research communications
μ-2,4,6-trimethylbenzoato-κ2O:O′)bis[(nicotinamide-κN1)copper(II)]
of tetrakis(aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, cInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan, and dAksaray University, Department of Physics, 68100, Aksaray, Turkey
*Correspondence e-mail: merzifon@hacettepe.edu.tr
In the title binuclear CuII complex, [Cu2(C10H11O2)4(C6H6N2O)2], the two CuII cations [Cu⋯Cu = 2.5990 (5) Å] are bridged by four 2,4,6-trimethylbenzoate (TMB) anions. The four nearest O atoms around each CuII cation form distorted square-planar arrangements and the distorted square-pyramidal coordinations are completed by the pyridine N atoms of nicotinamide molecules at distances of 2.164 (2) and 2.165 (2) Å, respectively. The CuII cations are displaced by −0.2045 (3) and 0.2029 (3) Å from the corresponding planes formed by the nearest four O atoms. In the molecule, the dihedral angles between the planes of the benzene rings and the adjacent carboxylate groups are 80.6 (2), 51.4 (2), 24.4 (2) and 32.5 (2)°, while the planes of the pyridine rings are oriented at a dihedral angle of 11.28 (10)°. In the crystal, bifurcated N—H⋯O and weak C—H⋯O hydrogen bonds link the molecules, enclosing R22(8) and R44(8) ring motifs, into a three-dimensional network. The structure contains a solvent-accessible void of 72 Å3, but there is no solvent molecule located within this void. The crystal studied was an refined with a minor component of 0.488 (8).
CCDC reference: 1414247
1. Chemical context
Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974). It is thus of interest to determine the manner in which copper interacts with niacin and nicotinamide. In the structures of some complexes obtained from the reactions of CuII ions with NA, e.g. [Cu(sal)2(NA)2] (sal is salicylate) (Hoang et al., 1993) and [Cu(C7H3ClFO2)2(NA)2] (Hoang et al., 1995), NA is a monodentate ligand coordinating to CuII via its pyridine N atom. In its rare earth complexes, NA coordinates to the rare earth ion via only the O atoms of the substituents, not by the pyridine N atom (Poray-Koshits et al., 1976). Coordination via the amide N atom may also occur. Hence, NA may form molecular or polymeric structures affecting such properties of the compounds as their solubility.
The structure–function–coordination relationships of the arylcarboxylate ion in CuII complexes of benzoic acid derivatives may change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the pH and temperature of synthesis as in ZnII complexes of benzoic acid derivatives (Shnulin et al., 1981; Nadzhafov et al., 1981; Antsyshkina et al., 1980; Adiwidjaja et al., 1978). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974). In this context, we synthesized a CuII-containing compound with 2,4,6-trimethylbenzoate (TMB) and NA ligands, namely tetrakis(μ-2,4,6-trimethylbenzoato-κ2O:O′)bis[(nicotinamide-κN1)copper(II)], [Cu2(TMB)4(NA)2], and report herein its crystal structure.
2. Structural commentary
The binuclear title complex, [Cu2(TMB)4(NA)2], contains two CuII atoms surrounded by four TMB and two NA ligands (Fig. 1). The TMB groups act as bidentate bridging ligands. The Cu1⋯Cu2 [2.5990 (5) Å] distance is shorter than in [Cu2(C6H5COO)4(C10H14N2O)2] [2.613 (1) Å; Hökelek et al., 1995], [Cu2(C8H7O2)4(C6H6N2O)2] [2.6375 (6)Å; Necefoğlu et al., 2010], [Cu2(C6H5COO)4(py)2] [py is pyridine; 2.681 (1) Å; Usubaliev et al., 1980] and [Cu2(CH3COO)4(H2O)2] (2.64 Å; van Niekerk & Schoening, 1953). In metallic copper, the Cu—Cu bond length is 2.55 Å (Lee, 1986). The title complex has the smallest Cu⋯Cu distance after metallic copper. Therefore, a weak orbital interaction may exist between the two Cu atoms.
The average Cu—O distance is 1.972 (10) Å (Table 1) and four O atoms (O1/O4/O5/O7 and O2/O3/O6/O7) of the bridging TMB ligands around each Cu atom (Cu1 and Cu2) form distorted square-planar arrangements. The Cu1 and Cu2 atoms lie 0.2045 (3) Å below and 0.2029 (3) Å above the corresponding least-squares planes formed by the nearest O atoms, respectively. The average O—Cu—O bond angles are the same (89.4°) for both of Cu atoms. The distorted square-pyramidal coordination around each Cu atom (Cu1 and Cu2) is completed by the N atoms (N3 and N1) of the NA ligands (Table 1). The N3—Cu1⋯Cu2 and N1—Cu2⋯Cu1 angles are 176.46 (6) and 174.66 (7)°, respectively, and the dihedral angle between plane through atoms Cu1, O1, O2, C1, Cu2, O3, O4 and C11, and that through atoms Cu1, O5, O6, C21, Cu2, O7, O8 and C31 is 87.88 (3)°.
|
The near equalities of the C—O bonds in the carboxylate groups (Table 1) indicate delocalized bonding arrangements, rather than localized single and double bonds. Bond lengths and angles are in good agreement with the values reported for other copper complexes: [Cu(CH3CO2)2(py)]2 (Barclay & Kennard, 1961; Hanic et al., 1964), [Cu(CH2ClCO2)2(2Me-py)]2 (2Me-py is 2-methylpyridine; Davey & Stephens, 1970), [Cu2(CH3CO2)4(pyrazine)] (Morosin et al., 1975) and [Cu(C6H5CO2)2(py)]2 (Speier & Fulop, 1989).
The dihedral angles between planar carboxylate groups O1/O2/C1, O3/O4/C11, O5/O6/C21 and O7/O8/C31 and the adjacent benzene rings A (C2–C7), B (C12–C17), C (C22–C27) and D (C32–C37) are 80.6 (2), 51.4 (2), 24.4 (2) and 32.5 (2)°, respectively, while those between rings A, B, C, D, E (N1/C41–C45) and F (N3/C47–C51) are A/B = 11.68 (12), A/C = 83.97 (12), A/D = 69.30 (11), A/E = 79.41 (11), A/F = 74.72 (10), B/C = 84.41 (12), B/D = 73.91 (13), B/E = 70.46 (11), B/F = 67.39 (10), C/D = 34.92 (13), C/E = 51.82 (11), C/F = 43.92 (12), D/E = 69.74 (11), D/F = 58.56 (10) and E/F = 11.28 (10)°.
3. Supramolecular features
In the crystal, bifurcated N—H⋯On (n = nicotinamide) and C—Hpy⋯Oc (py = pyridine and c = carboxylate) hydrogen bonds (Table 2) link the molecules, enclosing R22(8) and R44(8) ring motifs (Bernstein et al., 1995) into a three-dimensional network (Fig. 2).
4. Refinement
The experimental details including the crystal data, data collection and . N- and C-bound H atoms were positioned geometrically, with N—H = 0.86 Å (for NH2) and C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = kUeq(C,N), where k = 1.5 for methyl H atoms and k = 1.2 for NH2 and aromatic H atoms.
are summarized in Table 35. Synthesis and crystallization
The title compound was prepared by the reaction of CuSO4 (0.40 g, 2.5 mmol) in H2O (100 ml) and nicotinamide (0.61 g, 5 mmol) in H2O (25 ml) with sodium 2,4,6-trimethylbenzoate (0.93 g, 5 mmol) in H2O (150 ml). The mixture was set aside to crystallize at ambient temperature for three weeks, giving green single crystals.
Supporting information
CCDC reference: 1414247
https://doi.org/10.1107/S2056989015013882/xu5858sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013882/xu5858Isup2.hkl
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).[Cu2(C10H11O2)4(C6H6N2O)2] | F(000) = 2136 |
Mr = 1024.11 | Dx = 1.324 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 9983 reflections |
a = 27.9186 (7) Å | θ = 2.2–28.1° |
b = 17.2843 (5) Å | µ = 0.89 mm−1 |
c = 10.7570 (3) Å | T = 296 K |
β = 98.204 (2)° | Block, green |
V = 5137.7 (2) Å3 | 0.45 × 0.38 × 0.23 mm |
Z = 4 |
Bruker SMART BREEZE CCD diffractometer | 12762 independent reflections |
Radiation source: fine-focus sealed tube | 9682 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
φ and ω scans | θmax = 28.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −37→37 |
Tmin = 0.62, Tmax = 0.91 | k = −23→23 |
64770 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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0515P)2 + 0.2754P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
12762 reflections | Δρmax = 0.65 e Å−3 |
626 parameters | Δρmin = −0.27 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 5232 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.488 (8) |
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 > 2sigma(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 | 0.239902 (12) | 0.411564 (19) | 0.30231 (3) | 0.03970 (9) | |
Cu2 | 0.280625 (12) | 0.30456 (2) | 0.18371 (3) | 0.04180 (10) | |
O1 | 0.20128 (7) | 0.42725 (13) | 0.13420 (18) | 0.0509 (6) | |
O2 | 0.22783 (7) | 0.32167 (13) | 0.04546 (18) | 0.0515 (6) | |
O3 | 0.32599 (7) | 0.29941 (16) | 0.34120 (17) | 0.0535 (5) | |
O4 | 0.28428 (8) | 0.37737 (14) | 0.45109 (19) | 0.0527 (6) | |
O5 | 0.29283 (9) | 0.47641 (15) | 0.2605 (2) | 0.0615 (6) | |
O6 | 0.31786 (9) | 0.39256 (15) | 0.1280 (2) | 0.0596 (7) | |
O7 | 0.19297 (7) | 0.33013 (14) | 0.3270 (2) | 0.0507 (6) | |
O8 | 0.23743 (8) | 0.23502 (14) | 0.2633 (2) | 0.0541 (6) | |
O9 | 0.44557 (8) | 0.12811 (17) | 0.2878 (2) | 0.0652 (6) | |
O10 | 0.06281 (8) | 0.55162 (17) | 0.2345 (3) | 0.0716 (7) | |
N1 | 0.31634 (9) | 0.21015 (16) | 0.1016 (2) | 0.0443 (6) | |
N2 | 0.46313 (10) | 0.06819 (19) | 0.1157 (3) | 0.0676 (8) | |
H2A | 0.4920 | 0.0571 | 0.1503 | 0.081* | |
H2B | 0.4534 | 0.0542 | 0.0396 | 0.081* | |
N3 | 0.20298 (9) | 0.50200 (15) | 0.3904 (2) | 0.0426 (6) | |
N4 | 0.04618 (10) | 0.60685 (19) | 0.4118 (3) | 0.0677 (8) | |
H4A | 0.0161 | 0.6123 | 0.3820 | 0.081* | |
H4B | 0.0567 | 0.6223 | 0.4867 | 0.081* | |
C1 | 0.19966 (11) | 0.3779 (2) | 0.0476 (3) | 0.0458 (7) | |
C2 | 0.16007 (13) | 0.38795 (19) | −0.0621 (3) | 0.0527 (8) | |
C3 | 0.11368 (14) | 0.3644 (2) | −0.0520 (4) | 0.0672 (10) | |
C4 | 0.07795 (15) | 0.3761 (2) | −0.1561 (4) | 0.0807 (12) | |
H4 | 0.0465 | 0.3600 | −0.1515 | 0.097* | |
C5 | 0.08796 (16) | 0.4107 (3) | −0.2648 (3) | 0.0781 (12) | |
C6 | 0.13336 (17) | 0.4347 (2) | −0.2702 (3) | 0.0790 (13) | |
H6 | 0.1399 | 0.4598 | −0.3424 | 0.095* | |
C7 | 0.17125 (14) | 0.4234 (2) | −0.1717 (3) | 0.0624 (9) | |
C8 | 0.10128 (15) | 0.3257 (3) | 0.0654 (4) | 0.1026 (17) | |
H8A | 0.0669 | 0.3274 | 0.0652 | 0.154* | |
H8B | 0.1172 | 0.3525 | 0.1381 | 0.154* | |
H8C | 0.1119 | 0.2729 | 0.0675 | 0.154* | |
C9 | 0.04713 (19) | 0.4217 (3) | −0.3750 (4) | 0.121 (2) | |
H9A | 0.0186 | 0.3952 | −0.3574 | 0.181* | |
H9B | 0.0570 | 0.4010 | −0.4502 | 0.181* | |
H9C | 0.0402 | 0.4759 | −0.3863 | 0.181* | |
C10 | 0.22098 (18) | 0.4523 (4) | −0.1810 (4) | 0.0955 (15) | |
H10A | 0.2278 | 0.4454 | −0.2652 | 0.143* | |
H10B | 0.2441 | 0.4240 | −0.1239 | 0.143* | |
H10C | 0.2230 | 0.5063 | −0.1597 | 0.143* | |
C11 | 0.31862 (10) | 0.33173 (18) | 0.4411 (3) | 0.0429 (7) | |
C12 | 0.35379 (10) | 0.3143 (2) | 0.5561 (2) | 0.0437 (7) | |
C13 | 0.40357 (10) | 0.3205 (2) | 0.5505 (3) | 0.0553 (8) | |
C14 | 0.43536 (11) | 0.3010 (3) | 0.6573 (3) | 0.0687 (10) | |
H14 | 0.4684 | 0.3058 | 0.6553 | 0.082* | |
C15 | 0.42023 (13) | 0.2751 (2) | 0.7651 (3) | 0.0631 (10) | |
C16 | 0.37164 (14) | 0.2692 (2) | 0.7671 (3) | 0.0649 (10) | |
H16 | 0.3609 | 0.2514 | 0.8399 | 0.078* | |
C17 | 0.33741 (11) | 0.2886 (2) | 0.6652 (3) | 0.0553 (9) | |
C18 | 0.42314 (14) | 0.3460 (3) | 0.4338 (4) | 0.0879 (14) | |
H18A | 0.4014 | 0.3828 | 0.3890 | 0.132* | |
H18B | 0.4262 | 0.3020 | 0.3812 | 0.132* | |
H18C | 0.4543 | 0.3696 | 0.4567 | 0.132* | |
C19 | 0.45624 (16) | 0.2522 (3) | 0.8763 (4) | 0.0939 (15) | |
H19A | 0.4399 | 0.2452 | 0.9482 | 0.141* | |
H19B | 0.4802 | 0.2920 | 0.8935 | 0.141* | |
H19C | 0.4716 | 0.2046 | 0.8583 | 0.141* | |
C20 | 0.28484 (13) | 0.2766 (3) | 0.6738 (4) | 0.0895 (17) | |
H20A | 0.2816 | 0.2466 | 0.7473 | 0.134* | |
H20B | 0.2698 | 0.2496 | 0.6005 | 0.134* | |
H20C | 0.2694 | 0.3259 | 0.6793 | 0.134* | |
C21 | 0.32081 (11) | 0.4560 (2) | 0.1842 (3) | 0.0495 (8) | |
C22 | 0.36131 (12) | 0.5106 (2) | 0.1680 (3) | 0.0508 (8) | |
C23 | 0.40471 (15) | 0.4835 (3) | 0.1295 (4) | 0.0757 (11) | |
C24 | 0.44281 (16) | 0.5350 (3) | 0.1284 (5) | 0.0941 (15) | |
H24 | 0.4713 | 0.5166 | 0.1036 | 0.113* | |
C25 | 0.44094 (15) | 0.6109 (3) | 0.1614 (4) | 0.0848 (13) | |
C26 | 0.39781 (15) | 0.6374 (3) | 0.1929 (4) | 0.0729 (11) | |
H26 | 0.3949 | 0.6896 | 0.2117 | 0.087* | |
C27 | 0.35870 (12) | 0.5894 (2) | 0.1974 (3) | 0.0606 (9) | |
C28 | 0.41129 (19) | 0.4012 (3) | 0.0869 (6) | 0.117 (2) | |
H28A | 0.4060 | 0.3660 | 0.1526 | 0.176* | |
H28B | 0.4436 | 0.3947 | 0.0676 | 0.176* | |
H28C | 0.3885 | 0.3906 | 0.0133 | 0.176* | |
C29 | 0.48412 (19) | 0.6644 (4) | 0.1659 (6) | 0.125 (2) | |
H29A | 0.4937 | 0.6818 | 0.2505 | 0.188* | |
H29B | 0.4756 | 0.7082 | 0.1124 | 0.188* | |
H29C | 0.5105 | 0.6371 | 0.1375 | 0.188* | |
C30 | 0.31381 (15) | 0.6275 (3) | 0.2358 (6) | 0.1002 (17) | |
H30A | 0.2854 | 0.6049 | 0.1891 | 0.150* | |
H30B | 0.3144 | 0.6819 | 0.2185 | 0.150* | |
H30C | 0.3134 | 0.6196 | 0.3240 | 0.150* | |
C31 | 0.20049 (11) | 0.2598 (2) | 0.3071 (3) | 0.0449 (8) | |
C32 | 0.16422 (12) | 0.2020 (2) | 0.3347 (3) | 0.0522 (8) | |
C33 | 0.13735 (14) | 0.2143 (2) | 0.4338 (4) | 0.0671 (10) | |
C34 | 0.10455 (18) | 0.1582 (3) | 0.4569 (4) | 0.0922 (14) | |
H34 | 0.0868 | 0.1662 | 0.5228 | 0.111* | |
C35 | 0.0967 (2) | 0.0922 (3) | 0.3890 (6) | 0.1039 (17) | |
C36 | 0.12263 (19) | 0.0821 (3) | 0.2899 (5) | 0.0980 (16) | |
H36 | 0.1173 | 0.0377 | 0.2410 | 0.118* | |
C37 | 0.15580 (15) | 0.1348 (2) | 0.2611 (4) | 0.0687 (10) | |
C38 | 0.14293 (17) | 0.2838 (3) | 0.5166 (4) | 0.0919 (14) | |
H38A | 0.1767 | 0.2925 | 0.5453 | 0.138* | |
H38B | 0.1262 | 0.2756 | 0.5875 | 0.138* | |
H38C | 0.1295 | 0.3281 | 0.4702 | 0.138* | |
C39 | 0.0593 (3) | 0.0313 (4) | 0.4179 (8) | 0.193 (4) | |
H39A | 0.0600 | −0.0122 | 0.3627 | 0.290* | |
H39B | 0.0275 | 0.0538 | 0.4055 | 0.290* | |
H39C | 0.0670 | 0.0145 | 0.5034 | 0.290* | |
C40 | 0.18033 (17) | 0.1189 (3) | 0.1461 (4) | 0.0982 (15) | |
H40A | 0.1788 | 0.1644 | 0.0946 | 0.147* | |
H40B | 0.1641 | 0.0771 | 0.0988 | 0.147* | |
H40C | 0.2135 | 0.1051 | 0.1723 | 0.147* | |
C41 | 0.36040 (10) | 0.18707 (19) | 0.1549 (3) | 0.0455 (7) | |
H41 | 0.3755 | 0.2140 | 0.2246 | 0.055* | |
C42 | 0.38439 (10) | 0.12515 (18) | 0.1110 (3) | 0.0427 (7) | |
C43 | 0.36146 (12) | 0.0844 (2) | 0.0096 (3) | 0.0565 (8) | |
H43 | 0.3766 | 0.0423 | −0.0218 | 0.068* | |
C44 | 0.31598 (13) | 0.1064 (2) | −0.0448 (3) | 0.0620 (9) | |
H44 | 0.2998 | 0.0792 | −0.1126 | 0.074* | |
C45 | 0.29488 (11) | 0.1698 (2) | 0.0032 (3) | 0.0515 (8) | |
H45 | 0.2643 | 0.1852 | −0.0347 | 0.062* | |
C46 | 0.43379 (11) | 0.10668 (19) | 0.1795 (3) | 0.0501 (8) | |
C47 | 0.15598 (10) | 0.51250 (18) | 0.3511 (3) | 0.0418 (7) | |
H47 | 0.1412 | 0.4809 | 0.2868 | 0.050* | |
C48 | 0.12797 (10) | 0.56738 (19) | 0.3998 (3) | 0.0446 (7) | |
C49 | 0.15054 (12) | 0.61396 (19) | 0.4959 (3) | 0.0533 (8) | |
H49 | 0.1332 | 0.6520 | 0.5313 | 0.064* | |
C50 | 0.19866 (13) | 0.6030 (2) | 0.5376 (3) | 0.0578 (9) | |
H50 | 0.2144 | 0.6331 | 0.6025 | 0.069* | |
C51 | 0.22351 (11) | 0.5469 (2) | 0.4825 (3) | 0.0504 (8) | |
H51 | 0.2563 | 0.5402 | 0.5113 | 0.060* | |
C52 | 0.07610 (11) | 0.5748 (2) | 0.3426 (3) | 0.0523 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03574 (17) | 0.0471 (2) | 0.03418 (17) | 0.01540 (16) | −0.00220 (12) | −0.00320 (16) |
Cu2 | 0.03820 (18) | 0.0504 (2) | 0.03404 (16) | 0.01698 (16) | −0.00414 (12) | −0.00630 (16) |
O1 | 0.0585 (12) | 0.0539 (15) | 0.0354 (10) | 0.0202 (11) | −0.0096 (9) | −0.0022 (9) |
O2 | 0.0514 (12) | 0.0569 (15) | 0.0402 (11) | 0.0185 (11) | −0.0137 (8) | −0.0064 (10) |
O3 | 0.0450 (11) | 0.0702 (15) | 0.0398 (10) | 0.0234 (12) | −0.0125 (8) | −0.0096 (11) |
O4 | 0.0459 (12) | 0.0701 (15) | 0.0379 (11) | 0.0196 (11) | −0.0085 (9) | −0.0090 (10) |
O5 | 0.0594 (14) | 0.0630 (16) | 0.0648 (15) | 0.0031 (12) | 0.0180 (12) | −0.0096 (12) |
O6 | 0.0591 (14) | 0.0650 (17) | 0.0556 (14) | −0.0006 (11) | 0.0117 (11) | −0.0136 (12) |
O7 | 0.0409 (11) | 0.0566 (15) | 0.0546 (13) | 0.0093 (10) | 0.0073 (10) | 0.0002 (10) |
O8 | 0.0474 (13) | 0.0546 (14) | 0.0610 (14) | 0.0163 (11) | 0.0100 (11) | 0.0038 (11) |
O9 | 0.0413 (12) | 0.0855 (18) | 0.0675 (16) | 0.0228 (12) | 0.0033 (10) | −0.0023 (14) |
O10 | 0.0397 (12) | 0.094 (2) | 0.0800 (18) | 0.0205 (13) | 0.0049 (12) | −0.0113 (15) |
N1 | 0.0402 (14) | 0.0470 (15) | 0.0444 (14) | 0.0123 (12) | 0.0014 (11) | −0.0111 (12) |
N2 | 0.0439 (15) | 0.075 (2) | 0.086 (2) | 0.0193 (15) | 0.0162 (14) | −0.0060 (17) |
N3 | 0.0347 (13) | 0.0517 (16) | 0.0399 (13) | 0.0110 (11) | 0.0000 (10) | −0.0049 (11) |
N4 | 0.0443 (15) | 0.083 (2) | 0.079 (2) | 0.0186 (15) | 0.0207 (14) | −0.0020 (17) |
C1 | 0.0449 (17) | 0.0522 (19) | 0.0370 (15) | 0.0074 (15) | −0.0050 (12) | 0.0058 (14) |
C2 | 0.063 (2) | 0.0490 (19) | 0.0398 (16) | 0.0163 (15) | −0.0152 (14) | −0.0035 (13) |
C3 | 0.063 (2) | 0.066 (2) | 0.063 (2) | 0.0056 (19) | −0.0241 (17) | 0.0057 (18) |
C4 | 0.070 (2) | 0.070 (3) | 0.087 (3) | 0.008 (2) | −0.040 (2) | −0.003 (2) |
C5 | 0.099 (3) | 0.061 (2) | 0.058 (2) | 0.024 (3) | −0.043 (2) | −0.009 (2) |
C6 | 0.116 (4) | 0.068 (3) | 0.0424 (19) | 0.020 (2) | −0.026 (2) | 0.0018 (17) |
C7 | 0.080 (2) | 0.061 (2) | 0.0410 (16) | 0.013 (2) | −0.0097 (15) | −0.0024 (16) |
C8 | 0.066 (2) | 0.138 (5) | 0.095 (3) | −0.022 (3) | −0.017 (2) | 0.039 (3) |
C9 | 0.132 (4) | 0.113 (4) | 0.091 (3) | 0.038 (4) | −0.077 (3) | −0.015 (3) |
C10 | 0.118 (4) | 0.114 (4) | 0.055 (2) | 0.002 (3) | 0.012 (2) | 0.013 (2) |
C11 | 0.0367 (15) | 0.0481 (18) | 0.0405 (15) | 0.0096 (13) | −0.0058 (11) | −0.0015 (13) |
C12 | 0.0389 (14) | 0.0513 (19) | 0.0367 (13) | 0.0109 (14) | −0.0093 (11) | 0.0003 (14) |
C13 | 0.0410 (16) | 0.068 (2) | 0.0523 (17) | 0.0044 (15) | −0.0076 (13) | −0.0041 (16) |
C14 | 0.0374 (16) | 0.090 (3) | 0.072 (2) | 0.0075 (19) | −0.0146 (14) | −0.018 (2) |
C15 | 0.062 (2) | 0.070 (2) | 0.0477 (19) | 0.0130 (18) | −0.0232 (16) | −0.0085 (16) |
C16 | 0.071 (2) | 0.079 (3) | 0.0398 (17) | 0.010 (2) | −0.0087 (15) | 0.0056 (17) |
C17 | 0.0466 (16) | 0.074 (3) | 0.0427 (16) | 0.0091 (16) | −0.0047 (12) | 0.0017 (16) |
C18 | 0.056 (2) | 0.134 (4) | 0.072 (3) | −0.020 (3) | 0.0045 (19) | 0.002 (3) |
C19 | 0.087 (3) | 0.111 (4) | 0.069 (3) | 0.028 (3) | −0.040 (2) | −0.009 (2) |
C20 | 0.054 (2) | 0.150 (5) | 0.065 (2) | 0.006 (2) | 0.0123 (19) | 0.023 (3) |
C21 | 0.0439 (17) | 0.061 (2) | 0.0411 (16) | 0.0079 (16) | −0.0030 (13) | 0.0019 (16) |
C22 | 0.0495 (17) | 0.059 (2) | 0.0427 (16) | 0.0067 (16) | 0.0032 (14) | 0.0028 (15) |
C23 | 0.076 (3) | 0.081 (3) | 0.076 (3) | 0.000 (2) | 0.030 (2) | −0.005 (2) |
C24 | 0.073 (3) | 0.097 (4) | 0.123 (4) | −0.001 (3) | 0.050 (3) | 0.008 (3) |
C25 | 0.065 (2) | 0.099 (4) | 0.091 (3) | −0.014 (2) | 0.015 (2) | 0.013 (3) |
C26 | 0.075 (3) | 0.072 (3) | 0.070 (2) | −0.005 (2) | 0.002 (2) | 0.001 (2) |
C27 | 0.0500 (19) | 0.071 (3) | 0.055 (2) | 0.0028 (18) | −0.0093 (15) | −0.0002 (18) |
C28 | 0.109 (4) | 0.096 (4) | 0.165 (5) | 0.016 (3) | 0.085 (4) | −0.014 (4) |
C29 | 0.095 (4) | 0.124 (5) | 0.163 (6) | −0.040 (3) | 0.040 (4) | 0.010 (4) |
C30 | 0.059 (2) | 0.064 (3) | 0.173 (5) | 0.008 (2) | −0.001 (3) | −0.016 (3) |
C31 | 0.0452 (18) | 0.055 (2) | 0.0322 (14) | 0.0157 (15) | −0.0033 (12) | 0.0054 (13) |
C32 | 0.0571 (19) | 0.052 (2) | 0.0453 (17) | 0.0112 (16) | 0.0001 (14) | 0.0084 (15) |
C33 | 0.069 (2) | 0.076 (3) | 0.059 (2) | 0.003 (2) | 0.0191 (18) | 0.0084 (19) |
C34 | 0.102 (3) | 0.104 (4) | 0.079 (3) | −0.004 (3) | 0.040 (3) | 0.015 (3) |
C35 | 0.119 (4) | 0.089 (4) | 0.110 (4) | −0.030 (3) | 0.039 (3) | 0.011 (3) |
C36 | 0.116 (4) | 0.069 (3) | 0.110 (4) | −0.019 (3) | 0.019 (3) | −0.003 (3) |
C37 | 0.071 (2) | 0.064 (2) | 0.070 (2) | 0.003 (2) | 0.0060 (19) | 0.001 (2) |
C38 | 0.102 (3) | 0.105 (4) | 0.080 (3) | −0.003 (3) | 0.052 (3) | −0.012 (3) |
C39 | 0.249 (10) | 0.116 (6) | 0.240 (10) | −0.080 (6) | 0.123 (9) | −0.005 (6) |
C40 | 0.102 (3) | 0.103 (4) | 0.091 (3) | −0.011 (3) | 0.017 (3) | −0.051 (3) |
C41 | 0.0357 (15) | 0.0547 (19) | 0.0455 (16) | 0.0095 (14) | 0.0040 (12) | −0.0031 (14) |
C42 | 0.0355 (14) | 0.0430 (16) | 0.0519 (17) | 0.0049 (13) | 0.0140 (13) | 0.0034 (14) |
C43 | 0.059 (2) | 0.0456 (19) | 0.067 (2) | 0.0119 (16) | 0.0185 (17) | −0.0113 (16) |
C44 | 0.058 (2) | 0.067 (2) | 0.059 (2) | 0.0052 (18) | 0.0034 (16) | −0.0252 (18) |
C45 | 0.0437 (16) | 0.064 (2) | 0.0456 (16) | 0.0121 (16) | 0.0026 (13) | −0.0119 (15) |
C46 | 0.0408 (16) | 0.0447 (18) | 0.067 (2) | 0.0086 (14) | 0.0162 (15) | 0.0073 (16) |
C47 | 0.0399 (15) | 0.0433 (17) | 0.0415 (15) | 0.0073 (13) | 0.0031 (12) | −0.0060 (13) |
C48 | 0.0370 (15) | 0.0455 (17) | 0.0534 (18) | 0.0042 (14) | 0.0136 (13) | 0.0031 (14) |
C49 | 0.0557 (19) | 0.0428 (18) | 0.065 (2) | 0.0053 (15) | 0.0224 (16) | −0.0139 (16) |
C50 | 0.062 (2) | 0.057 (2) | 0.0554 (19) | −0.0052 (17) | 0.0093 (16) | −0.0178 (16) |
C51 | 0.0388 (16) | 0.062 (2) | 0.0492 (17) | 0.0019 (15) | 0.0005 (13) | −0.0077 (15) |
C52 | 0.0390 (16) | 0.0495 (19) | 0.070 (2) | 0.0109 (14) | 0.0142 (15) | 0.0038 (17) |
Cu1—Cu2 | 2.5990 (4) | C19—H19C | 0.9600 |
Cu1—O1 | 1.9874 (18) | C20—H20A | 0.9600 |
Cu1—O4 | 1.970 (2) | C20—H20B | 0.9600 |
Cu1—O5 | 1.958 (2) | C20—H20C | 0.9600 |
Cu1—O7 | 1.967 (2) | C21—C22 | 1.502 (5) |
Cu1—N3 | 2.164 (2) | C22—C23 | 1.415 (5) |
Cu2—O2 | 1.9611 (18) | C22—C27 | 1.403 (5) |
Cu2—O3 | 1.9671 (18) | C24—C25 | 1.362 (7) |
Cu2—O6 | 1.983 (3) | C24—C23 | 1.388 (6) |
Cu2—O8 | 1.981 (2) | C24—H24 | 0.9300 |
Cu2—N1 | 2.165 (2) | C25—C29 | 1.514 (6) |
O1—C1 | 1.258 (4) | C26—C25 | 1.375 (6) |
O2—C1 | 1.253 (4) | C26—C27 | 1.377 (6) |
O3—C11 | 1.254 (3) | C26—H26 | 0.9300 |
O4—C11 | 1.258 (3) | C27—C30 | 1.523 (6) |
O5—C21 | 1.262 (4) | C28—C23 | 1.515 (6) |
O6—C21 | 1.248 (4) | C28—H28A | 0.9600 |
O7—C31 | 1.258 (4) | C28—H28B | 0.9600 |
O8—C31 | 1.268 (4) | C28—H28C | 0.9600 |
O9—C46 | 1.222 (4) | C29—H29A | 0.9600 |
O10—C52 | 1.236 (4) | C29—H29B | 0.9600 |
N1—C41 | 1.342 (4) | C29—H29C | 0.9600 |
N1—C45 | 1.336 (4) | C30—H30A | 0.9600 |
N2—H2A | 0.8600 | C30—H30B | 0.9600 |
N2—H2B | 0.8600 | C30—H30C | 0.9600 |
N3—C47 | 1.333 (4) | C31—C32 | 1.482 (5) |
N3—C51 | 1.323 (4) | C32—C33 | 1.404 (5) |
N4—H4A | 0.8600 | C32—C37 | 1.406 (5) |
N4—H4B | 0.8600 | C34—C33 | 1.380 (6) |
C1—C2 | 1.508 (4) | C34—C35 | 1.356 (7) |
C2—C3 | 1.377 (5) | C34—H34 | 0.9300 |
C2—C7 | 1.402 (5) | C35—C36 | 1.382 (7) |
C3—C4 | 1.404 (5) | C35—C39 | 1.547 (7) |
C3—C8 | 1.512 (6) | C36—H36 | 0.9300 |
C4—H4 | 0.9300 | C37—C36 | 1.366 (6) |
C5—C4 | 1.377 (6) | C37—C40 | 1.522 (5) |
C5—C6 | 1.343 (6) | C38—C33 | 1.491 (6) |
C5—C9 | 1.535 (5) | C38—H38A | 0.9600 |
C6—H6 | 0.9300 | C38—H38B | 0.9600 |
C7—C6 | 1.400 (5) | C38—H38C | 0.9600 |
C7—C10 | 1.493 (6) | C39—H39A | 0.9600 |
C8—H8A | 0.9600 | C39—H39B | 0.9600 |
C8—H8B | 0.9600 | C39—H39C | 0.9600 |
C8—H8C | 0.9600 | C40—H40A | 0.9600 |
C9—H9A | 0.9600 | C40—H40B | 0.9600 |
C9—H9B | 0.9600 | C40—H40C | 0.9600 |
C9—H9C | 0.9600 | C41—C42 | 1.381 (4) |
C10—H10A | 0.9600 | C41—H41 | 0.9300 |
C10—H10B | 0.9600 | C42—C43 | 1.377 (5) |
C10—H10C | 0.9600 | C42—C46 | 1.502 (4) |
C12—C11 | 1.496 (4) | C43—C44 | 1.374 (5) |
C12—C13 | 1.404 (4) | C43—H43 | 0.9300 |
C12—C17 | 1.392 (4) | C44—H44 | 0.9300 |
C13—C14 | 1.390 (4) | C45—C44 | 1.379 (5) |
C13—C18 | 1.505 (5) | C45—H45 | 0.9300 |
C14—H14 | 0.9300 | C46—N2 | 1.321 (4) |
C15—C14 | 1.364 (5) | C47—H47 | 0.9300 |
C15—C16 | 1.364 (5) | C48—C52 | 1.496 (4) |
C15—C19 | 1.502 (5) | C48—C47 | 1.379 (4) |
C16—H16 | 0.9300 | C48—C49 | 1.389 (5) |
C17—C16 | 1.388 (4) | C49—C50 | 1.368 (5) |
C17—C20 | 1.498 (5) | C49—H49 | 0.9300 |
C18—H18A | 0.9600 | C50—C51 | 1.374 (5) |
C18—H18B | 0.9600 | C50—H50 | 0.9300 |
C18—H18C | 0.9600 | C51—H51 | 0.9300 |
C19—H19A | 0.9600 | C52—N4 | 1.317 (4) |
C19—H19B | 0.9600 | ||
O1—Cu1—Cu2 | 82.47 (6) | H19B—C19—H19C | 109.5 |
O4—Cu1—Cu2 | 85.23 (6) | C17—C20—H20A | 109.5 |
O5—Cu1—Cu2 | 84.10 (7) | C17—C20—H20B | 109.5 |
O7—Cu1—Cu2 | 84.47 (7) | C17—C20—H20C | 109.5 |
N3—Cu1—Cu2 | 176.46 (6) | H20A—C20—H20B | 109.5 |
O4—Cu1—O1 | 167.66 (9) | H20A—C20—H20C | 109.5 |
O5—Cu1—O1 | 92.42 (10) | H20B—C20—H20C | 109.5 |
O7—Cu1—O1 | 86.28 (9) | O5—C21—C22 | 116.5 (3) |
O5—Cu1—O4 | 87.16 (10) | O6—C21—O5 | 123.8 (3) |
O7—Cu1—O4 | 91.69 (10) | O6—C21—C22 | 119.6 (3) |
O5—Cu1—O7 | 168.56 (10) | C23—C22—C21 | 121.1 (3) |
O1—Cu1—N3 | 93.99 (9) | C27—C22—C21 | 121.3 (3) |
O4—Cu1—N3 | 98.31 (9) | C27—C22—C23 | 117.5 (3) |
O5—Cu1—N3 | 96.28 (10) | C22—C23—C28 | 123.0 (4) |
O7—Cu1—N3 | 95.14 (9) | C24—C23—C22 | 118.7 (4) |
O2—Cu2—Cu1 | 86.03 (6) | C24—C23—C28 | 118.3 (4) |
O3—Cu2—Cu1 | 83.25 (7) | C23—C24—H24 | 118.1 |
O6—Cu2—Cu1 | 83.53 (7) | C25—C24—C23 | 123.8 (4) |
O8—Cu2—Cu1 | 83.33 (7) | C25—C24—H24 | 118.1 |
N1—Cu2—Cu1 | 174.66 (7) | C24—C25—C26 | 116.9 (4) |
O2—Cu2—O3 | 169.03 (9) | C24—C25—C29 | 122.4 (4) |
O2—Cu2—O6 | 91.44 (10) | C26—C25—C29 | 120.7 (5) |
O3—Cu2—O6 | 89.65 (11) | C25—C26—C27 | 122.3 (4) |
O8—Cu2—O6 | 166.79 (10) | C25—C26—H26 | 118.8 |
O2—Cu2—O8 | 88.92 (9) | C27—C26—H26 | 118.8 |
O3—Cu2—O8 | 87.55 (10) | C26—C27—C22 | 120.7 (4) |
O2—Cu2—N1 | 98.31 (9) | C26—C27—C30 | 115.9 (4) |
O3—Cu2—N1 | 92.28 (9) | C22—C27—C30 | 123.4 (4) |
O6—Cu2—N1 | 99.40 (9) | C23—C28—H28A | 109.5 |
O8—Cu2—N1 | 93.61 (10) | C23—C28—H28B | 109.5 |
C1—O1—Cu1 | 122.58 (19) | C23—C28—H28C | 109.5 |
C1—O2—Cu2 | 120.58 (19) | H28A—C28—H28B | 109.5 |
C11—O3—Cu2 | 123.63 (18) | H28A—C28—H28C | 109.5 |
C11—O4—Cu1 | 121.18 (18) | H28B—C28—H28C | 109.5 |
C21—O5—Cu1 | 123.2 (2) | C25—C29—H29A | 109.5 |
C21—O6—Cu2 | 121.9 (2) | C25—C29—H29B | 109.5 |
C31—O7—Cu1 | 122.6 (2) | C25—C29—H29C | 109.5 |
C31—O8—Cu2 | 122.2 (2) | H29A—C29—H29B | 109.5 |
C41—N1—Cu2 | 119.8 (2) | H29A—C29—H29C | 109.5 |
C45—N1—Cu2 | 122.4 (2) | H29B—C29—H29C | 109.5 |
C45—N1—C41 | 117.6 (3) | C27—C30—H30A | 109.5 |
C46—N2—H2A | 120.0 | C27—C30—H30B | 109.5 |
C46—N2—H2B | 120.0 | C27—C30—H30C | 109.5 |
H2A—N2—H2B | 120.0 | H30A—C30—H30B | 109.5 |
C47—N3—Cu1 | 117.9 (2) | H30A—C30—H30C | 109.5 |
C51—N3—Cu1 | 124.7 (2) | H30B—C30—H30C | 109.5 |
C51—N3—C47 | 117.4 (3) | O7—C31—O8 | 123.6 (3) |
C52—N4—H4A | 120.0 | O7—C31—C32 | 118.8 (3) |
C52—N4—H4B | 120.0 | O8—C31—C32 | 117.5 (3) |
H4A—N4—H4B | 120.0 | C33—C32—C31 | 120.3 (3) |
O1—C1—C2 | 116.5 (3) | C33—C32—C37 | 119.2 (3) |
O2—C1—O1 | 125.7 (3) | C37—C32—C31 | 120.5 (3) |
O2—C1—C2 | 117.8 (3) | C32—C33—C38 | 123.6 (4) |
C3—C2—C1 | 119.8 (3) | C34—C33—C32 | 118.1 (4) |
C3—C2—C7 | 121.3 (3) | C34—C33—C38 | 118.3 (4) |
C7—C2—C1 | 118.8 (3) | C33—C34—H34 | 118.2 |
C2—C3—C4 | 117.6 (4) | C35—C34—C33 | 123.6 (4) |
C2—C3—C8 | 121.8 (3) | C35—C34—H34 | 118.2 |
C4—C3—C8 | 120.6 (4) | C34—C35—C36 | 117.4 (4) |
C3—C4—H4 | 118.9 | C34—C35—C39 | 121.7 (5) |
C5—C4—C3 | 122.2 (4) | C36—C35—C39 | 120.8 (6) |
C5—C4—H4 | 118.9 | C35—C36—H36 | 118.8 |
C4—C5—C9 | 119.4 (5) | C37—C36—C35 | 122.5 (5) |
C6—C5—C4 | 118.6 (3) | C37—C36—H36 | 118.8 |
C6—C5—C9 | 122.0 (4) | C32—C37—C40 | 123.3 (4) |
C5—C6—C7 | 122.7 (4) | C36—C37—C32 | 119.2 (4) |
C5—C6—H6 | 118.7 | C36—C37—C40 | 117.5 (4) |
C7—C6—H6 | 118.7 | C33—C38—H38A | 109.5 |
C2—C7—C10 | 121.6 (3) | C33—C38—H38B | 109.5 |
C6—C7—C2 | 117.6 (4) | C33—C38—H38C | 109.5 |
C6—C7—C10 | 120.8 (4) | H38A—C38—H38B | 109.5 |
C3—C8—H8A | 109.5 | H38A—C38—H38C | 109.5 |
C3—C8—H8B | 109.5 | H38B—C38—H38C | 109.5 |
C3—C8—H8C | 109.5 | C35—C39—H39A | 109.5 |
H8A—C8—H8B | 109.5 | C35—C39—H39B | 109.5 |
H8A—C8—H8C | 109.5 | C35—C39—H39C | 109.5 |
H8B—C8—H8C | 109.5 | H39A—C39—H39B | 109.5 |
C5—C9—H9A | 109.5 | H39A—C39—H39C | 109.5 |
C5—C9—H9B | 109.5 | H39B—C39—H39C | 109.5 |
C5—C9—H9C | 109.5 | C37—C40—H40A | 109.5 |
H9A—C9—H9B | 109.5 | C37—C40—H40B | 109.5 |
H9A—C9—H9C | 109.5 | C37—C40—H40C | 109.5 |
H9B—C9—H9C | 109.5 | H40A—C40—H40B | 109.5 |
C7—C10—H10A | 109.5 | H40A—C40—H40C | 109.5 |
C7—C10—H10B | 109.5 | H40B—C40—H40C | 109.5 |
C7—C10—H10C | 109.5 | N1—C41—C42 | 123.0 (3) |
H10A—C10—H10B | 109.5 | N1—C41—H41 | 118.5 |
H10A—C10—H10C | 109.5 | C42—C41—H41 | 118.5 |
H10B—C10—H10C | 109.5 | C41—C42—C46 | 116.9 (3) |
O3—C11—O4 | 124.9 (3) | C43—C42—C41 | 118.3 (3) |
O3—C11—C12 | 116.8 (2) | C43—C42—C46 | 124.8 (3) |
O4—C11—C12 | 118.3 (3) | C42—C43—H43 | 120.2 |
C13—C12—C11 | 119.1 (3) | C44—C43—C42 | 119.5 (3) |
C17—C12—C11 | 120.4 (2) | C44—C43—H43 | 120.2 |
C17—C12—C13 | 120.4 (3) | C43—C44—C45 | 118.6 (3) |
C12—C13—C18 | 122.5 (3) | C43—C44—H44 | 120.7 |
C14—C13—C12 | 117.8 (3) | C45—C44—H44 | 120.7 |
C14—C13—C18 | 119.7 (3) | N1—C45—C44 | 123.0 (3) |
C13—C14—H14 | 118.5 | N1—C45—H45 | 118.5 |
C15—C14—C13 | 122.9 (3) | C44—C45—H45 | 118.5 |
C15—C14—H14 | 118.5 | O9—C46—N2 | 123.0 (3) |
C14—C15—C19 | 120.6 (4) | O9—C46—C42 | 120.4 (3) |
C16—C15—C14 | 117.9 (3) | N2—C46—C42 | 116.5 (3) |
C16—C15—C19 | 121.5 (4) | N3—C47—C48 | 124.0 (3) |
C15—C16—C17 | 122.9 (3) | N3—C47—H47 | 118.0 |
C15—C16—H16 | 118.5 | C48—C47—H47 | 118.0 |
C17—C16—H16 | 118.5 | C47—C48—C49 | 117.4 (3) |
C12—C17—C20 | 122.6 (3) | C47—C48—C52 | 118.1 (3) |
C16—C17—C12 | 118.1 (3) | C49—C48—C52 | 124.5 (3) |
C16—C17—C20 | 119.2 (3) | C48—C49—H49 | 120.5 |
C13—C18—H18A | 109.5 | C50—C49—C48 | 118.9 (3) |
C13—C18—H18B | 109.5 | C50—C49—H49 | 120.5 |
C13—C18—H18C | 109.5 | C49—C50—C51 | 119.3 (3) |
H18A—C18—H18B | 109.5 | C49—C50—H50 | 120.4 |
H18A—C18—H18C | 109.5 | C51—C50—H50 | 120.4 |
H18B—C18—H18C | 109.5 | N3—C51—C50 | 123.0 (3) |
C15—C19—H19A | 109.5 | N3—C51—H51 | 118.5 |
C15—C19—H19B | 109.5 | C50—C51—H51 | 118.5 |
C15—C19—H19C | 109.5 | O10—C52—N4 | 122.6 (3) |
H19A—C19—H19B | 109.5 | O10—C52—C48 | 120.1 (3) |
H19A—C19—H19C | 109.5 | N4—C52—C48 | 117.3 (3) |
O1—Cu1—Cu2—O2 | −10.92 (9) | C1—C2—C3—C4 | 179.0 (3) |
O1—Cu1—Cu2—O3 | 171.40 (11) | C1—C2—C3—C8 | −2.2 (6) |
O1—Cu1—Cu2—O6 | 80.98 (10) | C7—C2—C3—C4 | 0.9 (6) |
O1—Cu1—Cu2—O8 | −100.30 (10) | C7—C2—C3—C8 | 179.7 (4) |
O4—Cu1—Cu2—O2 | 168.21 (10) | C1—C2—C7—C6 | −177.6 (3) |
O4—Cu1—Cu2—O3 | −9.47 (11) | C1—C2—C7—C10 | −1.0 (5) |
O4—Cu1—Cu2—O6 | −99.89 (10) | C3—C2—C7—C6 | 0.6 (5) |
O4—Cu1—Cu2—O8 | 78.84 (10) | C3—C2—C7—C10 | 177.1 (4) |
O5—Cu1—Cu2—O2 | −104.16 (10) | C2—C3—C4—C5 | −0.8 (6) |
O5—Cu1—Cu2—O3 | 78.16 (11) | C8—C3—C4—C5 | −179.6 (4) |
O5—Cu1—Cu2—O6 | −12.25 (11) | C6—C5—C4—C3 | −0.8 (6) |
O5—Cu1—Cu2—O8 | 166.47 (10) | C9—C5—C4—C3 | −180.0 (4) |
O7—Cu1—Cu2—O2 | 76.04 (10) | C4—C5—C6—C7 | 2.4 (7) |
O7—Cu1—Cu2—O3 | −101.64 (10) | C9—C5—C6—C7 | −178.5 (4) |
O7—Cu1—Cu2—O6 | 167.94 (10) | C2—C7—C6—C5 | −2.3 (6) |
O7—Cu1—Cu2—O8 | −13.33 (9) | C10—C7—C6—C5 | −178.9 (4) |
Cu2—Cu1—O1—C1 | 16.1 (2) | C13—C12—C11—O3 | 49.5 (4) |
O4—Cu1—O1—C1 | 12.1 (6) | C13—C12—C11—O4 | −130.2 (3) |
O5—Cu1—O1—C1 | 99.8 (2) | C17—C12—C11—O3 | −127.3 (3) |
O7—Cu1—O1—C1 | −68.8 (2) | C17—C12—C11—O4 | 53.0 (5) |
N3—Cu1—O1—C1 | −163.7 (2) | C11—C12—C13—C14 | −177.5 (3) |
Cu2—Cu1—O4—C11 | 10.9 (2) | C11—C12—C13—C18 | 1.6 (6) |
O1—Cu1—O4—C11 | 15.0 (6) | C17—C12—C13—C14 | −0.7 (5) |
O5—Cu1—O4—C11 | −73.4 (2) | C17—C12—C13—C18 | 178.4 (4) |
O7—Cu1—O4—C11 | 95.2 (2) | C11—C12—C17—C16 | 176.5 (3) |
N3—Cu1—O4—C11 | −169.3 (2) | C11—C12—C17—C20 | 0.4 (6) |
Cu2—Cu1—O5—C21 | 11.1 (3) | C13—C12—C17—C16 | −0.2 (5) |
O1—Cu1—O5—C21 | −71.1 (3) | C13—C12—C17—C20 | −176.4 (4) |
O4—Cu1—O5—C21 | 96.6 (3) | C12—C13—C14—C15 | 1.2 (6) |
O7—Cu1—O5—C21 | 12.1 (7) | C18—C13—C14—C15 | −177.9 (4) |
N3—Cu1—O5—C21 | −165.4 (3) | C16—C15—C14—C13 | −0.7 (6) |
Cu2—Cu1—O7—C31 | 13.6 (2) | C19—C15—C14—C13 | 177.8 (4) |
O1—Cu1—O7—C31 | 96.4 (2) | C14—C15—C16—C17 | −0.3 (6) |
O5—Cu1—O7—C31 | 12.6 (7) | C19—C15—C16—C17 | −178.9 (4) |
O4—Cu1—O7—C31 | −71.4 (2) | C12—C17—C16—C15 | 0.8 (6) |
N3—Cu1—O7—C31 | −169.9 (2) | C20—C17—C16—C15 | 177.0 (4) |
O1—Cu1—N3—C47 | 35.0 (2) | O6—C21—O5—Cu1 | −0.3 (5) |
O1—Cu1—N3—C51 | −146.3 (3) | C22—C21—O5—Cu1 | −176.7 (2) |
O4—Cu1—N3—C47 | −144.1 (2) | O5—C21—C22—C23 | 153.9 (3) |
O4—Cu1—N3—C51 | 34.6 (3) | O5—C21—C22—C27 | −22.3 (5) |
O5—Cu1—N3—C47 | 127.9 (2) | O6—C21—C22—C23 | −22.6 (5) |
O5—Cu1—N3—C51 | −53.4 (3) | O6—C21—C22—C27 | 161.2 (3) |
O7—Cu1—N3—C47 | −51.6 (2) | C21—C22—C23—C24 | −173.5 (4) |
O7—Cu1—N3—C51 | 127.1 (3) | C21—C22—C23—C28 | 7.8 (6) |
Cu1—Cu2—O2—C1 | 9.9 (2) | C27—C22—C23—C24 | 2.8 (6) |
O3—Cu2—O2—C1 | 22.1 (7) | C27—C22—C23—C28 | −175.9 (4) |
O6—Cu2—O2—C1 | −73.5 (2) | C21—C22—C27—C26 | 174.1 (3) |
O8—Cu2—O2—C1 | 93.3 (2) | C21—C22—C27—C30 | −5.8 (6) |
N1—Cu2—O2—C1 | −173.2 (2) | C23—C22—C27—C26 | −2.2 (5) |
Cu1—Cu2—O3—C11 | 11.8 (3) | C23—C22—C27—C30 | 177.8 (4) |
O2—Cu2—O3—C11 | −0.4 (8) | C25—C24—C23—C22 | −0.5 (8) |
O6—Cu2—O3—C11 | 95.4 (3) | C25—C24—C23—C28 | 178.3 (5) |
O8—Cu2—O3—C11 | −71.7 (3) | C23—C24—C25—C26 | −2.5 (8) |
N1—Cu2—O3—C11 | −165.3 (3) | C23—C24—C25—C29 | 176.6 (5) |
Cu1—Cu2—O6—C21 | 18.6 (3) | C27—C26—C25—C24 | 3.2 (7) |
O2—Cu2—O6—C21 | 104.4 (3) | C27—C26—C25—C29 | −175.9 (4) |
O3—Cu2—O6—C21 | −64.6 (3) | C25—C26—C27—C22 | −0.9 (6) |
O8—Cu2—O6—C21 | 13.0 (6) | C25—C26—C27—C30 | 179.1 (4) |
N1—Cu2—O6—C21 | −156.9 (3) | O7—C31—C32—C33 | −32.4 (4) |
Cu1—Cu2—O8—C31 | 18.5 (2) | O7—C31—C32—C37 | 146.7 (3) |
O2—Cu2—O8—C31 | −67.6 (2) | O8—C31—C32—C33 | 148.2 (3) |
O3—Cu2—O8—C31 | 102.0 (2) | O8—C31—C32—C37 | −32.6 (4) |
O6—Cu2—O8—C31 | 24.1 (6) | C31—C32—C33—C34 | −179.0 (4) |
N1—Cu2—O8—C31 | −165.9 (2) | C31—C32—C33—C38 | −0.1 (6) |
O2—Cu2—N1—C41 | 168.5 (2) | C37—C32—C33—C34 | 1.8 (5) |
O2—Cu2—N1—C45 | −15.9 (3) | C37—C32—C33—C38 | −179.3 (4) |
O3—Cu2—N1—C41 | −14.4 (3) | C31—C32—C37—C36 | 179.1 (4) |
O3—Cu2—N1—C45 | 161.2 (3) | C31—C32—C37—C40 | −3.7 (6) |
O6—Cu2—N1—C41 | 75.6 (3) | C33—C32—C37—C36 | −1.8 (6) |
O6—Cu2—N1—C45 | −108.8 (3) | C33—C32—C37—C40 | 175.5 (4) |
O8—Cu2—N1—C41 | −102.1 (3) | C35—C34—C33—C32 | −0.3 (8) |
O8—Cu2—N1—C45 | 73.5 (3) | C35—C34—C33—C38 | −179.3 (5) |
Cu1—O1—C1—O2 | −14.3 (4) | C33—C34—C35—C36 | −1.3 (9) |
Cu1—O1—C1—C2 | 165.4 (2) | C33—C34—C35—C39 | −179.6 (6) |
Cu2—O2—C1—O1 | −0.7 (4) | C34—C35—C36—C37 | 1.4 (9) |
Cu2—O2—C1—C2 | 179.6 (2) | C39—C35—C36—C37 | 179.6 (6) |
Cu2—O3—C11—O4 | −7.4 (5) | C32—C37—C36—C35 | 0.1 (8) |
Cu2—O3—C11—C12 | 172.9 (2) | C40—C37—C36—C35 | −177.3 (5) |
Cu1—O4—C11—O3 | −5.7 (4) | N1—C41—C42—C43 | −1.5 (5) |
Cu1—O4—C11—C12 | 174.0 (2) | N1—C41—C42—C46 | 179.3 (3) |
Cu2—O6—C21—O5 | −16.6 (5) | C41—C42—C43—C44 | 0.3 (5) |
Cu2—O6—C21—C22 | 159.6 (2) | C46—C42—C43—C44 | 179.5 (3) |
Cu1—O7—C31—O8 | −3.9 (4) | C41—C42—C46—O9 | 22.0 (4) |
Cu1—O7—C31—C32 | 176.79 (19) | C41—C42—C46—N2 | −156.7 (3) |
Cu2—O8—C31—O7 | −14.5 (4) | C43—C42—C46—O9 | −157.2 (3) |
Cu2—O8—C31—C32 | 164.9 (2) | C43—C42—C46—N2 | 24.1 (5) |
Cu2—N1—C41—C42 | 177.1 (2) | C42—C43—C44—C45 | 0.9 (6) |
C45—N1—C41—C42 | 1.3 (5) | N1—C45—C44—C43 | −1.1 (6) |
Cu2—N1—C45—C44 | −175.6 (3) | C49—C48—C47—N3 | −0.2 (5) |
C41—N1—C45—C44 | 0.0 (5) | C52—C48—C47—N3 | 177.5 (3) |
Cu1—N3—C47—C48 | 179.3 (2) | C47—C48—C49—C50 | −0.4 (5) |
C51—N3—C47—C48 | 0.5 (5) | C52—C48—C49—C50 | −178.0 (3) |
Cu1—N3—C51—C50 | −178.9 (3) | C47—C48—C52—O10 | −22.2 (5) |
C47—N3—C51—C50 | −0.2 (5) | C47—C48—C52—N4 | 158.1 (3) |
O1—C1—C2—C3 | −79.3 (4) | C49—C48—C52—O10 | 155.3 (3) |
O1—C1—C2—C7 | 98.9 (4) | C49—C48—C52—N4 | −24.4 (5) |
O2—C1—C2—C3 | 100.5 (4) | C48—C49—C50—C51 | 0.8 (5) |
O2—C1—C2—C7 | −81.3 (4) | C49—C50—C51—N3 | −0.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O10i | 0.86 | 2.06 | 2.906 (4) | 170 |
N4—H4A···O9ii | 0.86 | 2.10 | 2.955 (4) | 173 |
N4—H4B···O9iii | 0.86 | 2.44 | 3.228 (4) | 153 |
C50—H50···O8iii | 0.93 | 2.54 | 3.448 (4) | 166 |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, y+1/2, −z+1. |
Acknowledgements
The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization).
References
Adiwidjaja, G., Rossmanith, E. & Küppers, H. (1978). Acta Cryst. B34, 3079–3083. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Antsyshkina, A. S., Chiragov, F. M. & Poray-Koshits, M. A. (1980). Koord. Khim. 15, 1098–1103. Google Scholar
Barclay, G. A. & Kennard, C. H. L. (1961). J. Chem. Soc. pp. 5244. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Catterick (née Drew), J., Hursthouse, M. B., New, D. B. & Thornton, P. (1974). J. Chem. Soc. Chem. Commun. pp. 843. Google Scholar
Davey, G. & Stephens, F. S. (1970). J. Chem. Soc. A, pp. 2803–2805. CSD CrossRef Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hanic, F., Štempelová, D. & Hanicová, K. (1964). Acta Cryst. 17, 633–639. CSD CrossRef IUCr Journals Web of Science Google Scholar
Hoang, N. N., Valach, F. & Dunaj-Jurčo, M. (1995). Acta Cryst. C51, 1095–1097. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hoang, N. N., Valach, F. & Melník, M. (1993). Z. Kristallogr. 208, 27–33. CrossRef Web of Science Google Scholar
Hökelek, T., Necefoǧlu, H. & Balcı, M. (1995). Acta Cryst. C51, 2020–2023. CSD CrossRef IUCr Journals Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CAS PubMed Web of Science Google Scholar
Lee, J. D. (1986). Inorganic Chemistry, 3rd ed., p. 379. London: van Nostrand Reinhold. Google Scholar
Morosin, B., Hughes, R. C. & Soos, Z. G. (1975). Acta Cryst. B31, 762–770. CSD CrossRef CAS IUCr Journals Google Scholar
Nadzhafov, G. N., Shnulin, A. N. & Mamedov, Kh. S. (1981). Zh. Strukt. Khim. 22, 124–128. CAS Google Scholar
Necefoğlu, H., Çimen, E., Tercan, B., Dal, H. & Hökelek, T. (2010). Acta Cryst. E66, m334–m335. Web of Science CSD CrossRef IUCr Journals Google Scholar
Niekerk, J. N. van & Schoening, F. R. L. (1953). Acta Cryst. 6, 227–232. CSD CrossRef IUCr Journals Web of Science Google Scholar
Poray-Koshits, M. A., Aslanov, L. A. & Korytniy, E. F. (1976). Itogi Nauki Tekh. Kristallokhim. 11, 5–94. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shnulin, A. N., Nadzhafov, G. N., Amiraslanov, I. R., Usubaliev, B. T. & Mamedov, Kh. S. (1981). Koord. Khim. 7, 1409–1416. CAS Google Scholar
Speier, G. & Fulop, V. (1989). J. Chem. Soc. Dalton Trans. pp. 2331. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Usubaliev, B. T., Movsumov, E. M., Musaev, F. N., Nadzhafov, G. N., Amiraslanov, I. R. & Mamedov, Kh. S. (1980). Koord. Khim. 6, 1091–1096. CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.