Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616003144/fa3382sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616003144/fa3382Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S2053229616003144/fa3382Isup3.mol |
CCDC reference: 1455408
Transition metal complexes of Schiff base ligands have been of interest for many years, with particular application in catalysis and magnetism, and their structures have been extensively investigated (Archer & Wang, 1990; Chang et al., 1998; Chaturvedi, 1997; Costamagna et al., 1992). Since the 2014 Cambridge Structural Database (CSD) search mentioned in our previous report of one particular Schiff base ligand and one of its complexes (Clegg et al., 2015), the number of entries in the CSD (Version 5.37, including one update, November 2015; Allen, 2002; Groom & Allen, 2014) for purely organic compounds containing the skeleton R—CH═ N—CH2CH2—N═CH—R, in which R is any alkyl or aryl group, has increased to 165 and the number of metal complexes of such ligands to 1872. The chemistry of copper complexes is of particular interest owing to their importance in biological and industrial processes (Que & Tolman, 2002). In recent years, metal complexes of Schiff bases have attracted considerable attention due to their antifungal, antibacterial and antitumour activity (Usha & Chandra, 1992; Garg & Kapur, 1990). Biological activities may be related to the redox properties of complexes: for some copper(II) complexes a lower reduction potential seems to be related to an increased antifungal activity (Haiduc & Silvestru, 1990). Mononuclear and dinuclear copper complexes can mimic the abilities of superoxide dismutase (SOD), catechol oxidase and chemical nucleases (Liu et al., 1996). Complexes of copper(II) with Schiff base ligands (Marten et al., 2005) are frequently studied, for example, for their antibacterial properties (You & Zhu, 2006). Dicopper(II) Schiff base and related complexes have been probed electrochemically (Zolezzi et al., 2002), magnetically (Zeyrek et al., 2006) and by electron paramagnetic resonance (EPR) (Griebel et al., 2006) for their electronic structure.
We have continued our exploration of complexes of the ligand N,N'-bis(trans-2-nitrocinnamaldehyde)ethylenediamine (Nca2en) and report here its first dinuclear complex, namely [Cu2Cl3(OH)(Nca2en)2]·1.5CH2Cl2, (I). The 11 previously reported complexes (referenced in Clegg et al., 2015) of cobalt, nickel, copper, zinc and silver are all mononuclear and four-coordinate, with a single Nca2en ligand and either one other bidentate or two monodentate ligands, except for the homoleptic salt [(Nca2en)2Cu]ClO4 (Dehghanpour et al., 2006). The structure reported here thus introduces new features to the series.
To a stirred solution of CuCl (99 mg, 1 mmol) in dichloromethane (5 ml) was added dropwise a solution of N,N'-bis(trans-2-nitrocinnamaldehyde)ethylenediamine (378 mg, 1 mmol) in dichloromethane (10 ml) at room temperature, and stirring was continued for 1 h. After filtration, the volume of the solution was reduced under vacuum to about 4 ml. Slow diffusion of diethyl ether vapour into this concentrated solution gave yellow crystals suitable for X-ray diffraction, albeit with relatively weak diffraction at higher angles (yield 291 mg, 58%). Analysis calculated for C40H37Cl3Cu2N8O9: C 47.70, H 3.70, N 11.12%; calculated for C40H37Cl3Cu2N8O9·1.5CH2Cl2: C 43.93, H 3.55, N 9.87%; found, C 47.66, H 3.67, N 11.07%. This indicates that solvent of crystallization was lost in the preparation for analysis following removal from the mother liquor.
Crystal data, data collection and structure refinement details are summarized in Table 1. One dichloromethane solvent molecule was found to be ordered in a general position, and another lies across a mirror plane with the CH2 group disordered unequally [0.91 (2):0.09 (2)] over two positions in the mirror plane; similarity restraints were applied to the C—Cl distances and anisotropic displacement parameters of this molecule, and the displacement parameters were also subject to a `rigid-bond' restraint. The H atom of the bridging OH ligand was located in a difference map and was refined with the O—H distance restrained to 0.84 (1) Å, but with no contraint or restraint on its isotropic displacement parameter. All other H atoms were included in calculated positions and refined with a riding model, and with Uiso(H) = 1.2Ueq(C). A number of reflections (amounting to around 30 in the unique set) were rejected during processing of the raw data because of inconsistent intensities; these are likely to have been affected by overlap of diffraction from a minor second crystal component.
The source of the hydroxide ligand in the product of the synthesis is unclear; presumably it is derived from water in one of the reagents, the solvent or the atmosphere, as no precautions were taken to exclude air or moisture.
The dinuclear complex (Fig. 1) has hydroxide and chloride bridges between the two CuII atoms. Both metal centres have a coordination geometry best described as distorted trigonal bipyramidal, with the axial sites occupied by the bridging OH and one N atom (N3 or N7), the interaxial angles being essentially identical and deviating from the ideal value of 180° by only about 5° (Table 2). There is a difference, however, in the pattern of distortions from the ideal 120° angles in the equatorial planes: at Cu1 the Cl1—Cu1—Cl2 angle is significantly expanded to 150.99 (9)°, but at Cu2 the widest equatorial angle is Cl3—Cu2—N2 at 135.58 (18)°, and in each case the other two equatorial angles are approximately equal. This difference leads to a marked asymmetry in the central Cu2OCl3 core of the complex, which might have been expected to display an approximate mirror plane passing through the bridging ligands; the asymmetry can also be seen in the significantly different Cu—Cl bond lengths to the chloride bridge and in the Cu—N bond lengths to the Schiff base ligands. The τ parameter (Addison et al., 1984) is 0.40 for Cu1 and 0.66 for Cu2, indicating a geometry intermediate between ideal trigonal bipyramidal (τ = 1) and square-based pyramidal (τ = 0) and significantly different for the two metal centres. The closer approach to square-based pyramidal geometry for Cu1 is mainly a consequence of the wide Cl1—Cu1—Cl2 angle. The oxidation state +2 is confirmed for both CuII atoms by bond valence calculations (Brese & O'Keeffe, 1991; Brown, 2002), a bond valence sum of 2.1 being obtained in each case.
The four-membered Cu2OCl ring is folded, with a dihedral (hinge) angle of 152.0 (3)° between the two OCuCl planes. A search of the CSD for the Cu2OCl3 core finds just eight previous examples that are not parts of larger clusters with more than two Cu atoms; all have two five-coordinate CuII atoms, the other two coordination sites being taken by N atoms of uncharged ligands in each case. Of these, six have a tetradentate ligand that plays both chelating and bridging roles, imposing a marked fold on the central four-membered ring, the hinge angle ranging from 135.6 to 142.7° with phthalazine-based ligands (Marongiu & Lingafelter, 1982; Mandal et al., 1985; Thompson et al., 1987; Chen et al., 1993, 1996) and the more open 159.6° for one 1,8-naphthyridine-based ligand (Tikkanen et al., 1984); the hinge angle is widened to 168.2° for a complex with chelating but nonbridging propylenediamine ligands (Walther et al., 1997) and 178.9° (virtually planar) for a complex with monodentate pyrazole ligands (Mezei & Raptis, 2004). Within this small set of structures, there is thus a strong correlation between the degree of folding of the four-membered ring and the N—Cu—N bite angle and bridging geometry restrictions imposed by the N-donor ligands. Interestingly, almost all of these structures have approximately symmetrical chloride bridges, the difference in the two Cu—Cl bond lengths being <0.08 Å, except in the structure with the most similar ligand environment to that of the present compound (Walther et al., 1997), where the distances are 2.507 and 2.648 Å, a difference of 0.141 Å, essentially identical to the one found here; all the hydroxide bridges are approximately symmetrical.
Each of the two Nca2en ligands has two substituents attached to the central chelate ring, consisting of three essentially planar groups that are twisted relative to each other. In each case, the nitro group and the conjugated N═ C—C═C chain are rotated in the same direction (clockwise or anticlockwise) out of the plane of the benzene ring; the dihedral angles between the ring and nitro group range from 15.7 (8) to 34.8 (9)°, and those between the ring and the chain range from 19.7 (7) to 36.8 (6)°. The two ligands differ significantly in the conformation of their chelate rings: the ring containing atom Cu1 is best described as an envelope with atom C30 as the flap atom displaced from the mean plane of the other four atoms, while the ring containing atom Cu2 is twisted on the N2—C10 bond (these two atoms lie above and below the plane of the other three atoms). This difference contributes further to the asymmetry of the molecule and leads to a much more strongly marked bowing of the Cu2-coordinated ligand.
The benzene rings containing atoms C15 and C35, one in each of the two ligands, are approximately parallel [dihedral angle = 20.0 (4)°] and sufficiently close together [separation of centroids = 3.915 (6) Å] to indicate a possible weak intramolecular ring-stacking interaction; this can be seen in Fig. 1. More significant interactions are found for rings of the Cu2-coordinated ligand (containing atoms C6 and C15) in pairs of inversion-related cations, with a centroid–centroid separation of 3.730 (6) Å and dihedral angle of 7.8 (4)°. The space between these two molecules is occupied by two dichloromethane molecules having close contacts with the two bridging chloride ligands (see Supporting information and Fig. 2), which may be considered as C—H···Cl secondary hydrogen-bonding interactions supporting the ring stacking in dimer formation. Other close C—H···X contacts listed in the Supporting information involve the terminal chloride ligands and O atoms of the nitro groups.
Transition metal complexes of Schiff base ligands have been of interest for many years, with particular application in catalysis and magnetism, and their structures have been extensively investigated (Archer & Wang, 1990; Chang et al., 1998; Chaturvedi, 1997; Costamagna et al., 1992). Since the 2014 Cambridge Structural Database (CSD) search mentioned in our previous report of one particular Schiff base ligand and one of its complexes (Clegg et al., 2015), the number of entries in the CSD (Version 5.37, including one update, November 2015; Allen, 2002; Groom & Allen, 2014) for purely organic compounds containing the skeleton R—CH═ N—CH2CH2—N═CH—R, in which R is any alkyl or aryl group, has increased to 165 and the number of metal complexes of such ligands to 1872. The chemistry of copper complexes is of particular interest owing to their importance in biological and industrial processes (Que & Tolman, 2002). In recent years, metal complexes of Schiff bases have attracted considerable attention due to their antifungal, antibacterial and antitumour activity (Usha & Chandra, 1992; Garg & Kapur, 1990). Biological activities may be related to the redox properties of complexes: for some copper(II) complexes a lower reduction potential seems to be related to an increased antifungal activity (Haiduc & Silvestru, 1990). Mononuclear and dinuclear copper complexes can mimic the abilities of superoxide dismutase (SOD), catechol oxidase and chemical nucleases (Liu et al., 1996). Complexes of copper(II) with Schiff base ligands (Marten et al., 2005) are frequently studied, for example, for their antibacterial properties (You & Zhu, 2006). Dicopper(II) Schiff base and related complexes have been probed electrochemically (Zolezzi et al., 2002), magnetically (Zeyrek et al., 2006) and by electron paramagnetic resonance (EPR) (Griebel et al., 2006) for their electronic structure.
We have continued our exploration of complexes of the ligand N,N'-bis(trans-2-nitrocinnamaldehyde)ethylenediamine (Nca2en) and report here its first dinuclear complex, namely [Cu2Cl3(OH)(Nca2en)2]·1.5CH2Cl2, (I). The 11 previously reported complexes (referenced in Clegg et al., 2015) of cobalt, nickel, copper, zinc and silver are all mononuclear and four-coordinate, with a single Nca2en ligand and either one other bidentate or two monodentate ligands, except for the homoleptic salt [(Nca2en)2Cu]ClO4 (Dehghanpour et al., 2006). The structure reported here thus introduces new features to the series.
The source of the hydroxide ligand in the product of the synthesis is unclear; presumably it is derived from water in one of the reagents, the solvent or the atmosphere, as no precautions were taken to exclude air or moisture.
The dinuclear complex (Fig. 1) has hydroxide and chloride bridges between the two CuII atoms. Both metal centres have a coordination geometry best described as distorted trigonal bipyramidal, with the axial sites occupied by the bridging OH and one N atom (N3 or N7), the interaxial angles being essentially identical and deviating from the ideal value of 180° by only about 5° (Table 2). There is a difference, however, in the pattern of distortions from the ideal 120° angles in the equatorial planes: at Cu1 the Cl1—Cu1—Cl2 angle is significantly expanded to 150.99 (9)°, but at Cu2 the widest equatorial angle is Cl3—Cu2—N2 at 135.58 (18)°, and in each case the other two equatorial angles are approximately equal. This difference leads to a marked asymmetry in the central Cu2OCl3 core of the complex, which might have been expected to display an approximate mirror plane passing through the bridging ligands; the asymmetry can also be seen in the significantly different Cu—Cl bond lengths to the chloride bridge and in the Cu—N bond lengths to the Schiff base ligands. The τ parameter (Addison et al., 1984) is 0.40 for Cu1 and 0.66 for Cu2, indicating a geometry intermediate between ideal trigonal bipyramidal (τ = 1) and square-based pyramidal (τ = 0) and significantly different for the two metal centres. The closer approach to square-based pyramidal geometry for Cu1 is mainly a consequence of the wide Cl1—Cu1—Cl2 angle. The oxidation state +2 is confirmed for both CuII atoms by bond valence calculations (Brese & O'Keeffe, 1991; Brown, 2002), a bond valence sum of 2.1 being obtained in each case.
The four-membered Cu2OCl ring is folded, with a dihedral (hinge) angle of 152.0 (3)° between the two OCuCl planes. A search of the CSD for the Cu2OCl3 core finds just eight previous examples that are not parts of larger clusters with more than two Cu atoms; all have two five-coordinate CuII atoms, the other two coordination sites being taken by N atoms of uncharged ligands in each case. Of these, six have a tetradentate ligand that plays both chelating and bridging roles, imposing a marked fold on the central four-membered ring, the hinge angle ranging from 135.6 to 142.7° with phthalazine-based ligands (Marongiu & Lingafelter, 1982; Mandal et al., 1985; Thompson et al., 1987; Chen et al., 1993, 1996) and the more open 159.6° for one 1,8-naphthyridine-based ligand (Tikkanen et al., 1984); the hinge angle is widened to 168.2° for a complex with chelating but nonbridging propylenediamine ligands (Walther et al., 1997) and 178.9° (virtually planar) for a complex with monodentate pyrazole ligands (Mezei & Raptis, 2004). Within this small set of structures, there is thus a strong correlation between the degree of folding of the four-membered ring and the N—Cu—N bite angle and bridging geometry restrictions imposed by the N-donor ligands. Interestingly, almost all of these structures have approximately symmetrical chloride bridges, the difference in the two Cu—Cl bond lengths being <0.08 Å, except in the structure with the most similar ligand environment to that of the present compound (Walther et al., 1997), where the distances are 2.507 and 2.648 Å, a difference of 0.141 Å, essentially identical to the one found here; all the hydroxide bridges are approximately symmetrical.
Each of the two Nca2en ligands has two substituents attached to the central chelate ring, consisting of three essentially planar groups that are twisted relative to each other. In each case, the nitro group and the conjugated N═ C—C═C chain are rotated in the same direction (clockwise or anticlockwise) out of the plane of the benzene ring; the dihedral angles between the ring and nitro group range from 15.7 (8) to 34.8 (9)°, and those between the ring and the chain range from 19.7 (7) to 36.8 (6)°. The two ligands differ significantly in the conformation of their chelate rings: the ring containing atom Cu1 is best described as an envelope with atom C30 as the flap atom displaced from the mean plane of the other four atoms, while the ring containing atom Cu2 is twisted on the N2—C10 bond (these two atoms lie above and below the plane of the other three atoms). This difference contributes further to the asymmetry of the molecule and leads to a much more strongly marked bowing of the Cu2-coordinated ligand.
The benzene rings containing atoms C15 and C35, one in each of the two ligands, are approximately parallel [dihedral angle = 20.0 (4)°] and sufficiently close together [separation of centroids = 3.915 (6) Å] to indicate a possible weak intramolecular ring-stacking interaction; this can be seen in Fig. 1. More significant interactions are found for rings of the Cu2-coordinated ligand (containing atoms C6 and C15) in pairs of inversion-related cations, with a centroid–centroid separation of 3.730 (6) Å and dihedral angle of 7.8 (4)°. The space between these two molecules is occupied by two dichloromethane molecules having close contacts with the two bridging chloride ligands (see Supporting information and Fig. 2), which may be considered as C—H···Cl secondary hydrogen-bonding interactions supporting the ring stacking in dimer formation. Other close C—H···X contacts listed in the Supporting information involve the terminal chloride ligands and O atoms of the nitro groups.
To a stirred solution of CuCl (99 mg, 1 mmol) in dichloromethane (5 ml) was added dropwise a solution of N,N'-bis(trans-2-nitrocinnamaldehyde)ethylenediamine (378 mg, 1 mmol) in dichloromethane (10 ml) at room temperature, and stirring was continued for 1 h. After filtration, the volume of the solution was reduced under vacuum to about 4 ml. Slow diffusion of diethyl ether vapour into this concentrated solution gave yellow crystals suitable for X-ray diffraction, albeit with relatively weak diffraction at higher angles (yield 291 mg, 58%). Analysis calculated for C40H37Cl3Cu2N8O9: C 47.70, H 3.70, N 11.12%; calculated for C40H37Cl3Cu2N8O9·1.5CH2Cl2: C 43.93, H 3.55, N 9.87%; found, C 47.66, H 3.67, N 11.07%. This indicates that solvent of crystallization was lost in the preparation for analysis following removal from the mother liquor.
Crystal data, data collection and structure refinement details are summarized in Table 1. One dichloromethane solvent molecule was found to be ordered in a general position, and another lies across a mirror plane with the CH2 group disordered unequally [0.91 (2):0.09 (2)] over two positions in the mirror plane; similarity restraints were applied to the C—Cl distances and anisotropic displacement parameters of this molecule, and the displacement parameters were also subject to a `rigid-bond' restraint. The H atom of the bridging OH ligand was located in a difference map and was refined with the O—H distance restrained to 0.84 (1) Å, but with no contraint or restraint on its isotropic displacement parameter. All other H atoms were included in calculated positions and refined with a riding model, and with Uiso(H) = 1.2Ueq(C). A number of reflections (amounting to around 30 in the unique set) were rejected during processing of the raw data because of inconsistent intensities; these are likely to have been affected by overlap of diffraction from a minor second crystal component.
Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and local programs.
[Cu2Cl3(OH)(C20H18N4O4)2]·1.5CH2Cl2 | F(000) = 4616 |
Mr = 1134.59 | Dx = 1.534 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 33.62 (3) Å | Cell parameters from 7202 reflections |
b = 14.897 (11) Å | θ = 2.3–26.2° |
c = 20.948 (16) Å | µ = 1.25 mm−1 |
β = 110.544 (14)° | T = 150 K |
V = 9825 (13) Å3 | Block, yellow |
Z = 8 | 0.34 × 0.30 × 0.30 mm |
Bruker SMART 1K CCD diffractometer | 4768 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.119 |
thin–slice ω scans | θmax = 24.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −38→38 |
Tmin = 0.681, Tmax = 0.710 | k = −17→17 |
29716 measured reflections | l = −23→23 |
7672 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.067 | Hydrogen site location: mixed |
wR(F2) = 0.223 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1276P)2] where P = (Fo2 + 2Fc2)/3 |
7672 reflections | (Δ/σ)max < 0.001 |
610 parameters | Δρmax = 0.98 e Å−3 |
20 restraints | Δρmin = −0.86 e Å−3 |
[Cu2Cl3(OH)(C20H18N4O4)2]·1.5CH2Cl2 | V = 9825 (13) Å3 |
Mr = 1134.59 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.62 (3) Å | µ = 1.25 mm−1 |
b = 14.897 (11) Å | T = 150 K |
c = 20.948 (16) Å | 0.34 × 0.30 × 0.30 mm |
β = 110.544 (14)° |
Bruker SMART 1K CCD diffractometer | 7672 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 4768 reflections with I > 2σ(I) |
Tmin = 0.681, Tmax = 0.710 | Rint = 0.119 |
29716 measured reflections | θmax = 24.0° |
R[F2 > 2σ(F2)] = 0.067 | 20 restraints |
wR(F2) = 0.223 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.98 e Å−3 |
7672 reflections | Δρmin = −0.86 e Å−3 |
610 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.25480 (3) | 0.56019 (5) | 0.30938 (5) | 0.0282 (3) | |
Cu2 | 0.22336 (3) | 0.42622 (5) | 0.39632 (4) | 0.0282 (3) | |
O1 | 0.21615 (16) | 0.4631 (3) | 0.3046 (2) | 0.0308 (12) | |
H1 | 0.219 (3) | 0.420 (4) | 0.282 (4) | 0.05 (3)* | |
Cl1 | 0.25122 (6) | 0.58769 (11) | 0.42137 (10) | 0.0361 (5) | |
Cl2 | 0.28260 (8) | 0.48552 (12) | 0.23880 (13) | 0.0586 (7) | |
Cl3 | 0.27602 (6) | 0.32646 (12) | 0.39843 (10) | 0.0393 (5) | |
N1 | 0.0210 (3) | 0.6736 (5) | 0.1857 (4) | 0.059 (2) | |
O2 | −0.0133 (2) | 0.7131 (5) | 0.1626 (4) | 0.075 (2) | |
O3 | 0.0233 (3) | 0.5912 (5) | 0.1863 (5) | 0.109 (3) | |
N2 | 0.1597 (2) | 0.4179 (4) | 0.3787 (3) | 0.0353 (15) | |
N3 | 0.22556 (19) | 0.3912 (4) | 0.4903 (3) | 0.0341 (15) | |
N4 | 0.4020 (2) | 0.3775 (4) | 0.7412 (4) | 0.0469 (18) | |
O4 | 0.4245 (2) | 0.3797 (4) | 0.8024 (3) | 0.0597 (17) | |
O5 | 0.3769 (2) | 0.3158 (4) | 0.7156 (3) | 0.0616 (18) | |
C1 | 0.0607 (3) | 0.7258 (5) | 0.2093 (4) | 0.0383 (19) | |
C2 | 0.0608 (3) | 0.8054 (6) | 0.1754 (5) | 0.051 (2) | |
H2 | 0.0363 | 0.8246 | 0.1389 | 0.061* | |
C3 | 0.0974 (4) | 0.8561 (6) | 0.1960 (6) | 0.062 (3) | |
H3 | 0.0987 | 0.9094 | 0.1720 | 0.075* | |
C4 | 0.1321 (3) | 0.8302 (5) | 0.2512 (6) | 0.056 (3) | |
H4 | 0.1565 | 0.8677 | 0.2660 | 0.068* | |
C5 | 0.1320 (3) | 0.7505 (5) | 0.2854 (4) | 0.0393 (19) | |
H5 | 0.1562 | 0.7339 | 0.3235 | 0.047* | |
C6 | 0.0961 (3) | 0.6942 (5) | 0.2638 (4) | 0.039 (2) | |
C7 | 0.0958 (3) | 0.6082 (5) | 0.2973 (4) | 0.0369 (19) | |
H7 | 0.0703 | 0.5892 | 0.3031 | 0.044* | |
C8 | 0.1306 (2) | 0.5544 (5) | 0.3203 (4) | 0.0343 (18) | |
H8 | 0.1562 | 0.5710 | 0.3137 | 0.041* | |
C9 | 0.1284 (2) | 0.4719 (5) | 0.3551 (4) | 0.0380 (19) | |
H9 | 0.1024 | 0.4571 | 0.3608 | 0.046* | |
C10 | 0.1551 (3) | 0.3383 (5) | 0.4178 (5) | 0.047 (2) | |
H10A | 0.1645 | 0.2831 | 0.4008 | 0.056* | |
H10B | 0.1253 | 0.3307 | 0.4149 | 0.056* | |
C11 | 0.1842 (2) | 0.3590 (6) | 0.4917 (4) | 0.047 (2) | |
H11A | 0.1711 | 0.4055 | 0.5116 | 0.057* | |
H11B | 0.1884 | 0.3042 | 0.5200 | 0.057* | |
C12 | 0.2555 (2) | 0.3938 (5) | 0.5468 (4) | 0.0344 (18) | |
H12 | 0.2500 | 0.3716 | 0.5854 | 0.041* | |
C13 | 0.2977 (2) | 0.4281 (4) | 0.5578 (4) | 0.0316 (17) | |
H13 | 0.3055 | 0.4453 | 0.5202 | 0.038* | |
C14 | 0.3257 (2) | 0.4354 (4) | 0.6218 (4) | 0.0322 (18) | |
H14 | 0.3178 | 0.4113 | 0.6576 | 0.039* | |
C15 | 0.3681 (2) | 0.4782 (5) | 0.6406 (4) | 0.0328 (18) | |
C16 | 0.3722 (3) | 0.5530 (5) | 0.6031 (4) | 0.0367 (19) | |
H16 | 0.3489 | 0.5711 | 0.5643 | 0.044* | |
C17 | 0.4103 (3) | 0.6016 (5) | 0.6221 (4) | 0.046 (2) | |
H17 | 0.4126 | 0.6523 | 0.5961 | 0.055* | |
C18 | 0.4450 (3) | 0.5755 (5) | 0.6795 (4) | 0.046 (2) | |
H18 | 0.4710 | 0.6078 | 0.6918 | 0.055* | |
C19 | 0.4411 (3) | 0.5023 (5) | 0.7182 (4) | 0.043 (2) | |
H19 | 0.4642 | 0.4848 | 0.7576 | 0.052* | |
C20 | 0.4028 (3) | 0.4551 (5) | 0.6981 (4) | 0.0360 (19) | |
N5 | 0.0608 (3) | 0.5335 (6) | −0.0240 (4) | 0.061 (2) | |
O6 | 0.0313 (4) | 0.5281 (7) | −0.0756 (5) | 0.142 (4) | |
O7 | 0.0865 (3) | 0.5890 (5) | −0.0194 (4) | 0.087 (2) | |
N6 | 0.21390 (19) | 0.6619 (4) | 0.2452 (3) | 0.0279 (14) | |
N7 | 0.2979 (2) | 0.6568 (4) | 0.3229 (3) | 0.0280 (14) | |
N8 | 0.4795 (2) | 0.5391 (4) | 0.5511 (3) | 0.0388 (16) | |
O8 | 0.51637 (19) | 0.5214 (4) | 0.5873 (3) | 0.0572 (17) | |
O9 | 0.46738 (19) | 0.6159 (4) | 0.5332 (3) | 0.0513 (15) | |
C21 | 0.0666 (3) | 0.4692 (6) | 0.0326 (4) | 0.045 (2) | |
C22 | 0.0439 (3) | 0.3901 (7) | 0.0139 (6) | 0.069 (3) | |
H22 | 0.0254 | 0.3819 | −0.0319 | 0.083* | |
C23 | 0.0478 (3) | 0.3240 (6) | 0.0604 (7) | 0.071 (3) | |
H23 | 0.0324 | 0.2694 | 0.0479 | 0.085* | |
C24 | 0.0755 (3) | 0.3388 (6) | 0.1279 (6) | 0.066 (3) | |
H24 | 0.0788 | 0.2941 | 0.1618 | 0.079* | |
C25 | 0.0982 (3) | 0.4196 (5) | 0.1449 (5) | 0.047 (2) | |
H25 | 0.1168 | 0.4280 | 0.1906 | 0.056* | |
C26 | 0.0948 (3) | 0.4871 (5) | 0.0989 (4) | 0.0385 (19) | |
C27 | 0.1191 (3) | 0.5714 (5) | 0.1203 (4) | 0.0356 (19) | |
H27 | 0.1068 | 0.6256 | 0.0981 | 0.043* | |
C28 | 0.1573 (3) | 0.5754 (5) | 0.1691 (4) | 0.0356 (19) | |
H28 | 0.1701 | 0.5209 | 0.1900 | 0.043* | |
C29 | 0.1803 (2) | 0.6587 (5) | 0.1920 (4) | 0.0320 (18) | |
H29 | 0.1701 | 0.7122 | 0.1668 | 0.038* | |
C30 | 0.2353 (2) | 0.7484 (4) | 0.2670 (4) | 0.0341 (18) | |
H30A | 0.2317 | 0.7686 | 0.3096 | 0.041* | |
H30B | 0.2231 | 0.7945 | 0.2314 | 0.041* | |
C31 | 0.2826 (2) | 0.7345 (5) | 0.2787 (4) | 0.0378 (19) | |
H31A | 0.2865 | 0.7244 | 0.2345 | 0.045* | |
H31B | 0.2989 | 0.7886 | 0.3002 | 0.045* | |
C32 | 0.3368 (3) | 0.6516 (5) | 0.3599 (4) | 0.0359 (19) | |
H32 | 0.3556 | 0.6988 | 0.3590 | 0.043* | |
C33 | 0.3536 (2) | 0.5725 (5) | 0.4048 (4) | 0.0372 (19) | |
H33 | 0.3335 | 0.5328 | 0.4124 | 0.045* | |
C34 | 0.3942 (3) | 0.5537 (5) | 0.4348 (4) | 0.0368 (19) | |
H34 | 0.4144 | 0.5949 | 0.4296 | 0.044* | |
C35 | 0.4100 (2) | 0.4737 (5) | 0.4753 (4) | 0.0342 (18) | |
C36 | 0.3849 (3) | 0.3962 (5) | 0.4600 (4) | 0.041 (2) | |
H36 | 0.3583 | 0.3980 | 0.4236 | 0.049* | |
C37 | 0.3975 (3) | 0.3172 (5) | 0.4960 (5) | 0.047 (2) | |
H37 | 0.3790 | 0.2668 | 0.4842 | 0.056* | |
C38 | 0.4358 (3) | 0.3093 (6) | 0.5482 (5) | 0.060 (3) | |
H38 | 0.4438 | 0.2543 | 0.5722 | 0.072* | |
C39 | 0.4632 (3) | 0.3838 (5) | 0.5658 (4) | 0.047 (2) | |
H39 | 0.4900 | 0.3805 | 0.6016 | 0.056* | |
C40 | 0.4493 (2) | 0.4641 (5) | 0.5283 (4) | 0.0340 (18) | |
C41 | 0.3071 (4) | 0.8150 (6) | 0.4835 (6) | 0.080 (4) | |
H41A | 0.2944 | 0.7553 | 0.4682 | 0.096* | |
H41B | 0.2993 | 0.8334 | 0.5230 | 0.096* | |
Cl4 | 0.36367 (10) | 0.8074 (2) | 0.50904 (19) | 0.0970 (10) | |
Cl5 | 0.28670 (12) | 0.89185 (19) | 0.41790 (16) | 0.0938 (10) | |
C42 | 0.0000 | 0.3843 (12) | 0.2500 | 0.109 (8) | 0.91 (2) |
H42A | −0.0016 | 0.4232 | 0.2874 | 0.131* | 0.454 (11) |
H42B | 0.0016 | 0.4232 | 0.2126 | 0.131* | 0.454 (11) |
C42' | 0.0000 | 0.243 (3) | 0.2500 | 0.110 (18) | 0.09 (2) |
H42C | 0.0016 | 0.2041 | 0.2126 | 0.132* | 0.046 (11) |
H42D | −0.0016 | 0.2041 | 0.2874 | 0.132* | 0.046 (11) |
Cl6 | 0.04555 (12) | 0.3145 (2) | 0.2798 (2) | 0.1118 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0355 (5) | 0.0190 (4) | 0.0315 (6) | 0.0024 (4) | 0.0136 (4) | 0.0041 (4) |
Cu2 | 0.0303 (5) | 0.0250 (5) | 0.0287 (5) | 0.0026 (4) | 0.0098 (4) | 0.0073 (4) |
O1 | 0.047 (3) | 0.019 (2) | 0.026 (3) | 0.000 (2) | 0.013 (3) | 0.000 (2) |
Cl1 | 0.0514 (12) | 0.0251 (9) | 0.0390 (12) | −0.0047 (8) | 0.0247 (10) | −0.0023 (8) |
Cl2 | 0.0998 (19) | 0.0244 (10) | 0.0821 (18) | −0.0003 (11) | 0.0700 (16) | −0.0042 (10) |
Cl3 | 0.0456 (12) | 0.0321 (10) | 0.0400 (12) | 0.0116 (9) | 0.0148 (10) | 0.0055 (8) |
N1 | 0.061 (5) | 0.041 (5) | 0.063 (6) | 0.016 (4) | 0.006 (4) | 0.010 (4) |
O2 | 0.054 (4) | 0.065 (4) | 0.096 (6) | 0.017 (4) | 0.014 (4) | 0.016 (4) |
O3 | 0.087 (6) | 0.038 (4) | 0.150 (9) | 0.009 (4) | −0.022 (6) | −0.014 (5) |
N2 | 0.043 (4) | 0.029 (3) | 0.033 (4) | 0.002 (3) | 0.012 (3) | 0.013 (3) |
N3 | 0.030 (4) | 0.036 (4) | 0.035 (4) | 0.004 (3) | 0.010 (3) | 0.011 (3) |
N4 | 0.051 (5) | 0.029 (4) | 0.053 (5) | −0.010 (3) | 0.008 (4) | −0.004 (3) |
O4 | 0.074 (5) | 0.054 (4) | 0.041 (4) | −0.012 (3) | 0.008 (4) | 0.004 (3) |
O5 | 0.075 (5) | 0.036 (3) | 0.059 (4) | −0.002 (3) | 0.004 (4) | 0.012 (3) |
C1 | 0.044 (5) | 0.027 (4) | 0.046 (5) | 0.005 (4) | 0.018 (4) | −0.002 (4) |
C2 | 0.067 (6) | 0.040 (5) | 0.057 (6) | 0.019 (5) | 0.036 (5) | 0.004 (4) |
C3 | 0.102 (9) | 0.033 (5) | 0.084 (8) | 0.027 (6) | 0.074 (7) | 0.020 (5) |
C4 | 0.059 (6) | 0.030 (5) | 0.100 (8) | 0.001 (4) | 0.052 (6) | −0.003 (5) |
C5 | 0.040 (5) | 0.036 (4) | 0.042 (5) | 0.010 (4) | 0.014 (4) | 0.005 (4) |
C6 | 0.049 (5) | 0.021 (4) | 0.055 (6) | 0.012 (4) | 0.029 (5) | 0.005 (4) |
C7 | 0.040 (5) | 0.035 (4) | 0.038 (5) | 0.001 (4) | 0.017 (4) | 0.004 (4) |
C8 | 0.031 (4) | 0.034 (4) | 0.036 (5) | 0.010 (3) | 0.009 (4) | 0.009 (3) |
C9 | 0.032 (5) | 0.037 (4) | 0.047 (5) | 0.004 (4) | 0.016 (4) | 0.012 (4) |
C10 | 0.039 (5) | 0.031 (4) | 0.066 (6) | −0.001 (4) | 0.013 (5) | 0.020 (4) |
C11 | 0.034 (5) | 0.058 (5) | 0.052 (6) | 0.004 (4) | 0.019 (4) | 0.025 (4) |
C12 | 0.043 (5) | 0.031 (4) | 0.033 (5) | 0.003 (4) | 0.018 (4) | 0.007 (3) |
C13 | 0.037 (5) | 0.030 (4) | 0.029 (5) | 0.002 (3) | 0.013 (4) | −0.003 (3) |
C14 | 0.045 (5) | 0.028 (4) | 0.028 (5) | 0.005 (3) | 0.019 (4) | −0.001 (3) |
C15 | 0.039 (5) | 0.030 (4) | 0.030 (4) | 0.002 (3) | 0.013 (4) | −0.010 (3) |
C16 | 0.046 (5) | 0.034 (4) | 0.031 (5) | 0.005 (4) | 0.014 (4) | −0.006 (3) |
C17 | 0.065 (6) | 0.041 (5) | 0.042 (5) | 0.003 (4) | 0.031 (5) | −0.001 (4) |
C18 | 0.049 (5) | 0.046 (5) | 0.046 (6) | −0.015 (4) | 0.022 (5) | −0.012 (4) |
C19 | 0.044 (5) | 0.039 (5) | 0.041 (5) | 0.000 (4) | 0.008 (4) | −0.009 (4) |
C20 | 0.050 (5) | 0.027 (4) | 0.035 (5) | −0.004 (4) | 0.021 (4) | −0.004 (3) |
N5 | 0.063 (6) | 0.067 (5) | 0.044 (5) | −0.026 (5) | 0.008 (5) | −0.013 (4) |
O6 | 0.157 (9) | 0.140 (9) | 0.078 (7) | −0.058 (8) | −0.020 (7) | 0.019 (6) |
O7 | 0.118 (7) | 0.073 (5) | 0.056 (5) | −0.032 (5) | 0.014 (5) | 0.003 (4) |
N6 | 0.034 (4) | 0.021 (3) | 0.031 (4) | 0.006 (3) | 0.016 (3) | 0.004 (3) |
N7 | 0.035 (4) | 0.026 (3) | 0.024 (3) | 0.001 (3) | 0.011 (3) | 0.003 (3) |
N8 | 0.036 (4) | 0.040 (4) | 0.041 (4) | −0.010 (3) | 0.015 (4) | −0.011 (3) |
O8 | 0.031 (4) | 0.053 (4) | 0.074 (5) | −0.006 (3) | 0.002 (3) | −0.011 (3) |
O9 | 0.057 (4) | 0.030 (3) | 0.067 (4) | −0.008 (3) | 0.022 (3) | −0.001 (3) |
C21 | 0.049 (5) | 0.047 (5) | 0.042 (5) | −0.006 (4) | 0.020 (5) | 0.005 (4) |
C22 | 0.061 (7) | 0.065 (7) | 0.083 (8) | −0.026 (5) | 0.026 (6) | −0.018 (6) |
C23 | 0.074 (7) | 0.044 (6) | 0.108 (10) | −0.026 (5) | 0.049 (7) | −0.022 (6) |
C24 | 0.087 (8) | 0.033 (5) | 0.093 (9) | −0.004 (5) | 0.051 (7) | −0.006 (5) |
C25 | 0.059 (6) | 0.033 (4) | 0.053 (6) | −0.001 (4) | 0.025 (5) | 0.004 (4) |
C26 | 0.049 (5) | 0.031 (4) | 0.040 (5) | 0.002 (4) | 0.021 (4) | 0.003 (4) |
C27 | 0.049 (5) | 0.026 (4) | 0.028 (5) | 0.003 (4) | 0.009 (4) | 0.002 (3) |
C28 | 0.049 (5) | 0.026 (4) | 0.034 (5) | 0.003 (4) | 0.017 (4) | 0.003 (3) |
C29 | 0.047 (5) | 0.029 (4) | 0.022 (4) | 0.013 (4) | 0.014 (4) | 0.009 (3) |
C30 | 0.043 (5) | 0.019 (4) | 0.042 (5) | 0.005 (3) | 0.017 (4) | 0.005 (3) |
C31 | 0.049 (5) | 0.027 (4) | 0.039 (5) | 0.004 (4) | 0.017 (4) | 0.008 (3) |
C32 | 0.046 (5) | 0.030 (4) | 0.039 (5) | −0.008 (4) | 0.024 (4) | 0.000 (4) |
C33 | 0.035 (5) | 0.035 (4) | 0.039 (5) | 0.000 (4) | 0.010 (4) | 0.009 (4) |
C34 | 0.042 (5) | 0.034 (4) | 0.038 (5) | 0.000 (4) | 0.018 (4) | −0.003 (4) |
C35 | 0.038 (5) | 0.036 (4) | 0.033 (5) | −0.006 (4) | 0.018 (4) | −0.003 (3) |
C36 | 0.034 (5) | 0.035 (4) | 0.056 (6) | −0.006 (4) | 0.019 (4) | −0.001 (4) |
C37 | 0.047 (5) | 0.032 (4) | 0.055 (6) | −0.013 (4) | 0.010 (5) | 0.004 (4) |
C38 | 0.080 (7) | 0.038 (5) | 0.065 (7) | 0.003 (5) | 0.029 (6) | 0.018 (5) |
C39 | 0.050 (6) | 0.045 (5) | 0.043 (5) | −0.003 (4) | 0.015 (5) | 0.001 (4) |
C40 | 0.035 (5) | 0.027 (4) | 0.042 (5) | −0.003 (3) | 0.016 (4) | −0.003 (3) |
C41 | 0.133 (10) | 0.049 (6) | 0.091 (9) | 0.006 (6) | 0.080 (8) | −0.001 (6) |
Cl4 | 0.095 (2) | 0.088 (2) | 0.115 (3) | 0.0090 (18) | 0.046 (2) | 0.0016 (19) |
Cl5 | 0.142 (3) | 0.0618 (17) | 0.076 (2) | 0.0238 (18) | 0.036 (2) | −0.0086 (15) |
C42 | 0.046 (9) | 0.062 (10) | 0.20 (2) | 0.000 | 0.019 (9) | 0.000 |
C42' | 0.096 (14) | 0.104 (18) | 0.13 (4) | 0.000 | 0.037 (15) | 0.000 |
Cl6 | 0.100 (3) | 0.099 (2) | 0.139 (3) | 0.009 (2) | 0.045 (2) | −0.006 (2) |
Cu1—O1 | 1.923 (5) | N5—O7 | 1.176 (9) |
Cu1—Cl1 | 2.426 (3) | N5—C21 | 1.482 (12) |
Cu1—Cl2 | 2.295 (2) | N6—C29 | 1.280 (9) |
Cu1—N6 | 2.168 (6) | N6—C30 | 1.468 (9) |
Cu1—N7 | 1.991 (6) | N7—C31 | 1.458 (9) |
Cu2—O1 | 1.930 (5) | N7—C32 | 1.269 (9) |
Cu2—Cl1 | 2.568 (3) | N8—O8 | 1.234 (8) |
Cu2—Cl3 | 2.300 (2) | N8—O9 | 1.228 (8) |
Cu2—N2 | 2.043 (7) | N8—C40 | 1.471 (9) |
Cu2—N3 | 2.012 (6) | C21—C22 | 1.385 (12) |
O1—H1 | 0.837 (10) | C21—C26 | 1.406 (12) |
N1—O2 | 1.234 (9) | C22—H22 | 0.950 |
N1—O3 | 1.230 (9) | C22—C23 | 1.359 (15) |
N1—C1 | 1.472 (11) | C23—H23 | 0.950 |
N2—C9 | 1.280 (9) | C23—C24 | 1.411 (15) |
N2—C10 | 1.480 (9) | C24—H24 | 0.950 |
N3—C11 | 1.480 (9) | C24—C25 | 1.403 (12) |
N3—C12 | 1.257 (9) | C25—H25 | 0.950 |
N4—O4 | 1.239 (9) | C25—C26 | 1.370 (11) |
N4—O5 | 1.237 (8) | C26—C27 | 1.479 (10) |
N4—C20 | 1.472 (10) | C27—H27 | 0.950 |
C1—C2 | 1.383 (11) | C27—C28 | 1.332 (11) |
C1—C6 | 1.411 (11) | C28—H28 | 0.950 |
C2—H2 | 0.950 | C28—C29 | 1.452 (10) |
C2—C3 | 1.377 (13) | C29—H29 | 0.950 |
C3—H3 | 0.950 | C30—H30A | 0.990 |
C3—C4 | 1.378 (14) | C30—H30B | 0.990 |
C4—H4 | 0.950 | C30—C31 | 1.534 (10) |
C4—C5 | 1.388 (11) | C31—H31A | 0.990 |
C5—H5 | 0.950 | C31—H31B | 0.990 |
C5—C6 | 1.408 (11) | C32—H32 | 0.950 |
C6—C7 | 1.463 (10) | C32—C33 | 1.489 (10) |
C7—H7 | 0.950 | C33—H33 | 0.950 |
C7—C8 | 1.360 (10) | C33—C34 | 1.318 (11) |
C8—H8 | 0.950 | C34—H34 | 0.950 |
C8—C9 | 1.444 (10) | C34—C35 | 1.450 (10) |
C9—H9 | 0.950 | C35—C36 | 1.399 (10) |
C10—H10A | 0.990 | C35—C40 | 1.405 (11) |
C10—H10B | 0.990 | C36—H36 | 0.950 |
C10—C11 | 1.543 (12) | C36—C37 | 1.382 (11) |
C11—H11A | 0.990 | C37—H37 | 0.950 |
C11—H11B | 0.990 | C37—C38 | 1.373 (12) |
C12—H12 | 0.950 | C38—H38 | 0.950 |
C12—C13 | 1.448 (10) | C38—C39 | 1.405 (12) |
C13—H13 | 0.950 | C39—H39 | 0.950 |
C13—C14 | 1.346 (10) | C39—C40 | 1.417 (11) |
C14—H14 | 0.950 | C41—H41A | 0.990 |
C14—C15 | 1.482 (10) | C41—H41B | 0.990 |
C15—C16 | 1.396 (10) | C41—Cl4 | 1.790 (12) |
C15—C20 | 1.396 (11) | C41—Cl5 | 1.734 (11) |
C16—H16 | 0.950 | C42—H42A | 0.990 |
C16—C17 | 1.401 (11) | C42—H42B | 0.990 |
C17—H17 | 0.950 | C42—Cl6 | 1.774 (11) |
C17—C18 | 1.405 (12) | C42—Cl6i | 1.774 (11) |
C18—H18 | 0.950 | C42'—H42C | 0.990 |
C18—C19 | 1.392 (11) | C42'—H42D | 0.990 |
C19—H19 | 0.950 | C42'—Cl6 | 1.79 (2) |
C19—C20 | 1.397 (11) | C42'—Cl6i | 1.79 (2) |
N5—O6 | 1.186 (11) | ||
O1—Cu1—Cl1 | 85.14 (15) | N4—C20—C15 | 122.2 (7) |
O1—Cu1—Cl2 | 91.30 (16) | N4—C20—C19 | 115.2 (7) |
O1—Cu1—N6 | 102.9 (2) | C15—C20—C19 | 122.6 (7) |
O1—Cu1—N7 | 174.7 (2) | O6—N5—O7 | 118.6 (10) |
Cl1—Cu1—Cl2 | 150.99 (9) | O6—N5—C21 | 121.2 (9) |
Cl1—Cu1—N6 | 104.25 (16) | O7—N5—C21 | 120.1 (8) |
Cl1—Cu1—N7 | 91.17 (17) | Cu1—N6—C29 | 133.5 (5) |
Cl2—Cu1—N6 | 104.61 (17) | Cu1—N6—C30 | 106.6 (4) |
Cl2—Cu1—N7 | 90.12 (18) | C29—N6—C30 | 119.4 (6) |
N6—Cu1—N7 | 81.6 (2) | Cu1—N7—C31 | 114.0 (5) |
Cu1—O1—Cu2 | 108.4 (2) | Cu1—N7—C32 | 125.9 (5) |
Cu1—O1—H1 | 113 (6) | C31—N7—C32 | 119.7 (6) |
Cu2—O1—H1 | 111 (6) | O8—N8—O9 | 122.7 (7) |
O1—Cu2—Cl1 | 81.13 (15) | O8—N8—C40 | 117.9 (7) |
O1—Cu2—Cl3 | 91.73 (16) | O9—N8—C40 | 119.4 (7) |
O1—Cu2—N2 | 94.6 (2) | N5—C21—C22 | 114.7 (9) |
O1—Cu2—N3 | 174.9 (2) | N5—C21—C26 | 121.4 (7) |
Cl1—Cu2—Cl3 | 112.22 (9) | C22—C21—C26 | 123.7 (9) |
Cl1—Cu2—N2 | 112.20 (17) | C21—C22—H22 | 119.7 |
Cl1—Cu2—N3 | 99.05 (19) | C21—C22—C23 | 120.6 (10) |
Cl3—Cu2—N2 | 135.58 (18) | H22—C22—C23 | 119.7 |
Cl3—Cu2—N3 | 92.87 (18) | C22—C23—H23 | 121.0 |
N2—Cu2—N3 | 80.7 (2) | C22—C23—C24 | 118.0 (9) |
Cu1—Cl1—Cu2 | 77.44 (6) | H23—C23—C24 | 121.0 |
O2—N1—O3 | 121.9 (8) | C23—C24—H24 | 120.1 |
O2—N1—C1 | 119.5 (7) | C23—C24—C25 | 119.8 (9) |
O3—N1—C1 | 118.5 (8) | H24—C24—C25 | 120.1 |
Cu2—N2—C9 | 134.4 (5) | C24—C25—H25 | 118.4 |
Cu2—N2—C10 | 104.7 (5) | C24—C25—C26 | 123.3 (9) |
C9—N2—C10 | 119.1 (6) | H25—C25—C26 | 118.4 |
Cu2—N3—C11 | 113.0 (5) | C21—C26—C25 | 114.6 (7) |
Cu2—N3—C12 | 131.0 (5) | C21—C26—C27 | 124.8 (7) |
C11—N3—C12 | 116.0 (7) | C25—C26—C27 | 120.6 (8) |
O4—N4—O5 | 122.9 (7) | C26—C27—H27 | 118.3 |
O4—N4—C20 | 118.5 (6) | C26—C27—C28 | 123.4 (7) |
O5—N4—C20 | 118.4 (7) | H27—C27—C28 | 118.3 |
N1—C1—C2 | 116.6 (8) | C27—C28—H28 | 118.4 |
N1—C1—C6 | 120.3 (7) | C27—C28—C29 | 123.3 (7) |
C2—C1—C6 | 123.2 (8) | H28—C28—C29 | 118.4 |
C1—C2—H2 | 120.9 | N6—C29—C28 | 121.6 (7) |
C1—C2—C3 | 118.2 (9) | N6—C29—H29 | 119.2 |
H2—C2—C3 | 120.9 | C28—C29—H29 | 119.2 |
C2—C3—H3 | 119.7 | N6—C30—H30A | 110.2 |
C2—C3—C4 | 120.6 (8) | N6—C30—H30B | 110.2 |
H3—C3—C4 | 119.7 | N6—C30—C31 | 107.4 (6) |
C3—C4—H4 | 119.4 | H30A—C30—H30B | 108.5 |
C3—C4—C5 | 121.2 (9) | H30A—C30—C31 | 110.2 |
H4—C4—C5 | 119.4 | H30B—C30—C31 | 110.2 |
C4—C5—H5 | 120.0 | N7—C31—C30 | 108.9 (6) |
C4—C5—C6 | 120.0 (8) | N7—C31—H31A | 109.9 |
H5—C5—C6 | 120.0 | N7—C31—H31B | 109.9 |
C1—C6—C5 | 116.6 (7) | C30—C31—H31A | 109.9 |
C1—C6—C7 | 122.3 (7) | C30—C31—H31B | 109.9 |
C5—C6—C7 | 121.2 (7) | H31A—C31—H31B | 108.3 |
C6—C7—H7 | 118.8 | N7—C32—H32 | 119.5 |
C6—C7—C8 | 122.4 (7) | N7—C32—C33 | 121.0 (7) |
H7—C7—C8 | 118.8 | H32—C32—C33 | 119.5 |
C7—C8—H8 | 120.4 | C32—C33—H33 | 117.7 |
C7—C8—C9 | 119.3 (7) | C32—C33—C34 | 124.6 (7) |
H8—C8—C9 | 120.4 | H33—C33—C34 | 117.7 |
N2—C9—C8 | 123.2 (7) | C33—C34—H34 | 118.0 |
N2—C9—H9 | 118.4 | C33—C34—C35 | 123.9 (7) |
C8—C9—H9 | 118.4 | H34—C34—C35 | 118.0 |
N2—C10—H10A | 110.9 | C34—C35—C36 | 118.5 (7) |
N2—C10—H10B | 110.9 | C34—C35—C40 | 126.5 (7) |
N2—C10—C11 | 104.1 (6) | C36—C35—C40 | 115.0 (7) |
H10A—C10—H10B | 109.0 | C35—C36—H36 | 118.9 |
H10A—C10—C11 | 110.9 | C35—C36—C37 | 122.2 (8) |
H10B—C10—C11 | 110.9 | H36—C36—C37 | 118.9 |
N3—C11—C10 | 108.3 (7) | C36—C37—H37 | 119.0 |
N3—C11—H11A | 110.0 | C36—C37—C38 | 122.0 (8) |
N3—C11—H11B | 110.0 | H37—C37—C38 | 119.0 |
C10—C11—H11A | 110.0 | C37—C38—H38 | 120.4 |
C10—C11—H11B | 110.0 | C37—C38—C39 | 119.1 (8) |
H11A—C11—H11B | 108.4 | H38—C38—C39 | 120.4 |
N3—C12—H12 | 117.4 | C38—C39—H39 | 121.2 |
N3—C12—C13 | 125.2 (7) | C38—C39—C40 | 117.6 (8) |
H12—C12—C13 | 117.4 | H39—C39—C40 | 121.2 |
C12—C13—H13 | 120.3 | N8—C40—C35 | 122.0 (7) |
C12—C13—C14 | 119.5 (7) | N8—C40—C39 | 114.0 (7) |
H13—C13—C14 | 120.3 | C35—C40—C39 | 124.0 (7) |
C13—C14—H14 | 117.6 | H41A—C41—H41B | 108.0 |
C13—C14—C15 | 124.8 (7) | H41A—C41—Cl4 | 109.4 |
H14—C14—C15 | 117.6 | H41A—C41—Cl5 | 109.4 |
C14—C15—C16 | 118.0 (7) | H41B—C41—Cl4 | 109.4 |
C14—C15—C20 | 123.9 (7) | H41B—C41—Cl5 | 109.4 |
C16—C15—C20 | 117.6 (7) | Cl4—C41—Cl5 | 111.2 (6) |
C15—C16—H16 | 119.5 | H42A—C42—H42B | 108.4 |
C15—C16—C17 | 121.0 (8) | H42A—C42—Cl6 | 110.1 |
H16—C16—C17 | 119.5 | H42A—C42—Cl6i | 110.1 |
C16—C17—H17 | 120.0 | H42B—C42—Cl6 | 110.1 |
C16—C17—C18 | 120.1 (8) | H42B—C42—Cl6i | 110.1 |
H17—C17—C18 | 120.0 | Cl6—C42—Cl6i | 108.2 (9) |
C17—C18—H18 | 120.1 | H42C—C42'—H42D | 108.6 |
C17—C18—C19 | 119.8 (8) | H42C—C42'—Cl6 | 110.4 |
H18—C18—C19 | 120.1 | H42C—C42'—Cl6i | 110.4 |
C18—C19—H19 | 120.5 | H42D—C42'—Cl6 | 110.4 |
C18—C19—C20 | 118.9 (8) | H42D—C42'—Cl6i | 110.4 |
H19—C19—C20 | 120.5 | Cl6—C42'—Cl6i | 107 (2) |
O2—N1—C1—C2 | −32.0 (12) | O6—N5—C21—C22 | 19.0 (14) |
O2—N1—C1—C6 | 147.9 (8) | O6—N5—C21—C26 | −164.1 (11) |
O3—N1—C1—C2 | 144.1 (9) | O7—N5—C21—C22 | −158.2 (9) |
O3—N1—C1—C6 | −36.0 (13) | O7—N5—C21—C26 | 18.8 (13) |
N1—C1—C2—C3 | −180.0 (7) | N5—C21—C22—C23 | 177.2 (9) |
C6—C1—C2—C3 | 0.0 (12) | C26—C21—C22—C23 | 0.4 (15) |
C1—C2—C3—C4 | −3.3 (12) | C21—C22—C23—C24 | 0.2 (15) |
C2—C3—C4—C5 | 3.2 (13) | C22—C23—C24—C25 | −0.5 (15) |
C3—C4—C5—C6 | 0.3 (12) | C23—C24—C25—C26 | 0.4 (14) |
C4—C5—C6—C1 | −3.3 (11) | C24—C25—C26—C21 | 0.1 (12) |
C4—C5—C6—C7 | 177.6 (7) | C24—C25—C26—C27 | 179.0 (8) |
N1—C1—C6—C5 | −176.8 (7) | N5—C21—C26—C25 | −177.1 (8) |
N1—C1—C6—C7 | 2.3 (11) | N5—C21—C26—C27 | 4.1 (13) |
C2—C1—C6—C5 | 3.2 (11) | C22—C21—C26—C25 | −0.5 (12) |
C2—C1—C6—C7 | −177.7 (7) | C22—C21—C26—C27 | −179.3 (8) |
C1—C6—C7—C8 | 143.7 (8) | C21—C26—C27—C28 | −148.9 (8) |
C5—C6—C7—C8 | −37.2 (11) | C25—C26—C27—C28 | 32.4 (12) |
C6—C7—C8—C9 | 177.8 (7) | C26—C27—C28—C29 | −177.4 (7) |
Cu2—N2—C9—C8 | 13.5 (13) | Cu1—N6—C29—C28 | 11.3 (11) |
C10—N2—C9—C8 | 175.7 (7) | C30—N6—C29—C28 | −178.5 (6) |
C7—C8—C9—N2 | −179.7 (8) | C27—C28—C29—N6 | 169.9 (7) |
Cu2—N2—C10—C11 | 57.0 (7) | Cu1—N6—C30—C31 | 42.5 (6) |
C9—N2—C10—C11 | −109.9 (8) | C29—N6—C30—C31 | −130.2 (7) |
Cu2—N3—C11—C10 | 15.0 (8) | Cu1—N7—C31—C30 | 33.9 (7) |
C12—N3—C11—C10 | −166.2 (7) | C32—N7—C31—C30 | −153.4 (7) |
N2—C10—C11—N3 | −47.0 (8) | N6—C30—C31—N7 | −50.9 (8) |
Cu2—N3—C12—C13 | 2.5 (11) | Cu1—N7—C32—C33 | −7.3 (10) |
C11—N3—C12—C13 | −176.0 (7) | C31—N7—C32—C33 | −179.0 (6) |
N3—C12—C13—C14 | 173.5 (7) | N7—C32—C33—C34 | 166.8 (8) |
C12—C13—C14—C15 | −173.1 (6) | C32—C33—C34—C35 | −176.4 (7) |
C13—C14—C15—C16 | 35.4 (10) | C33—C34—C35—C36 | 28.6 (11) |
C13—C14—C15—C20 | −152.3 (7) | C33—C34—C35—C40 | −153.6 (8) |
C14—C15—C16—C17 | 174.1 (7) | C34—C35—C36—C37 | −180.0 (8) |
C20—C15—C16—C17 | 1.2 (10) | C40—C35—C36—C37 | 2.0 (11) |
C15—C16—C17—C18 | 0.0 (11) | C35—C36—C37—C38 | −1.3 (13) |
C16—C17—C18—C19 | −1.2 (12) | C36—C37—C38—C39 | 0.0 (14) |
C17—C18—C19—C20 | 1.2 (11) | C37—C38—C39—C40 | 0.3 (13) |
C14—C15—C20—N4 | 7.7 (11) | C34—C35—C40—N8 | 2.4 (11) |
C14—C15—C20—C19 | −173.6 (7) | C34—C35—C40—C39 | −179.5 (7) |
C16—C15—C20—N4 | −179.9 (6) | C36—C35—C40—N8 | −179.8 (6) |
C16—C15—C20—C19 | −1.2 (11) | C36—C35—C40—C39 | −1.7 (11) |
C18—C19—C20—N4 | 178.8 (7) | C38—C39—C40—N8 | 178.8 (7) |
C18—C19—C20—C15 | 0.0 (11) | C38—C39—C40—C35 | 0.5 (12) |
O4—N4—C20—C15 | −151.6 (8) | O8—N8—C40—C35 | −165.2 (7) |
O4—N4—C20—C19 | 29.6 (10) | O8—N8—C40—C39 | 16.5 (10) |
O5—N4—C20—C15 | 24.0 (11) | O9—N8—C40—C35 | 14.2 (10) |
O5—N4—C20—C19 | −154.8 (7) | O9—N8—C40—C39 | −164.1 (7) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl2 | 0.84 (1) | 2.76 (8) | 3.027 (6) | 100 (6) |
C2—H2···O8ii | 0.95 | 2.52 | 3.218 (10) | 130 |
C4—H4···Cl2iii | 0.95 | 2.73 | 3.633 (9) | 160 |
C7—H7···O3 | 0.95 | 2.40 | 2.726 (11) | 100 |
C8—H8···O1 | 0.95 | 2.64 | 3.300 (9) | 127 |
C9—H9···Cl6 | 0.95 | 2.96 | 3.559 (9) | 122 |
C10—H10B···O7iv | 0.99 | 2.51 | 3.219 (12) | 129 |
C11—H11B···Cl3v | 0.99 | 2.59 | 3.544 (8) | 162 |
C13—H13···Cl3 | 0.95 | 2.97 | 3.502 (8) | 116 |
C14—H14···O5 | 0.95 | 2.40 | 2.761 (9) | 102 |
C27—H27···O7 | 0.95 | 2.38 | 2.754 (11) | 103 |
C28—H28···O1 | 0.95 | 2.51 | 3.290 (9) | 140 |
C30—H30B···Cl2iii | 0.99 | 2.93 | 3.579 (7) | 124 |
C30—H30B···Cl3iii | 0.99 | 2.77 | 3.546 (8) | 136 |
C33—H33···Cl1 | 0.95 | 2.95 | 3.584 (9) | 125 |
C34—H34···O9 | 0.95 | 2.29 | 2.757 (10) | 109 |
C41—H41A···Cl1 | 0.99 | 2.88 | 3.869 (11) | 176 |
C41—H41B···Cl1vi | 0.99 | 2.65 | 3.558 (10) | 153 |
Symmetry codes: (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y+1, z+1/2; (v) −x+1/2, −y+1/2, −z+1; (vi) −x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Cl3(OH)(C20H18N4O4)2]·1.5CH2Cl2 |
Mr | 1134.59 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 33.62 (3), 14.897 (11), 20.948 (16) |
β (°) | 110.544 (14) |
V (Å3) | 9825 (13) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.34 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.681, 0.710 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29716, 7672, 4768 |
Rint | 0.119 |
θmax (°) | 24.0 |
(sin θ/λ)max (Å−1) | 0.572 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.223, 1.05 |
No. of reflections | 7672 |
No. of parameters | 610 |
No. of restraints | 20 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.98, −0.86 |
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXTL (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXL2014 (Sheldrick, 2015) and local programs.
Cu1—O1 | 1.923 (5) | Cu2—O1 | 1.930 (5) |
Cu1—Cl1 | 2.426 (3) | Cu2—Cl1 | 2.568 (3) |
Cu1—Cl2 | 2.295 (2) | Cu2—Cl3 | 2.300 (2) |
Cu1—N6 | 2.168 (6) | Cu2—N2 | 2.043 (7) |
Cu1—N7 | 1.991 (6) | Cu2—N3 | 2.012 (6) |
O1—Cu1—Cl1 | 85.14 (15) | O1—Cu2—Cl1 | 81.13 (15) |
O1—Cu1—Cl2 | 91.30 (16) | O1—Cu2—Cl3 | 91.73 (16) |
O1—Cu1—N6 | 102.9 (2) | O1—Cu2—N2 | 94.6 (2) |
O1—Cu1—N7 | 174.7 (2) | O1—Cu2—N3 | 174.9 (2) |
Cl1—Cu1—Cl2 | 150.99 (9) | Cl1—Cu2—Cl3 | 112.22 (9) |
Cl1—Cu1—N6 | 104.25 (16) | Cl1—Cu2—N2 | 112.20 (17) |
Cl1—Cu1—N7 | 91.17 (17) | Cl1—Cu2—N3 | 99.05 (19) |
Cl2—Cu1—N6 | 104.61 (17) | Cl3—Cu2—N2 | 135.58 (18) |
Cl2—Cu1—N7 | 90.12 (18) | Cl3—Cu2—N3 | 92.87 (18) |
N6—Cu1—N7 | 81.6 (2) | N2—Cu2—N3 | 80.7 (2) |
Cu1—O1—Cu2 | 108.4 (2) | Cu1—Cl1—Cu2 | 77.44 (6) |
N2—C10—C11—N3 | −47.0 (8) | N6—C30—C31—N7 | −50.9 (8) |