The hydrothermal reaction of cobalt acetate, vanadium pentoxide and 2,5-bis(4-pyridyl)-1,3,4-thiadiazole resulted in the title complex, [Co(V2O6)(C12H8N4S)(H2O)3], in which the cobalt(II) cation shows distorted octahedral geometry, coordinated by one pyridine N atom, two O atoms from tetravanadate and three water molecules.
Supporting information
CCDC reference: 252764
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.039
- wR factor = 0.094
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6
Alert level G
FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C12 H14 Co1 N4 O9 S1 V2
Atom count from _chemical_formula_moiety:
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97.
catena-poly[bis[cobalt(II)-2,5-bis(4-pyridyl)
-1,3,4-thiadiazole](tetravanadate)(hexahydrate)]
top
Crystal data top
[Co(C12H8N4S)(V2O6)3(H2O)] | Z = 2 |
Mr = 551.14 | F(000) = 550 |
Triclinic, P1 | Dx = 2.001 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0562 (18) Å | Cell parameters from 86 reflections |
b = 8.2506 (18) Å | θ = 2.5–25.2° |
c = 14.253 (3) Å | µ = 2.07 mm−1 |
α = 96.313 (3)° | T = 293 K |
β = 91.631 (3)° | Block, red |
γ = 103.402 (3)° | 0.28 × 0.21 × 0.12 mm |
V = 914.6 (3) Å3 | |
Data collection top
Bruker SMART Apex CCD Diffractometer | 3483 independent reflections |
Radiation source: fine-focus sealed tube | 3035 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 26.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→9 |
Tmin = 0.595, Tmax = 0.789 | k = −10→7 |
4126 measured reflections | l = −14→17 |
Refinement top
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)] = 0.039 | Hydrogen site location: difmap (O-H) and geom (C-H) |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0485P)2] where P = (Fo2 + 2Fc2)/3 |
3483 reflections | (Δ/σ)max < 0.001 |
262 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.23745 (6) | 0.15653 (5) | 0.38131 (3) | 0.01374 (14) | |
V1 | 0.09244 (7) | −0.25405 (7) | 0.46779 (4) | 0.01310 (15) | |
V2 | 0.19563 (7) | −0.43253 (7) | 0.64109 (4) | 0.01500 (16) | |
S1 | 0.68596 (12) | −0.41363 (11) | 0.12653 (6) | 0.0197 (2) | |
N1 | 0.4249 (4) | 0.0801 (3) | 0.29940 (18) | 0.0148 (6) | |
N2 | 0.6583 (4) | −0.1980 (4) | 0.0162 (2) | 0.0224 (7) | |
N3 | 0.7116 (4) | −0.3198 (4) | −0.0381 (2) | 0.0217 (7) | |
C11 | 0.8823 (5) | −0.8395 (4) | −0.0293 (3) | 0.0232 (8) | |
H11A | 0.9049 | −0.9247 | 0.0066 | 0.080* | |
O1 | 0.1785 (3) | −0.0811 (3) | 0.42268 (15) | 0.0190 (5) | |
O2 | −0.0650 (3) | −0.2329 (3) | 0.53529 (15) | 0.0199 (6) | |
O3 | 0.2475 (3) | −0.3182 (3) | 0.53858 (16) | 0.0186 (5) | |
O4 | 0.3511 (3) | −0.5304 (3) | 0.65283 (16) | 0.0204 (6) | |
O5 | 0.1903 (3) | −0.3036 (3) | 0.73515 (16) | 0.0218 (6) | |
O6 | −0.0145 (3) | −0.5768 (3) | 0.62458 (15) | 0.0177 (5) | |
C1 | 0.5054 (5) | −0.0304 (4) | 0.3291 (2) | 0.0195 (8) | |
H1A | 0.5073 | −0.0423 | 0.3953 | 0.080* | |
C2 | 0.5852 (5) | −0.1293 (4) | 0.2702 (2) | 0.0191 (8) | |
H2A | 0.6435 | −0.2061 | 0.2947 | 0.080* | |
C3 | 0.5805 (4) | −0.1132 (4) | 0.1739 (2) | 0.0167 (7) | |
C4 | 0.5083 (5) | 0.0112 (4) | 0.1437 (2) | 0.0189 (8) | |
H4A | 0.5122 | 0.0322 | 0.0787 | 0.080* | |
C5 | 0.4323 (4) | 0.1039 (4) | 0.2075 (2) | 0.0181 (8) | |
H5A | 0.3822 | 0.1889 | 0.1857 | 0.080* | |
C6 | 0.6413 (4) | −0.2272 (4) | 0.1041 (2) | 0.0178 (8) | |
C7 | 0.7318 (4) | −0.4413 (4) | 0.0088 (2) | 0.0179 (8) | |
C8 | 0.7913 (5) | −0.5854 (4) | −0.0348 (2) | 0.0187 (8) | |
C9 | 0.8209 (5) | −0.5973 (4) | −0.1313 (2) | 0.0213 (8) | |
H9A | 0.8015 | −0.5136 | −0.1693 | 0.080* | |
C10 | 0.8787 (5) | −0.7333 (5) | −0.1701 (3) | 0.0241 (9) | |
H10A | 0.8966 | −0.7432 | −0.2365 | 0.080* | |
N4 | 0.9109 (4) | −0.8529 (4) | −0.1214 (2) | 0.0228 (7) | |
C12 | 0.8231 (5) | −0.7097 (4) | 0.0169 (2) | 0.0204 (8) | |
H12A | 0.8037 | −0.7052 | 0.0832 | 0.080* | |
O1W | 0.4151 (3) | 0.2473 (3) | 0.49621 (16) | 0.0200 (5) | |
O2W | 0.0464 (3) | 0.0856 (3) | 0.27223 (17) | 0.0247 (6) | |
O3W | 0.2934 (3) | 0.3962 (3) | 0.33170 (16) | 0.0215 (6) | |
H3WA | 0.4075 | 0.4462 | 0.3431 | 0.050* | |
H1WA | 0.5275 | 0.2806 | 0.4877 | 0.050* | |
H3WB | 0.2439 | 0.4717 | 0.3557 | 0.050* | |
H2WA | 0.0523 | 0.0354 | 0.2207 | 0.050* | |
H2WB | −0.0256 | 0.1544 | 0.2674 | 0.050* | |
H1WB | 0.3891 | 0.3240 | 0.5440 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0152 (3) | 0.0119 (3) | 0.0140 (2) | 0.00247 (19) | 0.00297 (18) | 0.00214 (18) |
V1 | 0.0139 (3) | 0.0109 (3) | 0.0143 (3) | 0.0020 (2) | 0.0026 (2) | 0.0024 (2) |
V2 | 0.0159 (3) | 0.0138 (3) | 0.0151 (3) | 0.0026 (2) | 0.0012 (2) | 0.0023 (2) |
S1 | 0.0274 (5) | 0.0179 (5) | 0.0159 (4) | 0.0091 (4) | 0.0038 (4) | 0.0021 (3) |
N1 | 0.0167 (16) | 0.0144 (15) | 0.0138 (14) | 0.0034 (12) | 0.0035 (12) | 0.0034 (11) |
N2 | 0.0313 (19) | 0.0206 (17) | 0.0188 (16) | 0.0113 (14) | 0.0070 (13) | 0.0047 (13) |
N3 | 0.0297 (19) | 0.0223 (17) | 0.0158 (15) | 0.0113 (14) | 0.0039 (13) | 0.0025 (13) |
C11 | 0.021 (2) | 0.0169 (19) | 0.031 (2) | 0.0034 (15) | 0.0032 (16) | 0.0031 (16) |
O1 | 0.0231 (14) | 0.0131 (12) | 0.0207 (13) | 0.0021 (10) | 0.0033 (11) | 0.0055 (10) |
O2 | 0.0207 (14) | 0.0207 (13) | 0.0181 (13) | 0.0046 (11) | 0.0041 (10) | 0.0012 (10) |
O3 | 0.0168 (13) | 0.0189 (13) | 0.0217 (13) | 0.0038 (10) | 0.0020 (10) | 0.0097 (10) |
O4 | 0.0210 (14) | 0.0199 (13) | 0.0222 (13) | 0.0070 (11) | 0.0013 (11) | 0.0056 (10) |
O5 | 0.0257 (15) | 0.0196 (14) | 0.0183 (13) | 0.0038 (11) | 0.0009 (11) | −0.0027 (10) |
O6 | 0.0205 (14) | 0.0145 (12) | 0.0154 (12) | −0.0001 (10) | 0.0007 (10) | 0.0000 (9) |
C1 | 0.022 (2) | 0.0179 (19) | 0.0195 (19) | 0.0047 (15) | 0.0029 (15) | 0.0052 (15) |
C2 | 0.023 (2) | 0.0186 (19) | 0.0181 (18) | 0.0074 (15) | 0.0026 (15) | 0.0064 (15) |
C3 | 0.0153 (19) | 0.0128 (17) | 0.0206 (18) | 0.0016 (14) | 0.0023 (14) | −0.0006 (14) |
C4 | 0.020 (2) | 0.0192 (19) | 0.0170 (18) | 0.0038 (15) | 0.0038 (15) | 0.0043 (14) |
C5 | 0.020 (2) | 0.0159 (18) | 0.0179 (18) | 0.0026 (15) | 0.0029 (15) | 0.0036 (14) |
C6 | 0.0140 (19) | 0.0182 (19) | 0.0208 (19) | 0.0024 (14) | 0.0002 (14) | 0.0041 (14) |
C7 | 0.0184 (19) | 0.0199 (19) | 0.0145 (17) | 0.0041 (15) | 0.0008 (14) | −0.0012 (14) |
C8 | 0.019 (2) | 0.0160 (18) | 0.0202 (18) | 0.0029 (15) | 0.0011 (15) | −0.0010 (14) |
C9 | 0.022 (2) | 0.022 (2) | 0.0195 (19) | 0.0062 (16) | 0.0012 (15) | 0.0013 (15) |
C10 | 0.025 (2) | 0.022 (2) | 0.023 (2) | 0.0040 (16) | 0.0053 (16) | −0.0031 (16) |
N4 | 0.0216 (18) | 0.0184 (17) | 0.0256 (17) | 0.0026 (13) | 0.0020 (13) | −0.0049 (13) |
C12 | 0.022 (2) | 0.0193 (19) | 0.0187 (18) | 0.0028 (15) | 0.0008 (15) | 0.0021 (15) |
O1W | 0.0167 (14) | 0.0243 (14) | 0.0175 (12) | 0.0027 (10) | 0.0009 (10) | 0.0004 (10) |
O2W | 0.0276 (16) | 0.0248 (14) | 0.0222 (13) | 0.0124 (12) | −0.0063 (11) | −0.0062 (11) |
O3W | 0.0241 (15) | 0.0155 (13) | 0.0254 (13) | 0.0052 (11) | 0.0041 (11) | 0.0035 (10) |
Geometric parameters (Å, º) top
Co1—O2i | 2.019 (2) | O6—V1ii | 1.794 (2) |
Co1—O1 | 2.063 (2) | C1—C2 | 1.380 (5) |
Co1—O2W | 2.092 (2) | C1—H1A | 0.9600 |
Co1—O1W | 2.096 (2) | C2—C3 | 1.395 (5) |
Co1—N1 | 2.102 (3) | C2—H2A | 0.9600 |
Co1—O3W | 2.127 (2) | C3—C4 | 1.391 (5) |
V1—O1 | 1.643 (2) | C3—C6 | 1.466 (5) |
V1—O2 | 1.643 (2) | C4—C5 | 1.372 (5) |
V1—O3 | 1.792 (2) | C4—H4A | 0.9599 |
V1—O6ii | 1.794 (2) | C5—H5A | 0.9601 |
V2—O5 | 1.625 (2) | C7—C8 | 1.465 (5) |
V2—O4 | 1.654 (2) | C8—C12 | 1.392 (5) |
V2—O6 | 1.822 (2) | C8—C9 | 1.400 (5) |
V2—O3 | 1.831 (2) | C9—C10 | 1.379 (5) |
S1—C6 | 1.719 (4) | C9—H9A | 0.9599 |
S1—C7 | 1.730 (3) | C10—N4 | 1.335 (5) |
N1—C1 | 1.332 (4) | C10—H10A | 0.9600 |
N1—C5 | 1.347 (4) | C12—H12A | 0.9599 |
N2—C6 | 1.306 (4) | O1W—H1WA | 0.8991 |
N2—N3 | 1.357 (4) | O1W—H1WB | 0.9391 |
N3—C7 | 1.303 (4) | O2W—H2WA | 0.8111 |
C11—N4 | 1.337 (5) | O2W—H2WB | 0.9063 |
C11—C12 | 1.381 (5) | O3W—H3WA | 0.9176 |
C11—H11A | 0.9600 | O3W—H3WB | 0.8606 |
O2—Co1i | 2.019 (2) | | |
| | | |
O2i—Co1—O1 | 92.51 (9) | C2—C1—H1A | 118.2 |
O2i—Co1—O2W | 88.19 (10) | C1—C2—C3 | 118.1 (3) |
O1—Co1—O2W | 91.26 (10) | C1—C2—H2A | 121.2 |
O2i—Co1—O1W | 86.38 (10) | C3—C2—H2A | 120.7 |
O1—Co1—O1W | 91.95 (9) | C4—C3—C2 | 118.1 (3) |
O2W—Co1—O1W | 173.81 (9) | C4—C3—C6 | 119.6 (3) |
O2i—Co1—N1 | 177.54 (10) | C2—C3—C6 | 122.2 (3) |
O1—Co1—N1 | 87.41 (10) | C5—C4—C3 | 119.5 (3) |
O2W—Co1—N1 | 94.27 (10) | C5—C4—H4A | 120.3 |
O1W—Co1—N1 | 91.16 (10) | C3—C4—H4A | 120.2 |
O2i—Co1—O3W | 88.71 (9) | N1—C5—C4 | 122.5 (3) |
O1—Co1—O3W | 177.14 (9) | N1—C5—H5A | 118.7 |
O2W—Co1—O3W | 86.19 (10) | C4—C5—H5A | 118.7 |
O1W—Co1—O3W | 90.71 (9) | N2—C6—C3 | 121.7 (3) |
N1—Co1—O3W | 91.48 (10) | N2—C6—S1 | 113.7 (3) |
O1—V1—O2 | 112.63 (12) | C3—C6—S1 | 124.5 (3) |
O1—V1—O3 | 111.07 (12) | N3—C7—C8 | 122.4 (3) |
O2—V1—O3 | 107.25 (11) | N3—C7—S1 | 113.7 (3) |
O1—V1—O6ii | 110.37 (11) | C8—C7—S1 | 123.9 (3) |
O2—V1—O6ii | 108.94 (12) | C12—C8—C9 | 118.5 (3) |
O3—V1—O6ii | 106.32 (11) | C12—C8—C7 | 122.3 (3) |
O5—V2—O4 | 110.76 (13) | C9—C8—C7 | 119.1 (3) |
O5—V2—O6 | 106.41 (12) | C10—C9—C8 | 117.8 (3) |
O4—V2—O6 | 112.50 (12) | C10—C9—H9A | 121.1 |
O5—V2—O3 | 110.72 (12) | C8—C9—H9A | 121.1 |
O4—V2—O3 | 104.82 (11) | N4—C10—C9 | 124.4 (3) |
O6—V2—O3 | 111.72 (11) | N4—C10—H10A | 117.6 |
C6—S1—C7 | 86.83 (17) | C9—C10—H10A | 118.0 |
C1—N1—C5 | 117.5 (3) | C10—N4—C11 | 117.0 (3) |
C1—N1—Co1 | 119.8 (2) | C11—C12—C8 | 118.6 (3) |
C5—N1—Co1 | 120.3 (2) | C11—C12—H12A | 120.9 |
C6—N2—N3 | 113.1 (3) | C8—C12—H12A | 120.5 |
C7—N3—N2 | 112.7 (3) | Co1—O1W—H1WA | 121.3 |
N4—C11—C12 | 123.6 (3) | Co1—O1W—H1WB | 118.1 |
N4—C11—H11A | 117.9 | H1WA—O1W—H1WB | 107.1 |
C12—C11—H11A | 118.5 | Co1—O2W—H2WA | 127.0 |
V1—O1—Co1 | 165.77 (15) | Co1—O2W—H2WB | 116.8 |
V1—O2—Co1i | 168.36 (15) | H2WA—O2W—H2WB | 109.3 |
V1—O3—V2 | 123.74 (13) | Co1—O3W—H3WA | 109.9 |
V1ii—O6—V2 | 128.55 (13) | Co1—O3W—H3WB | 119.0 |
N1—C1—C2 | 123.9 (3) | H3WA—O3W—H3WB | 103.3 |
N1—C1—H1A | 117.9 | | |
| | | |
O1—Co1—N1—C1 | −32.6 (3) | C1—C2—C3—C4 | 5.3 (5) |
O2W—Co1—N1—C1 | −123.7 (3) | C1—C2—C3—C6 | −171.8 (3) |
O1W—Co1—N1—C1 | 59.3 (3) | C2—C3—C4—C5 | −5.3 (5) |
O3W—Co1—N1—C1 | 150.0 (3) | C6—C3—C4—C5 | 171.9 (3) |
O1—Co1—N1—C5 | 129.2 (3) | C1—N1—C5—C4 | 4.6 (5) |
O2W—Co1—N1—C5 | 38.1 (3) | Co1—N1—C5—C4 | −157.6 (3) |
O1W—Co1—N1—C5 | −138.9 (3) | C3—C4—C5—N1 | 0.3 (5) |
O3W—Co1—N1—C5 | −48.2 (3) | N3—N2—C6—C3 | −178.3 (3) |
C6—N2—N3—C7 | 1.0 (4) | N3—N2—C6—S1 | −1.4 (4) |
O2—V1—O1—Co1 | −6.3 (6) | C4—C3—C6—N2 | 12.4 (5) |
O3—V1—O1—Co1 | −126.6 (6) | C2—C3—C6—N2 | −170.5 (3) |
O6ii—V1—O1—Co1 | 115.7 (6) | C4—C3—C6—S1 | −164.1 (3) |
O2i—Co1—O1—V1 | 9.7 (6) | C2—C3—C6—S1 | 13.0 (5) |
O2W—Co1—O1—V1 | −78.5 (6) | C7—S1—C6—N2 | 1.1 (3) |
O1W—Co1—O1—V1 | 96.2 (6) | C7—S1—C6—C3 | 177.9 (3) |
N1—Co1—O1—V1 | −172.7 (6) | N2—N3—C7—C8 | −179.0 (3) |
O1—V1—O2—Co1i | −18.0 (8) | N2—N3—C7—S1 | −0.1 (4) |
O3—V1—O2—Co1i | 104.5 (7) | C6—S1—C7—N3 | −0.5 (3) |
O6ii—V1—O2—Co1i | −140.8 (7) | C6—S1—C7—C8 | 178.3 (3) |
O1—V1—O3—V2 | 149.75 (14) | N3—C7—C8—C12 | 175.9 (3) |
O2—V1—O3—V2 | 26.29 (19) | S1—C7—C8—C12 | −2.9 (5) |
O6ii—V1—O3—V2 | −90.15 (16) | N3—C7—C8—C9 | −2.7 (5) |
O5—V2—O3—V1 | −84.03 (18) | S1—C7—C8—C9 | 178.5 (3) |
O4—V2—O3—V1 | 156.50 (15) | C12—C8—C9—C10 | 0.6 (5) |
O6—V2—O3—V1 | 34.39 (19) | C7—C8—C9—C10 | 179.2 (3) |
O5—V2—O6—V1ii | 178.61 (16) | C8—C9—C10—N4 | −1.1 (6) |
O4—V2—O6—V1ii | −59.93 (19) | C9—C10—N4—C11 | 1.0 (6) |
O3—V2—O6—V1ii | 57.65 (19) | C12—C11—N4—C10 | −0.4 (5) |
C5—N1—C1—C2 | −4.6 (5) | N4—C11—C12—C8 | −0.1 (6) |
Co1—N1—C1—C2 | 157.7 (3) | C9—C8—C12—C11 | −0.1 (5) |
N1—C1—C2—C3 | −0.4 (5) | C7—C8—C12—C11 | −178.7 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y−1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H3WA···O4iii | 0.92 | 1.90 | 2.813 (3) | 171 |
O1W—H1WA···O3iii | 0.90 | 1.82 | 2.716 (3) | 172 |
O3W—H3WB···O6i | 0.86 | 2.23 | 3.014 (3) | 152 |
O2W—H2WA···N4iv | 0.81 | 2.03 | 2.804 (4) | 160 |
O2W—H2WB···O5i | 0.91 | 2.01 | 2.916 (3) | 176 |
O1W—H1WB···O4v | 0.94 | 1.93 | 2.867 (3) | 173 |
Symmetry codes: (i) −x, −y, −z+1; (iii) −x+1, −y, −z+1; (iv) −x+1, −y−1, −z; (v) x, y+1, z. |