Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103029445/na1629sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103029445/na1629Isup2.hkl |
CCDC reference: 235314
The title compound was synthesized by a hydrothermal method from a mixture of 1,2,4,5-benzenetetracarboxylic acid (1 mmol, 0.257 g), Co(SO4)2·6H2O(1 mmol, 0.281 g), 1,10-phenanthroline (0.05 mmol, 0.0991 g) and 2-aminopyrimidine (2 mmol, 0.192 g) in a 30 ml teflon-lined stainless steel reactor. The solution was heated at 403 K for 5 d, and then the solution was cooled slowly to room temperature; red prism-shaped crystals of (I) were collected for X-ray analysis.
The O—H distance was refined subject to a distance restraint [O—H = 0.82 (1) Å]. The other H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.93 Å, with Uiso(H) equal to 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Co(C10H4O8)(C12H8N2)(H2O)] | Z = 2 |
Mr = 509.28 | F(000) = 518 |
Triclinic, P1 | Dx = 1.753 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6876 (9) Å | Cell parameters from 248 reflections |
b = 10.2079 (10) Å | θ = 2.4–23.0° |
c = 11.3561 (11) Å | µ = 0.95 mm−1 |
α = 86.808 (1)° | T = 273 K |
β = 72.141 (1)° | Prism, red |
γ = 64.928 (1)° | 0.59 × 0.55 × 0.34 mm |
V = 964.58 (16) Å3 |
Bruker SMART CCD area-detector diffractometer | 3371 independent reflections |
Radiation source: fine-focus sealed tube | 3215 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→11 |
Tmin = 0.571, Tmax = 0.722 | k = −12→11 |
6669 measured reflections | l = −13→13 |
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)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0313P)2 + 0.522P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3371 reflections | Δρmax = 0.28 e Å−3 |
315 parameters | Δρmin = −0.29 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: 0.0414 (17) |
[Co(C10H4O8)(C12H8N2)(H2O)] | γ = 64.928 (1)° |
Mr = 509.28 | V = 964.58 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.6876 (9) Å | Mo Kα radiation |
b = 10.2079 (10) Å | µ = 0.95 mm−1 |
c = 11.3561 (11) Å | T = 273 K |
α = 86.808 (1)° | 0.59 × 0.55 × 0.34 mm |
β = 72.141 (1)° |
Bruker SMART CCD area-detector diffractometer | 3371 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 3215 reflections with I > 2σ(I) |
Tmin = 0.571, Tmax = 0.722 | Rint = 0.012 |
6669 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 1 restraint |
wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.28 e Å−3 |
3371 reflections | Δρmin = −0.29 e Å−3 |
315 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. The O—H distance was refined subject to a distance restraint [O—H = 0.82 (1) %A]. H9 can be positioned with a SHELXL HFIX 147 command, but H9b only can be positioned from a difference map and refined subject to a distance restraint [O—H = 0.82 (1) Å], so that H9b approximately same as H9, which is why these two water H atoms [H9 and H9B] were treated differently. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.03047 (3) | 0.64435 (2) | 0.26583 (2) | 0.01981 (10) | |
O1 | −0.15217 (15) | 0.58018 (14) | 0.36161 (11) | 0.0274 (3) | |
O2 | −0.24254 (18) | 0.55106 (18) | 0.21105 (12) | 0.0379 (4) | |
H2 | −0.1881 | 0.5914 | 0.1709 | 0.057* | |
O3 | −0.31281 (14) | 0.65972 (13) | 0.65043 (12) | 0.0255 (3) | |
O4 | −0.15180 (14) | 0.42311 (13) | 0.59928 (11) | 0.0232 (3) | |
O5 | −0.07601 (15) | 0.68519 (13) | 0.12147 (11) | 0.0256 (3) | |
O6 | −0.19525 (18) | 0.76792 (14) | −0.02205 (12) | 0.0340 (3) | |
O7 | 0.37471 (16) | 1.00736 (15) | −0.20818 (14) | 0.0391 (4) | |
O8 | 0.38653 (17) | 0.78590 (15) | −0.21772 (15) | 0.0440 (4) | |
H8 | 0.4760 | 0.7671 | −0.2666 | 0.066* | |
O9 | 0.18396 (17) | 0.44222 (14) | 0.16821 (13) | 0.0320 (3) | |
H9 | 0.2270 | 0.3861 | 0.2142 | 0.048* | |
N1 | −0.10232 (18) | 0.85251 (15) | 0.36087 (13) | 0.0239 (3) | |
N2 | 0.19074 (17) | 0.73961 (16) | 0.19143 (13) | 0.0234 (3) | |
C1 | −0.2458 (2) | 0.9054 (2) | 0.44578 (18) | 0.0336 (4) | |
H1 | −0.3007 | 0.8474 | 0.4663 | 0.040* | |
C2 | −0.3181 (3) | 1.0449 (2) | 0.5059 (2) | 0.0437 (5) | |
H2A | −0.4195 | 1.0788 | 0.5647 | 0.052* | |
C3 | −0.2382 (3) | 1.1305 (2) | 0.4771 (2) | 0.0450 (6) | |
H3 | −0.2855 | 1.2238 | 0.5160 | 0.054* | |
C4 | −0.0847 (3) | 1.0783 (2) | 0.38913 (18) | 0.0348 (5) | |
C5 | 0.0121 (3) | 1.1573 (2) | 0.3574 (2) | 0.0442 (6) | |
H5 | −0.0288 | 1.2509 | 0.3942 | 0.053* | |
C6 | 0.1603 (3) | 1.0987 (2) | 0.2760 (2) | 0.0438 (6) | |
H6 | 0.2206 | 1.1522 | 0.2581 | 0.053* | |
C7 | 0.2283 (3) | 0.9555 (2) | 0.21557 (18) | 0.0330 (4) | |
C8 | 0.3838 (3) | 0.8874 (3) | 0.1315 (2) | 0.0426 (5) | |
H8A | 0.4494 | 0.9358 | 0.1105 | 0.051* | |
C9 | 0.4380 (3) | 0.7500 (3) | 0.0809 (2) | 0.0424 (5) | |
H9A | 0.5414 | 0.7034 | 0.0260 | 0.051* | |
C10 | 0.3374 (2) | 0.6799 (2) | 0.11196 (18) | 0.0329 (4) | |
H10 | 0.3752 | 0.5869 | 0.0752 | 0.040* | |
C11 | 0.1359 (2) | 0.87599 (19) | 0.24367 (16) | 0.0239 (4) | |
C12 | −0.0216 (2) | 0.93725 (18) | 0.33264 (16) | 0.0247 (4) | |
C13 | −0.2456 (2) | 0.55366 (18) | 0.32534 (16) | 0.0214 (4) | |
C14 | −0.37430 (19) | 0.52296 (17) | 0.41623 (15) | 0.0191 (3) | |
C15 | −0.38829 (19) | 0.52132 (17) | 0.54273 (15) | 0.0182 (3) | |
C16 | −0.5140 (2) | 0.49829 (17) | 0.62414 (15) | 0.0201 (3) | |
H16 | −0.5241 | 0.4970 | 0.7083 | 0.024* | |
C17 | −0.27171 (19) | 0.53728 (17) | 0.59906 (14) | 0.0185 (3) | |
C18 | −0.1196 (2) | 0.77691 (17) | 0.04299 (15) | 0.0204 (3) | |
C19 | −0.0615 (2) | 0.89547 (17) | 0.02549 (15) | 0.0194 (3) | |
C20 | 0.0892 (2) | 0.86184 (18) | −0.05910 (15) | 0.0211 (3) | |
H20 | 0.1498 | 0.7689 | −0.0993 | 0.025* | |
C21 | 0.1519 (2) | 0.96457 (18) | −0.08526 (15) | 0.0204 (3) | |
C22 | 0.3159 (2) | 0.92358 (19) | −0.17620 (16) | 0.0239 (4) | |
H9B | 0.171 (3) | 0.393 (2) | 0.1223 (18) | 0.042 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01856 (14) | 0.02002 (14) | 0.02412 (15) | −0.01067 (10) | −0.00741 (10) | 0.00112 (9) |
O1 | 0.0270 (7) | 0.0426 (8) | 0.0246 (6) | −0.0253 (6) | −0.0099 (5) | 0.0082 (5) |
O2 | 0.0484 (9) | 0.0664 (10) | 0.0230 (7) | −0.0466 (8) | −0.0131 (6) | 0.0136 (6) |
O3 | 0.0231 (6) | 0.0226 (6) | 0.0322 (7) | −0.0096 (5) | −0.0100 (5) | −0.0036 (5) |
O4 | 0.0202 (6) | 0.0237 (6) | 0.0264 (6) | −0.0069 (5) | −0.0111 (5) | −0.0006 (5) |
O5 | 0.0317 (7) | 0.0300 (7) | 0.0274 (7) | −0.0217 (6) | −0.0149 (5) | 0.0121 (5) |
O6 | 0.0517 (9) | 0.0355 (7) | 0.0354 (7) | −0.0293 (7) | −0.0268 (7) | 0.0105 (6) |
O7 | 0.0302 (7) | 0.0365 (8) | 0.0486 (9) | −0.0213 (6) | 0.0018 (6) | −0.0032 (6) |
O8 | 0.0297 (8) | 0.0295 (7) | 0.0564 (10) | −0.0136 (6) | 0.0129 (7) | −0.0142 (7) |
O9 | 0.0407 (8) | 0.0237 (7) | 0.0342 (7) | −0.0098 (6) | −0.0200 (6) | −0.0038 (6) |
N1 | 0.0235 (8) | 0.0233 (7) | 0.0244 (7) | −0.0080 (6) | −0.0098 (6) | 0.0016 (6) |
N2 | 0.0233 (8) | 0.0249 (7) | 0.0256 (7) | −0.0128 (6) | −0.0091 (6) | 0.0032 (6) |
C1 | 0.0260 (10) | 0.0363 (11) | 0.0324 (10) | −0.0076 (8) | −0.0090 (8) | 0.0009 (8) |
C2 | 0.0352 (12) | 0.0395 (12) | 0.0359 (11) | 0.0021 (10) | −0.0085 (9) | −0.0053 (9) |
C3 | 0.0565 (14) | 0.0248 (10) | 0.0377 (11) | 0.0024 (10) | −0.0206 (11) | −0.0065 (8) |
C4 | 0.0538 (13) | 0.0213 (9) | 0.0323 (10) | −0.0108 (9) | −0.0255 (10) | 0.0040 (8) |
C5 | 0.0801 (18) | 0.0235 (10) | 0.0433 (12) | −0.0257 (11) | −0.0338 (13) | 0.0064 (9) |
C6 | 0.0784 (17) | 0.0380 (12) | 0.0457 (13) | −0.0425 (12) | −0.0371 (13) | 0.0176 (10) |
C7 | 0.0496 (12) | 0.0381 (11) | 0.0329 (10) | −0.0320 (10) | −0.0247 (9) | 0.0156 (8) |
C8 | 0.0484 (13) | 0.0621 (15) | 0.0435 (12) | −0.0443 (12) | −0.0222 (10) | 0.0211 (11) |
C9 | 0.0290 (11) | 0.0589 (14) | 0.0435 (12) | −0.0255 (10) | −0.0084 (9) | 0.0112 (10) |
C10 | 0.0274 (10) | 0.0361 (10) | 0.0333 (10) | −0.0144 (8) | −0.0052 (8) | 0.0016 (8) |
C11 | 0.0323 (10) | 0.0246 (9) | 0.0239 (9) | −0.0161 (8) | −0.0161 (8) | 0.0064 (7) |
C12 | 0.0349 (10) | 0.0204 (8) | 0.0242 (9) | −0.0116 (8) | −0.0170 (8) | 0.0042 (7) |
C13 | 0.0226 (9) | 0.0219 (8) | 0.0230 (9) | −0.0123 (7) | −0.0076 (7) | 0.0028 (6) |
C14 | 0.0179 (8) | 0.0171 (8) | 0.0232 (8) | −0.0082 (7) | −0.0066 (7) | 0.0019 (6) |
C15 | 0.0164 (8) | 0.0161 (8) | 0.0234 (8) | −0.0070 (6) | −0.0078 (6) | 0.0012 (6) |
C16 | 0.0217 (8) | 0.0222 (8) | 0.0188 (8) | −0.0112 (7) | −0.0070 (7) | 0.0027 (6) |
C17 | 0.0168 (8) | 0.0238 (9) | 0.0166 (8) | −0.0113 (7) | −0.0040 (6) | 0.0021 (6) |
C18 | 0.0212 (8) | 0.0214 (8) | 0.0183 (8) | −0.0101 (7) | −0.0039 (7) | −0.0006 (6) |
C19 | 0.0232 (8) | 0.0208 (8) | 0.0184 (8) | −0.0112 (7) | −0.0099 (7) | 0.0038 (6) |
C20 | 0.0234 (9) | 0.0180 (8) | 0.0220 (8) | −0.0091 (7) | −0.0068 (7) | 0.0005 (6) |
C21 | 0.0211 (9) | 0.0228 (8) | 0.0194 (8) | −0.0102 (7) | −0.0084 (7) | 0.0025 (6) |
C22 | 0.0231 (9) | 0.0258 (9) | 0.0239 (9) | −0.0110 (7) | −0.0080 (7) | 0.0014 (7) |
Co1—O9 | 2.0834 (13) | C4—C12 | 1.406 (2) |
Co1—N1 | 2.1028 (15) | C4—C5 | 1.436 (3) |
Co1—N2 | 2.1103 (14) | C5—C6 | 1.339 (4) |
Co1—O1 | 2.1131 (12) | C5—H5 | 0.9300 |
Co1—O4i | 2.1220 (12) | C6—C7 | 1.436 (3) |
Co1—O5 | 2.1266 (12) | C6—H6 | 0.9300 |
O1—C13 | 1.229 (2) | C7—C8 | 1.403 (3) |
O2—C13 | 1.291 (2) | C7—C11 | 1.405 (2) |
O2—H2 | 0.8200 | C8—C9 | 1.361 (3) |
O3—C17 | 1.256 (2) | C8—H8A | 0.9300 |
O4—C17 | 1.250 (2) | C9—C10 | 1.393 (3) |
O4—Co1i | 2.1220 (12) | C9—H9A | 0.9300 |
O5—C18 | 1.285 (2) | C10—H10 | 0.9300 |
O6—C18 | 1.220 (2) | C11—C12 | 1.434 (3) |
O7—C22 | 1.200 (2) | C13—C14 | 1.491 (2) |
O8—C22 | 1.314 (2) | C14—C16ii | 1.394 (2) |
O8—H8 | 0.8200 | C14—C15 | 1.401 (2) |
O9—H9 | 0.8200 | C15—C16 | 1.386 (2) |
O9—H9B | 0.816 (10) | C15—C17 | 1.524 (2) |
N1—C1 | 1.324 (2) | C16—C14ii | 1.394 (2) |
N1—C12 | 1.360 (2) | C16—H16 | 0.9300 |
N2—C10 | 1.321 (2) | C18—C19 | 1.517 (2) |
N2—C11 | 1.358 (2) | C19—C20 | 1.387 (2) |
C1—C2 | 1.397 (3) | C19—C21iii | 1.397 (2) |
C1—H1 | 0.9300 | C20—C21 | 1.397 (2) |
C2—C3 | 1.363 (3) | C20—H20 | 0.9300 |
C2—H2A | 0.9300 | C21—C19iii | 1.397 (2) |
C3—C4 | 1.404 (3) | C21—C22 | 1.498 (2) |
C3—H3 | 0.9300 | ||
O9—Co1—N1 | 173.81 (6) | C8—C7—C6 | 124.17 (19) |
O9—Co1—N2 | 94.98 (6) | C11—C7—C6 | 118.6 (2) |
N1—Co1—N2 | 79.21 (6) | C9—C8—C7 | 119.57 (18) |
O9—Co1—O1 | 94.40 (6) | C9—C8—H8A | 120.2 |
N1—Co1—O1 | 91.33 (5) | C7—C8—H8A | 120.2 |
N2—Co1—O1 | 170.41 (5) | C8—C9—C10 | 119.5 (2) |
O9—Co1—O4i | 87.74 (5) | C8—C9—H9A | 120.2 |
N1—Co1—O4i | 89.54 (5) | C10—C9—H9A | 120.2 |
N2—Co1—O4i | 84.46 (5) | N2—C10—C9 | 122.85 (19) |
O1—Co1—O4i | 93.95 (5) | N2—C10—H10 | 118.6 |
O9—Co1—O5 | 85.42 (5) | C9—C10—H10 | 118.6 |
N1—Co1—O5 | 97.40 (5) | N2—C11—C7 | 122.60 (18) |
N2—Co1—O5 | 97.47 (5) | N2—C11—C12 | 117.39 (15) |
O1—Co1—O5 | 85.23 (5) | C7—C11—C12 | 120.00 (17) |
O4i—Co1—O5 | 173.03 (5) | N1—C12—C4 | 122.75 (18) |
C13—O1—Co1 | 131.03 (11) | N1—C12—C11 | 117.43 (15) |
C13—O2—H2 | 109.5 | C4—C12—C11 | 119.80 (17) |
C17—O4—Co1i | 129.86 (11) | O1—C13—O2 | 124.50 (16) |
C18—O5—Co1 | 143.28 (11) | O1—C13—C14 | 119.91 (15) |
C22—O8—H8 | 109.5 | O2—C13—C14 | 115.59 (14) |
Co1—O9—H9 | 109.5 | C16ii—C14—C15 | 119.55 (15) |
Co1—O9—H9B | 131.2 (17) | C16ii—C14—C13 | 119.73 (15) |
H9—O9—H9B | 105.5 | C15—C14—C13 | 120.67 (14) |
C1—N1—C12 | 118.31 (16) | C16—C15—C14 | 118.44 (15) |
C1—N1—Co1 | 128.59 (13) | C16—C15—C17 | 116.36 (14) |
C12—N1—Co1 | 113.01 (12) | C14—C15—C17 | 125.16 (14) |
C10—N2—C11 | 118.19 (15) | C15—C16—C14ii | 122.01 (15) |
C10—N2—Co1 | 128.66 (13) | C15—C16—H16 | 119.0 |
C11—N2—Co1 | 112.83 (11) | C14ii—C16—H16 | 119.0 |
N1—C1—C2 | 122.8 (2) | O4—C17—O3 | 126.60 (15) |
N1—C1—H1 | 118.6 | O4—C17—C15 | 115.95 (14) |
C2—C1—H1 | 118.6 | O3—C17—C15 | 117.08 (14) |
C3—C2—C1 | 119.1 (2) | O6—C18—O5 | 123.67 (15) |
C3—C2—H2A | 120.5 | O6—C18—C19 | 119.30 (15) |
C1—C2—H2A | 120.5 | O5—C18—C19 | 116.88 (14) |
C2—C3—C4 | 120.24 (19) | C20—C19—C21iii | 118.91 (15) |
C2—C3—H3 | 119.9 | C20—C19—C18 | 116.76 (14) |
C4—C3—H3 | 119.9 | C21iii—C19—C18 | 124.29 (15) |
C3—C4—C12 | 116.83 (19) | C19—C20—C21 | 121.42 (16) |
C3—C4—C5 | 124.31 (19) | C19—C20—H20 | 119.3 |
C12—C4—C5 | 118.8 (2) | C21—C20—H20 | 119.3 |
C6—C5—C4 | 121.19 (19) | C20—C21—C19iii | 119.67 (16) |
C6—C5—H5 | 119.4 | C20—C21—C22 | 119.83 (15) |
C4—C5—H5 | 119.4 | C19iii—C21—C22 | 120.50 (15) |
C5—C6—C7 | 121.62 (19) | O7—C22—O8 | 124.14 (16) |
C5—C6—H6 | 119.2 | O7—C22—C21 | 123.77 (16) |
C7—C6—H6 | 119.2 | O8—C22—C21 | 112.08 (14) |
C8—C7—C11 | 117.26 (19) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x−1, −y+1, −z+1; (iii) −x, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O5 | 0.82 | 1.69 | 2.494 (3) | 166 |
C20—H20···O8 | 0.93 | 2.35 | 2.688 (2) | 101 |
O8—H8···O3iv | 0.82 | 1.82 | 2.597 (2) | 158 |
O9—H9B···O6v | 0.81 (3) | 1.94 (2) | 2.730 (2) | 163 (2) |
O9—H9···O3i | 0.82 | 1.91 | 2.668 (2) | 153 |
C8—H8A···O7vi | 0.93 | 2.56 | 3.297 (4) | 137 |
C16—H16···O2ii | 0.93 | 2.41 | 2.741 (2) | 101 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x−1, −y+1, −z+1; (iv) x+1, y, z−1; (v) −x, −y+1, −z; (vi) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C10H4O8)(C12H8N2)(H2O)] |
Mr | 509.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 273 |
a, b, c (Å) | 9.6876 (9), 10.2079 (10), 11.3561 (11) |
α, β, γ (°) | 86.808 (1), 72.141 (1), 64.928 (1) |
V (Å3) | 964.58 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.59 × 0.55 × 0.34 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.571, 0.722 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6669, 3371, 3215 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.07 |
No. of reflections | 3371 |
No. of parameters | 315 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.29 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
Co1—O9 | 2.0834 (13) | Co1—O1 | 2.1131 (12) |
Co1—N1 | 2.1028 (15) | Co1—O4i | 2.1220 (12) |
Co1—N2 | 2.1103 (14) | Co1—O5 | 2.1266 (12) |
O9—Co1—N1 | 173.81 (6) | N2—Co1—O4i | 84.46 (5) |
O9—Co1—N2 | 94.98 (6) | O1—Co1—O4i | 93.95 (5) |
N1—Co1—N2 | 79.21 (6) | O9—Co1—O5 | 85.42 (5) |
O9—Co1—O1 | 94.40 (6) | N1—Co1—O5 | 97.40 (5) |
N1—Co1—O1 | 91.33 (5) | N2—Co1—O5 | 97.47 (5) |
N2—Co1—O1 | 170.41 (5) | O1—Co1—O5 | 85.23 (5) |
O9—Co1—O4i | 87.74 (5) | O4i—Co1—O5 | 173.03 (5) |
N1—Co1—O4i | 89.54 (5) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O5 | 0.82 | 1.69 | 2.494 (3) | 166 |
C20—H20···O8 | 0.93 | 2.35 | 2.688 (2) | 101 |
O8—H8···O3ii | 0.82 | 1.82 | 2.597 (2) | 158 |
O9—H9B···O6iii | 0.81 (3) | 1.94 (2) | 2.730 (2) | 163 (2) |
O9—H9···O3i | 0.82 | 1.91 | 2.668 (2) | 153 |
C8—H8A···O7iv | 0.93 | 2.56 | 3.297 (4) | 137 |
C16—H16···O2v | 0.93 | 2.41 | 2.741 (2) | 101 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z−1; (iii) −x, −y+1, −z; (iv) −x+1, −y+2, −z; (v) −x−1, −y+1, −z+1. |
Research on metal-directed coordination polymers has been expanding rapidily owing to their interesting topologies and potential applications as functional materials (Kitagawa & Kondo, 1998; Seo & Whang, 2000; Yaghi & Li, 1998). Bi- or multidentate ligands containing O– or N-donors are often used to coordinate to metal centers (Fujita & Ogura, 1996; Mori & Takamizawa, 2000). Accordingly, benzene- 1,2,4,5-tetracarboxylic acid (H4TCB) is a good bridging ligand that can sometimes be used to generate unexpected interesting coordination polymers (Gutschke, et al., 2001), and small changes in experimental conditions (concentration, molecular ratio, solvent etc.) can lead to very different architectures. We report here the hydrothermal synthesis and crystal structure of a two-dimensional-network coordination polymer.
In the title compound, (I), each cobalt(II) cation has a six-coordinated environment, composed of one aqua O atom, three carboxyl O atoms belonging to three H2TCB2− anions and two N atoms from a phen molecule (Fig. 1). The geometry around the cobalt(II) cation is octahedral, with the four equatorial positions occupied by the two phen N atoms, one carboxyl O atom and the aqua O atom, and with all distances lying in the 2.083 (1)–2.127 (1) Å range. The two apical positions are filled by two carboxyl O atoms from another two H2TCB2− anions, the corresponding axial bond lengths [Co—O4 = 2.1220 (12) Å and Co—O5 = 2.1266 (12) Å] being longer than the equatorial bond lengths.
The µ-H2TCB2− ligands exhibit two coordination modes. The first is that four carboxylate groups, involving two undeprotonated carboxylate groups, bond to four cobalt(II) cations. ??A similar coordination mode of undeprotonated carboxylate groups was reported by reported Livage et al. (2001), with four carboxylate groups binding to? four cobalt(II) cations in monodentate fashion. In the second mode, only the two deprotonated carboxylate groups at ?opposite positions? bind to two cobalt(II) cations (Fig. 2); this mode is similar to that reported for Cu(phen)(H2TCB) (Hu et al., 2003). The µ2-H2TCB2− ligands are parallel to two neighboring phen molecules, but the diheral angle between the µ4-H2 TCB2− ring and the neighboring phen ring is 65.35 (4)°. A two-dimensional network is thus formed by µ4-H2TCB2− and µ2-H2TCB2− ligands, central cobalt(II) cations, aqua molecules and terminal phen molecules. The µ4-H2TCB2− and µ2-H2TCB2− ligands and phen molecules are almost linear along [1 1 1]. Moreover, the O(carboxyl)···O(carboxyl) and O(carboxyl)···O(water) hydrogen-bond interactions, with H···A distances in the 1.69–1.82 Å and 1.91–1.94 Å ranges, respectively, connect the two-dimensional networks, resulting in a three-dimensional stucture.