Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103026453/sx1128sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103026453/sx1128Isup2.hkl |
CCDC reference: 231036
All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. CuCl2·2H2O (1.705 g, 10.0 mmol) was dissolved in water (80 ml), and 1,10-phenanthroline (1.98 g, 10 mmol) was dissolved in water (20 ml) with a few drops of HCl. L-glutamic acid (1,47 g, 10.0 mmol) was then added to the copper(II) chloride solution with stirring at 333 K until all the L-glutamic acid had dissolved. The two solutions were then mixed, the pH adjusted to 3 with HCl and the solution stirred at room temperature for 2 h. The blue solution was filtered and the filtrate left at 277 K. Blue crystals of (I) appeared from the solution after several weeks, by slow evaporation of the aqueous solvent. Elemental analysis, calculated for C17H16ClCuN3O4·H2O: C 46.06, H 4.09, N 9.48%; found: C 45.98, H 4.17, N 9.35%.
H atoms attached to C and N atoms were placed in geometrically idealized positions, with Csp3—H = 0.99, Csp2—H = 0.95, α-Csp3—H = 1.000 and Nsp3—H = 0.92 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N). H atoms attached to O atoms (L-glutamic acid and solvent water) were located from difference Fourier maps and their global Uiso value was refined. The O—H distances are in the range 0.81 (5)–0.90 (5) Å.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.
[CuCl(C5H8NO4)(C12H8N2)]·H2O | Z = 2 |
Mr = 443.33 | F(000) = 454 |
Triclinic, P1 | Dx = 1.693 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3022 (14) Å | Cell parameters from 3499 reflections |
b = 10.0591 (17) Å | θ = 2.3–27.2° |
c = 12.393 (2) Å | µ = 1.45 mm−1 |
α = 66.730 (2)° | T = 183 K |
β = 72.047 (2)° | Block, blue |
γ = 68.828 (2)° | 0.55 × 0.40 × 0.40 mm |
V = 869.9 (3) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 3578 independent reflections |
Radiation source: fine-focus sealed tube | 3455 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −9→9 |
Tmin = 0.474, Tmax = 0.561 | k = −11→8 |
4229 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0562P)2 + 2.5194P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
3578 reflections | Δρmax = 0.52 e Å−3 |
506 parameters | Δρmin = −0.75 e Å−3 |
9 restraints | Absolute structure: Flack (1983), with x Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (3) |
[CuCl(C5H8NO4)(C12H8N2)]·H2O | γ = 68.828 (2)° |
Mr = 443.33 | V = 869.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3022 (14) Å | Mo Kα radiation |
b = 10.0591 (17) Å | µ = 1.45 mm−1 |
c = 12.393 (2) Å | T = 183 K |
α = 66.730 (2)° | 0.55 × 0.40 × 0.40 mm |
β = 72.047 (2)° |
Bruker SMART 1K CCD area-detector diffractometer | 3578 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 3455 reflections with I > 2σ(I) |
Tmin = 0.474, Tmax = 0.561 | Rint = 0.022 |
4229 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.121 | Δρmax = 0.52 e Å−3 |
S = 1.10 | Δρmin = −0.75 e Å−3 |
3578 reflections | Absolute structure: Flack (1983), with x Friedel pairs |
506 parameters | Absolute structure parameter: −0.02 (3) |
9 restraints |
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 | 0.27011 (10) | 0.95620 (8) | 0.66301 (7) | 0.0258 (3) | |
Cu2 | 0.48343 (10) | 0.28453 (9) | 0.85224 (7) | 0.0257 (3) | |
Cl1 | 0.6759 (3) | 0.4730 (3) | 0.7447 (2) | 0.0296 (6) | |
Cl2 | 0.0761 (3) | 0.7714 (3) | 0.7697 (2) | 0.0293 (6) | |
N1 | 0.1037 (13) | 1.1118 (11) | 0.5554 (9) | 0.023 (2) | |
N2 | 0.3848 (12) | 0.8895 (12) | 0.5133 (8) | 0.024 (2) | |
N3 | 0.4529 (14) | 0.8288 (11) | 0.7609 (10) | 0.028 (2) | |
H3A | 0.4804 | 0.7302 | 0.7644 | 0.033* | |
H3B | 0.5535 | 0.8606 | 0.7278 | 0.033* | |
N4 | 0.3802 (12) | 0.3553 (10) | 0.9945 (9) | 0.026 (2) | |
N5 | 0.6526 (14) | 0.1349 (12) | 0.9559 (9) | 0.026 (2) | |
N6 | 0.3012 (13) | 0.4185 (12) | 0.7519 (8) | 0.027 (2) | |
H6A | 0.1911 | 0.4278 | 0.8001 | 0.033* | |
H6B | 0.3191 | 0.5127 | 0.7155 | 0.033* | |
C1 | −0.0297 (17) | 1.2233 (15) | 0.5803 (12) | 0.033 (3) | |
H1 | −0.0535 | 1.2378 | 0.6556 | 0.040* | |
C2 | −0.1355 (14) | 1.3200 (14) | 0.4962 (11) | 0.031 (3) | |
H2 | −0.2301 | 1.4006 | 0.5146 | 0.038* | |
C3 | −0.1052 (16) | 1.3005 (15) | 0.3875 (11) | 0.032 (3) | |
H3 | −0.1786 | 1.3661 | 0.3311 | 0.038* | |
C4 | 0.0328 (17) | 1.1846 (14) | 0.3617 (11) | 0.028 (3) | |
C5 | 0.1366 (15) | 1.0922 (13) | 0.4512 (11) | 0.025 (2) | |
C6 | 0.2869 (17) | 0.9733 (14) | 0.4251 (10) | 0.028 (2) | |
C7 | 0.0847 (16) | 1.1484 (14) | 0.2519 (11) | 0.029 (2) | |
H7 | 0.0168 | 1.2080 | 0.1913 | 0.035* | |
C8 | 0.2252 (17) | 1.0338 (15) | 0.2308 (11) | 0.035 (3) | |
H8 | 0.2529 | 1.0146 | 0.1571 | 0.042* | |
C9 | 0.3331 (16) | 0.9406 (14) | 0.3199 (11) | 0.031 (3) | |
C10 | 0.4810 (19) | 0.8257 (16) | 0.3017 (12) | 0.039 (3) | |
H10 | 0.5141 | 0.8013 | 0.2298 | 0.047* | |
C11 | 0.5796 (17) | 0.7469 (15) | 0.3902 (12) | 0.035 (3) | |
H11 | 0.6822 | 0.6677 | 0.3794 | 0.042* | |
C12 | 0.5287 (16) | 0.7836 (14) | 0.4958 (12) | 0.033 (3) | |
H12 | 0.5992 | 0.7312 | 0.5555 | 0.040* | |
C13 | 0.2543 (13) | 1.0017 (12) | 0.8710 (10) | 0.023 (2) | |
C14 | 0.3798 (11) | 0.8427 (9) | 0.8834 (7) | 0.0235 (17) | |
H14 | 0.3037 | 0.7723 | 0.9253 | 0.028* | |
C15 | 0.5145 (15) | 0.7928 (13) | 0.9585 (11) | 0.035 (3) | |
H15A | 0.5840 | 0.8669 | 0.9249 | 0.042* | |
H15B | 0.4519 | 0.7960 | 1.0400 | 0.042* | |
C16 | 0.6398 (15) | 0.6399 (14) | 0.9697 (10) | 0.026 (2) | |
H16A | 0.5743 | 0.5709 | 0.9769 | 0.031* | |
H16B | 0.7297 | 0.6455 | 0.8950 | 0.031* | |
C17 | 0.7274 (16) | 0.5769 (14) | 1.0683 (12) | 0.040 (3) | |
C18 | 0.2381 (15) | 0.4686 (13) | 1.0153 (11) | 0.029 (2) | |
H18 | 0.1683 | 0.5260 | 0.9556 | 0.035* | |
C19 | 0.1901 (17) | 0.5046 (14) | 1.1201 (12) | 0.035 (3) | |
H19 | 0.0876 | 0.5841 | 1.1306 | 0.042* | |
C20 | 0.2856 (18) | 0.4294 (14) | 1.2072 (12) | 0.035 (3) | |
H20 | 0.2523 | 0.4566 | 1.2778 | 0.042* | |
C21 | 0.4366 (16) | 0.3090 (15) | 1.1919 (11) | 0.029 (3) | |
C22 | 0.4730 (15) | 0.2814 (13) | 1.0815 (11) | 0.024 (2) | |
C23 | 0.6195 (17) | 0.1588 (14) | 1.0654 (10) | 0.025 (2) | |
C24 | 0.5470 (16) | 0.2163 (15) | 1.2781 (11) | 0.032 (3) | |
H24 | 0.5197 | 0.2359 | 1.3516 | 0.039* | |
C25 | 0.689 (2) | 0.1018 (17) | 1.2592 (13) | 0.041 (3) | |
H25 | 0.7617 | 0.0441 | 1.3169 | 0.049* | |
C26 | 0.7254 (15) | 0.0699 (13) | 1.1502 (11) | 0.027 (2) | |
C27 | 0.8694 (15) | −0.0539 (14) | 1.1234 (12) | 0.031 (3) | |
H27 | 0.9439 | −0.1189 | 1.1792 | 0.038* | |
C28 | 0.8962 (16) | −0.0756 (14) | 1.0166 (11) | 0.031 (3) | |
H28 | 0.9894 | −0.1568 | 0.9978 | 0.038* | |
C29 | 0.7874 (15) | 0.0207 (13) | 0.9358 (11) | 0.026 (2) | |
H29 | 0.8108 | 0.0040 | 0.8615 | 0.031* | |
C30 | 0.4791 (16) | 0.2286 (13) | 0.6536 (10) | 0.027 (3) | |
C31 | 0.3098 (11) | 0.3566 (9) | 0.6597 (8) | 0.0259 (18) | |
H31 | 0.2100 | 0.3099 | 0.6888 | 0.031* | |
C32 | 0.2859 (15) | 0.4708 (13) | 0.5397 (11) | 0.034 (2) | |
H32A | 0.2881 | 0.4205 | 0.4848 | 0.041* | |
H32B | 0.3845 | 0.5178 | 0.5059 | 0.041* | |
C33 | 0.1101 (18) | 0.5936 (14) | 0.5495 (12) | 0.035 (3) | |
H33A | 0.0155 | 0.5447 | 0.5992 | 0.042* | |
H33B | 0.1184 | 0.6565 | 0.5910 | 0.042* | |
C34 | 0.0593 (17) | 0.6951 (12) | 0.4290 (11) | 0.037 (3) | |
O1 | 0.1805 (10) | 1.0619 (9) | 0.7796 (7) | 0.0263 (18) | |
O2 | 0.2261 (12) | 1.0633 (10) | 0.9466 (8) | 0.035 (2) | |
O3 | 0.7081 (11) | 0.6263 (9) | 1.1466 (8) | 0.060 (3) | |
O4 | 0.8524 (13) | 0.4391 (10) | 1.0784 (9) | 0.044 (2) | |
H4A | 0.867 (12) | 0.438 (10) | 1.011 (5) | 0.020 (8)* | |
O5 | 0.5650 (11) | 0.1780 (9) | 0.7368 (7) | 0.0275 (18) | |
O6 | 0.5196 (12) | 0.1761 (10) | 0.5703 (7) | 0.035 (2) | |
O7 | 0.1283 (12) | 0.6655 (8) | 0.3374 (7) | 0.056 (2) | |
O8 | −0.0643 (12) | 0.8215 (11) | 0.4284 (9) | 0.044 (2) | |
H8A | −0.076 (11) | 0.846 (9) | 0.488 (6) | 0.020 (8)* | |
O9 | 0.7884 (11) | 0.9109 (10) | 0.6139 (9) | 0.034 (2) | |
H9A | 0.861 (10) | 0.897 (9) | 0.661 (7) | 0.020 (8)* | |
H9B | 0.763 (11) | 1.004 (6) | 0.569 (6) | 0.020 (8)* | |
O10 | 0.9680 (12) | 0.3349 (11) | 0.8998 (9) | 0.038 (2) | |
H10A | 0.922 (11) | 0.377 (9) | 0.840 (6) | 0.020 (8)* | |
H10B | 1.051 (9) | 0.250 (7) | 0.896 (7) | 0.020 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0257 (7) | 0.0265 (8) | 0.0245 (7) | −0.0012 (6) | −0.0083 (6) | −0.0103 (6) |
Cu2 | 0.0260 (7) | 0.0268 (7) | 0.0220 (7) | 0.0010 (6) | −0.0090 (5) | −0.0098 (6) |
Cl1 | 0.0300 (14) | 0.0275 (15) | 0.0300 (15) | −0.0051 (12) | −0.0061 (12) | −0.0102 (12) |
Cl2 | 0.0325 (14) | 0.0244 (14) | 0.0314 (15) | −0.0058 (11) | −0.0103 (12) | −0.0083 (12) |
N1 | 0.025 (5) | 0.019 (5) | 0.022 (5) | −0.005 (4) | −0.009 (4) | −0.001 (4) |
N2 | 0.022 (4) | 0.037 (5) | 0.018 (4) | −0.008 (4) | 0.000 (3) | −0.015 (4) |
N3 | 0.032 (5) | 0.021 (5) | 0.042 (6) | −0.005 (4) | −0.014 (4) | −0.018 (4) |
N4 | 0.020 (4) | 0.017 (4) | 0.032 (5) | 0.004 (3) | −0.013 (4) | −0.002 (4) |
N5 | 0.026 (5) | 0.034 (6) | 0.018 (5) | −0.006 (4) | −0.003 (4) | −0.013 (4) |
N6 | 0.027 (5) | 0.030 (5) | 0.013 (5) | 0.002 (4) | −0.008 (4) | −0.002 (4) |
C1 | 0.033 (7) | 0.037 (7) | 0.026 (7) | −0.009 (6) | −0.002 (5) | −0.011 (6) |
C2 | 0.018 (5) | 0.034 (7) | 0.033 (7) | 0.003 (5) | −0.007 (5) | −0.009 (5) |
C3 | 0.028 (6) | 0.040 (7) | 0.021 (6) | −0.007 (5) | −0.014 (5) | 0.002 (5) |
C4 | 0.033 (6) | 0.029 (6) | 0.025 (6) | −0.016 (5) | −0.012 (5) | −0.001 (5) |
C5 | 0.019 (5) | 0.019 (5) | 0.031 (6) | 0.000 (4) | −0.007 (4) | −0.005 (4) |
C6 | 0.035 (6) | 0.030 (5) | 0.016 (5) | −0.006 (4) | −0.011 (4) | −0.001 (4) |
C7 | 0.028 (5) | 0.035 (6) | 0.023 (5) | −0.003 (4) | −0.016 (4) | −0.005 (4) |
C8 | 0.044 (7) | 0.042 (7) | 0.016 (5) | −0.008 (5) | −0.013 (5) | −0.006 (5) |
C9 | 0.030 (5) | 0.027 (6) | 0.031 (6) | 0.000 (4) | −0.010 (5) | −0.008 (4) |
C10 | 0.051 (7) | 0.044 (7) | 0.020 (6) | −0.013 (6) | −0.003 (5) | −0.012 (5) |
C11 | 0.033 (6) | 0.030 (6) | 0.032 (7) | 0.001 (5) | −0.002 (5) | −0.010 (5) |
C12 | 0.036 (6) | 0.029 (6) | 0.038 (7) | −0.003 (5) | −0.017 (5) | −0.011 (5) |
C13 | 0.016 (5) | 0.022 (5) | 0.028 (6) | 0.000 (4) | 0.001 (4) | −0.014 (4) |
C14 | 0.026 (4) | 0.028 (5) | 0.020 (4) | −0.003 (3) | −0.010 (3) | −0.011 (3) |
C15 | 0.039 (6) | 0.035 (5) | 0.034 (6) | 0.003 (4) | −0.021 (5) | −0.014 (5) |
C16 | 0.023 (6) | 0.031 (6) | 0.026 (6) | 0.004 (5) | −0.010 (5) | −0.017 (5) |
C17 | 0.035 (5) | 0.042 (7) | 0.044 (7) | 0.000 (5) | −0.002 (5) | −0.029 (5) |
C18 | 0.023 (5) | 0.029 (6) | 0.025 (6) | −0.003 (4) | −0.002 (4) | −0.005 (4) |
C19 | 0.041 (6) | 0.025 (6) | 0.036 (7) | 0.002 (5) | −0.011 (5) | −0.013 (5) |
C20 | 0.043 (7) | 0.026 (6) | 0.027 (6) | −0.001 (5) | −0.005 (5) | −0.008 (5) |
C21 | 0.030 (5) | 0.041 (7) | 0.025 (6) | −0.016 (5) | 0.003 (4) | −0.020 (5) |
C22 | 0.019 (5) | 0.029 (5) | 0.026 (6) | −0.006 (4) | −0.002 (4) | −0.012 (4) |
C23 | 0.036 (6) | 0.033 (6) | 0.010 (5) | −0.014 (5) | −0.007 (4) | −0.004 (4) |
C24 | 0.036 (6) | 0.040 (7) | 0.032 (6) | −0.010 (5) | −0.010 (5) | −0.020 (5) |
C25 | 0.043 (7) | 0.044 (7) | 0.039 (7) | −0.012 (6) | −0.019 (5) | −0.008 (5) |
C26 | 0.020 (5) | 0.023 (5) | 0.033 (6) | 0.001 (4) | −0.006 (4) | −0.009 (4) |
C27 | 0.019 (5) | 0.027 (6) | 0.039 (7) | 0.002 (4) | −0.009 (5) | −0.005 (5) |
C28 | 0.029 (6) | 0.024 (6) | 0.037 (7) | −0.008 (5) | 0.002 (5) | −0.011 (5) |
C29 | 0.027 (6) | 0.022 (6) | 0.028 (6) | −0.008 (5) | −0.005 (5) | −0.007 (5) |
C30 | 0.034 (6) | 0.027 (6) | 0.019 (5) | −0.010 (5) | −0.009 (4) | −0.001 (4) |
C31 | 0.024 (4) | 0.022 (4) | 0.035 (5) | −0.002 (3) | −0.010 (4) | −0.014 (4) |
C32 | 0.031 (5) | 0.034 (5) | 0.028 (5) | 0.003 (4) | −0.009 (4) | −0.010 (4) |
C33 | 0.041 (7) | 0.027 (7) | 0.032 (7) | 0.002 (5) | −0.016 (6) | −0.009 (5) |
C34 | 0.057 (7) | 0.024 (5) | 0.030 (6) | 0.005 (4) | −0.028 (5) | −0.008 (4) |
O1 | 0.023 (4) | 0.029 (4) | 0.029 (5) | −0.003 (3) | −0.005 (3) | −0.015 (4) |
O2 | 0.037 (5) | 0.029 (5) | 0.043 (6) | 0.005 (4) | −0.020 (4) | −0.017 (4) |
O3 | 0.070 (6) | 0.056 (5) | 0.052 (5) | 0.023 (4) | −0.039 (4) | −0.031 (4) |
O4 | 0.049 (5) | 0.039 (5) | 0.035 (4) | 0.014 (3) | −0.024 (4) | −0.014 (3) |
O5 | 0.033 (4) | 0.023 (4) | 0.024 (5) | 0.002 (3) | −0.019 (4) | −0.004 (3) |
O6 | 0.036 (5) | 0.041 (5) | 0.020 (5) | 0.009 (4) | −0.008 (4) | −0.017 (4) |
O7 | 0.076 (6) | 0.043 (4) | 0.031 (4) | 0.023 (4) | −0.024 (4) | −0.017 (3) |
O8 | 0.051 (5) | 0.040 (4) | 0.034 (5) | 0.016 (4) | −0.025 (4) | −0.017 (4) |
O9 | 0.028 (4) | 0.031 (5) | 0.044 (6) | 0.000 (4) | −0.009 (4) | −0.019 (4) |
O10 | 0.033 (5) | 0.037 (5) | 0.039 (5) | 0.007 (4) | −0.016 (4) | −0.015 (4) |
Cu1—O1 | 1.937 (8) | C14—H14 | 1.0000 |
Cu1—N3 | 1.979 (11) | C15—C16 | 1.494 (16) |
Cu1—N1 | 2.016 (10) | C15—H15A | 0.9900 |
Cu1—N2 | 2.057 (9) | C15—H15B | 0.9900 |
Cu1—Cl2 | 2.590 (3) | C16—C17 | 1.423 (17) |
Cu2—O5 | 1.934 (8) | C16—H16A | 0.9900 |
Cu2—N5 | 1.986 (11) | C16—H16B | 0.9900 |
Cu2—N4 | 1.993 (10) | C17—O3 | 1.202 (14) |
Cu2—N6 | 2.004 (10) | C17—O4 | 1.385 (15) |
Cu2—Cl1 | 2.608 (3) | C18—C19 | 1.387 (17) |
N1—C5 | 1.313 (15) | C18—H18 | 0.9500 |
N1—C1 | 1.321 (17) | C19—C20 | 1.348 (18) |
N2—C12 | 1.308 (17) | C19—H19 | 0.9500 |
N2—C6 | 1.374 (16) | C20—C21 | 1.418 (18) |
N3—C14 | 1.495 (12) | C20—H20 | 0.9500 |
N3—H3A | 0.9200 | C21—C22 | 1.424 (16) |
N3—H3B | 0.9200 | C21—C24 | 1.432 (18) |
N4—C22 | 1.331 (15) | C22—C23 | 1.415 (17) |
N4—C18 | 1.353 (16) | C23—C26 | 1.392 (18) |
N5—C29 | 1.327 (16) | C24—C25 | 1.35 (2) |
N5—C23 | 1.398 (14) | C24—H24 | 0.9500 |
N6—C31 | 1.475 (12) | C25—C26 | 1.427 (18) |
N6—H6A | 0.9200 | C25—H25 | 0.9500 |
N6—H6B | 0.9200 | C26—C27 | 1.448 (16) |
C1—C2 | 1.397 (18) | C27—C28 | 1.363 (17) |
C1—H1 | 0.9500 | C27—H27 | 0.9500 |
C2—C3 | 1.372 (17) | C28—C29 | 1.384 (18) |
C2—H2 | 0.9500 | C28—H28 | 0.9500 |
C3—C4 | 1.371 (19) | C29—H29 | 0.9500 |
C3—H3 | 0.9500 | C30—O6 | 1.243 (14) |
C4—C5 | 1.426 (17) | C30—O5 | 1.269 (13) |
C4—C7 | 1.444 (17) | C30—C31 | 1.531 (15) |
C5—C6 | 1.439 (17) | C31—C32 | 1.496 (15) |
C6—C9 | 1.377 (17) | C31—H31 | 1.0000 |
C7—C8 | 1.355 (18) | C32—C33 | 1.542 (17) |
C7—H7 | 0.9500 | C32—H32A | 0.9900 |
C8—C9 | 1.444 (17) | C32—H32B | 0.9900 |
C8—H8 | 0.9500 | C33—C34 | 1.524 (16) |
C9—C10 | 1.380 (19) | C33—H33A | 0.9900 |
C10—C11 | 1.378 (19) | C33—H33B | 0.9900 |
C10—H10 | 0.9500 | C34—O7 | 1.204 (14) |
C11—C12 | 1.399 (17) | C34—O8 | 1.313 (14) |
C11—H11 | 0.9500 | O4—H4A | 0.81 (5) |
C12—H12 | 0.9500 | O8—H8A | 0.84 (4) |
C13—O2 | 1.239 (13) | O9—H9A | 0.90 (5) |
C13—O1 | 1.281 (13) | O9—H9B | 0.87 (5) |
C13—C14 | 1.539 (13) | O10—H10A | 0.83 (5) |
C14—C15 | 1.495 (13) | O10—H10B | 0.89 (5) |
O1—Cu1—N3 | 84.6 (4) | C15—C14—C13 | 116.0 (8) |
O1—Cu1—N1 | 92.4 (4) | N3—C14—H14 | 105.8 |
N3—Cu1—N1 | 170.8 (4) | C15—C14—H14 | 105.8 |
O1—Cu1—N2 | 166.2 (4) | C13—C14—H14 | 105.8 |
N3—Cu1—N2 | 99.2 (4) | C16—C15—C14 | 116.8 (9) |
N1—Cu1—N2 | 81.8 (4) | C16—C15—H15A | 108.1 |
O1—Cu1—Cl2 | 95.9 (3) | C14—C15—H15A | 108.1 |
N3—Cu1—Cl2 | 93.1 (3) | C16—C15—H15B | 108.1 |
N1—Cu1—Cl2 | 95.9 (3) | C14—C15—H15B | 108.1 |
N2—Cu1—Cl2 | 97.2 (3) | H15A—C15—H15B | 107.3 |
O5—Cu2—N5 | 93.4 (3) | C17—C16—C15 | 115.2 (9) |
O5—Cu2—N4 | 167.4 (4) | C17—C16—H16A | 108.5 |
N5—Cu2—N4 | 81.9 (4) | C15—C16—H16A | 108.5 |
O5—Cu2—N6 | 84.1 (4) | C17—C16—H16B | 108.5 |
N5—Cu2—N6 | 174.1 (4) | C15—C16—H16B | 108.5 |
N4—Cu2—N6 | 99.3 (4) | H16A—C16—H16B | 107.5 |
O5—Cu2—Cl1 | 97.8 (3) | O3—C17—O4 | 113.7 (12) |
N5—Cu2—Cl1 | 94.6 (3) | O3—C17—C16 | 129.0 (11) |
N4—Cu2—Cl1 | 94.2 (3) | O4—C17—C16 | 117.3 (10) |
N6—Cu2—Cl1 | 91.0 (3) | N4—C18—C19 | 122.8 (11) |
C5—N1—C1 | 119.8 (11) | N4—C18—H18 | 118.6 |
C5—N1—Cu1 | 113.0 (8) | C19—C18—H18 | 118.6 |
C1—N1—Cu1 | 127.2 (9) | C20—C19—C18 | 121.4 (12) |
C12—N2—C6 | 120.7 (10) | C20—C19—H19 | 119.3 |
C12—N2—Cu1 | 128.8 (9) | C18—C19—H19 | 119.3 |
C6—N2—Cu1 | 110.5 (8) | C19—C20—C21 | 119.0 (11) |
C14—N3—Cu1 | 107.3 (6) | C19—C20—H20 | 120.5 |
C14—N3—H3A | 110.3 | C21—C20—H20 | 120.5 |
Cu1—N3—H3A | 110.2 | C20—C21—C22 | 114.8 (12) |
C14—N3—H3B | 110.3 | C20—C21—C24 | 125.2 (10) |
Cu1—N3—H3B | 110.3 | C22—C21—C24 | 120.0 (11) |
H3A—N3—H3B | 108.5 | N4—C22—C23 | 117.2 (10) |
C22—N4—C18 | 115.1 (10) | N4—C22—C21 | 126.8 (11) |
C22—N4—Cu2 | 113.5 (8) | C23—C22—C21 | 116.0 (11) |
C18—N4—Cu2 | 131.3 (9) | C26—C23—N5 | 122.1 (12) |
C29—N5—C23 | 117.6 (11) | C26—C23—C22 | 123.2 (10) |
C29—N5—Cu2 | 129.9 (9) | N5—C23—C22 | 114.7 (11) |
C23—N5—Cu2 | 112.5 (9) | C25—C24—C21 | 122.7 (11) |
C31—N6—Cu2 | 110.8 (7) | C25—C24—H24 | 118.7 |
C31—N6—H6A | 109.5 | C21—C24—H24 | 118.7 |
Cu2—N6—H6A | 109.5 | C24—C25—C26 | 118.3 (13) |
C31—N6—H6B | 109.5 | C24—C25—H25 | 120.8 |
Cu2—N6—H6B | 109.5 | C26—C25—H25 | 120.8 |
H6A—N6—H6B | 108.1 | C23—C26—C25 | 119.8 (12) |
N1—C1—C2 | 120.1 (12) | C23—C26—C27 | 117.5 (11) |
N1—C1—H1 | 119.9 | C25—C26—C27 | 122.7 (12) |
C2—C1—H1 | 119.9 | C28—C27—C26 | 118.9 (12) |
C3—C2—C1 | 121.1 (12) | C28—C27—H27 | 120.6 |
C3—C2—H2 | 119.4 | C26—C27—H27 | 120.6 |
C1—C2—H2 | 119.4 | C27—C28—C29 | 119.9 (11) |
C4—C3—C2 | 118.8 (12) | C27—C28—H28 | 120.0 |
C4—C3—H3 | 120.6 | C29—C28—H28 | 120.0 |
C2—C3—H3 | 120.6 | N5—C29—C28 | 123.9 (11) |
C3—C4—C5 | 116.8 (11) | N5—C29—H29 | 118.0 |
C3—C4—C7 | 126.3 (12) | C28—C29—H29 | 118.0 |
C5—C4—C7 | 116.9 (12) | O6—C30—O5 | 124.0 (11) |
N1—C5—C4 | 123.4 (11) | O6—C30—C31 | 118.0 (10) |
N1—C5—C6 | 118.4 (11) | O5—C30—C31 | 117.9 (9) |
C4—C5—C6 | 118.2 (11) | N6—C31—C32 | 114.8 (8) |
N2—C6—C9 | 120.3 (11) | N6—C31—C30 | 109.2 (8) |
N2—C6—C5 | 116.0 (10) | C32—C31—C30 | 112.8 (8) |
C9—C6—C5 | 123.7 (11) | N6—C31—H31 | 106.5 |
C8—C7—C4 | 123.4 (11) | C32—C31—H31 | 106.5 |
C8—C7—H7 | 118.3 | C30—C31—H31 | 106.5 |
C4—C7—H7 | 118.3 | C31—C32—C33 | 111.0 (9) |
C7—C8—C9 | 120.3 (11) | C31—C32—H32A | 109.4 |
C7—C8—H8 | 119.8 | C33—C32—H32A | 109.4 |
C9—C8—H8 | 119.8 | C31—C32—H32B | 109.4 |
C6—C9—C10 | 119.8 (12) | C33—C32—H32B | 109.4 |
C6—C9—C8 | 117.4 (11) | H32A—C32—H32B | 108.0 |
C10—C9—C8 | 122.8 (11) | C34—C33—C32 | 113.8 (11) |
C11—C10—C9 | 118.5 (11) | C34—C33—H33A | 108.8 |
C11—C10—H10 | 120.7 | C32—C33—H33A | 108.8 |
C9—C10—H10 | 120.7 | C34—C33—H33B | 108.8 |
C10—C11—C12 | 120.1 (12) | C32—C33—H33B | 108.8 |
C10—C11—H11 | 120.0 | H33A—C33—H33B | 107.7 |
C12—C11—H11 | 120.0 | O7—C34—O8 | 120.3 (10) |
N2—C12—C11 | 120.6 (12) | O7—C34—C33 | 123.3 (11) |
N2—C12—H12 | 119.7 | O8—C34—C33 | 116.4 (11) |
C11—C12—H12 | 119.7 | C13—O1—Cu1 | 115.7 (7) |
O2—C13—O1 | 123.6 (10) | C17—O4—H4A | 99 (6) |
O2—C13—C14 | 121.2 (10) | C30—O5—Cu2 | 116.6 (8) |
O1—C13—C14 | 115.2 (8) | C34—O8—H8A | 112 (6) |
N3—C14—C15 | 114.6 (8) | H9A—O9—H9B | 109 (8) |
N3—C14—C13 | 108.0 (8) | H10A—O10—H10B | 112 (8) |
O1—Cu1—N1—C5 | 171.7 (8) | Cu1—N3—C14—C15 | −162.6 (7) |
N2—Cu1—N1—C5 | 4.3 (8) | Cu1—N3—C14—C13 | −31.5 (9) |
Cl2—Cu1—N1—C5 | −92.2 (7) | O2—C13—C14—N3 | −153.3 (10) |
O1—Cu1—N1—C1 | −9.6 (10) | O1—C13—C14—N3 | 28.1 (12) |
N2—Cu1—N1—C1 | −177.0 (10) | O2—C13—C14—C15 | −23.1 (14) |
Cl2—Cu1—N1—C1 | 86.6 (10) | O1—C13—C14—C15 | 158.3 (9) |
O1—Cu1—N2—C12 | 110.1 (18) | N3—C14—C15—C16 | −51.8 (13) |
N3—Cu1—N2—C12 | 5.4 (11) | C13—C14—C15—C16 | −178.8 (10) |
N1—Cu1—N2—C12 | 176.2 (11) | C14—C15—C16—C17 | −161.1 (10) |
Cl2—Cu1—N2—C12 | −88.9 (11) | C15—C16—C17—O3 | 4 (2) |
O1—Cu1—N2—C6 | −70.4 (18) | C15—C16—C17—O4 | −176.3 (10) |
N3—Cu1—N2—C6 | −175.1 (7) | C22—N4—C18—C19 | −0.9 (16) |
N1—Cu1—N2—C6 | −4.3 (7) | Cu2—N4—C18—C19 | −177.5 (9) |
Cl2—Cu1—N2—C6 | 90.6 (7) | N4—C18—C19—C20 | 1.3 (18) |
O1—Cu1—N3—C14 | 22.5 (6) | C18—C19—C20—C21 | −1.2 (18) |
N2—Cu1—N3—C14 | −171.0 (6) | C19—C20—C21—C22 | 0.8 (16) |
Cl2—Cu1—N3—C14 | −73.1 (6) | C19—C20—C21—C24 | −177.9 (12) |
O5—Cu2—N4—C22 | 73 (2) | C18—N4—C22—C23 | 178.0 (10) |
N5—Cu2—N4—C22 | 4.0 (8) | Cu2—N4—C22—C23 | −4.8 (12) |
N6—Cu2—N4—C22 | 178.2 (8) | C18—N4—C22—C21 | 0.6 (16) |
Cl1—Cu2—N4—C22 | −90.1 (7) | Cu2—N4—C22—C21 | 177.8 (9) |
O5—Cu2—N4—C18 | −110.2 (18) | C20—C21—C22—N4 | −0.5 (17) |
N5—Cu2—N4—C18 | −179.3 (11) | C24—C21—C22—N4 | 178.3 (11) |
N6—Cu2—N4—C18 | −5.2 (11) | C20—C21—C22—C23 | −178.0 (10) |
Cl1—Cu2—N4—C18 | 86.6 (10) | C24—C21—C22—C23 | 0.8 (15) |
O5—Cu2—N5—C29 | 9.5 (10) | C29—N5—C23—C26 | 1.7 (15) |
N4—Cu2—N5—C29 | 177.8 (11) | Cu2—N5—C23—C26 | −178.0 (9) |
Cl1—Cu2—N5—C29 | −88.6 (10) | C29—N5—C23—C22 | −179.4 (10) |
O5—Cu2—N5—C23 | −170.9 (8) | Cu2—N5—C23—C22 | 0.9 (12) |
N4—Cu2—N5—C23 | −2.6 (7) | N4—C22—C23—C26 | −178.5 (10) |
Cl1—Cu2—N5—C23 | 91.0 (7) | C21—C22—C23—C26 | −0.8 (16) |
O5—Cu2—N6—C31 | 7.5 (7) | N4—C22—C23—N5 | 2.6 (15) |
N4—Cu2—N6—C31 | −160.3 (7) | C21—C22—C23—N5 | −179.7 (10) |
Cl1—Cu2—N6—C31 | 105.3 (7) | C20—C21—C24—C25 | 179.3 (13) |
C5—N1—C1—C2 | 0.1 (17) | C22—C21—C24—C25 | 0.6 (18) |
Cu1—N1—C1—C2 | −178.5 (8) | C21—C24—C25—C26 | −2.0 (19) |
N1—C1—C2—C3 | 0.8 (18) | N5—C23—C26—C25 | 178.3 (11) |
C1—C2—C3—C4 | −0.7 (18) | C22—C23—C26—C25 | −0.5 (17) |
C2—C3—C4—C5 | −0.4 (17) | N5—C23—C26—C27 | −2.3 (16) |
C2—C3—C4—C7 | −179.4 (10) | C22—C23—C26—C27 | 178.9 (11) |
C1—N1—C5—C4 | −1.2 (17) | C24—C25—C26—C23 | 1.9 (18) |
Cu1—N1—C5—C4 | 177.6 (8) | C24—C25—C26—C27 | −177.4 (12) |
C1—N1—C5—C6 | 177.6 (11) | C23—C26—C27—C28 | 1.2 (16) |
Cu1—N1—C5—C6 | −3.5 (13) | C25—C26—C27—C28 | −179.4 (11) |
C3—C4—C5—N1 | 1.3 (17) | C26—C27—C28—C29 | 0.5 (16) |
C7—C4—C5—N1 | −179.5 (10) | C23—N5—C29—C28 | 0.2 (16) |
C3—C4—C5—C6 | −177.5 (12) | Cu2—N5—C29—C28 | 179.8 (8) |
C7—C4—C5—C6 | 1.6 (15) | C27—C28—C29—N5 | −1.3 (17) |
C12—N2—C6—C9 | 4.0 (17) | Cu2—N6—C31—C32 | −139.7 (7) |
Cu1—N2—C6—C9 | −175.6 (10) | Cu2—N6—C31—C30 | −11.8 (10) |
C12—N2—C6—C5 | −176.7 (11) | O6—C30—C31—N6 | −170.9 (10) |
Cu1—N2—C6—C5 | 3.8 (12) | O5—C30—C31—N6 | 12.3 (13) |
N1—C5—C6—N2 | −0.3 (16) | O6—C30—C31—C32 | −41.9 (13) |
C4—C5—C6—N2 | 178.6 (9) | O5—C30—C31—C32 | 141.3 (10) |
N1—C5—C6—C9 | 179.0 (11) | N6—C31—C32—C33 | −56.5 (12) |
C4—C5—C6—C9 | −2.0 (18) | C30—C31—C32—C33 | 177.5 (9) |
C3—C4—C7—C8 | 178.6 (13) | C31—C32—C33—C34 | −168.2 (10) |
C5—C4—C7—C8 | −0.5 (17) | C32—C33—C34—O7 | 14.4 (17) |
C4—C7—C8—C9 | −0.4 (19) | C32—C33—C34—O8 | −164.4 (11) |
N2—C6—C9—C10 | −1.6 (18) | O2—C13—O1—Cu1 | 171.7 (9) |
C5—C6—C9—C10 | 179.1 (12) | C14—C13—O1—Cu1 | −9.7 (11) |
N2—C6—C9—C8 | −179.6 (10) | N3—Cu1—O1—C13 | −7.7 (8) |
C5—C6—C9—C8 | 1.1 (18) | N1—Cu1—O1—C13 | −179.0 (8) |
C7—C8—C9—C6 | 0.1 (18) | N2—Cu1—O1—C13 | −114.0 (17) |
C7—C8—C9—C10 | −177.8 (13) | Cl2—Cu1—O1—C13 | 84.9 (7) |
C6—C9—C10—C11 | −0.5 (18) | O6—C30—O5—Cu2 | 177.0 (9) |
C8—C9—C10—C11 | 177.4 (12) | C31—C30—O5—Cu2 | −6.4 (12) |
C9—C10—C11—C12 | 0.3 (19) | N5—Cu2—O5—C30 | 173.9 (8) |
C6—N2—C12—C11 | −4.2 (17) | N4—Cu2—O5—C30 | 106.0 (18) |
Cu1—N2—C12—C11 | 175.3 (8) | N6—Cu2—O5—C30 | −0.7 (8) |
C10—C11—C12—N2 | 2.0 (18) | Cl1—Cu2—O5—C30 | −90.9 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10B···O1i | 0.89 (5) | 2.56 (6) | 3.313 (12) | 143 (6) |
O10—H10B···O2i | 0.89 (5) | 1.92 (5) | 2.771 (13) | 159 (7) |
O9—H9B···O6ii | 0.87 (5) | 2.13 (7) | 2.774 (12) | 130 (7) |
O8—H8A···O9iii | 0.84 (4) | 1.82 (6) | 2.587 (12) | 152 (8) |
O4—H4A···O10 | 0.81 (5) | 1.86 (6) | 2.592 (13) | 149 (9) |
O10—H10A···Cl1 | 0.83 (5) | 2.38 (6) | 3.136 (10) | 153 (8) |
O9—H9A···Cl2iv | 0.90 (5) | 2.26 (6) | 3.112 (10) | 157 (7) |
N6—H6B···Cl2 | 0.92 | 2.84 | 3.423 (11) | 123 |
N6—H6A···O10iii | 0.92 | 2.18 | 3.009 (14) | 149 |
N3—H3B···O9 | 0.92 | 2.12 | 3.017 (14) | 164 |
N3—H3A···Cl1 | 0.92 | 2.57 | 3.440 (10) | 158 |
Symmetry codes: (i) x+1, y−1, z; (ii) x, y+1, z; (iii) x−1, y, z; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [CuCl(C5H8NO4)(C12H8N2)]·H2O |
Mr | 443.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 8.3022 (14), 10.0591 (17), 12.393 (2) |
α, β, γ (°) | 66.730 (2), 72.047 (2), 68.828 (2) |
V (Å3) | 869.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.55 × 0.40 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.474, 0.561 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4229, 3578, 3455 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.121, 1.10 |
No. of reflections | 3578 |
No. of parameters | 506 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.75 |
Absolute structure | Flack (1983), with x Friedel pairs |
Absolute structure parameter | −0.02 (3) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1999), SHELXTL/PC.
Cu1—O1 | 1.937 (8) | N3—C14 | 1.495 (12) |
Cu1—N3 | 1.979 (11) | N6—C31 | 1.475 (12) |
Cu1—N1 | 2.016 (10) | C13—O2 | 1.239 (13) |
Cu1—N2 | 2.057 (9) | C13—O1 | 1.281 (13) |
Cu1—Cl2 | 2.590 (3) | C17—O3 | 1.202 (14) |
Cu2—O5 | 1.934 (8) | C17—O4 | 1.385 (15) |
Cu2—N5 | 1.986 (11) | C30—O6 | 1.243 (14) |
Cu2—N4 | 1.993 (10) | C30—O5 | 1.269 (13) |
Cu2—N6 | 2.004 (10) | C34—O7 | 1.204 (14) |
Cu2—Cl1 | 2.608 (3) | C34—O8 | 1.313 (14) |
O1—Cu1—N3 | 84.6 (4) | O5—Cu2—Cl1 | 97.8 (3) |
N1—Cu1—N2 | 81.8 (4) | N5—Cu2—Cl1 | 94.6 (3) |
O1—Cu1—Cl2 | 95.9 (3) | N4—Cu2—Cl1 | 94.2 (3) |
N3—Cu1—Cl2 | 93.1 (3) | N6—Cu2—Cl1 | 91.0 (3) |
N1—Cu1—Cl2 | 95.9 (3) | O2—C13—O1 | 123.6 (10) |
N2—Cu1—Cl2 | 97.2 (3) | O3—C17—O4 | 113.7 (12) |
O5—Cu2—N5 | 93.4 (3) | O6—C30—O5 | 124.0 (11) |
O5—Cu2—N6 | 84.1 (4) | O7—C34—O8 | 120.3 (10) |
O1—Cu1—N1—C5 | 171.7 (8) | O5—Cu2—N4—C22 | 73 (2) |
Cl2—Cu1—N1—C5 | −92.2 (7) | N6—Cu2—N4—C22 | 178.2 (8) |
O1—Cu1—N1—C1 | −9.6 (10) | N6—Cu2—N4—C18 | −5.2 (11) |
N3—Cu1—N2—C12 | 5.4 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10B···O1i | 0.89 (5) | 2.56 (6) | 3.313 (12) | 143 (6) |
O10—H10B···O2i | 0.89 (5) | 1.92 (5) | 2.771 (13) | 159 (7) |
O9—H9B···O6ii | 0.87 (5) | 2.13 (7) | 2.774 (12) | 130 (7) |
O8—H8A···O9iii | 0.84 (4) | 1.82 (6) | 2.587 (12) | 152 (8) |
O4—H4A···O10 | 0.81 (5) | 1.86 (6) | 2.592 (13) | 149 (9) |
O10—H10A···Cl1 | 0.83 (5) | 2.38 (6) | 3.136 (10) | 153 (8) |
O9—H9A···Cl2iv | 0.90 (5) | 2.26 (6) | 3.112 (10) | 157 (7) |
N6—H6A···O10iii | 0.92 | 2.18 | 3.009 (14) | 149 |
N3—H3B···O9 | 0.92 | 2.12 | 3.017 (14) | 164 |
N3—H3A···Cl1 | 0.92 | 2.57 | 3.440 (10) | 158 |
Symmetry codes: (i) x+1, y−1, z; (ii) x, y+1, z; (iii) x−1, y, z; (iv) x+1, y, z. |
In recent years, ternary copper(II) complexes have attracted significant attention due to their range of properties, which include interactions with DNA (Chikira et al., 2002), anticonvulsant activity (Viossat et al., 2003), nuclease activity (Garcýa-Raso et al., 2003), and interactions of copper(II) with nucleotides and nucleosides (Gasowska, 2003; Lomozik & Jastrzáb, 2003). A variety of ternary complexes involving copper, 1,10-phenanthroline (phen) and α-amino acids have been described (Anitolini et al., 1983, 1985; Moreno-Esparza et al., 1995; Solans et al., 1988; Venkatraman et al., 1999). Here, we report the crystal structure of the title novel copper, phenanthroline and α-amino acid ternary complex, (I). \sch
Some features of the molecular geometry of (I) are listed in Table 1. The molecular conformation and crystal packing are illustrated in Figs. 1 and 2, respectively. In this ternary complex, there are two neutral molecules in the asymmetric unit. The Cu ions in each complex have distorted square-pyramidal coordination geometry, with one bidentate phenanthroline ligand, one O,N-bidentate L-glutamic acid monovalent anion (with protonated γ-carboxylate) and an apical Cl− anion, in contrast with the structure of [Cu(phen)(L-glu)(H2O)] (Anitolini et al., 1985), in which the Cu ions also have distorted square-pyramidal coordination geometry with a bidentate phenanthroline ligand, but an O,N-bidentate L-glutamic acid divalent anion (with ionized γ-carboxyl) and an apical coordinating water O atom.
The four equatorial donor atoms in (I) (N1, N2, N3 and O1, or N4, N5, N6 and O5) are nearly coplanar, with respective r.m.s. deviations of 0.0347 and 0.0526 Å in the two independent molecules, and the displacements of the Cu atoms toward the apical Cl− ligand are 0.191 (5) and 0.151 (5) Å, respectively. The angles between the planes of the Cu-phenanthroline (atoms C1—C12/N1/N2/Cu1 or C18–29/N4/N5/Cu2) and the aminocarboxylate chelation ring (atoms C13/C14/Cu1/O1/N3 or C30/C31/Cu2/O5/N6) are 6.1 (5) and 11.8 (5)°, respectively, i.e. somewhat different in the two molecules. This variability in the angles between planes defined by chelation rings is also observed in ternary copper complexes with phenanthroline and other amino acids (Anitolini et al. 1985; Moreno-Esparza et al., 1995).
The Cu coordination distances are listed in Table 1. The Cu—N coordination bond lengths to the phenanthroline ligand are in the range 1.986 (11)–2.057 (9) Å; these and the other Cu coordination distances are typically observed in many other related structures (Anitolini et al., 1983, 1985; Moreno-Esparza et al., 1995; Solans et al., 1988; Venkatraman et al., 1999). The Cu—Cl bond lengths are 2.608 (3) and 2.590 (3) Å in the two molecules, slightly longer than the value of 2.546 Å observed for the Cu—Cl bond in the analogous chloro(glycinato)(1,10-phenanthroline)copper complex (Solans et al., 1988), but similar to that (2.602 Å) observed in the complex [Cu2(phen)2(OH)2(H2O)2][Cu2(phen)2(OH)2Cl2]Cl2·6H2O (Lu et al., 2003). In addition, Fig.2 shows that the Cu ions are coordinated by the O atom of an α-carboxylate group from a neighbouring asymmetric unit, forming a weak sixth coordination ligand, with Cu2—O2i and Cu1—O6ii distances of 3.275 and 3.215 Å, respectively [symmetry codes: (i) x, y − 1, z; x, y + 1, z]. Therefore, the overall coordination geometry is actually octahedral. This octahedral coordination geometry is also found in a similar L-proline ternary complex (Venkatraman et al., 1999), in which the weak sixth coordinating α-carboxyl O atom is from another ternary complex in same asymmetric unit.
The hydrogen-bonding geometry in (I) is listed in Table 2. As illustrated in Figs. 1 and 2 and Table 2, a number of intra- and intermolecular hydrogen bonds stabilize the crystal structure of (I). These hydrogen bonds are formed mainly between water molecules and α-amino N atoms, α-carboxyl and γ-carboxyl O atoms, and O atoms and the coordinating Cl− anions. Hydrogen bonds also exist between α-amino N atoms and the Cl− ligands. It is worthy of mention that atom H10B is involved in an intermolecular three-centred hydrogen bond with atoms O1 and O2. Furthermore, the weak coordination by the sixth ligand also contributes to the intermolecular interactions observed in the crystal packing. The Cl− and carboxylate ligands together contribute to the extension of the intermolecular packing interactions throughout the crystal. Additionally, the complex molecules are arranged in such a way that symmetry-related phenanthroline planes of neighbouring complexes [the plane containing atoms C1—C12/N1/N2 and that containing atoms C18iii—C31iii/N4iii/N5iii; symmetry code: (iii) x, y + 1, z − 1] are orientated in parallel planes with phen-phen separations of about 3.42 Å, indicating siginificant π–π stacking interactions.