Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107028557/dn3044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107028557/dn3044Isup2.hkl |
CCDC reference: 661790
For related literature, see: Allen (2002); Athimoolam & Natarajan (2006, 2007a, 2007b); Bernstein et al. (1995); Brown (1992); Crans (1998); Etter et al. (1990); Maďarová et al. (2004); Pacigová et al. (2007); Sivák et al. (2000).
The orange crystals of (C6H7N2O)6V10O28·2H2O crystallized within 6–7 d from the V2O5–H2O2–nicotinamide–H2O solution prepared as follows. For the preparation of solution A, V2O5 (0.181 g, 1 mmol) was dissolved in H2O2 (3 ml, w = 0.3) under continuous stiring in an ice bath. For the preparation of solution B, nicotinamide (0.122 g, 1 mmol) was dissolved in 5 ml of water. Solution B was added dropwise to A and the resulting solution was acidified by two drops of concentrated HClO4. The obtained solution (pH = 1.8) was allowed to crystallize in refrigerator at 279 K. The crystals were dried in dissicator above silica gel at the same temperature.
H atoms of the cations were placed in geometrically idealized positions (C—H = 0.95 Å and N—H = 0.89 Å) and constrained to ride on their parent atoms [with Uiso(H) = 1.2Ueq(C,N)]. H atoms of the water molecules were located in a difference map and refined with O—H interatomic distances restrained to be equal with standard deviation set to 0.05 Å and with Uiso(H) values of 1.5Ueq(O), which leads to reasonable geometry [O1W—H1 = O1W—H2 = 0.83 (3) Å and H1—O1W—H2 = 108 (3)°].
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXL97, DIAMOND and publCIF (Westrip, 2007).
(C6H7N2O)6[V10O28]·2H2O | F(000) = 3456 |
Mr = 1732.25 | Dx = 2.067 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 24882 reflections |
a = 25.806 (9) Å | θ = 3.0–27° |
b = 9.5460 (13) Å | µ = 1.71 mm−1 |
c = 23.577 (10) Å | T = 120 K |
β = 106.60 (4)° | Prism, orange |
V = 5566 (3) Å3 | 0.50 × 0.25 × 0.15 mm |
Z = 4 |
Kuma KM-4 CCD diffractometer | 5811 independent reflections |
Radiation source: fine-focus sealed tube | 5173 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
Detector resolution: 0.06 pixels mm-1 | θmax = 27.0°, θmin = 3.1° |
ω scans | h = −31→31 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −7→12 |
Tmin = 0.481, Tmax = 0.783 | l = −29→30 |
34597 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0341P)2 + 8.29P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
5811 reflections | Δρmax = 0.50 e Å−3 |
431 parameters | Δρmin = −0.51 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00011 (2) |
(C6H7N2O)6[V10O28]·2H2O | V = 5566 (3) Å3 |
Mr = 1732.25 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.806 (9) Å | µ = 1.71 mm−1 |
b = 9.5460 (13) Å | T = 120 K |
c = 23.577 (10) Å | 0.50 × 0.25 × 0.15 mm |
β = 106.60 (4)° |
Kuma KM-4 CCD diffractometer | 5811 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 5173 reflections with I > 2σ(I) |
Tmin = 0.481, Tmax = 0.783 | Rint = 0.012 |
34597 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 1 restraint |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.50 e Å−3 |
5811 reflections | Δρmin = −0.51 e Å−3 |
431 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 | ||
V1 | 0.008016 (10) | 0.67129 (3) | −0.000302 (11) | 0.00823 (7) | |
V2 | 0.101695 (10) | 0.48085 (3) | −0.013492 (12) | 0.00924 (7) | |
V3 | −0.022611 (11) | 0.68118 (3) | 0.117265 (12) | 0.01042 (7) | |
V4 | 0.074926 (11) | 0.50109 (3) | 0.108273 (12) | 0.00898 (7) | |
V5 | 0.028767 (11) | 0.64077 (3) | −0.122361 (12) | 0.01115 (7) | |
O1 | −0.01095 (4) | 0.50851 (11) | 0.05138 (5) | 0.0095 (2) | |
O2 | 0.04199 (5) | 0.75765 (13) | −0.16496 (5) | 0.0175 (3) | |
O3 | −0.02840 (5) | 0.81248 (13) | 0.15729 (5) | 0.0166 (3) | |
O4 | 0.05394 (4) | 0.64270 (12) | 0.14404 (5) | 0.0116 (2) | |
O5 | 0.04560 (4) | 0.36132 (12) | 0.14549 (5) | 0.0119 (2) | |
O6 | 0.13862 (5) | 0.48444 (12) | 0.14146 (5) | 0.0146 (2) | |
O7 | −0.03366 (5) | 0.52692 (12) | 0.15828 (5) | 0.0125 (2) | |
O8 | 0.02113 (4) | 0.76726 (12) | −0.05441 (5) | 0.0116 (2) | |
O9 | −0.07043 (4) | 0.64440 (12) | −0.04140 (5) | 0.0094 (2) | |
O10 | 0.16525 (5) | 0.46465 (13) | 0.02131 (5) | 0.0146 (2) | |
O11 | 0.09879 (4) | 0.60730 (12) | −0.06788 (5) | 0.0118 (2) | |
O12 | 0.09035 (4) | 0.32674 (12) | −0.06437 (5) | 0.0115 (2) | |
O13 | −0.00126 (4) | 0.78422 (12) | 0.05094 (5) | 0.0112 (2) | |
O14 | 0.07921 (4) | 0.61289 (12) | 0.03944 (5) | 0.0093 (2) | |
C11 | −0.26951 (7) | 0.53389 (18) | 0.03997 (7) | 0.0123 (3) | |
C21 | −0.28286 (7) | 0.39449 (19) | 0.02525 (7) | 0.0169 (4) | |
H21 | −0.2599 | 0.3217 | 0.0457 | 0.020* | |
C31 | −0.32974 (7) | 0.36168 (19) | −0.01940 (8) | 0.0197 (4) | |
H31 | −0.3385 | 0.2669 | −0.0302 | 0.024* | |
C41 | −0.36327 (7) | 0.4686 (2) | −0.04773 (8) | 0.0178 (4) | |
H41 | −0.3958 | 0.4477 | −0.0776 | 0.021* | |
N11 | −0.34971 (6) | 0.60192 (16) | −0.03287 (6) | 0.0148 (3) | |
H11 | −0.3713 | 0.6692 | −0.0513 | 0.018* | |
C51 | −0.30434 (7) | 0.63621 (18) | 0.00906 (7) | 0.0131 (3) | |
H51 | −0.2959 | 0.7322 | 0.0177 | 0.016* | |
C61 | −0.22104 (6) | 0.58422 (18) | 0.08837 (7) | 0.0128 (3) | |
O15 | −0.20970 (5) | 0.71052 (13) | 0.09074 (5) | 0.0166 (3) | |
N21 | −0.19367 (6) | 0.49098 (15) | 0.12688 (7) | 0.0160 (3) | |
H21A | −0.1658 | 0.5176 | 0.1561 | 0.019* | |
H21B | −0.2033 | 0.4023 | 0.1233 | 0.019* | |
C12 | 0.15642 (6) | 0.06569 (18) | 0.30448 (7) | 0.0123 (3) | |
C22 | 0.13039 (7) | −0.06365 (19) | 0.29364 (7) | 0.0166 (3) | |
H22 | 0.1456 | −0.1431 | 0.3167 | 0.020* | |
C32 | 0.08183 (7) | −0.0756 (2) | 0.24875 (8) | 0.0197 (4) | |
H32 | 0.0635 | −0.1630 | 0.2412 | 0.024* | |
C42 | 0.06067 (7) | 0.0402 (2) | 0.21544 (8) | 0.0180 (4) | |
H42 | 0.0278 | 0.0328 | 0.1845 | 0.022* | |
N12 | 0.08637 (6) | 0.16358 (16) | 0.22656 (6) | 0.0154 (3) | |
H12 | 0.0724 | 0.2365 | 0.2047 | 0.019* | |
C52 | 0.13267 (7) | 0.17933 (18) | 0.27000 (7) | 0.0142 (3) | |
H52 | 0.1493 | 0.2689 | 0.2772 | 0.017* | |
C62 | 0.20976 (7) | 0.09143 (18) | 0.35067 (7) | 0.0132 (3) | |
O16 | 0.22781 (5) | 0.21222 (13) | 0.35845 (6) | 0.0202 (3) | |
N22 | 0.23514 (6) | −0.01731 (15) | 0.38076 (6) | 0.0162 (3) | |
H22A | 0.2664 | −0.0056 | 0.4078 | 0.019* | |
H22B | 0.2208 | −0.1015 | 0.3738 | 0.019* | |
C13 | −0.19492 (6) | 0.94662 (18) | −0.17085 (7) | 0.0110 (3) | |
C23 | −0.17462 (7) | 1.08220 (18) | −0.15903 (7) | 0.0151 (3) | |
H23 | −0.1931 | 1.1590 | −0.1815 | 0.018* | |
C33 | −0.12701 (7) | 1.10382 (19) | −0.11400 (8) | 0.0176 (4) | |
H33 | −0.1129 | 1.1957 | −0.1050 | 0.021* | |
C43 | −0.10052 (7) | 0.99000 (18) | −0.08250 (8) | 0.0149 (3) | |
H43 | −0.0675 | 1.0043 | −0.0524 | 0.018* | |
N13 | −0.12026 (5) | 0.86005 (15) | −0.09350 (6) | 0.0121 (3) | |
H13 | −0.1029 | 0.7891 | −0.0727 | 0.015* | |
C53 | −0.16645 (7) | 0.83824 (18) | −0.13626 (7) | 0.0123 (3) | |
H53 | −0.1802 | 0.7456 | −0.1432 | 0.015* | |
C63 | −0.24579 (6) | 0.90844 (18) | −0.21832 (7) | 0.0127 (3) | |
O17 | −0.26308 (5) | 0.78670 (13) | −0.22180 (5) | 0.0186 (3) | |
N23 | −0.26996 (6) | 1.00972 (15) | −0.25507 (6) | 0.0161 (3) | |
H23A | −0.2997 | 0.9918 | −0.2835 | 0.019* | |
H23B | −0.2562 | 1.0948 | −0.2509 | 0.019* | |
O1W | −0.10168 (6) | 0.5378 (2) | 0.23014 (6) | 0.0363 (4) | |
H2 | −0.0771 (11) | 0.539 (3) | 0.2137 (13) | 0.054* | |
H1 | −0.0897 (12) | 0.575 (3) | 0.2633 (12) | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.00763 (13) | 0.00696 (14) | 0.00844 (13) | −0.00015 (10) | −0.00035 (10) | 0.00004 (10) |
V2 | 0.00626 (13) | 0.01072 (14) | 0.00942 (14) | 0.00002 (10) | 0.00013 (10) | −0.00067 (10) |
V3 | 0.00883 (13) | 0.01176 (15) | 0.00939 (14) | 0.00046 (10) | 0.00056 (10) | −0.00228 (10) |
V4 | 0.00727 (13) | 0.01030 (14) | 0.00724 (14) | 0.00031 (10) | −0.00137 (10) | −0.00014 (10) |
V5 | 0.01071 (14) | 0.01250 (15) | 0.00939 (14) | −0.00027 (11) | 0.00147 (10) | 0.00189 (10) |
O1 | 0.0092 (5) | 0.0092 (6) | 0.0089 (5) | 0.0001 (4) | 0.0005 (4) | 0.0000 (4) |
O2 | 0.0192 (6) | 0.0186 (6) | 0.0150 (6) | −0.0003 (5) | 0.0052 (5) | 0.0045 (5) |
O3 | 0.0148 (6) | 0.0184 (6) | 0.0157 (6) | 0.0005 (5) | 0.0028 (5) | −0.0054 (5) |
O4 | 0.0097 (5) | 0.0136 (6) | 0.0096 (5) | −0.0004 (4) | 0.0000 (4) | −0.0015 (4) |
O5 | 0.0116 (5) | 0.0128 (6) | 0.0094 (5) | 0.0010 (4) | −0.0002 (4) | 0.0020 (4) |
O6 | 0.0111 (6) | 0.0173 (6) | 0.0121 (6) | 0.0013 (5) | −0.0019 (4) | −0.0008 (5) |
O7 | 0.0111 (5) | 0.0166 (6) | 0.0092 (5) | 0.0008 (5) | 0.0019 (4) | −0.0001 (5) |
O8 | 0.0116 (5) | 0.0098 (6) | 0.0122 (5) | −0.0003 (4) | 0.0012 (4) | 0.0013 (4) |
O9 | 0.0075 (5) | 0.0095 (6) | 0.0095 (5) | 0.0009 (4) | −0.0005 (4) | 0.0002 (4) |
O10 | 0.0093 (5) | 0.0182 (6) | 0.0145 (6) | 0.0008 (5) | 0.0005 (4) | −0.0024 (5) |
O11 | 0.0094 (5) | 0.0135 (6) | 0.0119 (5) | −0.0016 (4) | 0.0020 (4) | −0.0004 (5) |
O12 | 0.0088 (5) | 0.0129 (6) | 0.0117 (5) | 0.0014 (4) | 0.0009 (4) | −0.0016 (4) |
O13 | 0.0103 (5) | 0.0095 (6) | 0.0124 (5) | 0.0000 (4) | 0.0008 (4) | −0.0009 (4) |
O14 | 0.0076 (5) | 0.0092 (5) | 0.0096 (5) | −0.0004 (4) | −0.0001 (4) | −0.0007 (4) |
C11 | 0.0129 (8) | 0.0129 (8) | 0.0120 (8) | −0.0003 (6) | 0.0048 (6) | 0.0002 (6) |
C21 | 0.0198 (9) | 0.0139 (9) | 0.0150 (8) | 0.0019 (7) | 0.0015 (7) | 0.0018 (7) |
C31 | 0.0245 (9) | 0.0141 (9) | 0.0183 (9) | −0.0046 (7) | 0.0028 (7) | −0.0008 (7) |
C41 | 0.0153 (8) | 0.0227 (10) | 0.0143 (8) | −0.0037 (7) | 0.0024 (7) | 0.0006 (7) |
N11 | 0.0133 (7) | 0.0175 (8) | 0.0132 (7) | 0.0028 (6) | 0.0030 (5) | 0.0028 (6) |
C51 | 0.0154 (8) | 0.0129 (8) | 0.0118 (8) | −0.0001 (6) | 0.0052 (6) | 0.0001 (6) |
C61 | 0.0126 (8) | 0.0144 (8) | 0.0125 (8) | 0.0007 (6) | 0.0055 (6) | −0.0014 (6) |
O15 | 0.0205 (6) | 0.0120 (6) | 0.0164 (6) | −0.0027 (5) | 0.0039 (5) | −0.0009 (5) |
N21 | 0.0138 (7) | 0.0140 (7) | 0.0167 (7) | −0.0006 (6) | −0.0011 (6) | −0.0001 (6) |
C12 | 0.0129 (8) | 0.0148 (8) | 0.0088 (7) | 0.0003 (6) | 0.0024 (6) | −0.0008 (6) |
C22 | 0.0183 (8) | 0.0153 (9) | 0.0147 (8) | −0.0007 (7) | 0.0025 (7) | 0.0025 (7) |
C32 | 0.0188 (9) | 0.0186 (9) | 0.0200 (9) | −0.0061 (7) | 0.0030 (7) | −0.0011 (7) |
C42 | 0.0128 (8) | 0.0245 (10) | 0.0146 (8) | −0.0005 (7) | 0.0008 (6) | −0.0002 (7) |
N12 | 0.0141 (7) | 0.0177 (8) | 0.0133 (7) | 0.0039 (6) | 0.0020 (5) | 0.0030 (6) |
C52 | 0.0133 (8) | 0.0148 (8) | 0.0141 (8) | 0.0006 (6) | 0.0035 (6) | −0.0007 (6) |
C62 | 0.0130 (8) | 0.0152 (9) | 0.0107 (8) | −0.0001 (7) | 0.0023 (6) | −0.0013 (6) |
O16 | 0.0195 (6) | 0.0125 (6) | 0.0231 (7) | −0.0009 (5) | −0.0030 (5) | −0.0022 (5) |
N22 | 0.0135 (7) | 0.0144 (7) | 0.0158 (7) | −0.0012 (6) | −0.0035 (6) | 0.0016 (6) |
C13 | 0.0114 (7) | 0.0124 (8) | 0.0091 (7) | 0.0010 (6) | 0.0026 (6) | 0.0002 (6) |
C23 | 0.0168 (8) | 0.0109 (8) | 0.0147 (8) | 0.0016 (7) | 0.0002 (6) | 0.0027 (6) |
C33 | 0.0198 (9) | 0.0115 (8) | 0.0187 (9) | −0.0036 (7) | 0.0009 (7) | 0.0014 (7) |
C43 | 0.0124 (8) | 0.0172 (9) | 0.0132 (8) | −0.0020 (7) | 0.0004 (6) | 0.0004 (6) |
N13 | 0.0118 (6) | 0.0121 (7) | 0.0111 (6) | 0.0035 (5) | 0.0010 (5) | 0.0038 (5) |
C53 | 0.0134 (8) | 0.0112 (8) | 0.0123 (8) | −0.0001 (6) | 0.0035 (6) | −0.0002 (6) |
C63 | 0.0117 (8) | 0.0143 (8) | 0.0115 (8) | 0.0014 (6) | 0.0022 (6) | −0.0020 (6) |
O17 | 0.0184 (6) | 0.0127 (6) | 0.0202 (6) | −0.0018 (5) | −0.0019 (5) | −0.0024 (5) |
N23 | 0.0142 (7) | 0.0153 (7) | 0.0138 (7) | −0.0010 (6) | −0.0042 (6) | 0.0012 (6) |
O1W | 0.0161 (7) | 0.0776 (13) | 0.0151 (7) | −0.0057 (7) | 0.0041 (5) | −0.0094 (8) |
V1—O1 | 2.1165 (12) | N11—H11 | 0.8800 |
V1—O1i | 2.1105 (12) | C51—H51 | 0.9500 |
V1—O8 | 1.6817 (12) | C61—O15 | 1.238 (2) |
V1—O9 | 1.9955 (14) | C61—N21 | 1.323 (2) |
V1—O13 | 1.6864 (12) | N21—H21A | 0.8800 |
V1—O14 | 1.8923 (13) | N21—H21B | 0.8800 |
V2—O1i | 2.2576 (14) | C12—C52 | 1.389 (2) |
V2—O9i | 2.0862 (12) | C12—C22 | 1.394 (2) |
V2—O10 | 1.6182 (13) | C12—C62 | 1.511 (2) |
V2—O11 | 1.7470 (12) | C22—C32 | 1.395 (2) |
V2—O12 | 1.8677 (12) | C22—H22 | 0.9500 |
V2—O14 | 1.9739 (12) | C32—C42 | 1.376 (3) |
V3—O1 | 2.3425 (12) | C32—H32 | 0.9500 |
V3—O3 | 1.6014 (12) | C42—N12 | 1.340 (2) |
V3—O4 | 1.9296 (13) | C42—H42 | 0.9500 |
V3—O7 | 1.8282 (12) | N12—C52 | 1.342 (2) |
V3—O12i | 1.8362 (14) | N12—H12 | 0.8800 |
V3—O13 | 2.0516 (13) | C52—H52 | 0.9500 |
V4—O1 | 2.2401 (15) | C62—O16 | 1.237 (2) |
V4—O4 | 1.7587 (12) | C62—N22 | 1.321 (2) |
V4—O5 | 1.8714 (12) | N22—H22A | 0.8800 |
V4—O6 | 1.6139 (14) | N22—H22B | 0.8800 |
V4—O9i | 2.0793 (12) | C13—C53 | 1.390 (2) |
V4—O14 | 1.9717 (13) | C13—C23 | 1.394 (2) |
V5—O1i | 2.3415 (13) | C13—C63 | 1.507 (2) |
V5—O2 | 1.6017 (12) | C23—C33 | 1.391 (2) |
V5—O5i | 1.8394 (13) | C23—H23 | 0.9500 |
V5—O7i | 1.8322 (12) | C33—C43 | 1.382 (2) |
V5—O8 | 2.0600 (13) | C33—H33 | 0.9500 |
V5—O11 | 1.9214 (14) | C43—N13 | 1.338 (2) |
C11—C51 | 1.385 (2) | C43—H43 | 0.9500 |
C11—C21 | 1.393 (2) | N13—C53 | 1.339 (2) |
C11—C61 | 1.511 (2) | N13—H13 | 0.8800 |
C21—C31 | 1.394 (2) | C53—H53 | 0.9500 |
C21—H21 | 0.9500 | C63—O17 | 1.239 (2) |
C31—C41 | 1.380 (3) | C63—N23 | 1.329 (2) |
C31—H31 | 0.9500 | N23—H23A | 0.8800 |
C41—N11 | 1.340 (2) | N23—H23B | 0.8800 |
C41—H41 | 0.9500 | O1W—H2 | 0.83 (3) |
N11—C51 | 1.339 (2) | O1W—H1 | 0.83 (3) |
O8—V1—O13 | 107.20 (6) | V2i—O1—V3 | 85.16 (5) |
O8—V1—O14 | 99.14 (6) | V5i—O1—V3 | 82.28 (4) |
O13—V1—O14 | 98.63 (6) | V4—O4—V3 | 114.59 (6) |
O8—V1—O9 | 95.60 (6) | V5i—O5—V4 | 113.33 (6) |
O13—V1—O9 | 95.64 (6) | V3—O7—V5i | 114.68 (6) |
O14—V1—O9 | 155.41 (5) | V1—O8—V5 | 110.82 (6) |
O8—V1—O1i | 87.84 (6) | V1—O9—V4i | 106.46 (6) |
O13—V1—O1i | 164.63 (5) | V1—O9—V2i | 106.91 (6) |
O14—V1—O1i | 81.66 (5) | V4i—O9—V2i | 98.04 (5) |
O9—V1—O1i | 79.35 (5) | V2—O11—V5 | 116.14 (6) |
O8—V1—O1 | 165.12 (5) | V3i—O12—V2 | 114.38 (6) |
O13—V1—O1 | 87.33 (6) | V1—O13—V3 | 111.32 (6) |
O14—V1—O1 | 81.38 (5) | V1—O14—V4 | 106.99 (6) |
O9—V1—O1 | 79.38 (5) | V1—O14—V2 | 107.11 (6) |
O1i—V1—O1 | 77.49 (5) | V4—O14—V2 | 105.69 (6) |
O10—V2—O11 | 105.24 (6) | C51—C11—C21 | 117.72 (15) |
O10—V2—O12 | 101.57 (6) | C51—C11—C61 | 116.49 (15) |
O11—V2—O12 | 96.13 (6) | C21—C11—C61 | 125.76 (15) |
O10—V2—O14 | 100.30 (6) | C11—C21—C31 | 120.15 (16) |
O11—V2—O14 | 93.67 (6) | C11—C21—H21 | 119.9 |
O12—V2—O14 | 152.70 (5) | C31—C21—H21 | 119.9 |
O10—V2—O9i | 98.41 (6) | C41—C31—C21 | 119.22 (17) |
O11—V2—O9i | 155.26 (5) | C41—C31—H31 | 120.4 |
O12—V2—O9i | 85.96 (5) | C21—C31—H31 | 120.4 |
O14—V2—O9i | 74.82 (5) | N11—C41—C31 | 119.66 (16) |
O10—V2—O1i | 172.52 (5) | N11—C41—H41 | 120.2 |
O11—V2—O1i | 81.74 (5) | C31—C41—H41 | 120.2 |
O12—V2—O1i | 80.02 (5) | C51—N11—C41 | 122.21 (15) |
O14—V2—O1i | 76.26 (5) | C51—N11—H11 | 118.9 |
O9i—V2—O1i | 74.33 (5) | C41—N11—H11 | 118.9 |
O3—V3—O7 | 105.29 (6) | N11—C51—C11 | 121.00 (16) |
O3—V3—O12i | 101.63 (6) | N11—C51—H51 | 119.5 |
O7—V3—O12i | 93.67 (6) | C11—C51—H51 | 119.5 |
O3—V3—O4 | 102.43 (6) | O15—C61—N21 | 123.46 (16) |
O7—V3—O4 | 88.48 (5) | O15—C61—C11 | 118.54 (15) |
O12i—V3—O4 | 154.35 (5) | N21—C61—C11 | 117.98 (15) |
O3—V3—O13 | 99.47 (6) | C61—N21—H21A | 120.0 |
O7—V3—O13 | 154.93 (5) | C61—N21—H21B | 120.0 |
O12i—V3—O13 | 85.00 (6) | H21A—N21—H21B | 120.0 |
O4—V3—O13 | 82.41 (5) | C52—C12—C22 | 118.40 (15) |
O3—V3—O1 | 173.12 (5) | C52—C12—C62 | 116.97 (15) |
O7—V3—O1 | 81.55 (5) | C22—C12—C62 | 124.62 (15) |
O12i—V3—O1 | 78.36 (5) | C12—C22—C32 | 119.54 (16) |
O4—V3—O1 | 76.68 (5) | C12—C22—H22 | 120.2 |
O13—V3—O1 | 73.65 (5) | C32—C22—H22 | 120.2 |
O6—V4—O4 | 104.70 (6) | C42—C32—C22 | 119.44 (17) |
O6—V4—O5 | 101.23 (6) | C42—C32—H32 | 120.3 |
O4—V4—O5 | 95.86 (6) | C22—C32—H32 | 120.3 |
O6—V4—O14 | 99.41 (6) | N12—C42—C32 | 120.06 (16) |
O4—V4—O14 | 94.36 (6) | N12—C42—H42 | 120.0 |
O5—V4—O14 | 153.78 (5) | C32—C42—H42 | 120.0 |
O6—V4—O9i | 97.49 (6) | C42—N12—C52 | 122.07 (15) |
O4—V4—O9i | 156.76 (5) | C42—N12—H12 | 119.0 |
O5—V4—O9i | 86.38 (5) | C52—N12—H12 | 119.0 |
O14—V4—O9i | 75.02 (5) | N12—C52—C12 | 120.48 (16) |
O6—V4—O1 | 171.85 (5) | N12—C52—H52 | 119.8 |
O4—V4—O1 | 82.84 (5) | C12—C52—H52 | 119.8 |
O5—V4—O1 | 80.79 (5) | O16—C62—N22 | 123.01 (15) |
O14—V4—O1 | 76.61 (5) | O16—C62—C12 | 119.01 (15) |
O9i—V4—O1 | 74.67 (5) | N22—C62—C12 | 117.98 (15) |
O2—V5—O7i | 105.28 (6) | C62—N22—H22A | 120.0 |
O2—V5—O5i | 102.28 (6) | C62—N22—H22B | 120.0 |
O7i—V5—O5i | 93.29 (5) | H22A—N22—H22B | 120.0 |
O2—V5—O11 | 101.94 (6) | C53—C13—C23 | 117.91 (15) |
O7i—V5—O11 | 89.30 (5) | C53—C13—C63 | 117.27 (15) |
O5i—V5—O11 | 154.01 (5) | C23—C13—C63 | 124.82 (15) |
O2—V5—O8 | 99.45 (6) | C33—C23—C13 | 119.34 (16) |
O7i—V5—O8 | 154.97 (5) | C33—C23—H23 | 120.3 |
O5i—V5—O8 | 85.03 (6) | C13—C23—H23 | 120.3 |
O11—V5—O8 | 81.85 (5) | C43—C33—C23 | 119.15 (16) |
O2—V5—O1i | 173.01 (5) | C43—C33—H33 | 120.4 |
O7i—V5—O1i | 81.50 (5) | C23—C33—H33 | 120.4 |
O5i—V5—O1i | 78.70 (5) | N13—C43—C33 | 121.49 (16) |
O11—V5—O1i | 76.12 (5) | N13—C43—H43 | 119.3 |
O8—V5—O1i | 73.68 (5) | C33—C43—H43 | 119.3 |
V1i—O1—V1 | 102.51 (5) | C43—N13—C53 | 119.85 (14) |
V1i—O1—V4 | 97.20 (5) | C43—N13—H13 | 120.1 |
V1—O1—V4 | 90.92 (5) | C53—N13—H13 | 120.1 |
V1i—O1—V2i | 90.75 (5) | N13—C53—C13 | 122.24 (16) |
V1—O1—V2i | 97.09 (5) | N13—C53—H53 | 118.9 |
V4—O1—V2i | 167.25 (6) | C13—C53—H53 | 118.9 |
V1i—O1—V5i | 87.66 (5) | O17—C63—N23 | 123.11 (15) |
V1—O1—V5i | 169.49 (6) | O17—C63—C13 | 119.79 (15) |
V4—O1—V5i | 85.15 (5) | N23—C63—C13 | 117.10 (15) |
V2i—O1—V5i | 85.24 (5) | C63—N23—H23A | 120.0 |
V1i—O1—V3 | 169.42 (6) | C63—N23—H23B | 120.0 |
V1—O1—V3 | 87.70 (5) | H23A—N23—H23B | 120.0 |
V4—O1—V3 | 85.28 (4) | H2—O1W—H1 | 108 (3) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O12ii | 0.88 | 1.78 | 2.6257 (19) | 161 |
N21—H21A···O1W | 0.88 | 2.04 | 2.909 (2) | 168 |
N21—H21B···O16iii | 0.88 | 2.01 | 2.855 (2) | 161 |
N12—H12···O5 | 0.88 | 1.81 | 2.679 (2) | 167 |
N22—H22A···O10iv | 0.88 | 2.07 | 2.929 (2) | 163 |
N22—H22B···O15v | 0.88 | 2.03 | 2.808 (2) | 146 |
N13—H13···O9 | 0.88 | 1.67 | 2.5492 (18) | 173 |
N23—H23A···O6vi | 0.88 | 2.03 | 2.869 (2) | 160 |
N23—H23B···O17vii | 0.88 | 2.05 | 2.878 (2) | 156 |
O1W—H1···O4iii | 0.83 (3) | 2.21 (3) | 3.039 (2) | 172 (3) |
O1W—H2···O7 | 0.83 (3) | 1.95 (3) | 2.768 (2) | 166 (3) |
C21—H21···O16iii | 0.95 | 2.41 | 3.216 (2) | 142 |
C31—H31···O11viii | 0.95 | 2.21 | 3.066 (2) | 149 |
C51—H51···O10ii | 0.95 | 2.45 | 3.265 (2) | 144 |
C22—H22···O15v | 0.95 | 2.72 | 3.617 (2) | 158 |
C32—H32···O3ix | 0.95 | 2.63 | 3.222 (2) | 121 |
C42—H42···O2i | 0.95 | 2.64 | 3.218 (2) | 119 |
C42—H42···O3ix | 0.95 | 2.53 | 3.176 (2) | 125 |
C23—H23···O17vii | 0.95 | 2.55 | 3.422 (2) | 153 |
C33—H33···O4x | 0.95 | 2.52 | 3.267 (2) | 136 |
C33—H33···O14x | 0.95 | 2.39 | 3.269 (2) | 154 |
C43—H43···O13x | 0.95 | 2.68 | 3.314 (2) | 125 |
C53—H53···O6i | 0.95 | 2.44 | 3.173 (2) | 134 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1/2, y+1/2, z; (iii) −x, y, −z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x, y−1, −z+1/2; (vi) x−1/2, −y+3/2, z−1/2; (vii) −x−1/2, y+1/2, −z−1/2; (viii) x−1/2, y−1/2, z; (ix) x, y−1, z; (x) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | (C6H7N2O)6[V10O28]·2H2O |
Mr | 1732.25 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 25.806 (9), 9.5460 (13), 23.577 (10) |
β (°) | 106.60 (4) |
V (Å3) | 5566 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.71 |
Crystal size (mm) | 0.50 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.481, 0.783 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34597, 5811, 5173 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.062, 1.07 |
No. of reflections | 5811 |
No. of parameters | 431 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.50, −0.51 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and DIAMOND (Brandenburg, 2007), SHELXL97, DIAMOND and publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O12i | 0.88 | 1.78 | 2.6257 (19) | 161.1 |
N21—H21A···O1W | 0.88 | 2.04 | 2.909 (2) | 168.0 |
N21—H21B···O16ii | 0.88 | 2.01 | 2.855 (2) | 161.2 |
N12—H12···O5 | 0.88 | 1.81 | 2.679 (2) | 166.5 |
N22—H22A···O10iii | 0.88 | 2.07 | 2.929 (2) | 163.4 |
N22—H22B···O15iv | 0.88 | 2.03 | 2.808 (2) | 146.1 |
N13—H13···O9 | 0.88 | 1.67 | 2.5492 (18) | 172.7 |
N23—H23A···O6v | 0.88 | 2.03 | 2.869 (2) | 160.1 |
N23—H23B···O17vi | 0.88 | 2.05 | 2.878 (2) | 156.4 |
O1W—H1···O4ii | 0.83 (3) | 2.21 (3) | 3.039 (2) | 172 (3) |
O1W—H2···O7 | 0.83 (3) | 1.95 (3) | 2.768 (2) | 166 (3) |
C21—H21···O16ii | 0.95 | 2.41 | 3.216 (2) | 142.2 |
C31—H31···O11vii | 0.95 | 2.21 | 3.066 (2) | 148.6 |
C51—H51···O10i | 0.95 | 2.45 | 3.265 (2) | 144.2 |
C22—H22···O15iv | 0.95 | 2.72 | 3.617 (2) | 157.9 |
C32—H32···O3viii | 0.95 | 2.63 | 3.222 (2) | 120.8 |
C42—H42···O2ix | 0.95 | 2.64 | 3.218 (2) | 119.4 |
C42—H42···O3viii | 0.95 | 2.53 | 3.176 (2) | 125.3 |
C23—H23···O17vi | 0.95 | 2.55 | 3.422 (2) | 153.2 |
C33—H33···O4x | 0.95 | 2.52 | 3.267 (2) | 135.8 |
C33—H33···O14x | 0.95 | 2.39 | 3.269 (2) | 153.5 |
C43—H43···O13x | 0.95 | 2.68 | 3.314 (2) | 124.5 |
C53—H53···O6ix | 0.95 | 2.44 | 3.173 (2) | 133.9 |
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x, y, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x, y−1, −z+1/2; (v) x−1/2, −y+3/2, z−1/2; (vi) −x−1/2, y+1/2, −z−1/2; (vii) x−1/2, y−1/2, z; (viii) x, y−1, z; (ix) −x, −y+1, −z; (x) −x, −y+2, −z. |
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The title compound, (I), was synthesized as a part of our studies focused on interaction between both oxovanadium and oxoperoxovanadium species with biologically important organic substrates. The oxovanadates(V) and peroxovanadium compounds are of great interest in biochemistry and medicine because of their diverse biological activity; the former compounds also have applications in catalysis and materials science. The interaction of nicotinamide with vanadium(V) compounds, and the nature of the products formed, are of interest with respect to the use of amides of pyridine- and pyrazinecarboxylic acids as antituberculotics, and to the potential use of vanadium compounds as insulin mimetic drugs in human medicine (Crans, 1998). From the same reaction solution, V2O5–H2O2–H2O, but containing picolinamide or pyrazinamide, we have isolated and structurally characterized monoperoxovanadium(V) complexes (Sivák et al., 2000; Maďarová et al., 2004; Pacigová et al., 2007).
The asymmetric unit of (I) consists of one-half decavanadate anion of Ci symmetry (although its symmetry is close to the D2h point group) lying on a special position on the glide plane, three 1-H-nicotinamidium(1+) cations and one water molecule of crystallization (Fig. 1). The angle between the (020) glide plane and the central plane of the V10O286– anion [formed by atoms V1, V1i, V3, V3i, V5 and V5i; symmetry code: (i) -x, -y + 1, -z] is 86.29 (1)°. The terminal vanadium–oxygen bond lengths, V—OT, are in the range 1.601 (1)–1.618 (1) Å, with an average value 1.609 (9) Å. The bond lengths of the bridging O atoms with coordination numbers two, three and six have mean values 1.85 (12), 2.00 (7) and 2.24 (10) Å.
The supramolecular structure is formed by D—H···O hydrogen bonds [(D = N, O or C, with H···O ≤ 2.72 Å and D—H···O > 119°, as defined by Brown (1992)] between cations and anions, cations and cations, water molecules and anions, and water molecules and cations, and by non-parallel displaced π-stacking interactions between the pyridine rings.
Two V10O286– anions are bridged via two water molecules, forming rings with graph-set N2 = R44(12) (Etter et al., 1990 and Bernstein et al., 1995) and subsequently chains along the c axis (Fig. 2a, detail in Fig. 3a). The colinearly arranged O5, O9 and O12 atoms act as acceptors of pyridinium H atoms H12, H13 and H11, and terminal O atoms O6 and O10 are acceptors of amide H atoms H23A and H22A. The anion-bridging water molecule acts as an acceptor of the corresponding H21A atom. The 1-H-nicotinamidium(1+) cations form two types of hydrogen-bonded chains along the b axis, almost parallel to the (101) plane (Figs. 2b, 3b and 3c). One type is formed by chains with graph set N1= C(4) containing crystallographically equivalent nicotinamidium molecules containing the Cx1/N11 (x = 1–5) pyridinium ring. The next two chains, with graph set N2= C22(8) and running in opposite directions, are formed by the alternation of the two remaining nicotinamidium cations; both types form sheet-like structures (Athimoolam & Natarajan, 2006). There are two types of C—H···O bond, the first containing decavanadate O atoms and the second containing carboxamide O atoms as acceptors. Bonds of the second type reinforce interactions in the cationic chains mentioned above. All nicotinamidium chains present are mutually π-stacked.
To evaluate the π–π interactions between the pyridine rings, least-square planes n defined by atoms C1n–C5n and N1n were calculated. The mean distance of the plane 1 atoms from plane 3, R(31), is 3.32 (17) Å, and the mean distance of the plane 3 atoms from plane 1,R(13), is 3.32 (17) Å, with an angle between the planes, γ(1), of 9.42 (9)°, corresponding centroid–centroid distance, Rct(1), is 3.5 Å, and the closest interatomic distance, Rclo(C51···N13), is 3.156 (2) Å; for planes 3 and 2, R(32) = 3.44 (11) Å, R(23) = 3.40 (11) Å, γ(2) = 5.77 (9)°, Rct(2) = 3.6 Å and Rclo(N12···C53) = 3.364 (2) Å. The carboxamide groups of the cations are somewhat twisted from the pyridine ring planes n by 13.61 (14)° (for 1), 5.21 (11)° (for 2) and 6.84 (10)° (for 3), respectively, which is obvious for 1-H-nicotinamidium(1+) compounds (Athimoolam & Natarajan, 2007a,b). In comparison with other 1-H-nicotinaminium(1+) compounds from the Cambridge Structural Database (Version 5.27, update to September 2006; Allen, 2002), the Rct and Rclo distances in (I) are the shortest among all nonparallel displaced structures (Rct in the other nonparallel displaced structures lies between 3.8 and 4.9 Å, and Rclo lies between 3.3 and 3.6 Å) and the Rct values are close to the interplanar distances of parallel-displaced π-stacked structures containing 1-H-nicotinamidium(1+) molecules, which lie between 3.1 and 3.5 Å (Rct in the parallel-displaced structures lies between 3.4 and 3.9 Å).