Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109009731/sk3299sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109009731/sk3299Isup2.hkl |
CCDC reference: 735113
For related literature, see: Andrezálová et al. (1998); Hill & Warda (1999); Kohútová et al. (2000); Langer et al. (2003); Langer, Gyepesová, Scholtzová, Mach, Kohútová, Valent & Smrčok (2004); Langer, Scholtzová, Gyepesová, Kohútová & Valent (2004); Nakao et al. (1967); Sivý et al. (1994); Valent et al. (2004); Warda (1998).
The title complex, (I), was synthesized by the reaction of (diaqua N-salicylidene-L-glutamato)copper(II) monohydrate, prepared according to Nakao et al. (1967), and isoquinoline in the molar ratio 1:1 with 10% of excess of isoquinoline (molecular ligand) in ethanol at ambient temperature. The precipitated green coloured product was isolated, washed with ethanol and dried in air. The synthesis of the title compound resulted in a racemic mixture of Cu(N-salicylidene-rac-glutamato)(isoquinoline)diethanolate even though an optically active parent complex [Cu(N-salicylidene-L-glutamato)(H2O)2] was used in the reaction with isoquinoline. The racemization of the Schiff base ligand readily occurs under mild conditions even in neutral or weak acidic aqueous or alcoholic solutions (Sivý et al., 1994).
H atoms were refined isotropically and their positions were constrained to an ideal geometry using an appropriate riding model, with C—H distances of 0.95–1.00 Å. For the methyl group, the O—C—H angles (109.5°) were kept fixed, while the torsion angle was allowed to refine with the starting positions based on the circular Fourier synthesis averaged using the local threefold axis. For the hydroxy groups, the O—H distances (0.84 Å) and C—O—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting positions based on the circular Fourier synthesis. The ethanol molecule is slightly disordered (the maximum residual density peak is in this region).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu2(C12H11NO5)2(C9H7N)2]·2C2H6O | Z = 1 |
Mr = 975.98 | F(000) = 506 |
Triclinic, P1 | Dx = 1.506 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4211 (16) Å | Cell parameters from 1943 reflections |
b = 10.949 (3) Å | θ = 2.3–23.9° |
c = 12.565 (3) Å | µ = 1.06 mm−1 |
α = 66.477 (5)° | T = 153 K |
β = 69.288 (3)° | Drop-like irregular, green–blue |
γ = 69.139 (3)° | 0.21 × 0.19 × 0.12 mm |
V = 1076.1 (4) Å3 |
Siemens SMART CCD area-detector diffractometer | 3744 independent reflections |
Radiation source: fine-focus sealed tube | 2710 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Detector resolution: 120 µm pixels mm-1 | θmax = 25.0°, θmin = 2.3° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.808, Tmax = 0.884 | l = −14→14 |
8414 measured reflections |
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) = 0.124 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.8014P] where P = (Fo2 + 2Fc2)/3 |
3744 reflections | (Δ/σ)max < 0.001 |
292 parameters | Δρmax = 0.84 e Å−3 |
18 restraints | Δρmin = −0.52 e Å−3 |
[Cu2(C12H11NO5)2(C9H7N)2]·2C2H6O | γ = 69.139 (3)° |
Mr = 975.98 | V = 1076.1 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.4211 (16) Å | Mo Kα radiation |
b = 10.949 (3) Å | µ = 1.06 mm−1 |
c = 12.565 (3) Å | T = 153 K |
α = 66.477 (5)° | 0.21 × 0.19 × 0.12 mm |
β = 69.288 (3)° |
Siemens SMART CCD area-detector diffractometer | 3744 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2710 reflections with I > 2σ(I) |
Tmin = 0.808, Tmax = 0.884 | Rint = 0.064 |
8414 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 18 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.84 e Å−3 |
3744 reflections | Δρmin = −0.52 e Å−3 |
292 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | −0.07835 (6) | −0.11298 (5) | 0.49788 (5) | 0.02484 (18) | |
O1 | 0.4807 (5) | −0.4562 (4) | 0.6903 (4) | 0.0698 (13) | |
H1 | 0.5223 | −0.4605 | 0.7412 | 0.084* | |
O2 | 0.4285 (4) | −0.6479 (4) | 0.8206 (3) | 0.0562 (10) | |
O3 | −0.0301 (3) | 0.0539 (3) | 0.3801 (2) | 0.0258 (6) | |
O4 | −0.1218 (3) | −0.2904 (3) | 0.6019 (3) | 0.0301 (7) | |
O5 | −0.0232 (3) | −0.5165 (3) | 0.6437 (3) | 0.0338 (7) | |
N1 | 0.1137 (4) | −0.2279 (3) | 0.4295 (3) | 0.0256 (8) | |
C1 | 0.2032 (5) | −0.1898 (4) | 0.3246 (4) | 0.0268 (9) | |
H1A | 0.2890 | −0.2586 | 0.2989 | 0.032* | |
C2 | 0.1849 (4) | −0.0530 (4) | 0.2433 (4) | 0.0245 (9) | |
C3 | 0.2884 (5) | −0.0326 (5) | 0.1291 (4) | 0.0321 (10) | |
H3 | 0.3662 | −0.1094 | 0.1097 | 0.039* | |
C4 | 0.2807 (5) | 0.0949 (5) | 0.0449 (4) | 0.0361 (11) | |
H4 | 0.3523 | 0.1069 | −0.0318 | 0.043* | |
C5 | 0.1660 (5) | 0.2059 (5) | 0.0740 (4) | 0.0351 (11) | |
H5 | 0.1583 | 0.2946 | 0.0160 | 0.042* | |
C6 | 0.0631 (5) | 0.1905 (4) | 0.1851 (4) | 0.0304 (10) | |
H6 | −0.0136 | 0.2690 | 0.2024 | 0.036* | |
C7 | 0.0689 (4) | 0.0617 (4) | 0.2734 (3) | 0.0225 (9) | |
C8 | 0.1451 (5) | −0.3706 (4) | 0.5051 (4) | 0.0291 (10) | |
H8 | 0.1917 | −0.4336 | 0.4550 | 0.035* | |
C9 | 0.2567 (5) | −0.3911 (4) | 0.5764 (4) | 0.0316 (10) | |
H9A | 0.2098 | −0.3243 | 0.6218 | 0.038* | |
H9B | 0.3552 | −0.3693 | 0.5196 | 0.038* | |
C10 | 0.2973 (5) | −0.5349 (4) | 0.6641 (4) | 0.0366 (11) | |
H10A | 0.1992 | −0.5577 | 0.7205 | 0.044* | |
H10B | 0.3468 | −0.6019 | 0.6189 | 0.044* | |
C11 | 0.4057 (5) | −0.5504 (5) | 0.7347 (4) | 0.0363 (11) | |
C13 | −0.0118 (5) | −0.3963 (4) | 0.5896 (4) | 0.0260 (9) | |
N1Q | −0.3003 (4) | −0.0194 (3) | 0.5629 (3) | 0.0239 (8) | |
C2Q | −0.3766 (5) | 0.1003 (4) | 0.4940 (4) | 0.0248 (9) | |
H2Q | −0.3200 | 0.1431 | 0.4162 | 0.030* | |
C3Q | −0.5291 (5) | 0.1609 (4) | 0.5313 (4) | 0.0271 (9) | |
H3Q | −0.5769 | 0.2455 | 0.4804 | 0.033* | |
C4Q | −0.7803 (5) | 0.1549 (5) | 0.6898 (4) | 0.0324 (10) | |
H4Q | −0.8344 | 0.2400 | 0.6439 | 0.039* | |
C5Q | −0.8568 (5) | 0.0845 (5) | 0.7986 (4) | 0.0373 (11) | |
H5Q | −0.9651 | 0.1214 | 0.8287 | 0.045* | |
C6Q | −0.7795 (5) | −0.0410 (5) | 0.8674 (4) | 0.0395 (12) | |
H6Q | −0.8364 | −0.0890 | 0.9426 | 0.047* | |
C7Q | −0.6239 (5) | −0.0954 (5) | 0.8282 (4) | 0.0361 (11) | |
H7Q | −0.5719 | −0.1802 | 0.8761 | 0.043* | |
C8Q | −0.3801 (5) | −0.0783 (4) | 0.6697 (4) | 0.0264 (9) | |
H8Q | −0.3270 | −0.1614 | 0.7185 | 0.032* | |
C9Q | −0.6183 (5) | 0.0996 (4) | 0.6453 (4) | 0.0258 (9) | |
C10Q | −0.5403 (5) | −0.0245 (4) | 0.7157 (4) | 0.0265 (9) | |
O1E | 0.6852 (5) | −0.4945 (6) | 0.8002 (4) | 0.0885 (16) | |
H1E | 0.7682 | −0.5010 | 0.7458 | 0.106* | |
C1E | 0.7895 (8) | −0.5641 (7) | 0.9681 (6) | 0.0746 (19) | |
H1E1 | 0.8917 | −0.5486 | 0.9172 | 0.112* | |
H1E2 | 0.8043 | −0.6436 | 1.0395 | 0.112* | |
H1E3 | 0.7256 | −0.4823 | 0.9924 | 0.112* | |
C2E | 0.7081 (8) | −0.5912 (7) | 0.8999 (6) | 0.0759 (19) | |
H2E1 | 0.7705 | −0.6775 | 0.8811 | 0.091* | |
H2E2 | 0.6051 | −0.6063 | 0.9526 | 0.091* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0200 (3) | 0.0253 (3) | 0.0273 (3) | −0.0059 (2) | −0.0049 (2) | −0.0070 (2) |
O1 | 0.075 (3) | 0.077 (3) | 0.064 (3) | −0.054 (2) | −0.044 (2) | 0.026 (2) |
O2 | 0.062 (2) | 0.049 (2) | 0.052 (2) | −0.0164 (18) | −0.033 (2) | 0.0080 (19) |
O3 | 0.0236 (15) | 0.0259 (15) | 0.0263 (16) | −0.0051 (12) | −0.0047 (13) | −0.0088 (12) |
O4 | 0.0218 (15) | 0.0261 (15) | 0.0359 (18) | −0.0042 (13) | −0.0046 (13) | −0.0071 (13) |
O5 | 0.0272 (16) | 0.0272 (16) | 0.0401 (19) | −0.0083 (13) | −0.0068 (14) | −0.0039 (14) |
N1 | 0.0231 (18) | 0.0231 (18) | 0.028 (2) | −0.0066 (14) | −0.0100 (16) | −0.0017 (15) |
C1 | 0.018 (2) | 0.031 (2) | 0.032 (3) | −0.0068 (18) | −0.0057 (19) | −0.0107 (19) |
C2 | 0.017 (2) | 0.034 (2) | 0.024 (2) | −0.0106 (17) | −0.0038 (17) | −0.0083 (18) |
C3 | 0.027 (2) | 0.037 (3) | 0.037 (3) | −0.0090 (19) | −0.006 (2) | −0.017 (2) |
C4 | 0.033 (3) | 0.050 (3) | 0.024 (2) | −0.020 (2) | −0.001 (2) | −0.007 (2) |
C5 | 0.032 (3) | 0.039 (3) | 0.029 (3) | −0.014 (2) | −0.006 (2) | −0.002 (2) |
C6 | 0.028 (2) | 0.031 (2) | 0.033 (3) | −0.0061 (19) | −0.013 (2) | −0.008 (2) |
C7 | 0.017 (2) | 0.034 (2) | 0.019 (2) | −0.0104 (17) | −0.0055 (17) | −0.0073 (18) |
C8 | 0.022 (2) | 0.026 (2) | 0.036 (3) | −0.0033 (17) | −0.0084 (19) | −0.0081 (19) |
C9 | 0.027 (2) | 0.030 (2) | 0.036 (3) | −0.0097 (19) | −0.009 (2) | −0.006 (2) |
C10 | 0.030 (2) | 0.032 (2) | 0.048 (3) | −0.010 (2) | −0.020 (2) | −0.003 (2) |
C11 | 0.028 (2) | 0.040 (3) | 0.038 (3) | −0.009 (2) | −0.006 (2) | −0.010 (2) |
C13 | 0.025 (2) | 0.030 (2) | 0.025 (2) | −0.0098 (19) | −0.0093 (18) | −0.0043 (19) |
N1Q | 0.0211 (18) | 0.0272 (18) | 0.027 (2) | −0.0078 (15) | −0.0089 (15) | −0.0084 (16) |
C2Q | 0.027 (2) | 0.024 (2) | 0.030 (2) | −0.0095 (18) | −0.0102 (19) | −0.0084 (18) |
C3Q | 0.029 (2) | 0.021 (2) | 0.036 (3) | −0.0036 (18) | −0.016 (2) | −0.0090 (19) |
C4Q | 0.023 (2) | 0.037 (2) | 0.048 (3) | −0.0022 (19) | −0.013 (2) | −0.025 (2) |
C5Q | 0.022 (2) | 0.055 (3) | 0.045 (3) | −0.011 (2) | 0.000 (2) | −0.032 (3) |
C6Q | 0.037 (3) | 0.055 (3) | 0.030 (3) | −0.021 (2) | 0.000 (2) | −0.016 (2) |
C7Q | 0.032 (3) | 0.040 (3) | 0.033 (3) | −0.008 (2) | −0.006 (2) | −0.011 (2) |
C8Q | 0.027 (2) | 0.026 (2) | 0.029 (2) | −0.0063 (18) | −0.011 (2) | −0.0088 (19) |
C9Q | 0.023 (2) | 0.032 (2) | 0.033 (2) | −0.0093 (18) | −0.0076 (19) | −0.018 (2) |
C10Q | 0.023 (2) | 0.033 (2) | 0.028 (2) | −0.0083 (18) | −0.0072 (19) | −0.0128 (19) |
O1E | 0.060 (3) | 0.160 (4) | 0.045 (2) | −0.070 (3) | −0.020 (2) | 0.012 (3) |
C1E | 0.099 (5) | 0.073 (4) | 0.067 (4) | −0.023 (3) | −0.042 (4) | −0.016 (3) |
C2E | 0.061 (3) | 0.092 (4) | 0.068 (4) | −0.021 (3) | −0.025 (3) | −0.008 (3) |
Cu1—O3 | 1.922 (3) | C9—H9B | 0.9900 |
Cu1—N1 | 1.933 (3) | C10—C11 | 1.502 (6) |
Cu1—O4 | 1.952 (3) | C10—H10A | 0.9900 |
Cu1—N1Q | 2.006 (3) | C10—H10B | 0.9900 |
Cu1—O3i | 2.487 (3) | N1Q—C8Q | 1.312 (5) |
O1—C11 | 1.286 (5) | N1Q—C2Q | 1.359 (5) |
O1—H1 | 0.8400 | C2Q—C3Q | 1.348 (6) |
O2—C11 | 1.196 (5) | C2Q—H2Q | 0.9500 |
O3—C7 | 1.325 (5) | C3Q—C9Q | 1.411 (6) |
O4—C13 | 1.271 (5) | C3Q—H3Q | 0.9500 |
O5—C13 | 1.242 (5) | C4Q—C5Q | 1.357 (6) |
N1—C1 | 1.284 (5) | C4Q—C9Q | 1.420 (6) |
N1—C8 | 1.454 (5) | C4Q—H4Q | 0.9500 |
C1—C2 | 1.427 (6) | C5Q—C6Q | 1.396 (7) |
C1—H1A | 0.9500 | C5Q—H5Q | 0.9500 |
C2—C3 | 1.403 (6) | C6Q—C7Q | 1.359 (6) |
C2—C7 | 1.423 (6) | C6Q—H6Q | 0.9500 |
C3—C4 | 1.370 (6) | C7Q—C10Q | 1.412 (6) |
C3—H3 | 0.9500 | C7Q—H7Q | 0.9500 |
C4—C5 | 1.385 (6) | C8Q—C10Q | 1.407 (5) |
C4—H4 | 0.9500 | C8Q—H8Q | 0.9500 |
C5—C6 | 1.374 (6) | C9Q—C10Q | 1.399 (6) |
C5—H5 | 0.9500 | O1E—C2E | 1.306 (7) |
C6—C7 | 1.401 (6) | O1E—H1E | 0.8400 |
C6—H6 | 0.9500 | C1E—C2E | 1.497 (8) |
C8—C9 | 1.516 (6) | C1E—H1E1 | 0.9800 |
C8—C13 | 1.529 (6) | C1E—H1E2 | 0.9800 |
C8—H8 | 1.0000 | C1E—H1E3 | 0.9800 |
C9—C10 | 1.524 (6) | C2E—H2E1 | 0.9900 |
C9—H9A | 0.9900 | C2E—H2E2 | 0.9900 |
O3—Cu1—N1 | 93.08 (12) | H10A—C10—H10B | 107.7 |
O3—Cu1—O4 | 173.30 (12) | O2—C11—O1 | 122.7 (4) |
N1—Cu1—O4 | 82.64 (12) | O2—C11—C10 | 122.4 (4) |
O3—Cu1—N1Q | 93.97 (12) | O1—C11—C10 | 114.7 (4) |
N1—Cu1—N1Q | 167.18 (13) | O5—C13—O4 | 124.3 (4) |
O4—Cu1—N1Q | 89.31 (12) | O5—C13—C8 | 119.1 (4) |
C11—O1—H1 | 109.5 | O4—C13—C8 | 116.5 (3) |
C7—O3—Cu1 | 124.8 (2) | C8Q—N1Q—C2Q | 118.0 (3) |
C13—O4—Cu1 | 116.2 (3) | C8Q—N1Q—Cu1 | 120.7 (3) |
C1—N1—C8 | 120.7 (4) | C2Q—N1Q—Cu1 | 121.0 (3) |
C1—N1—Cu1 | 125.5 (3) | C3Q—C2Q—N1Q | 122.8 (4) |
C8—N1—Cu1 | 113.5 (3) | C3Q—C2Q—H2Q | 118.6 |
N1—C1—C2 | 125.7 (4) | N1Q—C2Q—H2Q | 118.6 |
N1—C1—H1A | 117.1 | C2Q—C3Q—C9Q | 120.5 (4) |
C2—C1—H1A | 117.1 | C2Q—C3Q—H3Q | 119.8 |
C3—C2—C7 | 119.4 (4) | C9Q—C3Q—H3Q | 119.8 |
C3—C2—C1 | 117.5 (4) | C5Q—C4Q—C9Q | 119.2 (4) |
C7—C2—C1 | 123.1 (4) | C5Q—C4Q—H4Q | 120.4 |
C4—C3—C2 | 121.9 (4) | C9Q—C4Q—H4Q | 120.4 |
C4—C3—H3 | 119.0 | C4Q—C5Q—C6Q | 121.3 (4) |
C2—C3—H3 | 119.0 | C4Q—C5Q—H5Q | 119.3 |
C3—C4—C5 | 118.5 (4) | C6Q—C5Q—H5Q | 119.3 |
C3—C4—H4 | 120.8 | C7Q—C6Q—C5Q | 120.9 (4) |
C5—C4—H4 | 120.8 | C7Q—C6Q—H6Q | 119.6 |
C6—C5—C4 | 121.5 (4) | C5Q—C6Q—H6Q | 119.6 |
C6—C5—H5 | 119.3 | C6Q—C7Q—C10Q | 119.3 (4) |
C4—C5—H5 | 119.3 | C6Q—C7Q—H7Q | 120.3 |
C5—C6—C7 | 121.4 (4) | C10Q—C7Q—H7Q | 120.3 |
C5—C6—H6 | 119.3 | N1Q—C8Q—C10Q | 123.4 (4) |
C7—C6—H6 | 119.3 | N1Q—C8Q—H8Q | 118.3 |
O3—C7—C6 | 118.7 (4) | C10Q—C8Q—H8Q | 118.3 |
O3—C7—C2 | 123.9 (4) | C4Q—C9Q—C3Q | 123.9 (4) |
C6—C7—C2 | 117.4 (4) | C4Q—C9Q—C10Q | 119.3 (4) |
N1—C8—C9 | 108.7 (3) | C3Q—C9Q—C10Q | 116.8 (4) |
N1—C8—C13 | 107.0 (3) | C7Q—C10Q—C8Q | 121.5 (4) |
C9—C8—C13 | 110.1 (4) | C7Q—C10Q—C9Q | 119.9 (4) |
N1—C8—H8 | 110.4 | C8Q—C10Q—C9Q | 118.5 (4) |
C9—C8—H8 | 110.4 | C2E—O1E—H1E | 109.5 |
C13—C8—H8 | 110.4 | C2E—C1E—H1E1 | 109.5 |
C8—C9—C10 | 115.4 (3) | C2E—C1E—H1E2 | 109.5 |
C8—C9—H9A | 108.4 | H1E1—C1E—H1E2 | 109.5 |
C10—C9—H9A | 108.4 | C2E—C1E—H1E3 | 109.5 |
C8—C9—H9B | 108.4 | H1E1—C1E—H1E3 | 109.5 |
C10—C9—H9B | 108.4 | H1E2—C1E—H1E3 | 109.5 |
H9A—C9—H9B | 107.5 | O1E—C2E—C1E | 115.8 (6) |
C11—C10—C9 | 113.8 (4) | O1E—C2E—H2E1 | 108.3 |
C11—C10—H10A | 108.8 | C1E—C2E—H2E1 | 108.3 |
C9—C10—H10A | 108.8 | O1E—C2E—H2E2 | 108.3 |
C11—C10—H10B | 108.8 | C1E—C2E—H2E2 | 108.3 |
C9—C10—H10B | 108.8 | H2E1—C2E—H2E2 | 107.4 |
N1—Cu1—O3—C7 | 21.8 (3) | C9—C10—C11—O2 | 167.2 (5) |
N1Q—Cu1—O3—C7 | −147.5 (3) | C9—C10—C11—O1 | −17.9 (6) |
N1—Cu1—O4—C13 | 5.3 (3) | Cu1—O4—C13—O5 | −175.7 (3) |
N1Q—Cu1—O4—C13 | 175.3 (3) | Cu1—O4—C13—C8 | 6.3 (4) |
O3—Cu1—N1—C1 | −15.7 (3) | N1—C8—C13—O5 | 163.6 (4) |
O4—Cu1—N1—C1 | 159.1 (4) | C9—C8—C13—O5 | −78.5 (5) |
N1Q—Cu1—N1—C1 | 107.6 (6) | N1—C8—C13—O4 | −18.3 (5) |
O3—Cu1—N1—C8 | 169.2 (3) | C9—C8—C13—O4 | 99.6 (4) |
O4—Cu1—N1—C8 | −16.0 (3) | O3—Cu1—N1Q—C8Q | −160.6 (3) |
N1Q—Cu1—N1—C8 | −67.5 (7) | N1—Cu1—N1Q—C8Q | 76.2 (7) |
C8—N1—C1—C2 | −179.4 (4) | O4—Cu1—N1Q—C8Q | 25.2 (3) |
Cu1—N1—C1—C2 | 5.8 (6) | O3—Cu1—N1Q—C2Q | 25.3 (3) |
N1—C1—C2—C3 | −175.9 (4) | N1—Cu1—N1Q—C2Q | −97.9 (6) |
N1—C1—C2—C7 | 4.9 (6) | O4—Cu1—N1Q—C2Q | −148.9 (3) |
C7—C2—C3—C4 | −0.5 (6) | C8Q—N1Q—C2Q—C3Q | 0.7 (6) |
C1—C2—C3—C4 | −179.8 (4) | Cu1—N1Q—C2Q—C3Q | 174.9 (3) |
C2—C3—C4—C5 | −0.5 (6) | N1Q—C2Q—C3Q—C9Q | −1.1 (6) |
C3—C4—C5—C6 | 1.0 (7) | C9Q—C4Q—C5Q—C6Q | −0.2 (6) |
C4—C5—C6—C7 | −0.5 (7) | C4Q—C5Q—C6Q—C7Q | 1.3 (7) |
Cu1—O3—C7—C6 | 163.3 (3) | C5Q—C6Q—C7Q—C10Q | −0.9 (7) |
Cu1—O3—C7—C2 | −18.4 (5) | C2Q—N1Q—C8Q—C10Q | 0.7 (6) |
C5—C6—C7—O3 | 177.9 (4) | Cu1—N1Q—C8Q—C10Q | −173.6 (3) |
C5—C6—C7—C2 | −0.5 (6) | C5Q—C4Q—C9Q—C3Q | 177.0 (4) |
C3—C2—C7—O3 | −177.3 (4) | C5Q—C4Q—C9Q—C10Q | −1.4 (6) |
C1—C2—C7—O3 | 2.0 (6) | C2Q—C3Q—C9Q—C4Q | −178.2 (4) |
C3—C2—C7—C6 | 0.9 (5) | C2Q—C3Q—C9Q—C10Q | 0.3 (6) |
C1—C2—C7—C6 | −179.8 (4) | C6Q—C7Q—C10Q—C8Q | −178.3 (4) |
C1—N1—C8—C9 | 87.8 (5) | C6Q—C7Q—C10Q—C9Q | −0.7 (6) |
Cu1—N1—C8—C9 | −96.9 (3) | N1Q—C8Q—C10Q—C7Q | 176.2 (4) |
C1—N1—C8—C13 | −153.5 (4) | N1Q—C8Q—C10Q—C9Q | −1.4 (6) |
Cu1—N1—C8—C13 | 21.9 (4) | C4Q—C9Q—C10Q—C7Q | 1.8 (6) |
N1—C8—C9—C10 | 177.9 (4) | C3Q—C9Q—C10Q—C7Q | −176.7 (4) |
C13—C8—C9—C10 | 61.0 (5) | C4Q—C9Q—C10Q—C8Q | 179.5 (3) |
C8—C9—C10—C11 | −178.9 (4) | C3Q—C9Q—C10Q—C8Q | 0.9 (6) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1E | 0.84 | 1.79 | 2.576 (5) | 154 |
O1E—H1E···O5ii | 0.84 | 1.92 | 2.750 (5) | 169 |
Symmetry code: (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C12H11NO5)2(C9H7N)2]·2C2H6O |
Mr | 975.98 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 153 |
a, b, c (Å) | 9.4211 (16), 10.949 (3), 12.565 (3) |
α, β, γ (°) | 66.477 (5), 69.288 (3), 69.139 (3) |
V (Å3) | 1076.1 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.21 × 0.19 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.808, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8414, 3744, 2710 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.124, 1.00 |
No. of reflections | 3744 |
No. of parameters | 292 |
No. of restraints | 18 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.84, −0.52 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2008).
Cu1—O3 | 1.922 (3) | Cu1—N1Q | 2.006 (3) |
Cu1—N1 | 1.933 (3) | Cu1—O3i | 2.487 (3) |
Cu1—O4 | 1.952 (3) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1E | 0.84 | 1.79 | 2.576 (5) | 154 |
O1E—H1E···O5ii | 0.84 | 1.92 | 2.750 (5) | 169 |
Symmetry code: (ii) x+1, y, z. |
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Copper(II) complexes containing a Schiff base derived from salicylaldehyde and various amino acids have received considerable attention in view of their impact in many fields of bioinorganic chemistry. A series of copper(II) complexes containing the Schiff base derived from salicylaldehyde and L-glutamic acid were synthesized (Andrezálová et al., 1998; Kohútová et al., 2000) and studied on account of their antimicrobial and antiradical activities, especially for their observed capability to imitate the role of the natural superoxidedismutase enzyme. Several structures of these complexes containing the molecular ligands such as water, pyridine, pyrazole, imidazole and its derivatives have already been described, namely (1-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer et al., 2003), (N-salicylidene-D,L-glutamato)(2-methylimidazole)copper(II) (Langer, Scholtzová et al., 2004) and aqua(N-salicylidene-methylester-L-glutamato)copper(II) monohydrate (Langer, Gyepesová et al., 2004). The title compound, (I), showed antimicrobial activity tested against G- bacteria Escherichia coli (IC50 = 0.60 mmol dm-3), yeasts Candida parapsilosis (IC50 = 0.63 mmol dm-3), and filamentous fungi Microsporum gypseum and Botrytis cinerea (IC50 = 0.45 and 0.44 mmol dm-3, respectively) (Valent et al., 2004). Its crystal and molecular structures are presented here.
The crystal structure of (I) consists of centrosymmetric dimers of Cu(N-salicylidene-rac-glutamato)(isoquinoline) and ethanol solvent molecules (for the numbering of the asymmetric part of the structure see Fig. 1). Each copper ion in the title complex displays a slightly distorted square-pyramidal coordination geometry. The base of the pyramid is formed by the phenol O3, carboxylate O4 and azomethine N1 atoms of the Schiff base N-salicylidenglutamate dianion and by atom N1Q of the isoquinoline ligand. The apex of the pyramid consists of the weakly bonded phenol O3 atom of an adjacent molecule at the apical distance of 2.487 (3) Å (Table 1 and Fig. 2). The size of the pyramidal base and the apical bond length are comparable to the corresponding bond lengths found in other compounds of this structure type, e.g. dimeric (imidazole-N3)(N-salicylidene-rac-alaninato-O,N,O')copper(II) (Warda, 1998), dimeric (pyrazole-N2)(N-salicylidene-2,2- dimethylglycinato-O,N,O')copper(II)pyrazole solvate (Hill & Warda, 1999) and (imidazole)(N-salicylidene-β-alaninato)copper(II) (Plesch et al. 1998). In (I), the Cu1—O3 distance of 1.922 (3) Å is considerably shorter than the Cu1—O4 distance of 1.952 (3) Å, as is the case in the above-mentioned related compounds, indicating that more negative charge is localized on the phenol O3 atom than on the carboxy O4 atom; the C1=N1 bond formed by the condensation reaction of length 1.284 (5) Å is in the normal double-bond range of 1.28–1.30 Å. In the structures of copper(II) complexes containing various N-salicylidene–amino acid Schiff bases and different neutral ligands, the local environment in the plane where the chelate and neutral ligands are bound undergoes only slight changes. A rich variety of axial distortions ranging from square-planar to square-pyramidal has been found. Such structural adaptability may be one of the reason for the diversity of interactions of these complexes with biological systems (Plesch et al., 1998). As an example, (1-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer et al., 2003) adopts square-planar copper(II) coordination mode with the tridentate N-salicylidenglutamate Schiff base dianion and the1-methylimidazole ligand with dimers of centrosymmetrically related molecules [the Cu···Cu distance within dimers is 4.0429 (5) Å]; the distance of the phenol O atom from the Cu atom within the dimer is 3.2206 (16) Å and a weak interaction was formed. The Cu···Cui distance in (I) within the dimers is 3.3264 (12) Å [symmetry code: (i) -x, -y, -z + 1]. The dimers are linked into infinite chains running parallel to the a axis via medium-strong hydrogen bonds (Table 2), with the hydroxy group of the ethanol solvent molecule playing the role of both H-atom donor and acceptor (Fig. 3). In addition, there is a strong π–π interaction between the isoquinone ring systems of neighbouring dimers, with a perpendicular distance of 3.236 (2) Å between the parallel planes.