Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100019132/gg1035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019132/gg1035Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019132/gg1035IIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270100019132/gg1035sup4.pdf |
CCDC references: 162549; 162550
(NH4)2Ce(NO3)6 (2.0 g, 3.6 mmol) in acetonitrile (180 ml) was added to VIVO(salen) (1.0 g, 3 mmol) in acetonitrile (90 ml). The volume was reduced to 90 ml by means of a rotary evaporator. The crude product was filtered and then dissolved in 1.5 M nitric acid (90 ml), from which dark violet crystals of the two polymorphs, (I) and (II), were obtained after 24 h (yield 0.7 g, 1.7 mmol). IR spectra (KBr): ν(V═O) 965, 972 cm-1.
The H atoms of the water molecules were obtained from a difference map. For (I), these coordinates and an isotropic displacement parameter were refined; for (II), the H-atom coordinates were kept fixed at the observed positions. For both structures, the H atoms of the ligand were constrained to have C—H = 0.95 Å and Uiso = 1.2Ueq of the parent atom. The weighting scheme employed was w = 1/[σcs(F)]2, where = σcs(F) = [σcs(F2) + 1.03 F2]1/2 - |F|, i.e σcs(F) = σcs(F2)/2 F for large F and small σcs(F2), and σcs(F) = [σcs(F2)]1/2 for small F2.
For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Busing et al., 1962) and KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.
[VO(C16H14N2O2)(H2O)]·NO3 | Z = 2 |
Mr = 413.28 | F(000) = 424 |
Triclinic, P1 | Dx = 1.582 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.663 (2) Å | Cell parameters from 4080 reflections |
b = 8.956 (2) Å | θ = 2.7–29.8° |
c = 13.293 (3) Å | µ = 0.62 mm−1 |
α = 73.029 (3)° | T = 120 K |
β = 83.852 (4)° | Plate, dark violet |
γ = 61.662 (3)° | 0.40 × 0.23 × 0.10 mm |
V = 867.7 (3) Å3 |
Siemens SMART CCD diffractometer | 4960 independent reflections |
Radiation source: X-ray tube | 3763 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.082 |
ω rotation scans | θmax = 29.8°, θmin = 2.7° |
Absorption correction: integration (XPREP; Siemens, 1995) | h = −11→11 |
Tmin = 0.765, Tmax = 0.943 | k = −12→12 |
16803 measured reflections | l = −18→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.042 | Weighting scheme based on measured s.u.'s |
S = 1.33 | (Δ/σ)max < 0.001 |
3763 reflections | Δρmax = 0.49 (7) e Å−3 |
252 parameters | Δρmin = −0.52 (7) e Å−3 |
[VO(C16H14N2O2)(H2O)]·NO3 | γ = 61.662 (3)° |
Mr = 413.28 | V = 867.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.663 (2) Å | Mo Kα radiation |
b = 8.956 (2) Å | µ = 0.62 mm−1 |
c = 13.293 (3) Å | T = 120 K |
α = 73.029 (3)° | 0.40 × 0.23 × 0.10 mm |
β = 83.852 (4)° |
Siemens SMART CCD diffractometer | 4960 independent reflections |
Absorption correction: integration (XPREP; Siemens, 1995) | 3763 reflections with I > 3σ(I) |
Tmin = 0.765, Tmax = 0.943 | Rint = 0.082 |
16803 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.33 | Δρmax = 0.49 (7) e Å−3 |
3763 reflections | Δρmin = −0.52 (7) e Å−3 |
252 parameters |
x | y | z | Uiso*/Ueq | ||
V | 0.36830 (4) | 0.30276 (4) | 0.21034 (2) | 0.0165 (2) | |
O1 | 0.3522 (2) | 0.1617 (2) | 0.1415 (1) | 0.0235 (9) | |
O2 | 0.5850 (2) | 0.2938 (2) | 0.1859 (1) | 0.0200 (9) | |
O3 | 0.2470 (2) | 0.4954 (2) | 0.1367 (1) | 0.0241 (9) | |
O4 | 0.5271 (2) | 0.0478 (2) | 0.3332 (1) | 0.0227 (9) | |
O5 | 0.5994 (2) | 0.1776 (2) | 0.5547 (1) | 0.0264 (10) | |
O6 | 0.7903 (2) | 0.2631 (2) | 0.4827 (1) | 0.0346 (12) | |
O7 | 0.7816 (2) | 0.0478 (2) | 0.4440 (1) | 0.0329 (11) | |
N1 | 0.1604 (2) | 0.2805 (2) | 0.2995 (1) | 0.0190 (10) | |
N2 | 0.3586 (2) | 0.4078 (2) | 0.3338 (1) | 0.0171 (10) | |
N3 | 0.7249 (2) | 0.1628 (2) | 0.4940 (1) | 0.0205 (10) | |
C1 | 0.2618 (2) | 0.0723 (2) | 0.1466 (1) | 0.0179 (11) | |
C2 | 0.2916 (2) | −0.0217 (2) | 0.0724 (1) | 0.0205 (12) | |
C3 | 0.2012 (2) | −0.1169 (2) | 0.0784 (1) | 0.0249 (13) | |
C4 | 0.0813 (3) | −0.1199 (2) | 0.1567 (2) | 0.0286 (14) | |
C5 | 0.0482 (2) | −0.0243 (2) | 0.2287 (2) | 0.0253 (13) | |
C6 | 0.1384 (2) | 0.0734 (2) | 0.2243 (1) | 0.0190 (11) | |
C7 | 0.0915 (2) | 0.1812 (2) | 0.2966 (1) | 0.0198 (12) | |
C8 | 0.0885 (2) | 0.3925 (2) | 0.3731 (1) | 0.0237 (13) | |
C9 | 0.2454 (2) | 0.3836 (2) | 0.4211 (1) | 0.0213 (12) | |
C10 | 0.4340 (2) | 0.5033 (2) | 0.3317 (1) | 0.0174 (11) | |
C11 | 0.5546 (2) | 0.5277 (2) | 0.2528 (1) | 0.0168 (11) | |
C12 | 0.6081 (2) | 0.6554 (2) | 0.2495 (1) | 0.0196 (12) | |
C13 | 0.7261 (2) | 0.6808 (2) | 0.1771 (1) | 0.0224 (12) | |
C14 | 0.7979 (2) | 0.5750 (2) | 0.1078 (1) | 0.0226 (12) | |
C15 | 0.7517 (2) | 0.4446 (2) | 0.1108 (1) | 0.0208 (12) | |
C16 | 0.6282 (2) | 0.4219 (2) | 0.1819 (1) | 0.0170 (11) | |
HO4a | 0.608 (3) | 0.044 (3) | 0.372 (2) | 0.032 (6)* | |
HO4b | 0.490 (4) | −0.010 (3) | 0.372 (2) | 0.055 (8)* | |
H2 | 0.3728 | −0.0201 | 0.0186 | 0.0245* | |
H3 | 0.2215 | −0.1810 | 0.0285 | 0.0299* | |
H4 | 0.0221 | −0.1875 | 0.1606 | 0.0343* | |
H5 | −0.0354 | −0.0246 | 0.2812 | 0.0304* | |
H7 | 0.0038 | 0.1787 | 0.3455 | 0.0238* | |
H8a | 0.0266 | 0.3486 | 0.4265 | 0.0284* | |
H8b | 0.0118 | 0.5107 | 0.3361 | 0.0284* | |
H9a | 0.2074 | 0.4747 | 0.4549 | 0.0255* | |
H9b | 0.3074 | 0.2723 | 0.4708 | 0.0255* | |
H10 | 0.4084 | 0.5612 | 0.3855 | 0.0209* | |
H12 | 0.5621 | 0.7250 | 0.2978 | 0.0235* | |
H13 | 0.7583 | 0.7696 | 0.1743 | 0.0269* | |
H14 | 0.8794 | 0.5923 | 0.0581 | 0.0271* | |
H15 | 0.8037 | 0.3714 | 0.0647 | 0.0250* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V | 0.0199 (2) | 0.0205 (2) | 0.0165 (1) | −0.0144 (1) | 0.0041 (1) | −0.0079 (1) |
O1 | 0.0295 (7) | 0.0323 (7) | 0.0249 (6) | −0.0245 (6) | 0.0097 (5) | −0.0157 (5) |
O2 | 0.0233 (7) | 0.0221 (6) | 0.0231 (6) | −0.0164 (5) | 0.0065 (5) | −0.0098 (5) |
O3 | 0.0298 (7) | 0.0255 (7) | 0.0200 (6) | −0.0148 (6) | −0.0003 (5) | −0.0066 (5) |
O4 | 0.0258 (7) | 0.0217 (7) | 0.0263 (7) | −0.0164 (6) | 0.0026 (6) | −0.0053 (5) |
O5 | 0.0274 (7) | 0.0313 (7) | 0.0276 (7) | −0.0208 (6) | 0.0118 (6) | −0.0093 (6) |
O6 | 0.0347 (8) | 0.0397 (8) | 0.0463 (9) | −0.0301 (7) | 0.0136 (7) | −0.0170 (7) |
O7 | 0.0281 (8) | 0.0387 (8) | 0.0393 (8) | −0.0144 (7) | 0.0051 (6) | −0.0245 (7) |
N1 | 0.0180 (7) | 0.0221 (7) | 0.0207 (7) | −0.0109 (6) | 0.0023 (6) | −0.0090 (6) |
N2 | 0.0171 (7) | 0.0207 (7) | 0.0165 (7) | −0.0113 (6) | 0.0024 (5) | −0.0055 (5) |
N3 | 0.0207 (8) | 0.0240 (8) | 0.0194 (7) | −0.0129 (6) | 0.0004 (6) | −0.0048 (6) |
C1 | 0.0198 (9) | 0.0175 (8) | 0.0199 (8) | −0.0118 (7) | −0.0031 (7) | −0.0030 (6) |
C2 | 0.0211 (9) | 0.0214 (8) | 0.0223 (8) | −0.0121 (7) | −0.0004 (7) | −0.0064 (7) |
C3 | 0.0266 (10) | 0.0227 (9) | 0.0316 (10) | −0.0137 (8) | −0.0015 (8) | −0.0113 (8) |
C4 | 0.0256 (10) | 0.0271 (10) | 0.0445 (12) | −0.0189 (8) | 0.0027 (8) | −0.0144 (9) |
C5 | 0.0210 (9) | 0.0247 (9) | 0.0361 (10) | −0.0153 (8) | 0.0053 (8) | −0.0098 (8) |
C6 | 0.0171 (8) | 0.0175 (8) | 0.0244 (9) | −0.0095 (7) | −0.0013 (7) | −0.0052 (7) |
C7 | 0.0169 (9) | 0.0224 (8) | 0.0228 (8) | −0.0114 (7) | 0.0014 (7) | −0.0062 (7) |
C8 | 0.0212 (9) | 0.0305 (10) | 0.0279 (9) | −0.0153 (8) | 0.0082 (7) | −0.0167 (8) |
C9 | 0.0246 (9) | 0.0287 (9) | 0.0193 (8) | −0.0182 (8) | 0.0068 (7) | −0.0107 (7) |
C10 | 0.0183 (8) | 0.0182 (8) | 0.0186 (8) | −0.0097 (7) | −0.0003 (6) | −0.0066 (6) |
C11 | 0.0167 (8) | 0.0177 (8) | 0.0183 (8) | −0.0100 (7) | −0.0005 (6) | −0.0042 (6) |
C12 | 0.0205 (9) | 0.0203 (8) | 0.0222 (8) | −0.0119 (7) | −0.0009 (7) | −0.0069 (7) |
C13 | 0.0234 (9) | 0.0224 (9) | 0.0262 (9) | −0.0157 (8) | −0.0021 (7) | −0.0032 (7) |
C14 | 0.0219 (9) | 0.0286 (9) | 0.0218 (9) | −0.0176 (8) | 0.0026 (7) | −0.0036 (7) |
C15 | 0.0219 (9) | 0.0245 (9) | 0.0198 (8) | −0.0139 (8) | 0.0026 (7) | −0.0066 (7) |
C16 | 0.0181 (8) | 0.0175 (8) | 0.0186 (8) | −0.0116 (7) | −0.0006 (6) | −0.0031 (6) |
V—O1 | 1.823 (2) | C10—C11 | 1.445 (2) |
V—O2 | 1.838 (2) | C11—C12 | 1.412 (2) |
V—O3 | 1.598 (2) | C11—C16 | 1.418 (2) |
V—O4 | 2.257 (2) | C12—C13 | 1.380 (3) |
V—N1 | 2.106 (2) | C13—C14 | 1.400 (3) |
V—N2 | 2.093 (2) | C14—C15 | 1.393 (2) |
O1—C1 | 1.345 (2) | C15—C16 | 1.399 (2) |
O2—C16 | 1.352 (2) | O4—HO4b | 0.78 (3) |
O5—N3 | 1.260 (2) | O4—HO4a | 0.89 (2) |
O6—N3 | 1.240 (2) | C2—H2 | 0.950 |
O7—N3 | 1.263 (2) | C3—H3 | 0.950 |
N1—C7 | 1.295 (2) | C4—H4 | 0.950 |
N1—C8 | 1.483 (2) | C5—H5 | 0.950 |
N2—C10 | 1.293 (2) | C7—H7 | 0.950 |
N2—C9 | 1.472 (2) | C8—H8a | 0.950 |
C1—C6 | 1.404 (2) | C8—H8b | 0.950 |
C1—C2 | 1.404 (2) | C9—H9a | 0.950 |
C2—C3 | 1.388 (2) | C9—H9b | 0.950 |
C3—C4 | 1.393 (3) | C10—H10 | 0.950 |
C4—C5 | 1.385 (3) | C12—H12 | 0.950 |
C5—C6 | 1.410 (2) | C13—H13 | 0.950 |
C6—C7 | 1.451 (2) | C14—H14 | 0.950 |
C8—C9 | 1.521 (3) | C15—H15 | 0.950 |
O1—V—O2 | 107.77 (5) | C12—C11—C16 | 118.7 (2) |
O1—V—O3 | 101.94 (6) | C10—C11—C12 | 118.9 (1) |
O1—V—O4 | 84.82 (6) | C10—C11—C16 | 122.4 (1) |
O1—V—N1 | 85.70 (5) | C11—C12—C13 | 121.0 (2) |
O1—V—N2 | 159.04 (6) | C12—C13—C14 | 119.6 (2) |
O2—V—O3 | 100.15 (6) | C13—C14—C15 | 120.9 (2) |
O2—V—O4 | 81.57 (5) | C14—C15—C16 | 119.7 (2) |
O2—V—N1 | 157.18 (6) | O2—C16—C15 | 119.7 (1) |
O2—V—N2 | 85.82 (5) | O2—C16—C11 | 120.1 (1) |
O3—V—O4 | 172.02 (6) | C11—C16—C15 | 120.1 (1) |
O3—V—N1 | 94.73 (6) | HO4a—O4—HO4b | 104 (2) |
O3—V—N2 | 90.90 (6) | C3—C2—H2 | 120.3 |
O4—V—N1 | 81.43 (6) | C1—C2—H2 | 120.3 |
O4—V—N2 | 81.43 (5) | C2—C3—H3 | 119.5 |
N1—V—N2 | 76.69 (5) | C4—C3—H3 | 119.5 |
V—O1—C1 | 138.8 (1) | C5—C4—H4 | 120.0 |
V—O2—C16 | 127.3 (1) | C3—C4—H4 | 120.0 |
V—O4—HO4b | 126 (2) | C4—C5—H5 | 120.0 |
V—O4—HO4a | 118 (1) | C6—C5—H5 | 120.0 |
V—N1—C7 | 127.2 (1) | N1—C7—H7 | 117.6 |
V—N1—C8 | 114.7 (1) | C6—C7—H7 | 117.6 |
V—N2—C9 | 116.8 (1) | H8a—C8—H8b | 109.5 |
V—N2—C10 | 123.1 (1) | N1—C8—H8a | 110.3 |
C7—N1—C8 | 118.1 (1) | C9—C8—H8a | 110.3 |
C9—N2—C10 | 119.8 (1) | N1—C8—H8b | 110.3 |
O5—N3—O6 | 119.7 (1) | C9—C8—H8b | 110.3 |
O6—N3—O7 | 120.4 (2) | H9a—C9—H9b | 109.5 |
O5—N3—O7 | 119.9 (1) | N2—C9—H9a | 110.2 |
O1—C1—C6 | 120.8 (1) | C8—C9—H9a | 110.2 |
O1—C1—C2 | 119.1 (2) | N2—C9—H9b | 110.2 |
C2—C1—C6 | 120.1 (1) | C8—C9—H9b | 110.2 |
C1—C2—C3 | 119.4 (2) | N2—C10—H10 | 117.9 |
C2—C3—C4 | 121.0 (2) | C11—C10—H10 | 117.9 |
C3—C4—C5 | 120.1 (2) | C13—C12—H12 | 119.5 |
C4—C5—C6 | 120.1 (2) | C11—C12—H12 | 119.5 |
C1—C6—C5 | 119.4 (2) | C12—C13—H13 | 120.2 |
C1—C6—C7 | 122.1 (1) | C14—C13—H13 | 120.2 |
C5—C6—C7 | 118.4 (2) | C15—C14—H14 | 119.5 |
N1—C7—C6 | 124.9 (2) | C13—C14—H14 | 119.5 |
N1—C8—C9 | 106.3 (1) | C14—C15—H15 | 120.2 |
N2—C9—C8 | 106.6 (1) | C16—C15—H15 | 120.2 |
N2—C10—C11 | 124.2 (1) |
[VO(C16H14N2O2)(H2O)]·NO3 | F(000) = 1696 |
Mr = 413.28 | Dx = 1.609 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2493 reflections |
a = 16.413 (2) Å | θ = 1.6–29.8° |
b = 8.1634 (8) Å | µ = 0.63 mm−1 |
c = 25.628 (3) Å | T = 120 K |
β = 96.619 (2)° | Plate, dark violet |
V = 3411.1 (6) Å3 | 0.41 × 0.19 × 0.12 mm |
Z = 8 |
Siemens SMART CCD diffractometer | 4831 independent reflections |
Radiation source: X-ray tube | 2461 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.135 |
ω rotation scans | θmax = 29.8°, θmin = 1.6° |
Absorption correction: integration (XPREP; Siemens, 1995) | h = −22→22 |
Tmin = 0.820, Tmax = 0.992 | k = −11→11 |
19982 measured reflections | l = −35→35 |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.047 | Weighting scheme based on measured s.u.'s |
S = 1.06 | (Δ/σ)max < 0.001 |
2461 reflections | Δρmax = 0.33 (5) e Å−3 |
244 parameters | Δρmin = −0.39 (5) e Å−3 |
[VO(C16H14N2O2)(H2O)]·NO3 | V = 3411.1 (6) Å3 |
Mr = 413.28 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.413 (2) Å | µ = 0.63 mm−1 |
b = 8.1634 (8) Å | T = 120 K |
c = 25.628 (3) Å | 0.41 × 0.19 × 0.12 mm |
β = 96.619 (2)° |
Siemens SMART CCD diffractometer | 4831 independent reflections |
Absorption correction: integration (XPREP; Siemens, 1995) | 2461 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.992 | Rint = 0.135 |
19982 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.047 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.33 (5) e Å−3 |
2461 reflections | Δρmin = −0.39 (5) e Å−3 |
244 parameters |
x | y | z | Uiso*/Ueq | ||
V | 0.70238 (4) | 0.20354 (8) | 0.14587 (3) | 0.0163 (3) | |
O1 | 0.7245 (1) | 0.4190 (3) | 0.1623 (1) | 0.019 (1) | |
O2 | 0.7920 (2) | 0.0862 (3) | 0.1702 (1) | 0.022 (2) | |
O3 | 0.6407 (2) | 0.1654 (3) | 0.1877 (1) | 0.021 (1) | |
O4 | 0.7752 (2) | 0.2674 (3) | 0.0804 (1) | 0.022 (2) | |
O5 | 0.7142 (2) | 0.5151 (3) | 0.0102 (1) | 0.027 (2) | |
O6 | 0.5994 (2) | 0.6487 (3) | 0.0030 (1) | 0.031 (2) | |
O7 | 0.6124 (2) | 0.4360 (3) | −0.0459 (1) | 0.024 (2) | |
N1 | 0.6079 (2) | 0.2906 (4) | 0.0929 (1) | 0.017 (2) | |
N2 | 0.6707 (2) | 0.0000 (3) | 0.0984 (1) | 0.016 (2) | |
N3 | 0.6419 (2) | 0.5339 (4) | −0.0108 (1) | 0.020 (2) | |
C1 | 0.6694 (2) | 0.5335 (4) | 0.1716 (1) | 0.016 (2) | |
C2 | 0.6924 (2) | 0.6554 (4) | 0.2088 (1) | 0.020 (2) | |
C3 | 0.6375 (2) | 0.7748 (4) | 0.2178 (1) | 0.022 (2) | |
C4 | 0.5600 (2) | 0.7823 (5) | 0.1898 (1) | 0.024 (2) | |
C5 | 0.5376 (2) | 0.6658 (4) | 0.1519 (1) | 0.019 (2) | |
C6 | 0.5919 (2) | 0.5389 (4) | 0.1425 (1) | 0.017 (2) | |
C7 | 0.5677 (2) | 0.4228 (4) | 0.1004 (1) | 0.018 (2) | |
C8 | 0.5802 (2) | 0.1849 (5) | 0.0478 (1) | 0.021 (2) | |
C9 | 0.5899 (2) | 0.0122 (5) | 0.0673 (1) | 0.023 (2) | |
C10 | 0.7154 (2) | −0.1270 (4) | 0.0919 (1) | 0.019 (2) | |
C11 | 0.7933 (2) | −0.1611 (4) | 0.1211 (1) | 0.016 (2) | |
C12 | 0.8329 (2) | −0.3081 (5) | 0.1123 (1) | 0.023 (2) | |
C13 | 0.9043 (3) | −0.3507 (5) | 0.1425 (2) | 0.027 (2) | |
C14 | 0.9386 (2) | −0.2473 (5) | 0.1821 (2) | 0.026 (2) | |
C15 | 0.9005 (2) | −0.1006 (5) | 0.1914 (1) | 0.020 (2) | |
C16 | 0.8291 (2) | −0.0565 (4) | 0.1609 (1) | 0.017 (2) | |
HO4a | 0.7556 | 0.3408 | 0.0551 | 0.030* | |
HO4b | 0.8033 | 0.2101 | 0.0575 | 0.030* | |
H2 | 0.7457 | 0.6551 | 0.2277 | 0.024* | |
H3 | 0.6528 | 0.8551 | 0.2439 | 0.026* | |
H4 | 0.5228 | 0.8667 | 0.1966 | 0.029* | |
H5 | 0.4851 | 0.6713 | 0.1321 | 0.023* | |
H7 | 0.5196 | 0.4455 | 0.0773 | 0.021* | |
H8a | 0.6129 | 0.2027 | 0.0201 | 0.025* | |
H8b | 0.5244 | 0.2067 | 0.0357 | 0.025* | |
H9a | 0.5479 | −0.0132 | 0.0887 | 0.027* | |
H9b | 0.5868 | −0.0615 | 0.0385 | 0.027* | |
H10 | 0.6951 | −0.2037 | 0.0657 | 0.023* | |
H12 | 0.8101 | −0.3794 | 0.0852 | 0.028* | |
H13 | 0.9305 | −0.4514 | 0.1362 | 0.033* | |
H14 | 0.9881 | −0.2772 | 0.2028 | 0.031* | |
H15 | 0.9235 | −0.0304 | 0.2188 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V | 0.0179 (3) | 0.0118 (3) | 0.0182 (3) | 0.0033 (3) | −0.0027 (3) | −0.0012 (3) |
O1 | 0.017 (1) | 0.012 (1) | 0.025 (1) | 0.001 (1) | −0.002 (1) | −0.005 (1) |
O2 | 0.022 (2) | 0.017 (1) | 0.025 (2) | 0.007 (1) | −0.007 (1) | −0.004 (1) |
O3 | 0.024 (2) | 0.017 (1) | 0.020 (1) | 0.003 (1) | 0.001 (1) | 0.000 (1) |
O4 | 0.030 (2) | 0.015 (1) | 0.023 (1) | 0.006 (1) | 0.007 (1) | 0.000 (1) |
O5 | 0.023 (2) | 0.029 (2) | 0.026 (2) | 0.004 (1) | −0.006 (1) | 0.000 (1) |
O6 | 0.036 (2) | 0.021 (2) | 0.037 (2) | 0.016 (1) | 0.001 (1) | −0.011 (1) |
O7 | 0.024 (2) | 0.020 (1) | 0.026 (2) | 0.003 (1) | −0.002 (1) | −0.005 (1) |
N1 | 0.020 (2) | 0.014 (2) | 0.016 (2) | −0.001 (1) | 0.000 (1) | 0.000 (1) |
N2 | 0.018 (2) | 0.013 (2) | 0.017 (2) | 0.001 (1) | −0.002 (1) | −0.001 (1) |
N3 | 0.025 (2) | 0.018 (2) | 0.017 (2) | 0.001 (2) | 0.002 (1) | 0.004 (1) |
C1 | 0.021 (2) | 0.010 (2) | 0.019 (2) | 0.001 (2) | 0.007 (2) | 0.004 (2) |
C2 | 0.024 (2) | 0.017 (2) | 0.018 (2) | −0.001 (2) | −0.001 (2) | 0.001 (2) |
C3 | 0.033 (2) | 0.011 (2) | 0.021 (2) | −0.002 (2) | 0.006 (2) | −0.002 (2) |
C4 | 0.035 (2) | 0.014 (2) | 0.025 (2) | 0.008 (2) | 0.009 (2) | 0.004 (2) |
C5 | 0.019 (2) | 0.013 (2) | 0.025 (2) | 0.003 (2) | 0.003 (2) | 0.004 (2) |
C6 | 0.022 (2) | 0.009 (2) | 0.019 (2) | 0.001 (2) | 0.004 (2) | 0.001 (2) |
C7 | 0.015 (2) | 0.018 (2) | 0.019 (2) | −0.001 (2) | −0.001 (2) | 0.004 (2) |
C8 | 0.026 (2) | 0.018 (2) | 0.017 (2) | 0.004 (2) | −0.006 (2) | −0.003 (2) |
C9 | 0.022 (2) | 0.019 (2) | 0.025 (2) | 0.003 (2) | −0.004 (2) | −0.004 (2) |
C10 | 0.025 (2) | 0.015 (2) | 0.018 (2) | 0.004 (2) | 0.003 (2) | 0.003 (2) |
C11 | 0.015 (2) | 0.014 (2) | 0.019 (2) | 0.000 (1) | 0.005 (2) | 0.004 (2) |
C12 | 0.025 (2) | 0.016 (2) | 0.027 (2) | 0.001 (2) | 0.001 (2) | −0.002 (2) |
C13 | 0.026 (2) | 0.019 (2) | 0.037 (3) | 0.011 (2) | 0.005 (2) | 0.002 (2) |
C14 | 0.021 (2) | 0.022 (2) | 0.034 (2) | 0.009 (2) | 0.003 (2) | 0.006 (2) |
C15 | 0.018 (2) | 0.023 (2) | 0.020 (2) | −0.001 (2) | 0.001 (2) | 0.002 (2) |
C16 | 0.019 (2) | 0.013 (2) | 0.020 (2) | 0.002 (2) | 0.006 (2) | 0.004 (2) |
V—O1 | 1.835 (3) | C10—C11 | 1.432 (5) |
V—O2 | 1.805 (3) | C11—C12 | 1.395 (5) |
V—O3 | 1.588 (3) | C11—C16 | 1.406 (5) |
V—O4 | 2.230 (3) | C12—C13 | 1.373 (5) |
V—N1 | 2.066 (3) | C13—C14 | 1.388 (6) |
V—N2 | 2.089 (3) | C14—C15 | 1.385 (5) |
O1—C1 | 1.341 (4) | C15—C16 | 1.379 (5) |
O2—C16 | 1.349 (4) | O4—HO4a | 0.914 |
O5—N3 | 1.254 (4) | O4—HO4b | 0.915 |
O6—N3 | 1.243 (4) | C2—H2 | 0.950 |
O7—N3 | 1.258 (4) | C3—H3 | 0.950 |
N1—C7 | 1.291 (5) | C4—H4 | 0.950 |
N1—C8 | 1.471 (4) | C5—H5 | 0.950 |
N2—C10 | 1.292 (4) | C7—H7 | 0.950 |
N2—C9 | 1.470 (5) | C8—H8b | 0.950 |
C1—C2 | 1.400 (5) | C8—H8a | 0.950 |
C1—C6 | 1.401 (5) | C9—H9b | 0.950 |
C2—C3 | 1.363 (5) | C9—H9a | 0.950 |
C3—C4 | 1.389 (5) | C10—H10 | 0.950 |
C4—C5 | 1.378 (5) | C12—H12 | 0.950 |
C5—C6 | 1.405 (5) | C13—H13 | 0.950 |
C6—C7 | 1.455 (5) | C14—H14 | 0.950 |
C8—C9 | 1.498 (5) | C15—H15 | 0.950 |
O1—V—O2 | 107.3 (1) | C12—C11—C16 | 118.4 (3) |
O1—V—O3 | 99.0 (1) | C10—C11—C12 | 119.1 (3) |
O1—V—O4 | 80.8 (1) | C10—C11—C16 | 122.4 (3) |
O1—V—N1 | 86.3 (1) | C11—C12—C13 | 120.7 (4) |
O1—V—N2 | 157.7 (1) | C12—C13—C14 | 120.3 (4) |
O2—V—O3 | 102.7 (1) | C13—C14—C15 | 120.0 (4) |
O2—V—O4 | 84.2 (1) | C14—C15—C16 | 119.9 (4) |
O2—V—N1 | 158.4 (1) | O2—C16—C15 | 119.8 (3) |
O2—V—N2 | 85.3 (1) | O2—C16—C11 | 119.5 (3) |
O3—V—O4 | 172.8 (1) | C11—C16—C15 | 120.7 (3) |
O3—V—N1 | 91.3 (1) | HO4a—O4—HO4b | 92.4 |
O3—V—N2 | 95.9 (1) | C3—C2—H2 | 120.3 |
O4—V—N1 | 81.5 (1) | C1—C2—H2 | 120.3 |
O4—V—N2 | 82.3 (1) | C2—C3—H3 | 119.0 |
N1—V—N2 | 76.9 (1) | C4—C3—H3 | 119.0 |
V—O1—C1 | 126.2 (2) | C5—C4—H4 | 120.4 |
V—O2—C16 | 139.8 (2) | C3—C4—H4 | 120.4 |
V—O4—HO4a | 120.8 | C4—C5—H5 | 119.8 |
V—O4—HO4b | 135.7 | C6—C5—H5 | 119.8 |
V—N1—C7 | 123.1 (2) | N1—C7—H7 | 118.1 |
V—N1—C8 | 117.1 (2) | C6—C7—H7 | 118.1 |
V—N2—C9 | 114.2 (2) | H8a—C8—H8b | 109.5 |
V—N2—C10 | 127.3 (3) | N1—C8—H8b | 110.3 |
C7—N1—C8 | 119.4 (3) | C9—C8—H8b | 110.3 |
C9—N2—C10 | 118.4 (3) | N1—C8—H8a | 110.3 |
O5—N3—O6 | 120.3 (3) | C9—C8—H8a | 110.3 |
O6—N3—O7 | 120.0 (3) | H9a—C9—H9b | 109.5 |
O5—N3—O7 | 119.8 (3) | N2—C9—H9b | 110.0 |
O1—C1—C2 | 118.9 (3) | C8—C9—H9b | 110.0 |
O1—C1—C6 | 121.1 (3) | N2—C9—H9a | 110.0 |
C2—C1—C6 | 119.9 (3) | C8—C9—H9a | 110.0 |
C1—C2—C3 | 119.4 (4) | N2—C10—H10 | 117.5 |
C2—C3—C4 | 121.9 (3) | C11—C10—H10 | 117.5 |
C3—C4—C5 | 119.2 (4) | C13—C12—H12 | 119.6 |
C4—C5—C6 | 120.5 (4) | C11—C12—H12 | 119.6 |
C1—C6—C5 | 119.1 (3) | C12—C13—H13 | 119.8 |
C1—C6—C7 | 121.9 (3) | C14—C13—H13 | 119.8 |
C5—C6—C7 | 118.9 (3) | C15—C14—H14 | 120.0 |
N1—C7—C6 | 123.7 (3) | C13—C14—H14 | 120.0 |
N1—C8—C9 | 106.2 (3) | C16—C15—H15 | 120.1 |
N2—C9—C8 | 107.4 (3) | C14—C15—H15 | 120.1 |
N2—C10—C11 | 125.1 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [VO(C16H14N2O2)(H2O)]·NO3 | [VO(C16H14N2O2)(H2O)]·NO3 |
Mr | 413.28 | 413.28 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.663 (2), 8.956 (2), 13.293 (3) | 16.413 (2), 8.1634 (8), 25.628 (3) |
α, β, γ (°) | 73.029 (3), 83.852 (4), 61.662 (3) | 90, 96.619 (2), 90 |
V (Å3) | 867.7 (3) | 3411.1 (6) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.62 | 0.63 |
Crystal size (mm) | 0.40 × 0.23 × 0.10 | 0.41 × 0.19 × 0.12 |
Data collection | ||
Diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Integration (XPREP; Siemens, 1995) | Integration (XPREP; Siemens, 1995) |
Tmin, Tmax | 0.765, 0.943 | 0.820, 0.992 |
No. of measured, independent and observed reflections | 16803, 4960, 3763 [I > 3σ(I)] | 19982, 4831, 2461 [I > 2σ(I)] |
Rint | 0.082 | 0.135 |
(sin θ/λ)max (Å−1) | 0.699 | 0.699 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.042, 1.33 | 0.050, 0.047, 1.06 |
No. of reflections | 3763 | 2461 |
No. of parameters | 252 | 244 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49 (7), −0.52 (7) | 0.33 (5), −0.39 (5) |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell, 1995), modified ORFLS (Busing et al., 1962) and KRYSTAL, ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL, KRYSTAL.
V—O1 | 1.823 (2) | V—O4 | 2.257 (2) |
V—O2 | 1.838 (2) | V—N1 | 2.106 (2) |
V—O3 | 1.598 (2) | V—N2 | 2.093 (2) |
O1—V—N2 | 159.04 (6) | O3—V—O4 | 172.02 (6) |
O2—V—N1 | 157.18 (6) |
V—O1 | 1.835 (3) | V—O4 | 2.230 (3) |
V—O2 | 1.805 (3) | V—N1 | 2.066 (3) |
V—O3 | 1.588 (3) | V—N2 | 2.089 (3) |
O1—V—N2 | 157.7 (1) | O3—V—O4 | 172.8 (1) |
O2—V—N1 | 158.4 (1) |
Complexes of the type VVO(Schiff base)Y (Y is Cl, ClO4 or NO3) can be prepared by oxidizing VIVO(Schiff base) with (NH4)2Ce(NO3)6 in acetonitrile, followed by the addition of HY (Nakajima et al., 1990). The structure of [VVO(salen)](ClO4) [salen is bis(salicylidene)ethylenediaminato-N,N'] has been studied by X-ray diffraction by Bonadies et al. (1987) and the V shown to have a distorted octahedral coordination, with a long [2.456 (3) Å] V—Operchlorate bond trans to V═O. Nakajima et al. (1987) proposed, on the basis of absorption spectra, that their VVO(Schiff base)Y complexes had structures analogous to that of the [VVO(salen)]·ClO4 complex. A structural investigation of [VVO(salen)]NO3 prepared by Nakajima's method showed the product to contain two polymorphs, a triclinic form, (I), and a monoclinic form, (II), which contain the [VVO(salen)(H2O)]+ and NO3- ions. The structures of these two polymorphs are presented here. \sch
In both forms the cations are linked by hydrogen bonds via the nitrates to give centrosymmetric dimers (Fig. 1a and b). The V atoms are coordinated to two N atoms and two O atoms of the salen ligand, to the vanadyl oxygen and to a water molecule which is trans to the V═O oxygen. This octahedral arrangement is distorted, in that the V atom is displaced out of the N2O2 plane in the direction of the vanadyl oxygen by 0.255 Å in (I) and 0.260 Å in (II), which is similar to the value of 0.270 Å observed in the cation of [VVO(salen)(H2O)]2·Cu2Cl4, (III) (Banci et al., 1984). The V═O distances in compounds (I), (II), and (III) are 1.598 (2), 1.588 (3) and 1.590 (5) Å, respectively, and the V—Owater distances are 2.257 (2), 2.230 (3) and 2.310 (5) Å, respectively. These latter values are much longer than the usual VV—O distance; cf. V—Osalen of 1.823 (2) and 1.838 (2) Å in (I), and 1.835 (3) and 1.805 (3) Å in (II). An indication that the V═O distances in (I) and (II) really are different is that the V═O absorption in the IR spectrum of the bulk sample is a doublet.
The water molecules are hydrogen bonded to the nitrate ion so that there are two nitrate bridges between pairs of cations; Owater···Onitrate distances are 2.737 (2) and 2.779 (2) Å in (I), and 2.705 (4) and 2.813 (4) in (II). The V···V distance in the dimers is almost identical: 7.846 (1) Å in (I) and 7.850 (2) Å in (II). In both cases, the N—O bond for the non-hydrogen-bonded O atom is the shortest: 1.240 (2) Å in (I) and 1.243 (4) Å in (II), compared with 1.260 (2) and 1.263 (2) Å for the remaining two N—O bonds in (I), and 1.254 (4) and 1.258 (4) Å for the remaining two N—O bonds in (II).
Packing diagrams have been deposited as Fig. 2 and Fig. 3. In the triclinic form, (I), the dimers pack so that the salen groups are parallel to each other, whereas in the monoclinic form, (II), there is a herring-bone arrangement, with an angle of 50° between the planes through the salen ligands. The monoclinic form, (II), is the denser, with ρ = 1.609, cf. 1.582 for (I).