Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106025972/sq3025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106025972/sq3025Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106025972/sq3025IIsup3.hkl |
CCDC references: 609281; 621300
BiI3 (175 mg, 0.3 mmol; Alfa Aesar, 99.999%), 2,2'-bipyridine (54 mg, 0.3 mmol; Acros, 99+%) and RuI3 (48 mg, 0.1 mmol; Aldrich, reagent grade) were placed in a 15 ml glass pressure vessel (Ace glass) and covered with aqueous ethanol (10 ml, 50% v/v). The reaction vessel was subsequently sealed with a threaded Teflon plug (with a back seal FETFE O-ring; Ace glass) and heated at rate of 0.1 K min-1 to 433 K, where the temperature was held for 5 d. At the end of this period, the vessel was cooled at a rate of 0.1 K min-1 to 353 K and this temperature was maintained for 6 h, afer which the reaction vessel was cooled to room temperature at a rate of 0.1 K min-1. Red–orange blocks of (I), red–orange prisms of (II) and red–orange polycrystalline material were isolated from the reaction. Suitable red–orange crystals were selected for the structure determinations of (I) and (II).
For compound (I), all atoms of the anion were refined with anisotropic displacement parameters. H atoms bonded to C atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). No N-bound H atoms were located or calculated. The highest residual electron-density map peak is located 0.57 Å from C13 and the lowest hole is located 2.88 Å from I5.
For compound (II), all non-H atoms of the structure were refined with anisotropic displacement parameters. H atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The highest residual electron-density map peak is located 0.93 Å from Bi3 and the lowest hole is located 0.54 Å from I4.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
(C10H9N2)4[Bi6I22] | Z = 1 |
Mr = 4674.45 | F(000) = 1996 |
TriclinicP1 | Dx = 3.748 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3334 (6) Å | Cell parameters from 8486 reflections |
b = 12.9913 (7) Å | θ = 2.3–27.7° |
c = 15.7999 (9) Å | µ = 20.93 mm−1 |
α = 78.778 (1)° | T = 150 K |
β = 79.520 (1)° | Block, orange |
γ = 66.023 (1)° | 0.12 × 0.11 × 0.08 mm |
V = 2071.2 (2) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 9709 independent reflections |
Radiation source: fine-focus sealed tube | 8250 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 27.7°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −14→14 |
Tmin = 0.501, Tmax = 1.000 | k = −17→16 |
27864 measured reflections | l = −20→20 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0369P)2 + 1.7243P] where P = (Fo2 + 2Fc2)/3 |
9709 reflections | (Δ/σ)max = 0.001 |
223 parameters | Δρmax = 1.83 e Å−3 |
0 restraints | Δρmin = −2.90 e Å−3 |
(C10H9N2)4[Bi6I22] | γ = 66.023 (1)° |
Mr = 4674.45 | V = 2071.2 (2) Å3 |
TriclinicP1 | Z = 1 |
a = 11.3334 (6) Å | Mo Kα radiation |
b = 12.9913 (7) Å | µ = 20.93 mm−1 |
c = 15.7999 (9) Å | T = 150 K |
α = 78.778 (1)° | 0.12 × 0.11 × 0.08 mm |
β = 79.520 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 9709 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 8250 reflections with I > 2σ(I) |
Tmin = 0.501, Tmax = 1.000 | Rint = 0.039 |
27864 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.83 e Å−3 |
9709 reflections | Δρmin = −2.90 e Å−3 |
223 parameters |
Experimental. Crystal red at room temperature, orange at 150 K. |
Geometry. I3 I9 3.7390 (7) 1_465 ? I8 I8 3.7317 (10) 2_566 ? 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. Ellipsoids of 2,2'-bipy atoms strongly elongated, indicating disorder of these species. Disorder unresolved and these atoms refined isotropically. Due to the disorder the assignment of N atom positions also uncertain. No N-bound proton located or calculated. Owing to these difficulties, only the general location of the 2,2'-bipy groups is reliable. 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 | ||
Bi1 | 0.19109 (3) | 0.17040 (2) | 0.190490 (18) | 0.01939 (7) | |
Bi2 | 0.62188 (3) | −0.06638 (2) | 0.244952 (17) | 0.01877 (7) | |
Bi3 | 0.28086 (2) | 0.11827 (2) | 0.473134 (17) | 0.01844 (7) | |
I1 | 0.28566 (6) | 0.25786 (5) | 0.02151 (3) | 0.03366 (13) | |
I2 | 0.01213 (5) | 0.09132 (4) | 0.14214 (3) | 0.02739 (12) | |
I3 | 0.00622 (5) | 0.39492 (4) | 0.22357 (4) | 0.03144 (13) | |
I4 | 0.73211 (5) | 0.01627 (4) | 0.08179 (3) | 0.02918 (12) | |
I5 | 0.41292 (5) | −0.08997 (4) | 0.17011 (4) | 0.02722 (12) | |
I6 | 0.41409 (4) | 0.19590 (4) | 0.28983 (3) | 0.02060 (10) | |
I7 | 0.09823 (5) | 0.06735 (4) | 0.39344 (3) | 0.02522 (11) | |
I8 | 0.10872 (5) | 0.34867 (4) | 0.49082 (4) | 0.03088 (12) | |
I9 | 0.79429 (5) | −0.30062 (4) | 0.24246 (3) | 0.02700 (12) | |
I10 | 0.49434 (4) | −0.14591 (4) | 0.44488 (3) | 0.02090 (10) | |
I11 | 0.18747 (5) | 0.02127 (4) | 0.64927 (3) | 0.02305 (11) | |
C1 | 0.1220 (12) | 0.5950 (10) | 0.0593 (8) | 0.068 (3)* | |
H1 | 0.0780 | 0.5523 | 0.0464 | 0.082* | |
C2 | 0.0639 (11) | 0.7007 (9) | 0.0590 (7) | 0.057 (3)* | |
H2 | −0.0238 | 0.7356 | 0.0465 | 0.069* | |
C3 | 0.1188 (10) | 0.7637 (9) | 0.0750 (7) | 0.051 (3)* | |
H3 | 0.0712 | 0.8431 | 0.0748 | 0.061* | |
C4 | 0.2607 (10) | 0.7101 (9) | 0.0942 (7) | 0.051 (3)* | |
H4 | 0.3053 | 0.7537 | 0.1047 | 0.061* | |
C5 | 0.3173 (8) | 0.5967 (7) | 0.0952 (5) | 0.0280 (17)* | |
C6 | 0.4523 (8) | 0.5254 (7) | 0.1134 (5) | 0.0279 (17)* | |
C7 | 0.5290 (8) | 0.5714 (7) | 0.1336 (5) | 0.0287 (17)* | |
H7 | 0.4979 | 0.6510 | 0.1347 | 0.034* | |
C8 | 0.6522 (8) | 0.5024 (7) | 0.1526 (6) | 0.0335 (19)* | |
H8 | 0.7081 | 0.5331 | 0.1668 | 0.040* | |
C9 | 0.6937 (9) | 0.3858 (8) | 0.1508 (6) | 0.038 (2)* | |
H9 | 0.7781 | 0.3354 | 0.1647 | 0.045* | |
C10 | 0.6111 (9) | 0.3459 (8) | 0.1287 (6) | 0.039 (2)* | |
H10 | 0.6405 | 0.2667 | 0.1264 | 0.047* | |
C11 | 0.7215 (12) | 0.4664 (10) | 0.4173 (8) | 0.064 (3)* | |
H11 | 0.7782 | 0.4956 | 0.4323 | 0.076* | |
C12 | 0.7590 (14) | 0.3534 (12) | 0.4160 (9) | 0.083 (4)* | |
H12 | 0.8434 | 0.3035 | 0.4301 | 0.100* | |
C13 | 0.6861 (15) | 0.3128 (14) | 0.3969 (10) | 0.092 (5)* | |
H13 | 0.7167 | 0.2329 | 0.3974 | 0.110* | |
C14 | 0.5621 (10) | 0.3803 (8) | 0.3748 (7) | 0.046 (2)* | |
H14 | 0.5094 | 0.3471 | 0.3596 | 0.055* | |
C15 | 0.5180 (8) | 0.4915 (7) | 0.3753 (6) | 0.0349 (19)* | |
C16 | 0.3853 (8) | 0.5605 (7) | 0.3534 (6) | 0.035 (2)* | |
C17 | 0.3095 (8) | 0.5126 (7) | 0.3360 (5) | 0.0275 (17)* | |
H17 | 0.3416 | 0.4326 | 0.3371 | 0.033* | |
C18 | 0.1876 (10) | 0.5778 (9) | 0.3168 (7) | 0.047 (2)* | |
H18 | 0.1353 | 0.5421 | 0.3046 | 0.057* | |
C19 | 0.1387 (11) | 0.6885 (9) | 0.3144 (7) | 0.057 (3)* | |
H19 | 0.0522 | 0.7321 | 0.3013 | 0.068* | |
C20 | 0.2115 (12) | 0.7386 (11) | 0.3304 (8) | 0.065 (3)* | |
H20 | 0.1751 | 0.8190 | 0.3282 | 0.078* | |
N1 | 0.2474 (7) | 0.5410 (6) | 0.0781 (5) | 0.0417 (18)* | |
N2 | 0.4892 (7) | 0.4133 (6) | 0.1099 (5) | 0.0403 (18)* | |
N3 | 0.5952 (8) | 0.5402 (7) | 0.3956 (5) | 0.048 (2)* | |
N4 | 0.3409 (10) | 0.6788 (9) | 0.3508 (7) | 0.069 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.01891 (14) | 0.01941 (14) | 0.01990 (14) | −0.00701 (11) | −0.00221 (11) | −0.00359 (11) |
Bi2 | 0.01805 (14) | 0.01862 (14) | 0.01875 (14) | −0.00573 (11) | −0.00083 (10) | −0.00465 (10) |
Bi3 | 0.01800 (14) | 0.01872 (14) | 0.01782 (14) | −0.00593 (11) | −0.00155 (10) | −0.00371 (10) |
I1 | 0.0460 (3) | 0.0380 (3) | 0.0234 (3) | −0.0261 (3) | 0.0051 (2) | −0.0050 (2) |
I2 | 0.0282 (3) | 0.0342 (3) | 0.0263 (3) | −0.0180 (2) | −0.0037 (2) | −0.0047 (2) |
I3 | 0.0276 (3) | 0.0222 (3) | 0.0388 (3) | −0.0032 (2) | −0.0012 (2) | −0.0078 (2) |
I4 | 0.0370 (3) | 0.0328 (3) | 0.0222 (3) | −0.0202 (2) | 0.0012 (2) | −0.0027 (2) |
I5 | 0.0215 (2) | 0.0238 (2) | 0.0384 (3) | −0.0059 (2) | −0.0076 (2) | −0.0115 (2) |
I6 | 0.0205 (2) | 0.0206 (2) | 0.0211 (2) | −0.00879 (19) | −0.00040 (18) | −0.00368 (18) |
I7 | 0.0260 (3) | 0.0334 (3) | 0.0218 (2) | −0.0173 (2) | −0.0046 (2) | −0.0014 (2) |
I8 | 0.0332 (3) | 0.0207 (2) | 0.0298 (3) | −0.0011 (2) | −0.0014 (2) | −0.0058 (2) |
I9 | 0.0275 (3) | 0.0199 (2) | 0.0279 (3) | −0.0029 (2) | −0.0020 (2) | −0.0055 (2) |
I10 | 0.0205 (2) | 0.0212 (2) | 0.0223 (2) | −0.00905 (19) | −0.00158 (18) | −0.00452 (19) |
I11 | 0.0245 (2) | 0.0289 (3) | 0.0193 (2) | −0.0146 (2) | −0.00204 (19) | −0.00182 (19) |
Bi1—I2 | 2.8837 (5) | C6—C7 | 1.347 (11) |
Bi1—I1 | 2.8871 (6) | C6—N2 | 1.351 (10) |
Bi1—I3 | 2.8981 (6) | C7—C8 | 1.369 (11) |
Bi1—I5 | 3.3292 (6) | C7—H7 | 0.9500 |
Bi1—I6 | 3.3596 (5) | C8—C9 | 1.395 (12) |
Bi1—I7 | 3.3806 (6) | C8—H8 | 0.9500 |
Bi2—I4 | 2.8637 (6) | C9—C10 | 1.362 (12) |
Bi2—I9 | 2.8750 (5) | C9—H9 | 0.9500 |
Bi2—I5 | 2.9750 (6) | C10—N2 | 1.352 (11) |
Bi2—I11i | 3.2449 (5) | C10—H10 | 0.9500 |
Bi2—I10 | 3.3790 (6) | C11—C12 | 1.356 (17) |
Bi2—I6 | 3.3868 (5) | C11—N3 | 1.422 (14) |
Bi3—I8 | 2.8679 (6) | C11—H11 | 0.9500 |
Bi3—I7 | 2.9484 (5) | C12—C13 | 1.248 (18) |
Bi3—I11 | 3.0166 (5) | C12—H12 | 0.9500 |
Bi3—I6 | 3.1929 (5) | C13—C14 | 1.386 (17) |
Bi3—I10i | 3.2285 (5) | C13—H13 | 0.9500 |
Bi3—I10 | 3.3595 (5) | C14—C15 | 1.325 (13) |
I10—Bi3i | 3.2285 (5) | C14—H14 | 0.9500 |
I11—Bi2i | 3.2449 (5) | C15—N3 | 1.377 (11) |
C1—C2 | 1.258 (15) | C15—C16 | 1.470 (13) |
C1—N1 | 1.365 (13) | C16—C17 | 1.337 (11) |
C1—H1 | 0.9500 | C16—N4 | 1.404 (13) |
C2—C3 | 1.293 (14) | C17—C18 | 1.349 (12) |
C2—H2 | 0.9500 | C17—H17 | 0.9500 |
C3—C4 | 1.533 (14) | C18—C19 | 1.310 (14) |
C3—H3 | 0.9500 | C18—H18 | 0.9500 |
C4—C5 | 1.346 (12) | C19—C20 | 1.321 (15) |
C4—H4 | 0.9500 | C19—H19 | 0.9500 |
C5—N1 | 1.357 (10) | C20—N4 | 1.417 (14) |
C5—C6 | 1.479 (11) | C20—H20 | 0.9500 |
I2—Bi1—I1 | 100.270 (17) | C3—C2—H2 | 118.7 |
I2—Bi1—I3 | 97.672 (17) | C2—C3—C4 | 119.9 (10) |
I1—Bi1—I3 | 92.085 (18) | C2—C3—H3 | 120.0 |
I2—Bi1—I5 | 85.835 (15) | C4—C3—H3 | 120.0 |
I1—Bi1—I5 | 91.187 (17) | C5—C4—C3 | 114.8 (9) |
I3—Bi1—I5 | 174.704 (17) | C5—C4—H4 | 122.6 |
I2—Bi1—I6 | 163.460 (16) | C3—C4—H4 | 122.6 |
I1—Bi1—I6 | 93.196 (16) | C4—C5—N1 | 118.9 (8) |
I3—Bi1—I6 | 91.341 (15) | C4—C5—C6 | 125.1 (8) |
I5—Bi1—I6 | 84.316 (13) | N1—C5—C6 | 116.0 (7) |
I2—Bi1—I7 | 83.376 (15) | C7—C6—N2 | 124.1 (8) |
I1—Bi1—I7 | 176.143 (17) | C7—C6—C5 | 120.9 (7) |
I3—Bi1—I7 | 88.652 (16) | N2—C6—C5 | 115.0 (7) |
I5—Bi1—I7 | 87.811 (15) | C6—C7—C8 | 119.3 (8) |
I6—Bi1—I7 | 83.000 (13) | C6—C7—H7 | 120.3 |
I4—Bi2—I9 | 95.744 (17) | C8—C7—H7 | 120.3 |
I4—Bi2—I5 | 94.576 (17) | C7—C8—C9 | 118.5 (8) |
I9—Bi2—I5 | 94.454 (16) | C7—C8—H8 | 120.7 |
I4—Bi2—I11i | 91.960 (15) | C9—C8—H8 | 120.7 |
I9—Bi2—I11i | 91.532 (15) | C10—C9—C8 | 118.7 (9) |
I5—Bi2—I11i | 170.651 (16) | C10—C9—H9 | 120.7 |
I4—Bi2—I10 | 175.012 (16) | C8—C9—H9 | 120.7 |
I9—Bi2—I10 | 87.448 (15) | N2—C10—C9 | 123.3 (9) |
I5—Bi2—I10 | 88.983 (15) | N2—C10—H10 | 118.4 |
I11i—Bi2—I10 | 84.109 (14) | C9—C10—H10 | 118.4 |
I4—Bi2—I6 | 94.168 (15) | C12—C11—N3 | 118.4 (12) |
I9—Bi2—I6 | 168.984 (16) | C12—C11—H11 | 120.8 |
I5—Bi2—I6 | 89.528 (14) | N3—C11—H11 | 120.8 |
I11i—Bi2—I6 | 83.327 (14) | C13—C12—C11 | 122.1 (15) |
I10—Bi2—I6 | 82.350 (13) | C13—C12—H12 | 118.9 |
I8—Bi3—I7 | 94.847 (17) | C11—C12—H12 | 118.9 |
I8—Bi3—I11 | 94.685 (16) | C12—C13—C14 | 122.3 (15) |
I7—Bi3—I11 | 89.936 (15) | C12—C13—H13 | 118.9 |
I8—Bi3—I6 | 91.418 (16) | C14—C13—H13 | 118.9 |
I7—Bi3—I6 | 93.227 (15) | C15—C14—C13 | 119.2 (11) |
I11—Bi3—I6 | 172.868 (15) | C15—C14—H14 | 120.4 |
I8—Bi3—I10i | 91.706 (16) | C13—C14—H14 | 120.4 |
I7—Bi3—I10i | 173.374 (16) | C14—C15—N3 | 120.6 (9) |
I11—Bi3—I10i | 90.508 (14) | C14—C15—C16 | 117.9 (9) |
I6—Bi3—I10i | 85.618 (14) | N3—C15—C16 | 121.5 (8) |
I8—Bi3—I10 | 176.741 (16) | C17—C16—N4 | 121.1 (8) |
I7—Bi3—I10 | 86.680 (15) | C17—C16—C15 | 121.3 (8) |
I11—Bi3—I10 | 88.189 (14) | N4—C16—C15 | 117.6 (9) |
I6—Bi3—I10 | 85.617 (13) | C16—C17—C18 | 120.1 (8) |
I10i—Bi3—I10 | 86.726 (14) | C16—C17—H17 | 119.9 |
Bi2—I5—Bi1 | 96.952 (15) | C18—C17—H17 | 119.9 |
Bi3—I6—Bi1 | 89.655 (13) | C19—C18—C17 | 122.4 (10) |
Bi3—I6—Bi2 | 97.402 (14) | C19—C18—H18 | 118.8 |
Bi1—I6—Bi2 | 88.927 (13) | C17—C18—H18 | 118.8 |
Bi3—I7—Bi1 | 93.539 (15) | C18—C19—C20 | 119.0 (12) |
Bi3i—I10—Bi3 | 93.275 (14) | C18—C19—H19 | 120.5 |
Bi3i—I10—Bi2 | 89.164 (13) | C20—C19—H19 | 120.5 |
Bi3—I10—Bi2 | 94.416 (13) | C19—C20—N4 | 123.4 (12) |
Bi3—I11—Bi2i | 95.550 (15) | C19—C20—H20 | 118.3 |
C2—C1—N1 | 120.7 (12) | N4—C20—H20 | 118.3 |
C2—C1—H1 | 119.7 | C5—N1—C1 | 123.0 (8) |
N1—C1—H1 | 119.7 | C6—N2—C10 | 116.1 (8) |
C1—C2—C3 | 122.6 (12) | C15—N3—C11 | 117.5 (8) |
C1—C2—H2 | 118.7 | C16—N4—C20 | 114.0 (10) |
I4—Bi2—I5—Bi1 | −90.026 (18) | I6—Bi3—I10—Bi2 | −3.564 (12) |
I9—Bi2—I5—Bi1 | 173.835 (16) | I10i—Bi3—I10—Bi2 | −89.414 (14) |
I10—Bi2—I5—Bi1 | 86.475 (15) | I9—Bi2—I10—Bi3i | 85.996 (15) |
I6—Bi2—I5—Bi1 | 4.118 (15) | I5—Bi2—I10—Bi3i | −179.500 (13) |
I2—Bi1—I5—Bi2 | −170.866 (18) | I11i—Bi2—I10—Bi3i | −5.809 (13) |
I1—Bi1—I5—Bi2 | 88.922 (18) | I6—Bi2—I10—Bi3i | −89.840 (13) |
I6—Bi1—I5—Bi2 | −4.172 (15) | I9—Bi2—I10—Bi3 | 179.216 (15) |
I7—Bi1—I5—Bi2 | −87.351 (16) | I5—Bi2—I10—Bi3 | −86.280 (14) |
I8—Bi3—I6—Bi1 | −88.906 (15) | I11i—Bi2—I10—Bi3 | 87.411 (14) |
I7—Bi3—I6—Bi1 | 6.031 (14) | I6—Bi2—I10—Bi3 | 3.380 (12) |
I10i—Bi3—I6—Bi1 | 179.492 (13) | I8—Bi3—I11—Bi2i | −85.247 (17) |
I10—Bi3—I6—Bi1 | 92.448 (13) | I7—Bi3—I11—Bi2i | 179.894 (14) |
I8—Bi3—I6—Bi2 | −177.779 (15) | I10i—Bi3—I11—Bi2i | 6.506 (14) |
I7—Bi3—I6—Bi2 | −82.842 (16) | I10—Bi3—I11—Bi2i | 93.214 (14) |
I10i—Bi3—I6—Bi2 | 90.619 (14) | C1—C2—C3—C4 | 0.7 (18) |
I10—Bi3—I6—Bi2 | 3.575 (12) | C2—C3—C4—C5 | −1.8 (15) |
I2—Bi1—I6—Bi3 | −40.04 (6) | C3—C4—C5—N1 | 1.2 (13) |
I1—Bi1—I6—Bi3 | 175.352 (15) | C3—C4—C5—C6 | −179.1 (8) |
I3—Bi1—I6—Bi3 | 83.188 (16) | C4—C5—C6—C7 | 2.2 (14) |
I5—Bi1—I6—Bi3 | −93.772 (14) | N1—C5—C6—C7 | −178.1 (8) |
I7—Bi1—I6—Bi3 | −5.289 (13) | C4—C5—C6—N2 | −179.2 (9) |
I2—Bi1—I6—Bi2 | 57.37 (6) | N1—C5—C6—N2 | 0.5 (11) |
I1—Bi1—I6—Bi2 | −87.239 (16) | N2—C6—C7—C8 | −0.4 (13) |
I3—Bi1—I6—Bi2 | −179.402 (15) | C5—C6—C7—C8 | 178.0 (8) |
I5—Bi1—I6—Bi2 | 3.637 (13) | C6—C7—C8—C9 | −0.4 (13) |
I7—Bi1—I6—Bi2 | 92.121 (14) | C7—C8—C9—C10 | 1.2 (13) |
I4—Bi2—I6—Bi3 | −179.985 (15) | C8—C9—C10—N2 | −1.2 (14) |
I9—Bi2—I6—Bi3 | −25.89 (9) | C13—C14—C15—N3 | 1.4 (16) |
I5—Bi2—I6—Bi3 | 85.461 (16) | C13—C14—C15—C16 | −178.8 (11) |
I11i—Bi2—I6—Bi3 | −88.496 (15) | C14—C15—C16—C17 | 2.0 (14) |
I10—Bi2—I6—Bi3 | −3.576 (12) | N3—C15—C16—C17 | −178.2 (8) |
I4—Bi2—I6—Bi1 | 90.503 (15) | C14—C15—C16—N4 | −177.6 (8) |
I9—Bi2—I6—Bi1 | −115.40 (8) | N3—C15—C16—N4 | 2.2 (14) |
I5—Bi2—I6—Bi1 | −4.051 (15) | N4—C16—C17—C18 | −1.0 (14) |
I11i—Bi2—I6—Bi1 | −178.008 (13) | C15—C16—C17—C18 | 179.4 (9) |
I10—Bi2—I6—Bi1 | −93.089 (13) | C16—C17—C18—C19 | 0.0 (16) |
I8—Bi3—I7—Bi1 | 85.695 (17) | C17—C18—C19—C20 | 0.7 (18) |
I11—Bi3—I7—Bi1 | −179.609 (14) | C18—C19—C20—N4 | −0.3 (19) |
I6—Bi3—I7—Bi1 | −6.005 (14) | C4—C5—N1—C1 | 0.3 (14) |
I10—Bi3—I7—Bi1 | −91.419 (14) | C6—C5—N1—C1 | −179.4 (9) |
I2—Bi1—I7—Bi3 | 176.338 (16) | C2—C1—N1—C5 | −1.5 (17) |
I3—Bi1—I7—Bi3 | −85.778 (17) | C7—C6—N2—C10 | 0.4 (13) |
I5—Bi1—I7—Bi3 | 90.279 (15) | C5—C6—N2—C10 | −178.1 (7) |
I6—Bi1—I7—Bi3 | 5.740 (14) | C9—C10—N2—C6 | 0.5 (13) |
I7—Bi3—I10—Bi3i | 179.346 (16) | C14—C15—N3—C11 | −1.2 (14) |
I11—Bi3—I10—Bi3i | −90.614 (14) | C16—C15—N3—C11 | 179.1 (9) |
I6—Bi3—I10—Bi3i | 85.849 (14) | C12—C11—N3—C15 | 0.6 (16) |
I10i—Bi3—I10—Bi3i | 0.0 | C17—C16—N4—C20 | 1.3 (15) |
I7—Bi3—I10—Bi2 | 89.932 (15) | C15—C16—N4—C20 | −179.1 (9) |
I11—Bi3—I10—Bi2 | 179.973 (14) | C19—C20—N4—C16 | −0.6 (17) |
Symmetry code: (i) −x+1, −y, −z+1. |
[Ru(C10H8N2)3][Bi6I22] | Z = 1 |
Mr = 5184.92 | F(000) = 2244 |
TriclinicP1 | Dx = 3.459 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7346 (7) Å | Cell parameters from 6398 reflections |
b = 13.6135 (7) Å | θ = 2.3–26.4° |
c = 14.5978 (8) Å | µ = 17.72 mm−1 |
α = 91.380 (1)° | T = 150 K |
β = 100.077 (1)° | Block, red |
γ = 92.010 (1)° | 0.18 × 0.14 × 0.10 mm |
V = 2489.0 (2) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 10135 independent reflections |
Radiation source: fine-focus sealed tube | 8993 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 26.4°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→15 |
Tmin = 0.686, Tmax = 1.000 | k = −17→16 |
23253 measured reflections | l = −18→18 |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0252P)2 + 2.3445P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
10135 reflections | Δρmax = 1.41 e Å−3 |
461 parameters | Δρmin = −1.37 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000139 (15) |
[Ru(C10H8N2)3][Bi6I22] | γ = 92.010 (1)° |
Mr = 5184.92 | V = 2489.0 (2) Å3 |
TriclinicP1 | Z = 1 |
a = 12.7346 (7) Å | Mo Kα radiation |
b = 13.6135 (7) Å | µ = 17.72 mm−1 |
c = 14.5978 (8) Å | T = 150 K |
α = 91.380 (1)° | 0.18 × 0.14 × 0.10 mm |
β = 100.077 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 10135 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 8993 reflections with I > 2σ(I) |
Tmin = 0.686, Tmax = 1.000 | Rint = 0.033 |
23253 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.41 e Å−3 |
10135 reflections | Δρmin = −1.37 e Å−3 |
461 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 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 | ||
Bi1 | 0.41886 (2) | 0.30390 (2) | 0.291703 (19) | 0.01988 (7) | |
Bi2 | 0.30928 (2) | 0.50057 (2) | 0.529847 (18) | 0.01762 (7) | |
Bi3 | 0.20117 (2) | 0.58442 (2) | 0.200418 (19) | 0.02028 (7) | |
I1 | 0.21144 (4) | 0.34315 (4) | 0.16333 (4) | 0.02646 (12) | |
I2 | 0.38479 (4) | 0.08969 (4) | 0.27127 (4) | 0.02917 (12) | |
I3 | 0.54385 (4) | 0.34293 (4) | 0.14993 (4) | 0.03105 (13) | |
I4 | 0.28655 (4) | 0.28758 (4) | 0.47181 (3) | 0.02503 (12) | |
I5 | 0.63497 (4) | 0.27280 (4) | 0.43249 (4) | 0.02656 (12) | |
I6 | 0.44314 (4) | 0.53729 (3) | 0.35133 (3) | 0.01839 (10) | |
I7 | 0.20787 (4) | 0.47348 (4) | 0.68771 (3) | 0.02542 (12) | |
I8 | 0.11192 (4) | 0.53220 (4) | 0.40310 (3) | 0.02387 (11) | |
I9 | 0.23948 (4) | 0.79036 (4) | 0.26637 (3) | 0.02690 (12) | |
I10 | 0.26680 (4) | 0.61919 (4) | 0.02466 (4) | 0.03173 (13) | |
I11 | −0.02140 (4) | 0.58406 (4) | 0.12845 (4) | 0.03035 (13) | |
Ru1 | 0.20609 (4) | 0.05816 (4) | 0.79301 (4) | 0.01556 (12) | |
C1 | 0.3029 (6) | −0.0056 (6) | 0.6255 (5) | 0.0227 (16) | |
H1 | 0.2554 | −0.0616 | 0.6214 | 0.027* | |
C2 | 0.3613 (6) | 0.0065 (5) | 0.5566 (5) | 0.0218 (16) | |
H2 | 0.3512 | −0.0379 | 0.5043 | 0.026* | |
C3 | 0.4358 (6) | 0.0845 (6) | 0.5637 (5) | 0.0268 (18) | |
H3 | 0.4792 | 0.0935 | 0.5176 | 0.032* | |
C4 | 0.4447 (6) | 0.1482 (5) | 0.6392 (5) | 0.0225 (16) | |
H4 | 0.4963 | 0.2012 | 0.6466 | 0.027* | |
C5 | 0.3788 (6) | 0.1359 (5) | 0.7051 (5) | 0.0180 (15) | |
C6 | 0.3731 (5) | 0.2081 (5) | 0.7818 (5) | 0.0164 (15) | |
C7 | 0.4423 (6) | 0.2891 (6) | 0.8040 (5) | 0.0246 (17) | |
H7 | 0.5002 | 0.2994 | 0.7717 | 0.029* | |
C8 | 0.4269 (6) | 0.3540 (5) | 0.8722 (5) | 0.0255 (17) | |
H8 | 0.4744 | 0.4096 | 0.8884 | 0.031* | |
C9 | 0.3416 (6) | 0.3385 (6) | 0.9178 (5) | 0.0277 (18) | |
H9 | 0.3284 | 0.3842 | 0.9643 | 0.033* | |
C10 | 0.2757 (6) | 0.2554 (5) | 0.8945 (5) | 0.0226 (16) | |
H10 | 0.2178 | 0.2440 | 0.9266 | 0.027* | |
C11 | 0.0882 (6) | 0.1942 (5) | 0.6516 (5) | 0.0237 (17) | |
H11 | 0.1430 | 0.2417 | 0.6758 | 0.028* | |
C12 | 0.0097 (6) | 0.2200 (6) | 0.5803 (5) | 0.0269 (18) | |
H12 | 0.0109 | 0.2837 | 0.5552 | 0.032* | |
C13 | −0.0705 (7) | 0.1518 (6) | 0.5459 (6) | 0.033 (2) | |
H13 | −0.1271 | 0.1685 | 0.4980 | 0.039* | |
C14 | −0.0678 (6) | 0.0596 (6) | 0.5815 (5) | 0.0298 (19) | |
H14 | −0.1225 | 0.0117 | 0.5580 | 0.036* | |
C15 | 0.0147 (6) | 0.0363 (6) | 0.6519 (5) | 0.0223 (16) | |
C16 | 0.0316 (6) | −0.0632 (5) | 0.6874 (5) | 0.0205 (16) | |
C17 | −0.0355 (7) | −0.1456 (6) | 0.6585 (5) | 0.0295 (19) | |
H17 | −0.1015 | −0.1384 | 0.6178 | 0.035* | |
C18 | −0.0062 (7) | −0.2370 (6) | 0.6888 (6) | 0.034 (2) | |
H18 | −0.0515 | −0.2932 | 0.6690 | 0.041* | |
C19 | 0.0893 (7) | −0.2465 (6) | 0.7481 (6) | 0.0315 (19) | |
H19 | 0.1123 | −0.3092 | 0.7687 | 0.038* | |
C20 | 0.1500 (6) | −0.1628 (6) | 0.7763 (5) | 0.0270 (18) | |
H20 | 0.2152 | −0.1693 | 0.8183 | 0.032* | |
C21 | 0.3924 (6) | −0.0538 (5) | 0.8959 (6) | 0.0261 (18) | |
H21 | 0.4221 | −0.0500 | 0.8407 | 0.031* | |
C22 | 0.4429 (7) | −0.1084 (6) | 0.9676 (6) | 0.034 (2) | |
H22 | 0.5065 | −0.1409 | 0.9624 | 0.041* | |
C23 | 0.3990 (7) | −0.1146 (6) | 1.0468 (6) | 0.039 (2) | |
H23 | 0.4310 | −0.1535 | 1.0965 | 0.047* | |
C24 | 0.3096 (7) | −0.0651 (6) | 1.0543 (6) | 0.0315 (19) | |
H24 | 0.2795 | −0.0691 | 1.1093 | 0.038* | |
C25 | 0.2628 (6) | −0.0091 (5) | 0.9818 (5) | 0.0196 (16) | |
C26 | 0.1662 (6) | 0.0470 (5) | 0.9831 (5) | 0.0206 (16) | |
C27 | 0.1273 (6) | 0.0703 (6) | 1.0624 (5) | 0.0291 (19) | |
H27 | 0.1612 | 0.0480 | 1.1210 | 0.035* | |
C28 | 0.0384 (7) | 0.1263 (6) | 1.0562 (6) | 0.0308 (19) | |
H28 | 0.0121 | 0.1450 | 1.1109 | 0.037* | |
C29 | −0.0125 (6) | 0.1553 (5) | 0.9697 (6) | 0.0285 (18) | |
H29 | −0.0752 | 0.1921 | 0.9636 | 0.034* | |
C30 | 0.0307 (6) | 0.1291 (5) | 0.8933 (6) | 0.0240 (17) | |
H30 | −0.0039 | 0.1486 | 0.8339 | 0.029* | |
N1 | 0.3084 (5) | 0.0570 (4) | 0.6992 (4) | 0.0205 (13) | |
N2 | 0.2911 (5) | 0.1899 (4) | 0.8276 (4) | 0.0178 (13) | |
N3 | 0.0911 (5) | 0.1042 (4) | 0.6889 (4) | 0.0195 (13) | |
N4 | 0.1244 (5) | −0.0727 (4) | 0.7491 (4) | 0.0189 (13) | |
N5 | 0.3024 (5) | −0.0053 (4) | 0.9007 (4) | 0.0204 (13) | |
N6 | 0.1194 (5) | 0.0774 (4) | 0.8978 (4) | 0.0193 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.02196 (15) | 0.01732 (14) | 0.02009 (14) | 0.00007 (11) | 0.00342 (12) | −0.00202 (11) |
Bi2 | 0.01565 (14) | 0.01760 (14) | 0.01942 (14) | 0.00009 (11) | 0.00257 (11) | 0.00111 (11) |
Bi3 | 0.01814 (15) | 0.02053 (15) | 0.02202 (15) | 0.00111 (11) | 0.00282 (11) | 0.00236 (11) |
I1 | 0.0247 (3) | 0.0225 (3) | 0.0294 (3) | −0.0004 (2) | −0.0025 (2) | −0.0003 (2) |
I2 | 0.0346 (3) | 0.0179 (3) | 0.0320 (3) | 0.0009 (2) | −0.0016 (2) | −0.0039 (2) |
I3 | 0.0359 (3) | 0.0328 (3) | 0.0262 (3) | −0.0044 (2) | 0.0124 (2) | −0.0049 (2) |
I4 | 0.0271 (3) | 0.0193 (3) | 0.0286 (3) | 0.0006 (2) | 0.0045 (2) | 0.0004 (2) |
I5 | 0.0265 (3) | 0.0175 (2) | 0.0325 (3) | 0.0019 (2) | −0.0036 (2) | −0.0004 (2) |
I6 | 0.0168 (2) | 0.0180 (2) | 0.0203 (2) | −0.00018 (19) | 0.00311 (19) | 0.00111 (19) |
I7 | 0.0242 (3) | 0.0304 (3) | 0.0227 (2) | −0.0009 (2) | 0.0072 (2) | 0.0024 (2) |
I8 | 0.0193 (2) | 0.0277 (3) | 0.0242 (3) | 0.0050 (2) | 0.0013 (2) | 0.0047 (2) |
I9 | 0.0310 (3) | 0.0226 (3) | 0.0266 (3) | −0.0001 (2) | 0.0040 (2) | −0.0002 (2) |
I10 | 0.0333 (3) | 0.0358 (3) | 0.0286 (3) | −0.0047 (2) | 0.0140 (2) | −0.0010 (2) |
I11 | 0.0184 (3) | 0.0398 (3) | 0.0321 (3) | −0.0002 (2) | 0.0019 (2) | 0.0051 (2) |
Ru1 | 0.0153 (3) | 0.0144 (3) | 0.0171 (3) | −0.0004 (2) | 0.0035 (2) | −0.0001 (2) |
C1 | 0.020 (4) | 0.025 (4) | 0.025 (4) | 0.002 (3) | 0.007 (3) | 0.001 (3) |
C2 | 0.031 (4) | 0.014 (4) | 0.022 (4) | 0.007 (3) | 0.007 (3) | 0.000 (3) |
C3 | 0.024 (4) | 0.027 (4) | 0.033 (4) | 0.011 (3) | 0.012 (4) | 0.008 (4) |
C4 | 0.016 (4) | 0.020 (4) | 0.033 (4) | 0.004 (3) | 0.007 (3) | 0.004 (3) |
C5 | 0.018 (4) | 0.013 (3) | 0.023 (4) | 0.002 (3) | 0.003 (3) | 0.003 (3) |
C6 | 0.012 (3) | 0.019 (4) | 0.016 (3) | 0.004 (3) | −0.005 (3) | 0.008 (3) |
C7 | 0.015 (4) | 0.031 (4) | 0.029 (4) | −0.002 (3) | 0.006 (3) | 0.008 (4) |
C8 | 0.024 (4) | 0.019 (4) | 0.028 (4) | −0.004 (3) | −0.009 (3) | 0.002 (3) |
C9 | 0.033 (5) | 0.019 (4) | 0.029 (4) | 0.001 (3) | 0.000 (4) | −0.011 (3) |
C10 | 0.028 (4) | 0.023 (4) | 0.016 (4) | 0.000 (3) | 0.004 (3) | 0.000 (3) |
C11 | 0.027 (4) | 0.019 (4) | 0.023 (4) | 0.003 (3) | 0.000 (3) | −0.001 (3) |
C12 | 0.028 (4) | 0.031 (5) | 0.023 (4) | 0.004 (4) | 0.008 (3) | 0.000 (3) |
C13 | 0.030 (5) | 0.041 (5) | 0.024 (4) | 0.013 (4) | −0.003 (4) | 0.000 (4) |
C14 | 0.024 (4) | 0.037 (5) | 0.027 (4) | 0.002 (4) | 0.000 (3) | −0.006 (4) |
C15 | 0.016 (4) | 0.037 (5) | 0.013 (3) | 0.001 (3) | 0.003 (3) | −0.004 (3) |
C16 | 0.020 (4) | 0.028 (4) | 0.014 (3) | −0.006 (3) | 0.006 (3) | −0.007 (3) |
C17 | 0.029 (4) | 0.032 (5) | 0.026 (4) | −0.006 (4) | 0.004 (4) | −0.009 (4) |
C18 | 0.046 (6) | 0.028 (5) | 0.029 (4) | −0.020 (4) | 0.011 (4) | −0.005 (4) |
C19 | 0.044 (5) | 0.017 (4) | 0.036 (5) | −0.003 (4) | 0.016 (4) | 0.002 (3) |
C20 | 0.029 (4) | 0.024 (4) | 0.030 (4) | 0.001 (3) | 0.010 (4) | −0.002 (3) |
C21 | 0.023 (4) | 0.019 (4) | 0.033 (4) | −0.002 (3) | −0.002 (3) | −0.010 (3) |
C22 | 0.027 (5) | 0.019 (4) | 0.049 (5) | 0.007 (3) | −0.011 (4) | −0.007 (4) |
C23 | 0.043 (6) | 0.027 (5) | 0.039 (5) | −0.005 (4) | −0.013 (4) | 0.010 (4) |
C24 | 0.036 (5) | 0.028 (4) | 0.025 (4) | −0.009 (4) | −0.008 (4) | −0.001 (4) |
C25 | 0.024 (4) | 0.019 (4) | 0.012 (3) | −0.009 (3) | −0.003 (3) | −0.001 (3) |
C26 | 0.025 (4) | 0.014 (4) | 0.022 (4) | −0.006 (3) | 0.005 (3) | 0.001 (3) |
C27 | 0.031 (5) | 0.028 (4) | 0.027 (4) | −0.013 (4) | 0.004 (4) | −0.001 (4) |
C28 | 0.038 (5) | 0.023 (4) | 0.033 (5) | −0.013 (4) | 0.014 (4) | −0.006 (4) |
C29 | 0.025 (4) | 0.019 (4) | 0.043 (5) | −0.003 (3) | 0.015 (4) | −0.008 (4) |
C30 | 0.024 (4) | 0.015 (4) | 0.034 (4) | 0.002 (3) | 0.006 (3) | 0.000 (3) |
N1 | 0.015 (3) | 0.025 (3) | 0.022 (3) | 0.002 (3) | 0.003 (3) | 0.006 (3) |
N2 | 0.020 (3) | 0.013 (3) | 0.021 (3) | 0.005 (2) | 0.003 (3) | 0.003 (2) |
N3 | 0.022 (3) | 0.019 (3) | 0.019 (3) | 0.004 (3) | 0.007 (3) | 0.003 (3) |
N4 | 0.028 (3) | 0.017 (3) | 0.014 (3) | −0.001 (3) | 0.009 (3) | −0.002 (2) |
N5 | 0.020 (3) | 0.013 (3) | 0.026 (3) | −0.004 (3) | 0.001 (3) | −0.001 (3) |
N6 | 0.020 (3) | 0.012 (3) | 0.026 (3) | −0.004 (2) | 0.007 (3) | −0.005 (3) |
Bi1—I3 | 2.8715 (6) | C10—N2 | 1.350 (9) |
Bi1—I2 | 2.9335 (6) | C10—H10 | 0.9500 |
Bi1—I1 | 3.0315 (6) | C11—N3 | 1.352 (9) |
Bi1—I5 | 3.1813 (6) | C11—C12 | 1.372 (10) |
Bi1—I6 | 3.2637 (5) | C11—H11 | 0.9500 |
Bi1—I4 | 3.3695 (6) | C12—C13 | 1.374 (11) |
Bi2—I7 | 2.8571 (5) | C12—H12 | 0.9500 |
Bi2—I8 | 2.9004 (6) | C13—C14 | 1.369 (11) |
Bi2—I4 | 2.9909 (6) | C13—H13 | 0.9500 |
Bi2—I5i | 3.1548 (6) | C14—C15 | 1.387 (10) |
Bi2—I6i | 3.3850 (6) | C14—H14 | 0.9500 |
Bi2—I6 | 3.3918 (5) | C15—N3 | 1.349 (9) |
Bi3—I11 | 2.8450 (6) | C15—C16 | 1.471 (11) |
Bi3—I10 | 2.8786 (6) | C16—N4 | 1.367 (9) |
Bi3—I9 | 2.9384 (6) | C16—C17 | 1.396 (10) |
Bi3—I1 | 3.3268 (6) | C17—C18 | 1.374 (12) |
Bi3—I8 | 3.4311 (6) | C17—H17 | 0.9500 |
Bi3—I6 | 3.5484 (5) | C18—C19 | 1.375 (12) |
I5—Bi2i | 3.1548 (6) | C18—H18 | 0.9500 |
I6—Bi2i | 3.3850 (5) | C19—C20 | 1.369 (10) |
Ru1—N3 | 2.044 (6) | C19—H19 | 0.9500 |
Ru1—N5 | 2.047 (6) | C20—N4 | 1.332 (9) |
Ru1—N1 | 2.048 (6) | C20—H20 | 0.9500 |
Ru1—N6 | 2.054 (6) | C21—N5 | 1.354 (9) |
Ru1—N4 | 2.061 (6) | C21—C22 | 1.377 (11) |
Ru1—N2 | 2.067 (6) | C21—H21 | 0.9500 |
C1—N1 | 1.347 (9) | C22—C23 | 1.373 (12) |
C1—C2 | 1.362 (10) | C22—H22 | 0.9500 |
C1—H1 | 0.9500 | C23—C24 | 1.362 (12) |
C2—C3 | 1.389 (10) | C23—H23 | 0.9500 |
C2—H2 | 0.9500 | C24—C25 | 1.381 (10) |
C3—C4 | 1.373 (10) | C24—H24 | 0.9500 |
C3—H3 | 0.9500 | C25—N5 | 1.367 (9) |
C4—C5 | 1.391 (10) | C25—C26 | 1.473 (10) |
C4—H4 | 0.9500 | C26—N6 | 1.363 (9) |
C5—N1 | 1.366 (9) | C26—C27 | 1.372 (10) |
C5—C6 | 1.485 (10) | C27—C28 | 1.378 (11) |
C6—N2 | 1.354 (9) | C27—H27 | 0.9500 |
C6—C7 | 1.384 (10) | C28—C29 | 1.388 (11) |
C7—C8 | 1.359 (11) | C28—H28 | 0.9500 |
C7—H7 | 0.9500 | C29—C30 | 1.373 (10) |
C8—C9 | 1.383 (11) | C29—H29 | 0.9500 |
C8—H8 | 0.9500 | C30—N6 | 1.344 (9) |
C9—C10 | 1.385 (10) | C30—H30 | 0.9500 |
C9—H9 | 0.9500 | ||
I3—Bi1—I2 | 101.416 (17) | C8—C7—H7 | 120.2 |
I3—Bi1—I1 | 92.679 (17) | C6—C7—H7 | 120.2 |
I2—Bi1—I1 | 93.372 (16) | C7—C8—C9 | 119.5 (7) |
I3—Bi1—I5 | 88.424 (17) | C7—C8—H8 | 120.3 |
I2—Bi1—I5 | 89.118 (15) | C9—C8—H8 | 120.3 |
I1—Bi1—I5 | 177.022 (16) | C8—C9—C10 | 118.9 (7) |
I3—Bi1—I6 | 88.703 (15) | C8—C9—H9 | 120.6 |
I2—Bi1—I6 | 169.475 (16) | C10—C9—H9 | 120.6 |
I1—Bi1—I6 | 88.991 (14) | N2—C10—C9 | 122.0 (7) |
I5—Bi1—I6 | 88.269 (14) | N2—C10—H10 | 119.0 |
I3—Bi1—I4 | 172.149 (16) | C9—C10—H10 | 119.0 |
I2—Bi1—I4 | 85.859 (15) | N3—C11—C12 | 123.1 (7) |
I1—Bi1—I4 | 89.804 (15) | N3—C11—H11 | 118.5 |
I5—Bi1—I4 | 88.746 (15) | C12—C11—H11 | 118.5 |
I6—Bi1—I4 | 83.892 (13) | C11—C12—C13 | 118.6 (8) |
I7—Bi2—I8 | 94.395 (16) | C11—C12—H12 | 120.7 |
I7—Bi2—I4 | 93.795 (16) | C13—C12—H12 | 120.7 |
I8—Bi2—I4 | 88.622 (16) | C14—C13—C12 | 119.2 (7) |
I7—Bi2—I5i | 96.159 (16) | C14—C13—H13 | 120.4 |
I8—Bi2—I5i | 93.814 (15) | C12—C13—H13 | 120.4 |
I4—Bi2—I5i | 169.536 (17) | C13—C14—C15 | 119.9 (8) |
I7—Bi2—I6i | 94.164 (15) | C13—C14—H14 | 120.0 |
I8—Bi2—I6i | 171.336 (15) | C15—C14—H14 | 120.0 |
I4—Bi2—I6i | 89.471 (14) | N3—C15—C14 | 121.1 (7) |
I5i—Bi2—I6i | 86.602 (14) | N3—C15—C16 | 114.6 (6) |
I7—Bi2—I6 | 176.570 (16) | C14—C15—C16 | 124.1 (7) |
I8—Bi2—I6 | 88.683 (14) | N4—C16—C17 | 120.1 (7) |
I4—Bi2—I6 | 87.784 (14) | N4—C16—C15 | 114.8 (6) |
I5i—Bi2—I6 | 82.106 (14) | C17—C16—C15 | 125.0 (7) |
I6i—Bi2—I6 | 82.798 (13) | C18—C17—C16 | 120.1 (8) |
I11—Bi3—I10 | 95.152 (18) | C18—C17—H17 | 120.0 |
I11—Bi3—I9 | 100.273 (18) | C16—C17—H17 | 120.0 |
I10—Bi3—I9 | 93.966 (17) | C17—C18—C19 | 119.5 (7) |
I11—Bi3—I1 | 92.663 (16) | C17—C18—H18 | 120.3 |
I10—Bi3—I1 | 90.128 (16) | C19—C18—H18 | 120.3 |
I9—Bi3—I1 | 166.008 (17) | C20—C19—C18 | 117.7 (8) |
I11—Bi3—I8 | 82.427 (15) | C20—C19—H19 | 121.1 |
I10—Bi3—I8 | 176.493 (17) | C18—C19—H19 | 121.1 |
I9—Bi3—I8 | 88.974 (15) | N4—C20—C19 | 124.7 (8) |
I1—Bi3—I8 | 87.457 (14) | N4—C20—H20 | 117.6 |
I11—Bi3—I6 | 159.653 (16) | C19—C20—H20 | 117.6 |
I10—Bi3—I6 | 103.687 (16) | N5—C21—C22 | 122.9 (8) |
I9—Bi3—I6 | 86.192 (14) | N5—C21—H21 | 118.6 |
I1—Bi3—I6 | 79.838 (13) | C22—C21—H21 | 118.6 |
I8—Bi3—I6 | 78.392 (13) | C23—C22—C21 | 118.3 (8) |
Bi1—I1—Bi3 | 99.941 (15) | C23—C22—H22 | 120.9 |
Bi2—I4—Bi1 | 96.877 (15) | C21—C22—H22 | 120.9 |
Bi2i—I5—Bi1 | 94.705 (15) | C24—C23—C22 | 120.1 (8) |
Bi1—I6—Bi2i | 88.990 (13) | C24—C23—H23 | 119.9 |
Bi1—I6—Bi2 | 91.440 (13) | C22—C23—H23 | 119.9 |
Bi2i—I6—Bi2 | 97.202 (13) | C23—C24—C25 | 119.9 (8) |
Bi1—I6—Bi3 | 91.229 (13) | C23—C24—H24 | 120.1 |
Bi2i—I6—Bi3 | 172.104 (16) | C25—C24—H24 | 120.1 |
Bi2—I6—Bi3 | 90.684 (13) | N5—C25—C24 | 121.0 (7) |
Bi2—I8—Bi3 | 102.174 (16) | N5—C25—C26 | 114.9 (6) |
N3—Ru1—N5 | 170.4 (2) | C24—C25—C26 | 124.1 (7) |
N3—Ru1—N1 | 88.0 (2) | N6—C26—C27 | 122.0 (7) |
N5—Ru1—N1 | 98.1 (2) | N6—C26—C25 | 114.0 (6) |
N3—Ru1—N6 | 95.8 (2) | C27—C26—C25 | 124.0 (7) |
N5—Ru1—N6 | 79.3 (2) | C26—C27—C28 | 119.3 (8) |
N1—Ru1—N6 | 170.7 (2) | C26—C27—H27 | 120.4 |
N3—Ru1—N4 | 78.8 (2) | C28—C27—H27 | 120.4 |
N5—Ru1—N4 | 93.0 (2) | C27—C28—C29 | 119.6 (8) |
N1—Ru1—N4 | 97.2 (2) | C27—C28—H28 | 120.2 |
N6—Ru1—N4 | 91.8 (2) | C29—C28—H28 | 120.2 |
N3—Ru1—N2 | 99.3 (2) | C30—C29—C28 | 117.9 (8) |
N5—Ru1—N2 | 89.1 (2) | C30—C29—H29 | 121.1 |
N1—Ru1—N2 | 78.9 (2) | C28—C29—H29 | 121.1 |
N6—Ru1—N2 | 92.1 (2) | N6—C30—C29 | 123.6 (8) |
N4—Ru1—N2 | 175.9 (2) | N6—C30—H30 | 118.2 |
N1—C1—C2 | 124.0 (7) | C29—C30—H30 | 118.2 |
N1—C1—H1 | 118.0 | C1—N1—C5 | 117.2 (6) |
C2—C1—H1 | 118.0 | C1—N1—Ru1 | 126.3 (5) |
C1—C2—C3 | 119.2 (7) | C5—N1—Ru1 | 115.8 (5) |
C1—C2—H2 | 120.4 | C10—N2—C6 | 118.1 (6) |
C3—C2—H2 | 120.4 | C10—N2—Ru1 | 125.9 (5) |
C4—C3—C2 | 118.0 (7) | C6—N2—Ru1 | 115.8 (5) |
C4—C3—H3 | 121.0 | C15—N3—C11 | 117.9 (6) |
C2—C3—H3 | 121.0 | C15—N3—Ru1 | 116.2 (5) |
C3—C4—C5 | 120.7 (7) | C11—N3—Ru1 | 125.8 (5) |
C3—C4—H4 | 119.7 | C20—N4—C16 | 117.8 (6) |
C5—C4—H4 | 119.7 | C20—N4—Ru1 | 127.6 (5) |
N1—C5—C4 | 120.9 (7) | C16—N4—Ru1 | 114.6 (5) |
N1—C5—C6 | 114.8 (6) | C21—N5—C25 | 117.8 (6) |
C4—C5—C6 | 124.2 (6) | C21—N5—Ru1 | 126.6 (5) |
N2—C6—C7 | 121.9 (7) | C25—N5—Ru1 | 115.0 (5) |
N2—C6—C5 | 114.1 (6) | C30—N6—C26 | 117.5 (6) |
C7—C6—C5 | 124.0 (6) | C30—N6—Ru1 | 126.2 (5) |
C8—C7—C6 | 119.6 (7) | C26—N6—Ru1 | 115.5 (5) |
I3—Bi1—I1—Bi3 | −88.346 (17) | N5—C25—C26—N6 | 12.5 (9) |
I2—Bi1—I1—Bi3 | 170.044 (16) | C24—C25—C26—N6 | −165.1 (7) |
I6—Bi1—I1—Bi3 | 0.308 (15) | N5—C25—C26—C27 | −165.5 (7) |
I4—Bi1—I1—Bi3 | 84.203 (15) | C25—C26—C27—C28 | 177.6 (7) |
I11—Bi3—I1—Bi1 | −161.238 (17) | C2—C1—N1—Ru1 | 168.5 (6) |
I10—Bi3—I1—Bi1 | 103.598 (18) | C6—C5—N1—C1 | 173.7 (6) |
I9—Bi3—I1—Bi1 | −3.56 (7) | C4—C5—N1—Ru1 | −173.4 (5) |
I8—Bi3—I1—Bi1 | −78.946 (16) | C6—C5—N1—Ru1 | 2.7 (8) |
I6—Bi3—I1—Bi1 | −0.288 (14) | N3—Ru1—N1—C1 | −69.0 (6) |
I7—Bi2—I4—Bi1 | −176.382 (15) | N5—Ru1—N1—C1 | 103.6 (6) |
I8—Bi2—I4—Bi1 | 89.303 (16) | N4—Ru1—N1—C1 | 9.4 (6) |
I5i—Bi2—I4—Bi1 | −14.35 (10) | N2—Ru1—N1—C1 | −169.0 (6) |
I6i—Bi2—I4—Bi1 | −82.245 (15) | N3—Ru1—N1—C5 | 101.0 (5) |
I6—Bi2—I4—Bi1 | 0.568 (14) | N5—Ru1—N1—C5 | −86.4 (5) |
I2—Bi1—I4—Bi2 | 177.005 (17) | N4—Ru1—N1—C5 | 179.5 (5) |
I1—Bi1—I4—Bi2 | −89.600 (16) | N2—Ru1—N1—C5 | 1.1 (5) |
I5—Bi1—I4—Bi2 | 87.799 (16) | C9—C10—N2—Ru1 | 175.1 (5) |
I6—Bi1—I4—Bi2 | −0.593 (14) | C5—C6—N2—C10 | −175.8 (6) |
I3—Bi1—I5—Bi2i | 79.297 (17) | C7—C6—N2—Ru1 | −174.2 (5) |
I2—Bi1—I5—Bi2i | −179.256 (16) | C5—C6—N2—Ru1 | 7.9 (7) |
I6—Bi1—I5—Bi2i | −9.453 (15) | N3—Ru1—N2—C10 | 92.9 (6) |
I4—Bi1—I5—Bi2i | −93.379 (15) | N5—Ru1—N2—C10 | −82.6 (6) |
I3—Bi1—I6—Bi2i | −79.686 (16) | N1—Ru1—N2—C10 | 178.9 (6) |
I2—Bi1—I6—Bi2i | 84.47 (9) | N6—Ru1—N2—C10 | −3.3 (6) |
I1—Bi1—I6—Bi2i | −172.390 (14) | N3—Ru1—N2—C6 | −91.1 (5) |
I5—Bi1—I6—Bi2i | 8.776 (14) | N5—Ru1—N2—C6 | 93.4 (5) |
I4—Bi1—I6—Bi2i | 97.700 (14) | N1—Ru1—N2—C6 | −5.1 (5) |
I3—Bi1—I6—Bi2 | −176.866 (16) | N6—Ru1—N2—C6 | 172.7 (5) |
I2—Bi1—I6—Bi2 | −12.71 (9) | C16—C15—N3—C11 | 171.9 (6) |
I1—Bi1—I6—Bi2 | 90.430 (15) | C14—C15—N3—Ru1 | 179.4 (5) |
I5—Bi1—I6—Bi2 | −88.404 (14) | C16—C15—N3—Ru1 | −4.9 (7) |
I4—Bi1—I6—Bi2 | 0.520 (12) | C12—C11—N3—Ru1 | 178.6 (5) |
I3—Bi1—I6—Bi3 | 92.419 (16) | N1—Ru1—N3—C15 | 105.4 (5) |
I2—Bi1—I6—Bi3 | −103.42 (9) | N6—Ru1—N3—C15 | −83.2 (5) |
I1—Bi1—I6—Bi3 | −0.285 (14) | N4—Ru1—N3—C15 | 7.6 (5) |
I5—Bi1—I6—Bi3 | −179.119 (14) | N2—Ru1—N3—C15 | −176.2 (5) |
I4—Bi1—I6—Bi3 | −90.195 (13) | N1—Ru1—N3—C11 | −71.2 (6) |
I8—Bi2—I6—Bi1 | −89.254 (15) | N6—Ru1—N3—C11 | 100.3 (6) |
I4—Bi2—I6—Bi1 | −0.582 (14) | N4—Ru1—N3—C11 | −169.0 (6) |
I5i—Bi2—I6—Bi1 | 176.711 (14) | N2—Ru1—N3—C11 | 7.2 (6) |
I6i—Bi2—I6—Bi1 | 89.164 (13) | C19—C20—N4—Ru1 | 176.4 (6) |
I8—Bi2—I6—Bi2i | −178.418 (16) | C15—C16—N4—C20 | −173.0 (6) |
I4—Bi2—I6—Bi2i | −89.747 (15) | C17—C16—N4—Ru1 | −174.7 (5) |
I5i—Bi2—I6—Bi2i | 87.547 (14) | C15—C16—N4—Ru1 | 9.1 (7) |
I6i—Bi2—I6—Bi2i | 0.0 | N3—Ru1—N4—C20 | 173.4 (6) |
I8—Bi2—I6—Bi3 | 1.992 (14) | N5—Ru1—N4—C20 | −11.7 (6) |
I4—Bi2—I6—Bi3 | 90.664 (14) | N1—Ru1—N4—C20 | 86.9 (6) |
I5i—Bi2—I6—Bi3 | −92.042 (13) | N6—Ru1—N4—C20 | −91.1 (6) |
I6i—Bi2—I6—Bi3 | −179.589 (17) | N3—Ru1—N4—C16 | −9.0 (5) |
I11—Bi3—I6—Bi1 | 69.93 (5) | N5—Ru1—N4—C16 | 165.9 (5) |
I10—Bi3—I6—Bi1 | −87.369 (16) | N1—Ru1—N4—C16 | −95.5 (5) |
I9—Bi3—I6—Bi1 | 179.471 (14) | N6—Ru1—N4—C16 | 86.5 (5) |
I1—Bi3—I6—Bi1 | 0.264 (13) | C22—C21—N5—Ru1 | −168.8 (6) |
I8—Bi3—I6—Bi1 | 89.737 (13) | C26—C25—N5—C21 | 178.7 (6) |
I11—Bi3—I6—Bi2 | −21.53 (5) | C24—C25—N5—Ru1 | 168.2 (5) |
I10—Bi3—I6—Bi2 | −178.824 (15) | C26—C25—N5—Ru1 | −9.5 (7) |
I9—Bi3—I6—Bi2 | 88.015 (14) | N1—Ru1—N5—C21 | −14.6 (6) |
I1—Bi3—I6—Bi2 | −91.192 (13) | N6—Ru1—N5—C21 | 174.4 (6) |
I7—Bi2—I8—Bi3 | 176.376 (16) | N4—Ru1—N5—C21 | 83.2 (6) |
I4—Bi2—I8—Bi3 | −89.923 (16) | N2—Ru1—N5—C21 | −93.3 (6) |
I5i—Bi2—I8—Bi3 | 79.890 (16) | N1—Ru1—N5—C25 | 174.4 (5) |
I6—Bi2—I8—Bi3 | −2.108 (15) | N6—Ru1—N5—C25 | 3.5 (5) |
I11—Bi3—I8—Bi2 | 175.228 (19) | N4—Ru1—N5—C25 | −87.8 (5) |
I9—Bi3—I8—Bi2 | −84.267 (17) | N2—Ru1—N5—C25 | 95.7 (5) |
I1—Bi3—I8—Bi2 | 82.200 (16) | C29—C30—N6—Ru1 | −167.1 (6) |
I6—Bi3—I8—Bi2 | 2.056 (14) | C25—C26—N6—C30 | 180.0 (6) |
C3—C4—C5—C6 | −171.7 (7) | C27—C26—N6—Ru1 | 168.5 (5) |
N1—C5—C6—N2 | −6.9 (9) | C25—C26—N6—Ru1 | −9.5 (7) |
C4—C5—C6—N2 | 169.0 (7) | N3—Ru1—N6—C30 | −15.2 (6) |
N1—C5—C6—C7 | 175.2 (7) | N5—Ru1—N6—C30 | 173.1 (6) |
C5—C6—C7—C8 | 176.3 (7) | N4—Ru1—N6—C30 | −94.1 (6) |
C13—C14—C15—C16 | −172.7 (7) | N2—Ru1—N6—C30 | 84.4 (6) |
N3—C15—C16—N4 | −2.9 (9) | N3—Ru1—N6—C26 | 175.3 (5) |
C14—C15—C16—N4 | 172.7 (7) | N5—Ru1—N6—C26 | 3.6 (5) |
N3—C15—C16—C17 | −178.8 (7) | N4—Ru1—N6—C26 | 96.3 (5) |
C15—C16—C17—C18 | 173.0 (7) | N2—Ru1—N6—C26 | −85.1 (5) |
C23—C24—C25—C26 | 180.0 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C10H9N2)4[Bi6I22] | [Ru(C10H8N2)3][Bi6I22] |
Mr | 4674.45 | 5184.92 |
Crystal system, space group | TriclinicP1 | TriclinicP1 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 11.3334 (6), 12.9913 (7), 15.7999 (9) | 12.7346 (7), 13.6135 (7), 14.5978 (8) |
α, β, γ (°) | 78.778 (1), 79.520 (1), 66.023 (1) | 91.380 (1), 100.077 (1), 92.010 (1) |
V (Å3) | 2071.2 (2) | 2489.0 (2) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 20.93 | 17.72 |
Crystal size (mm) | 0.12 × 0.11 × 0.08 | 0.18 × 0.14 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.501, 1.000 | 0.686, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27864, 9709, 8250 | 23253, 10135, 8993 |
Rint | 0.039 | 0.033 |
(sin θ/λ)max (Å−1) | 0.654 | 0.625 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.085, 1.03 | 0.032, 0.070, 1.02 |
No. of reflections | 9709 | 10135 |
No. of parameters | 223 | 461 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.83, −2.90 | 1.41, −1.37 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
The chemistry of main group halometallate materials has been of interest to chemists and materials scientists for some time, due to their promising physical characteristics and their interesting structural diversity. With respect to the physical properties, behaviors such as semiconductivity, luminescence and second-order non-linear optical activity have been observed in this family of materials (Papavassiliou et al., 1995; Zhu et al., 2003; Mitzi & Brock, 2001; Mousdis et al., 1998). The main group halometallate materials display extensive structural diversity, as the anionic inorganic component ranges from discrete clusters (zero-dimensional) to polymeric structures (one-, two- or three-dimensional) depending on the main group metal and on the specific synthetic conditions employed. To date, main group halometallate materials based on CuI (Yu et al., 2003), SnII (Xu & Mitzi, 2003), SbIII (Mousdis et al., 1998), TeIV (Ryan & Xu, 2004), PbII (Zhu et al., 2003) and BiIII (Mousdis et al., 1998; Eickmeier et al., 1999; Lindsjo et al., 2005) have been synthesized and structurally characterized.
We have been interested in the synthesis of new main group halometallate materials containing BiIII and have been successful in the synthesis of many new iodobismuthate(III) materials having either organic or inorganic cations for charge balance (Goforth et al., 2004; Goforth, Gardinier et al., 2005; Goforth, Peterson et al., 2005). Many halobismuthate compounds have been synthesized by us and others, and most of these compounds contain either discrete anions (of varying sizes) or one-dimensional polymeric anions. In either case, the anion is generally composed of connected BiI6 polyhedra, which are corner-, edge- or face-sharing. The number of connected polyhedra, and the mode of connectivity and the spatial arrangement of these polyhedra, may vary within a given metal halide system, e.g. iodobismuthates, such that one can envision a large number of possible halometallate anion structures. In fact, certain synthetic conditions, such as cation size and geometry, solvent system and reagent stoichiometry, may be adjusted to affect the identity of the iodobismuthate anion (Eickmeier et al., 1999; Goforth, Peterson et al., 2005; Krautscheid, 1994).
While the vast majority of iodobismuthate materials known to date have contained an organic cation for charge balance, our group has recently demonstrated that a d-metal coordination cation is a viable charge-balancing species for iodobismuthate anions and that the use of such cations may lead to new iodobismuthate anions (Goforth, Gardinier et al., 2005; Goforth, 2005). Here, we report the synthesis and single-crystal X-ray structures of two co-crystallizing iodobismuthate compounds, one of which has a coordination cation for charge balance while the other has an organic counter-cation. Both compounds contain [Bi6I22]4- anions. However, the polyhedral arrangements of the six BiI6 octahedra in the two compounds differ.
The title compounds, [H(2,2'-bipy)]4[Bi6I22] {[H(2,2'-bipy)]+ is protonated 2,2'-bipyridine}, (I), and [Ru(2,2'-bipy)3]2[Bi6I22], (II), were synthesized solvothermally from RuI3, 2,2'-bipyridyl and BiI3 in aqueous ethanol (50% v/v) using a 1:3:3 molar ratio. Crystals of (I) were isolated as the major phase, and crystals of both (I) and (II) were characterized by single-crystal X-ray diffraction. The structure of (II) reveals that the compound contains a novel [Bi6I22]4- anion that has not previously been reported in iodobismuthate chemistry, and this anion is discussed in detail following the structure description of (I). Relevant bond distances and angles for the two compounds are presented in Tables 1 and 2. [Please clarify, as no values are flagged in the CIF for publication. Do you wish to add tables?]
Compund (I) crystallizes in the triclinic space group P1 and contains two crystallographically independent 2,2'-bipyridinium cations and a [Bi6I22]4- iodobismuthate anion in its asymmetric unit. For the structure solution, the 2,2'-bipyridinium cations were refined isotropically, due to disorder. Anisotropic refinement of the cations resulted in unreasonable ellipsoids for these atoms, most probably due to unresolved disorder in the form of the N atoms oriented in the opposite direction. N-atom positions were assigned based on the magnitude of the Uiso parameter, but are uncertain due to the disorder and probably represent only the major orientation. The position of the H atoms was not calculated or located. However, the H atom is necessary to maintain charge neutrality for the compound. The atoms of the [Bi6I22]4- anion were refined anisotropically. The centrosymmetric anion consists of six BiI6 octahedra, which are connected such that two sets of three trans edge-sharing octahedra share five cis edges (Fig. 1). The arrangement of the six BiI6 octahedra in (I) is a known arrangement of the [Bi6I22]4- anion. For example, the [Bi6I22]4- anions of [(THF)6Na]4[Bi6I22] (THF is tetrahydrofuran; Krautscheid, 1994), [EtMe2PhN]4[Bi6I22] (Eickmeier et al., 1999) and [H2TMDP]2[Bi6I22] {H2TMDP]2+ is 1,3-bis(4-piperidinium)propane; Goforth, Peterson et al., 2005} have the same polyhedral connectivity as the anion of (I), and the bond distances and angles of the anion of (I) are comparable with those determined for these compounds. The average terminal Bi—I distance in (I) is 2.8793 Å, the average Bi—µ2-I distance is 3.1491 Å and the average Bi—µ3-I distance is 3.3177 Å. The cis I—Bi—I angles in (I) range from 82.350 (13) to 100.270 (17)° and the trans I—Bi—I angles range from 163.460 (16) to 176.741 (16)°.
When the structure of compound (I) is viewed along [001] (Fig. 2), stacks of [H2,2'-bipy]+ cations and rows of [Bi6I22]4- anions are observed. Weak I···I bonding interactions between [Bi6I22]4- anions of neighboring rows are also observed [I3···I9i = 3.739 (1) Å and I8···I8ii = 3.732 (1) Å; symmetry codes: (i) x - 1, y + 1, z; (ii) -x, 1 - y, 1 - z; van der Waals radius of I = 1.98 Å, I···I = 3.96 Å; Bondi, 1964], and when these interactions are taken into account, the structure may be viewed as an array of weakly bonded inorganic chains, with organic cations situated above and below the chains.
Compound (II) crystallizes in the triclinic space group P1 and contains the well known tris-chelate cation [Ru(2,2'-bipy)3]2+ and a novel arrangement of the [Bi6I22]4- anion (Fig. 3). The bond distances and angles of the cation are normal [2.044 (6)–2.067 (6) Å; Biner et al., 1992]. Due to the crystallographic inversion symmetry in the crystal, both the Λ- and Δ- enantiomers of the cation are present in the structure.
The centrosymmetric [Bi6I22]4- anion of (II) consists of a central Bi4I16 core (containing atoms Bi1 and Bi2), with two BiI3 units (containing atom Bi3) connected to the core by three relatively long Bi—I bonds [3.3268 (6), 3.4311 (6) and 3.5484 (5) Å; Fig. 3). Alternatively, the BiI3 units can be considered as part of very distorted Bi(3)I6 octahedra, each of which shares two cis edges with the Bi4I16 cluster core. The bond lengths and angles of the Bi4I16 core are within the normal ranges and are comparable with those found in previously reported [Bi4I16]4- anions (Goforth, Gardinier et al., 2005). The average terminal Bi—I distance is 2.897 Å and the average Bi—µ2-I distance is 3.166 Å.
Considering the pendant BiI3 units of the anion, an unusual bonding feature of the anion of compound (II) is the presence of an essentially µ4-bridging iodide ligand. However, the average Bi—µ4-I distance of 3.397 Å is within the reported ranges for Bi—µ3-I distances in related compounds (Feldmann, 2003), further supporting the description of the anion as a Bi4I16 core with two pendant BiI3 groups. In fact, many of the larger known discrete iodobismuthate anions may be considered to be based on Bi4I16 cores, either joined with one or more pendant BiI3 units {as in [Bi5I19]4- (Krautscheid, 1994), or the typical arrangement of [Bi6I22]4- (Eickmeier et al., 1999; Pohl et al., 1994; Goforth, Peterson et al., 2005; Krautscheid et al., 1994)}, or connected to another such core through a single edge {as in [Bi8I30]6- (Feldmann, 2003)}. The cis I—Bi—I angles of the anion of (II) range from 78.39 (1) to 103.69 (2)° and the trans I—Bi—I angles from 159.65 (2) to 177.02 (2)°, where the largest deviations from the ideal octahedral angles are observed in the Bi3 polyhedron.
A [100] view of the crystal packing in compound (II) is shown in Fig. 4, where it can be seen that the discrete anions are arranged in layers which are interleaved by layers of the cations. As in compound (I), the discrete anions in (II) are close enough to one another in space that certain I atoms of neighboring anions are closer than the sum of their van der Waals radii (see above), thus leading to the formation of very weak I···I bonding interactions [I10···I3i = 3.834 (1) Å and I11···I7ii = 3.957 (1) Å; symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -x, 1 - y, z - 1]. When the I···I interactions are taken into consideration, the anionic component of the structure may be viewed as an array of weakly bonded two-dimensional sheets, which lie in the ac plane (Fig. 5). These pseudo-two-dimenional sheets may have an interesting consequence in terms of dimensionality-dependent optical properties, i.e. quantum confinement behavior, in that they serve to extend the dimensionality of the discrete anionic component (Ryan & Xu, 2004). Experiments aimed at isolating the phase-pure compound for optical measurements are in progress.
While it is reasonable to believe that compounds (I) and (II) contain anions of different polyhedral arrangements because they crystallize with different cations, it is also of interest to note that we have prepared another iodobismuthate compound, [Ru(2,2'-bipy)3]2[Bi4I16] (Goforth, Gardinier et al., 2005), which contains the same [Ru(2,2'-bipy)3]2+ cation as compound (II). However, [Ru(2,2'-bipy)3]2[Bi4I16] was synthesized from [Ru(2,2'-bipy)3]I2 tetrahydrate and BiI3, rather than from RuI3, BiI3, and 2,2'-bipyridine. Thus, it may be concluded that several reaction conditions, including choice of starting materials and nature of the counter-cation, simultaneously affect the identity of the iodobismuthate anion formed. The anion of [Ru(2,2'-bipy)3]2[Bi4I16] is the same as the Bi4I16 core in the [Bi6I22]4- anion of compound (II).