Poly[[μ2-aqua-bis[(1,10-phenanthroline)nickel(II)]]-di-μ2,μ4-5-nitro-1,3-benzenedicarboxylato]
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104023431/av1206sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104023431/av1206Isup2.hkl |
CCDC reference: 244112
A mixture of Ni(CH3COO)2·4H2O (0.0376 g,0.15 mmol), 5-nitro-1,3-benzenedicaroxylic acid (0.0318 g, 0.15 mmol), 1,10-phenanthroline (0.0304 g, 0.15 mmol) and water (10 ml) in a molar ratio of ca 1:1:1:3700 was sealed in to a 25 ml Teflon-lined stainless-steel reactor and heated at 453 K for 72 h. After cooling, plate-like blue crystals of (I) were collected by filtration. Analysis calculated for C40H46N6Ni2O13: C 51.70, H 2.65, N 9.19%; found: C 51.64, H 2.70, N 9.36%. Weight loss in the temperature range 574–637 K corresponds to the release of the water molecule (calculated 1.97%, found 1.73%).
H atoms attached to the benzne ring were positioned geometrically and treated as riding, with C—H distances of 0.93 Å and Uiso(H) values of 1.2Ueq(parent). Water H atoms were found in a difference Fourier map and included in the refinement with an O—H distance restraint (0.85 Å) and with Uiso(H) set at 0.05 Å2.
Data collection: SMART (Bruker,1997); cell refinement: SMART; data reduction: SHELXTL (Bruker,1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cu2(C8H3NO6)2(C12H8N2)2(H2O)] | Dx = 1.724 Mg m−3 |
Mr = 914.03 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnna | Cell parameters from 3176 reflections |
a = 29.5645 (13) Å | θ = 2.6–50.4° |
b = 18.0613 (7) Å | µ = 1.15 mm−1 |
c = 6.5961 (3) Å | T = 293 K |
V = 3522.1 (3) Å3 | Plate, blue |
Z = 4 | 0.54 × 0.45 × 0.06 mm |
F(000) = 1864 |
Bruker SMART CCD area-detector diffractometer | 3176 independent reflections |
Radiation source: fine-focus sealed tube | 2953 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 25.2°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −23→35 |
Tmin = 0.575, Tmax = 0.934 | k = −21→21 |
17323 measured reflections | l = −7→7 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.039P)2 + 7.1492P] where P = (Fo2 + 2Fc2)/3 |
3176 reflections | (Δ/σ)max = 0.001 |
282 parameters | Δρmax = 0.38 e Å−3 |
1 restraint | Δρmin = −0.33 e Å−3 |
[Cu2(C8H3NO6)2(C12H8N2)2(H2O)] | V = 3522.1 (3) Å3 |
Mr = 914.03 | Z = 4 |
Orthorhombic, Pnna | Mo Kα radiation |
a = 29.5645 (13) Å | µ = 1.15 mm−1 |
b = 18.0613 (7) Å | T = 293 K |
c = 6.5961 (3) Å | 0.54 × 0.45 × 0.06 mm |
Bruker SMART CCD area-detector diffractometer | 3176 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2953 reflections with I > 2σ(I) |
Tmin = 0.575, Tmax = 0.934 | Rint = 0.034 |
17323 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 1 restraint |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.38 e Å−3 |
3176 reflections | Δρmin = −0.33 e Å−3 |
282 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 | ||
Ni1 | 0.306836 (13) | 0.52748 (2) | 0.99129 (6) | 0.02044 (14) | |
O1 | 0.34417 (7) | 0.44444 (12) | 0.8217 (4) | 0.0303 (5) | |
O2 | 0.28576 (8) | 0.38532 (13) | 0.6797 (4) | 0.0345 (6) | |
O3 | 0.49061 (9) | 0.19494 (15) | 0.8146 (5) | 0.0481 (7) | |
O4 | 0.27473 (7) | 0.61324 (11) | 1.1358 (3) | 0.0241 (5) | |
O5 | 0.20897 (7) | 0.55445 (11) | 1.1890 (4) | 0.0266 (5) | |
O6 | 0.07096 (9) | 0.69074 (16) | 1.2370 (5) | 0.0494 (7) | |
N1 | 0.36813 (9) | 0.53974 (13) | 1.1381 (4) | 0.0236 (6) | |
N2 | 0.33847 (9) | 0.60372 (14) | 0.7961 (4) | 0.0243 (6) | |
N3 | 0.47096 (13) | 0.2500 | 0.7500 | 0.0318 (10) | |
N4 | 0.09075 (13) | 0.7500 | 1.2500 | 0.0294 (9) | |
C1 | 0.32311 (12) | 0.6383 (2) | 0.6334 (6) | 0.0352 (8) | |
H1 | 0.2924 | 0.6356 | 0.6036 | 0.042* | |
C2 | 0.35140 (14) | 0.6789 (2) | 0.5043 (6) | 0.0467 (10) | |
H2 | 0.3393 | 0.7029 | 0.3921 | 0.056* | |
C3 | 0.39653 (13) | 0.6832 (2) | 0.5424 (6) | 0.0417 (9) | |
H3 | 0.4155 | 0.7093 | 0.4556 | 0.050* | |
C4 | 0.41405 (12) | 0.64771 (19) | 0.7145 (5) | 0.0315 (8) | |
C5 | 0.46118 (13) | 0.6477 (2) | 0.7675 (6) | 0.0401 (9) | |
H5 | 0.4817 | 0.6723 | 0.6847 | 0.048* | |
C6 | 0.47613 (12) | 0.6129 (2) | 0.9343 (6) | 0.0405 (9) | |
H6 | 0.5069 | 0.6132 | 0.9631 | 0.049* | |
C7 | 0.44580 (11) | 0.5754 (2) | 1.0689 (6) | 0.0337 (8) | |
C8 | 0.45863 (13) | 0.5397 (2) | 1.2492 (7) | 0.0432 (10) | |
H8 | 0.4889 | 0.5392 | 1.2882 | 0.052* | |
C9 | 0.42694 (14) | 0.5060 (2) | 1.3670 (6) | 0.0441 (10) | |
H9 | 0.4355 | 0.4819 | 1.4857 | 0.053* | |
C10 | 0.38160 (12) | 0.50766 (19) | 1.3086 (5) | 0.0316 (8) | |
H10 | 0.3601 | 0.4856 | 1.3920 | 0.038* | |
C11 | 0.39953 (11) | 0.57365 (17) | 1.0208 (5) | 0.0256 (7) | |
C12 | 0.38359 (11) | 0.60936 (17) | 0.8385 (5) | 0.0248 (7) | |
C13 | 0.32519 (11) | 0.38840 (16) | 0.7474 (5) | 0.0217 (7) | |
C14 | 0.35205 (10) | 0.31691 (16) | 0.7441 (4) | 0.0204 (6) | |
C15 | 0.39883 (10) | 0.31726 (17) | 0.7455 (5) | 0.0222 (7) | |
H15 | 0.4148 | 0.3616 | 0.7434 | 0.027* | |
C16 | 0.42136 (15) | 0.2500 | 0.7500 | 0.0223 (9) | |
C17 | 0.32898 (15) | 0.2500 | 0.7500 | 0.0206 (9) | |
H17 | 0.2975 | 0.2500 | 0.7500 | 0.025* | |
C18 | 0.23344 (10) | 0.61052 (16) | 1.1809 (5) | 0.0208 (7) | |
C19 | 0.20974 (10) | 0.68353 (16) | 1.2238 (4) | 0.0184 (6) | |
C20 | 0.16264 (10) | 0.68355 (17) | 1.2263 (4) | 0.0201 (6) | |
H20 | 0.1465 | 0.6396 | 1.2123 | 0.024* | |
C21 | 0.14037 (14) | 0.7500 | 1.2500 | 0.0207 (9) | |
C22 | 0.23292 (14) | 0.7500 | 1.2500 | 0.0200 (9) | |
H22 | 0.2644 | 0.7500 | 1.2500 | 0.024* | |
O7 | 0.2500 | 0.5000 | 0.8224 (5) | 0.0215 (7) | |
H7A | 0.2631 (13) | 0.4662 (17) | 0.754 (6) | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0182 (2) | 0.0144 (2) | 0.0287 (2) | −0.00080 (15) | 0.00051 (17) | 0.00021 (16) |
O1 | 0.0256 (12) | 0.0184 (11) | 0.0469 (15) | 0.0009 (9) | 0.0012 (11) | −0.0075 (11) |
O2 | 0.0290 (13) | 0.0280 (13) | 0.0466 (15) | 0.0085 (10) | −0.0109 (12) | −0.0131 (11) |
O3 | 0.0285 (14) | 0.0495 (16) | 0.066 (2) | 0.0140 (12) | −0.0081 (14) | −0.0011 (15) |
O4 | 0.0192 (11) | 0.0160 (11) | 0.0372 (13) | 0.0006 (8) | 0.0023 (10) | −0.0055 (9) |
O5 | 0.0261 (12) | 0.0157 (11) | 0.0379 (13) | −0.0051 (9) | 0.0047 (10) | −0.0068 (10) |
O6 | 0.0250 (14) | 0.0504 (17) | 0.073 (2) | −0.0125 (12) | 0.0024 (14) | −0.0099 (15) |
N1 | 0.0271 (14) | 0.0134 (12) | 0.0304 (15) | −0.0024 (10) | −0.0013 (12) | −0.0026 (11) |
N2 | 0.0202 (14) | 0.0182 (13) | 0.0344 (15) | −0.0029 (10) | 0.0013 (12) | 0.0016 (12) |
N3 | 0.023 (2) | 0.036 (2) | 0.036 (2) | 0.000 | 0.000 | −0.0103 (19) |
N4 | 0.019 (2) | 0.042 (3) | 0.028 (2) | 0.000 | 0.000 | −0.0054 (18) |
C1 | 0.0295 (19) | 0.0343 (19) | 0.042 (2) | 0.0009 (16) | −0.0045 (16) | 0.0107 (17) |
C2 | 0.043 (2) | 0.051 (2) | 0.045 (2) | −0.0053 (19) | −0.0012 (19) | 0.022 (2) |
C3 | 0.039 (2) | 0.045 (2) | 0.041 (2) | −0.0131 (18) | 0.0067 (18) | 0.0118 (18) |
C4 | 0.0283 (18) | 0.0310 (18) | 0.035 (2) | −0.0087 (15) | 0.0094 (15) | −0.0052 (15) |
C5 | 0.031 (2) | 0.046 (2) | 0.044 (2) | −0.0139 (17) | 0.0106 (18) | −0.0056 (18) |
C6 | 0.0185 (18) | 0.052 (2) | 0.051 (2) | −0.0082 (16) | 0.0010 (17) | −0.007 (2) |
C7 | 0.0256 (18) | 0.0324 (19) | 0.043 (2) | −0.0028 (15) | −0.0026 (16) | −0.0092 (17) |
C8 | 0.0291 (19) | 0.044 (2) | 0.056 (3) | −0.0026 (17) | −0.017 (2) | 0.001 (2) |
C9 | 0.044 (2) | 0.042 (2) | 0.046 (2) | −0.0048 (19) | −0.020 (2) | 0.0096 (19) |
C10 | 0.036 (2) | 0.0260 (18) | 0.0326 (19) | −0.0066 (15) | −0.0043 (16) | 0.0019 (15) |
C11 | 0.0217 (16) | 0.0205 (16) | 0.0347 (18) | −0.0049 (13) | −0.0020 (14) | −0.0062 (14) |
C12 | 0.0232 (17) | 0.0189 (15) | 0.0323 (18) | −0.0037 (13) | 0.0058 (14) | −0.0053 (13) |
C13 | 0.0272 (17) | 0.0168 (15) | 0.0212 (15) | 0.0012 (13) | 0.0037 (14) | −0.0018 (12) |
C14 | 0.0239 (16) | 0.0210 (16) | 0.0162 (15) | 0.0001 (13) | 0.0021 (13) | −0.0025 (12) |
C15 | 0.0269 (17) | 0.0173 (15) | 0.0225 (16) | −0.0058 (13) | 0.0013 (13) | −0.0020 (12) |
C16 | 0.018 (2) | 0.028 (2) | 0.021 (2) | 0.000 | 0.000 | −0.0028 (18) |
C17 | 0.018 (2) | 0.028 (2) | 0.016 (2) | 0.000 | 0.000 | −0.0037 (17) |
C18 | 0.0218 (16) | 0.0187 (16) | 0.0219 (16) | −0.0020 (12) | −0.0031 (13) | −0.0010 (12) |
C19 | 0.0200 (15) | 0.0164 (15) | 0.0187 (15) | 0.0000 (12) | −0.0007 (12) | 0.0001 (12) |
C20 | 0.0192 (15) | 0.0213 (16) | 0.0198 (15) | −0.0056 (12) | 0.0000 (13) | −0.0007 (12) |
C21 | 0.018 (2) | 0.029 (2) | 0.015 (2) | 0.000 | 0.000 | −0.0022 (18) |
C22 | 0.017 (2) | 0.021 (2) | 0.022 (2) | 0.000 | 0.000 | 0.0009 (18) |
O7 | 0.0221 (16) | 0.0163 (15) | 0.0260 (17) | 0.0044 (12) | 0.000 | 0.000 |
Ni1—O5i | 2.027 (2) | C5—C6 | 1.341 (6) |
Ni1—O4 | 2.052 (2) | C5—H5 | 0.9300 |
Ni1—N1 | 2.067 (3) | C6—C7 | 1.432 (5) |
Ni1—O7 | 2.0762 (17) | C6—H6 | 0.9300 |
Ni1—N2 | 2.104 (3) | C7—C8 | 1.405 (6) |
Ni1—O1 | 2.172 (2) | C7—C11 | 1.405 (5) |
O1—C13 | 1.257 (4) | C8—C9 | 1.361 (6) |
O2—C13 | 1.250 (4) | C8—H8 | 0.9300 |
O3—N3 | 1.228 (3) | C9—C10 | 1.395 (5) |
O4—C18 | 1.257 (4) | C9—H9 | 0.9300 |
O5—C18 | 1.246 (4) | C10—H10 | 0.9300 |
O6—N4 | 1.223 (3) | C11—C12 | 1.443 (5) |
N1—C10 | 1.326 (4) | C13—C14 | 1.516 (4) |
N1—C11 | 1.355 (4) | C14—C15 | 1.383 (4) |
N2—C1 | 1.322 (4) | C14—C17 | 1.388 (4) |
N2—C12 | 1.367 (4) | C15—C16 | 1.386 (4) |
N3—C16 | 1.466 (6) | C15—H15 | 0.9300 |
N4—C21 | 1.467 (6) | C17—H17 | 0.9300 |
C1—C2 | 1.400 (5) | C18—C19 | 1.520 (4) |
C1—H1 | 0.9300 | C19—C20 | 1.393 (4) |
C2—C3 | 1.360 (6) | C19—C22 | 1.393 (4) |
C2—H2 | 0.9300 | C20—C21 | 1.378 (4) |
C3—C4 | 1.402 (5) | C20—H20 | 0.9300 |
C3—H3 | 0.9300 | C22—H22 | 0.9300 |
C4—C12 | 1.400 (5) | O7—H7A | 0.85 (3) |
C4—C5 | 1.437 (5) | ||
O5i—Ni1—O4 | 98.38 (9) | C1—C2—H2 | 119.9 |
O5i—Ni1—N1 | 88.80 (10) | C2—C3—C4 | 119.1 (3) |
O4—Ni1—N1 | 96.15 (9) | C2—C3—H3 | 120.5 |
O5i—Ni1—O7 | 89.08 (9) | C4—C3—H3 | 120.5 |
O4—Ni1—O7 | 93.17 (7) | C12—C4—C3 | 117.5 (3) |
N1—Ni1—O7 | 170.65 (8) | C12—C4—C5 | 118.8 (3) |
O5i—Ni1—N2 | 166.85 (10) | C3—C4—C5 | 123.7 (3) |
O4—Ni1—N2 | 89.76 (10) | C6—C5—C4 | 121.3 (3) |
N1—Ni1—N2 | 80.04 (10) | C6—C5—H5 | 119.4 |
O7—Ni1—N2 | 100.83 (10) | C4—C5—H5 | 119.4 |
O5i—Ni1—O1 | 86.81 (9) | C5—C6—C7 | 121.6 (3) |
O4—Ni1—O1 | 174.63 (9) | C5—C6—H6 | 119.2 |
N1—Ni1—O1 | 82.52 (9) | C7—C6—H6 | 119.2 |
O7—Ni1—O1 | 88.27 (8) | C8—C7—C11 | 116.4 (3) |
N2—Ni1—O1 | 84.89 (10) | C8—C7—C6 | 124.9 (3) |
O5i—Ni1—Ni1ii | 114.87 (7) | C11—C7—C6 | 118.7 (4) |
O4—Ni1—Ni1ii | 28.77 (6) | C9—C8—C7 | 120.2 (4) |
N1—Ni1—Ni1ii | 73.63 (7) | C9—C8—H8 | 119.9 |
O7—Ni1—Ni1ii | 115.450 (19) | C7—C8—H8 | 119.9 |
N2—Ni1—Ni1ii | 68.70 (7) | C8—C9—C10 | 119.6 (4) |
O1—Ni1—Ni1ii | 146.80 (6) | C8—C9—H9 | 120.2 |
O5i—Ni1—Ni1iii | 110.76 (7) | C10—C9—H9 | 120.2 |
O4—Ni1—Ni1iii | 13.03 (6) | N1—C10—C9 | 122.1 (3) |
N1—Ni1—Ni1iii | 92.13 (7) | N1—C10—H10 | 118.9 |
O7—Ni1—Ni1iii | 97.14 (3) | C9—C10—H10 | 118.9 |
N2—Ni1—Ni1iii | 76.84 (7) | N1—C11—C7 | 123.2 (3) |
O1—Ni1—Ni1iii | 161.60 (6) | N1—C11—C12 | 117.0 (3) |
Ni1ii—Ni1—Ni1iii | 19.326 (4) | C7—C11—C12 | 119.7 (3) |
O5i—Ni1—Ni1iv | 59.92 (7) | N2—C12—C4 | 123.0 (3) |
O4—Ni1—Ni1iv | 149.34 (6) | N2—C12—C11 | 117.1 (3) |
N1—Ni1—Ni1iv | 104.12 (7) | C4—C12—C11 | 119.9 (3) |
O7—Ni1—Ni1iv | 67.032 (13) | O2—C13—O1 | 126.3 (3) |
N2—Ni1—Ni1iv | 116.01 (7) | O2—C13—C14 | 116.5 (3) |
O1—Ni1—Ni1iv | 35.52 (6) | O1—C13—C14 | 117.2 (3) |
Ni1ii—Ni1—Ni1iv | 174.612 (10) | C15—C14—C17 | 119.7 (3) |
Ni1iii—Ni1—Ni1iv | 160.569 (4) | C15—C14—C13 | 121.3 (3) |
O5i—Ni1—Ni1v | 26.04 (7) | C17—C14—C13 | 118.9 (3) |
O4—Ni1—Ni1v | 124.40 (6) | C14—C15—C16 | 118.5 (3) |
N1—Ni1—Ni1v | 87.15 (7) | C14—C15—H15 | 120.8 |
O7—Ni1—Ni1v | 86.94 (3) | C16—C15—H15 | 120.8 |
N2—Ni1—Ni1v | 144.75 (7) | C15—C16—C15iv | 122.5 (4) |
O1—Ni1—Ni1v | 60.82 (6) | C15—C16—N3 | 118.7 (2) |
Ni1ii—Ni1—Ni1v | 138.189 (9) | C15iv—C16—N3 | 118.7 (2) |
Ni1iii—Ni1—Ni1v | 136.774 (8) | C14—C17—C14iv | 121.1 (4) |
Ni1iv—Ni1—Ni1v | 36.422 (3) | C14—C17—H17 | 119.4 |
C13—O1—Ni1 | 122.0 (2) | C14iv—C17—H17 | 119.4 |
C18—O4—Ni1 | 121.98 (19) | O5—C18—O4 | 127.3 (3) |
C18—O5—Ni1i | 134.4 (2) | O5—C18—C19 | 115.4 (3) |
C10—N1—C11 | 118.4 (3) | O4—C18—C19 | 117.2 (3) |
C10—N1—Ni1 | 127.9 (2) | C20—C19—C22 | 119.4 (3) |
C11—N1—Ni1 | 112.4 (2) | C20—C19—C18 | 117.6 (3) |
C1—N2—C12 | 117.8 (3) | C22—C19—C18 | 123.0 (3) |
C1—N2—Ni1 | 130.8 (2) | C21—C20—C19 | 118.6 (3) |
C12—N2—Ni1 | 110.9 (2) | C21—C20—H20 | 120.7 |
O3iv—N3—O3 | 123.5 (4) | C19—C20—H20 | 120.7 |
O3iv—N3—C16 | 118.2 (2) | C20ii—C21—C20 | 122.9 (4) |
O3—N3—C16 | 118.2 (2) | C20ii—C21—N4 | 118.5 (2) |
O6—N4—O6ii | 122.8 (4) | C20—C21—N4 | 118.5 (2) |
O6—N4—C21 | 118.6 (2) | C19—C22—C19ii | 121.1 (4) |
O6ii—N4—C21 | 118.6 (2) | C19—C22—H22 | 119.5 |
N2—C1—C2 | 122.4 (3) | C19ii—C22—H22 | 119.5 |
N2—C1—H1 | 118.8 | Ni1—O7—Ni1i | 115.11 (15) |
C2—C1—H1 | 118.8 | Ni1—O7—H7A | 95 (3) |
C3—C2—C1 | 120.2 (4) | Ni1i—O7—H7A | 119 (3) |
C3—C2—H2 | 119.9 |
Symmetry codes: (i) −x+1/2, −y+1, z; (ii) x, −y+3/2, −z+5/2; (iii) −x+1/2, y+1/2, −z+5/2; (iv) x, −y+1/2, −z+3/2; (v) x, −y+1/2, −z+5/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O1 | 0.85 (3) | 2.47 (4) | 2.959 (2) | 117 (3) |
O7—H7A···O2 | 0.85 (3) | 1.68 (2) | 2.509 (2) | 163 (4) |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C8H3NO6)2(C12H8N2)2(H2O)] |
Mr | 914.03 |
Crystal system, space group | Orthorhombic, Pnna |
Temperature (K) | 293 |
a, b, c (Å) | 29.5645 (13), 18.0613 (7), 6.5961 (3) |
V (Å3) | 3522.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.54 × 0.45 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.575, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17323, 3176, 2953 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.108, 1.15 |
No. of reflections | 3176 |
No. of parameters | 282 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.33 |
Computer programs: SMART (Bruker,1997), SMART, SHELXTL (Bruker,1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Ni1—O5i | 2.027 (2) | Ni1—O7 | 2.0762 (17) |
Ni1—O4 | 2.052 (2) | Ni1—N2 | 2.104 (3) |
Ni1—N1 | 2.067 (3) | Ni1—O1 | 2.172 (2) |
O5i—Ni1—O4 | 98.38 (9) | N1—Ni1—N2 | 80.04 (10) |
O5i—Ni1—N1 | 88.80 (10) | O7—Ni1—N2 | 100.83 (10) |
O4—Ni1—N1 | 96.15 (9) | O5i—Ni1—O1 | 86.81 (9) |
O5i—Ni1—O7 | 89.08 (9) | O4—Ni1—O1 | 174.63 (9) |
O4—Ni1—O7 | 93.17 (7) | N1—Ni1—O1 | 82.52 (9) |
N1—Ni1—O7 | 170.65 (8) | O7—Ni1—O1 | 88.27 (8) |
O5i—Ni1—N2 | 166.85 (10) | N2—Ni1—O1 | 84.89 (10) |
O4—Ni1—N2 | 89.76 (10) |
Symmetry code: (i) −x+1/2, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O1 | 0.85 (3) | 2.47 (4) | 2.959 (2) | 117 (3) |
O7—H7A···O2 | 0.85 (3) | 1.680 (16) | 2.509 (2) | 163 (4) |
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Binuclear nickel units with both bridged water and carboxylate ligands have been found to be important structural moieties in some metalloenzymes, such as urease; these units? can catalyze the hydrolysis of urease to form ammonia and carbamate (Person et al., 1997; Jabri et al., 1995). Recently, several binuclear complexes were prepared as models for urease, in order to explore the nature of urea hydrolysis (Sung et al., 2001; Barrios & Lippard, 1999; Barrios & Lippard, 2000). However, only a few such nickel binuclear carboxylate complexes whave been structurally characterized, and all of these complexes were synthesized using ligands with one carboxyl group. In the present study, we use a dicarboxylate (5-nitro-1,3-benzenedicarboxylic acid, H2nmbdc) to prepare the first reported two-dimensional compound with a µ2-H2O dimeric motifs, namely [Ni2(H2O)(nmbdc)2(phen)2]n, (I).
Compound (I) consists of a two-dimensional NiII complex in which the Ni atom has a six-coordinate geometry completed by two N atoms from one 1,10-phenanthroline group, one O atom from a coordinated water molecule and three O atoms from three nmbdc2− ligands (Fig. 1 and Table 1). The water molecule occupies a special position in the mirror plane, and the 5-nitro-1,3-benzenedicarboxylate group occupies a special position on a twofold axis. There are two nmbdc2− coordination modes in the title compound; one is a bis-monodentate mode, namely µ2-nmbdc2−, and the other is a bis-bridging mode, namely µ4-nmbdc2−. The basic motif in the two-dimensional framework is a dimeric unit, [Ni2(µ2-H2O)(phen)2(µ2-nmbdc)2(µ4-nmbdc)2], in which the water molecule bridges two Ni atoms, with an Ni···Ni distance of 3.5042 (8) Å; this value agrees well with the Ni···Ni distance observed in urease (3.5 Å).
In general, a binuclear unit constructed from bridged carboxylate groups has four carboxyl groups around two metal centers, with short metal–metal distances, and a paddle-wheel motif is expected (Braqun et al., 2001; Li et al., 1998; Gao et al., 2003). In the title compound, the dimeric unit comprises two bridged and two monodentate carboxyl groups. The bridged water molecule and intramolecular hydrogen bonds assemble the monodentate carboxyl groups into pseudo-bridging linkers. Therefore, the dimeric motif in (I) could be considered as a pseudo-paddle-wheel motif; even nmbdc2− ligands are roughly parallel (the dihedral angle is 6.19 °). This dimeric motif in (I) is found in several reported binuclear water-bridged nickel complexes, such as [Ni2(µ2-H2O)(OOCC(CH3)3)2(µ2-OOCC(CH3)3)2(2,2'-bipy)2], (II) (Eremenko et al., 1999). The difference between the coordination geometries in (I) and (II) is the orientation of the carboxylate ligands wit respect to the Ni atoms.
In the two-dimensional framework in (I) (Fig. 2), the [Ni(µ4-nmbdc)] building blocks form a one-dimensional chain (Fig. 3a), while the [Ni(µ2-nmbdc)] blocks form dimeric species; the dmeric units are held together by µ2-H2O molecules and extend into a one-dimensional chain (Fig. 3 b). The combination of [Ni(µ4-nmbdc)] and [Ni(µ2-nmbdc)(µ2-H2O)] units leads to the assembly of a two-dimensional architecture. The Ni···Ni separations in these two one-dimensional chains are 8.7326 (8), 10.2223 (5), 10.5166 (8) and 10.5884 (8) Å, respectively.
Two complexes based on the M2+/phen/H2nmbdc system were by Zhou et al. (2004). The copper compound, [Cu(nmbdc)(phen)]2, (III), is a two-dimensional network with a square-pyramidal copper center, in which the nmbdc2− ligand has a µ3-bridging monoatomic monodentate coordination mode. The cobalt compound, [Co2(nmbdc)2(phen)2]n(IV), is a one-dimensional chain and the nmbdc2− ligand has a chelating-bridging coordination mode. The µ2-nmbdc2− and µ2-nmbdc2− coordination modes in (I) create a new assembly compared with the topologies of (III) and (IV). Moreover, in (I), the ability of the water molecule to serve as a bridge for two NiII ions seems to be both an unexpected and a remarkable phenomenon, accounting for the absence of coordination water molecules in (III) and (IV).
Intramolecular hydrogen bonds exist between water molecules and uncoordinated carboxylate O atoms [O7W···O2 = 2.509 (2) Å]. There are abundant strong π–π interactions in the two-dimensional network. As well as a π–π stacking interaction (3.23 Å) between µ2-nmbdc2− and µ4-nmbdc2− ligands in the dimeric motif, π–π stacking interactions exist between pairs of µ2-nmbdc2− and neighboring µ4-nmbdc2− ligands???. Moreover, π–π stacking of phen ligands among neighboring dimeric motifs is observed (3.48 and 3.60 Å).