Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016948/de1175sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016948/de1175Isup2.hkl |
CCDC reference: 180128
A mixture of 1.0 mmol of copper(II) nitrate hexahydrate, 2 mmol of 1,10-phenanthroline and 2 mmol sodium azide in 60 ml mixed solvent of water and ethanol(volume 2:1) is stirred for 30 min at room temperature. After four days, dark green crystals of the title compound are obtained in 85% yield.
Also, all the H atoms have been constrained and all constrained C—H distances were 0.94 Å.
Data collection: SMART1000 (Bruker, 1998); cell refinement: SMART1000; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXL97.
[Cu2(C12H8N2)4(N3)3]·N3·4H2O | Z = 1 |
Mr = 1088.08 | F(000) = 558 |
Triclinic, P1 | Dx = 1.529 Mg m−3 |
a = 8.676 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.843 (8) Å | θ = 1.5–24.3° |
c = 12.279 (8) Å | µ = 0.97 mm−1 |
α = 80.81 (1)° | T = 293 K |
β = 71.74 (1)° | Block, dark green |
γ = 84.60 (1)° | 0.20 × 0.15 × 0.12 mm |
V = 1181.4 (13) Å3 |
CCD area detector diffractometer | 4133 independent reflections |
Radiation source: fine-focus sealed tube | 3239 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996) | h = −9→10 |
Tmin = 0.858, Tmax = 0.890 | k = −14→13 |
6191 measured reflections | l = −14→12 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Calculated w = 1/[σ2(Fo2) + (0.0587P)2 + 0.7136P] where P = (Fo2 + 2Fc2)/3 |
4133 reflections | (Δ/σ)max < 0.001 |
337 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
[Cu2(C12H8N2)4(N3)3]·N3·4H2O | γ = 84.60 (1)° |
Mr = 1088.08 | V = 1181.4 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.676 (5) Å | Mo Kα radiation |
b = 11.843 (8) Å | µ = 0.97 mm−1 |
c = 12.279 (8) Å | T = 293 K |
α = 80.81 (1)° | 0.20 × 0.15 × 0.12 mm |
β = 71.74 (1)° |
CCD area detector diffractometer | 4133 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996) | 3239 reflections with I > 2σ(I) |
Tmin = 0.858, Tmax = 0.890 | Rint = 0.021 |
6191 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.37 e Å−3 |
4133 reflections | Δρmin = −0.43 e Å−3 |
337 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 | 0.12897 (5) | 0.26244 (4) | 0.36525 (3) | 0.04023 (16) | |
N1 | 0.0460 (4) | 0.0373 (3) | 0.4007 (4) | 0.0671 (10) | |
N2 | 0.0000 | 0.0000 | 0.5000 | 0.0552 (12) | |
N3 | −0.1025 (4) | 0.3100 (3) | 0.4176 (3) | 0.0519 (8) | |
N4 | −0.1658 (4) | 0.3764 (3) | 0.3619 (3) | 0.0631 (9) | |
N5 | −0.2339 (7) | 0.4393 (6) | 0.3104 (4) | 0.143 (3) | |
N6 | 0.1401 (3) | 0.2288 (2) | 0.5283 (2) | 0.0378 (6) | |
N7 | 0.3610 (3) | 0.1903 (2) | 0.3309 (2) | 0.0373 (6) | |
N8 | 0.2513 (4) | 0.4353 (3) | 0.3252 (2) | 0.0444 (7) | |
N9 | 0.1444 (3) | 0.3108 (3) | 0.1971 (2) | 0.0414 (7) | |
N10 | 0.1188 (7) | −0.0298 (6) | 0.0179 (4) | 0.122 (2) | |
N11 | 0.0000 | 0.0000 | 0.0000 | 0.0647 (13) | |
C1 | 0.0247 (4) | 0.2452 (3) | 0.6260 (3) | 0.0485 (9) | |
H1A | −0.0821 | 0.2713 | 0.6225 | 0.080* | |
C2 | 0.0546 (5) | 0.2263 (4) | 0.7328 (3) | 0.0570 (10) | |
H2A | −0.0317 | 0.2387 | 0.8019 | 0.080* | |
C3 | 0.2056 (5) | 0.1903 (4) | 0.7385 (3) | 0.0540 (10) | |
H3A | 0.2275 | 0.1768 | 0.8115 | 0.080* | |
C4 | 0.3316 (4) | 0.1724 (3) | 0.6369 (3) | 0.0410 (8) | |
C5 | 0.2910 (4) | 0.1926 (3) | 0.5339 (3) | 0.0346 (7) | |
C6 | 0.4114 (4) | 0.1739 (3) | 0.4268 (3) | 0.0362 (7) | |
C7 | 0.5701 (4) | 0.1392 (3) | 0.4262 (3) | 0.0417 (8) | |
C8 | 0.6827 (4) | 0.1209 (3) | 0.3181 (3) | 0.0511 (9) | |
H8A | 0.7940 | 0.0989 | 0.3124 | 0.080* | |
C9 | 0.6312 (5) | 0.1356 (3) | 0.2223 (4) | 0.0568 (10) | |
H9A | 0.7068 | 0.1222 | 0.1490 | 0.080* | |
C10 | 0.4690 (4) | 0.1699 (3) | 0.2317 (3) | 0.0478 (9) | |
H10A | 0.4347 | 0.1794 | 0.1635 | 0.080* | |
C11 | 0.6092 (4) | 0.1214 (3) | 0.5328 (4) | 0.0500 (9) | |
H11A | 0.7185 | 0.0980 | 0.5321 | 0.080* | |
C12 | 0.4942 (5) | 0.1366 (3) | 0.6333 (3) | 0.0486 (9) | |
H12A | 0.5231 | 0.1235 | 0.7038 | 0.080* | |
C13 | 0.3111 (5) | 0.4915 (3) | 0.3864 (4) | 0.0535 (10) | |
H13A | 0.2973 | 0.4614 | 0.4661 | 0.080* | |
C14 | 0.3920 (5) | 0.5926 (4) | 0.3411 (4) | 0.0611 (11) | |
H14A | 0.4371 | 0.6297 | 0.3874 | 0.080* | |
C15 | 0.4093 (5) | 0.6377 (4) | 0.2294 (4) | 0.0635 (11) | |
H15A | 0.4631 | 0.7082 | 0.1976 | 0.080* | |
C16 | 0.3453 (4) | 0.5814 (3) | 0.1606 (3) | 0.0509 (9) | |
C17 | 0.2696 (4) | 0.4784 (3) | 0.2130 (3) | 0.0411 (8) | |
C18 | 0.2102 (4) | 0.4137 (3) | 0.1462 (3) | 0.0414 (8) | |
C19 | 0.2197 (4) | 0.4579 (3) | 0.0306 (3) | 0.0500 (9) | |
C20 | 0.1561 (5) | 0.3930 (4) | −0.0302 (3) | 0.0604 (11) | |
H20A | 0.1618 | 0.4198 | −0.1094 | 0.080* | |
C21 | 0.0873 (5) | 0.2920 (4) | 0.0232 (3) | 0.0581 (11) | |
H21A | 0.0408 | 0.2481 | −0.0170 | 0.080* | |
C22 | 0.0854 (4) | 0.2528 (4) | 0.1366 (3) | 0.0487 (9) | |
H22A | 0.0384 | 0.1809 | 0.1731 | 0.080* | |
C23 | 0.2941 (5) | 0.5659 (4) | −0.0181 (4) | 0.0649 (12) | |
H23A | 0.3033 | 0.5950 | −0.0974 | 0.080* | |
C24 | 0.3527 (5) | 0.6238 (4) | 0.0438 (4) | 0.0638 (12) | |
H24A | 0.3996 | 0.6962 | 0.0095 | 0.080* | |
O1W | 0.2627 (4) | −0.0484 (4) | 0.1944 (3) | 0.0935 (11) | |
H1WA | 0.2658 | 0.0061 | 0.1292 | 0.080* | |
H1WB | 0.2623 | −0.0157 | 0.2594 | 0.080* | |
O2W | 0.5689 (4) | −0.1273 (3) | 0.0509 (3) | 0.0857 (10) | |
H2WA | 0.6443 | −0.0694 | 0.0268 | 0.080* | |
H2WB | 0.4693 | −0.1006 | 0.0989 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0360 (2) | 0.0507 (3) | 0.0323 (2) | 0.00122 (18) | −0.00952 (17) | −0.00420 (18) |
N1 | 0.056 (2) | 0.072 (3) | 0.077 (3) | 0.0026 (19) | −0.020 (2) | −0.024 (2) |
N2 | 0.033 (2) | 0.056 (3) | 0.085 (4) | 0.008 (2) | −0.024 (3) | −0.030 (3) |
N3 | 0.0397 (17) | 0.067 (2) | 0.0435 (17) | 0.0062 (15) | −0.0103 (14) | −0.0003 (16) |
N4 | 0.054 (2) | 0.082 (3) | 0.0475 (19) | 0.0219 (19) | −0.0130 (17) | −0.0117 (18) |
N5 | 0.128 (5) | 0.191 (6) | 0.084 (3) | 0.094 (4) | −0.036 (3) | 0.007 (4) |
N6 | 0.0369 (15) | 0.0404 (16) | 0.0351 (15) | −0.0008 (12) | −0.0097 (12) | −0.0051 (12) |
N7 | 0.0365 (15) | 0.0392 (16) | 0.0332 (15) | −0.0031 (12) | −0.0057 (12) | −0.0055 (12) |
N8 | 0.0482 (17) | 0.0431 (17) | 0.0418 (17) | −0.0021 (13) | −0.0136 (14) | −0.0059 (13) |
N9 | 0.0379 (15) | 0.0498 (18) | 0.0357 (15) | 0.0014 (13) | −0.0111 (12) | −0.0054 (13) |
N10 | 0.088 (4) | 0.198 (7) | 0.072 (3) | 0.020 (4) | −0.022 (3) | −0.016 (3) |
N11 | 0.071 (4) | 0.075 (4) | 0.042 (3) | 0.002 (3) | −0.006 (3) | −0.017 (2) |
C1 | 0.040 (2) | 0.060 (2) | 0.039 (2) | 0.0023 (17) | −0.0048 (16) | −0.0067 (17) |
C2 | 0.056 (2) | 0.076 (3) | 0.034 (2) | 0.006 (2) | −0.0069 (17) | −0.0130 (19) |
C3 | 0.063 (3) | 0.064 (3) | 0.038 (2) | −0.002 (2) | −0.0195 (18) | −0.0100 (18) |
C4 | 0.048 (2) | 0.0357 (19) | 0.044 (2) | −0.0021 (15) | −0.0187 (16) | −0.0062 (15) |
C5 | 0.0384 (18) | 0.0307 (17) | 0.0352 (17) | −0.0040 (13) | −0.0106 (14) | −0.0061 (13) |
C6 | 0.0342 (17) | 0.0298 (17) | 0.0440 (19) | −0.0029 (13) | −0.0110 (15) | −0.0045 (14) |
C7 | 0.0355 (18) | 0.0356 (19) | 0.053 (2) | −0.0043 (14) | −0.0114 (16) | −0.0048 (15) |
C8 | 0.038 (2) | 0.048 (2) | 0.062 (3) | −0.0009 (16) | −0.0087 (18) | −0.0068 (18) |
C9 | 0.049 (2) | 0.053 (2) | 0.053 (2) | −0.0005 (18) | 0.0068 (19) | −0.0087 (19) |
C10 | 0.046 (2) | 0.050 (2) | 0.042 (2) | −0.0022 (17) | −0.0046 (16) | −0.0062 (16) |
C11 | 0.041 (2) | 0.045 (2) | 0.071 (3) | −0.0026 (16) | −0.0274 (19) | −0.0080 (19) |
C12 | 0.056 (2) | 0.044 (2) | 0.055 (2) | −0.0006 (17) | −0.0288 (19) | −0.0082 (17) |
C13 | 0.058 (2) | 0.048 (2) | 0.056 (2) | 0.0011 (19) | −0.0187 (19) | −0.0131 (18) |
C14 | 0.065 (3) | 0.050 (2) | 0.072 (3) | −0.006 (2) | −0.020 (2) | −0.016 (2) |
C15 | 0.060 (3) | 0.043 (2) | 0.078 (3) | −0.0114 (19) | −0.007 (2) | −0.005 (2) |
C16 | 0.047 (2) | 0.042 (2) | 0.052 (2) | 0.0039 (17) | −0.0026 (18) | −0.0012 (17) |
C17 | 0.0364 (18) | 0.040 (2) | 0.0398 (19) | 0.0062 (15) | −0.0048 (15) | −0.0048 (15) |
C18 | 0.0326 (17) | 0.050 (2) | 0.0363 (18) | 0.0100 (15) | −0.0070 (14) | −0.0039 (16) |
C19 | 0.044 (2) | 0.061 (2) | 0.0365 (19) | 0.0122 (18) | −0.0080 (16) | 0.0009 (17) |
C20 | 0.060 (3) | 0.082 (3) | 0.036 (2) | 0.022 (2) | −0.0153 (19) | −0.009 (2) |
C21 | 0.056 (2) | 0.080 (3) | 0.043 (2) | 0.015 (2) | −0.0188 (19) | −0.024 (2) |
C22 | 0.043 (2) | 0.062 (2) | 0.044 (2) | 0.0039 (17) | −0.0163 (17) | −0.0144 (18) |
C23 | 0.065 (3) | 0.066 (3) | 0.044 (2) | 0.015 (2) | −0.002 (2) | 0.010 (2) |
C24 | 0.064 (3) | 0.050 (3) | 0.060 (3) | −0.001 (2) | −0.004 (2) | 0.012 (2) |
O1W | 0.065 (2) | 0.132 (3) | 0.088 (2) | 0.003 (2) | −0.0223 (19) | −0.037 (2) |
O2W | 0.076 (2) | 0.074 (2) | 0.086 (2) | −0.0002 (17) | −0.0029 (18) | 0.0050 (18) |
Cu1—N3 | 1.964 (3) | C3—C4 | 1.408 (5) |
Cu1—N6 | 2.009 (3) | C4—C5 | 1.396 (5) |
Cu1—N9 | 2.018 (3) | C4—C12 | 1.424 (5) |
Cu1—N7 | 2.054 (3) | C5—C6 | 1.435 (5) |
Cu1—N8 | 2.306 (3) | C6—C7 | 1.397 (5) |
Cu1—N1 | 2.759 (4) | C7—C8 | 1.416 (5) |
N1—N2 | 1.182 (4) | C7—C11 | 1.431 (5) |
N1—O1W | 2.908 (5) | C8—C9 | 1.365 (6) |
N2—N1i | 1.182 (4) | C9—C10 | 1.402 (5) |
N3—N4 | 1.171 (4) | C9—N10iii | 3.411 (7) |
N4—N5 | 1.142 (5) | C11—C12 | 1.348 (5) |
N6—C1 | 1.329 (4) | C13—C14 | 1.392 (6) |
N6—C5 | 1.358 (4) | C14—C15 | 1.358 (6) |
N7—C10 | 1.325 (4) | C15—C16 | 1.417 (6) |
N7—C6 | 1.360 (4) | C16—C17 | 1.403 (5) |
N8—C13 | 1.321 (5) | C16—C24 | 1.426 (6) |
N8—C17 | 1.355 (4) | C17—C18 | 1.437 (5) |
N9—C22 | 1.325 (5) | C18—C19 | 1.412 (5) |
N9—C18 | 1.366 (5) | C19—C20 | 1.405 (6) |
N10—N11 | 1.133 (6) | C19—C23 | 1.442 (6) |
N10—O1W | 2.792 (6) | C20—C21 | 1.363 (6) |
N11—N10ii | 1.133 (6) | C21—C22 | 1.391 (5) |
C1—C2 | 1.396 (5) | C23—C24 | 1.335 (6) |
C2—C3 | 1.358 (6) | O1W—O2W | 2.857 (5) |
N3—Cu1—N6 | 92.21 (12) | C3—C4—C12 | 124.5 (3) |
N3—Cu1—N9 | 92.55 (12) | N6—C5—C4 | 123.5 (3) |
N6—Cu1—N9 | 171.83 (11) | N6—C5—C6 | 116.6 (3) |
N3—Cu1—N7 | 170.71 (12) | C4—C5—C6 | 120.0 (3) |
N6—Cu1—N7 | 81.49 (11) | N7—C6—C7 | 124.0 (3) |
N9—Cu1—N7 | 94.53 (11) | N7—C6—C5 | 116.6 (3) |
N3—Cu1—N8 | 101.94 (13) | C7—C6—C5 | 119.4 (3) |
N6—Cu1—N8 | 94.74 (11) | C6—C7—C8 | 116.7 (3) |
N9—Cu1—N8 | 77.76 (11) | C6—C7—C11 | 119.4 (3) |
N7—Cu1—N8 | 85.46 (11) | C8—C7—C11 | 123.8 (3) |
N3—Cu1—N1 | 89.61 (13) | C9—C8—C7 | 119.2 (3) |
N6—Cu1—N1 | 84.32 (12) | C8—C9—C10 | 119.9 (4) |
N9—Cu1—N1 | 102.36 (12) | C8—C9—N10iii | 117.3 (3) |
N7—Cu1—N1 | 83.02 (11) | C10—C9—N10iii | 121.4 (3) |
N8—Cu1—N1 | 168.45 (11) | N7—C10—C9 | 122.6 (4) |
N2—N1—Cu1 | 112.5 (2) | C12—C11—C7 | 120.6 (3) |
N2—N1—O1W | 134.6 (3) | C11—C12—C4 | 121.4 (3) |
Cu1—N1—O1W | 102.11 (16) | N8—C13—C14 | 123.1 (4) |
N1i—N2—N1 | 180.0 | C15—C14—C13 | 119.3 (4) |
N4—N3—Cu1 | 123.4 (3) | C14—C15—C16 | 119.7 (4) |
N5—N4—N3 | 177.0 (5) | C17—C16—C15 | 116.9 (4) |
C1—N6—C5 | 118.3 (3) | C17—C16—C24 | 119.2 (4) |
C1—N6—Cu1 | 128.5 (2) | C15—C16—C24 | 123.9 (4) |
C5—N6—Cu1 | 113.0 (2) | N8—C17—C16 | 122.7 (3) |
C10—N7—C6 | 117.5 (3) | N8—C17—C18 | 117.7 (3) |
C10—N7—Cu1 | 130.7 (2) | C16—C17—C18 | 119.7 (3) |
C6—N7—Cu1 | 111.3 (2) | N9—C18—C19 | 121.6 (3) |
C13—N8—C17 | 118.3 (3) | N9—C18—C17 | 118.8 (3) |
C13—N8—Cu1 | 132.9 (3) | C19—C18—C17 | 119.6 (3) |
C17—N8—Cu1 | 108.6 (2) | C20—C19—C18 | 117.6 (4) |
C22—N9—C18 | 118.7 (3) | C20—C19—C23 | 124.0 (4) |
C22—N9—Cu1 | 124.0 (3) | C18—C19—C23 | 118.5 (4) |
C18—N9—Cu1 | 117.1 (2) | C21—C20—C19 | 119.9 (4) |
N11—N10—O1W | 140.3 (4) | C20—C21—C22 | 119.3 (4) |
N10ii—N11—N10 | 180.0 | N9—C22—C21 | 122.9 (4) |
N6—C1—C2 | 121.9 (3) | C24—C23—C19 | 121.4 (4) |
C3—C2—C1 | 119.7 (4) | C23—C24—C16 | 121.5 (4) |
C2—C3—C4 | 120.2 (3) | N10—O1W—O2W | 92.79 (17) |
C5—C4—C3 | 116.4 (3) | N10—O1W—N1 | 112.09 (18) |
C5—C4—C12 | 119.1 (3) | O2W—O1W—N1 | 154.61 (17) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y, −z; (iii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···N10 | 0.94 | 2.25 | 2.792 (6) | 116 |
O1W—H1WB···N1 | 0.94 | 2.24 | 2.908 (5) | 128 |
O2W—H2WB···O1W | 0.94 | 1.92 | 2.857 (5) | 178 |
C9—H9A···N10iii | 0.94 | 2.50 | 3.411 (7) | 163 |
Symmetry code: (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C12H8N2)4(N3)3]·N3·4H2O |
Mr | 1088.08 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.676 (5), 11.843 (8), 12.279 (8) |
α, β, γ (°) | 80.81 (1), 71.74 (1), 84.60 (1) |
V (Å3) | 1181.4 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.97 |
Crystal size (mm) | 0.20 × 0.15 × 0.12 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick 1996) |
Tmin, Tmax | 0.858, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6191, 4133, 3239 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.121, 1.03 |
No. of reflections | 4133 |
No. of parameters | 337 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.43 |
Computer programs: SMART1000 (Bruker, 1998), SMART1000, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1998), SHELXL97.
Cu1—N3 | 1.964 (3) | Cu1—N8 | 2.306 (3) |
Cu1—N6 | 2.009 (3) | Cu1—N1 | 2.759 (4) |
Cu1—N9 | 2.018 (3) | N1—O1W | 2.908 (5) |
Cu1—N7 | 2.054 (3) | O1W—O2W | 2.857 (5) |
N3—Cu1—N6 | 92.21 (12) | N3—Cu1—N1 | 89.61 (13) |
N3—Cu1—N9 | 92.55 (12) | N6—Cu1—N1 | 84.32 (12) |
N6—Cu1—N9 | 171.83 (11) | N9—Cu1—N1 | 102.36 (12) |
N3—Cu1—N7 | 170.71 (12) | N7—Cu1—N1 | 83.02 (11) |
N6—Cu1—N7 | 81.49 (11) | N8—Cu1—N1 | 168.45 (11) |
N9—Cu1—N7 | 94.53 (11) | N2—N1—Cu1 | 112.5 (2) |
N3—Cu1—N8 | 101.94 (13) | N4—N3—Cu1 | 123.4 (3) |
N6—Cu1—N8 | 94.74 (11) | N10—O1W—O2W | 92.79 (17) |
N9—Cu1—N8 | 77.76 (11) | N10—O1W—N1 | 112.09 (18) |
N7—Cu1—N8 | 85.46 (11) | O2W—O1W—N1 | 154.61 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···N10 | 0.94 | 2.25 | 2.792 (6) | 116.1 |
O1W—H1WB···N1 | 0.94 | 2.24 | 2.908 (5) | 127.5 |
O2W—H2WB···O1W | 0.94 | 1.92 | 2.857 (5) | 178.2 |
C9—H9A···N10i | 0.94 | 2.50 | 3.411 (7) | 163.4 |
Symmetry code: (i) −x+1, −y, −z. |
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Studies on the synthesis and properties of bi- and polynuclear complexes bridged by the pseudohalide azide anion (N3-) have attracted a lot of attention in recent years (Ribas et al., 1999; Goher et al., 1998; Zhang et al., 2001), owing to their intriguing structural diversity, potential functions as models for metalloenzymes, and ferromagnetic or antiferromagnetic interactions (Baffert et al., 2001; Aebersold et al., 1998; Zhang et al., 2000). The azide anion can bind to metal ions in versatile modes: as a terminal ligand via one nitrogen donor, as a bridge in the µ1,1 way via one nitrogen donor, and in the µ1,3 way via both of the peripheral donor N atoms (Sheppard et al., 1996). Despite the fact that a substantial array of copper(II) azido complexes have been synthesized (Goher et al., 1999), to our knowledge, its dimeric single-bridged compounds with 1,10-phenanthroline have not been reported so far. We firstly report here the preparation and crystal structure of a dimeric azido complex of copper(II), namely [Cu2(phen)4(m1,3-azido)(N3)2](N3)·4H2O (I).
The molecular unit of the title compound comprises a dimeric cation [Cu2(phen)4(m1,3-azido)(N3)2]+, two azide anions and four water molecules. As shown in Fig. 1, the Cu atom is surrounded by two N atoms of two azide anions and four N atoms of two 1,10-phenanthroline ligands to form a elongated CuN6 octahedron. The Cu—N bond lengths in apical positions [2.306 (3), 2.759 (4) Å] are much longer than the Cu—N bond lengths in equatorial positions [1.964 (3), 2.009 (3), 2.018 (3), 2.054 (3) Å], due to the Jahn-Teller effects of CuII. An ideally linear µ1,3-azide anion bridges two Cu atoms to form a dimeric entity with N2 located on a centre of inversion, with the Cu···Cu distance at 6.783 (4) Å.
It should be noted that hydrogen bonding interactions and π-π interactions play an important role in the solid state structure of (I), as shown in Fig. 2. The adjacent dimeric units are connected by hydrogen-bond interactions (O1w···O2w, O1w···N10, O1w···N1, C9···N10I) [2.857 (5), 2.792 (6), 2.908 (5), 3.411 (7) Å], to produce chains. It is interesting that there are interchain π-π interactions between the 1,10-phenanthroline rings of adjacent chains with the face-to-face separation of ca 3.47 Å, which is different from other related compounds (Diaz et al., 2001), resulting in an interesting two-dimensional structure.