Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006018/wn6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006018/wn6011Isup2.hkl |
CCDC reference: 165632
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.012 Å
- R factor = 0.069
- wR factor = 0.130
- Data-to-parameter ratio = 10.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was synthesized by the hydro(solvo)thermal method. 0.5 g Cu(NO3)2nH2O, 0.2 g 1,10-phenanthroline and 6 ml H2O were added to a 25 ml Teflon-lined Parr autoclave. The autoclave was sealed and heated under static conditions for 96 h at 443 K; the reaction was cooled to room temperature over a period of 50 h.
Data collection: SMART (Siemens, 1998); cell refinement: SMART; data reduction: SAINT (Siemens, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: please provide.
Fig. 1. The cationic structure of the title compound. Displacement ellipsoids are shown at the 50% probability level. H atoms have been omitted for clarity. |
[Cu4(OH)4(C10H8N2)4(H2O)2](NO3)4·2H2O | Z = 1 |
Mr = 1355.04 | F(000) = 684 |
Triclinic, P1 | Dx = 1.715 Mg m−3 |
a = 10.1504 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.9299 (3) Å | Cell parameters from 47 reflections |
c = 12.6337 (1) Å | θ = 1.8–25.0° |
α = 111.073 (1)° | µ = 1.69 mm−1 |
β = 90.906 (2)° | T = 293 K |
γ = 111.218 (2)° | Cube, blue |
V = 1311.91 (4) Å3 | 0.30 × 0.18 × 0.12 mm |
Siemens SMART CCD diffractometer | 4544 independent reflections |
Radiation source: fine-focus sealed tube | 2762 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −12→7 |
Tmin = 0.597, Tmax = 0.816 | k = −14→14 |
6772 measured reflections | l = −14→15 |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.39 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
4544 reflections | (Δ/σ)max = 0.008 |
440 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[Cu4(OH)4(C10H8N2)4(H2O)2](NO3)4·2H2O | γ = 111.218 (2)° |
Mr = 1355.04 | V = 1311.91 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.1504 (1) Å | Mo Kα radiation |
b = 11.9299 (3) Å | µ = 1.69 mm−1 |
c = 12.6337 (1) Å | T = 293 K |
α = 111.073 (1)° | 0.30 × 0.18 × 0.12 mm |
β = 90.906 (2)° |
Siemens SMART CCD diffractometer | 4544 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2762 reflections with I > 2σ(I) |
Tmin = 0.597, Tmax = 0.816 | Rint = 0.040 |
6772 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.39 | Δρmax = 0.76 e Å−3 |
4544 reflections | Δρmin = −0.57 e Å−3 |
440 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 | ||
Cu1 | −0.07137 (8) | −0.20032 (7) | −0.22381 (7) | 0.0364 (3) | |
Cu2 | −0.14418 (8) | −0.00019 (7) | −0.05315 (7) | 0.0344 (3) | |
N1 | −0.2437 (5) | 0.0087 (5) | 0.0859 (4) | 0.0319 (13) | |
N4 | 0.0184 (6) | −0.2146 (5) | −0.3673 (5) | 0.0385 (14) | |
N2 | −0.2270 (5) | 0.1286 (5) | −0.0570 (5) | 0.0345 (14) | |
N3 | −0.0024 (5) | −0.3416 (5) | −0.2306 (5) | 0.0317 (13) | |
N5 | −0.3649 (8) | −0.1851 (10) | −0.4818 (7) | 0.075 (2) | |
N6 | −0.2649 (9) | −0.3516 (6) | 0.0738 (7) | 0.0555 (18) | |
O1 | −0.2986 (5) | −0.3374 (4) | −0.3010 (4) | 0.0545 (15) | |
O2 | −0.1000 (4) | −0.0444 (4) | −0.2066 (3) | 0.0375 (12) | |
H2A | −0.0943 | −0.0029 | −0.2572 | 0.045* | |
O3 | −0.0799 (7) | −0.1384 (6) | −0.0574 (5) | 0.0357 (15) | |
O4 | −0.3005 (7) | −0.0855 (6) | −0.3920 (6) | 0.0792 (19) | |
O5 | −0.3808 (9) | −0.2949 (8) | −0.4920 (6) | 0.122 (3) | |
O6 | −0.4296 (9) | −0.1768 (8) | −0.5602 (7) | 0.151 (4) | |
O7 | −0.3077 (7) | −0.3558 (6) | −0.0207 (6) | 0.095 (2) | |
O8 | −0.3485 (7) | −0.3906 (7) | 0.1331 (7) | 0.109 (3) | |
O9 | −0.1363 (7) | −0.3044 (6) | 0.1056 (6) | 0.095 (2) | |
O10 | −0.4166 (6) | −0.5632 (5) | −0.2601 (5) | 0.0904 (19) | |
C15 | 0.1308 (9) | −0.5131 (8) | −0.2544 (8) | 0.057 (3) | |
C7 | −0.3895 (7) | 0.2288 (6) | 0.0337 (6) | 0.0382 (18) | |
C2 | −0.3346 (8) | −0.0450 (7) | 0.2428 (7) | 0.045 (2) | |
C9 | −0.2824 (8) | 0.2743 (7) | −0.1227 (8) | 0.046 (2) | |
C1 | −0.2501 (7) | −0.0531 (7) | 0.1566 (6) | 0.0387 (18) | |
C22 | 0.0276 (9) | −0.1505 (8) | −0.4352 (7) | 0.057 (2) | |
C20 | 0.1858 (9) | −0.2381 (9) | −0.5420 (8) | 0.065 (3) | |
C8 | −0.3689 (8) | 0.2925 (7) | −0.0442 (7) | 0.046 (2) | |
C14 | 0.0467 (8) | −0.4945 (7) | −0.1714 (8) | 0.051 (2) | |
C18 | 0.2473 (9) | −0.3962 (8) | −0.4876 (7) | 0.063 (3) | |
H10A | 0.3038 | −0.4072 | −0.5446 | 0.076* | |
C19 | 0.1765 (7) | −0.3100 (7) | −0.4740 (7) | 0.047 (2) | |
C16 | 0.1477 (7) | −0.4499 (7) | −0.3311 (7) | 0.0429 (19) | |
C17 | 0.2339 (10) | −0.4609 (10) | −0.4204 (9) | 0.066 (3) | |
C21 | 0.1112 (9) | −0.1581 (8) | −0.5222 (7) | 0.070 (3) | |
H14A | 0.1166 | −0.1095 | −0.5665 | 0.084* | |
C13 | −0.0180 (8) | −0.4048 (7) | −0.1621 (7) | 0.043 (2) | |
C6 | −0.4797 (7) | 0.2402 (7) | 0.1211 (7) | 0.043 (2) | |
C3 | −0.4167 (8) | 0.0293 (7) | 0.2580 (7) | 0.048 (2) | |
C10 | −0.2136 (8) | 0.1898 (7) | −0.1279 (7) | 0.0428 (19) | |
C4 | −0.4121 (6) | 0.0963 (6) | 0.1830 (6) | 0.0357 (17) | |
C5 | −0.4882 (8) | 0.1784 (7) | 0.1930 (7) | 0.042 (2) | |
C24 | 0.0779 (7) | −0.3640 (6) | −0.3145 (6) | 0.0346 (17) | |
C23 | 0.0900 (7) | −0.2957 (6) | −0.3879 (6) | 0.0369 (18) | |
C12 | −0.3248 (6) | 0.0821 (6) | 0.0997 (6) | 0.0333 (17) | |
C11 | −0.3131 (7) | 0.1469 (6) | 0.0234 (6) | 0.0328 (17) | |
H13 | −0.342 (6) | −0.091 (6) | 0.286 (5) | 0.04 (2)* | |
H12 | −0.143 (6) | 0.185 (5) | −0.171 (5) | 0.023 (17)* | |
H11 | −0.482 (7) | 0.027 (7) | 0.317 (6) | 0.07 (2)* | |
H10 | −0.416 (6) | 0.340 (6) | −0.041 (5) | 0.04 (2)* | |
H9 | −0.540 (6) | 0.189 (6) | 0.247 (6) | 0.04 (2)* | |
H8 | 0.262 (8) | −0.244 (7) | −0.594 (7) | 0.10 (3)* | |
H6 | −0.072 (6) | −0.393 (6) | −0.100 (5) | 0.05 (2)* | |
H5 | 0.033 (6) | −0.531 (6) | −0.115 (5) | 0.04 (2)* | |
H4 | −0.269 (6) | 0.312 (5) | −0.170 (5) | 0.018 (17)* | |
H3 | −0.023 (6) | −0.097 (5) | −0.422 (5) | 0.034 (19)* | |
H2 | −0.527 (7) | 0.306 (7) | 0.128 (6) | 0.08 (3)* | |
H1 | 0.169 (10) | −0.570 (9) | −0.263 (8) | 0.12 (4)* | |
H17 | −0.127 (8) | −0.180 (7) | −0.051 (8) | 0.05 (3)* | |
H16 | −0.194 (8) | −0.118 (7) | 0.151 (6) | 0.09 (3)* | |
H15 | 0.262 (7) | −0.502 (6) | −0.414 (6) | 0.03 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0417 (6) | 0.0350 (5) | 0.0389 (6) | 0.0226 (4) | 0.0178 (4) | 0.0138 (4) |
Cu2 | 0.0365 (6) | 0.0374 (5) | 0.0378 (6) | 0.0230 (4) | 0.0156 (4) | 0.0152 (4) |
N1 | 0.031 (3) | 0.034 (3) | 0.031 (3) | 0.015 (3) | 0.008 (3) | 0.010 (3) |
N4 | 0.044 (4) | 0.037 (3) | 0.039 (4) | 0.018 (3) | 0.017 (3) | 0.017 (3) |
N2 | 0.038 (4) | 0.035 (3) | 0.039 (4) | 0.021 (3) | 0.015 (3) | 0.016 (3) |
N3 | 0.029 (3) | 0.029 (3) | 0.037 (4) | 0.013 (3) | 0.010 (3) | 0.010 (3) |
N5 | 0.058 (5) | 0.115 (8) | 0.063 (6) | 0.031 (6) | 0.010 (5) | 0.051 (6) |
N6 | 0.065 (6) | 0.045 (4) | 0.068 (5) | 0.025 (4) | 0.015 (5) | 0.031 (4) |
O1 | 0.041 (3) | 0.047 (3) | 0.065 (4) | 0.019 (3) | 0.005 (3) | 0.010 (3) |
O2 | 0.060 (3) | 0.041 (3) | 0.031 (3) | 0.034 (2) | 0.024 (2) | 0.021 (2) |
O3 | 0.039 (4) | 0.036 (3) | 0.041 (3) | 0.021 (3) | 0.020 (3) | 0.017 (3) |
O4 | 0.080 (5) | 0.098 (5) | 0.064 (4) | 0.032 (4) | 0.012 (4) | 0.040 (4) |
O5 | 0.160 (7) | 0.118 (6) | 0.103 (6) | 0.090 (6) | −0.008 (5) | 0.026 (5) |
O6 | 0.169 (8) | 0.154 (7) | 0.110 (7) | 0.013 (6) | −0.035 (6) | 0.083 (6) |
O7 | 0.099 (5) | 0.097 (5) | 0.089 (5) | 0.034 (4) | 0.001 (4) | 0.042 (4) |
O8 | 0.088 (5) | 0.146 (6) | 0.151 (7) | 0.058 (5) | 0.080 (5) | 0.107 (6) |
O9 | 0.057 (4) | 0.101 (5) | 0.145 (7) | 0.030 (4) | 0.010 (4) | 0.069 (5) |
O10 | 0.108 (5) | 0.078 (4) | 0.084 (5) | 0.032 (4) | 0.042 (4) | 0.033 (4) |
C15 | 0.045 (5) | 0.042 (5) | 0.075 (7) | 0.026 (4) | 0.000 (5) | 0.004 (5) |
C7 | 0.028 (4) | 0.030 (4) | 0.046 (5) | 0.013 (3) | 0.001 (3) | 0.002 (4) |
C2 | 0.045 (5) | 0.044 (5) | 0.048 (5) | 0.014 (4) | 0.016 (4) | 0.025 (4) |
C9 | 0.052 (5) | 0.042 (5) | 0.056 (6) | 0.025 (4) | 0.009 (4) | 0.026 (4) |
C1 | 0.035 (5) | 0.036 (4) | 0.041 (5) | 0.010 (4) | 0.009 (4) | 0.015 (4) |
C22 | 0.067 (6) | 0.055 (6) | 0.053 (6) | 0.028 (5) | 0.029 (5) | 0.022 (5) |
C20 | 0.055 (6) | 0.069 (6) | 0.055 (6) | 0.023 (5) | 0.032 (5) | 0.007 (5) |
C8 | 0.047 (5) | 0.045 (5) | 0.056 (6) | 0.028 (4) | 0.010 (4) | 0.023 (4) |
C14 | 0.046 (5) | 0.046 (5) | 0.060 (6) | 0.020 (4) | 0.008 (4) | 0.018 (5) |
C18 | 0.067 (6) | 0.076 (6) | 0.049 (6) | 0.044 (5) | 0.034 (5) | 0.010 (5) |
C19 | 0.043 (5) | 0.048 (5) | 0.038 (5) | 0.016 (4) | 0.015 (4) | 0.007 (4) |
C16 | 0.034 (5) | 0.040 (5) | 0.049 (5) | 0.020 (4) | 0.008 (4) | 0.006 (4) |
C17 | 0.052 (6) | 0.066 (7) | 0.070 (8) | 0.040 (6) | 0.007 (5) | −0.001 (6) |
C21 | 0.091 (7) | 0.071 (6) | 0.050 (6) | 0.024 (6) | 0.023 (5) | 0.033 (5) |
C13 | 0.036 (5) | 0.039 (5) | 0.057 (6) | 0.018 (4) | 0.017 (4) | 0.017 (4) |
C6 | 0.037 (5) | 0.047 (5) | 0.044 (5) | 0.028 (4) | 0.007 (4) | 0.003 (4) |
C3 | 0.034 (5) | 0.050 (5) | 0.041 (5) | 0.005 (4) | 0.017 (4) | 0.010 (4) |
C10 | 0.033 (5) | 0.045 (5) | 0.052 (5) | 0.017 (4) | 0.010 (4) | 0.018 (4) |
C4 | 0.025 (4) | 0.045 (4) | 0.030 (4) | 0.010 (3) | 0.012 (3) | 0.010 (4) |
C5 | 0.034 (5) | 0.042 (5) | 0.044 (5) | 0.021 (4) | 0.017 (4) | 0.005 (4) |
C24 | 0.029 (4) | 0.031 (4) | 0.036 (4) | 0.014 (3) | 0.010 (3) | 0.003 (3) |
C23 | 0.031 (4) | 0.034 (4) | 0.033 (4) | 0.009 (3) | 0.007 (3) | 0.002 (3) |
C12 | 0.023 (4) | 0.031 (4) | 0.033 (4) | 0.009 (3) | 0.005 (3) | 0.001 (3) |
C11 | 0.025 (4) | 0.032 (4) | 0.034 (4) | 0.010 (3) | 0.001 (3) | 0.006 (3) |
Cu1—O2 | 1.922 (4) | C2—C3 | 1.392 (10) |
Cu1—O3 | 1.977 (6) | C2—C1 | 1.394 (10) |
Cu1—N4 | 2.022 (6) | C2—H13 | 0.89 (6) |
Cu1—N3 | 2.022 (5) | C9—C8 | 1.345 (11) |
Cu1—O1 | 2.235 (4) | C9—C10 | 1.404 (9) |
Cu1—Cu2 | 2.9191 (10) | C9—H4 | 0.85 (5) |
Cu2—O2 | 1.924 (4) | C1—H16 | 1.10 (7) |
Cu2—O3 | 1.966 (6) | C22—C21 | 1.396 (11) |
Cu2—N2 | 2.013 (5) | C22—H3 | 0.93 (5) |
Cu2—N1 | 2.029 (5) | C20—C21 | 1.379 (11) |
Cu2—O3i | 2.318 (6) | C20—C19 | 1.399 (11) |
N1—C1 | 1.337 (8) | C20—H8 | 1.02 (8) |
N1—C12 | 1.375 (7) | C8—H10 | 0.85 (5) |
N4—C22 | 1.323 (9) | C14—C13 | 1.418 (9) |
N4—C23 | 1.366 (8) | C14—H5 | 0.96 (6) |
N2—C10 | 1.326 (9) | C18—C17 | 1.317 (13) |
N2—C11 | 1.360 (8) | C18—C19 | 1.420 (10) |
N3—C13 | 1.316 (9) | C18—H10A | 0.9300 |
N3—C24 | 1.357 (8) | C19—C23 | 1.411 (9) |
N5—O5 | 1.218 (9) | C16—C24 | 1.404 (8) |
N5—O6 | 1.233 (8) | C16—C17 | 1.435 (13) |
N5—O4 | 1.253 (9) | C17—H15 | 0.68 (5) |
N6—O9 | 1.213 (7) | C21—H14A | 0.9300 |
N6—O8 | 1.217 (9) | C13—H6 | 0.97 (6) |
N6—O7 | 1.241 (8) | C6—C5 | 1.347 (10) |
O2—H2A | 0.9300 | C6—H2 | 1.04 (7) |
O3—Cu2i | 2.318 (6) | C3—C4 | 1.435 (10) |
O3—H17 | 0.58 (7) | C3—H11 | 1.01 (7) |
C15—C14 | 1.369 (11) | C10—H12 | 0.91 (5) |
C15—C16 | 1.405 (11) | C4—C12 | 1.389 (9) |
C15—H1 | 0.87 (8) | C4—C5 | 1.426 (9) |
C7—C8 | 1.421 (10) | C5—H9 | 0.87 (6) |
C7—C11 | 1.425 (8) | C24—C23 | 1.419 (9) |
C7—C6 | 1.446 (10) | C12—C11 | 1.420 (9) |
O2—Cu1—O3 | 81.9 (2) | C1—C2—H13 | 122 (4) |
O2—Cu1—N4 | 95.8 (2) | C8—C9—C10 | 119.2 (8) |
O3—Cu1—N4 | 157.3 (2) | C8—C9—H4 | 122 (4) |
O2—Cu1—N3 | 169.30 (19) | C10—C9—H4 | 119 (4) |
O3—Cu1—N3 | 96.5 (2) | N1—C1—C2 | 122.5 (7) |
N4—Cu1—N3 | 81.6 (2) | N1—C1—H16 | 124 (4) |
O2—Cu1—O1 | 95.62 (17) | C2—C1—H16 | 114 (4) |
O3—Cu1—O1 | 102.1 (2) | N4—C22—C21 | 123.1 (8) |
N4—Cu1—O1 | 100.7 (2) | N4—C22—H3 | 117 (4) |
N3—Cu1—O1 | 95.06 (18) | C21—C22—H3 | 120 (4) |
O2—Cu1—Cu2 | 40.65 (13) | C21—C20—C19 | 119.2 (8) |
O3—Cu1—Cu2 | 42.09 (17) | C21—C20—H8 | 128 (5) |
N4—Cu1—Cu2 | 135.16 (16) | C19—C20—H8 | 112 (4) |
N3—Cu1—Cu2 | 138.57 (17) | C9—C8—C7 | 120.8 (7) |
O1—Cu1—Cu2 | 95.07 (12) | C9—C8—H10 | 122 (5) |
O2—Cu2—O3 | 82.1 (2) | C7—C8—H10 | 117 (5) |
O2—Cu2—N2 | 96.9 (2) | C15—C14—C13 | 117.7 (9) |
O3—Cu2—N2 | 174.9 (2) | C15—C14—H5 | 126 (4) |
O2—Cu2—N1 | 164.44 (19) | C13—C14—H5 | 116 (4) |
O3—Cu2—N1 | 97.7 (2) | C17—C18—C19 | 120.7 (8) |
N2—Cu2—N1 | 81.9 (2) | C17—C18—H10A | 119.6 |
O2—Cu2—O3i | 101.9 (2) | C19—C18—H10A | 119.6 |
O3—Cu2—O3i | 83.7 (3) | C20—C19—C23 | 117.2 (7) |
N2—Cu2—O3i | 101.4 (2) | C20—C19—C18 | 123.9 (8) |
N1—Cu2—O3i | 93.6 (2) | C23—C19—C18 | 118.9 (8) |
O2—Cu2—Cu1 | 40.60 (11) | C24—C16—C15 | 116.0 (8) |
O3—Cu2—Cu1 | 42.39 (18) | C24—C16—C17 | 117.8 (8) |
N2—Cu2—Cu1 | 135.62 (17) | C15—C16—C17 | 126.2 (8) |
N1—Cu2—Cu1 | 134.52 (15) | C18—C17—C16 | 122.9 (9) |
O3i—Cu2—Cu1 | 100.32 (13) | C18—C17—H15 | 135 (7) |
C1—N1—C12 | 117.8 (6) | C16—C17—H15 | 102 (7) |
C1—N1—Cu2 | 129.8 (4) | C20—C21—C22 | 119.7 (9) |
C12—N1—Cu2 | 112.1 (4) | C20—C21—H14A | 120.2 |
C22—N4—C23 | 117.5 (7) | C22—C21—H14A | 120.2 |
C22—N4—Cu1 | 130.2 (5) | N3—C13—C14 | 122.8 (8) |
C23—N4—Cu1 | 112.1 (5) | N3—C13—H6 | 123 (4) |
C10—N2—C11 | 118.4 (6) | C14—C13—H6 | 114 (4) |
C10—N2—Cu2 | 129.4 (5) | C5—C6—C7 | 121.1 (7) |
C11—N2—Cu2 | 112.1 (5) | C5—C6—H2 | 124 (4) |
C13—N3—C24 | 118.6 (6) | C7—C6—H2 | 114 (4) |
C13—N3—Cu1 | 129.0 (5) | C2—C3—C4 | 118.3 (7) |
C24—N3—Cu1 | 112.3 (5) | C2—C3—H11 | 117 (4) |
O5—N5—O6 | 116.4 (10) | C4—C3—H11 | 124 (4) |
O5—N5—O4 | 123.2 (8) | N2—C10—C9 | 123.0 (8) |
O6—N5—O4 | 120.0 (10) | N2—C10—H12 | 114 (4) |
O9—N6—O8 | 121.4 (8) | C9—C10—H12 | 122 (4) |
O9—N6—O7 | 117.1 (8) | C12—C4—C5 | 119.7 (7) |
O8—N6—O7 | 121.4 (9) | C12—C4—C3 | 117.1 (7) |
Cu1—O2—Cu2 | 98.75 (19) | C5—C4—C3 | 123.1 (7) |
Cu1—O2—H2A | 130.6 | C6—C5—C4 | 121.1 (7) |
Cu2—O2—H2A | 130.6 | C6—C5—H9 | 120 (4) |
Cu2—O3—Cu1 | 95.5 (3) | C4—C5—H9 | 119 (4) |
Cu2—O3—Cu2i | 96.3 (3) | N3—C24—C16 | 123.4 (7) |
Cu1—O3—Cu2i | 111.9 (3) | N3—C24—C23 | 116.9 (6) |
Cu2—O3—H17 | 109 (9) | C16—C24—C23 | 119.7 (7) |
Cu1—O3—H17 | 107 (9) | N4—C23—C19 | 123.4 (7) |
Cu2i—O3—H17 | 131 (9) | N4—C23—C24 | 116.5 (6) |
C14—C15—C16 | 121.4 (8) | C19—C23—C24 | 120.1 (7) |
C14—C15—H1 | 119 (7) | N1—C12—C4 | 123.9 (7) |
C16—C15—H1 | 120 (7) | N1—C12—C11 | 115.7 (6) |
C8—C7—C11 | 116.0 (7) | C4—C12—C11 | 120.4 (6) |
C8—C7—C6 | 125.9 (7) | N2—C11—C12 | 117.8 (6) |
C11—C7—C6 | 118.1 (7) | N2—C11—C7 | 122.5 (7) |
C3—C2—C1 | 120.2 (8) | C12—C11—C7 | 119.7 (7) |
C3—C2—H13 | 118 (4) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(OH)4(C10H8N2)4(H2O)2](NO3)4·2H2O |
Mr | 1355.04 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.1504 (1), 11.9299 (3), 12.6337 (1) |
α, β, γ (°) | 111.073 (1), 90.906 (2), 111.218 (2) |
V (Å3) | 1311.91 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.69 |
Crystal size (mm) | 0.30 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.597, 0.816 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6772, 4544, 2762 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.130, 1.39 |
No. of reflections | 4544 |
No. of parameters | 440 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.76, −0.57 |
Computer programs: SMART (Siemens, 1998), SMART, SAINT (Siemens, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), please provide.
Cu1—O2 | 1.922 (4) | Cu2—O2 | 1.924 (4) |
Cu1—O3 | 1.977 (6) | Cu2—O3 | 1.966 (6) |
Cu1—N4 | 2.022 (6) | Cu2—N2 | 2.013 (5) |
Cu1—N3 | 2.022 (5) | Cu2—N1 | 2.029 (5) |
Cu1—O1 | 2.235 (4) | Cu2—O3i | 2.318 (6) |
Cu1—Cu2 | 2.9191 (10) | O3—Cu2i | 2.318 (6) |
O2—Cu1—O3 | 81.9 (2) | O3—Cu2—N1 | 97.7 (2) |
O2—Cu1—N4 | 95.8 (2) | N2—Cu2—N1 | 81.9 (2) |
O3—Cu1—N4 | 157.3 (2) | O2—Cu2—O3i | 101.9 (2) |
O2—Cu1—N3 | 169.30 (19) | O3—Cu2—O3i | 83.7 (3) |
O3—Cu1—N3 | 96.5 (2) | N2—Cu2—O3i | 101.4 (2) |
N4—Cu1—N3 | 81.6 (2) | N1—Cu2—O3i | 93.6 (2) |
O2—Cu1—O1 | 95.62 (17) | O2—Cu2—Cu1 | 40.60 (11) |
O3—Cu1—O1 | 102.1 (2) | O3—Cu2—Cu1 | 42.39 (18) |
N4—Cu1—O1 | 100.7 (2) | N2—Cu2—Cu1 | 135.62 (17) |
N3—Cu1—O1 | 95.06 (18) | N1—Cu2—Cu1 | 134.52 (15) |
O2—Cu1—Cu2 | 40.65 (13) | O3i—Cu2—Cu1 | 100.32 (13) |
O3—Cu1—Cu2 | 42.09 (17) | C1—N1—C12 | 117.8 (6) |
N4—Cu1—Cu2 | 135.16 (16) | C1—N1—Cu2 | 129.8 (4) |
N3—Cu1—Cu2 | 138.57 (17) | C12—N1—Cu2 | 112.1 (4) |
O1—Cu1—Cu2 | 95.07 (12) | Cu1—O2—Cu2 | 98.75 (19) |
O2—Cu2—O3 | 82.1 (2) | Cu2—O3—Cu1 | 95.5 (3) |
O2—Cu2—N2 | 96.9 (2) | Cu2—O3—Cu2i | 96.3 (3) |
O3—Cu2—N2 | 174.9 (2) | Cu1—O3—Cu2i | 111.9 (3) |
O2—Cu2—N1 | 164.44 (19) |
Symmetry code: (i) −x, −y, −z. |
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Current research work on the structures, fluorescence and magnetic properties of polynuclear transition metal compounds is aimed at understanding the structural and chemical features governing electronic exchange coupling through multiatom bridging ligands. Although the greatest effort and success have been in the study of dinuclear Cu2+ complexes, there has been little work on oligomeric copper complexes with more than two copper ions (Gutieramento et al., 2000), particulary on chair form tetranuclear copper complexes connected by µ-hydroxo which have generally been observed as central bridging ligands (Ferrer et al., 2000). We report here a chair-form tetranuclear copper complex, [Cu4(µ3OH)2(µ2OH)2(phen)4(H2O)2](NO3)4·2H2O (phen is phenanthroline), (I).
The cation structure of the title compound is shown in Fig. 1. In the chair-form tetranuclear copper structure, each copper has a tetragonal pyramidal coordination geometry. The bond lengths from the µ2-O atoms (O2 and O2a) to Cu atoms are shorter than those from the µ3-O atoms (O2 and O2a) to Cu (Cu1, Cu2 and Cu2a, Cu1a) atoms. In particular, the bond lengths O1—Cu2a and O2—Cu2 are 2.322 (19) and 2.34 (2) Å, respectively. Selected bond lengths and bond angles are listed in Table 1. The two 1,10-phenanthroline molecules coordinating with Cu1 and Cu2 are almost coplanar and the two pairs of 1,10-phenanthroline molecules are parallel. The Cu1—Cu2 and Cu2—Cu2a distances are 2.919 and 2.926 Å, respectively. The short metal–metal bond distance may permit a direct interaction or the spin–spin coupling may be accomplished by a super-exchange mechanism (Carlin, 1969).