109.5	N5—C11—H11B	109.5
H4A—C4A—H4C	109.5	H11A—C11—H11B	109.5
H4B—C4A—H4C	109.5	N5—C11—H11C	109.5
N2A—C5A—H5A	109.5	H11A—C11—H11C	109.5
N2A—C5A—H5B	109.5	H11B—C11—H11C	109.5
H5A—C5A—H5B	109.5	N5—C12—H12A	109.5
N2A—C5A—H5C	109.5	N5—C12—H12B	109.5
H5A—C5A—H5C	109.5	H12A—C12—H12B	109.5
H5B—C5A—H5C	109.5	N5—C12—H12C	109.5
C1A—N3A—C6A	122.0 (3)	H12A—C12—H12C	109.5
C1A—N3A—C7A	122.0 (2)	H12B—C12—H12C	109.5
C6A—N3A—C7A	116.0 (3)	N6—C13—H13A	109.5
N3A—C6A—H6A	109.6	N6—C13—H13B	109.5
N3A—C6A—H6B	109.4	H13A—C13—H13B	109.5
H6A—C6A—H6B	109.5	N6—C13—H13C	109.5
N3A—C6A—H6C	109.4	H13A—C13—H13C	109.5
H6A—C6A—H6C	109.5	H13B—C13—H13C	109.5
H6B—C6A—H6C	109.5	N6—C14—H14A	109.5
N3A—C7A—H7A	109.5	N6—C14—H14B	109.5
N3A—C7A—H7B	109.5	H14A—C14—H14B	109.5
H7A—C7A—H7B	109.5	N6—C14—H14C	109.5
N3A—C7A—H7C	109.5	H14A—C14—H14C	109.5
H7A—C7A—H7C	109.5	H14B—C14—H14C	109.5
H7B—C7A—H7C	109.5	C16A—C15A—H15A	109.5
N2B—C1B—N3B	120 (2)	C16A—C15A—H15B	109.5
N2B—C1B—N1B	120 (2)	H15A—C15A—H15B	109.5
N3B—C1B—N1B	119 (2)	C16A—C15A—H15C	109.5
C1B—N1B—C3B	124 (2)	H15A—C15A—H15C	109.5
C1B—N1B—C2B	120 (2)	H15B—C15A—H15C	109.5
C3B—N1B—C2B	116 (2)	N7A—C16A—C15A	178.0 (6)
N1B—C2B—H2D	109.4	C16B—C15B—H15D	109.5
N1B—C2B—H2E	109.6	C16B—C15B—H15E	109.5
H2D—C2B—H2E	109.5	H15D—C15B—H15E	109.5
N1B—C2B—H2F	109.4	C16B—C15B—H15F	109.5
H2D—C2B—H2F	109.5	H15D—C15B—H15F	109.5
H2E—C2B—H2F	109.5	H15E—C15B—H15F	109.5
N1B—C3B—H3D	109.4	N7B—C16B—C15B	176 (3)
N1B—C3B—H3E	109.3

N2A—C1A—N1A—C3A	−29.6 (5)	N3B—C1B—N2B—C4B	−144 (5)
N3A—C1A—N1A—C3A	147.4 (3)	N1B—C1B—N2B—C4B	53 (8)
N2A—C1A—N1A—C2A	146.6 (4)	N2B—C1B—N3B—C6B	45 (8)
N3A—C1A—N1A—C2A	−36.4 (5)	N1B—C1B—N3B—C6B	−152 (5)
N1A—C1A—N2A—C5A	146.7 (3)	N2B—C1B—N3B—C7B	−137 (7)
N3A—C1A—N2A—C5A	−30.3 (5)	N1B—C1B—N3B—C7B	26 (9)
N1A—C1A—N2A—C4A	−36.4 (5)	C9—N4—C8—N6	145.2 (2)
N3A—C1A—N2A—C4A	146.5 (3)	C10—N4—C8—N6	−37.6 (3)
N1A—C1A—N3A—C6A	145.0 (4)	C9—N4—C8—N5	−34.4 (3)
N2A—C1A—N3A—C6A	−37.9 (5)	C10—N4—C8—N5	142.8 (2)
N1A—C1A—N3A—C7A	−31.0 (5)	N6—C8—N5—C12	145.5 (2)
N2A—C1A—N3A—C7A	146.1 (3)	N4—C8—N5—C12	−34.9 (3)
N2B—C1B—N1B—C3B	30 (8)	N6—C8—N5—C11	−30.2 (4)
N3B—C1B—N1B—C3B	−133 (5)	N4—C8—N5—C11	149.5 (2)
N2B—C1B—N1B—C2B	−155 (6)	N5—C8—N6—C13	148.4 (2)
N3B—C1B—N1B—C2B	42 (9)	N4—C8—N6—C13	−31.2 (4)
N3B—C1B—N2B—C5B	19 (10)	N5—C8—N6—C14	−34.0 (4)
N1B—C1B—N2B—C5B	−144 (7)	N4—C8—N6—C14	146.4 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2B—H2E···Cl2	0.98	2.48	3.382 (3)	153
C3B—H3F···Cl8ⁱⁱ	0.98	2.81	3.464 (3)	125
C4B—H4F···Cl4	0.98	2.80	3.632 (3)	143
C6A—H6B···Cl1ⁱⁱⁱ	0.98	2.82	3.577 (3)	134
C6B—H6F···Cl6^iv	0.98	2.67	3.193 (3)	113
C7B—H7E···Cl5ⁱⁱⁱ	0.98	2.71	3.594 (3)	151
C11—H11A···Cl2^v	0.98	2.59	3.488 (3)	153

Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z−1/2.

Acknowledgements

The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the diffraction data.

References

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