Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017339/ta1302sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017339/ta1302Isup2.hkl |
CCDC reference: 162543
For related literature, see: DeBord, Zhang, Haushalter, Zubieta & O'Connor (1996); Lin & Liu (2000); Liu et al. (2000); Wang et al. (1999); Yang et al. (1998); Zhang et al. (1996, 1997, 1999).
The hydrothermal synthesis of (I) was carried out in a 17 ml Teflon-lined stainless vessel with a ca 40% fill factor. A mixture of V2O5 (0.092 g), NiO (0.081 g), 2,2'-bipyridine (0.083 g) and H2O in the molar ratio of 1:1.2:1:778 was heated at 448 K for 72 h. Green plate crystals of (I) were formed in 25% yield based on V, contaminated by a small amount of unreacted NiO. The pH of the synthesis increased from 6.7 before heating to 7.5 at the end of reaction. Attempts to prepare (I) as a monophasic material were unsuccessful. Besides a series of characteristic bands of 2,2'-bipyridine in the region of 1100–1600 cm-1, the IR spectrum of (I) exhibits a strong band at 925 cm-1, which is attributed to ν(V—O).
All H atoms were fixed geometrically and allowed to ride on their parent C atoms, with C—H distances of 0.93 Å and with common isotropic displacement parameters (Uiso = 0.08 Å2).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1987); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1987); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL/PC (Sheldrick, 1990b); software used to prepare material for publication: SHELXL93.
[{Ni(C10H8N2)2}2{V6O17}] | F(000) = 1316 |
Mr = 1319.80 | Dx = 1.825 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 15.529 (3) Å | Cell parameters from 25 reflections |
b = 14.770 (3) Å | θ = 10–15° |
c = 10.477 (2) Å | µ = 1.96 mm−1 |
β = 92.02 (3)° | T = 294 K |
V = 2401.5 (8) Å3 | Plate, green |
Z = 2 | 0.60 × 0.40 × 0.15 mm |
Rigaku AFC-5R diffractometer | 3558 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 26.0°, θmin = 1.9° |
ω/2θ scans | h = −19→19 |
Absorption correction: ψ-scan (North et al., 1968) | k = −18→0 |
Tmin = 0.320, Tmax = 0.745 | l = 0→12 |
4798 measured reflections | 3 standard reflections every 150 reflections |
4718 independent reflections | intensity decay: 0.5% |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.7027P] where P = (Fo2 + 2Fc2)/3 |
4718 reflections | (Δ/σ)max = 0.001 |
331 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −0.76 e Å−3 |
[{Ni(C10H8N2)2}2{V6O17}] | V = 2401.5 (8) Å3 |
Mr = 1319.80 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.529 (3) Å | µ = 1.96 mm−1 |
b = 14.770 (3) Å | T = 294 K |
c = 10.477 (2) Å | 0.60 × 0.40 × 0.15 mm |
β = 92.02 (3)° |
Rigaku AFC-5R diffractometer | 3558 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.320, Tmax = 0.745 | 3 standard reflections every 150 reflections |
4798 measured reflections | intensity decay: 0.5% |
4718 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.83 e Å−3 |
4718 reflections | Δρmin = −0.76 e Å−3 |
331 parameters |
Experimental. crystal coated in epoxy glue |
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(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 | ||
Ni1 | 0.23327 (3) | 0.47906 (3) | 0.20088 (5) | 0.02628 (15) | |
V1 | 0.31294 (4) | 0.69860 (4) | 0.31442 (6) | 0.0246 (2) | |
V2 | 0.25034 (4) | 0.64316 (4) | 0.60422 (6) | 0.0288 (2) | |
V3 | 0.08534 (4) | 0.55778 (4) | 0.42474 (6) | 0.0271 (2) | |
O1 | 0.2776 (2) | 0.6022 (2) | 0.2578 (3) | 0.0473 (8) | |
O2 | 0.3049 (2) | 0.7001 (3) | 0.4861 (3) | 0.0527 (9) | |
O3 | 0.4132 (2) | 0.7112 (2) | 0.2835 (3) | 0.0464 (8) | |
O4 | 0.2499 (2) | 0.7895 (2) | 0.2419 (3) | 0.0466 (8) | |
O5 | 0.2988 (3) | 0.5513 (3) | 0.6370 (4) | 0.088 (2) | |
O6 | 0.1460 (2) | 0.6210 (3) | 0.5473 (3) | 0.0592 (10) | |
O7 | 0.1473 (2) | 0.4858 (2) | 0.3493 (3) | 0.0372 (7) | |
O8 | 0 | 1/2 | 1/2 | 0.0553 (14) | |
O9 | 0.0463 (2) | 0.6304 (2) | 0.3235 (3) | 0.0535 (9) | |
N1 | 0.3259 (2) | 0.4165 (2) | 0.3157 (3) | 0.0313 (7) | |
N2 | 0.3345 (2) | 0.4618 (2) | 0.0717 (3) | 0.0357 (8) | |
N3 | 0.1778 (2) | 0.3613 (2) | 0.1252 (3) | 0.0337 (7) | |
N4 | 0.1510 (2) | 0.5317 (2) | 0.0616 (3) | 0.0299 (7) | |
C1 | 0.3211 (3) | 0.4035 (3) | 0.4415 (4) | 0.0433 (10) | |
H1 | 0.2699 | 0.4165 | 0.4811 | 0.080* | |
C2 | 0.3907 (4) | 0.3710 (4) | 0.5147 (5) | 0.0586 (14) | |
H2 | 0.3855 | 0.3611 | 0.6018 | 0.080* | |
C3 | 0.4663 (4) | 0.3538 (4) | 0.4583 (5) | 0.064 (2) | |
H3 | 0.5136 | 0.3331 | 0.5069 | 0.080* | |
C4 | 0.4731 (3) | 0.3670 (4) | 0.3285 (5) | 0.0526 (13) | |
H4 | 0.5245 | 0.3560 | 0.2884 | 0.080* | |
C5 | 0.4643 (3) | 0.3788 (4) | 0.0436 (5) | 0.0505 (12) | |
H5 | 0.5082 | 0.3428 | 0.0789 | 0.080* | |
C6 | 0.4618 (4) | 0.3988 (4) | −0.0860 (5) | 0.0615 (15) | |
H6 | 0.5036 | 0.3765 | −0.1391 | 0.080* | |
C7 | 0.3965 (3) | 0.4523 (4) | −0.1335 (5) | 0.0557 (13) | |
H7 | 0.3940 | 0.4681 | −0.2195 | 0.080* | |
C8 | 0.3340 (3) | 0.4827 (3) | −0.0528 (4) | 0.0446 (11) | |
H8 | 0.2900 | 0.5192 | −0.0863 | 0.080* | |
C9 | 0.4008 (3) | 0.3971 (3) | 0.2599 (4) | 0.0356 (9) | |
C10 | 0.4008 (3) | 0.4129 (3) | 0.1197 (4) | 0.0368 (9) | |
C11 | 0.1891 (3) | 0.2775 (3) | 0.1681 (5) | 0.0467 (11) | |
H11 | 0.2221 | 0.2684 | 0.2428 | 0.080* | |
C12 | 0.1532 (4) | 0.2021 (3) | 0.1049 (5) | 0.0569 (14) | |
H12 | 0.1616 | 0.1441 | 0.1373 | 0.080* | |
C13 | 0.1054 (4) | 0.2160 (3) | −0.0056 (5) | 0.0566 (14) | |
H13 | 0.0814 | 0.1670 | −0.0498 | 0.080* | |
C14 | 0.0928 (3) | 0.3027 (3) | −0.0512 (5) | 0.0468 (12) | |
H14 | 0.0606 | 0.3127 | −0.1263 | 0.080* | |
C15 | 0.0738 (3) | 0.4967 (3) | −0.1330 (4) | 0.0436 (11) | |
H15 | 0.0512 | 0.4537 | −0.1897 | 0.080* | |
C16 | 0.0650 (3) | 0.5886 (4) | −0.1596 (4) | 0.0486 (12) | |
H16 | 0.0366 | 0.6076 | −0.2345 | 0.080* | |
C17 | 0.0982 (3) | 0.6505 (3) | −0.0750 (4) | 0.0406 (10) | |
H17 | 0.0922 | 0.7121 | −0.0912 | 0.080* | |
C18 | 0.1413 (3) | 0.6207 (3) | 0.0357 (4) | 0.0353 (9) | |
H18 | 0.1640 | 0.6631 | 0.0933 | 0.080* | |
C19 | 0.1290 (3) | 0.3750 (3) | 0.0164 (4) | 0.0332 (9) | |
C20 | 0.1164 (3) | 0.4704 (3) | −0.0217 (4) | 0.0327 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0314 (3) | 0.0207 (3) | 0.0267 (3) | 0.0019 (2) | −0.0001 (2) | −0.0008 (2) |
V1 | 0.0310 (3) | 0.0230 (3) | 0.0197 (3) | −0.0031 (3) | −0.0011 (2) | 0.0037 (2) |
V2 | 0.0424 (4) | 0.0238 (3) | 0.0200 (3) | 0.0003 (3) | −0.0025 (3) | 0.0001 (2) |
V3 | 0.0270 (3) | 0.0224 (3) | 0.0322 (4) | −0.0052 (2) | 0.0029 (3) | −0.0065 (3) |
O1 | 0.066 (2) | 0.026 (2) | 0.048 (2) | −0.0107 (15) | −0.021 (2) | 0.0023 (13) |
O2 | 0.063 (2) | 0.073 (2) | 0.0213 (14) | −0.022 (2) | 0.0015 (13) | 0.0039 (15) |
O3 | 0.037 (2) | 0.055 (2) | 0.047 (2) | −0.0057 (15) | 0.0055 (13) | 0.005 (2) |
O4 | 0.063 (2) | 0.044 (2) | 0.033 (2) | 0.022 (2) | 0.0058 (14) | 0.0092 (14) |
O5 | 0.148 (4) | 0.051 (2) | 0.062 (3) | 0.051 (3) | −0.027 (3) | −0.002 (2) |
O6 | 0.056 (2) | 0.078 (3) | 0.044 (2) | −0.027 (2) | 0.003 (2) | −0.026 (2) |
O7 | 0.039 (2) | 0.034 (2) | 0.039 (2) | 0.0061 (13) | 0.0074 (13) | −0.0023 (13) |
O8 | 0.042 (3) | 0.047 (3) | 0.078 (4) | −0.023 (2) | 0.029 (2) | −0.019 (3) |
O9 | 0.068 (2) | 0.036 (2) | 0.056 (2) | 0.013 (2) | −0.009 (2) | −0.004 (2) |
N1 | 0.040 (2) | 0.026 (2) | 0.027 (2) | 0.0061 (14) | −0.0013 (14) | 0.0000 (13) |
N2 | 0.035 (2) | 0.038 (2) | 0.034 (2) | 0.004 (2) | 0.0004 (14) | 0.0025 (15) |
N3 | 0.041 (2) | 0.023 (2) | 0.037 (2) | −0.0036 (14) | 0.0059 (15) | −0.0043 (14) |
N4 | 0.030 (2) | 0.027 (2) | 0.032 (2) | 0.0016 (13) | −0.0036 (13) | −0.0025 (13) |
C1 | 0.059 (3) | 0.041 (2) | 0.031 (2) | 0.009 (2) | 0.002 (2) | 0.001 (2) |
C2 | 0.085 (4) | 0.057 (3) | 0.033 (2) | 0.016 (3) | −0.013 (2) | 0.003 (2) |
C3 | 0.067 (4) | 0.068 (4) | 0.056 (3) | 0.029 (3) | −0.024 (3) | 0.002 (3) |
C4 | 0.045 (3) | 0.059 (3) | 0.054 (3) | 0.021 (2) | −0.006 (2) | 0.001 (2) |
C5 | 0.047 (3) | 0.057 (3) | 0.048 (3) | 0.018 (2) | 0.006 (2) | 0.000 (2) |
C6 | 0.070 (4) | 0.066 (4) | 0.049 (3) | 0.014 (3) | 0.021 (3) | −0.008 (3) |
C7 | 0.059 (3) | 0.074 (4) | 0.035 (2) | 0.006 (3) | 0.009 (2) | 0.000 (2) |
C8 | 0.050 (3) | 0.052 (3) | 0.032 (2) | 0.002 (2) | 0.009 (2) | 0.008 (2) |
C9 | 0.041 (2) | 0.031 (2) | 0.034 (2) | 0.011 (2) | −0.007 (2) | −0.002 (2) |
C10 | 0.036 (2) | 0.036 (2) | 0.038 (2) | 0.006 (2) | 0.004 (2) | −0.001 (2) |
C11 | 0.064 (3) | 0.029 (2) | 0.048 (3) | −0.002 (2) | 0.016 (2) | 0.000 (2) |
C12 | 0.085 (4) | 0.025 (2) | 0.062 (3) | −0.010 (2) | 0.025 (3) | −0.005 (2) |
C13 | 0.073 (4) | 0.037 (3) | 0.062 (3) | −0.019 (3) | 0.018 (3) | −0.021 (2) |
C14 | 0.048 (3) | 0.042 (3) | 0.051 (3) | −0.009 (2) | 0.006 (2) | −0.021 (2) |
C15 | 0.047 (3) | 0.054 (3) | 0.030 (2) | 0.001 (2) | −0.005 (2) | −0.009 (2) |
C16 | 0.047 (3) | 0.066 (3) | 0.032 (2) | 0.008 (2) | −0.004 (2) | 0.008 (2) |
C17 | 0.044 (2) | 0.038 (2) | 0.041 (2) | 0.002 (2) | 0.003 (2) | 0.009 (2) |
C18 | 0.038 (2) | 0.027 (2) | 0.040 (2) | −0.001 (2) | −0.003 (2) | 0.003 (2) |
C19 | 0.034 (2) | 0.031 (2) | 0.035 (2) | −0.006 (2) | 0.007 (2) | −0.011 (2) |
C20 | 0.032 (2) | 0.037 (2) | 0.029 (2) | −0.003 (2) | 0.001 (2) | −0.007 (2) |
Ni1—O1 | 2.027 (3) | C2—H2 | 0.93 |
Ni1—N4 | 2.057 (3) | C3—C4 | 1.381 (7) |
Ni1—N1 | 2.060 (3) | C3—H3 | 0.93 |
Ni1—N3 | 2.085 (3) | C4—C9 | 1.385 (6) |
Ni1—O7 | 2.087 (3) | C4—H4 | 0.93 |
Ni1—N2 | 2.125 (4) | C5—C10 | 1.385 (6) |
V1—O3 | 1.612 (3) | C5—C6 | 1.389 (7) |
V1—O1 | 1.630 (3) | C5—H5 | 0.93 |
V1—O2 | 1.808 (3) | C6—C7 | 1.365 (8) |
V1—O4 | 1.814 (3) | C6—H6 | 0.93 |
V2—O5 | 1.584 (4) | C7—C8 | 1.384 (7) |
V2—O6 | 1.738 (3) | C7—H7 | 0.93 |
V2—O2 | 1.740 (3) | C8—H8 | 0.93 |
V2—O4i | 1.752 (3) | C9—C10 | 1.487 (6) |
V3—O9 | 1.612 (3) | C11—C12 | 1.400 (7) |
V3—O7 | 1.654 (3) | C11—H11 | 0.93 |
V3—O8 | 1.7833 (7) | C12—C13 | 1.369 (8) |
V3—O6 | 1.822 (3) | C12—H12 | 0.93 |
O4—V2ii | 1.752 (3) | C13—C14 | 1.378 (7) |
O8—V3iii | 1.7833 (7) | C13—H13 | 0.93 |
N1—C1 | 1.337 (5) | C14—C19 | 1.388 (6) |
N1—C9 | 1.351 (5) | C14—H14 | 0.93 |
N2—C8 | 1.340 (6) | C15—C20 | 1.377 (6) |
N2—C10 | 1.341 (5) | C15—C16 | 1.391 (7) |
N3—C11 | 1.327 (5) | C15—H15 | 0.93 |
N3—C19 | 1.361 (5) | C16—C17 | 1.362 (7) |
N4—C18 | 1.350 (5) | C16—H16 | 0.93 |
N4—C20 | 1.355 (5) | C17—C18 | 1.389 (6) |
C1—C2 | 1.388 (7) | C17—H17 | 0.93 |
C1—H1 | 0.93 | C18—H18 | 0.93 |
C2—C3 | 1.358 (8) | C19—C20 | 1.476 (6) |
O1—Ni1—N4 | 93.77 (12) | C1—C2—H2 | 120 |
O1—Ni1—N1 | 90.42 (13) | C2—C3—C4 | 120.0 (5) |
N4—Ni1—N1 | 170.52 (13) | C2—C3—H3 | 120 |
O1—Ni1—N3 | 172.68 (13) | C4—C3—H3 | 120 |
N4—Ni1—N3 | 78.90 (13) | C3—C4—C9 | 117.9 (5) |
N1—Ni1—N3 | 96.81 (13) | C3—C4—H4 | 121 |
O1—Ni1—O7 | 87.59 (13) | C9—C4—H4 | 121 |
N4—Ni1—O7 | 96.49 (13) | C10—C5—C6 | 119.3 (5) |
N1—Ni1—O7 | 92.18 (12) | C10—C5—H5 | 120 |
N3—Ni1—O7 | 93.24 (12) | C6—C5—H5 | 120 |
O1—Ni1—N2 | 92.52 (14) | C7—C6—C5 | 118.3 (5) |
N4—Ni1—N2 | 92.76 (13) | C7—C6—H6 | 121 |
N1—Ni1—N2 | 78.55 (13) | C5—C6—H6 | 121 |
N3—Ni1—N2 | 87.83 (14) | C6—C7—C8 | 119.5 (5) |
O7—Ni1—N2 | 170.72 (13) | C6—C7—H7 | 120 |
O3—V1—O1 | 110.0 (2) | C8—C7—H7 | 120 |
O3—V1—O2 | 107.4 (2) | N2—C8—C7 | 122.7 (5) |
O1—V1—O2 | 109.8 (2) | N2—C8—H8 | 119 |
O3—V1—O4 | 110.0 (2) | C7—C8—H8 | 119 |
O1—V1—O4 | 108.9 (2) | N1—C9—C4 | 122.5 (4) |
O2—V1—O4 | 110.6 (2) | N1—C9—C10 | 115.1 (3) |
O5—V2—O6 | 110.1 (2) | C4—C9—C10 | 122.3 (4) |
O5—V2—O2 | 109.2 (2) | N2—C10—C5 | 122.2 (4) |
O6—V2—O2 | 108.5 (2) | N2—C10—C9 | 115.3 (4) |
O5—V2—O4i | 108.9 (2) | C5—C10—C9 | 122.4 (4) |
O6—V2—O4i | 111.0 (2) | N3—C11—C12 | 122.4 (5) |
O2—V2—O4i | 109.1 (2) | N3—C11—H11 | 119 |
O9—V3—O7 | 109.0 (2) | C12—C11—H11 | 119 |
O9—V3—O8 | 109.95 (14) | C13—C12—C11 | 118.4 (5) |
O7—V3—O8 | 110.95 (11) | C13—C12—H12 | 121 |
O9—V3—O6 | 107.2 (2) | C11—C12—H12 | 121 |
O7—V3—O6 | 111.8 (2) | C12—C13—C14 | 119.8 (4) |
O8—V3—O6 | 107.90 (11) | C12—C13—H13 | 120 |
V1—O1—Ni1 | 175.8 (2) | C14—C13—H13 | 120 |
V2—O2—V1 | 138.9 (2) | C13—C14—C19 | 119.2 (5) |
V2ii—O4—V1 | 138.4 (2) | C13—C14—H14 | 120 |
V2—O6—V3 | 142.3 (2) | C19—C14—H14 | 120 |
V3—O7—Ni1 | 141.7 (2) | C20—C15—C16 | 119.1 (4) |
V3iii—O8—V3 | 180.0 | C20—C15—H15 | 121 |
C1—N1—C9 | 118.3 (4) | C16—C15—H15 | 121 |
C1—N1—Ni1 | 125.4 (3) | C17—C16—C15 | 119.5 (4) |
C9—N1—Ni1 | 115.9 (3) | C17—C16—H16 | 120 |
C8—N2—C10 | 117.8 (4) | C15—C16—H16 | 120 |
C8—N2—Ni1 | 127.9 (3) | C16—C17—C18 | 119.4 (4) |
C10—N2—Ni1 | 113.6 (3) | C16—C17—H17 | 120 |
C11—N3—C19 | 119.0 (4) | C18—C17—H17 | 120 |
C11—N3—Ni1 | 127.0 (3) | N4—C18—C17 | 121.6 (4) |
C19—N3—Ni1 | 113.9 (3) | N4—C18—H18 | 119 |
C18—N4—C20 | 118.8 (4) | C17—C18—H18 | 119 |
C18—N4—Ni1 | 124.9 (3) | N3—C19—C14 | 121.1 (4) |
C20—N4—Ni1 | 115.2 (3) | N3—C19—C20 | 115.6 (3) |
N1—C1—C2 | 121.8 (4) | C14—C19—C20 | 123.3 (4) |
N1—C1—H1 | 119 | N4—C20—C15 | 121.6 (4) |
C2—C1—H1 | 119 | N4—C20—C19 | 114.7 (3) |
C3—C2—C1 | 119.5 (5) | C15—C20—C19 | 123.7 (4) |
C3—C2—H2 | 120 | ||
O3—V1—O1—Ni1 | 110 (3) | N2—Ni1—N3—C19 | −83.9 (3) |
O2—V1—O1—Ni1 | −8 (3) | O1—Ni1—N4—C18 | −0.2 (3) |
O4—V1—O1—Ni1 | −130 (3) | N1—Ni1—N4—C18 | −116.3 (8) |
N4—Ni1—O1—V1 | 138 (3) | N3—Ni1—N4—C18 | 179.9 (4) |
N1—Ni1—O1—V1 | −50 (3) | O7—Ni1—N4—C18 | 87.8 (3) |
N3—Ni1—O1—V1 | 139 (2) | N2—Ni1—N4—C18 | −92.9 (3) |
O7—Ni1—O1—V1 | 42 (3) | O1—Ni1—N4—C20 | 168.2 (3) |
N2—Ni1—O1—V1 | −129 (3) | N1—Ni1—N4—C20 | 52.1 (9) |
O5—V2—O2—V1 | 81.5 (4) | N3—Ni1—N4—C20 | −11.7 (3) |
O6—V2—O2—V1 | −38.5 (4) | O7—Ni1—N4—C20 | −103.8 (3) |
O4i—V2—O2—V1 | −159.6 (3) | N2—Ni1—N4—C20 | 75.5 (3) |
O3—V1—O2—V2 | −138.6 (3) | C9—N1—C1—C2 | 0.1 (7) |
O1—V1—O2—V2 | −18.9 (4) | Ni1—N1—C1—C2 | −171.8 (4) |
O4—V1—O2—V2 | 101.3 (4) | N1—C1—C2—C3 | 1.5 (8) |
O3—V1—O4—V2ii | 33.9 (4) | C1—C2—C3—C4 | −1.2 (9) |
O1—V1—O4—V2ii | −86.8 (3) | C2—C3—C4—C9 | −0.5 (9) |
O2—V1—O4—V2ii | 152.5 (3) | C10—C5—C6—C7 | 0.3 (9) |
O5—V2—O6—V3 | −55.3 (4) | C5—C6—C7—C8 | −1.6 (9) |
O2—V2—O6—V3 | 64.2 (4) | C10—N2—C8—C7 | 3.3 (7) |
O4i—V2—O6—V3 | −175.9 (3) | Ni1—N2—C8—C7 | −166.6 (4) |
O9—V3—O6—V2 | −109.1 (4) | C6—C7—C8—N2 | −0.2 (8) |
O7—V3—O6—V2 | 10.3 (4) | C1—N1—C9—C4 | −2.0 (7) |
O8—V3—O6—V2 | 132.6 (4) | Ni1—N1—C9—C4 | 170.7 (4) |
O9—V3—O7—Ni1 | 35.3 (3) | C1—N1—C9—C10 | 179.6 (4) |
O8—V3—O7—Ni1 | 156.6 (2) | Ni1—N1—C9—C10 | −7.7 (5) |
O6—V3—O7—Ni1 | −83.0 (3) | C3—C4—C9—N1 | 2.2 (8) |
O1—Ni1—O7—V3 | 38.1 (3) | C3—C4—C9—C10 | −179.5 (5) |
N4—Ni1—O7—V3 | −55.4 (3) | C8—N2—C10—C5 | −4.6 (7) |
N1—Ni1—O7—V3 | 128.4 (3) | Ni1—N2—C10—C5 | 166.7 (4) |
N3—Ni1—O7—V3 | −134.6 (3) | C8—N2—C10—C9 | 176.0 (4) |
N2—Ni1—O7—V3 | 129.0 (7) | Ni1—N2—C10—C9 | −12.7 (5) |
O9—V3—O8—V3iii | −14.100 | C6—C5—C10—N2 | 2.9 (8) |
O7—V3—O8—V3iii | −134.100 | C6—C5—C10—C9 | −177.7 (5) |
O6—V3—O8—V3iii | 103.100 | N1—C9—C10—N2 | 13.7 (6) |
O1—Ni1—N1—C1 | 80.5 (4) | C4—C9—C10—N2 | −164.6 (4) |
N4—Ni1—N1—C1 | −163.2 (7) | N1—C9—C10—C5 | −165.7 (4) |
N3—Ni1—N1—C1 | −100.6 (4) | C4—C9—C10—C5 | 15.9 (7) |
O7—Ni1—N1—C1 | −7.1 (4) | C19—N3—C11—C12 | 0.6 (7) |
N2—Ni1—N1—C1 | 173.0 (4) | Ni1—N3—C11—C12 | −175.6 (3) |
O1—Ni1—N1—C9 | −91.6 (3) | N3—C11—C12—C13 | 0.6 (8) |
N4—Ni1—N1—C9 | 24.7 (10) | C11—C12—C13—C14 | −0.7 (8) |
N3—Ni1—N1—C9 | 87.2 (3) | C12—C13—C14—C19 | −0.2 (7) |
O7—Ni1—N1—C9 | −179.2 (3) | C20—C15—C16—C17 | −0.3 (7) |
N2—Ni1—N1—C9 | 0.8 (3) | C15—C16—C17—C18 | 0.8 (7) |
O1—Ni1—N2—C8 | −93.1 (4) | C20—N4—C18—C17 | −1.2 (6) |
N4—Ni1—N2—C8 | 0.8 (4) | Ni1—N4—C18—C17 | 166.8 (3) |
N1—Ni1—N2—C8 | 177.0 (4) | C16—C17—C18—N4 | 0.0 (7) |
N3—Ni1—N2—C8 | 79.6 (4) | C11—N3—C19—C14 | −1.5 (6) |
O7—Ni1—N2—C8 | 176.4 (7) | Ni1—N3—C19—C14 | 175.2 (3) |
O1—Ni1—N2—C10 | 96.7 (3) | C11—N3—C19—C20 | 177.4 (4) |
N4—Ni1—N2—C10 | −169.4 (3) | Ni1—N3—C19—C20 | −5.9 (4) |
N1—Ni1—N2—C10 | 6.8 (3) | C13—C14—C19—N3 | 1.3 (7) |
N3—Ni1—N2—C10 | −90.6 (3) | C13—C14—C19—C20 | −177.5 (4) |
O7—Ni1—N2—C10 | 6.2 (10) | C18—N4—C20—C15 | 1.7 (6) |
O1—Ni1—N3—C11 | −174.6 (10) | Ni1—N4—C20—C15 | −167.5 (3) |
N4—Ni1—N3—C11 | −174.3 (4) | C18—N4—C20—C19 | −178.8 (3) |
N1—Ni1—N3—C11 | 14.3 (4) | Ni1—N4—C20—C19 | 12.0 (4) |
O7—Ni1—N3—C11 | −78.3 (4) | C16—C15—C20—N4 | −0.9 (7) |
N2—Ni1—N3—C11 | 92.5 (4) | C16—C15—C20—C19 | 179.6 (4) |
O1—Ni1—N3—C19 | 9.0 (13) | N3—C19—C20—N4 | −3.9 (5) |
N4—Ni1—N3—C19 | 9.4 (3) | C14—C19—C20—N4 | 175.0 (4) |
N1—Ni1—N3—C19 | −162.1 (3) | N3—C19—C20—C15 | 175.6 (4) |
O7—Ni1—N3—C19 | 105.3 (3) | C14—C19—C20—C15 | −5.5 (7) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [{Ni(C10H8N2)2}2{V6O17}] |
Mr | 1319.80 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 15.529 (3), 14.770 (3), 10.477 (2) |
β (°) | 92.02 (3) |
V (Å3) | 2401.5 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.60 × 0.40 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.320, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4798, 4718, 3558 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.115, 1.05 |
No. of reflections | 4718 |
No. of parameters | 331 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.76 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1987), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1987), SHELXS86 (Sheldrick, 1990a), SHELXL93 (Sheldrick, 1993), SHELXTL/PC (Sheldrick, 1990b), SHELXL93.
Ni1—O1 | 2.027 (3) | V1—O4 | 1.814 (3) |
Ni1—N4 | 2.057 (3) | V2—O5 | 1.584 (4) |
Ni1—N1 | 2.060 (3) | V2—O6 | 1.738 (3) |
Ni1—N3 | 2.085 (3) | V2—O2 | 1.740 (3) |
Ni1—O7 | 2.087 (3) | V2—O4i | 1.752 (3) |
Ni1—N2 | 2.125 (4) | V3—O9 | 1.612 (3) |
V1—O3 | 1.612 (3) | V3—O7 | 1.654 (3) |
V1—O1 | 1.630 (3) | V3—O8 | 1.7833 (7) |
V1—O2 | 1.808 (3) | V3—O6 | 1.822 (3) |
O1—Ni1—N4 | 93.77 (12) | O1—V1—O2 | 109.8 (2) |
O1—Ni1—N1 | 90.42 (13) | O3—V1—O4 | 110.0 (2) |
N4—Ni1—N1 | 170.52 (13) | O1—V1—O4 | 108.9 (2) |
O1—Ni1—N3 | 172.68 (13) | O2—V1—O4 | 110.6 (2) |
N4—Ni1—N3 | 78.90 (13) | O5—V2—O6 | 110.1 (2) |
N1—Ni1—N3 | 96.81 (13) | O5—V2—O2 | 109.2 (2) |
O1—Ni1—O7 | 87.59 (13) | O6—V2—O2 | 108.5 (2) |
N4—Ni1—O7 | 96.49 (13) | O5—V2—O4i | 108.9 (2) |
N1—Ni1—O7 | 92.18 (12) | O6—V2—O4i | 111.0 (2) |
N3—Ni1—O7 | 93.24 (12) | O2—V2—O4i | 109.1 (2) |
O1—Ni1—N2 | 92.52 (14) | O9—V3—O7 | 109.0 (2) |
N4—Ni1—N2 | 92.76 (13) | O9—V3—O8 | 109.95 (14) |
N1—Ni1—N2 | 78.55 (13) | O7—V3—O8 | 110.95 (11) |
N3—Ni1—N2 | 87.83 (14) | O9—V3—O6 | 107.2 (2) |
O7—Ni1—N2 | 170.72 (13) | O7—V3—O6 | 111.8 (2) |
O3—V1—O1 | 110.0 (2) | O8—V3—O6 | 107.90 (11) |
O3—V1—O2 | 107.4 (2) |
Symmetry code: (i) x, −y+3/2, z+1/2. |
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Recently, it has been demonstrated that the hydrothermal technique is an effective approach to the synthesis of vanadium oxides incorporating complex cations, such as [Zn(bipy)2]2[V4O12] and [Zn(bipy)3]2[V4O12].11H2O (bipy is 2,2'-bipyridine; Zhang et al., 1997), [Ni(bipy)3]2[V4O12].11H2O (Yang et al., 1998), [Cu(en)][V2O6] and [Cu(bipy)2]2[V2O6] (en is ethylenediamine; DeBord et al., 1996), [Ni(en)3][V2O6] (Liu et al., 2000), [M(en)2][V6O14] (M is Cu or Zn), [Zn(bipy)2]2[V6O17] and [Cu(en)2]2[V10O25] (Zhang et al., 1996), [N(CH3)4]2[Co(H2O)4V12O28] (Wang et al., 1999) and [Cd(1,2-pn)2][V8O20] (1,2-pn is 1,2-diamopropane; Zhang et al., 1999). The present work reports the crystal structure of a new compound, [Ni(bipy)2]2[V6O17], (I), built from sinusoidal vanadium oxide layers, [V6O17]4-, and complex nickel(II) cations, [Ni(bipy)2]2+. \sch
Compound (I) is isostructural with the recently reported compound [Zn(bipy)2]2[V6O17] (Zhang et al., 1996). The crystal structure of (I) is depicted in Fig. 1. The vanadium oxide layers are constructed solely from VO4 tetrahedra by sharing corners and clearly display a sinusoidal ruffling, with an amplitude of about 6.5 Å and a period of about 14.8 Å. The [Ni(bipy)2]2+ complex cations occupy the interlamellar space and attach to the vanadium oxide layers through Ni—O covalent interactions, with distances of 2.027 (3) and 2.087 (3) Å.
A view perpendicular to the vanadium oxide layers is shown in Fig. 2. Along with one unshared terminal O atom, the other three O atoms of each tetrahedron around V2 and two O atoms of each V1 and V3 unit are shared between neighboring tetrahedra, forming an extended two-dimensional pore network. These pores, consisting of fourteen-membered polyhedral rings, lie alternately in planes approximately parallel to (110) and (110), with a transannular V···V distance of about 10 Å. Atoms O1 from the V1 tetrahedron and O7 from the V3 tetrahedron are coordinated to Ni atoms (Fig. 3). The octahedral geometry of each NiII is defined by four N atoms from two 2,2'-bipyridine ligands and two cis-oxo groups from a vanadium oxide layer. Two {Ni(bipy)2O2} motifs are bonded to each V14 ring, on either side of the 1 site in the centre of the ring. The organic ligands protrude above and below the mean plane of the V14 rings and fill the troughs of the ruffled vanadium oxide layers (Fig. 1).
The vanadium oxide layer structure in [M(bipy)2]2[V6O17] (M is Ni or Zn) is a very rare topology, where the pore size in the Ni compound, defined by the transannular V···V distance along the c axis, is slightly smaller than that in the Zn compound. It is interesting that the coordination of the O atoms from the vanadium oxide layers to the M atoms in these two compounds is different from that in other layered vanadium oxides incorporating six-coordinated interlamellar cations, namely [M(en)2][V6O14] (M is Cu or Zn) and [Cu(en)2][V10O25] (Zhang et al., 1996), and [Ni(en)2][V6O14] (Lin & Liu, 2000). In the structures of the latter compounds, the two oxo groups come from the two neighbouring layers and are covalently connected to each M atom in a trans fashion, forming a three-dimensional framework. In contrast, in (I) the two cis-oxo groups around each Ni atom come from a single vanadium oxide layer, maintaining the two-dimensional network structure.