trans-Bis(2,2-diphenyl­ethyl­amine-[kappa]N)bis­(5,5-diphenyl­hydantoinato-[kappa]N³)copper(II) and its chloro­form disolvate

The crystal structures of the title compounds, [Cu(C₁₅H₁₁N₂O₂)₂(C₁₄H₁₅N)₂] and [Cu(C₁₅H₁₁N₂O₂)₂(C₁₄H₁₅N)₂]·2CHCl₃, respectively, have been determined. The red disolvate complex affords a square-planar CuN₄ coordination environment in which the Cu^II atom lies on a centre of symmetry. The blue solvent-free complex affords a distorted square-pyramidal CuN₄O coordination environment and adjacent mol­ecules form centrosymmetric dimers. A comparison of the different crystal structures focuses on the role of the solvent mol­ecules in supramolecular assemblies of the copper(II) complexes.

S1. Comment

In recent years, studies of supramolecular self-assembling metal–organic frameworks of metal complexes have been extensively carried out, with the aim of rational construction of desired crystal structures and fine-tuning of their functions (Eddaoudi et al., 2001; Evans et al., 2002; Yaghi et al., 1998). In particular, host–guest inclusion of small molecules and hydrogen-bonded flexible self-assemblies enable the realisation of appropriate crystal packing containing guest molecules (Holman et al., 2001), which depends on the novelty of the secondary building units as a synthon. In this respect, for example, vapochromic switching of optoelectronic properties may be one of the most promising strategies for the preparation of functional materials (Kato et al., 2002; Fernandez et al., 2003). It is well known that copper(II) complexes exhibit a remarkable variety in their coordination geometries and corresponding optoelectronic properties. Some copper(II) complexes incorporating monodentate 5,5-diphenylhydantoinate ligands have been studied previously. In the solid state, most of the related complexes afford a four-coordinated square-planar CuN₄ coordination geometry (Akitsu, Komorita & Urushiyama, 2001) with the aid of crystal-packing forces. Appropriate steric factors of the ligands can lead to a tetrahedrally distorted square-planar CuN₄ coordination geometry (Akitsu et al., 2003) or a five-coordinated square-pyramidal CuN₄O coordination geometry (Akitsu et al., 1997). To date, structural regulation by other means, such as solvent in the crystal (Tynan et al., 2004), has not been observed for analogous complexes. We report here a structural comparison of trans-bis(2,2-diphenylethylamine)bis(5,5-diphenylhydantoinato)copper(II)chloroform disolvate, (I), and dimeric trans-bis(2,2-diphenylethylamine)bis(5,5-diphenylhydantoinato)copper(II), (II).

Complex (I), the chloroform disolvate, affords a square-planar CuN₄ coordination geometry, in which the Cu atom lies on an inversion centre (Fig. 1). Both the neutral 2,2-diphenylethylamine ligands and the anionic deprotonated 5,5-diphenylhydantoinate ligands act as monodentate ligands with N-atom donors, and they are coordinated on trans sites with respect to the Cu atom. The Cu—N bond distances (Table 1) are within the range found in related complexes, some of which are planar and some of which exhibit some tetrahedral distortion, viz. the Cu—N(imide) distances range from 1.975 (5) to 2.05 (1) Å, whereas the Cu—N(amine) distances range from 1.97 (1) to 2.030 (4) Å (Akitsu, Komorita & Kushi, 2001; Akitsu et al., 2003; Akitsu & Einaga, 2004). The cis-N1—Cu1—N3 angles are close to right angles. The dihedral angle between the Cu1/N1/N3/N1ⁱ/N3ⁱ mean plane of the coordination sphere and the N1/C1/N2/C2/C3 plane of the ligands is 139.4 (1)°, and those between the five-membered C3/C2/N1/C1/N2 ring of the 5,5-diphenylhydantoinate ligand and the connecting phenyl groups, i.e. C4/C5/C6/C7/C8/C9 and C10/C11/C12/C13/C14/C15, are 57.7 (1) and 123.0 (1)°, respectively [symmetry code: (i) 1 − x, 1 − y, 1 − z].

The solvent-free complex, (II), affords a slightly distorted pyramidal CuN₄ coordination geometry (Fig. 2) and adjacent molecules form centrosymmetric dimers, with Cu1—O3ⁱⁱⁱ 2.397 (4) Å [symmetry code: (iii) 2 − x, 1 − y, 1 − z] (Fig. 3). The Cu—N bond distances are also within the range found in related complexes (Table 3). The dihedral angle between the N1/Cu1/N3 and N4/Cu1/N6 planes is 16.69 (1)°. The Cu atom deviates slightly from the N1/N3/N4/N6 plane, by 0.178 (2) Å. The dihedral angle between the Cu1/N1/N3/N4/N6 and N1/C1/N2/C2/C3 planes is 94.7 (2)°, while that between the Cu1/N1/N3/N4/N6 and N4/C30/N5/C31/C32 planes is 35.2 (2)°. Although the planarity of the coordination environment is broken, the sp² character of the N-donor atoms of the 5,5-diphenylhydantoinate ligands is still maintained; the C1—N1—C3 and C30—N4—C31 bond angles are 108.0 (5) and 106.2 (5)°, respectively.

To the best of our knowledge, this is the first case of related complexes which exhibit different coordination geometries in the presence or absence of solvent molecules in the crystal. In the crystal structure of (I), four intramolecular hydrogen bonds are formed around the coordination sphere, i.e. N3—H13···O2 and N3—H12···O1ⁱ (Table 2). Furthermore, adjacent molecules are linked by double complementary intermolecular N2—H1···O1ⁱⁱ hydrogen bonds along the crystallographic b axis [N···O 2.900 (3) Å; symmetry code: (ii) 1 − x, 1 − y, −z]. The chloroform solvent molecules also play an important role in stabilizing the crystal packing of (I) via a C30—H27···O2 hydrogen bond [C···O 3.507 (5) Å]. On the other hand, the crystal-packing mode of (II) is quite different. Only two intramolecular hydrogen bonds, namely N3—H12···O4 and N6—H39···O3, are formed on one side of the coordination sphere (Table 4). Moreover, intermolecular hydrogen bonds, i.e. N5—H27···O2ⁱⁱⁱ and N2—H1···O4^iv, link adjacent molecules to form hydrogen-bonded networks [symmetry codes: (iii) 2 − x, 1 − y, 1 − z; (iv) 2 − x, 1 − y, −z].

S2. Experimental

Treatment of equimolar quantities of copper(II) acetate (0.454 g, 2.50 mmol), 5,5-diphenylhydantoin (1.26 g, 5.00 mmol) and 2,2-diphenylethylamine (0.99 g, 5.00 mmol) in ethanol (100 ml) at 323 K for 2 h gave rise to crude precipitates. Red–violet plate-like crystals of (I) were obtained from a solution in chloroform–methanol (4:1 v/v) at 298 K over a period of several days. IR (KBr): 1644 cm⁻¹ (amide I band); m.p. 629 K (decomposition). Recrystallization of the crude precipitates from a solution in chloroform–methanol (4:1 v/v) at 283 K overnight yielded only a small amount of blue–violet plate-like crystals of the solvent-free complex, (II). IR (KBr): 1645 cm⁻¹ (amide I band); m.p. 605 K (decomposition).

S3. Refinement

All H atoms were placed in calculated positions, with C—H = N—H = 0.95 Å, and included in the final cycles of refinement using a riding model, with U_iso(H) = 1.2U_eq(parent atom). The C atoms of the phenyl groups, viz. C4–C9, C10–C15, C18–C23 and C24–C29 for (I), and C4–C9, C10–C15, C18–C23, C24–C29, C33–C38, C39–C44, C47–C52 and C53–C58 for (II), were treated as rigid groups of anisotropic atoms. The intensity of the data was relatively weak, similar to some analogous mononuclear copper complexes with large organic ligands. The largest hole in the difference map of (II) is near atom Cu1, at (0.9919, 0.4909, 0.2953).

Computing details

For both compounds, data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Only one chloroform solvent molecule is shown. [Symmetry code: (i) 1 − x, 1 − y, 1 − z]. Fig. 2. The molecular structure of (II) as a monomer, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Fig. 3. The dimeric structure of (II). Displacement ellipsoids are drawn at the 30% probability level. H atoms and phenyl groups have been omitted for clarity. [Symmetry code: (iii) 2 − x, 1 − y, 1 − z].

(I)

Crystal data

[Cu(C15H11N2O2)2(C14H15N)2]·2CHCl3	F(000) = 2476.0
Mr = 1199.34	Dx = 1.393 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 19.37 (1) Å	θ = 10.3–12.6°
b = 29.796 (7) Å	µ = 0.72 mm^−1
c = 9.910 (3) Å	T = 298 K
V = 5720 (4) Å^3	Plate-like, red–violet
Z = 4	0.41 × 0.16 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.021
ω/2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −10→25
Tmin = 0.872, Tmax = 0.931	k = 0→38
8516 measured reflections	l = −12→5
6565 independent reflections	3 standard reflections every 150 reflections
3338 reflections with I > 2σ(I)	intensity decay: 0.2%

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.163	(Δ/σ)max < 0.001
S = 0.99	Δρmax = 0.43 e Å^−3
3338 reflections	Δρmin = −0.46 e Å^−3
302 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	0.5000	0.0307 (1)
Cl1	0.14371 (8)	0.44923 (5)	0.42211 (2)	0.1146 (6)
Cl2	0.1733 (1)	0.37426 (8)	0.5972 (2)	0.1334 (7)
Cl3	0.17950 (7)	0.36416 (6)	0.3122 (2)	0.1019 (5)
O1	0.5246 (1)	0.51803 (8)	0.1754 (2)	0.0439 (6)
O2	0.3656 (1)	0.43479 (8)	0.4037 (2)	0.0395 (6)
N1	0.4545 (1)	0.48014 (9)	0.3279 (3)	0.0318 (6)
N2	0.4543 (2)	0.46060 (9)	0.1070 (3)	0.0346 (6)
N3	0.4891 (2)	0.43761 (9)	0.5727 (3)	0.0392 (7)
C1	0.4814 (2)	0.4887 (1)	0.1992 (4)	0.0334 (8)
C2	0.4025 (2)	0.4493 (1)	0.3137 (4)	0.0331 (7)
C3	0.3996 (2)	0.4330 (1)	0.1652 (3)	0.0314 (7)
C4	0.3313 (1)	0.44243 (8)	0.0926 (2)	0.0375 (8)
C5	0.2762 (1)	0.46458 (9)	0.1527 (2)	0.055 (1)
C6	0.2169 (1)	0.4736 (1)	0.0784 (3)	0.074 (1)
C7	0.2128 (1)	0.4605 (1)	−0.0559 (3)	0.075 (2)
C8	0.2679 (2)	0.4383 (1)	−0.1160 (2)	0.067 (1)
C9	0.3272 (1)	0.42931 (9)	−0.0418 (2)	0.051 (1)
C10	0.4162 (1)	0.38285 (5)	0.1652 (3)	0.0341 (7)
C11	0.36363 (9)	0.35262 (7)	0.1946 (3)	0.0417 (8)
C12	0.3778 (1)	0.30693 (7)	0.2008 (3)	0.050 (1)
C13	0.4444 (1)	0.29147 (6)	0.1776 (3)	0.059 (1)
C14	0.4970 (1)	0.32170 (8)	0.1482 (3)	0.059 (1)
C15	0.4828 (1)	0.36739 (7)	0.1419 (3)	0.0480 (10)
C16	0.5351 (2)	0.4026 (1)	0.5163 (4)	0.0427 (9)
C17	0.5388 (2)	0.3603 (1)	0.6065 (4)	0.0431 (9)
C18	0.4681 (1)	0.34290 (8)	0.6445 (2)	0.0387 (8)
C19	0.4542 (1)	0.33384 (9)	0.7793 (2)	0.053 (1)
C20	0.3889 (2)	0.3193 (1)	0.8178 (2)	0.066 (1)
C21	0.3375 (1)	0.31388 (9)	0.7214 (3)	0.066 (1)
C22	0.3513 (1)	0.32295 (9)	0.5865 (3)	0.061 (1)
C23	0.4166 (1)	0.33746 (9)	0.5480 (2)	0.0494 (10)
C24	0.5871 (1)	0.32564 (8)	0.5414 (3)	0.0477 (10)
C25	0.5617 (1)	0.28857 (9)	0.4721 (4)	0.072 (1)
C26	0.6071 (2)	0.25845 (9)	0.4122 (4)	0.097 (2)
C27	0.6779 (2)	0.2654 (1)	0.4216 (4)	0.097 (2)
C28	0.7033 (1)	0.3024 (1)	0.4909 (4)	0.087 (2)
C29	0.6579 (1)	0.3326 (1)	0.5508 (3)	0.070 (1)
C30	0.1934 (2)	0.4010 (2)	0.4437 (6)	0.072 (1)
H1	0.4690	0.4589	0.0157	0.0416*
H2	0.2790	0.4737	0.2448	0.0668*
H3	0.1792	0.4889	0.1197	0.0870*
H4	0.1722	0.4667	−0.1064	0.0899*
H5	0.2651	0.4295	−0.2076	0.0825*
H6	0.3649	0.4142	−0.0826	0.0626*
H7	0.3180	0.3632	0.2107	0.0501*
H8	0.3418	0.2862	0.2211	0.0597*
H9	0.4541	0.2602	0.1820	0.0710*
H10	0.5425	0.3111	0.1323	0.0712*
H11	0.5187	0.3881	0.1219	0.0581*
H12	0.4967	0.4388	0.6670	0.0474*
H13	0.4427	0.4286	0.5555	0.0474*
H14	0.5184	0.3942	0.4297	0.0514*
H15	0.5802	0.4148	0.5076	0.0514*
H16	0.5602	0.3693	0.6883	0.0520*
H17	0.4893	0.3375	0.8452	0.0636*
H18	0.3794	0.3131	0.9099	0.0798*
H19	0.2928	0.3040	0.7474	0.0795*
H20	0.3162	0.3193	0.5204	0.0730*
H21	0.4262	0.3437	0.4558	0.0593*
H22	0.5133	0.2838	0.4659	0.0860*
H23	0.5897	0.2331	0.3650	0.1183*
H24	0.7089	0.2448	0.3804	0.1161*
H25	0.7516	0.3072	0.4968	0.1047*
H26	0.6752	0.3579	0.5977	0.0825*
H27	0.2406	0.4092	0.4449	0.0864*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0421 (3)	0.0223 (2)	0.0279 (3)	−0.0042 (3)	−0.0015 (3)	−0.0007 (3)
Cl1	0.0811 (10)	0.0693 (9)	0.193 (2)	0.0002 (8)	−0.023 (1)	0.021 (1)
Cl2	0.115 (1)	0.189 (2)	0.096 (1)	−0.005 (1)	−0.004 (1)	−0.025 (1)
Cl3	0.0743 (9)	0.110 (1)	0.121 (1)	−0.0162 (9)	−0.0226 (9)	0.050 (1)
O1	0.055 (2)	0.044 (1)	0.032 (1)	−0.021 (1)	0.004 (1)	−0.002 (1)
O2	0.042 (1)	0.040 (1)	0.037 (1)	−0.006 (1)	0.007 (1)	0.001 (1)
N1	0.040 (2)	0.027 (1)	0.029 (1)	−0.007 (1)	0.002 (1)	−0.002 (1)
N2	0.043 (2)	0.032 (1)	0.028 (1)	−0.009 (1)	0.004 (1)	−0.002 (1)
N3	0.057 (2)	0.027 (1)	0.033 (2)	−0.006 (1)	−0.002 (1)	0.002 (1)
C1	0.038 (2)	0.029 (2)	0.032 (2)	−0.003 (1)	−0.001 (1)	0.000 (1)
C2	0.037 (2)	0.025 (2)	0.038 (2)	0.001 (1)	0.000 (2)	−0.002 (1)
C3	0.035 (2)	0.025 (2)	0.034 (2)	−0.003 (1)	−0.002 (1)	−0.001 (1)
C4	0.043 (2)	0.029 (2)	0.040 (2)	−0.003 (1)	−0.005 (2)	0.003 (1)
C5	0.049 (2)	0.051 (2)	0.066 (3)	0.007 (2)	−0.007 (2)	0.006 (2)
C6	0.045 (3)	0.071 (3)	0.106 (4)	0.013 (2)	−0.005 (3)	0.021 (3)
C7	0.062 (3)	0.067 (3)	0.097 (4)	−0.020 (3)	−0.036 (3)	0.037 (3)
C8	0.081 (3)	0.058 (3)	0.062 (3)	−0.015 (2)	−0.032 (3)	0.012 (2)
C9	0.059 (3)	0.047 (2)	0.048 (2)	−0.004 (2)	−0.017 (2)	0.002 (2)
C10	0.043 (2)	0.029 (2)	0.031 (2)	0.000 (1)	−0.004 (2)	−0.003 (1)
C11	0.046 (2)	0.034 (2)	0.045 (2)	−0.006 (2)	−0.001 (2)	−0.002 (2)
C12	0.061 (3)	0.033 (2)	0.056 (2)	−0.008 (2)	−0.003 (2)	−0.002 (2)
C13	0.078 (3)	0.031 (2)	0.068 (3)	0.009 (2)	−0.011 (2)	−0.003 (2)
C14	0.056 (2)	0.048 (2)	0.074 (3)	0.018 (2)	0.003 (2)	−0.005 (2)
C15	0.046 (2)	0.039 (2)	0.059 (3)	0.002 (2)	−0.003 (2)	−0.004 (2)
C16	0.050 (2)	0.031 (2)	0.047 (2)	−0.004 (2)	−0.003 (2)	0.006 (2)
C17	0.050 (2)	0.035 (2)	0.045 (2)	−0.004 (2)	−0.010 (2)	0.004 (2)
C18	0.046 (2)	0.025 (2)	0.045 (2)	0.002 (2)	−0.004 (2)	0.001 (1)
C19	0.067 (3)	0.045 (2)	0.046 (2)	−0.002 (2)	−0.001 (2)	−0.003 (2)
C20	0.086 (3)	0.061 (3)	0.052 (3)	−0.002 (3)	0.024 (3)	−0.004 (2)
C21	0.055 (3)	0.053 (3)	0.089 (4)	−0.004 (2)	0.016 (3)	−0.001 (3)
C22	0.049 (2)	0.055 (2)	0.080 (3)	−0.005 (2)	−0.011 (2)	−0.001 (2)
C23	0.056 (2)	0.043 (2)	0.049 (2)	−0.010 (2)	−0.007 (2)	0.007 (2)
C24	0.046 (2)	0.039 (2)	0.057 (2)	0.004 (2)	0.000 (2)	0.010 (2)
C25	0.055 (3)	0.046 (2)	0.115 (5)	−0.001 (2)	0.013 (3)	−0.016 (3)
C26	0.080 (4)	0.065 (3)	0.147 (6)	0.008 (3)	0.017 (4)	−0.033 (4)
C27	0.084 (4)	0.086 (4)	0.121 (5)	0.036 (3)	0.024 (4)	−0.005 (4)
C28	0.055 (3)	0.117 (5)	0.090 (4)	0.017 (3)	0.004 (3)	0.002 (4)
C29	0.055 (3)	0.077 (3)	0.078 (3)	−0.002 (2)	−0.004 (2)	0.001 (3)
C30	0.042 (2)	0.081 (3)	0.092 (4)	−0.008 (2)	−0.008 (2)	0.016 (3)

Geometric parameters (Å, º)

Cu1—N1	2.009 (3)	C13—C14	1.390 (3)
Cu1—N3	2.005 (3)	C13—H9	0.950
Cl1—C30	1.742 (5)	C14—C15	1.390 (3)
Cl2—C30	1.761 (6)	C14—H10	0.950
Cl3—C30	1.725 (6)	C15—H11	0.950
O1—C1	1.232 (4)	C16—C17	1.547 (5)
O2—C2	1.222 (4)	C16—H14	0.950
N1—C1	1.401 (4)	C16—H15	0.950
N1—C2	1.372 (4)	C17—C18	1.512 (4)
N2—C1	1.346 (4)	C17—C24	1.534 (4)
N2—C3	1.460 (4)	C17—H16	0.950
N2—H1	0.950	C18—C19	1.390 (3)
N3—C16	1.482 (4)	C18—C23	1.390 (3)
N3—H12	0.950	C19—C20	1.390 (4)
N3—H13	0.950	C19—H17	0.950
C2—C3	1.549 (5)	C20—C21	1.390 (4)
C3—C4	1.532 (4)	C20—H18	0.950
C3—C10	1.529 (3)	C21—C22	1.390 (4)
C4—C5	1.390 (4)	C21—H19	0.950
C4—C9	1.390 (3)	C22—C23	1.390 (3)
C5—C6	1.390 (4)	C22—H20	0.950
C5—H2	0.950	C23—H21	0.950
C6—C7	1.390 (5)	C24—C25	1.390 (4)
C6—H3	0.950	C24—C29	1.390 (4)
C7—C8	1.390 (4)	C25—C26	1.390 (4)
C7—H4	0.950	C25—H22	0.950
C8—C9	1.390 (4)	C26—C27	1.390 (5)
C8—H5	0.950	C26—H23	0.950
C9—H6	0.950	C27—C28	1.390 (5)
C10—C11	1.390 (3)	C27—H24	0.950
C10—C15	1.390 (3)	C28—C29	1.390 (4)
C11—C12	1.390 (3)	C28—H25	0.950
C11—H7	0.950	C29—H26	0.950
C12—C13	1.390 (4)	C30—H27	0.950
C12—H8	0.950
N1—Cu1—N1^i	180.0	C13—C14—H10	120.0
N1—Cu1—N3	89.2 (1)	C15—C14—H10	120.0
N1—Cu1—N3^i	90.8 (1)	C10—C15—C14	120.0 (2)
N3—Cu1—N3^i	180.0	C10—C15—H11	119.9
Cu1—N1—C1	123.8 (2)	C14—C15—H11	120.1
Cu1—N1—C2	127.3 (2)	N3—C16—C17	112.6 (3)
C1—N1—C2	107.6 (3)	N3—C16—H14	108.7
C1—N2—C3	111.4 (3)	N3—C16—H15	108.5
C1—N2—H1	124.3	C17—C16—H14	108.8
C3—N2—H1	124.3	C17—C16—H15	108.7
Cu1—N3—C16	117.0 (2)	H14—C16—H15	109.3
Cu1—N3—H12	107.6	C16—C17—C18	112.3 (3)
Cu1—N3—H13	107.3	C16—C17—C24	109.5 (3)
C16—N3—H12	107.8	C16—C17—H16	106.4
C16—N3—H13	107.5	C18—C17—C24	115.2 (3)
H12—N3—H13	109.5	C18—C17—H16	106.3
O1—C1—N1	123.8 (3)	C24—C17—H16	106.5
O1—C1—N2	125.2 (3)	C17—C18—C19	118.7 (2)
N1—C1—N2	111.1 (3)	C17—C18—C23	121.2 (2)
O2—C2—N1	126.3 (3)	C19—C18—C23	120.0 (2)
O2—C2—C3	124.2 (3)	C18—C19—C20	120.0 (2)
N1—C2—C3	109.4 (3)	C18—C19—H17	120.0
N2—C3—C2	100.0 (2)	C20—C19—H17	120.0
N2—C3—C4	109.8 (2)	C19—C20—C21	120.0 (2)
N2—C3—C10	113.4 (2)	C19—C20—H18	120.1
C2—C3—C4	114.9 (2)	C21—C20—H18	119.9
C2—C3—C10	107.3 (2)	C20—C21—C22	120.0 (2)
C4—C3—C10	111.1 (2)	C20—C21—H19	120.1
C3—C4—C5	123.3 (2)	C22—C21—H19	119.9
C3—C4—C9	116.6 (2)	C21—C22—C23	120.0 (2)
C5—C4—C9	120.0 (2)	C21—C22—H20	120.1
C4—C5—C6	120.0 (2)	C23—C22—H20	119.9
C4—C5—H2	120.1	C18—C23—C22	120.0 (2)
C6—C5—H2	119.9	C18—C23—H21	119.9
C5—C6—C7	120.0 (2)	C22—C23—H21	120.1
C5—C6—H3	119.9	C17—C24—C25	121.8 (2)
C7—C6—H3	120.1	C17—C24—C29	118.2 (3)
C6—C7—C8	120.0 (2)	C25—C24—C29	120.0 (2)
C6—C7—H4	119.8	C24—C25—C26	120.0 (2)
C8—C7—H4	120.2	C24—C25—H22	119.9
C7—C8—C9	120.0 (2)	C26—C25—H22	120.1
C7—C8—H5	119.9	C25—C26—C27	120.0 (3)
C9—C8—H5	120.1	C25—C26—H23	119.9
C4—C9—C8	120.0 (2)	C27—C26—H23	120.1
C4—C9—H6	119.9	C26—C27—C28	120.0 (3)
C8—C9—H6	120.1	C26—C27—H24	119.9
C3—C10—C11	118.7 (2)	C28—C27—H24	120.1
C3—C10—C15	121.3 (2)	C27—C28—C29	120.0 (2)
C11—C10—C15	120.0 (2)	C27—C28—H25	119.9
C10—C11—C12	120.0 (2)	C29—C28—H25	120.1
C10—C11—H7	120.0	C24—C29—C28	120.0 (3)
C12—C11—H7	120.0	C24—C29—H26	120.1
C11—C12—C13	120.0 (2)	C28—C29—H26	119.9
C11—C12—H8	120.0	Cl1—C30—Cl2	110.9 (3)
C13—C12—H8	120.0	Cl1—C30—Cl3	110.3 (3)
C12—C13—C14	120.0 (2)	Cl1—C30—H27	108.8
C12—C13—H9	120.0	Cl2—C30—Cl3	109.3 (3)
C14—C13—H9	120.0	Cl2—C30—H27	108.6
C13—C14—C15	120.0 (2)	Cl3—C30—H27	108.9
Cu1—N1—C1—O1	−18.9 (5)	C4—C3—C10—C11	−44.1 (3)
Cu1—N1—C1—N2	160.4 (2)	C4—C3—C10—C15	138.6 (3)
Cu1—N1—C2—O2	15.3 (5)	C4—C5—C6—C7	0.0 (4)
Cu1—N1—C2—C3	−161.7 (2)	C4—C9—C8—C7	0.0 (4)
Cu1—N1^i—C1^i—O1^i	18.9 (5)	C5—C4—C3—C10	123.3 (3)
Cu1—N1^i—C1^i—N2^i	−160.4 (2)	C5—C4—C9—C8	0.0 (4)
Cu1—N1^i—C2^i—O2^i	−15.3 (5)	C5—C6—C7—C8	0.0 (5)
Cu1—N1^i—C2^i—C3^i	161.7 (2)	C6—C5—C4—C9	0.0 (4)
Cu1—N3—C16—C17	162.3 (2)	C6—C7—C8—C9	0.0 (5)
Cu1—N3^i—C16^i—C17^i	−162.3 (2)	C9—C4—C3—C10	−59.4 (3)
O1—C1—N1—C2	173.1 (3)	C10—C11—C12—C13	0.0 (4)
O1—C1—N2—C3	−174.3 (3)	C10—C15—C14—C13	0.0 (4)
O2—C2—N1—C1	−177.3 (3)	C11—C10—C15—C14	0.0 (4)
O2—C2—C3—N2	−179.1 (3)	C11—C12—C13—C14	0.0 (4)
O2—C2—C3—C10	−60.5 (4)	C12—C11—C10—C15	0.0 (4)
N1—Cu1—N3^i—C16^i	106.8 (2)	C12—C13—C14—C15	0.0 (4)
N1—C1—N2—C3	6.4 (4)	C16—C17—C18—C19	−130.1 (3)
N1—C2—C3—N2	−2.0 (3)	C16—C17—C18—C23	47.7 (4)
N1—C2—C3—C4	−119.4 (3)	C16—C17—C24—C25	−102.2 (4)
N1—C2—C3—C10	116.6 (3)	C16—C17—C24—C29	76.6 (4)
N2—C1—N1—C2	−7.6 (4)	C17—C18—C19—C20	177.8 (3)
N2—C3—C4—C5	−110.4 (3)	C17—C18—C23—C22	−177.7 (3)
N2—C3—C4—C9	66.9 (3)	C17—C24—C25—C26	178.8 (3)
N2—C3—C10—C11	−168.3 (2)	C17—C24—C29—C28	−178.8 (3)
N2—C3—C10—C15	14.4 (4)	C18—C17—C24—C25	25.5 (4)
N3—Cu1—N1—C1	−130.9 (3)	C18—C17—C24—C29	−155.7 (3)
N3—Cu1—N1—C2	34.6 (3)	C18—C19—C20—C21	0.0 (4)
N3—Cu1—N1^i—C1^i	−49.1 (3)	C18—C23—C22—C21	0.0 (4)
N3—Cu1—N1^i—C2^i	145.4 (3)	C19—C18—C17—C24	103.7 (3)
N3—C16—C17—C24	179.8 (3)	C19—C18—C23—C22	0.0 (4)
C1—N1—C2—C3	5.7 (3)	C19—C20—C21—C22	0.0 (4)
C1—N2—C3—C2	−2.7 (3)	C20—C19—C18—C23	0.0 (4)
C1—N2—C3—C4	118.5 (3)	C20—C21—C22—C23	0.0 (4)
C1—N2—C3—C10	−116.6 (3)	C23—C18—C17—C24	−78.6 (4)
C2—C3—C4—C5	1.3 (4)	C24—C25—C26—C27	0.0 (5)
C2—C3—C4—C9	178.6 (2)	C24—C29—C28—C27	0.0 (5)
C2—C3—C10—C11	82.2 (3)	C25—C24—C29—C28	0.0 (5)
C2—C3—C10—C15	−95.1 (3)	C25—C26—C27—C28	0.0 (6)
C3—C4—C5—C6	177.2 (3)	C26—C25—C24—C29	0.0 (5)
C3—C4—C9—C8	−177.4 (2)	C26—C27—C28—C29	0.0 (6)
C3—C10—C11—C12	−177.3 (2)	C26—C27—C28—C29	0.0 (6)
C3—C10—C15—C14	177.2 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1^ii	0.95	2.02	2.900 (3)	153
N3—H12···O1^i	0.95	2.06	2.837 (3)	137
N3—H13···O2	0.95	2.13	2.922 (3)	140
C30—H27···O2	0.95	2.57	3.507 (5)	170

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z.

(II)

Crystal data

[Cu(C15H11N2O2)2(C14H15N)2]	Z = 2
Mr = 960.63	F(000) = 1006
Triclinic, P1	Dx = 1.327 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 14.313 (4) Å	Cell parameters from 25 reflections
b = 15.888 (5) Å	θ = 10.0–12.4°
c = 11.863 (4) Å	µ = 0.51 mm^−1
α = 90.13 (3)°	T = 298 K
β = 95.00 (3)°	Plate-like, blue–violet
γ = 63.58 (2)°	0.50 × 0.40 × 0.20 mm
V = 2404.7 (14) Å^3

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.087
ω/2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −18→18
Tmin = 0.783, Tmax = 0.903	k = −20→20
12233 measured reflections	l = −6→15
12233 independent reflections	3 standard reflections every 150 reflections
11075 reflections with I > 0σ(I)	intensity decay: 0.3%

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.069	w = 1/[σ^2(Fo^2) + (0.0502P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.161	(Δ/σ)max < 0.001
S = 0.85	Δρmax = 0.62 e Å^−3
11075 reflections	Δρmin = −1.31 e Å^−3
527 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.99199 (5)	0.48877 (4)	0.29269 (5)	0.0246 (2)
O1	1.0577 (2)	0.4010 (2)	0.0607 (3)	0.0412 (9)
O2	0.7685 (3)	0.4529 (2)	0.2396 (3)	0.0397 (9)
O3	1.1150 (2)	0.4528 (2)	0.5536 (3)	0.0298 (8)
O4	1.1108 (2)	0.6262 (2)	0.2463 (3)	0.0349 (8)
N1	0.9244 (3)	0.4360 (3)	0.1786 (3)	0.0279 (9)
N2	0.9004 (3)	0.4027 (3)	−0.0037 (3)	0.0324 (10)
N3	0.9143 (3)	0.6129 (3)	0.2026 (3)	0.0278 (9)
N4	1.0937 (3)	0.5284 (3)	0.3785 (3)	0.0235 (9)
N5	1.2063 (3)	0.5348 (3)	0.5203 (3)	0.0314 (10)
N6	1.0715 (3)	0.3589 (3)	0.3699 (3)	0.0317 (10)
C1	0.9685 (4)	0.4116 (3)	0.0750 (4)	0.030 (1)
C2	0.8292 (4)	0.4377 (3)	0.1662 (4)	0.031 (1)
C3	0.8029 (3)	0.4189 (3)	0.0426 (4)	0.025 (1)
C4	0.7880 (3)	0.3298 (2)	0.0300 (3)	0.034 (1)
C5	0.8239 (3)	0.2610 (3)	0.1168 (2)	0.072 (2)
C6	0.8201 (4)	0.1761 (2)	0.0992 (3)	0.092 (3)
C7	0.7802 (4)	0.1599 (2)	−0.0053 (4)	0.063 (2)
C8	0.7443 (3)	0.2287 (3)	−0.0921 (3)	0.059 (2)
C9	0.7481 (3)	0.3137 (2)	−0.0744 (3)	0.049 (1)
C10	0.7094 (2)	0.5085 (2)	−0.0082 (3)	0.030 (1)
C11	0.6111 (3)	0.5302 (2)	0.0261 (3)	0.043 (1)
C12	0.5255 (2)	0.6140 (3)	−0.0119 (4)	0.057 (2)
C13	0.5381 (3)	0.6760 (2)	−0.0843 (4)	0.068 (2)
C14	0.6364 (3)	0.6544 (2)	−0.1186 (3)	0.057 (2)
C15	0.7221 (2)	0.5706 (3)	−0.0806 (3)	0.044 (1)
C16	0.8022 (4)	0.6693 (3)	0.2186 (4)	0.033 (1)
C17	0.7472 (4)	0.7552 (3)	0.1361 (4)	0.033 (1)
C18	0.6293 (2)	0.8074 (3)	0.1473 (3)	0.039 (1)
C19	0.5650 (3)	0.8633 (3)	0.0552 (3)	0.058 (2)
C20	0.4577 (3)	0.9138 (3)	0.0619 (3)	0.073 (2)
C21	0.4148 (2)	0.9085 (3)	0.1607 (4)	0.068 (2)
C22	0.4791 (3)	0.8526 (3)	0.2528 (3)	0.081 (2)
C23	0.5864 (3)	0.8020 (3)	0.2462 (3)	0.077 (2)
C24	0.8010 (3)	0.8194 (2)	0.1466 (3)	0.038 (1)
C25	0.7791 (3)	0.8839 (3)	0.2317 (3)	0.058 (2)
C26	0.8346 (4)	0.9366 (3)	0.2466 (4)	0.074 (2)
C27	0.9119 (3)	0.9250 (3)	0.1763 (4)	0.082 (2)
C28	0.9338 (3)	0.8605 (3)	0.0912 (4)	0.077 (2)
C29	0.8784 (3)	0.8077 (3)	0.0763 (3)	0.057 (2)
C30	1.1366 (3)	0.5020 (3)	0.4901 (4)	0.025 (1)
C31	1.1328 (3)	0.5871 (3)	0.3411 (4)	0.027 (1)
C32	1.2061 (3)	0.6000 (3)	0.4340 (4)	0.027 (1)
C33	1.1617 (3)	0.6985 (2)	0.4796 (3)	0.032 (1)
C34	1.0631 (3)	0.7685 (3)	0.4410 (3)	0.061 (2)
C35	1.0255 (3)	0.8566 (2)	0.4874 (4)	0.086 (2)
C36	1.0864 (4)	0.8748 (2)	0.5724 (4)	0.068 (2)
C37	1.1851 (4)	0.8048 (3)	0.6111 (3)	0.072 (2)
C38	1.2227 (2)	0.7166 (3)	0.5647 (3)	0.056 (2)
C39	1.3152 (2)	0.5693 (3)	0.3915 (3)	0.034 (1)
C40	1.3475 (3)	0.6353 (2)	0.3584 (3)	0.052 (2)
C41	1.4448 (3)	0.6058 (3)	0.3175 (4)	0.072 (2)
C42	1.5098 (2)	0.5104 (3)	0.3096 (3)	0.066 (2)
C43	1.4775 (3)	0.4444 (2)	0.3426 (4)	0.075 (2)
C44	1.3801 (3)	0.4739 (2)	0.3836 (4)	0.058 (2)
C45	1.1778 (4)	0.3075 (3)	0.3330 (4)	0.040 (1)
C46	1.2445 (4)	0.2093 (4)	0.3910 (4)	0.039 (1)
C47	1.3600 (2)	0.1808 (3)	0.3729 (3)	0.043 (1)
C48	1.4149 (3)	0.2214 (3)	0.4356 (3)	0.061 (2)
C49	1.5179 (3)	0.1979 (3)	0.4167 (4)	0.078 (2)
C50	1.5660 (2)	0.1339 (3)	0.3352 (4)	0.076 (2)
C51	1.5111 (3)	0.0934 (3)	0.2725 (3)	0.072 (2)
C52	1.4081 (3)	0.1168 (3)	0.2914 (3)	0.054 (2)
C53	1.2101 (3)	0.1341 (2)	0.3606 (3)	0.041 (1)
C54	1.2504 (3)	0.0531 (3)	0.4303 (3)	0.054 (2)
C55	1.2255 (3)	−0.0200 (2)	0.4026 (4)	0.066 (2)
C56	1.1603 (3)	−0.0122 (3)	0.3051 (4)	0.072 (2)
C57	1.1200 (3)	0.0688 (3)	0.2354 (3)	0.074 (2)
C58	1.1449 (3)	0.1419 (2)	0.2632 (3)	0.060 (2)
H1	0.9141	0.3877	−0.0800	0.0386*
H2	0.8510	0.2720	0.1882	0.0871*
H3	0.8445	0.1291	0.1584	0.1109*
H4	0.7775	0.1019	−0.0175	0.0752*
H5	0.7171	0.2177	−0.1636	0.0711*
H6	0.7237	0.3607	−0.1338	0.0593*
H7	0.6025	0.4878	0.0756	0.0515*
H8	0.4583	0.6287	0.0116	0.0685*
H9	0.4795	0.7332	−0.1103	0.0812*
H10	0.6450	0.6967	−0.1681	0.0681*
H11	0.7893	0.5558	−0.1040	0.0522*
H12	0.9491	0.6505	0.2225	0.0331*
H13	0.9189	0.5997	0.1246	0.0331*
H14	0.7678	0.6303	0.2079	0.0397*
H15	0.7970	0.6905	0.2939	0.0397*
H16	0.7549	0.7321	0.0619	0.0388*
H17	0.5944	0.8670	−0.0123	0.0701*
H18	0.4138	0.9520	−0.0011	0.0879*
H19	0.3414	0.9430	0.1652	0.0807*
H20	0.4497	0.8489	0.3203	0.0979*
H21	0.6303	0.7639	0.3092	0.0925*
H22	0.7263	0.8918	0.2797	0.0701*
H23	0.8196	0.9807	0.3047	0.0880*
H24	0.9498	0.9611	0.1864	0.0983*
H25	0.9866	0.8526	0.0431	0.0923*
H26	0.8933	0.7637	0.0181	0.0684*
H27	1.2502	0.5178	0.5894	0.0375*
H28	1.0215	0.7561	0.3827	0.0732*
H29	0.9580	0.9045	0.4608	0.1035*
H30	1.0606	0.9351	0.6041	0.0813*
H31	1.2265	0.8173	0.6693	0.0859*
H32	1.2900	0.6689	0.5911	0.0676*
H33	1.3031	0.7005	0.3638	0.0630*
H34	1.4670	0.6509	0.2949	0.0869*
H35	1.5763	0.4903	0.2816	0.0787*
H36	1.5218	0.3792	0.3372	0.0898*
H37	1.3580	0.4288	0.4062	0.0698*
H38	1.0772	0.3656	0.4496	0.0380*
H39	1.0336	0.3237	0.3523	0.0380*
H40	1.1712	0.3000	0.2537	0.0480*
H41	1.2142	0.3446	0.3484	0.0480*
H42	1.2391	0.2174	0.4699	0.0468*
H43	1.3820	0.2650	0.4915	0.0733*
H44	1.5555	0.2256	0.4597	0.0940*
H45	1.6365	0.1179	0.3225	0.0920*
H46	1.5441	0.0497	0.2169	0.0871*
H47	1.3706	0.0891	0.2486	0.0647*
H48	1.2948	0.0479	0.4970	0.0651*
H49	1.2529	−0.0753	0.4503	0.0795*
H50	1.1432	−0.0622	0.2862	0.0863*
H51	1.0755	0.0741	0.1688	0.0883*
H52	1.1174	0.1972	0.2155	0.0720*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0241 (3)	0.0258 (3)	0.0235 (3)	−0.0109 (3)	0.0019 (3)	−0.0015 (3)
O1	0.026 (2)	0.060 (2)	0.043 (2)	−0.024 (2)	0.006 (2)	−0.004 (2)
O2	0.045 (2)	0.063 (2)	0.022 (2)	−0.031 (2)	0.015 (2)	−0.009 (2)
O3	0.035 (2)	0.033 (2)	0.024 (2)	−0.016 (2)	0.003 (1)	0.004 (1)
O4	0.040 (2)	0.048 (2)	0.021 (2)	−0.024 (2)	0.000 (2)	0.008 (2)
N1	0.030 (2)	0.036 (2)	0.016 (2)	−0.014 (2)	0.000 (2)	0.000 (2)
N2	0.033 (2)	0.049 (3)	0.018 (2)	−0.021 (2)	0.006 (2)	−0.006 (2)
N3	0.026 (2)	0.029 (2)	0.026 (2)	−0.012 (2)	−0.003 (2)	0.005 (2)
N4	0.022 (2)	0.031 (2)	0.019 (2)	−0.013 (2)	0.001 (2)	0.005 (2)
N5	0.028 (2)	0.039 (2)	0.027 (2)	−0.015 (2)	−0.003 (2)	0.004 (2)
N6	0.030 (2)	0.031 (2)	0.030 (2)	−0.011 (2)	−0.003 (2)	0.001 (2)
C1	0.037 (3)	0.034 (3)	0.026 (3)	−0.022 (2)	0.001 (2)	0.000 (2)
C2	0.037 (3)	0.036 (3)	0.020 (3)	−0.017 (2)	−0.002 (2)	0.004 (2)
C3	0.028 (3)	0.040 (3)	0.015 (2)	−0.021 (2)	0.006 (2)	−0.005 (2)
C4	0.039 (3)	0.033 (3)	0.034 (3)	−0.020 (2)	0.006 (2)	−0.003 (2)
C5	0.123 (6)	0.053 (4)	0.051 (4)	−0.053 (4)	−0.009 (4)	0.004 (3)
C6	0.181 (8)	0.066 (5)	0.046 (4)	−0.073 (5)	−0.007 (5)	0.001 (4)
C7	0.086 (5)	0.045 (4)	0.065 (4)	−0.034 (4)	0.003 (4)	−0.022 (3)
C8	0.073 (4)	0.055 (4)	0.052 (4)	−0.034 (4)	−0.007 (3)	−0.007 (3)
C9	0.079 (4)	0.054 (4)	0.032 (3)	−0.045 (3)	0.009 (3)	−0.009 (3)
C10	0.032 (3)	0.035 (3)	0.028 (3)	−0.019 (2)	0.004 (2)	−0.006 (2)
C11	0.037 (3)	0.044 (3)	0.051 (4)	−0.019 (3)	0.011 (3)	−0.003 (3)
C12	0.041 (4)	0.059 (4)	0.070 (4)	−0.020 (3)	0.009 (3)	−0.001 (3)
C13	0.047 (4)	0.057 (4)	0.087 (5)	−0.015 (3)	−0.011 (4)	0.009 (4)
C14	0.065 (4)	0.058 (4)	0.048 (4)	−0.030 (4)	−0.007 (3)	0.021 (3)
C15	0.045 (3)	0.055 (4)	0.044 (3)	−0.031 (3)	0.010 (3)	0.002 (3)
C16	0.032 (3)	0.031 (3)	0.033 (3)	−0.010 (2)	0.006 (2)	0.004 (2)
C17	0.035 (3)	0.027 (3)	0.028 (3)	−0.007 (2)	0.004 (2)	0.001 (2)
C18	0.037 (3)	0.023 (3)	0.047 (3)	−0.005 (2)	0.003 (3)	−0.001 (2)
C19	0.041 (3)	0.066 (4)	0.044 (4)	−0.003 (3)	0.002 (3)	0.005 (3)
C20	0.042 (4)	0.076 (5)	0.072 (5)	−0.002 (4)	−0.010 (3)	−0.007 (4)
C21	0.032 (3)	0.046 (4)	0.116 (6)	−0.009 (3)	0.010 (4)	−0.027 (4)
C22	0.045 (4)	0.094 (6)	0.084 (5)	−0.009 (4)	0.025 (4)	0.017 (4)
C23	0.040 (4)	0.090 (5)	0.073 (5)	−0.003 (4)	0.013 (3)	0.026 (4)
C24	0.030 (3)	0.033 (3)	0.037 (3)	−0.002 (2)	−0.003 (2)	0.010 (2)
C25	0.054 (4)	0.045 (4)	0.073 (5)	−0.019 (3)	0.009 (3)	−0.015 (3)
C26	0.054 (4)	0.054 (4)	0.111 (6)	−0.022 (4)	0.012 (4)	−0.034 (4)
C27	0.063 (5)	0.045 (4)	0.141 (8)	−0.029 (4)	−0.002 (5)	0.015 (5)
C28	0.066 (5)	0.065 (5)	0.108 (6)	−0.034 (4)	0.020 (4)	0.021 (4)
C29	0.064 (4)	0.056 (4)	0.058 (4)	−0.029 (3)	0.021 (3)	0.004 (3)
C30	0.021 (2)	0.026 (3)	0.026 (3)	−0.008 (2)	0.005 (2)	−0.001 (2)
C31	0.024 (3)	0.034 (3)	0.021 (3)	−0.011 (2)	0.005 (2)	−0.011 (2)
C32	0.030 (3)	0.036 (3)	0.019 (2)	−0.019 (2)	0.002 (2)	0.001 (2)
C33	0.040 (3)	0.047 (3)	0.023 (3)	−0.030 (3)	0.011 (2)	−0.004 (2)
C34	0.045 (4)	0.048 (4)	0.074 (5)	−0.009 (3)	−0.002 (3)	−0.016 (3)
C35	0.056 (4)	0.060 (5)	0.125 (7)	−0.013 (4)	−0.001 (4)	−0.018 (5)
C36	0.089 (5)	0.058 (4)	0.073 (5)	−0.043 (4)	0.033 (4)	−0.023 (4)
C37	0.113 (6)	0.068 (5)	0.057 (4)	−0.057 (5)	0.024 (4)	−0.029 (4)
C38	0.065 (4)	0.059 (4)	0.046 (4)	−0.030 (3)	−0.003 (3)	−0.007 (3)
C39	0.024 (3)	0.054 (3)	0.026 (3)	−0.019 (3)	0.000 (2)	0.000 (2)
C40	0.038 (3)	0.067 (4)	0.057 (4)	−0.026 (3)	0.010 (3)	0.010 (3)
C41	0.048 (4)	0.112 (6)	0.069 (5)	−0.044 (4)	0.013 (3)	0.020 (4)
C42	0.035 (4)	0.118 (6)	0.045 (4)	−0.034 (4)	0.007 (3)	0.002 (4)
C43	0.043 (4)	0.081 (5)	0.090 (5)	−0.016 (4)	0.024 (4)	−0.016 (4)
C44	0.045 (4)	0.057 (4)	0.075 (5)	−0.022 (3)	0.021 (3)	−0.016 (3)
C45	0.036 (3)	0.026 (3)	0.043 (3)	−0.001 (2)	0.002 (2)	0.002 (2)
C46	0.038 (3)	0.037 (3)	0.032 (3)	−0.007 (3)	0.006 (2)	−0.002 (2)
C47	0.044 (3)	0.027 (3)	0.047 (3)	−0.005 (3)	−0.006 (3)	0.010 (3)
C48	0.058 (4)	0.065 (4)	0.051 (4)	−0.021 (4)	−0.006 (3)	−0.005 (3)
C49	0.055 (5)	0.092 (6)	0.086 (6)	−0.034 (4)	−0.012 (4)	0.012 (5)
C50	0.038 (4)	0.075 (5)	0.097 (6)	−0.008 (4)	0.005 (4)	0.020 (4)
C51	0.055 (4)	0.056 (4)	0.092 (6)	−0.007 (4)	0.033 (4)	−0.005 (4)
C52	0.051 (4)	0.046 (4)	0.062 (4)	−0.018 (3)	0.012 (3)	−0.003 (3)
C53	0.031 (3)	0.037 (3)	0.047 (3)	−0.007 (3)	0.006 (3)	0.003 (3)
C54	0.048 (4)	0.035 (3)	0.069 (4)	−0.010 (3)	0.004 (3)	0.013 (3)
C55	0.057 (4)	0.050 (4)	0.093 (5)	−0.023 (3)	0.018 (4)	0.007 (4)
C56	0.053 (4)	0.049 (4)	0.120 (7)	−0.023 (4)	0.030 (4)	−0.021 (4)
C57	0.062 (4)	0.062 (5)	0.092 (6)	−0.024 (4)	−0.001 (4)	−0.022 (4)
C58	0.059 (4)	0.045 (4)	0.067 (4)	−0.018 (3)	−0.003 (3)	−0.006 (3)

Geometric parameters (Å, º)

Cu1—O3^i	2.397 (4)	C23—H21	0.950
Cu1—N1	1.990 (4)	C24—C25	1.390 (5)
Cu1—N3	2.030 (3)	C24—C29	1.390 (6)
Cu1—N4	2.026 (4)	C25—C26	1.390 (7)
Cu1—N6	2.032 (4)	C25—H22	0.950
O1—C1	1.238 (7)	C26—C27	1.390 (7)
O2—C2	1.232 (6)	C26—H23	0.950
O3—C30	1.237 (7)	C27—C28	1.390 (7)
O4—C31	1.232 (6)	C27—H24	0.950
N1—C1	1.405 (6)	C28—C29	1.390 (8)
N1—C2	1.345 (7)	C28—H25	0.950
N2—C1	1.343 (7)	C29—H26	0.950
N2—C3	1.459 (7)	C31—C32	1.532 (7)
N2—H1	0.950	C32—C33	1.522 (6)
N3—C16	1.478 (6)	C32—C39	1.545 (6)
N3—H12	0.950	C33—C34	1.390 (4)
N3—H13	0.950	C33—C38	1.390 (5)
N4—C30	1.392 (5)	C34—C35	1.390 (6)
N4—C31	1.374 (7)	C34—H28	0.950
N5—C30	1.340 (7)	C35—C36	1.390 (7)
N5—C32	1.457 (7)	C35—H29	0.950
N5—H27	0.950	C36—C37	1.390 (5)
N6—C45	1.478 (6)	C36—H30	0.950
N6—H38	0.950	C37—C38	1.390 (6)
N6—H39	0.950	C37—H31	0.950
C2—C3	1.544 (6)	C38—H32	0.950
C3—C4	1.528 (7)	C39—C40	1.390 (6)
C3—C10	1.532 (4)	C39—C44	1.390 (4)
C4—C5	1.390 (5)	C40—C41	1.390 (6)
C4—C9	1.390 (5)	C40—H33	0.950
C5—C6	1.390 (7)	C41—C42	1.390 (6)
C5—H2	0.950	C41—H34	0.950
C6—C7	1.390 (6)	C42—C43	1.390 (7)
C6—H3	0.950	C42—H35	0.950
C7—C8	1.390 (5)	C43—C44	1.390 (6)
C7—H4	0.950	C43—H36	0.950
C8—C9	1.390 (6)	C44—H37	0.950
C8—H5	0.950	C45—C46	1.544 (6)
C9—H6	0.950	C45—H40	0.950
C10—C11	1.390 (5)	C45—H41	0.950
C10—C15	1.390 (6)	C46—C47	1.541 (6)
C11—C12	1.390 (4)	C46—C53	1.515 (8)
C11—H7	0.950	C46—H42	0.950
C12—C13	1.390 (6)	C47—C48	1.390 (7)
C12—H8	0.950	C47—C52	1.390 (5)
C13—C14	1.390 (6)	C48—C49	1.390 (7)
C13—H9	0.950	C48—H43	0.950
C14—C15	1.390 (4)	C49—C50	1.390 (7)
C14—H10	0.950	C49—H44	0.950
C15—H11	0.950	C50—C51	1.390 (7)
C16—C17	1.536 (6)	C50—H45	0.950
C16—H14	0.950	C51—C52	1.390 (7)
C16—H15	0.950	C51—H46	0.950
C17—C18	1.532 (5)	C52—H47	0.950
C17—C24	1.526 (8)	C53—C54	1.390 (5)
C17—H16	0.950	C53—C58	1.390 (5)
C18—C19	1.390 (4)	C54—C55	1.390 (7)
C18—C23	1.390 (6)	C54—H48	0.950
C19—C20	1.390 (5)	C55—C56	1.390 (7)
C19—H17	0.950	C55—H49	0.950
C20—C21	1.390 (6)	C56—C57	1.390 (6)
C20—H18	0.950	C56—H50	0.950
C21—C22	1.390 (6)	C57—C58	1.390 (7)
C21—H19	0.950	C57—H51	0.950
C22—C23	1.390 (6)	C58—H52	0.950
C22—H20	0.950
O3^i—Cu1—N1	109.8 (1)	C17—C24—C29	119.5 (3)
O3^i—Cu1—N3	92.2 (1)	C25—C24—C29	120.0 (4)
O3^i—Cu1—N4	86.7 (1)	C24—C25—C26	120.0 (4)
O3^i—Cu1—N6	91.9 (1)	C24—C25—H22	120.0
N1—Cu1—N3	86.9 (2)	C26—C25—H22	120.0
N1—Cu1—N4	163.5 (2)	C25—C26—C27	120.0 (4)
N1—Cu1—N6	89.1 (2)	C25—C26—H23	120.0
N3—Cu1—N4	93.7 (2)	C27—C26—H23	120.0
N3—Cu1—N6	175.0 (2)	C26—C27—C28	120.0 (5)
N4—Cu1—N6	89.2 (2)	C26—C27—H24	120.0
Cu1—N1—C1	117.1 (4)	C28—C27—H24	120.0
Cu1—N1—C2	132.8 (3)	C27—C28—C29	120.0 (4)
C1—N1—C2	108.0 (4)	C27—C28—H25	120.0
C1—N2—C3	111.6 (4)	C29—C28—H25	120.0
C1—N2—H1	124.2	C24—C29—C28	120.0 (4)
C3—N2—H1	124.2	C24—C29—H26	120.0
Cu1—N3—C16	117.1 (3)	C28—C29—H26	120.0
Cu1—N3—H12	107.5	O3—C30—N4	124.7 (5)
Cu1—N3—H13	107.6	O3—C30—N5	123.7 (4)
C16—N3—H12	107.5	N4—C30—N5	111.7 (5)
C16—N3—H13	107.5	O4—C31—N4	125.0 (5)
H12—N3—H13	109.5	O4—C31—C32	123.8 (5)
Cu1—N4—C30	125.9 (4)	N4—C31—C32	111.2 (4)
Cu1—N4—C31	128.0 (3)	N5—C32—C31	98.9 (4)
C30—N4—C31	106.1 (4)	N5—C32—C33	108.9 (3)
C30—N5—C32	111.6 (4)	N5—C32—C39	112.7 (3)
C30—N5—H27	124.2	C31—C32—C33	113.5 (3)
C32—N5—H27	124.2	C31—C32—C39	109.7 (3)
Cu1—N6—C45	112.0 (3)	C33—C32—C39	112.5 (4)
Cu1—N6—H38	108.8	C32—C33—C34	122.4 (4)
Cu1—N6—H39	108.9	C32—C33—C38	117.6 (3)
C45—N6—H38	108.8	C34—C33—C38	120.0 (3)
C45—N6—H39	108.9	C33—C34—C35	120.0 (4)
H38—N6—H39	109.5	C33—C34—H28	120.0
O1—C1—N1	123.4 (5)	C35—C34—H28	120.0
O1—C1—N2	126.1 (4)	C34—C35—C36	120.0 (3)
N1—C1—N2	110.5 (5)	C34—C35—H29	120.0
O2—C2—N1	127.0 (4)	C36—C35—H29	120.0
O2—C2—C3	122.7 (5)	C35—C36—C37	120.0 (3)
N1—C2—C3	110.3 (4)	C35—C36—H30	119.9
N2—C3—C2	99.5 (4)	C37—C36—H30	120.1
N2—C3—C4	108.3 (3)	C36—C37—C38	120.0 (4)
N2—C3—C10	112.5 (4)	C36—C37—H31	119.9
C2—C3—C4	113.7 (4)	C38—C37—H31	120.1
C2—C3—C10	107.6 (3)	C33—C38—C37	120.0 (3)
C4—C3—C10	114.3 (4)	C33—C38—H32	120.0
C3—C4—C5	121.0 (4)	C37—C38—H32	120.0
C3—C4—C9	118.6 (3)	C32—C39—C40	121.2 (3)
C5—C4—C9	120.0 (4)	C32—C39—C44	118.8 (4)
C4—C5—C6	120.0 (3)	C40—C39—C44	120.0 (3)
C4—C5—H2	120.0	C39—C40—C41	120.0 (3)
C6—C5—H2	120.0	C39—C40—H33	120.0
C5—C6—C7	120.0 (3)	C41—C40—H33	120.0
C5—C6—H3	120.1	C40—C41—C42	120.0 (5)
C7—C6—H3	119.9	C40—C41—H34	120.0
C6—C7—C8	120.0 (4)	C42—C41—H34	120.0
C6—C7—H4	120.1	C41—C42—C43	120.0 (4)
C8—C7—H4	119.9	C41—C42—H35	120.0
C7—C8—C9	120.0 (3)	C43—C42—H35	120.0
C7—C8—H5	120.1	C42—C43—C44	120.0 (3)
C9—C8—H5	119.9	C42—C43—H36	120.0
C4—C9—C8	120.0 (3)	C44—C43—H36	120.0
C4—C9—H6	120.0	C39—C44—C43	120.0 (4)
C8—C9—H6	120.0	C39—C44—H37	120.0
C3—C10—C11	118.1 (3)	C43—C44—H37	120.0
C3—C10—C15	121.7 (3)	N6—C45—C46	115.0 (5)
C11—C10—C15	120.0 (2)	N6—C45—H40	108.1
C10—C11—C12	120.0 (4)	N6—C45—H41	108.1
C10—C11—H7	120.0	C46—C45—H40	108.1
C12—C11—H7	120.0	C46—C45—H41	108.0
C11—C12—C13	120.0 (3)	H40—C45—H41	109.3
C11—C12—H8	120.0	C45—C46—C47	107.5 (5)
C13—C12—H8	120.0	C45—C46—C53	116.4 (4)
C12—C13—C14	120.0 (3)	C45—C46—H42	106.2
C12—C13—H9	120.0	C47—C46—C53	113.6 (3)
C14—C13—H9	120.0	C47—C46—H42	106.4
C13—C14—C15	120.0 (4)	C53—C46—H42	106.1
C13—C14—H10	120.0	C46—C47—C48	120.0 (4)
C15—C14—H10	120.0	C46—C47—C52	120.0 (4)
C10—C15—C14	120.0 (3)	C48—C47—C52	120.0 (4)
C10—C15—H11	120.0	C47—C48—C49	120.0 (4)
C14—C15—H11	120.0	C47—C48—H43	120.0
N3—C16—C17	113.0 (4)	C49—C48—H43	120.0
N3—C16—H14	108.6	C48—C49—C50	120.0 (5)
N3—C16—H15	108.5	C48—C49—H44	119.9
C17—C16—H14	108.7	C50—C49—H44	120.1
C17—C16—H15	108.6	C49—C50—C51	120.0 (4)
H14—C16—H15	109.4	C49—C50—H45	119.9
C16—C17—C18	112.0 (4)	C51—C50—H45	120.1
C16—C17—C24	111.3 (4)	C50—C51—C52	120.0 (4)
C16—C17—H16	106.7	C50—C51—H46	119.9
C18—C17—C24	112.9 (3)	C52—C51—H46	120.1
C18—C17—H16	106.7	C47—C52—C51	120.0 (4)
C24—C17—H16	106.8	C47—C52—H47	120.0
C17—C18—C19	117.7 (4)	C51—C52—H47	120.0
C17—C18—C23	122.3 (3)	C46—C53—C54	117.9 (4)
C19—C18—C23	120.0 (3)	C46—C53—C58	122.0 (3)
C18—C19—C20	120.0 (3)	C54—C53—C58	120.0 (4)
C18—C19—H17	120.0	C53—C54—C55	120.0 (3)
C20—C19—H17	120.0	C53—C54—H48	120.0
C19—C20—C21	120.0 (3)	C55—C54—H48	120.0
C19—C20—H18	120.0	C54—C55—C56	120.0 (3)
C21—C20—H18	120.0	C54—C55—H49	120.0
C20—C21—C22	120.0 (3)	C56—C55—H49	120.0
C20—C21—H19	120.0	C55—C56—C57	120.0 (4)
C22—C21—H19	120.0	C55—C56—H50	120.0
C21—C22—C23	120.0 (4)	C57—C56—H50	120.0
C21—C22—H20	120.0	C56—C57—C58	120.0 (4)
C23—C22—H20	120.0	C56—C57—H51	120.0
C18—C23—C22	120.0 (3)	C58—C57—H51	120.0
C18—C23—H21	120.0	C53—C58—C57	120.0 (3)
C22—C23—H21	120.0	C53—C58—H52	120.0
C17—C24—C25	120.3 (4)	C57—C58—H52	120.0
Cu1—N1—C1—O1	17.0 (6)	C10—C15—C14—C13	0.0 (6)
Cu1—N1—C1—N2	−162.7 (3)	C11—C10—C15—C14	0.0 (6)
Cu1—N1—C2—O2	−20.2 (8)	C11—C12—C13—C14	0.0 (6)
Cu1—N1—C2—C3	158.9 (3)	C12—C11—C10—C15	0.0 (6)
Cu1—N3—C16—C17	−172.7 (3)	C12—C13—C14—C15	0.0 (6)
Cu1—N4—C30—O3	−2.8 (5)	C16—C17—C18—C19	−157.4 (4)
Cu1—N4—C30—N5	176.0 (2)	C16—C17—C18—C23	24.2 (6)
Cu1—N4—C31—O4	0.3 (6)	C16—C17—C24—C25	−81.9 (4)
Cu1—N4—C31—C32	178.9 (2)	C16—C17—C24—C29	92.9 (4)
Cu1—N6—C45—C46	178.1 (4)	C17—C18—C19—C20	−178.5 (4)
O1—C1—N1—C2	−177.3 (5)	C17—C18—C23—C22	178.4 (5)
O1—C1—N2—C3	179.2 (5)	C17—C24—C25—C26	174.7 (3)
O2—C2—N1—C1	177.2 (5)	C17—C24—C29—C28	−174.8 (3)
O2—C2—C3—N2	−178.0 (4)	C18—C17—C24—C25	45.0 (5)
O2—C2—C3—C4	−63.1 (5)	C18—C17—C24—C29	−140.2 (3)
O2—C2—C3—C10	64.6 (6)	C18—C19—C20—C21	0.0 (7)
O3—C30—N4—C31	176.2 (4)	C18—C23—C22—C21	0.0 (8)
O3—C30—N5—C32	−172.9 (4)	C19—C18—C17—C24	76.1 (5)
O4—C31—N4—C30	−178.6 (4)	C19—C18—C23—C22	0.0 (7)
O4—C31—C32—N5	−177.0 (4)	C19—C20—C21—C22	0.0 (7)
O4—C31—C32—C33	67.8 (5)	C20—C19—C18—C23	0.0 (7)
O4—C31—C32—C39	−59.0 (5)	C20—C21—C22—C23	0.0 (8)
N1—Cu1—N3—C16	78.7 (3)	C23—C18—C17—C24	−102.4 (5)
N1—Cu1—N4—C30	−122.3 (5)	C24—C25—C26—C27	0.0 (5)
N1—Cu1—N4—C31	59.0 (6)	C24—C29—C28—C27	0.0 (5)
N1—Cu1—N6—C45	96.1 (3)	C25—C24—C29—C28	0.0 (5)
N1—C1—N2—C3	−1.1 (5)	C25—C26—C27—C28	0.0 (6)
N1—C2—C3—N2	2.8 (5)	C26—C25—C24—C29	0.0 (5)
N1—C2—C3—C4	117.7 (4)	C26—C27—C28—C29	0.0 (6)
N1—C2—C3—C10	−114.6 (4)	C30—N4—C31—C32	0.0 (4)
N2—C1—N1—C2	3.1 (5)	C30—N5—C32—C31	−7.4 (4)
N2—C3—C4—C5	92.6 (4)	C30—N5—C32—C33	111.3 (4)
N2—C3—C4—C9	−80.3 (4)	C30—N5—C32—C39	−123.1 (4)
N2—C3—C10—C11	177.8 (4)	C31—C32—C33—C34	1.1 (6)
N2—C3—C10—C15	−6.6 (6)	C31—C32—C33—C38	179.7 (4)
N3—Cu1—N1—C1	79.3 (3)	C31—C32—C39—C40	104.1 (5)
N3—Cu1—N1—C2	−82.0 (4)	C31—C32—C39—C44	−74.1 (5)
N3—Cu1—N4—C30	146.0 (3)	C32—C33—C34—C35	178.6 (4)
N3—Cu1—N4—C31	−32.7 (3)	C32—C33—C38—C37	−178.7 (4)
N3—C16—C17—C18	174.9 (4)	C32—C39—C40—C41	−178.1 (4)
N3—C16—C17—C24	−57.6 (5)	C32—C39—C44—C43	178.2 (4)
N4—Cu1—N1—C1	−13.4 (7)	C33—C32—C39—C40	−23.2 (5)
N4—Cu1—N1—C2	−174.7 (5)	C33—C32—C39—C44	158.6 (3)
N4—Cu1—N3—C16	−117.8 (3)	C33—C34—C35—C36	0.0 (7)
N4—Cu1—N6—C45	−67.5 (3)	C33—C38—C37—C36	0.0 (7)
N4—C30—N5—C32	8.3 (5)	C34—C33—C32—C39	126.4 (4)
N4—C31—C32—N5	4.3 (4)	C34—C33—C38—C37	0.0 (6)
N4—C31—C32—C33	−110.9 (4)	C34—C35—C36—C37	0.0 (8)
N4—C31—C32—C39	122.3 (4)	C35—C34—C33—C38	0.0 (6)
N5—C30—N4—C31	−5.0 (4)	C35—C36—C37—C38	0.0 (8)
N5—C32—C33—C34	−108.0 (4)	C38—C33—C32—C39	−55.0 (5)
N5—C32—C33—C38	70.7 (5)	C39—C40—C41—C42	0.0 (6)
N5—C32—C39—C40	−146.8 (4)	C39—C44—C43—C42	0.0 (6)
N5—C32—C39—C44	35.0 (5)	C40—C39—C44—C43	0.0 (6)
N6—Cu1—N1—C1	−97.7 (3)	C40—C41—C42—C43	0.0 (6)
N6—Cu1—N1—C2	101.0 (4)	C41—C40—C39—C44	0.0 (6)
N6—Cu1—N4—C30	−38.0 (3)	C41—C42—C43—C44	0.0 (6)
N6—Cu1—N4—C31	143.3 (3)	C45—C46—C47—C48	75.4 (5)
N6—C45—C46—C47	−162.0 (4)	C45—C46—C47—C52	−102.5 (5)
N6—C45—C46—C53	69.3 (6)	C45—C46—C53—C54	−164.2 (4)
C1—N1—C2—C3	−3.7 (5)	C45—C46—C53—C58	19.3 (6)
C1—N2—C3—C2	−1.0 (5)	C46—C47—C48—C49	−177.9 (4)
C1—N2—C3—C4	−120.0 (4)	C46—C47—C52—C51	177.9 (4)
C1—N2—C3—C10	112.7 (4)	C46—C53—C54—C55	−176.6 (4)
C2—C3—C4—C5	−17.0 (5)	C46—C53—C58—C57	176.4 (4)
C2—C3—C4—C9	170.1 (4)	C47—C46—C53—C54	70.1 (5)
C2—C3—C10—C11	−73.5 (5)	C47—C46—C53—C58	−106.4 (4)
C2—C3—C10—C15	102.1 (5)	C47—C48—C49—C50	0.0 (6)
C3—C4—C5—C6	−172.9 (4)	C47—C52—C51—C50	0.0 (6)
C3—C4—C9—C8	173.0 (4)	C48—C47—C46—C53	−154.2 (4)
C3—C10—C11—C12	175.7 (4)	C48—C47—C52—C51	0.0 (6)
C3—C10—C15—C14	−175.5 (4)	C48—C49—C50—C51	0.0 (7)
C4—C3—C10—C11	53.8 (5)	C49—C48—C47—C52	0.0 (6)
C4—C3—C10—C15	−130.6 (4)	C49—C50—C51—C52	0.0 (7)
C4—C5—C6—C7	0.0 (7)	C52—C47—C46—C53	27.8 (5)
C4—C9—C8—C7	0.0 (6)	C53—C54—C55—C56	0.0 (6)
C5—C4—C3—C10	−141.1 (4)	C53—C58—C57—C56	0.0 (6)
C5—C4—C9—C8	0.0 (6)	C54—C53—C58—C57	0.0 (6)
C5—C6—C7—C8	0.0 (7)	C54—C55—C56—C57	0.0 (7)
C6—C5—C4—C9	0.0 (6)	C55—C54—C53—C58	0.0 (6)
C6—C7—C8—C9	0.0 (7)	C55—C56—C57—C58	0.0 (7)
C9—C4—C3—C10	45.9 (5)	C55—C56—C57—C58	0.0 (7)
C10—C11—C12—C13	0.0 (6)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O4^ii	0.95	2.00	2.915 (6)	160
N3—H12···O4	0.95	2.17	2.915 (6)	135
N5—H27···O2^i	0.95	2.09	2.857 (5)	136
N6—H39···O3	0.95	2.07	2.817 (5)	134

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z.