metal-organic compounds
N,N,N′,N′,N′′,N′′-Hexamethylguanidinium di-μ3-chlorido-tetra-μ2-chlorido-decachloridotetrabismuthate acetonitrile disolvate
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@hs-aalen.de
The 7H18N3)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 BiIII 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 is stabilized by a three-dimensional network of C—H⋯Cl hydrogen bonds.
of the solvated title compound, (CKeywords: 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 et al., 2016). One of them is the here presented title compound. The 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 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)].
(SEM), where the contrast and the 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 (KnoblochThe four BiIII 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 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).
of the title compound is stabilized by C—H⋯Cl hydrogen bonds, forming a three-dimensional network (Fig. 4Synthesis 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 . 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 Uij components of all disordered atoms were restrained to be similar if closer than 1.7 Å.
details are summarized in Table 2
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Structural data
CCDC reference: 1455405
https://doi.org/10.1107/S2414314616003175/zl4006sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616003175/zl4006Isup2.hkl
Data collection: APEX2 (Bruker, 2008); cell
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).(C7H18N3)4[Bi4Cl16]·2C2H3N | F(000) = 1944 |
Mr = 2062.20 | Dx = 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 |
Bruker Kappa APEXII DUO diffractometer | 10188 independent reflections |
Radiation source: fine-focus sealed tube | 8598 reflections with I > 2σ(I) |
Triumph monochromator | Rint = 0.047 |
φ scans, and ω scans | θmax = 30.6°, θmin = 1.8° |
Absorption correction: multi-scan Blessing, 1995 | h = −16→18 |
Tmin = 0.430, Tmax = 0.746 | k = −26→26 |
70365 measured reflections | l = −21→21 |
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(Fo2) + (0.0113P)2 + 0.8846P] where P = (Fo2 + 2Fc2)/3 |
10188 reflections | (Δ/σ)max < 0.001 |
395 parameters | Δρmax = 0.82 e Å−3 |
360 restraints | Δρmin = −1.16 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | 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) |
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) |
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. |
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···Cl6iv | 0.98 | 2.67 | 3.193 (3) | 113 |
C7B—H7E···Cl5iii | 0.98 | 2.71 | 3.594 (3) | 151 |
C11—H11A···Cl2v | 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.
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