Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106022761/sf3008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106022761/sf3008Isup2.hkl |
CCDC reference: 292357
For the preparation of the title compound, triethylamine (0.1 mmol) was added to a solution of 5-bromosalicylaldimine (0.0220 g, 0.1 mmol) in methanol (10 ml). After stirring the mixture for 10 min, 1,10-phenanthroline (0.0198 g, 0.1 mmol) was added. To the resulting solution, a methanolic solution (5 ml) of Cu(ClO4)2·6H2O (0.0370 g, 0.1 mmol) was added with stirring at room temperature. The solution was then heated and stirred for 2 h. After about 10 d, green block crystals of (I) suitable for X-ray analysis appeared. These were collected by filtration, washed with H2O and dried over silica gel (yield 58%). Analysis, calculated for C19H12BrClCuN2O6: C 42.01, H 2.23, N 5.16%; found: C 42.96, H 2.16, N 5.82%.
H atoms were included in calculated positions and refined as riding on their parent atoms, with C—H distances in the range 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C,N). The perchlorate ion is disordered. The occupancies of atoms O3, O4, O5 and O6 are 0.42 (1) and those of atoms O3', O4', O5' and O6' are 0.58 (1).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; 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 (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Cu(C7H4BrO2)(ClO4)(C12H8N2)] | Z = 2 |
Mr = 543.21 | F(000) = 538 |
Triclinic, P1 | Dx = 1.861 Mg m−3 |
a = 7.7560 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.336 (2) Å | Cell parameters from 1965 reflections |
c = 12.873 (3) Å | θ = 2.7–26.1° |
α = 83.802 (3)° | µ = 3.37 mm−1 |
β = 75.795 (3)° | T = 294 K |
γ = 76.010 (3)° | Block, green |
V = 969.5 (3) Å3 | 0.22 × 0.18 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 3353 independent reflections |
Radiation source: fine-focus sealed tube | 2427 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.763, Tmax = missing | k = −10→12 |
4860 measured reflections | l = −15→13 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0786P)2 + 0.9337P] where P = (Fo2 + 2Fc2)/3 |
3353 reflections | (Δ/σ)max = 0.002 |
308 parameters | Δρmax = 1.31 e Å−3 |
68 restraints | Δρmin = −0.53 e Å−3 |
[Cu(C7H4BrO2)(ClO4)(C12H8N2)] | γ = 76.010 (3)° |
Mr = 543.21 | V = 969.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.7560 (15) Å | Mo Kα radiation |
b = 10.336 (2) Å | µ = 3.37 mm−1 |
c = 12.873 (3) Å | T = 294 K |
α = 83.802 (3)° | 0.22 × 0.18 × 0.12 mm |
β = 75.795 (3)° |
Bruker SMART CCD area-detector diffractometer | 3353 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2427 reflections with I > 2σ(I) |
Tmin = 0.763, Tmax = missing | Rint = 0.019 |
4860 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 68 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.31 e Å−3 |
3353 reflections | Δρmin = −0.53 e Å−3 |
308 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 | Occ. (<1) | |
Cu1 | 0.06431 (9) | 0.56851 (6) | 0.60366 (5) | 0.0394 (2) | |
Br1 | 0.32031 (11) | 0.97317 (8) | 0.11163 (6) | 0.0758 (3) | |
O1 | 0.1859 (5) | 0.5492 (4) | 0.4571 (3) | 0.0478 (10) | |
O2 | −0.0713 (5) | 0.7494 (4) | 0.5756 (3) | 0.0442 (9) | |
N1 | −0.0730 (6) | 0.5590 (5) | 0.7572 (4) | 0.0424 (11) | |
N2 | 0.1948 (6) | 0.3846 (4) | 0.6423 (4) | 0.0429 (11) | |
C1 | 0.2141 (7) | 0.6467 (5) | 0.3877 (4) | 0.0386 (12) | |
C2 | 0.3525 (8) | 0.6171 (6) | 0.2927 (4) | 0.0450 (13) | |
H2 | 0.4248 | 0.5312 | 0.2842 | 0.054* | |
C3 | 0.3792 (8) | 0.7136 (7) | 0.2146 (5) | 0.0511 (15) | |
H3 | 0.4690 | 0.6928 | 0.1523 | 0.061* | |
C4 | 0.2741 (7) | 0.8440 (6) | 0.2257 (4) | 0.0447 (13) | |
C5 | 0.1413 (7) | 0.8787 (6) | 0.3155 (5) | 0.0436 (13) | |
H5 | 0.0714 | 0.9655 | 0.3220 | 0.052* | |
C6 | 0.1118 (7) | 0.7790 (5) | 0.3994 (4) | 0.0377 (12) | |
C7 | −0.0300 (7) | 0.8188 (5) | 0.4924 (4) | 0.0413 (12) | |
H7 | −0.0984 | 0.9060 | 0.4901 | 0.050* | |
C8 | −0.2066 (8) | 0.6495 (7) | 0.8089 (5) | 0.0553 (16) | |
H8 | −0.2447 | 0.7312 | 0.7740 | 0.066* | |
C9 | −0.2931 (10) | 0.6248 (9) | 0.9161 (6) | 0.076 (2) | |
H9 | −0.3882 | 0.6896 | 0.9518 | 0.092* | |
C10 | −0.2368 (11) | 0.5050 (9) | 0.9677 (6) | 0.077 (2) | |
H10 | −0.2915 | 0.4888 | 1.0392 | 0.092* | |
C11 | −0.0949 (9) | 0.4054 (7) | 0.9121 (5) | 0.0588 (17) | |
C12 | −0.0322 (12) | 0.2743 (9) | 0.9572 (6) | 0.074 (2) | |
H12 | −0.0854 | 0.2507 | 1.0274 | 0.089* | |
C13 | 0.1036 (12) | 0.1848 (8) | 0.8982 (6) | 0.073 (2) | |
H13 | 0.1436 | 0.1007 | 0.9290 | 0.088* | |
C14 | 0.1868 (9) | 0.2167 (6) | 0.7895 (5) | 0.0539 (16) | |
C15 | 0.3255 (10) | 0.1294 (6) | 0.7209 (6) | 0.0642 (19) | |
H15 | 0.3692 | 0.0427 | 0.7459 | 0.077* | |
C16 | 0.3960 (9) | 0.1704 (6) | 0.6187 (6) | 0.0607 (18) | |
H16 | 0.4884 | 0.1124 | 0.5742 | 0.073* | |
C17 | 0.3288 (8) | 0.3005 (6) | 0.5809 (5) | 0.0514 (15) | |
H17 | 0.3789 | 0.3287 | 0.5114 | 0.062* | |
C18 | 0.1271 (8) | 0.3438 (6) | 0.7450 (5) | 0.0451 (13) | |
C19 | −0.0167 (8) | 0.4388 (6) | 0.8065 (4) | 0.0465 (14) | |
Cl1 | 0.2990 (2) | 0.76688 (18) | 0.70234 (16) | 0.0691 (5) | |
O3 | 0.2947 (19) | 0.6829 (12) | 0.6188 (9) | 0.070 (4) | 0.423 (12) |
O4 | 0.1408 (15) | 0.8575 (13) | 0.7357 (12) | 0.102 (6) | 0.423 (12) |
O5 | 0.4650 (14) | 0.8130 (14) | 0.6673 (11) | 0.084 (5) | 0.423 (12) |
O6 | 0.331 (2) | 0.6660 (14) | 0.7934 (9) | 0.149 (8) | 0.423 (12) |
O3' | 0.3012 (15) | 0.6437 (7) | 0.6652 (10) | 0.083 (4) | 0.577 (12) |
O4' | 0.1370 (14) | 0.8166 (12) | 0.7807 (8) | 0.119 (5) | 0.577 (12) |
O5' | 0.4588 (14) | 0.7759 (12) | 0.7275 (12) | 0.127 (5) | 0.577 (12) |
O6' | 0.2738 (15) | 0.8692 (8) | 0.6082 (7) | 0.106 (4) | 0.577 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0431 (4) | 0.0416 (4) | 0.0301 (4) | −0.0109 (3) | −0.0030 (3) | 0.0035 (3) |
Br1 | 0.0839 (5) | 0.0861 (6) | 0.0548 (5) | −0.0333 (4) | −0.0124 (4) | 0.0327 (4) |
O1 | 0.059 (2) | 0.040 (2) | 0.036 (2) | −0.0109 (18) | 0.0016 (18) | 0.0006 (16) |
O2 | 0.045 (2) | 0.046 (2) | 0.036 (2) | −0.0079 (18) | −0.0018 (17) | −0.0023 (17) |
N1 | 0.042 (3) | 0.053 (3) | 0.033 (2) | −0.015 (2) | −0.006 (2) | 0.000 (2) |
N2 | 0.041 (3) | 0.043 (3) | 0.047 (3) | −0.013 (2) | −0.012 (2) | 0.001 (2) |
C1 | 0.041 (3) | 0.043 (3) | 0.034 (3) | −0.015 (2) | −0.009 (2) | 0.002 (2) |
C2 | 0.044 (3) | 0.052 (3) | 0.039 (3) | −0.012 (3) | −0.006 (2) | −0.005 (2) |
C3 | 0.052 (3) | 0.074 (4) | 0.030 (3) | −0.029 (3) | −0.001 (3) | 0.001 (3) |
C4 | 0.044 (3) | 0.060 (4) | 0.033 (3) | −0.021 (3) | −0.010 (3) | 0.010 (2) |
C5 | 0.043 (3) | 0.046 (3) | 0.045 (3) | −0.017 (3) | −0.014 (3) | 0.008 (2) |
C6 | 0.039 (3) | 0.052 (3) | 0.025 (3) | −0.019 (2) | −0.007 (2) | 0.004 (2) |
C7 | 0.042 (3) | 0.037 (3) | 0.042 (3) | −0.003 (2) | −0.010 (2) | −0.002 (2) |
C8 | 0.050 (4) | 0.077 (4) | 0.038 (3) | −0.020 (3) | −0.005 (3) | −0.001 (3) |
C9 | 0.060 (4) | 0.113 (7) | 0.050 (4) | −0.021 (4) | 0.005 (3) | −0.013 (4) |
C10 | 0.079 (5) | 0.121 (7) | 0.034 (4) | −0.042 (5) | −0.006 (4) | 0.001 (4) |
C11 | 0.073 (4) | 0.080 (5) | 0.037 (3) | −0.040 (4) | −0.020 (3) | 0.008 (3) |
C12 | 0.097 (6) | 0.098 (6) | 0.046 (4) | −0.052 (5) | −0.035 (4) | 0.027 (4) |
C13 | 0.110 (6) | 0.067 (5) | 0.068 (5) | −0.046 (5) | −0.058 (5) | 0.037 (4) |
C14 | 0.068 (4) | 0.048 (3) | 0.062 (4) | −0.024 (3) | −0.036 (3) | 0.007 (3) |
C15 | 0.082 (5) | 0.046 (4) | 0.085 (5) | −0.020 (4) | −0.057 (4) | 0.009 (3) |
C16 | 0.063 (4) | 0.045 (3) | 0.080 (5) | 0.000 (3) | −0.034 (4) | −0.012 (3) |
C17 | 0.048 (3) | 0.048 (3) | 0.061 (4) | −0.010 (3) | −0.017 (3) | −0.004 (3) |
C18 | 0.052 (3) | 0.051 (3) | 0.043 (3) | −0.027 (3) | −0.022 (3) | 0.009 (3) |
C19 | 0.049 (3) | 0.064 (4) | 0.036 (3) | −0.030 (3) | −0.017 (3) | 0.008 (3) |
Cl1 | 0.0562 (10) | 0.0699 (11) | 0.0835 (13) | −0.0170 (8) | −0.0099 (9) | −0.0219 (9) |
O3 | 0.066 (7) | 0.088 (8) | 0.066 (7) | −0.028 (6) | −0.022 (6) | −0.006 (6) |
O4 | 0.093 (9) | 0.088 (9) | 0.110 (10) | 0.008 (7) | −0.022 (7) | −0.002 (8) |
O5 | 0.080 (8) | 0.095 (8) | 0.088 (8) | −0.037 (6) | −0.017 (6) | −0.017 (7) |
O6 | 0.155 (11) | 0.148 (11) | 0.109 (10) | 0.006 (8) | −0.016 (8) | 0.023 (8) |
O3' | 0.072 (6) | 0.055 (5) | 0.134 (9) | −0.007 (4) | −0.054 (6) | −0.005 (5) |
O4' | 0.130 (8) | 0.102 (8) | 0.090 (8) | 0.004 (6) | 0.009 (6) | 0.006 (6) |
O5' | 0.112 (8) | 0.127 (9) | 0.173 (10) | −0.027 (6) | −0.092 (7) | −0.002 (7) |
O6' | 0.133 (8) | 0.088 (6) | 0.092 (7) | −0.029 (6) | −0.017 (6) | 0.008 (5) |
Cu1—O1 | 1.898 (4) | C9—H9 | 0.9300 |
Cu1—O2 | 1.955 (4) | C10—C11 | 1.417 (10) |
Cu1—N2 | 1.999 (4) | C10—H10 | 0.9300 |
Cu1—N1 | 2.007 (4) | C11—C19 | 1.388 (8) |
Cu1—O3 | 2.423 (11) | C11—C12 | 1.435 (10) |
Br1—C4 | 1.902 (5) | C12—C13 | 1.353 (11) |
O1—C1 | 1.295 (6) | C12—H12 | 0.9300 |
O2—C7 | 1.242 (6) | C13—C14 | 1.430 (10) |
N1—C8 | 1.311 (7) | C13—H13 | 0.9300 |
N1—C19 | 1.357 (7) | C14—C18 | 1.393 (8) |
N2—C17 | 1.329 (7) | C14—C15 | 1.410 (10) |
N2—C18 | 1.360 (7) | C15—C16 | 1.359 (10) |
C1—C6 | 1.408 (7) | C15—H15 | 0.9300 |
C1—C2 | 1.421 (8) | C16—C17 | 1.401 (9) |
C2—C3 | 1.353 (8) | C16—H16 | 0.9300 |
C2—H2 | 0.9300 | C17—H17 | 0.9300 |
C3—C4 | 1.398 (8) | C18—C19 | 1.428 (8) |
C3—H3 | 0.9300 | Cl1—O4 | 1.357 (7) |
C4—C5 | 1.361 (8) | Cl1—O5' | 1.382 (7) |
C5—C6 | 1.427 (7) | Cl1—O3' | 1.403 (6) |
C5—H5 | 0.9300 | Cl1—O4' | 1.427 (7) |
C6—C7 | 1.433 (7) | Cl1—O5 | 1.433 (8) |
C7—H7 | 0.9300 | Cl1—O3 | 1.464 (7) |
C8—C9 | 1.405 (9) | Cl1—O6 | 1.509 (8) |
C8—H8 | 0.9300 | Cl1—O6' | 1.538 (7) |
C9—C10 | 1.367 (11) | ||
O1—Cu1—O2 | 92.72 (16) | C13—C12—H12 | 119.8 |
O1—Cu1—N2 | 90.96 (18) | C11—C12—H12 | 119.8 |
O2—Cu1—N2 | 176.33 (17) | C12—C13—C14 | 121.4 (6) |
O1—Cu1—N1 | 170.43 (17) | C18—C14—C15 | 115.9 (6) |
O2—Cu1—N1 | 93.61 (17) | C18—C14—C13 | 118.6 (7) |
N2—Cu1—N1 | 82.74 (19) | C15—C14—C13 | 125.6 (6) |
O1—Cu1—O3 | 87.0 (3) | C16—C15—C14 | 120.7 (6) |
O2—Cu1—O3 | 83.3 (4) | C16—C15—H15 | 119.6 |
N2—Cu1—O3 | 96.9 (4) | C14—C15—H15 | 119.6 |
N1—Cu1—O3 | 100.8 (3) | C15—C16—C17 | 119.6 (6) |
C1—O1—Cu1 | 125.2 (3) | C15—C16—H16 | 120.2 |
C7—O2—Cu1 | 124.0 (3) | C17—C16—H16 | 120.2 |
C8—N1—C19 | 120.3 (5) | N2—C17—C16 | 121.4 (6) |
C8—N1—Cu1 | 128.2 (4) | N2—C17—H17 | 119.3 |
C19—N1—Cu1 | 111.4 (4) | C16—C17—H17 | 119.3 |
C17—N2—C18 | 118.7 (5) | C12—C13—H13 | 119.3 |
C17—N2—Cu1 | 128.8 (4) | C14—C13—H13 | 119.3 |
C18—N2—Cu1 | 112.4 (4) | N2—C18—C14 | 123.7 (6) |
O1—C1—C6 | 123.8 (5) | N2—C18—C19 | 115.9 (5) |
O1—C1—C2 | 117.9 (5) | C14—C18—C19 | 120.4 (6) |
C6—C1—C2 | 118.3 (5) | N1—C19—C11 | 122.7 (6) |
C3—C2—C1 | 120.2 (6) | N1—C19—C18 | 117.5 (5) |
C3—C2—H2 | 119.9 | C11—C19—C18 | 119.9 (6) |
C1—C2—H2 | 119.9 | O4—Cl1—O5' | 121.2 (10) |
C2—C3—C4 | 121.2 (5) | O4—Cl1—O3' | 121.7 (9) |
C2—C3—H3 | 119.4 | O5'—Cl1—O3' | 115.3 (6) |
C4—C3—H3 | 119.4 | O4—Cl1—O4' | 28.0 (7) |
C2—C3—C4 | 121.2 (5) | O5'—Cl1—O4' | 114.6 (7) |
C5—C4—C3 | 121.3 (5) | O3'—Cl1—O4' | 113.0 (6) |
C5—C4—Br1 | 120.3 (4) | O4—Cl1—O5 | 118.5 (7) |
C3—C4—Br1 | 118.4 (4) | O5'—Cl1—O5 | 33.9 (7) |
C4—C5—C6 | 118.5 (5) | O3'—Cl1—O5 | 116.0 (8) |
C4—C5—H5 | 120.7 | O4'—Cl1—O5 | 130.5 (8) |
C6—C5—H5 | 120.7 | O4—Cl1—O3 | 114.2 (7) |
C1—C6—C5 | 120.5 (5) | O5'—Cl1—O3 | 123.0 (9) |
C1—C6—C7 | 122.5 (5) | O3'—Cl1—O3 | 27.7 (6) |
C5—C6—C7 | 117.0 (5) | O4'—Cl1—O3 | 120.5 (9) |
O2—C7—C6 | 126.9 (5) | O5—Cl1—O3 | 106.5 (6) |
O2—C7—H7 | 116.5 | O4—Cl1—O6 | 109.1 (7) |
C6—C7—H7 | 116.5 | O5'—Cl1—O6 | 72.2 (8) |
N1—C8—C9 | 121.0 (7) | O3'—Cl1—O6 | 74.7 (7) |
N1—C8—H8 | 119.5 | O4'—Cl1—O6 | 81.1 (7) |
C9—C8—H8 | 119.5 | O5—Cl1—O6 | 104.6 (7) |
C10—C9—C8 | 119.6 (7) | O3—Cl1—O6 | 102.3 (6) |
C10—C9—H9 | 120.2 | O4—Cl1—O6' | 72.6 (7) |
C8—C9—H9 | 120.2 | O5'—Cl1—O6' | 105.9 (6) |
C9—C10—C11 | 119.9 (7) | O3'—Cl1—O6' | 105.5 (5) |
C9—C10—H10 | 120.0 | O4'—Cl1—O6' | 100.6 (5) |
C11—C10—H10 | 120.0 | O5—Cl1—O6' | 73.4 (7) |
C19—C11—C10 | 116.5 (6) | O3—Cl1—O6' | 77.8 (6) |
C19—C11—C12 | 119.3 (7) | O6—Cl1—O6' | 177.9 (7) |
C10—C11—C12 | 124.2 (7) | Cl1—O3—Cu1 | 130.6 (8) |
C13—C12—C11 | 120.4 (7) | ||
O2—Cu1—O1—C1 | 24.6 (4) | C8—C9—C10—C11 | −1.6 (11) |
N2—Cu1—O1—C1 | −155.4 (4) | C9—C10—C11—C19 | 1.8 (10) |
N1—Cu1—O1—C1 | 156.0 (9) | C9—C10—C11—C12 | −176.7 (7) |
O3—Cu1—O1—C1 | −58.5 (5) | C19—C11—C12—C13 | 1.1 (10) |
O1—Cu1—O2—C7 | −16.6 (4) | C10—C11—C12—C13 | 179.6 (7) |
N2—Cu1—O2—C7 | 164 (2) | C11—C12—C13—C14 | −0.9 (10) |
N1—Cu1—O2—C7 | 170.6 (4) | C12—C13—C14—C18 | 0.9 (9) |
O3—Cu1—O2—C7 | 70.1 (5) | C12—C13—C14—C15 | −178.3 (6) |
O1—Cu1—N1—C8 | −130.0 (10) | C18—C14—C15—C16 | 1.1 (8) |
O2—Cu1—N1—C8 | 1.3 (5) | C13—C14—C15—C16 | −179.6 (6) |
N2—Cu1—N1—C8 | −179.1 (5) | C14—C15—C16—C17 | −0.6 (9) |
O3—Cu1—N1—C8 | 85.2 (6) | C18—N2—C17—C16 | 2.3 (8) |
O1—Cu1—N1—C19 | 47.2 (12) | Cu1—N2—C17—C16 | −175.0 (4) |
O2—Cu1—N1—C19 | 178.5 (4) | C15—C16—C17—N2 | −1.1 (9) |
N2—Cu1—N1—C19 | −1.9 (3) | C17—N2—C18—C14 | −1.8 (8) |
O3—Cu1—N1—C19 | −97.6 (5) | Cu1—N2—C18—C14 | 176.0 (4) |
O1—Cu1—N2—C17 | 6.9 (5) | C17—N2—C18—C19 | −179.9 (5) |
O2—Cu1—N2—C17 | −174 (2) | Cu1—N2—C18—C19 | −2.2 (6) |
N1—Cu1—N2—C17 | 179.7 (5) | C15—C14—C18—N2 | 0.1 (8) |
O3—Cu1—N2—C17 | −80.2 (5) | C13—C14—C18—N2 | −179.2 (5) |
O1—Cu1—N2—C18 | −170.5 (4) | C15—C14—C18—C19 | 178.1 (5) |
O2—Cu1—N2—C18 | 9 (3) | C13—C14—C18—C19 | −1.2 (8) |
N1—Cu1—N2—C18 | 2.2 (3) | C8—N1—C19—C11 | −0.2 (8) |
O3—Cu1—N2—C18 | 102.3 (4) | Cu1—N1—C19—C11 | −177.7 (4) |
Cu1—O1—C1—C6 | −21.3 (7) | C8—N1—C19—C18 | 178.8 (5) |
Cu1—O1—C1—C2 | 160.8 (4) | Cu1—N1—C19—C18 | 1.3 (6) |
O1—C1—C2—C3 | 175.7 (5) | C10—C11—C19—N1 | −1.0 (8) |
C6—C1—C2—C3 | −2.3 (8) | C12—C11—C19—N1 | 177.7 (5) |
C1—C2—C3—C4 | 0.8 (8) | C10—C11—C19—C18 | −179.9 (5) |
C2—C3—C4—C5 | 0.0 (9) | C12—C11—C19—C18 | −1.3 (8) |
C2—C3—C4—Br1 | −179.8 (4) | N2—C18—C19—N1 | 0.6 (7) |
C3—C4—C5—C6 | 0.5 (8) | C14—C18—C19—N1 | −177.6 (5) |
Br1—C4—C5—C6 | −179.6 (4) | N2—C18—C19—C11 | 179.6 (5) |
O1—C1—C6—C5 | −174.9 (5) | C14—C18—C19—C11 | 1.4 (8) |
C2—C1—C6—C5 | 2.9 (7) | O4—Cl1—O3—Cu1 | −44.7 (14) |
O1—C1—C6—C7 | 2.4 (8) | O5'—Cl1—O3—Cu1 | 149.7 (9) |
C2—C1—C6—C7 | −179.8 (5) | O3'—Cl1—O3—Cu1 | 67.9 (17) |
C4—C5—C6—C1 | −2.1 (8) | O4'—Cl1—O3—Cu1 | −13.8 (14) |
C4—C5—C6—C7 | −179.5 (5) | O5—Cl1—O3—Cu1 | −177.4 (10) |
Cu1—O2—C7—C6 | 5.0 (8) | O6—Cl1—O3—Cu1 | 73.1 (12) |
C1—C6—C7—O2 | 6.2 (9) | O6'—Cl1—O3—Cu1 | −109.1 (11) |
C5—C6—C7—O2 | −176.4 (5) | O1—Cu1—O3—Cl1 | 164.7 (10) |
C19—N1—C8—C9 | 0.6 (9) | O2—Cu1—O3—Cl1 | 71.6 (10) |
Cu1—N1—C8—C9 | 177.6 (5) | N2—Cu1—O3—Cl1 | −104.7 (10) |
N1—C8—C9—C10 | 0.3 (11) | N1—Cu1—O3—Cl1 | −20.8 (11) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H4BrO2)(ClO4)(C12H8N2)] |
Mr | 543.21 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 7.7560 (15), 10.336 (2), 12.873 (3) |
α, β, γ (°) | 83.802 (3), 75.795 (3), 76.010 (3) |
V (Å3) | 969.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.37 |
Crystal size (mm) | 0.22 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.763, missing |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4860, 3353, 2427 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.138, 1.02 |
No. of reflections | 3353 |
No. of parameters | 308 |
No. of restraints | 68 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.31, −0.53 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
Cu1—O1 | 1.898 (4) | Cu1—N1 | 2.007 (4) |
Cu1—O2 | 1.955 (4) | Cu1—O3 | 2.423 (11) |
Cu1—N2 | 1.999 (4) | ||
O1—Cu1—O2 | 92.72 (16) | N2—Cu1—O3 | 96.9 (4) |
O1—Cu1—N2 | 90.96 (18) | N1—Cu1—O3 | 100.8 (3) |
O2—Cu1—N2 | 176.33 (17) | C1—O1—Cu1 | 125.2 (3) |
O1—Cu1—N1 | 170.43 (17) | C7—O2—Cu1 | 124.0 (3) |
O2—Cu1—N1 | 93.61 (17) | C8—N1—Cu1 | 128.2 (4) |
N2—Cu1—N1 | 82.74 (19) | C19—N1—Cu1 | 111.4 (4) |
O1—Cu1—O3 | 87.0 (3) | C17—N2—Cu1 | 128.8 (4) |
O2—Cu1—O3 | 83.3 (4) | C18—N2—Cu1 | 112.4 (4) |
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Studies of complexes containing salicylaldehyde and its derivatives have been reported by Janzen et al. (2004) and other groups. The five-coordinated CuII complexes have been extensively investigated and the relationship between their structures and reactivities is of major importance. In the light of conflicting opinions on how best to estimate the geometry of five-coordinated CuII complexes, Addison et al. (1984) introduced a very useful parameter, τ, which provides a measure of the degree of SP (square-pyramidal) versus TBP (trigonal–bipyramidal) geometry adopted by five-coordinate CuII complexes.
We report here the synthesis and structure of the title complex, (I). This is the first reported crystal structure of a complex involving Cu2+, 1,10-phenanthroline, 4-bromo-2-formylphenolate and ClO4−. Elemental analysis data for this compound are in good agreement with the experimental crystal pattern. The larger of the basal angles, O2—Cu1—N2, is 176.33 (17)° and the remaining angle, O1—Cu1—N1, is 170.43 (17)°. According to Addison's rule, we calculated the parameter τ to be 0.098. Thus, we can conclude that the complex in this paper will show a square-pyramidal coordination geometry.
In complex (I), the CuII ion is coordinated by phenolate atom O1, carbonyl atom O2, 1,10-phenanthroline atoms N1 and N2, and atom O3 of the ClO4− anion. Atom O3 lies in the axial position, and the equatorial positions are occupied by the other four donor atoms. The bond distances for Cu1—N1 and Cu1—N2 of 2.007 (4) and 1.999 (4) Å, respectively, are nearly as long as those found for the similar auxiliary ligand 1,10-phenanthroline (Youngme et al. 2005). The bond lengths for Cu1—O1 and Cu1—O2 are 1.898 (4) and 1.995 (4) Å, respectively, which are in the range of those reported for similar copper(II) complexes [1.953 (2) and 1.952 (2) Å; Yang et al., 2004]. The Cu1—O3 bond distance of 2.423 (11) Å is in the range observed in analogous compounds [2.381 (4) and 2.559 (4) Å; Plieger et al., 2004]. The larger angles around Cu are near 180° (see above), so the ligands form a satisfactory N2O2 square, with atom O3 inhabiting the axial position. In this way, a distorted square pyramid is formed (Fig. 1).
It is interesting that there are weak Cu···O interactions, π–π stacking interactions and intermolecular hydrogen bonds in this complex. There are no intramolecular hydrogen bonds in the structure of (I). The CH groups participate in a hydrogen bond with an O atom of the ClO4− anion, forming a C—H···O hydrogen bond, with the C—H···O angle being 161.6°. The Br atom and an H atom of the 1,10-phenanthroline ligand form a weaker hydrogen bond, with the C—H···Br angle being 135.8°. Adjacent dimers are then linked by face-to-face π–π stacking interactions between 4-bromo-2-formylphenolate and 1,10-phenanthroline ligands, the shortest centroid–centriod contact being 3.628 Å, which is in the range of average values in π–π stacking interactions (Janiak, 2000). In addition, the Cu···O(phenolate) distance in (I) is 2.820 Å, which is in the range of values in the previous literature [Lower limit?–3.076 (4) Å; Yang et al., 2004]. Dimers based on above-mentioned Cu···O weak interaction and π–π stacking interaction are linked along the crystallographic a axis by hydrogen bonding (Fig. 2).
The solid-state IR spectrum of (I) in the region 450–4000 cm−1 is in agreement with the X-ray diffraction data with respect to the mode of coordination. The absorption bands in the spectrum of (I) were red-shifted by 10–20 cm−1 relative to the bands in the spectrum of the free ligand. The two shortest absorption bands in the UV–vis spectrum of the free ligand, at about 230 nm, characterized by high molecular absorption coeffcients, can be attributed to the π–π* transition of the ligands. The longest wavelength band, at about 650 nm, can be characterized by a d–d transition of the metal ion. This case is very similar to those observed for the structurally well characterized square-bipyramidal geometry (Lever, 1984).