Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704473X/is2204sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704473X/is2204Isup2.hkl |
CCDC reference: 663624
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.009 Å
- R factor = 0.055
- wR factor = 0.109
- Data-to-parameter ratio = 11.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.99 From the CIF: _reflns_number_total 6743 Count of symmetry unique reflns 4046 Completeness (_total/calc) 166.66% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2697 Fraction of Friedel pairs measured 0.667 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C20 = . S PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.18 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2 (2) 2.28 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu3 (2) 2.46 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 8 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
Carnosine (67.8 mg, 0.3 mmol) dissolved in 10 ml deionized water and Cu(Ac)2.H20 (0.3 mmol) dissolved in 1 ml deionized water were mixed. To the solution ethanol (4.2 ml) was added. The purple block crystal was formed after one week.
H atoms bonded to N and O atoms were located in a difference map and their positional parameters were refined, with Uiso(H) = 1.2Ueq(N,O). The refined distances are O—H = 0.83 (8)–0.96 (7) Å and N—H = 0.85 (8)–0.87 (7) Å. Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C).
It has been reported that organic copper complexes can induce apoptosis in tumor tissues (Pang & Chau, 1999). Carnosine has been extensively investigated as a physiological buffer, an antioxidant, a metal chelator and a radical scavenger (Hobart et al., 2004; Babizhayev et al., 1994). To study the antioxidant activity and the copper-chelating capability of carnosine, the title compound was synthesized and characterized.
There are one and half dicopper complex molecules in the asymmetric unit (Fig. 1). The dicopper complex consists of two copper atoms, two ligand molecules and two coordinated water molecules. Two ligands bridge and form a circular configuration with two copper atoms. Each copper atom adopts a square pyramidal coordination with the copper atom in the center of the square. The square is formed by two N atoms and one O atom from one ligand and one N atom from another ligand, while the axial position is occupied by a coordinated water molecule. There are three chiral carbon atoms, C2, C11 and C20 in the molecules, which are in S configuration. In the crystal packing there are uncoordinated water molecules that bridge neighboring complex molecules by hydrogen bonds and are important for the 3-D structure (Fig. 2).
For related literature, see: Pang & Chau (1999); Hobart et al. (2004); Babizhayev et al. (1994).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
[Cu2(C9H10N4O3)2(H2O)2]·2H2O | F(000) = 1980 |
Mr = 643.56 | Dx = 1.669 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 2360 reflections |
a = 14.598 (9) Å | θ = 2.7–24.8° |
b = 8.627 (5) Å | µ = 1.73 mm−1 |
c = 30.508 (19) Å | T = 291 K |
β = 90.322 (3)° | Block, purple |
V = 3842 (4) Å3 | 0.30 × 0.26 × 0.24 mm |
Z = 6 |
Bruker SMART APEX CCD diffractometer | 6743 independent reflections |
Radiation source: sealed tube | 5342 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
φ and ω scans | θmax = 26.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −18→15 |
Tmin = 0.61, Tmax = 0.67 | k = −7→10 |
10436 measured reflections | l = −36→37 |
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)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0545P)2 + 1.22P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
6743 reflections | Δρmax = 0.42 e Å−3 |
568 parameters | Δρmin = −0.77 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 2717 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.020 (15) |
[Cu2(C9H10N4O3)2(H2O)2]·2H2O | V = 3842 (4) Å3 |
Mr = 643.56 | Z = 6 |
Monoclinic, C2 | Mo Kα radiation |
a = 14.598 (9) Å | µ = 1.73 mm−1 |
b = 8.627 (5) Å | T = 291 K |
c = 30.508 (19) Å | 0.30 × 0.26 × 0.24 mm |
β = 90.322 (3)° |
Bruker SMART APEX CCD diffractometer | 6743 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 5342 reflections with I > 2σ(I) |
Tmin = 0.61, Tmax = 0.67 | Rint = 0.030 |
10436 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | Δρmax = 0.42 e Å−3 |
S = 1.07 | Δρmin = −0.77 e Å−3 |
6743 reflections | Absolute structure: Flack (1983), 2717 Friedel pairs |
568 parameters | Absolute structure parameter: 0.020 (15) |
1 restraint |
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 | ||
C1 | 0.5715 (4) | 0.2703 (7) | 0.40534 (19) | 0.0465 (15) | |
C2 | 0.6209 (4) | 0.3479 (8) | 0.4437 (2) | 0.0526 (16) | |
H2A | 0.6138 | 0.2817 | 0.4696 | 0.063* | |
C3 | 0.7769 (5) | 0.3748 (9) | 0.4668 (2) | 0.0620 (19) | |
C4 | 0.8756 (4) | 0.4282 (9) | 0.4619 (2) | 0.0590 (18) | |
H4A | 0.8796 | 0.5377 | 0.4688 | 0.071* | |
H4C | 0.9140 | 0.3722 | 0.4825 | 0.071* | |
C5 | 0.9097 (5) | 0.4023 (9) | 0.4170 (2) | 0.0614 (19) | |
H5A | 0.9665 | 0.3544 | 0.4144 | 0.074* | |
C6 | 0.5815 (4) | 0.5047 (7) | 0.45415 (15) | 0.0374 (13) | |
H6A | 0.5162 | 0.4940 | 0.4591 | 0.045* | |
H6B | 0.6091 | 0.5426 | 0.4811 | 0.045* | |
C7 | 0.5963 (4) | 0.6198 (7) | 0.41921 (17) | 0.0403 (13) | |
C8 | 0.5681 (4) | 0.6289 (6) | 0.37706 (16) | 0.0357 (12) | |
H8A | 0.5298 | 0.5569 | 0.3636 | 0.043* | |
C9 | 0.6537 (4) | 0.8302 (8) | 0.38718 (17) | 0.0483 (14) | |
H9A | 0.6853 | 0.9227 | 0.3830 | 0.058* | |
C10 | 0.4564 (4) | 0.6099 (8) | 0.26138 (19) | 0.0459 (14) | |
C11 | 0.5162 (4) | 0.6449 (7) | 0.22274 (18) | 0.0429 (14) | |
H11A | 0.4775 | 0.6679 | 0.1972 | 0.051* | |
C12 | 0.6075 (4) | 0.8534 (8) | 0.19779 (19) | 0.0484 (15) | |
C13 | 0.6801 (4) | 0.9761 (8) | 0.20578 (18) | 0.0460 (14) | |
H13A | 0.7394 | 0.9311 | 0.1993 | 0.055* | |
H13C | 0.6700 | 1.0599 | 0.1851 | 0.055* | |
C14 | 0.6843 (4) | 1.0421 (9) | 0.24954 (19) | 0.0532 (17) | |
H14A | 0.6828 | 1.1495 | 0.2520 | 0.064* | |
C15 | 0.5762 (4) | 0.5020 (7) | 0.21278 (17) | 0.0412 (13) | |
H15A | 0.5367 | 0.4125 | 0.2092 | 0.049* | |
H15B | 0.6073 | 0.5189 | 0.1852 | 0.049* | |
C16 | 0.6435 (4) | 0.4680 (7) | 0.24593 (17) | 0.0379 (12) | |
C17 | 0.6350 (4) | 0.4175 (6) | 0.28876 (18) | 0.0364 (12) | |
H17A | 0.5795 | 0.3958 | 0.3023 | 0.044* | |
C18 | 0.7772 (4) | 0.4421 (8) | 0.27869 (18) | 0.0461 (15) | |
H18A | 0.8403 | 0.4390 | 0.2831 | 0.055* | |
C19 | 0.8858 (3) | 0.8743 (7) | 0.06998 (18) | 0.0393 (13) | |
C20 | 0.8977 (4) | 0.7637 (7) | 0.1103 (2) | 0.0421 (14) | |
H20A | 0.8676 | 0.8099 | 0.1358 | 0.051* | |
C21 | 0.8262 (4) | 0.5350 (8) | 0.13383 (19) | 0.0507 (16) | |
C22 | 0.7617 (5) | 0.4025 (9) | 0.1221 (2) | 0.065 (2) | |
H22A | 0.7556 | 0.3365 | 0.1476 | 0.078* | |
H22B | 0.7018 | 0.4461 | 0.1158 | 0.078* | |
C23 | 0.7884 (4) | 0.3043 (8) | 0.08456 (19) | 0.0517 (14) | |
H23A | 0.7858 | 0.1970 | 0.0871 | 0.062* | |
C24 | 0.9974 (4) | 0.7407 (7) | 0.12051 (19) | 0.0417 (13) | |
H24A | 1.0030 | 0.6802 | 0.1472 | 0.050* | |
H24B | 1.0252 | 0.8411 | 0.1260 | 0.050* | |
C25 | 1.0500 (4) | 0.6603 (7) | 0.0845 (2) | 0.0428 (13) | |
C26 | 1.0739 (4) | 0.6996 (8) | 0.0440 (2) | 0.0532 (16) | |
H26A | 1.0608 | 0.7951 | 0.0313 | 0.064* | |
C27 | 1.1294 (5) | 0.4756 (8) | 0.0539 (2) | 0.0515 (16) | |
H27A | 1.1604 | 0.3828 | 0.0495 | 0.062* | |
Cu1 | 0.73812 (5) | 0.34830 (9) | 0.37106 (3) | 0.0537 (2) | |
Cu2 | 0.58071 (5) | 0.81489 (9) | 0.29434 (2) | 0.0490 (2) | |
Cu3 | 0.84047 (5) | 0.58662 (8) | 0.03755 (2) | 0.04530 (19) | |
N1 | 0.7178 (3) | 0.3560 (7) | 0.43345 (17) | 0.0523 (14) | |
N2 | 0.8651 (4) | 0.4428 (8) | 0.37829 (19) | 0.0587 (16) | |
H2B | 0.889 (5) | 0.502 (10) | 0.359 (3) | 0.070* | |
N3 | 0.6032 (4) | 0.7577 (6) | 0.35642 (17) | 0.0517 (13) | |
N4 | 0.6521 (4) | 0.7493 (7) | 0.42513 (19) | 0.0541 (14) | |
H4B | 0.681 (5) | 0.774 (9) | 0.449 (2) | 0.065* | |
N5 | 0.5722 (4) | 0.7789 (6) | 0.23280 (16) | 0.0516 (14) | |
N6 | 0.6904 (4) | 0.9567 (7) | 0.28788 (18) | 0.0533 (14) | |
H6C | 0.735 (5) | 0.962 (9) | 0.307 (2) | 0.064* | |
N7 | 0.7169 (3) | 0.4038 (6) | 0.30806 (17) | 0.0467 (12) | |
N8 | 0.7368 (4) | 0.4864 (7) | 0.24148 (18) | 0.0527 (14) | |
H8B | 0.764 (5) | 0.520 (9) | 0.219 (2) | 0.063* | |
N9 | 0.8545 (3) | 0.6177 (6) | 0.10018 (16) | 0.0500 (14) | |
N10 | 0.8176 (4) | 0.3722 (7) | 0.04501 (18) | 0.0611 (16) | |
H10A | 0.826 (5) | 0.311 (10) | 0.023 (3) | 0.073* | |
N11 | 1.1189 (4) | 0.5860 (8) | 0.02374 (18) | 0.0619 (15) | |
N12 | 1.0886 (4) | 0.5171 (7) | 0.09179 (17) | 0.0522 (14) | |
H12E | 1.087 (5) | 0.465 (9) | 0.116 (2) | 0.063* | |
O1 | 0.6181 (3) | 0.2441 (5) | 0.37014 (15) | 0.0526 (11) | |
O2 | 0.4888 (3) | 0.2400 (5) | 0.40683 (14) | 0.0533 (11) | |
O3 | 0.7501 (3) | 0.3606 (6) | 0.50674 (16) | 0.0597 (13) | |
O4 | 0.4667 (3) | 0.6957 (6) | 0.29549 (15) | 0.0547 (11) | |
O5 | 0.3989 (3) | 0.5042 (5) | 0.25906 (13) | 0.0527 (11) | |
O6 | 0.5853 (3) | 0.8218 (7) | 0.15888 (15) | 0.0660 (13) | |
O7 | 0.8104 (3) | 0.1061 (7) | 0.35354 (17) | 0.0590 (13) | |
H7B | 0.860 (5) | 0.126 (9) | 0.339 (3) | 0.071* | |
H7A | 0.824 (5) | 0.050 (10) | 0.375 (3) | 0.071* | |
O8 | 0.4985 (3) | 1.0486 (5) | 0.31269 (14) | 0.0478 (10) | |
H8C | 0.493 (4) | 1.112 (9) | 0.287 (2) | 0.057* | |
H8D | 0.531 (4) | 1.104 (8) | 0.335 (2) | 0.057* | |
O9 | 0.8477 (2) | 0.8128 (5) | 0.03590 (13) | 0.0486 (10) | |
O10 | 0.9102 (3) | 1.0069 (5) | 0.07319 (15) | 0.0545 (11) | |
O11 | 0.8329 (3) | 0.5820 (7) | 0.17319 (12) | 0.0581 (12) | |
O12 | 0.6810 (3) | 0.6007 (6) | 0.01956 (18) | 0.0618 (13) | |
H12C | 0.670 (5) | 0.569 (10) | −0.006 (3) | 0.074* | |
H12B | 0.653 (6) | 0.550 (10) | 0.039 (3) | 0.074* | |
O13 | 0.5775 (4) | 0.6092 (6) | 0.09253 (17) | 0.0668 (15) | |
H13B | 0.522 (6) | 0.616 (11) | 0.086 (3) | 0.080* | |
H13D | 0.592 (6) | 0.687 (11) | 0.108 (3) | 0.080* | |
O14 | 0.4370 (4) | 0.2051 (7) | 0.24037 (17) | 0.0623 (14) | |
H14B | 0.409 (5) | 0.286 (10) | 0.249 (3) | 0.075* | |
H14D | 0.401 (5) | 0.149 (10) | 0.226 (3) | 0.075* | |
O15 | 0.8596 (3) | 0.9559 (6) | 0.42679 (14) | 0.0502 (11) | |
H15C | 0.885 (5) | 0.871 (9) | 0.419 (2) | 0.060* | |
H15E | 0.813 (5) | 0.936 (9) | 0.442 (2) | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.043 (3) | 0.061 (4) | 0.036 (3) | 0.016 (3) | −0.002 (2) | 0.007 (3) |
C2 | 0.038 (3) | 0.060 (4) | 0.059 (4) | 0.018 (3) | −0.003 (3) | 0.000 (3) |
C3 | 0.057 (4) | 0.081 (5) | 0.048 (4) | 0.023 (4) | 0.011 (3) | 0.016 (3) |
C4 | 0.045 (4) | 0.076 (5) | 0.056 (4) | 0.017 (3) | 0.004 (3) | 0.013 (3) |
C5 | 0.067 (4) | 0.068 (5) | 0.049 (4) | −0.031 (4) | −0.005 (3) | 0.008 (3) |
C6 | 0.036 (3) | 0.058 (4) | 0.019 (2) | 0.021 (2) | 0.0077 (19) | 0.000 (2) |
C7 | 0.044 (3) | 0.046 (4) | 0.030 (3) | −0.008 (2) | 0.005 (2) | −0.002 (2) |
C8 | 0.038 (3) | 0.036 (3) | 0.033 (3) | −0.003 (2) | −0.001 (2) | 0.002 (2) |
C9 | 0.056 (3) | 0.060 (4) | 0.029 (3) | −0.012 (3) | 0.000 (2) | 0.001 (3) |
C10 | 0.042 (3) | 0.051 (4) | 0.044 (3) | 0.010 (3) | −0.009 (2) | 0.015 (3) |
C11 | 0.046 (3) | 0.058 (4) | 0.024 (3) | −0.006 (3) | −0.008 (2) | 0.019 (2) |
C12 | 0.045 (3) | 0.061 (4) | 0.039 (3) | −0.011 (3) | −0.009 (2) | 0.005 (3) |
C13 | 0.039 (3) | 0.063 (4) | 0.036 (3) | −0.006 (3) | 0.011 (2) | 0.010 (3) |
C14 | 0.057 (4) | 0.068 (5) | 0.035 (3) | −0.016 (3) | 0.004 (3) | −0.006 (3) |
C15 | 0.045 (3) | 0.047 (4) | 0.032 (3) | −0.004 (3) | −0.007 (2) | 0.018 (2) |
C16 | 0.039 (3) | 0.044 (3) | 0.031 (3) | 0.006 (2) | −0.001 (2) | 0.006 (2) |
C17 | 0.030 (3) | 0.042 (3) | 0.037 (3) | 0.007 (2) | 0.006 (2) | 0.004 (2) |
C18 | 0.035 (3) | 0.072 (5) | 0.031 (3) | −0.010 (3) | −0.003 (2) | −0.015 (3) |
C19 | 0.034 (3) | 0.042 (3) | 0.041 (3) | 0.010 (2) | 0.007 (2) | −0.011 (2) |
C20 | 0.045 (3) | 0.038 (3) | 0.044 (3) | 0.004 (2) | 0.003 (2) | −0.017 (2) |
C21 | 0.040 (3) | 0.070 (5) | 0.043 (3) | −0.015 (3) | 0.014 (3) | −0.014 (3) |
C22 | 0.076 (5) | 0.088 (6) | 0.032 (3) | −0.052 (4) | 0.026 (3) | −0.017 (3) |
C23 | 0.057 (3) | 0.055 (4) | 0.044 (3) | −0.009 (3) | 0.001 (2) | −0.001 (3) |
C24 | 0.034 (3) | 0.046 (3) | 0.045 (3) | 0.003 (2) | 0.001 (2) | −0.010 (3) |
C25 | 0.033 (3) | 0.040 (3) | 0.055 (4) | 0.001 (2) | 0.010 (2) | 0.001 (3) |
C26 | 0.052 (4) | 0.062 (4) | 0.046 (3) | 0.023 (3) | 0.021 (3) | 0.010 (3) |
C27 | 0.060 (4) | 0.040 (3) | 0.055 (4) | 0.003 (3) | 0.023 (3) | 0.008 (3) |
Cu1 | 0.0456 (4) | 0.0658 (6) | 0.0497 (4) | 0.0228 (4) | 0.0038 (3) | 0.0082 (4) |
Cu2 | 0.0527 (4) | 0.0620 (5) | 0.0323 (3) | 0.0025 (4) | −0.0052 (3) | 0.0086 (3) |
Cu3 | 0.0475 (4) | 0.0476 (4) | 0.0409 (4) | −0.0152 (3) | 0.0141 (3) | −0.0183 (3) |
N1 | 0.026 (2) | 0.071 (4) | 0.061 (3) | 0.022 (2) | 0.009 (2) | 0.016 (3) |
N2 | 0.064 (4) | 0.068 (4) | 0.044 (3) | −0.007 (3) | 0.003 (3) | 0.024 (3) |
N3 | 0.062 (3) | 0.054 (3) | 0.039 (3) | −0.008 (2) | 0.003 (2) | 0.009 (2) |
N4 | 0.052 (3) | 0.066 (4) | 0.045 (3) | −0.009 (3) | 0.001 (2) | 0.001 (3) |
N5 | 0.071 (3) | 0.050 (4) | 0.034 (3) | −0.002 (3) | −0.009 (2) | 0.007 (2) |
N6 | 0.066 (4) | 0.053 (3) | 0.041 (3) | −0.005 (3) | −0.026 (2) | 0.010 (2) |
N7 | 0.032 (2) | 0.064 (4) | 0.044 (3) | 0.003 (2) | 0.003 (2) | −0.008 (2) |
N8 | 0.044 (3) | 0.070 (4) | 0.044 (3) | −0.010 (3) | 0.009 (2) | 0.015 (3) |
N9 | 0.053 (3) | 0.051 (3) | 0.046 (3) | −0.029 (2) | 0.020 (2) | −0.020 (2) |
N10 | 0.078 (4) | 0.064 (4) | 0.042 (3) | −0.025 (3) | 0.017 (3) | −0.007 (3) |
N11 | 0.055 (3) | 0.072 (4) | 0.058 (3) | 0.027 (3) | 0.016 (2) | 0.023 (3) |
N12 | 0.064 (4) | 0.055 (3) | 0.037 (3) | 0.021 (3) | 0.010 (2) | 0.023 (2) |
O1 | 0.055 (3) | 0.058 (3) | 0.045 (2) | 0.012 (2) | 0.0050 (19) | 0.006 (2) |
O2 | 0.053 (3) | 0.066 (3) | 0.041 (2) | −0.010 (2) | 0.0113 (18) | −0.014 (2) |
O3 | 0.049 (2) | 0.066 (3) | 0.064 (3) | 0.033 (2) | 0.007 (2) | 0.002 (2) |
O4 | 0.053 (2) | 0.056 (3) | 0.055 (3) | 0.017 (2) | 0.006 (2) | 0.000 (2) |
O5 | 0.068 (3) | 0.053 (3) | 0.037 (2) | −0.016 (2) | 0.017 (2) | −0.0008 (19) |
O6 | 0.083 (3) | 0.058 (3) | 0.057 (3) | −0.027 (3) | −0.018 (2) | 0.010 (3) |
O7 | 0.047 (2) | 0.075 (4) | 0.056 (3) | 0.028 (2) | 0.008 (2) | −0.001 (3) |
O8 | 0.053 (2) | 0.055 (3) | 0.034 (2) | −0.010 (2) | −0.0091 (18) | 0.0044 (19) |
O9 | 0.042 (2) | 0.053 (3) | 0.051 (2) | 0.001 (2) | 0.0033 (17) | −0.018 (2) |
O10 | 0.060 (3) | 0.041 (3) | 0.062 (3) | 0.009 (2) | −0.031 (2) | −0.009 (2) |
O11 | 0.073 (3) | 0.076 (3) | 0.026 (2) | −0.031 (3) | 0.0172 (18) | −0.016 (2) |
O12 | 0.064 (3) | 0.064 (3) | 0.058 (3) | −0.036 (3) | −0.004 (2) | −0.022 (3) |
O13 | 0.081 (3) | 0.056 (3) | 0.064 (3) | −0.035 (3) | 0.028 (3) | −0.029 (3) |
O14 | 0.067 (3) | 0.068 (4) | 0.052 (3) | −0.027 (3) | −0.031 (2) | 0.022 (3) |
O15 | 0.042 (2) | 0.070 (3) | 0.038 (2) | −0.008 (2) | 0.0117 (18) | 0.002 (2) |
C1—O2 | 1.237 (7) | C20—H20A | 0.9800 |
C1—O1 | 1.294 (7) | C21—O11 | 1.271 (7) |
C1—C2 | 1.526 (9) | C21—N9 | 1.319 (8) |
C2—N1 | 1.452 (7) | C21—C22 | 1.522 (9) |
C2—C6 | 1.505 (8) | C22—C23 | 1.478 (9) |
C2—H2A | 0.9800 | C22—H22A | 0.9700 |
C3—O3 | 1.289 (8) | C22—H22B | 0.9700 |
C3—N1 | 1.339 (9) | C23—N10 | 1.410 (8) |
C3—C4 | 1.519 (10) | C23—H23A | 0.9300 |
C4—C5 | 1.476 (10) | C24—C25 | 1.511 (8) |
C4—H4A | 0.9700 | C24—H24A | 0.9700 |
C4—H4C | 0.9700 | C24—H24B | 0.9700 |
C5—N2 | 1.390 (9) | C25—C26 | 1.331 (8) |
C5—H5A | 0.9300 | C25—N12 | 1.375 (8) |
C6—C7 | 1.474 (8) | C26—N11 | 1.334 (8) |
C6—H6A | 0.9700 | C26—H26A | 0.9300 |
C6—H6B | 0.9700 | C27—N11 | 1.333 (8) |
C7—C8 | 1.350 (7) | C27—N12 | 1.352 (8) |
C7—N4 | 1.393 (8) | C27—H27A | 0.9300 |
C8—N3 | 1.377 (7) | Cu1—N1 | 1.929 (5) |
C8—H8A | 0.9300 | Cu1—O1 | 1.970 (5) |
C9—N3 | 1.345 (8) | Cu1—N7 | 2.003 (5) |
C9—N4 | 1.352 (8) | Cu1—N2 | 2.036 (6) |
C9—H9A | 0.9300 | Cu1—O7 | 2.402 (5) |
C10—O5 | 1.242 (7) | Cu2—N5 | 1.906 (5) |
C10—O4 | 1.285 (8) | Cu2—O4 | 1.956 (5) |
C10—C11 | 1.501 (8) | Cu2—N3 | 1.983 (5) |
C11—N5 | 1.448 (8) | Cu2—N6 | 2.026 (6) |
C11—C15 | 1.544 (9) | Cu2—O8 | 2.414 (5) |
C11—H11A | 0.9800 | Cu3—N10 | 1.893 (6) |
C12—O6 | 1.258 (7) | Cu3—N9 | 1.939 (5) |
C12—N5 | 1.351 (8) | Cu3—O9 | 1.955 (5) |
C12—C13 | 1.517 (8) | Cu3—N11i | 1.965 (5) |
C13—C14 | 1.452 (8) | Cu3—O12 | 2.392 (5) |
C13—H13A | 0.9700 | N2—H2B | 0.85 (8) |
C13—H13C | 0.9700 | N4—H4B | 0.86 (7) |
C14—N6 | 1.385 (8) | N6—H6C | 0.87 (7) |
C14—H14A | 0.9300 | N8—H8B | 0.85 (7) |
C15—C16 | 1.436 (7) | N10—H10A | 0.87 (8) |
C15—H15A | 0.9700 | N11—Cu3i | 1.965 (5) |
C15—H15B | 0.9700 | N12—H12E | 0.86 (7) |
C16—N8 | 1.379 (7) | O7—H7B | 0.86 (8) |
C16—C17 | 1.383 (7) | O7—H7A | 0.83 (8) |
C17—N7 | 1.335 (7) | O8—H8C | 0.96 (7) |
C17—H17A | 0.9300 | O8—H8D | 0.95 (7) |
C18—N7 | 1.303 (8) | O12—H12C | 0.85 (8) |
C18—N8 | 1.332 (8) | O12—H12B | 0.85 (8) |
C18—H18A | 0.9300 | O13—H13B | 0.84 (8) |
C19—O10 | 1.202 (7) | O13—H13D | 0.85 (9) |
C19—O9 | 1.290 (7) | O14—H14B | 0.85 (8) |
C19—C20 | 1.565 (9) | O14—H14D | 0.84 (8) |
C20—N9 | 1.441 (7) | O15—H15C | 0.86 (7) |
C20—C24 | 1.500 (8) | O15—H15E | 0.85 (8) |
O2—C1—O1 | 120.7 (6) | C25—C24—H24A | 108.8 |
O2—C1—C2 | 121.5 (5) | C20—C24—H24B | 108.8 |
O1—C1—C2 | 117.7 (5) | C25—C24—H24B | 108.8 |
N1—C2—C6 | 112.1 (6) | H24A—C24—H24B | 107.7 |
N1—C2—C1 | 108.2 (5) | C26—C25—N12 | 105.6 (5) |
C6—C2—C1 | 112.1 (5) | C26—C25—C24 | 134.0 (6) |
N1—C2—H2A | 108.1 | N12—C25—C24 | 120.3 (5) |
C6—C2—H2A | 108.1 | C25—C26—N11 | 112.1 (6) |
C1—C2—H2A | 108.1 | C25—C26—H26A | 124.0 |
O3—C3—N1 | 120.5 (6) | N11—C26—H26A | 124.0 |
O3—C3—C4 | 114.5 (6) | N11—C27—N12 | 110.6 (6) |
N1—C3—C4 | 124.7 (6) | N11—C27—H27A | 124.7 |
C5—C4—C3 | 111.7 (6) | N12—C27—H27A | 124.7 |
C5—C4—H4A | 109.3 | N1—Cu1—O1 | 83.6 (2) |
C3—C4—H4A | 109.3 | N1—Cu1—N7 | 156.1 (2) |
C5—C4—H4C | 109.3 | O1—Cu1—N7 | 87.86 (19) |
C3—C4—H4C | 109.3 | N1—Cu1—N2 | 91.4 (2) |
H4A—C4—H4C | 107.9 | O1—Cu1—N2 | 173.6 (2) |
N2—C5—C4 | 126.2 (7) | N7—Cu1—N2 | 98.3 (2) |
N2—C5—H5A | 116.9 | N1—Cu1—O7 | 108.6 (2) |
C4—C5—H5A | 116.9 | O1—Cu1—O7 | 89.52 (19) |
C7—C6—C2 | 113.3 (4) | N7—Cu1—O7 | 93.47 (19) |
C7—C6—H6A | 108.9 | N2—Cu1—O7 | 88.4 (2) |
C2—C6—H6A | 108.9 | N5—Cu2—O4 | 83.2 (2) |
C7—C6—H6B | 108.9 | N5—Cu2—N3 | 155.5 (2) |
C2—C6—H6B | 108.9 | O4—Cu2—N3 | 89.3 (2) |
H6A—C6—H6B | 107.7 | N5—Cu2—N6 | 92.8 (2) |
C8—C7—N4 | 104.6 (5) | O4—Cu2—N6 | 172.8 (2) |
C8—C7—C6 | 133.1 (5) | N3—Cu2—N6 | 96.7 (2) |
N4—C7—C6 | 122.3 (5) | N5—Cu2—O8 | 109.57 (19) |
C7—C8—N3 | 111.7 (5) | O4—Cu2—O8 | 90.63 (18) |
C7—C8—H8A | 124.1 | N3—Cu2—O8 | 93.8 (2) |
N3—C8—H8A | 124.1 | N6—Cu2—O8 | 85.0 (2) |
N3—C9—N4 | 110.1 (6) | N10—Cu3—N9 | 92.0 (2) |
N3—C9—H9A | 124.9 | N10—Cu3—O9 | 171.0 (2) |
N4—C9—H9A | 124.9 | N9—Cu3—O9 | 83.2 (2) |
O5—C10—O4 | 123.0 (6) | N10—Cu3—N11i | 99.6 (3) |
O5—C10—C11 | 119.9 (6) | N9—Cu3—N11i | 155.1 (2) |
O4—C10—C11 | 117.0 (6) | O9—Cu3—N11i | 87.8 (2) |
N5—C11—C10 | 108.9 (5) | N10—Cu3—O12 | 84.6 (2) |
N5—C11—C15 | 111.0 (5) | N9—Cu3—O12 | 108.4 (2) |
C10—C11—C15 | 109.1 (4) | O9—Cu3—O12 | 89.78 (17) |
N5—C11—H11A | 109.3 | N11i—Cu3—O12 | 94.6 (2) |
C10—C11—H11A | 109.3 | C3—N1—C2 | 117.8 (5) |
C15—C11—H11A | 109.3 | C3—N1—Cu1 | 130.6 (4) |
O6—C12—N5 | 123.1 (6) | C2—N1—Cu1 | 111.5 (4) |
O6—C12—C13 | 118.6 (5) | C5—N2—Cu1 | 114.4 (4) |
N5—C12—C13 | 118.3 (5) | C5—N2—H2B | 123 (5) |
C14—C13—C12 | 116.6 (5) | Cu1—N2—H2B | 123 (5) |
C14—C13—H13A | 108.2 | C9—N3—C8 | 105.1 (5) |
C12—C13—H13A | 108.2 | C9—N3—Cu2 | 129.6 (4) |
C14—C13—H13C | 108.2 | C8—N3—Cu2 | 125.3 (4) |
C12—C13—H13C | 108.2 | C9—N4—C7 | 108.5 (5) |
H13A—C13—H13C | 107.3 | C9—N4—H4B | 126 (5) |
N6—C14—C13 | 124.7 (6) | C7—N4—H4B | 126 (5) |
N6—C14—H14A | 117.6 | C12—N5—C11 | 115.4 (5) |
C13—C14—H14A | 117.6 | C12—N5—Cu2 | 132.7 (4) |
C16—C15—C11 | 114.3 (5) | C11—N5—Cu2 | 111.8 (4) |
C16—C15—H15A | 108.7 | C14—N6—Cu2 | 110.9 (4) |
C11—C15—H15A | 108.7 | C14—N6—H6C | 125 (5) |
C16—C15—H15B | 108.7 | Cu2—N6—H6C | 124 (5) |
C11—C15—H15B | 108.7 | C18—N7—C17 | 106.4 (5) |
H15A—C15—H15B | 107.6 | C18—N7—Cu1 | 128.2 (4) |
N8—C16—C17 | 102.9 (5) | C17—N7—Cu1 | 125.3 (4) |
N8—C16—C15 | 125.4 (5) | C18—N8—C16 | 108.4 (5) |
C17—C16—C15 | 131.7 (5) | C18—N8—H8B | 126 (5) |
N7—C17—C16 | 111.1 (5) | C16—N8—H8B | 125 (5) |
N7—C17—H17A | 124.5 | C21—N9—C20 | 116.4 (5) |
C16—C17—H17A | 124.5 | C21—N9—Cu3 | 131.3 (4) |
N7—C18—N8 | 111.1 (5) | C20—N9—Cu3 | 112.1 (4) |
N7—C18—H18A | 124.4 | C23—N10—Cu3 | 124.3 (5) |
N8—C18—H18A | 124.4 | C23—N10—H10A | 117 (5) |
O10—C19—O9 | 125.6 (6) | Cu3—N10—H10A | 118 (5) |
O10—C19—C20 | 119.0 (5) | C27—N11—C26 | 105.1 (5) |
O9—C19—C20 | 115.3 (5) | C27—N11—Cu3i | 128.7 (5) |
N9—C20—C24 | 110.6 (5) | C26—N11—Cu3i | 126.2 (5) |
N9—C20—C19 | 108.6 (5) | C27—N12—C25 | 106.4 (5) |
C24—C20—C19 | 110.3 (5) | C27—N12—H12E | 127 (5) |
N9—C20—H20A | 109.1 | C25—N12—H12E | 126 (5) |
C24—C20—H20A | 109.1 | C1—O1—Cu1 | 112.3 (4) |
C19—C20—H20A | 109.1 | C10—O4—Cu2 | 112.6 (4) |
O11—C21—N9 | 122.7 (6) | Cu1—O7—H7B | 108 (5) |
O11—C21—C22 | 120.4 (5) | Cu1—O7—H7A | 116 (6) |
N9—C21—C22 | 114.8 (5) | H7B—O7—H7A | 108 (7) |
C23—C22—C21 | 116.6 (5) | Cu2—O8—H8C | 109 (4) |
C23—C22—H22A | 108.1 | Cu2—O8—H8D | 109 (4) |
C21—C22—H22A | 108.1 | H8C—O8—H8D | 110 (6) |
C23—C22—H22B | 108.1 | C19—O9—Cu3 | 114.4 (4) |
C21—C22—H22B | 108.1 | Cu3—O12—H12C | 112 (5) |
H22A—C22—H22B | 107.3 | Cu3—O12—H12B | 107 (5) |
N10—C23—C22 | 120.5 (6) | H12C—O12—H12B | 113 (7) |
N10—C23—H23A | 119.8 | H13B—O13—H13D | 109 (9) |
C22—C23—H23A | 119.8 | H14B—O14—H14D | 109 (8) |
C20—C24—C25 | 113.9 (5) | H15C—O15—H15E | 110 (7) |
C20—C24—H24A | 108.8 |
Symmetry code: (i) −x+2, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O8ii | 0.85 (8) | 2.18 (8) | 2.945 (7) | 149 (7) |
N4—H4B···O3iii | 0.86 (7) | 1.84 (7) | 2.692 (8) | 168 (7) |
N6—H6C···O7iv | 0.87 (7) | 2.19 (7) | 2.950 (8) | 147 (7) |
N8—H8B···O11 | 0.85 (7) | 1.80 (7) | 2.650 (6) | 173 (7) |
N10—H10A···O12v | 0.87 (8) | 2.23 (8) | 3.061 (9) | 160 (7) |
N12—H12E···O6ii | 0.86 (7) | 1.80 (8) | 2.652 (7) | 168 (7) |
O7—H7B···O4ii | 0.86 (8) | 2.15 (8) | 2.998 (7) | 170 (7) |
O7—H7A···O15vi | 0.83 (8) | 1.85 (8) | 2.678 (7) | 170 (8) |
O8—H8C···O14iv | 0.96 (7) | 1.83 (7) | 2.734 (6) | 158 (6) |
O8—H8D···O1iv | 0.95 (7) | 2.05 (7) | 2.988 (6) | 166 (6) |
O8—H8D···O2iv | 0.95 (7) | 2.57 (7) | 3.317 (6) | 135 (5) |
O12—H12C···O9v | 0.85 (8) | 2.40 (8) | 3.032 (7) | 131 (7) |
O12—H12C···O10v | 0.85 (8) | 2.40 (8) | 3.223 (6) | 162 (7) |
O12—H12B···O13 | 0.85 (8) | 2.03 (8) | 2.698 (7) | 134 (7) |
O13—H13B···O10vii | 0.84 (8) | 1.92 (9) | 2.661 (7) | 147 (9) |
O13—H13D···O6 | 0.85 (9) | 1.94 (9) | 2.734 (7) | 155 (8) |
O14—H14B···O5 | 0.85 (8) | 1.92 (9) | 2.701 (8) | 153 (8) |
O14—H14D···O11vii | 0.84 (8) | 1.97 (8) | 2.757 (7) | 155 (8) |
O15—H15C···O2viii | 0.86 (7) | 1.92 (7) | 2.722 (7) | 154 (7) |
O15—H15E···O3iii | 0.85 (8) | 1.93 (8) | 2.718 (6) | 155 (7) |
Symmetry codes: (ii) x+1/2, y−1/2, z; (iii) −x+3/2, y+1/2, −z+1; (iv) x, y+1, z; (v) −x+3/2, y−1/2, −z; (vi) x, y−1, z; (vii) x−1/2, y−1/2, z; (viii) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C9H10N4O3)2(H2O)2]·2H2O |
Mr | 643.56 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 291 |
a, b, c (Å) | 14.598 (9), 8.627 (5), 30.508 (19) |
β (°) | 90.322 (3) |
V (Å3) | 3842 (4) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 1.73 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.61, 0.67 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10436, 6743, 5342 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.109, 1.07 |
No. of reflections | 6743 |
No. of parameters | 568 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.77 |
Absolute structure | Flack (1983), 2717 Friedel pairs |
Absolute structure parameter | 0.020 (15) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O8i | 0.85 (8) | 2.18 (8) | 2.945 (7) | 149 (7) |
N4—H4B···O3ii | 0.86 (7) | 1.84 (7) | 2.692 (8) | 168 (7) |
N6—H6C···O7iii | 0.87 (7) | 2.19 (7) | 2.950 (8) | 147 (7) |
N8—H8B···O11 | 0.85 (7) | 1.80 (7) | 2.650 (6) | 173 (7) |
N10—H10A···O12iv | 0.87 (8) | 2.23 (8) | 3.061 (9) | 160 (7) |
N12—H12E···O6i | 0.86 (7) | 1.80 (8) | 2.652 (7) | 168 (7) |
O7—H7B···O4i | 0.86 (8) | 2.15 (8) | 2.998 (7) | 170 (7) |
O7—H7A···O15v | 0.83 (8) | 1.85 (8) | 2.678 (7) | 170 (8) |
O8—H8C···O14iii | 0.96 (7) | 1.83 (7) | 2.734 (6) | 158 (6) |
O8—H8D···O1iii | 0.95 (7) | 2.05 (7) | 2.988 (6) | 166 (6) |
O8—H8D···O2iii | 0.95 (7) | 2.57 (7) | 3.317 (6) | 135 (5) |
O12—H12C···O9iv | 0.85 (8) | 2.40 (8) | 3.032 (7) | 131 (7) |
O12—H12C···O10iv | 0.85 (8) | 2.40 (8) | 3.223 (6) | 162 (7) |
O12—H12B···O13 | 0.85 (8) | 2.03 (8) | 2.698 (7) | 134 (7) |
O13—H13B···O10vi | 0.84 (8) | 1.92 (9) | 2.661 (7) | 147 (9) |
O13—H13D···O6 | 0.85 (9) | 1.94 (9) | 2.734 (7) | 155 (8) |
O14—H14B···O5 | 0.85 (8) | 1.92 (9) | 2.701 (8) | 153 (8) |
O14—H14D···O11vi | 0.84 (8) | 1.97 (8) | 2.757 (7) | 155 (8) |
O15—H15C···O2vii | 0.86 (7) | 1.92 (7) | 2.722 (7) | 154 (7) |
O15—H15E···O3ii | 0.85 (8) | 1.93 (8) | 2.718 (6) | 155 (7) |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+3/2, y+1/2, −z+1; (iii) x, y+1, z; (iv) −x+3/2, y−1/2, −z; (v) x, y−1, z; (vi) x−1/2, y−1/2, z; (vii) x+1/2, y+1/2, z. |
It has been reported that organic copper complexes can induce apoptosis in tumor tissues (Pang & Chau, 1999). Carnosine has been extensively investigated as a physiological buffer, an antioxidant, a metal chelator and a radical scavenger (Hobart et al., 2004; Babizhayev et al., 1994). To study the antioxidant activity and the copper-chelating capability of carnosine, the title compound was synthesized and characterized.
There are one and half dicopper complex molecules in the asymmetric unit (Fig. 1). The dicopper complex consists of two copper atoms, two ligand molecules and two coordinated water molecules. Two ligands bridge and form a circular configuration with two copper atoms. Each copper atom adopts a square pyramidal coordination with the copper atom in the center of the square. The square is formed by two N atoms and one O atom from one ligand and one N atom from another ligand, while the axial position is occupied by a coordinated water molecule. There are three chiral carbon atoms, C2, C11 and C20 in the molecules, which are in S configuration. In the crystal packing there are uncoordinated water molecules that bridge neighboring complex molecules by hydrogen bonds and are important for the 3-D structure (Fig. 2).