Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100000263/av1032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100000263/av1032Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100000263/av1032IIsup3.hkl |
CCDC references: 144615; 144616
Compound (I): The reaction of 4-picoline (0.030 cm3, 0.300 mmol) and Bi(1,2-S2-4-MeC6H3)Br (0.300 mmol) in tetrahydrofuran (15 cm3) afforded an orange precipitate and an orange mother liquor. Yellow crystals of (I) were obtained by cooling of the orange mother liquor.
Compound (II): A solution of BiCl3 in pyridine (1.5 cm3) was layered with more pyridine (1.5 cm3) and then hexane (10 cm3) and colourless block-like crystals of (I) were grown over several days at room temprature. [pyH]2 [BiCl5(py)] requires C 28.80, N 6.70, H 2.75, Cl 28.4%, obtained C 25.30, N 5.55, H 2.35, Cl 22.50%.
Hydrogen atoms were constrained to idealized geometries and assigned isotropic displacement parameters 1.2 times Uiso value of their attached carbon for aromatic H atoms and 1.5 Uiso for methyl H atoms, with the exception of H3 in (I) which was located in the electron density difference map and the coordinates refined. In (I) the methyl H atoms on C4 are disordered over the twofold axis.
For both compounds, data collection: SMART (Siemens, 1995a); cell refinement: SAINT (Siemens, 1995a). Data reduction: SAINT (Siemens, 1995a) for (I); SAINT for (II). For both compounds, program(s) used to solve structure: SHELXTL (Siemens, 1995b). Program(s) used to refine structure: SHELXTL (Siemens, 1995b) for (I); SHELXTL for (II). Molecular graphics: SHELXTL (Siemens, 1995b) for (I); SHELXTL for (II). Software used to prepare material for publication: SHELXTL (Siemens, 1995b) for (I); SHELXTL for (II).
(C12H15N2)2[BiBr5(C6H7N)] | F(000) = 2040 |
Mr = 1076.18 | Dx = 1.948 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.789 (13) Å | Cell parameters from 272 reflections |
b = 13.140 (8) Å | θ = 5–25° |
c = 19.064 (16) Å | µ = 10.28 mm−1 |
β = 97.94 (3)° | T = 173 K |
V = 3669 (5) Å3 | Block, yellow |
Z = 4 | 0.25 × 0.25 × 0.20 mm |
Siemens SMART Area Detector diffractometer | 4188 independent reflections |
Radiation source: fine-focus sealed tube | 3306 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 1? pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω rotation with narrow frame scans | h = −19→18 |
Absorption correction: multi-scan SADABS: sheldrick (1997) ? | k = 0→17 |
Tmin = 0.097, Tmax = 0.100 | l = 0→24 |
4188 measured reflections |
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)] = 0.029 | H atoms: see text |
wR(F2) = 0.055 | Calculated w = 1/[σ2(Fo2) + (0.0238P)2] where P = [Max(Fo2,0) + 2Fc2]/3 |
S = 0.92 | (Δ/σ)max = 0.001 |
4188 reflections | Δρmax = 1.22 e Å−3 |
191 parameters | Δρmin = −0.89 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000125 (18) |
(C12H15N2)2[BiBr5(C6H7N)] | V = 3669 (5) Å3 |
Mr = 1076.18 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.789 (13) Å | µ = 10.28 mm−1 |
b = 13.140 (8) Å | T = 173 K |
c = 19.064 (16) Å | 0.25 × 0.25 × 0.20 mm |
β = 97.94 (3)° |
Siemens SMART Area Detector diffractometer | 4188 independent reflections |
Absorption correction: multi-scan SADABS: sheldrick (1997) ? | 3306 reflections with I > 2σ(I) |
Tmin = 0.097, Tmax = 0.100 | Rint = 0.000 |
4188 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.055 | H atoms: see text |
S = 0.92 | Δρmax = 1.22 e Å−3 |
4188 reflections | Δρmin = −0.89 e Å−3 |
191 parameters |
Experimental. Unit-cell dimensions were determined from reflections taken from three sets of 30 frames (at 0.3° steps in ω) at 10 s. A full hemisphere of reciprocal space was scanned by 0.3° ω steps at ϕ = 0, 90 and 180° at 20 s per frame with the area detector held at 2θ = -27°. The crystal-to-detector distance was 4.974 cm. Crystal decay was monitored by repeating the initial 50 frames at the end of data collection and analysing the duplicate reflections. No decay was observed for either data set. |
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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R factor obs 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 | 0.0000 | 0.886315 (18) | 0.2500 | 0.02002 (7) | |
Br1 | 0.0000 | 0.67534 (5) | 0.2500 | 0.03098 (16) | |
Br2 | 0.19559 (3) | 0.89852 (4) | 0.27138 (2) | 0.03611 (13) | |
Br3 | −0.00383 (3) | 0.90570 (4) | 0.39845 (2) | 0.03186 (12) | |
N1 | 0.0000 | 1.0856 (4) | 0.2500 | 0.0263 (12) | |
C1 | 0.0718 (3) | 1.1389 (3) | 0.2352 (2) | 0.0306 (11) | |
H1 | 0.1227 | 1.1037 | 0.2244 | 0.037* | |
C2 | 0.0740 (4) | 1.2428 (4) | 0.2351 (2) | 0.0408 (12) | |
H2 | 0.1258 | 1.2767 | 0.2248 | 0.049* | |
C3 | 0.0000 | 1.2971 (5) | 0.2500 | 0.0439 (19) | |
C4 | 0.0000 | 1.4121 (6) | 0.2500 | 0.078 (3) | |
H4A | 0.0607 | 1.4365 | 0.2476 | 0.116* | 0.50 |
H4B | −0.0203 | 1.4365 | 0.2927 | 0.116* | 0.50 |
H4C | −0.0404 | 1.4365 | 0.2097 | 0.116* | 0.50 |
N3 | −0.0818 (3) | 0.7179 (3) | 0.55482 (19) | 0.0363 (9) | |
H3 | −0.0357 | 0.6925 | 0.5380 | 0.044* | |
C11 | −0.1500 (3) | 0.6581 (4) | 0.5679 (2) | 0.0406 (12) | |
H11 | −0.1471 | 0.5888 | 0.5585 | 0.049* | |
C12 | −0.2234 (3) | 0.6952 (4) | 0.5943 (2) | 0.0380 (12) | |
H12 | −0.2702 | 0.6515 | 0.6027 | 0.046* | |
C13 | −0.2294 (3) | 0.7976 (4) | 0.6089 (2) | 0.0313 (11) | |
C14 | −0.1579 (3) | 0.8591 (4) | 0.5944 (2) | 0.0318 (11) | |
H14 | −0.1595 | 0.9288 | 0.6026 | 0.038* | |
C15 | −0.0850 (3) | 0.8168 (4) | 0.5679 (2) | 0.0327 (11) | |
H15 | −0.0369 | 0.8583 | 0.5589 | 0.039* | |
C16 | −0.3093 (3) | 0.8419 (5) | 0.6386 (3) | 0.0499 (14) | |
H16A | −0.3645 | 0.8098 | 0.6168 | 0.075* | |
H16B | −0.3126 | 0.9137 | 0.6293 | 0.075* | |
H16C | −0.3022 | 0.8306 | 0.6888 | 0.075* | |
N2 | 0.0691 (3) | 0.6475 (3) | 0.5093 (2) | 0.0417 (10) | |
C5 | 0.1462 (3) | 0.6291 (4) | 0.5538 (2) | 0.0439 (13) | |
H5 | 0.1435 | 0.6272 | 0.6022 | 0.053* | |
C6 | 0.2290 (3) | 0.6130 (4) | 0.5302 (2) | 0.0377 (11) | |
H6 | 0.2809 | 0.6007 | 0.5625 | 0.045* | |
C7 | 0.2351 (3) | 0.6151 (4) | 0.4586 (2) | 0.0360 (11) | |
C8 | 0.1559 (3) | 0.6335 (4) | 0.4134 (2) | 0.0374 (12) | |
H8 | 0.1569 | 0.6345 | 0.3647 | 0.045* | |
C9 | 0.0753 (3) | 0.6503 (4) | 0.4398 (2) | 0.0427 (13) | |
H9 | 0.0229 | 0.6641 | 0.4082 | 0.051* | |
C10 | 0.3238 (3) | 0.5982 (4) | 0.4308 (3) | 0.0536 (16) | |
H10A | 0.3629 | 0.5566 | 0.4635 | 0.080* | 0.50 |
H10B | 0.3528 | 0.6626 | 0.4255 | 0.080* | 0.50 |
H10C | 0.3126 | 0.5647 | 0.3857 | 0.080* | 0.50 |
H10D | 0.3226 | 0.6327 | 0.3863 | 0.080* | 0.50 |
H10E | 0.3327 | 0.5267 | 0.4243 | 0.080* | 0.50 |
H10F | 0.3729 | 0.6246 | 0.4640 | 0.080* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.01787 (11) | 0.02141 (13) | 0.02074 (11) | 0.000 | 0.00256 (8) | 0.000 |
Br1 | 0.0375 (4) | 0.0245 (4) | 0.0305 (3) | 0.000 | 0.0033 (3) | 0.000 |
Br2 | 0.0219 (2) | 0.0476 (3) | 0.0383 (2) | 0.0035 (2) | 0.00222 (18) | −0.0066 (2) |
Br3 | 0.0332 (2) | 0.0388 (3) | 0.0244 (2) | 0.0009 (2) | 0.00640 (18) | −0.00104 (19) |
N1 | 0.033 (3) | 0.023 (3) | 0.023 (3) | 0.000 | 0.004 (2) | 0.000 |
C1 | 0.031 (2) | 0.032 (3) | 0.029 (2) | −0.002 (2) | 0.0065 (19) | 0.001 (2) |
C2 | 0.053 (3) | 0.032 (3) | 0.034 (3) | −0.014 (3) | −0.005 (2) | 0.007 (2) |
C3 | 0.066 (5) | 0.018 (4) | 0.043 (4) | 0.000 | −0.007 (4) | 0.000 |
C4 | 0.118 (8) | 0.031 (5) | 0.078 (6) | 0.000 | −0.006 (6) | 0.000 |
N3 | 0.031 (2) | 0.046 (3) | 0.033 (2) | 0.006 (2) | 0.0071 (17) | −0.001 (2) |
C11 | 0.051 (3) | 0.031 (3) | 0.040 (3) | 0.000 (3) | 0.008 (2) | −0.005 (2) |
C12 | 0.038 (3) | 0.044 (3) | 0.033 (3) | −0.016 (2) | 0.005 (2) | 0.001 (2) |
C13 | 0.028 (2) | 0.044 (3) | 0.022 (2) | 0.000 (2) | 0.0021 (18) | 0.000 (2) |
C14 | 0.029 (2) | 0.033 (3) | 0.032 (2) | −0.006 (2) | 0.0023 (19) | −0.002 (2) |
C15 | 0.029 (2) | 0.040 (3) | 0.030 (2) | −0.004 (2) | 0.0047 (19) | 0.007 (2) |
C16 | 0.031 (3) | 0.067 (4) | 0.054 (3) | 0.001 (3) | 0.013 (2) | −0.003 (3) |
N2 | 0.039 (2) | 0.046 (3) | 0.041 (2) | 0.013 (2) | 0.0079 (19) | 0.001 (2) |
C5 | 0.052 (3) | 0.053 (4) | 0.026 (2) | 0.016 (3) | 0.003 (2) | 0.006 (2) |
C6 | 0.036 (3) | 0.041 (3) | 0.034 (2) | 0.009 (2) | −0.005 (2) | 0.002 (2) |
C7 | 0.031 (2) | 0.033 (3) | 0.043 (3) | 0.003 (2) | 0.003 (2) | −0.006 (2) |
C8 | 0.035 (3) | 0.049 (4) | 0.029 (2) | 0.006 (3) | 0.005 (2) | 0.003 (2) |
C9 | 0.037 (3) | 0.052 (4) | 0.036 (3) | 0.006 (3) | −0.004 (2) | 0.007 (2) |
C10 | 0.031 (3) | 0.076 (5) | 0.055 (3) | 0.010 (3) | 0.011 (2) | −0.003 (3) |
Bi1—N1 | 2.618 (5) | C13—C16 | 1.496 (6) |
Bi1—Br1 | 2.7723 (18) | C14—C15 | 1.370 (6) |
Bi1—Br3i | 2.850 (2) | C14—H14 | 0.9300 |
Bi1—Br3 | 2.850 (2) | C15—H15 | 0.9300 |
Bi1—Br2 | 2.869 (3) | C16—H16A | 0.9600 |
Bi1—Br2i | 2.869 (3) | C16—H16B | 0.9600 |
N1—C1 | 1.335 (5) | C16—H16C | 0.9600 |
N1—C1i | 1.335 (5) | N2—C9 | 1.341 (6) |
C1—C2 | 1.366 (6) | N2—C5 | 1.345 (6) |
C1—H1 | 0.9300 | C5—C6 | 1.379 (6) |
C2—C3 | 1.369 (6) | C5—H5 | 0.9300 |
C2—H2 | 0.9300 | C6—C7 | 1.380 (6) |
C3—C2i | 1.369 (6) | C6—H6 | 0.9300 |
C3—C4 | 1.511 (10) | C7—C8 | 1.376 (6) |
C4—H4A | 0.9600 | C7—C10 | 1.497 (6) |
C4—H4B | 0.9600 | C8—C9 | 1.375 (6) |
C4—H4C | 0.9600 | C8—H8 | 0.9300 |
N3—C15 | 1.325 (6) | C9—H9 | 0.9300 |
N3—C11 | 1.330 (6) | C10—H10A | 0.9600 |
N3—H3 | 0.8600 | C10—H10B | 0.9600 |
C11—C12 | 1.349 (6) | C10—H10C | 0.9600 |
C11—H11 | 0.9300 | C10—H10D | 0.9600 |
C12—C13 | 1.380 (7) | C10—H10E | 0.9600 |
C12—H12 | 0.9300 | C10—H10F | 0.9600 |
C13—C14 | 1.388 (6) | ||
N1—Bi1—Br1 | 180.000 (1) | C13—C14—H14 | 120.1 |
N1—Bi1—Br3i | 84.871 (12) | N3—C15—C14 | 121.1 (4) |
Br1—Bi1—Br3i | 95.129 (12) | N3—C15—H15 | 119.4 |
N1—Bi1—Br3 | 84.872 (11) | C14—C15—H15 | 119.4 |
Br1—Bi1—Br3 | 95.128 (11) | C13—C16—H16A | 109.5 |
Br3i—Bi1—Br3 | 169.74 (2) | C13—C16—H16B | 109.5 |
N1—Bi1—Br2 | 86.797 (12) | H16A—C16—H16B | 109.5 |
Br1—Bi1—Br2 | 93.203 (12) | C13—C16—H16C | 109.5 |
Br3i—Bi1—Br2 | 88.75 (3) | H16A—C16—H16C | 109.5 |
Br3—Bi1—Br2 | 90.68 (3) | H16B—C16—H16C | 109.5 |
N1—Bi1—Br2i | 86.797 (12) | C9—N2—C5 | 117.5 (4) |
Br1—Bi1—Br2i | 93.203 (12) | N2—C5—C6 | 122.3 (4) |
Br3i—Bi1—Br2i | 90.68 (3) | N2—C5—H5 | 118.8 |
Br3—Bi1—Br2i | 88.75 (3) | C6—C5—H5 | 118.8 |
Br2—Bi1—Br2i | 173.59 (2) | C5—C6—C7 | 120.1 (4) |
C1—N1—C1i | 116.7 (5) | C5—C6—H6 | 119.9 |
C1—N1—Bi1 | 121.6 (3) | C7—C6—H6 | 119.9 |
C1i—N1—Bi1 | 121.7 (3) | C8—C7—C6 | 117.2 (4) |
N1—C1—C2 | 123.0 (5) | C8—C7—C10 | 121.1 (4) |
N1—C1—H1 | 118.5 | C6—C7—C10 | 121.8 (4) |
C2—C1—H1 | 118.5 | C9—C8—C7 | 120.3 (4) |
C1—C2—C3 | 120.1 (5) | C9—C8—H8 | 119.8 |
C1—C2—H2 | 119.9 | C7—C8—H8 | 119.8 |
C3—C2—H2 | 119.9 | N2—C9—C8 | 122.5 (4) |
C2i—C3—C2 | 117.1 (6) | N2—C9—H9 | 118.7 |
C2i—C3—C4 | 121.4 (3) | C8—C9—H9 | 118.7 |
C2—C3—C4 | 121.4 (3) | C7—C10—H10A | 109.5 |
C3—C4—H4A | 109.5 | C7—C10—H10B | 109.5 |
C3—C4—H4B | 109.5 | H10A—C10—H10B | 109.5 |
H4A—C4—H4B | 109.5 | C7—C10—H10C | 109.5 |
C3—C4—H4C | 109.5 | H10A—C10—H10C | 109.5 |
H4A—C4—H4C | 109.5 | H10B—C10—H10C | 109.5 |
H4B—C4—H4C | 109.5 | C7—C10—H10D | 109.5 |
C15—N3—C11 | 119.8 (4) | H10A—C10—H10D | 141.1 |
C15—N3—H3 | 120.1 | H10B—C10—H10D | 56.3 |
C11—N3—H3 | 120.1 | H10C—C10—H10D | 56.3 |
N3—C11—C12 | 121.8 (5) | C7—C10—H10E | 109.5 |
N3—C11—H11 | 119.1 | H10A—C10—H10E | 56.3 |
C12—C11—H11 | 119.1 | H10B—C10—H10E | 141.1 |
C11—C12—C13 | 120.4 (5) | H10C—C10—H10E | 56.3 |
C11—C12—H12 | 119.8 | H10D—C10—H10E | 109.5 |
C13—C12—H12 | 119.8 | C7—C10—H10F | 109.5 |
C12—C13—C14 | 117.0 (4) | H10A—C10—H10F | 56.3 |
C12—C13—C16 | 122.2 (4) | H10B—C10—H10F | 56.3 |
C14—C13—C16 | 120.8 (5) | H10C—C10—H10F | 141.1 |
C15—C14—C13 | 119.9 (5) | H10D—C10—H10F | 109.5 |
C15—C14—H14 | 120.1 | H10E—C10—H10F | 109.5 |
Symmetry code: (i) −x, y, −z+1/2. |
(C5H6N)2[BiCl5(C5H5N)] | Dx = 2.015 Mg m−3 |
Mr = 625.55 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 158 reflections |
a = 18.699 (2) Å | θ = 5–25° |
b = 14.889 (3) Å | µ = 9.20 mm−1 |
c = 7.408 (3) Å | T = 173 K |
V = 2062.4 (9) Å3 | Block, yellow |
Z = 4 | 0.2 × 0.2 × 0.2 mm |
F(000) = 1184 |
Siemens SMART Area Detector diffractometer | 2459 independent reflections |
Radiation source: fine-focus sealed tube | 1956 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω rotation with narrow frame scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; sheldrick, 1997) ? | h = −24→24 |
Tmin = 0.137, Tmax = 0.158 | k = −18→19 |
12283 measured reflections | l = −9→6 |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.052 | Calculated w = 1/[σ2(Fo2) + (0.024P)2] where P = Max{(Fo2,0) + 2Fc2)/3} |
S = 1.05 | (Δ/σ)max = 0.001 |
2459 reflections | Δρmax = 0.77 e Å−3 |
119 parameters | Δρmin = −1.00 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Siemens, 1995b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00194 (10) |
(C5H6N)2[BiCl5(C5H5N)] | V = 2062.4 (9) Å3 |
Mr = 625.55 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 18.699 (2) Å | µ = 9.20 mm−1 |
b = 14.889 (3) Å | T = 173 K |
c = 7.408 (3) Å | 0.2 × 0.2 × 0.2 mm |
Siemens SMART Area Detector diffractometer | 2459 independent reflections |
Absorption correction: multi-scan (SADABS; sheldrick, 1997) ? | 1956 reflections with I > 2σ(I) |
Tmin = 0.137, Tmax = 0.158 | Rint = 0.057 |
12283 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.77 e Å−3 |
2459 reflections | Δρmin = −1.00 e Å−3 |
119 parameters |
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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R factor obs 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 | ||
Bi1 | 0.604453 (12) | −0.2500 | 1.16096 (3) | 0.02241 (9) | |
Cl1 | 0.60006 (6) | −0.06922 (7) | 1.1463 (2) | 0.0352 (3) | |
Cl2 | 0.67932 (9) | −0.2500 | 0.8532 (2) | 0.0351 (4) | |
Cl3 | 0.72604 (9) | −0.2500 | 1.3646 (2) | 0.0316 (4) | |
Cl4 | 0.52284 (9) | −0.2500 | 1.4619 (3) | 0.0381 (4) | |
N1 | 0.4894 (3) | −0.2500 | 0.9796 (8) | 0.0270 (12) | |
C1 | 0.4574 (2) | −0.1732 (3) | 0.9301 (7) | 0.0303 (11) | |
H1 | 0.4791 (2) | −0.1180 (3) | 0.9643 (7) | 0.036* | |
C2 | 0.3949 (3) | −0.1699 (3) | 0.8324 (7) | 0.0365 (11) | |
H2 | 0.3743 (3) | −0.1139 (3) | 0.7998 (7) | 0.044* | |
N2 | 0.6555 (5) | −0.0780 (3) | 1.5940 (8) | 0.079 (2) | |
H9 | 0.6613 (5) | −0.1364 (3) | 1.5826 (8) | 0.095* | |
C3 | 0.3624 (3) | −0.2500 | 0.7821 (10) | 0.035 (2) | |
H3 | 0.3191 (3) | −0.2500 | 0.7151 (10) | 0.043* | |
C4 | 0.7107 (4) | −0.0247 (6) | 1.5679 (10) | 0.078 (3) | |
H4 | 0.7557 (4) | −0.0490 (6) | 1.5340 (10) | 0.094* | |
C5 | 0.7032 (4) | 0.0623 (5) | 1.5889 (10) | 0.067 (2) | |
H5 | 0.7429 (4) | 0.1015 (5) | 1.5731 (10) | 0.081* | |
C6 | 0.6390 (4) | 0.0950 (4) | 1.6329 (9) | 0.060 (2) | |
H6 | 0.6331 (4) | 0.1580 (4) | 1.6476 (9) | 0.073* | |
C7 | 0.5832 (3) | 0.0409 (5) | 1.6564 (9) | 0.062 (2) | |
H7 | 0.5376 (3) | 0.0648 (5) | 1.6871 (9) | 0.075* | |
C8 | 0.5921 (4) | −0.0469 (5) | 1.6363 (8) | 0.070 (2) | |
H8 | 0.5529 (4) | −0.0868 (5) | 1.6524 (8) | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.01880 (12) | 0.01993 (13) | 0.02848 (14) | 0.000 | 0.00209 (13) | 0.000 |
Cl1 | 0.0332 (6) | 0.0223 (5) | 0.0502 (8) | −0.0013 (5) | −0.0052 (7) | 0.0006 (5) |
Cl2 | 0.0316 (8) | 0.0414 (9) | 0.0324 (10) | 0.000 | 0.0063 (9) | 0.000 |
Cl3 | 0.0262 (8) | 0.0327 (9) | 0.0361 (10) | 0.000 | −0.0037 (8) | 0.000 |
Cl4 | 0.0338 (9) | 0.0361 (9) | 0.0446 (11) | 0.000 | 0.0159 (9) | 0.000 |
N1 | 0.023 (3) | 0.023 (3) | 0.035 (3) | 0.000 | 0.000 (3) | 0.000 |
C1 | 0.030 (2) | 0.026 (3) | 0.034 (3) | 0.000 (2) | 0.000 (2) | −0.008 (2) |
C2 | 0.032 (2) | 0.029 (3) | 0.048 (3) | 0.003 (2) | −0.004 (3) | −0.003 (2) |
N2 | 0.168 (7) | 0.017 (3) | 0.053 (4) | 0.017 (4) | −0.035 (5) | −0.008 (2) |
C3 | 0.021 (3) | 0.043 (4) | 0.043 (5) | 0.000 | −0.008 (3) | 0.000 |
C4 | 0.061 (5) | 0.109 (7) | 0.065 (5) | 0.050 (5) | −0.023 (4) | −0.028 (5) |
C5 | 0.053 (4) | 0.081 (5) | 0.068 (5) | −0.029 (4) | −0.005 (4) | −0.011 (4) |
C6 | 0.086 (5) | 0.029 (3) | 0.066 (5) | 0.002 (3) | −0.022 (4) | −0.014 (3) |
C7 | 0.038 (3) | 0.093 (6) | 0.056 (4) | 0.013 (3) | 0.002 (3) | −0.035 (4) |
C8 | 0.098 (6) | 0.074 (5) | 0.040 (4) | −0.060 (5) | 0.007 (4) | −0.003 (4) |
Bi1—N1 | 2.536 (5) | C4—C5 | 1.312 (9) |
Bi1—Cl2 | 2.675 (2) | C5—C6 | 1.337 (9) |
Bi1—Cl1i | 2.6950 (12) | C6—C7 | 1.330 (9) |
Bi1—Cl1 | 2.6950 (12) | C7—C8 | 1.327 (10) |
Bi1—Cl4 | 2.702 (2) | Cl1—H2ii | 2.796 (5) |
Bi1—Cl3 | 2.728 (2) | Cl1—H7iii | 2.856 (6) |
N1—C1 | 1.342 (5) | Cl2—H9iv | 2.644 (6) |
N1—C1i | 1.342 (5) | Cl2—H9v | 2.644 (6) |
C1—C2 | 1.375 (7) | Cl3—H9 | 2.633 (7) |
C2—C3 | 1.389 (6) | Cl3—H9i | 2.633 (7) |
N2—C8 | 1.311 (9) | Cl4—H8 | 2.865 (7) |
N2—C4 | 1.317 (9) | Cl4—H8i | 2.865 (7) |
C3—C2i | 1.389 (6) | ||
N1—Bi1—Cl2 | 89.57 (13) | C8—N2—C4 | 122.1 (6) |
N1—Bi1—Cl1i | 87.30 (3) | C2i—C3—C2 | 118.2 (6) |
Cl2—Bi1—Cl1i | 88.95 (3) | C5—C4—N2 | 119.7 (6) |
N1—Bi1—Cl1 | 87.30 (3) | C4—C5—C6 | 118.9 (6) |
Cl2—Bi1—Cl1 | 88.95 (3) | C7—C6—C5 | 121.1 (6) |
Cl1i—Bi1—Cl1 | 174.21 (5) | C8—C7—C6 | 119.0 (6) |
N1—Bi1—Cl4 | 87.59 (13) | N2—C8—C7 | 119.2 (6) |
Cl2—Bi1—Cl4 | 177.16 (5) | Bi1—Cl1—H2ii | 164.29 (11) |
Cl1i—Bi1—Cl4 | 90.91 (3) | Bi1—Cl1—H7iii | 91.9 (2) |
Cl1—Bi1—Cl4 | 90.91 (3) | H2ii—Cl1—H7iii | 94.0 (2) |
N1—Bi1—Cl3 | 178.42 (13) | H9iv—Cl2—H9v | 79.5 (2) |
Cl2—Bi1—Cl3 | 92.01 (6) | H9iv—Cl2—Bi1 | 125.4 (2) |
Cl1i—Bi1—Cl3 | 92.73 (3) | H9v—Cl2—Bi1 | 125.4 (2) |
Cl1—Bi1—Cl3 | 92.73 (3) | H9—Cl3—H9i | 79.9 (3) |
Cl4—Bi1—Cl3 | 90.82 (6) | H9—Cl3—Bi1 | 87.5 (2) |
C1—N1—C1i | 116.9 (5) | H9i—Cl3—Bi1 | 87.5 (2) |
C1—N1—Bi1 | 121.5 (3) | Bi1—Cl4—H8 | 107.19 (13) |
C1i—N1—Bi1 | 121.5 (3) | Bi1—Cl4—H8i | 107.19 (14) |
N1—C1—C2 | 123.5 (4) | H8—Cl4—H8i | 116.0 (3) |
C1—C2—C3 | 118.9 (5) |
Symmetry codes: (i) x, −y−1/2, z; (ii) −x+1, −y, −z+2; (iii) −x+1, −y, −z+3; (iv) x, −y−1/2, z−1; (v) x, y, z−1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C12H15N2)2[BiBr5(C6H7N)] | (C5H6N)2[BiCl5(C5H5N)] |
Mr | 1076.18 | 625.55 |
Crystal system, space group | Monoclinic, C2/c | Orthorhombic, Pnma |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 14.789 (13), 13.140 (8), 19.064 (16) | 18.699 (2), 14.889 (3), 7.408 (3) |
α, β, γ (°) | 90, 97.94 (3), 90 | 90, 90, 90 |
V (Å3) | 3669 (5) | 2062.4 (9) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 10.28 | 9.20 |
Crystal size (mm) | 0.25 × 0.25 × 0.20 | 0.2 × 0.2 × 0.2 |
Data collection | ||
Diffractometer | Siemens SMART Area Detector diffractometer | Siemens SMART Area Detector diffractometer |
Absorption correction | Multi-scan SADABS: Sheldrick (1997) | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.097, 0.100 | 0.137, 0.158 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4188, 4188, 3306 | 12283, 2459, 1956 |
Rint | 0.000 | 0.057 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.055, 0.92 | 0.030, 0.052, 1.05 |
No. of reflections | 4188 | 2459 |
No. of parameters | 191 | 119 |
H-atom treatment | H atoms: see text | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.22, −0.89 | 0.77, −1.00 |
Computer programs: SMART (Siemens, 1995a), SAINT (Siemens, 1995a), SAINT, SHELXTL (Siemens, 1995b), SHELXTL.
Bi1—N1 | 2.618 (5) | Bi1—Br3 | 2.850 (2) |
Bi1—Br1 | 2.7723 (18) | Bi1—Br2 | 2.869 (3) |
N1—Bi1—Br1 | 180.000 (1) | Br1—Bi1—Br2 | 93.203 (12) |
N1—Bi1—Br3 | 84.872 (11) | Br3—Bi1—Br2 | 90.68 (3) |
Br1—Bi1—Br3 | 95.128 (11) | C1—N1—Bi1 | 121.6 (3) |
Bi1—N1 | 2.536 (5) | Cl1—H2i | 2.796 (5) |
Bi1—Cl2 | 2.675 (2) | Cl1—H7ii | 2.856 (6) |
Bi1—Cl1 | 2.6950 (12) | Cl2—H9iii | 2.644 (6) |
Bi1—Cl4 | 2.702 (2) | Cl3—H9 | 2.633 (7) |
Bi1—Cl3 | 2.728 (2) | Cl4—H8 | 2.865 (7) |
N1—Bi1—Cl2 | 89.57 (13) | Cl1—Bi1—Cl3 | 92.73 (3) |
N1—Bi1—Cl1 | 87.30 (3) | Cl4—Bi1—Cl3 | 90.82 (6) |
Cl2—Bi1—Cl1 | 88.95 (3) | C1—N1—Bi1 | 121.5 (3) |
Cl1iv—Bi1—Cl1 | 174.21 (5) | Bi1—Cl1—H2i | 164.29 (11) |
N1—Bi1—Cl4 | 87.59 (13) | Bi1—Cl1—H7ii | 91.9 (2) |
Cl2—Bi1—Cl4 | 177.16 (5) | H9v—Cl2—Bi1 | 125.4 (2) |
Cl1—Bi1—Cl4 | 90.91 (3) | H9—Cl3—Bi1 | 87.5 (2) |
N1—Bi1—Cl3 | 178.42 (13) | Bi1—Cl4—H8 | 107.19 (13) |
Cl2—Bi1—Cl3 | 92.01 (6) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+3; (iii) x, y, z−1; (iv) x, −y−1/2, z; (v) x, −y−1/2, z−1. |
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The crystal structure of [(4-pic)2H]2[BiBr5(4-pic)], (I) (4-pic = 4-picoline), contains the pentabromo(4-pic)bismuthate(III) dianion lying at a twofold axis of symmetry [along Br1—Bi1—N1—C4]. The cations are hydrogen-bonded containing two molecules of 4-picoline sharing a proton (Fig. 1). In the compound [(pyH)]2[BiCl5(py)], (II) (py = pyridine) (Fig. 2), the cations are simple pyridinium ions. In the anion of (I) the Br1—Bi1—N1 angle is exactly 180° and the symmetry-independent trans bond angles are 169.74 (2)° [Br3Bi1Br3i] and 173.59 (2)° [Br2Bi1Br2i]. The cis-angles range from 84.871 (12)° to 95.129 (12)°. Notably, the Bi—Br bond distance trans to the 4-picoline is shorter [Bi1—Br1 = 2.772 (2) Å] than the others [Bi1—Br2 = 2.869 (3) Å and Bi1—Br3 = 2.850 (2) Å] presumably due to the lower trans-influence of the N-donor ligand. \sch
In the anion of (II) which has mirror symmetry, the Bi—Cl bond distances range from 2.6950 (12)–2.728 (2) Å, but in this case the bond trans to the pyridine ligand is the longest of the Bi-halide bonds. The Bi—N distances in both anions [2.618 (5) Å in (I) and 2.536 (5) Å in (II)] are significantly shorter than the two Bi—N distances in cis-[BiI4(py)2]- [2.703 (2) and 2.751 (3) Å] (Carmalt et al., 1996) in which there are no discernible differences in Bi—I distances.
Two other salts containing the [BiCl5(py)]2- anion have been structurally characterized as N',N'-diethylthiocarbamoyl-pyridinium (Raston et al., 1981), (III), and N-(N',N'-diethylcarbamoyl)pyridine, (IV), (Bharadwaj et al., 1994) salts. In both cases the anion lies over a twofold axis. The symmetry independent Bi—Cl bond distances in (III) are 2.638 (2) Å (trans to N) and 2.699 (2) and 2.691 (3) Å (trans to Cl). Similarly for (IV) the bond lengths are 2.626 (2) Å (trans to N) and 2.694 (2) Å (trans to Cl, for two bonds). Thus, the Bi—Cl distance in (III) and (IV) trans to the N is shorter than those trans to Cl, the opposite of that in (II). That it is difficult to assess the relative trans-influences for nitrogen and chlorine in these complexes is probably due to the relative soft intra-molecular parameters. These are prone to distortion by so-called packing effects such as hydrogen bonding.
The geometry about the Bi centre in (II) is close to regular octahedral, with cis-angles 90±3°. The trans angle deviating most from 180° is Cl1Bi1Cl1i [174.21 (5)°]. Slightly larger distortions are found in the anions of (III) and (IV) with cis-angles deviating up to 6° and trans-angles 10° away from ideal geometries.
In (I) Br1 is involved in two weak hydrogen bonds with the [(4-pic)2H]+ cations in a bifurcated mode [Br1···H9 = 2.98 Å, Br1···H8 = 3.00 Å, C8—H8···Br1 = 127.2°, C9—H9···Br1 = 128.7°]. The cations contain a short hydrogen bond [N3—H3 0.92, H3···N2 = 1.76, N···N = 2.667 (6) Å and N3—H3···N2 = 167°], conistent with the formulation of the cations as [(4-pic)2H]+ rather than as separate [(4-pic)]+ cations and 4-pic solvent molecules.
The crystal structure of (I) is shown in Fig. 3. The packing can be best described as layers in an ABBA arrangement along the crystallographic c direction, with two [(4-pic)2H]+ cations encased by A layers of the anion. The driving force behind this packing arrangement appears to be ring-ring interactions affording a close-packed structure. As shown in Fig. 3 there are ring-ring interactions between the 4-pic ligand of the anion and a cation with a 3.31 Å separation. The inter-plane separation between the cations is 3.63 Å. In the b direction the separation between the cation rings is 4.19 Å.
The crystal structure of (II) is made up of chains of anions running approximately parallel to the crystallographic b axis that are hydrogen-bonded to cations which occupy the space between adjacent layers (Fig. 4). There are two different orientations of chains, tilted at an angle of 65.9° to each other (Bi1 Cl1 Cl1' Cl2 Cl4 plane), one of which is shown in detail in Fig. 4. There is a plethora of Bi—Cl···H—C/N hydrogen bonds [H···Cl distances = 2.633–2.865 Å] (see Table 2 for hydrogen-bond details) whilst ring-ring interactions that were important in the structure of (I) are absent. Anions in chains are held together by CH···Cl hydrogen bonds related by a centre of symmetry. The anion hydrogen bonds
to a cation (Cl1···H7) and Cl4 which is perpendicular to the anion chains hydrogen bonds to two separate cations. A tetrameric motif is formed between two chlorines in separate chains and the NH protons of two separate cations. The pyridinium cation is inclined at an angle of 45.3° to the pyridine ligand.