Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104028367/sq1182sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028367/sq1182Isup2.hkl |
CCDC reference: 263021
All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company, China, and were used without further purification. [Cu2(oxen)](ClO4)2 was synthesized by the literature method of Zhang et al. (2000). To a methanol solution (30 ml) of Cu(ClO4)2·6H2O (3.71 g, 10 mmol) was added an 80% methanol solution (30 ml) of oxen (Niu et al., 1994) (0.92 g, 5 mmol) with stirring. After a few minutes, a solution of 1M NaOH (10 ml) was added. The mixture was then refluxed for 2 h to obtain a green solid. The solid was filtered, washed with methanol and recrystallized from an 80% methanol solution (yield 77%). To prepare (I), a methanol solution (5 ml) of L (0.36 g, 2 mmol; Henderson et al., 1984) was added to a methanol solution (25 ml) of [Cu2(oxen)](ClO4)2 (0.50 g, 1 mmol) with stirring. The mixture was refluxed for 1 h to obtain a clear blue solution and, after standing at room temperature for three weeks, well shaped blue single crystals of (I) were obtained by slow evaporation.
All H atoms were placed in geometrically idealized positions, with Csp3—H = 0.97, Csp2 = 0.93 and Nsp3—H = 0.90 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97); software used to prepare material for publication: SHELXL97.
[Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2O | F(000) = 2496 |
Mr = 1226.89 | Dx = 1.617 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4667 reflections |
a = 26.5955 (1) Å | θ = 1.9–25.1° |
b = 11.4267 (3) Å | µ = 1.03 mm−1 |
c = 16.5915 (4) Å | T = 293 K |
β = 92.053 (1)° | Block, blue |
V = 5038.90 (18) Å3 | 0.44 × 0.40 × 0.36 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 4441 independent reflections |
Radiation source: fine-focus sealed tube | 3294 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −25→31 |
Tmin = 0.659, Tmax = 0.708 | k = −10→13 |
8436 measured reflections | l = −19→19 |
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) = 0.198 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0804P)2 + 32.9042P] where P = (Fo2 + 2Fc2)/3 |
4441 reflections | (Δ/σ)max < 0.001 |
355 parameters | Δρmax = 0.82 e Å−3 |
1 restraint | Δρmin = −0.58 e Å−3 |
[Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2O | V = 5038.90 (18) Å3 |
Mr = 1226.89 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.5955 (1) Å | µ = 1.03 mm−1 |
b = 11.4267 (3) Å | T = 293 K |
c = 16.5915 (4) Å | 0.44 × 0.40 × 0.36 mm |
β = 92.053 (1)° |
Siemens SMART CCD area-detector diffractometer | 4441 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3294 reflections with I > 2σ(I) |
Tmin = 0.659, Tmax = 0.708 | Rint = 0.040 |
8436 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 1 restraint |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0804P)2 + 32.9042P] where P = (Fo2 + 2Fc2)/3 |
4441 reflections | Δρmax = 0.82 e Å−3 |
355 parameters | Δρmin = −0.58 e Å−3 |
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 | ||
Cu | 0.43625 (2) | 0.30356 (7) | 0.36580 (4) | 0.0443 (3) | |
Cl | 0.37123 (7) | 0.61062 (16) | 0.37323 (11) | 0.0655 (5) | |
O1 | 0.4265 (2) | 0.0072 (6) | 0.6819 (4) | 0.1011 (14) | |
O2 | 0.2717 (3) | 0.0619 (7) | 0.7278 (3) | 0.113 (2) | |
O3 | 0.48910 (14) | 0.3153 (4) | 0.1440 (2) | 0.0470 (10) | |
O4 | 0.3665 (3) | 0.7167 (5) | 0.3297 (4) | 0.101 (2) | |
O5 | 0.3762 (3) | 0.6366 (6) | 0.4573 (3) | 0.105 (2) | |
O6 | 0.3285 (2) | 0.5386 (5) | 0.3581 (4) | 0.100 (2) | |
O7 | 0.4150 (2) | 0.5506 (6) | 0.3527 (4) | 0.1011 (14) | |
N1 | 0.43899 (17) | 0.3101 (5) | 0.4869 (3) | 0.0466 (12) | |
N2 | 0.44035 (17) | 0.0807 (5) | 0.4022 (3) | 0.0464 (12) | |
N3 | 0.31471 (19) | 0.3246 (5) | 0.5198 (3) | 0.0532 (13) | |
N4 | 0.31734 (18) | 0.0762 (5) | 0.4535 (3) | 0.0551 (13) | |
N5 | 0.43539 (16) | 0.3079 (4) | 0.2505 (3) | 0.0414 (11) | |
N6 | 0.36123 (16) | 0.2845 (4) | 0.3486 (3) | 0.0453 (11) | |
H6A | 0.3494 | 0.2323 | 0.3839 | 0.054* | |
H6B | 0.3456 | 0.3534 | 0.3559 | 0.054* | |
C1 | 0.4357 (2) | 0.2068 (6) | 0.5227 (3) | 0.0455 (14) | |
C2 | 0.4407 (2) | 0.4027 (6) | 0.5370 (4) | 0.0580 (16) | |
H2B | 0.4432 | 0.4772 | 0.5150 | 0.070* | |
C3 | 0.4389 (3) | 0.3919 (8) | 0.6203 (4) | 0.072 (2) | |
H3A | 0.4412 | 0.4584 | 0.6525 | 0.086* | |
C4 | 0.4338 (3) | 0.2834 (7) | 0.6555 (4) | 0.067 (2) | |
H4A | 0.4309 | 0.2752 | 0.7109 | 0.081* | |
C5 | 0.4332 (2) | 0.1879 (6) | 0.6049 (3) | 0.0544 (16) | |
C6 | 0.4310 (2) | 0.0594 (7) | 0.6178 (3) | 0.0597 (18) | |
C7 | 0.4354 (2) | 0.0035 (6) | 0.5373 (3) | 0.0502 (15) | |
C8 | 0.4388 (2) | −0.1093 (6) | 0.5110 (4) | 0.0583 (17) | |
H8A | 0.4384 | −0.1721 | 0.5467 | 0.070* | |
C9 | 0.4430 (2) | −0.1259 (6) | 0.4288 (4) | 0.0576 (16) | |
H9A | 0.4458 | −0.2011 | 0.4080 | 0.069* | |
C10 | 0.4428 (2) | −0.0311 (7) | 0.3782 (4) | 0.0570 (17) | |
H10A | 0.4446 | −0.0454 | 0.3232 | 0.068* | |
C11 | 0.4367 (2) | 0.0935 (5) | 0.4807 (3) | 0.0436 (13) | |
C12 | 0.3044 (2) | 0.2281 (6) | 0.5596 (4) | 0.0512 (16) | |
C13 | 0.3112 (2) | 0.4245 (7) | 0.5628 (4) | 0.0653 (19) | |
H13A | 0.3187 | 0.4945 | 0.5373 | 0.078* | |
C14 | 0.2972 (3) | 0.4295 (8) | 0.6415 (5) | 0.074 (2) | |
H14A | 0.2945 | 0.5014 | 0.6672 | 0.089* | |
C15 | 0.2872 (2) | 0.3267 (9) | 0.6825 (4) | 0.073 (2) | |
H15A | 0.2788 | 0.3276 | 0.7364 | 0.088* | |
C16 | 0.2903 (2) | 0.2235 (7) | 0.6403 (4) | 0.063 (2) | |
C17 | 0.2824 (3) | 0.0996 (8) | 0.6624 (4) | 0.074 (2) | |
C18 | 0.2924 (2) | 0.0308 (7) | 0.5880 (4) | 0.0634 (18) | |
C19 | 0.2900 (3) | −0.0869 (8) | 0.5719 (6) | 0.082 (2) | |
H19A | 0.2809 | −0.1411 | 0.6106 | 0.099* | |
C20 | 0.3022 (3) | −0.1205 (8) | 0.4942 (6) | 0.082 (2) | |
H20A | 0.3015 | −0.1993 | 0.4802 | 0.098* | |
C21 | 0.3149 (3) | −0.0388 (7) | 0.4383 (5) | 0.0672 (19) | |
H21A | 0.3223 | −0.0646 | 0.3869 | 0.081* | |
C22 | 0.3058 (2) | 0.1082 (6) | 0.5277 (4) | 0.0518 (15) | |
C23 | 0.3519 (2) | 0.2427 (7) | 0.2648 (4) | 0.0606 (17) | |
H23A | 0.3172 | 0.2581 | 0.2480 | 0.073* | |
H23B | 0.3574 | 0.1589 | 0.2624 | 0.073* | |
C24 | 0.3866 (2) | 0.3039 (7) | 0.2090 (4) | 0.0578 (17) | |
H24A | 0.3886 | 0.2611 | 0.1587 | 0.069* | |
H24B | 0.3746 | 0.3824 | 0.1972 | 0.069* | |
C25 | 0.47855 (19) | 0.3115 (5) | 0.2183 (3) | 0.0385 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0404 (4) | 0.0619 (5) | 0.0311 (4) | 0.0001 (3) | 0.0068 (3) | 0.0009 (3) |
Cl | 0.0746 (11) | 0.0564 (10) | 0.0655 (11) | −0.0064 (9) | 0.0022 (8) | 0.0006 (8) |
O1 | 0.106 (3) | 0.115 (4) | 0.084 (3) | 0.001 (3) | 0.014 (2) | 0.005 (3) |
O2 | 0.121 (5) | 0.167 (7) | 0.051 (3) | −0.057 (5) | 0.012 (3) | 0.031 (4) |
O3 | 0.037 (2) | 0.078 (3) | 0.0266 (18) | −0.0031 (19) | 0.0040 (15) | 0.0026 (18) |
O4 | 0.147 (6) | 0.074 (4) | 0.079 (4) | −0.027 (4) | −0.030 (4) | 0.021 (3) |
O5 | 0.163 (7) | 0.089 (4) | 0.063 (4) | −0.003 (4) | −0.002 (4) | 0.012 (3) |
O6 | 0.074 (4) | 0.079 (4) | 0.146 (6) | −0.018 (3) | −0.009 (4) | 0.013 (4) |
O7 | 0.106 (3) | 0.115 (4) | 0.084 (3) | 0.001 (3) | 0.014 (2) | 0.005 (3) |
N1 | 0.039 (3) | 0.063 (3) | 0.038 (3) | 0.005 (2) | 0.0056 (19) | −0.004 (2) |
N2 | 0.045 (3) | 0.062 (3) | 0.031 (2) | 0.003 (2) | 0.0024 (19) | −0.001 (2) |
N3 | 0.046 (3) | 0.067 (4) | 0.048 (3) | −0.003 (2) | 0.008 (2) | −0.003 (3) |
N4 | 0.044 (3) | 0.065 (4) | 0.056 (3) | 0.000 (2) | 0.006 (2) | 0.000 (3) |
N5 | 0.032 (2) | 0.061 (3) | 0.032 (2) | −0.001 (2) | 0.0031 (17) | 0.000 (2) |
N6 | 0.036 (2) | 0.056 (3) | 0.044 (3) | −0.005 (2) | 0.009 (2) | 0.000 (2) |
C1 | 0.035 (3) | 0.072 (4) | 0.030 (3) | 0.003 (3) | 0.004 (2) | −0.001 (3) |
C2 | 0.053 (4) | 0.064 (4) | 0.057 (4) | 0.005 (3) | 0.004 (3) | −0.014 (3) |
C3 | 0.077 (5) | 0.091 (6) | 0.048 (4) | 0.016 (4) | 0.002 (3) | −0.025 (4) |
C4 | 0.068 (4) | 0.099 (6) | 0.035 (3) | 0.014 (4) | 0.002 (3) | −0.011 (4) |
C5 | 0.046 (3) | 0.083 (5) | 0.034 (3) | 0.001 (3) | 0.007 (2) | −0.006 (3) |
C6 | 0.060 (4) | 0.099 (6) | 0.020 (3) | 0.002 (4) | 0.006 (2) | 0.014 (3) |
C7 | 0.041 (3) | 0.068 (4) | 0.041 (3) | −0.006 (3) | 0.001 (2) | 0.008 (3) |
C8 | 0.054 (4) | 0.065 (5) | 0.055 (4) | −0.006 (3) | −0.002 (3) | 0.014 (3) |
C9 | 0.050 (4) | 0.058 (4) | 0.064 (4) | −0.006 (3) | −0.006 (3) | −0.005 (3) |
C10 | 0.054 (4) | 0.079 (5) | 0.038 (3) | 0.003 (3) | −0.005 (3) | −0.008 (3) |
C11 | 0.037 (3) | 0.062 (4) | 0.032 (3) | −0.003 (3) | 0.004 (2) | 0.002 (3) |
C12 | 0.034 (3) | 0.079 (5) | 0.040 (3) | −0.002 (3) | 0.004 (2) | 0.001 (3) |
C13 | 0.053 (4) | 0.080 (5) | 0.063 (4) | −0.004 (3) | 0.006 (3) | −0.016 (4) |
C14 | 0.050 (4) | 0.092 (6) | 0.079 (5) | −0.013 (4) | 0.007 (3) | −0.032 (5) |
C15 | 0.039 (3) | 0.133 (8) | 0.048 (4) | −0.010 (4) | 0.006 (3) | −0.023 (5) |
C16 | 0.044 (3) | 0.107 (6) | 0.037 (3) | −0.017 (4) | 0.005 (3) | −0.005 (4) |
C17 | 0.058 (4) | 0.115 (7) | 0.048 (4) | −0.020 (4) | −0.002 (3) | 0.018 (4) |
C18 | 0.053 (4) | 0.079 (5) | 0.058 (4) | −0.007 (3) | −0.001 (3) | 0.014 (4) |
C19 | 0.066 (5) | 0.087 (6) | 0.095 (6) | −0.005 (4) | 0.006 (4) | 0.038 (5) |
C20 | 0.063 (5) | 0.071 (5) | 0.111 (7) | −0.002 (4) | 0.005 (5) | 0.004 (5) |
C21 | 0.055 (4) | 0.076 (5) | 0.071 (5) | 0.000 (4) | 0.006 (3) | −0.008 (4) |
C22 | 0.038 (3) | 0.075 (5) | 0.043 (3) | −0.005 (3) | 0.007 (2) | 0.005 (3) |
C23 | 0.046 (3) | 0.086 (5) | 0.050 (4) | −0.015 (3) | 0.004 (3) | −0.009 (3) |
C24 | 0.040 (3) | 0.097 (5) | 0.036 (3) | 0.001 (3) | 0.005 (2) | 0.000 (3) |
C25 | 0.038 (3) | 0.044 (3) | 0.034 (3) | 0.001 (2) | 0.003 (2) | −0.002 (2) |
Cu—N5 | 1.914 (4) | C4—H4A | 0.9300 |
Cu—O3i | 2.002 (4) | C5—C6 | 1.485 (10) |
Cu—N1 | 2.009 (5) | C6—C7 | 1.489 (9) |
Cu—N6 | 2.017 (4) | C7—C8 | 1.365 (9) |
Cu—N2 | 2.619 (5) | C7—C11 | 1.393 (8) |
Cu—O7 | 2.885 (7) | C8—C9 | 1.386 (9) |
Cl—O7 | 1.404 (6) | C8—H8A | 0.9300 |
Cl—O4 | 1.414 (6) | C9—C10 | 1.370 (9) |
Cl—O6 | 1.418 (6) | C9—H9A | 0.9300 |
Cl—O5 | 1.427 (6) | C10—H10A | 0.9300 |
O1—C6 | 1.229 (8) | C12—C16 | 1.405 (8) |
O2—C17 | 1.210 (8) | C12—C22 | 1.469 (10) |
O3—C25 | 1.274 (6) | C13—C14 | 1.370 (10) |
O3—Cui | 2.002 (4) | C13—H13A | 0.9300 |
N1—C1 | 1.325 (8) | C14—C15 | 1.388 (12) |
N1—C2 | 1.346 (8) | C14—H14A | 0.9300 |
N2—C11 | 1.318 (7) | C15—C16 | 1.376 (11) |
N2—C10 | 1.341 (8) | C15—H15A | 0.9300 |
N3—C12 | 1.320 (8) | C16—C17 | 1.480 (11) |
N3—C13 | 1.351 (9) | C17—C18 | 1.496 (11) |
N4—C22 | 1.331 (8) | C18—C19 | 1.371 (12) |
N4—C21 | 1.339 (9) | C18—C22 | 1.392 (9) |
N5—C25 | 1.284 (7) | C19—C20 | 1.394 (12) |
N5—C24 | 1.448 (7) | C19—H19A | 0.9300 |
N6—C23 | 1.482 (8) | C20—C21 | 1.367 (11) |
N6—H6A | 0.9000 | C20—H20A | 0.9300 |
N6—H6B | 0.9000 | C21—H21A | 0.9300 |
C1—C5 | 1.384 (8) | C23—C24 | 1.503 (9) |
C1—C11 | 1.472 (9) | C23—H23A | 0.9700 |
C2—C3 | 1.390 (9) | C23—H23B | 0.9700 |
C2—H2B | 0.9300 | C24—H24A | 0.9700 |
C3—C4 | 1.379 (11) | C24—H24B | 0.9700 |
C3—H3A | 0.9300 | C25—C25i | 1.524 (10) |
C4—C5 | 1.377 (9) | ||
N5—Cu—O3i | 83.87 (16) | C7—C8—C9 | 116.8 (6) |
N5—Cu—N1 | 176.1 (2) | C7—C8—H8A | 121.6 |
O3i—Cu—N1 | 94.49 (17) | C9—C8—H8A | 121.6 |
N5—Cu—N6 | 83.40 (18) | C10—C9—C8 | 119.8 (7) |
O3i—Cu—N6 | 166.98 (16) | C10—C9—H9A | 120.1 |
N1—Cu—N6 | 98.38 (19) | C8—C9—H9A | 120.1 |
N5—Cu—N2 | 104.78 (18) | N2—C10—C9 | 124.7 (6) |
O3i—Cu—N2 | 92.89 (16) | N2—C10—H10A | 117.6 |
N1—Cu—N2 | 78.79 (18) | C9—C10—H10A | 117.6 |
N6—Cu—N2 | 87.74 (18) | N2—C11—C7 | 126.0 (6) |
N5—Cu—O7 | 84.49 (19) | N2—C11—C1 | 124.7 (5) |
O3i—Cu—O7 | 96.92 (18) | C7—C11—C1 | 109.2 (5) |
N1—Cu—O7 | 92.23 (19) | N3—C12—C16 | 125.2 (7) |
N6—Cu—O7 | 84.6 (2) | N3—C12—C22 | 126.2 (5) |
N2—Cu—O7 | 167.20 (16) | C16—C12—C22 | 108.7 (6) |
O7—Cl—O4 | 110.8 (4) | N3—C13—C14 | 124.4 (8) |
O7—Cl—O6 | 109.9 (4) | N3—C13—H13A | 117.8 |
O4—Cl—O6 | 110.6 (4) | C14—C13—H13A | 117.8 |
O7—Cl—O5 | 106.8 (4) | C13—C14—C15 | 119.7 (7) |
O4—Cl—O5 | 108.9 (4) | C13—C14—H14A | 120.2 |
O6—Cl—O5 | 109.8 (4) | C15—C14—H14A | 120.2 |
C25—O3—Cui | 109.3 (3) | C16—C15—C14 | 117.4 (6) |
Cl—O7—Cu | 128.4 (4) | C16—C15—H15A | 121.3 |
C1—N1—C2 | 115.1 (5) | C14—C15—H15A | 121.3 |
C1—N1—Cu | 114.5 (4) | C15—C16—C12 | 118.4 (7) |
C2—N1—Cu | 130.3 (5) | C15—C16—C17 | 133.1 (6) |
C11—N2—C10 | 113.9 (5) | C12—C16—C17 | 108.5 (6) |
C11—N2—Cu | 96.7 (4) | O2—C17—C16 | 127.1 (8) |
C10—N2—Cu | 149.3 (4) | O2—C17—C18 | 127.4 (9) |
C12—N3—C13 | 115.0 (6) | C16—C17—C18 | 105.5 (6) |
C22—N4—C21 | 115.7 (6) | C19—C18—C22 | 119.7 (7) |
C25—N5—C24 | 127.1 (5) | C19—C18—C17 | 131.9 (7) |
C25—N5—Cu | 116.0 (4) | C22—C18—C17 | 108.5 (7) |
C24—N5—Cu | 116.9 (3) | C18—C19—C20 | 116.1 (7) |
C23—N6—Cu | 107.4 (3) | C18—C19—H19A | 122.0 |
C23—N6—H6A | 110.2 | C20—C19—H19A | 122.0 |
Cu—N6—H6A | 110.2 | C21—C20—C19 | 120.7 (8) |
C23—N6—H6B | 110.2 | C21—C20—H20A | 119.6 |
Cu—N6—H6B | 110.2 | C19—C20—H20A | 119.6 |
H6A—N6—H6B | 108.5 | N4—C21—C20 | 123.6 (8) |
N1—C1—C5 | 126.0 (6) | N4—C21—H21A | 118.2 |
N1—C1—C11 | 124.6 (5) | C20—C21—H21A | 118.2 |
C5—C1—C11 | 109.3 (6) | N4—C22—C18 | 124.3 (7) |
N1—C2—C3 | 122.9 (7) | N4—C22—C12 | 126.9 (6) |
N1—C2—H2B | 118.6 | C18—C22—C12 | 108.9 (6) |
C3—C2—H2B | 118.6 | N6—C23—C24 | 110.0 (5) |
C4—C3—C2 | 120.6 (7) | N6—C23—H23A | 109.7 |
C4—C3—H3A | 119.7 | C24—C23—H23A | 109.7 |
C2—C3—H3A | 119.7 | N6—C23—H23B | 109.7 |
C5—C4—C3 | 116.9 (6) | C24—C23—H23B | 109.7 |
C5—C4—H4A | 121.6 | H23A—C23—H23B | 108.2 |
C3—C4—H4A | 121.6 | N5—C24—C23 | 106.4 (5) |
C4—C5—C1 | 118.5 (7) | N5—C24—H24A | 110.4 |
C4—C5—C6 | 134.1 (6) | C23—C24—H24A | 110.4 |
C1—C5—C6 | 107.4 (6) | N5—C24—H24B | 110.4 |
O1—C6—C5 | 127.6 (7) | C23—C24—H24B | 110.4 |
O1—C6—C7 | 125.5 (7) | H24A—C24—H24B | 108.6 |
C5—C6—C7 | 106.9 (5) | O3—C25—N5 | 129.4 (5) |
C8—C7—C11 | 118.6 (6) | O3—C25—C25i | 118.9 (6) |
C8—C7—C6 | 134.4 (6) | N5—C25—C25i | 111.8 (6) |
C11—C7—C6 | 107.0 (6) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6A···N4 | 0.90 | 2.31 | 3.195 (7) | 169 |
N6—H6B···O6 | 0.90 | 2.17 | 3.037 (8) | 163 |
C10—H10A···O1ii | 0.93 | 2.42 | 3.281 (9) | 155 |
Symmetry code: (ii) x, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2O |
Mr | 1226.89 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 26.5955 (1), 11.4267 (3), 16.5915 (4) |
β (°) | 92.053 (1) |
V (Å3) | 5038.90 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.03 |
Crystal size (mm) | 0.44 × 0.40 × 0.36 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.659, 0.708 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8436, 4441, 3294 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.198, 1.09 |
No. of reflections | 4441 |
No. of parameters | 355 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0804P)2 + 32.9042P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.82, −0.58 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97), SHELXL97.
Cu—N5 | 1.914 (4) | Cu—O7 | 2.885 (7) |
Cu—O3i | 2.002 (4) | Cl—O7 | 1.404 (6) |
Cu—N1 | 2.009 (5) | Cl—O4 | 1.414 (6) |
Cu—N6 | 2.017 (4) | Cl—O6 | 1.418 (6) |
Cu—N2 | 2.619 (5) | Cl—O5 | 1.427 (6) |
N5—Cu—O3i | 83.87 (16) | N1—Cu—N2 | 78.79 (18) |
N5—Cu—N1 | 176.1 (2) | N6—Cu—N2 | 87.74 (18) |
O3i—Cu—N1 | 94.49 (17) | N5—Cu—O7 | 84.49 (19) |
N5—Cu—N6 | 83.40 (18) | O3i—Cu—O7 | 96.92 (18) |
O3i—Cu—N6 | 166.98 (16) | N1—Cu—O7 | 92.23 (19) |
N1—Cu—N6 | 98.38 (19) | N6—Cu—O7 | 84.6 (2) |
N5—Cu—N2 | 104.78 (18) | N2—Cu—O7 | 167.20 (16) |
O3i—Cu—N2 | 92.89 (16) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6A···N4 | 0.90 | 2.31 | 3.195 (7) | 169 |
N6—H6B···O6 | 0.90 | 2.17 | 3.037 (8) | 163 |
C10—H10A···O1ii | 0.93 | 2.42 | 3.281 (9) | 155 |
Symmetry code: (ii) x, −y, z−1/2. |
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Bridging oxamidates have played a key role in the design of polynuclear systems, owing to their ability to facilitate strong exchange interactions (Ojima & Nonoyama, 1988). One of the most important properties of these ligands is the very easy cis-trans conformational change affording symmetric and asymmetric oxamidato bridges. N,N'-Disubstituted oxamidates are multifunctional ligands. Coordination complexes of copper(II) with oxamidate are known to act as paramagnetic ligands towards other metal ions (Mathoniere et al., 1993). The crystal structures and magnetic properties of many polynuclear complexes have been previously reported, in which the bridging ligand is the oxamidate group (e.g. Lloret et al., 1992; Zhang et al., 1999). As part of our work in this area, we have designed and synthesized the title novel binuclear complex [Cu2(oxen)(L)2(ClO4)2]·2L, (I) [oxen is N,N'-ethylenediamide-bis(2-aminoethyl) and L is 1,10-N,N-fluorenone], for which we have undertaken the crystal structure determination. \sch
Details of the molecular geometry of (I) are given in Table 1 and the complex is shown in Fig. 1. The structure consists of a [Cu2(oxen)L2(ClO4)2] complex and two free L molecules. The oxen group adopts the trans configuration and acts as a bis-tridentate ligand to connect the two CuII atoms, to form a dinuclear complex with a distance between two Cu atoms of 5.215 (2) Å without direct interactions, slightly shorter than that in [Cu2(oxen)(4-APy)2(ClO4)2] (5.24 Å; Zhang et al., 1999). The two CuII atoms have the same coordination environment, namely a distorted octahedron, the meridional plane of which is composed of atom N1 of L and atoms N5, N6 and O3A of the oxen group. One of the apical positions is occupied by an O atom of the perchlorate group and the other site is weakly linked to atom N2 of L, with typical Jahn-Teller elongated distances comparable with the values reported in [Cu2(oxen)(4-APy)2(ClO4)2].
The angle between the L plane (atoms C1—C11/N1/N2/O1) and the plane of atoms Cu/N5/C25/O3/CuA/N5A/C25A/O3A is 91.20 (7)° [symmetry code: (A) 1 − x, y, 1/2 − z], which shows they are approximately perpendicular. The main structural features of the [Cu2(oxen)L2(ClO4)2] component are similar to the reported complexes [Cu2(oxen)(4-APy)2(ClO4)2] (4-APy = 4-aminopyridine) and [Cu2(oxen)(DAPM)2(Br)2] (DAPM = 4,4'-diaminodiphenylmethane) (Zhang et al., 1999), in that they all contain the oxen group. Their second ligands, however, are different. In [Cu2(oxen)(4-APy)2(ClO4)2] and [Cu2(oxen)(DAPM)2(Br)2], the second ligands are 4-APy and DAPM, respectively, and these are both monodentate, which results in the CuII atoms exhibiting square-pyramidal geometries. Although it may be thought that the CuII atoms in [Cu2(oxen)(4-APy)2(ClO4)2] are in a distorted octahedral environment, the sixth coordinated atom is very weakly linked to the CuII atom [Cu—N4b 3.077 Å; symmetry code: (b) ? Please provide missing symmetry code]. By contrast, in (I), the second ligand is 1,10-N,N-fluorenone and this is bidentate, with the result that the CuII atoms exhibit a Jahn-Teller-distorted octahedral geometry.
Details of the hydrogen-bonding in (I) are listed in Table 2. As illustrated in Fig. 2, the packing has a network of hydrogen bonds. These are mainly formed between atoms O1 and N6 of the [Cu2(oxen)L2(ClO4)2] component, atoms N4 of the free ligands, and atoms O6 of the ClO4− anion.
The π–π stacking interactions in the structure of (I) are also shown in Fig. 2. The [Cu2(oxen)L2(ClO4)2] components are interleaved regularly to form a chain along the c axis via π–π stacking interactions and intermolecular C—H···O hydrogen bonds. Planes 1 and 3 of L are stacked in a parallel fashion, the distance between the two planes being 3.2816 (8) Å. The free ligands insert into the interstices between the [Cu2(oxen)L2(ClO4)2] components along the a axis via π–π stacking interactions and N—H···N hydrogen bonds. The L planes 2 and 4 are also in a parallel arrangement, the distance between the two planes being 3.3040 (8) Å. The L plane 1 in [Cu2(oxen)L2(ClO4)2] and the free ligand L plane 2 are deviate somewhat from being parallel, the angle between them being 12.40 (5)°. The shortest interatomic distance between these planes is 3.3648 (8) Å, while the distance between the centres of the two planes is 3.7720 (8) Å. All these distances, between L planes 1 and 2, L planes 1 and 3 and L planes 2 and 4, are shorter than the distance between neighbouring base pairs in DNA (3.4 Å; Neidle, 1999). Therefore, stacking interactions dominate throughout the crystal structure, stabilizing the crystal packing together with the hydrogen-bonding interactions.