Acetato(N-phenyl­pyridine-2-carbox­amidato-κ²N,N)(N-phenyl­pyridine-2-carboxamide-κ²N¹,O)copper(II)

The title complex, [Cu(C₁₂H₉N₂O)(C₂H₃O₂)(C₁₂H₁₀N₂O)], is a neutral Cu^II complex with a primary N₃O₂ coordination sphere. The Cu centre coordinates to both a deprotonated and a neutral mol­ecule of N-phenyl­pyridine-2-carboxamide and also to an acetate anion. The coordination around the metal centre is asymmetric, the deprotonated ligand providing two N donor atoms [Cu—N = 1.995 (2) and 2.013 (2) Å] and the neutral ligand providing one N and one O donor atom to the coordination environment [Cu—N = 2.042 (2) Å and Cu—O = 2.2557 (19) Å], the fifth donor being an O atom of the acetate ion [Cu—O = 1.9534 (19) Å]. The remaining O atom from the acetate ion can be considered as a weak donor atom [Cu—O = 2.789 (2) Å], conferring to the Cu complex an asymmetric octa­hedral geometry. The crystal structure is stabilized by inter­molecular N—H...O, C—H...O and C—H...π inter­actions.

S1. Comment

The title complex, (I), assumes a different geometry to those previously reported in the literature with identical and similar ligands. In the Cu^II complex with the same ligand (Ray et al., 1994), the structure determination showed that the Cu complex is a four-coordinate one with a symmetric N₄ coordination environment, with the ligand assuming a cis conformation. A Cu complex with a similar ligand, [N-(2-chloro-6-methylphenyl) pyridine-2-carboxamide] has also been reported (Patra et al., 1999). In this case, the molecular structure determination showed that the Cu centre is five-coordinate in a distorted trigonal–bipyramidal geometry with an N₄O coordination environment, with the pyridine and the amide N atoms of each organic ligand providing an axial and an equatorial pyridine and amide N atom and the fifth coordination position occupied by a water molecule.

The N-phenylpyridine-2-carboxamide ligand was obtained by a condensation reaction between 2-pyridinecarboxylic acid and phenylamide in a basic reductive reaction medium following a modification of the procedure described by Barnes et al. (1978) and a similar procedure described by Ray et al. (1994). The ligand, potentially bidentate, reacted with copper(II) acetate forming a five-coordinate complex, (I). The synthesis of the complex was performed in a fashion similar to that reported previously (Ray et al., 1994) but using different reaction conditions. In their synthesis, the ligand (dissolved in ethanol) was allowed to react with an aqueous solution of CuSO₄·5H₂O, while in the synthesis reported here the ligand was dissolved in methanol and added to a methanol solution of Cu(CH₃COO)₂·H₂O.

A view of the structure of the complex and the coordination environment around Cu, together with its numbering scheme, is shown in Fig. 1. The coordination environment around copper is N₃O₂-type and is asymmetric. One of the N-phenylpyridine-2-carboxamide molecules (ligand A) provides a pyridine N and an amide O donor atoms. The second molecule (ligand B, labelled X4#, where X is the atom label and # is an integer) provides a pyridine and a deprotonated amide N donor atoms. The remaining donor O atom, O3, is from the acetate anion. Atom O31 of the acetate residue can be considered to be weakly interacting with the Cu^II ion [Cu1—O31 = 2.789 (2) Å]. In this case, the primary N₃O₂ five-coordination geometry gives place to an effective asymmetric octahedral elongated geometry (Kiani et al., 2002; Burčák et al., 2005). The primary Cu-atom geometry is a distorted square-based pyramid with a τ value of 0.10 [the structure index is defined as τ = (β - α)/60, where β and α are the largest coordination angles; τ = 0 for square–pyramidal (SP) and τ = 1 for trigonal–bipyramidal (TBP) geometry (Addison et al., 1984)]. Ligand B (providing two N donor atoms), an acetate O atom and the pyridine N atom of ligand A encompass the basal plane of the square pyramid [Cu1—N47(amide) = 1.995 (2) Å, Cu1—N41 and Cu1—N1(pyridine) = 2.013 (5) and 2.042 (2) Å, respectively, Cu1—O3(acetate) = 1.9534 (19) Å], from which the Cu atom is displaced 0.1253 (11) Å towards an apical amide O donor atom [Cu1—O2 = 2.2557 (19) Å]. The apical bond length Cu1—O2 is 0.26 Å longer than the mean distance presented by the basal ones. The bond angles involving the coordinated metal centre and the donor atoms are given in Table 1. The largest distortions from the square-pyramidal geometry are indicated by the N41—Cu1—N1 and O3—Cu1—N47 angles. These deviations can be attributed to steric effects imposed by the conformations assumed by the ligands.

Ligands A and B have different conformations. The presence of the H atom on N27 in ligand A precludes this atom being coordinated to the Cu atom; instead, ligand A is rotated by approximately 180° and the carbonyl atom O2 is the donor to the Cu atom, so that ligands A and B assume different conformations around the C2—C27 and C42—C47 bonds, the N1—C2—C27—N27 torsion angle in ligand A being 171.8 (2)°, and N41—C42—C47—N47, the corresponding torsion angle in ligand B, being 0.1 (3)°. In ligand A, the C27—N27—C21—C22 torsion angle is -174.7 (3)°, while the corresponding angle C47—N47—C421—C422 in ligand B is -96.9 (3)°. The C27—N27 bond [1.346 (3) Å] is significantly longer than the C47—N47 bond [1.323 (3) Å] at a 3σ level. Atom H27 is thus available for hydrogen bonding.

The supramolecular stucture is defined by an N—H···O, three C—H···O and one C—H···π hydrogen bonds, which combine to form a three-dimensional network. Atom N27 acts as a hydrogen-bond donor, via H27, to O4ⁱ (symmetry codes are given in Table 2). This is augmented by the C3—H3···O4ⁱ and C22—H22···O4ⁱ hydrogen bonds. These hydrogen bonds link the molecules into a chain that runs parallel to the c axis (Table 2 and Fig. 2). Atom C5 acts as a hydrogen-bond donor, via H5, to O3ⁱⁱ, thus linking the molecules into a chain that runs parallel to the a axis (Table 2 and Fig. 3). Finally, atom C45 is involved in a C—H···π contact with the pyridine ring containing atom N41ⁱⁱⁱ (Table 2 and Fig. 4).

Related literature

For related literature, see: Addison et al. (1984); Barnes et al. (1978); Burčák et al. (2005); Flack (1983); Kiani et al. (2002); Patra et al. (1999); Ray et al. (1994).

S2. Experimental

The ligand N-phenylpyridine-2-carboxamide was synthesized as follows: N-Phenyl-2-pyridynamide was prepared following a modification of the procedure described by Barnes et al. (1978). A solution consisting of a mixture of 2-pyridinecarboxylic acid (picolinic acid, 40 mmol), phenylamide (aniline, 40 mmol) and triphenylphosphite (40 mmol) in 50 ml of pyridine was kept for 3 h in a boiling water bath. The resulting solution was cooled and maintained at room temperature for 48 h. The resulting white fibrous crystals were filtered off and washed with a small amount of a 1:1 mixture of acetone/diethyl ether (78% yield). Analysis found: C 72.9, H 5.10, N 14.01%; C₁₂H₁₀N₂O requires: C 72.7, H 5.08, N 14.14%. For the synthesis of (I), a solution of copper(II) acetate monohydrate in methanol (2.5 mmol) was added to a solution of N-phenyl-2-pyridynamide (5.0 mmol) in methanol at 323 K. The resulting solution was left to cool for 24 h, allowing partial evaporation of the solvent. Single crystals were obtained by slow evaporation of the resulting solution at room temperature. They were collected and washed with a 1:1 mixture of acetone/diethyl ether and dried under low pressure. Analysis found: C 60.23, H 4.45, N 10.78%; C₂₆H₂₂CuN₄O₄ requires: C 60.28, H 4.28, N 10.82%.

S3. Refinement

Compound (I) crystallized in the orthorhombic system; space groups Pna2₁ and Pnma were permitted from the systematic absences, and Pna2₁ was confirmed by the analysis. H atoms were treated as riding atoms, with C—H distances of 0.95 Å (aromatic) and 0.98 Å (methyl), an N—H distance of 0.89 Å, and U_iso(H) values of 1.5 (methyl) or 1.2 times U_eq(C,N). The correct orientation of the structure with respect to the polar axis direction was established by means of the Flack (1983) parameter.

Computing details

Data collection: Stadi-4 Software (Stoe & Cie, 1996); cell refinement: X-RED (Stoe & Cie, 1996); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of (I), with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the chain parallel to the c axis formed by the action of one N—H···O hydrogen bond augmented by two C—H···O hydrogen bonds, all involving atom O4 as the acceptor. Atoms labelled with an asterisk (*) or a hash (#) are at the symmetry positions (1 - x, 1 - y, -1/2 + z) and (1 - x, 1 - y, 1/2 - z), respectively. H atoms not involved in the hydrogen bonding have been omitted for the sake of clarity.
	Fig. 3. A view of the chain parallel to the a axis formed by a C—H···O hydrogen bond. Atoms labelled with an asterisk (*) or a hash (#) are at the symmetry positions (-1 + x, y, z) and (1 + x, y, z), respectively. H atoms not involved in the hydrogen bonding have been omitted for the sake of clarity.
	Fig. 4. A stereoview of the chain formed by a C—H···π interaction. H atoms not involved in the hydrogen bonding have been omitted for the sake of clarity.

Acetato(N-phenylpyridine-2-carboxamidato-κ²N,N)(N- phenylpyridine-2-carboxamideκ²N¹,O)copper(II)

Crystal data

[Cu(C12H9N2O)(C2H3O2)(C12H10N2O)]	F(000) = 1068
Mr = 518.02	Dx = 1.417 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5831 reflections
a = 7.9604 (1) Å	θ = 1.8–28.0°
b = 23.057 (3) Å	µ = 0.94 mm^−1
c = 13.227 (2) Å	T = 120 K
V = 2427.7 (5) Å^3	Block, green
Z = 4	0.25 × 0.10 × 0.10 mm

Data collection

Stoe Stadi-4 diffractometer	4590 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 28.0°, θmin = 1.8°
profile fitted 2θ/w scans	h = −10→10
Absorption correction: multi-scan (North et al., 1968)	k = −30→0
Tmin = 0.799, Tmax = 0.912	l = −17→17
6079 measured reflections	10 standard reflections every 120 min
5831 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 0.0275P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5831 reflections	Δρmax = 0.21 e Å^−3
317 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Absolute structure: Flack (1983), 2827 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.003 (11)

Special details

Experimental. The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Cu1	0.67223 (3)	0.382359 (11)	0.29462 (2)	0.02485 (8)
O2	0.7315 (2)	0.47709 (8)	0.27127 (13)	0.0291 (4)
O3	0.7701 (3)	0.35655 (9)	0.16688 (14)	0.0299 (4)
O4	0.6360 (3)	0.38267 (9)	0.60211 (15)	0.0365 (5)
O31	0.6132 (3)	0.27856 (10)	0.19229 (17)	0.0489 (6)
N1	0.4623 (3)	0.41385 (10)	0.22490 (16)	0.0279 (5)
N27	0.6053 (3)	0.56152 (10)	0.22213 (17)	0.0294 (5)
N41	0.8433 (3)	0.33925 (9)	0.37781 (17)	0.0248 (4)
N47	0.5845 (3)	0.40094 (10)	0.43216 (16)	0.0289 (5)
C2	0.4465 (3)	0.47213 (12)	0.21947 (19)	0.0272 (5)
C3	0.2925 (4)	0.49801 (14)	0.2003 (2)	0.0363 (7)
C4	0.1553 (4)	0.46346 (17)	0.1800 (3)	0.0467 (8)
C5	0.1741 (4)	0.40399 (18)	0.1786 (3)	0.0453 (8)
C6	0.3284 (4)	0.38047 (14)	0.2040 (2)	0.0396 (7)
C21	0.7290 (4)	0.60269 (12)	0.2509 (2)	0.0303 (6)
C22	0.6914 (4)	0.66050 (13)	0.2324 (2)	0.0381 (7)
C23	0.8006 (4)	0.70367 (13)	0.2635 (2)	0.0426 (8)
C24	0.9448 (4)	0.69053 (13)	0.3141 (2)	0.0428 (8)
C25	0.9849 (5)	0.63295 (15)	0.3298 (3)	0.0510 (9)
C26	0.8780 (4)	0.58888 (12)	0.2992 (3)	0.0433 (7)
C27	0.6084 (3)	0.50401 (11)	0.23922 (18)	0.0255 (5)
C31	0.7137 (4)	0.30620 (13)	0.1411 (2)	0.0339 (6)
C32	0.7794 (5)	0.28252 (16)	0.0430 (3)	0.0511 (9)
C42	0.8148 (3)	0.34256 (11)	0.47805 (19)	0.0251 (5)
C43	0.9150 (4)	0.31426 (12)	0.5471 (2)	0.0332 (6)
C44	1.0454 (4)	0.27985 (14)	0.5123 (2)	0.0418 (7)
C45	1.0722 (4)	0.27585 (13)	0.4094 (2)	0.0390 (7)
C46	0.9688 (4)	0.30614 (11)	0.3441 (2)	0.0300 (6)
C47	0.6666 (3)	0.37792 (10)	0.5094 (2)	0.0260 (5)
C421	0.4515 (4)	0.44050 (12)	0.4546 (2)	0.0291 (6)
C422	0.2870 (4)	0.42223 (16)	0.4569 (3)	0.0435 (8)
C423	0.1582 (4)	0.46208 (18)	0.4756 (3)	0.0544 (9)
C424	0.1948 (4)	0.51951 (17)	0.4916 (3)	0.0487 (9)
C425	0.3592 (5)	0.53797 (14)	0.4894 (2)	0.0424 (7)
C426	0.4882 (4)	0.49894 (13)	0.47066 (19)	0.0329 (6)
H3	0.2818	0.5390	0.2010	0.044*
H4	0.0487	0.4804	0.1672	0.056*
H5	0.0827	0.3796	0.1604	0.054*
H6	0.3400	0.3395	0.2068	0.048*
H22	0.5905	0.6705	0.1982	0.046*
H23	0.7746	0.7431	0.2495	0.051*
H24	1.0165	0.7204	0.3380	0.051*
H25	1.0877	0.6234	0.3622	0.061*
H26	0.9067	0.5495	0.3113	0.052*
H27	0.5206	0.5754	0.1848	0.035*
H43	0.8949	0.3183	0.6176	0.040*
H44	1.1151	0.2594	0.5584	0.050*
H45	1.1609	0.2525	0.3838	0.047*
H46	0.9876	0.3033	0.2733	0.036*
H32A	0.9025	0.2828	0.0440	0.077*
H32B	0.7392	0.3066	−0.0131	0.077*
H32C	0.7395	0.2426	0.0339	0.077*
H422	0.2609	0.3825	0.4459	0.052*
H423	0.0448	0.4493	0.4773	0.065*
H424	0.1069	0.5464	0.5043	0.058*
H425	0.3845	0.5777	0.5007	0.051*
H426	0.6013	0.5120	0.4688	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02781 (13)	0.02482 (13)	0.02193 (12)	0.00124 (12)	0.00319 (16)	−0.00028 (15)
O2	0.0251 (8)	0.0278 (9)	0.0344 (11)	0.0021 (7)	−0.0034 (7)	0.0017 (7)
O3	0.0341 (10)	0.0311 (10)	0.0245 (9)	−0.0013 (9)	0.0053 (9)	−0.0005 (8)
O4	0.0410 (12)	0.0468 (12)	0.0218 (10)	0.0121 (10)	0.0037 (8)	−0.0039 (9)
O31	0.0606 (14)	0.0487 (13)	0.0375 (12)	−0.0209 (12)	0.0108 (11)	0.0022 (10)
N1	0.0268 (11)	0.0347 (12)	0.0223 (10)	−0.0052 (9)	0.0019 (9)	−0.0004 (9)
N27	0.0293 (11)	0.0305 (11)	0.0285 (11)	0.0031 (10)	−0.0076 (10)	0.0023 (9)
N41	0.0292 (11)	0.0204 (10)	0.0249 (11)	−0.0010 (8)	0.0027 (9)	−0.0021 (8)
N47	0.0311 (13)	0.0312 (11)	0.0243 (11)	0.0092 (10)	0.0039 (9)	−0.0005 (9)
C2	0.0235 (12)	0.0379 (14)	0.0202 (11)	−0.0011 (10)	0.0018 (10)	0.0027 (10)
C3	0.0289 (15)	0.0461 (17)	0.0338 (14)	0.0031 (12)	−0.0025 (12)	0.0079 (13)
C4	0.0275 (16)	0.069 (2)	0.0439 (19)	−0.0018 (15)	−0.0021 (14)	0.0142 (17)
C5	0.0321 (16)	0.067 (2)	0.0369 (17)	−0.0174 (16)	−0.0040 (13)	0.0050 (15)
C6	0.0363 (16)	0.0483 (18)	0.0343 (15)	−0.0117 (14)	−0.0003 (13)	0.0001 (13)
C21	0.0344 (14)	0.0306 (14)	0.0260 (13)	−0.0004 (11)	−0.0016 (12)	0.0003 (11)
C22	0.0407 (17)	0.0349 (15)	0.0387 (16)	0.0067 (12)	−0.0016 (13)	0.0009 (12)
C23	0.056 (2)	0.0269 (14)	0.0449 (17)	−0.0006 (13)	0.0019 (14)	0.0004 (12)
C24	0.0551 (19)	0.0356 (14)	0.038 (2)	−0.0129 (13)	−0.0048 (14)	−0.0016 (12)
C25	0.0479 (19)	0.0432 (18)	0.062 (2)	−0.0084 (15)	−0.0246 (17)	0.0050 (15)
C26	0.0424 (15)	0.0323 (13)	0.0551 (18)	−0.0019 (11)	−0.023 (2)	0.0048 (18)
C27	0.0266 (12)	0.0301 (12)	0.0197 (11)	0.0024 (11)	−0.0002 (10)	0.0015 (10)
C31	0.0441 (17)	0.0349 (15)	0.0226 (13)	−0.0029 (13)	0.0019 (11)	0.0010 (11)
C32	0.070 (2)	0.051 (2)	0.0322 (16)	−0.0003 (18)	0.0116 (16)	−0.0100 (15)
C42	0.0277 (13)	0.0207 (11)	0.0269 (13)	−0.0013 (10)	0.0022 (10)	−0.0028 (9)
C43	0.0408 (16)	0.0332 (14)	0.0256 (12)	0.0076 (13)	−0.0001 (12)	−0.0046 (11)
C44	0.0463 (18)	0.0422 (17)	0.0370 (16)	0.0159 (14)	−0.0043 (14)	0.0010 (13)
C45	0.0423 (17)	0.0361 (15)	0.0387 (16)	0.0166 (13)	0.0051 (13)	−0.0025 (13)
C46	0.0341 (14)	0.0255 (13)	0.0305 (14)	0.0002 (11)	0.0061 (11)	−0.0027 (10)
C47	0.0300 (13)	0.0236 (11)	0.0245 (12)	−0.0018 (11)	0.0040 (10)	−0.0018 (10)
C421	0.0327 (14)	0.0345 (14)	0.0200 (11)	0.0085 (11)	0.0039 (10)	0.0016 (11)
C422	0.0350 (16)	0.0484 (18)	0.0471 (18)	0.0019 (14)	0.0098 (13)	0.0001 (16)
C423	0.0353 (18)	0.064 (2)	0.064 (3)	0.0077 (17)	0.0123 (17)	0.0075 (18)
C424	0.051 (2)	0.057 (2)	0.0382 (17)	0.0297 (17)	0.0088 (15)	0.0052 (15)
C425	0.062 (2)	0.0366 (15)	0.0282 (14)	0.0167 (15)	0.0007 (14)	−0.0004 (12)
C426	0.0386 (15)	0.0347 (14)	0.0252 (13)	0.0059 (12)	−0.0028 (11)	−0.0021 (10)

Geometric parameters (Å, º)

Cu1—O2	2.2557 (19)	O3—C31	1.291 (3)
Cu1—O3	1.9534 (19)	C31—O31	1.227 (4)
Cu1—O31	2.789 (2)	C31—C32	1.502 (4)
Cu1—N1	2.042 (2)	C32—H32A	0.98
Cu1—N41	2.013 (2)	C32—H32B	0.98
Cu1—N47	1.995 (2)	C32—H32C	0.98
N1—C6	1.343 (4)	N41—C46	1.334 (3)
N1—C2	1.351 (4)	N41—C42	1.347 (3)
C2—C3	1.387 (4)	C42—C43	1.377 (4)
C2—C27	1.506 (4)	C42—C47	1.493 (4)
C27—O2	1.235 (3)	C47—O4	1.256 (3)
C27—N27	1.346 (3)	C47—N47	1.323 (3)
N27—C21	1.419 (4)	N47—C421	1.428 (3)
N27—H27	0.89	C421—C422	1.376 (4)
C21—C26	1.385 (4)	C421—C426	1.395 (4)
C21—C22	1.388 (4)	C422—C423	1.399 (5)
C22—C23	1.384 (4)	C422—H422	0.95
C22—H22	0.95	C423—C424	1.372 (6)
C23—C24	1.362 (5)	C423—H423	0.95
C23—H23	0.95	C424—C425	1.377 (5)
C24—C25	1.381 (4)	C424—H424	0.95
C24—H24	0.95	C425—C426	1.388 (4)
C25—C26	1.386 (4)	C425—H425	0.95
C25—H25	0.95	C426—H426	0.95
C26—H26	0.95	C43—C44	1.385 (4)
C3—C4	1.378 (4)	C43—H43	0.95
C3—H3	0.95	C44—C45	1.381 (4)
C4—C5	1.379 (6)	C44—H44	0.95
C4—H4	0.95	C45—C46	1.383 (4)
C5—C6	1.385 (5)	C45—H45	0.95
C5—H5	0.95	C46—H46	0.95
C6—H6	0.95
O3—Cu1—N47	173.55 (9)	C31—O3—Cu1	111.34 (17)
O3—Cu1—N41	93.02 (9)	O31—C31—O3	123.2 (3)
N47—Cu1—N41	81.05 (9)	O31—C31—C32	121.0 (3)
O3—Cu1—N1	92.53 (9)	O3—C31—C32	115.7 (3)
N47—Cu1—N1	92.81 (9)	C31—C32—H32A	109.5
N41—Cu1—N1	167.38 (8)	C31—C32—H32B	109.5
O3—Cu1—O2	95.35 (7)	H32A—C32—H32B	109.5
N47—Cu1—O2	89.43 (8)	C31—C32—H32C	109.5
N41—Cu1—O2	114.30 (8)	H32A—C32—H32C	109.5
N1—Cu1—O2	76.41 (8)	H32B—C32—H32C	109.5
C6—N1—C2	119.0 (3)	C46—N41—C42	119.2 (2)
C6—N1—Cu1	122.6 (2)	C46—N41—Cu1	127.33 (19)
C2—N1—Cu1	116.97 (17)	C42—N41—Cu1	113.34 (18)
N1—C2—C3	121.3 (3)	N41—C42—C43	121.9 (2)
N1—C2—C27	113.4 (2)	N41—C42—C47	115.9 (2)
C3—C2—C27	125.3 (3)	C43—C42—C47	122.2 (2)
O2—C27—N27	124.6 (3)	O4—C47—N47	128.5 (2)
O2—C27—C2	119.5 (2)	O4—C47—C42	118.2 (2)
N27—C27—C2	115.9 (2)	N47—C47—C42	113.3 (2)
C27—O2—Cu1	111.58 (17)	C47—N47—C421	117.5 (2)
C27—N27—C21	127.0 (2)	C47—N47—Cu1	116.39 (17)
C27—N27—H27	117.2	C421—N47—Cu1	125.85 (17)
C21—N27—H27	115.6	C422—C421—C426	119.4 (3)
C26—C21—C22	119.1 (3)	C422—C421—N47	121.0 (3)
C26—C21—N27	124.3 (2)	C426—C421—N47	119.6 (3)
C22—C21—N27	116.5 (3)	C421—C422—C423	120.0 (3)
C23—C22—C21	120.2 (3)	C421—C422—H422	120.0
C23—C22—H22	119.9	C423—C422—H422	120.0
C21—C22—H22	119.9	C424—C423—C422	120.4 (3)
C24—C23—C22	121.0 (3)	C424—C423—H423	119.8
C24—C23—H23	119.5	C422—C423—H423	119.8
C22—C23—H23	119.5	C423—C424—C425	119.8 (3)
C23—C24—C25	118.8 (3)	C423—C424—H424	120.1
C23—C24—H24	120.6	C425—C424—H424	120.1
C25—C24—H24	120.6	C424—C425—C426	120.5 (3)
C24—C25—C26	121.3 (3)	C424—C425—H425	119.8
C24—C25—H25	119.4	C426—C425—H425	119.8
C26—C25—H25	119.4	C425—C426—C421	119.9 (3)
C21—C26—C25	119.5 (3)	C425—C426—H426	120.0
C21—C26—H26	120.3	C421—C426—H426	120.0
C25—C26—H26	120.3	C42—C43—C44	119.0 (3)
C4—C3—C2	119.2 (3)	C42—C43—H43	120.5
C4—C3—H3	120.4	C44—C43—H43	120.5
C2—C3—H3	120.4	C45—C44—C43	118.8 (3)
C3—C4—C5	119.4 (3)	C45—C44—H44	120.6
C3—C4—H4	120.3	C43—C44—H44	120.6
C5—C4—H4	120.3	C44—C45—C46	119.4 (3)
C4—C5—C6	118.8 (3)	C44—C45—H45	120.3
C4—C5—H5	120.6	C46—C45—H45	120.3
C6—C5—H5	120.6	N41—C46—C45	121.7 (3)
N1—C6—C5	122.0 (3)	N41—C46—H46	119.1
N1—C6—H6	119.0	C45—C46—H46	119.1
C5—C6—H6	119.0
O3—Cu1—N1—C6	85.9 (2)	O3—Cu1—N41—C46	−0.9 (2)
N47—Cu1—N1—C6	−90.4 (2)	N47—Cu1—N41—C46	176.6 (2)
N41—Cu1—N1—C6	−30.1 (5)	N1—Cu1—N41—C46	115.1 (4)
O2—Cu1—N1—C6	−179.2 (2)	O2—Cu1—N41—C46	−98.1 (2)
O3—Cu1—N1—C2	−107.92 (19)	O3—Cu1—N41—C42	−176.04 (18)
N47—Cu1—N1—C2	75.71 (19)	N47—Cu1—N41—C42	1.42 (18)
N41—Cu1—N1—C2	136.1 (4)	N1—Cu1—N41—C42	−60.1 (5)
O2—Cu1—N1—C2	−13.02 (17)	O2—Cu1—N41—C42	86.71 (19)
C6—N1—C2—C3	4.9 (4)	C46—N41—C42—C43	2.2 (4)
Cu1—N1—C2—C3	−161.8 (2)	Cu1—N41—C42—C43	177.8 (2)
C6—N1—C2—C27	−176.9 (2)	C46—N41—C42—C47	−176.8 (2)
Cu1—N1—C2—C27	16.5 (3)	Cu1—N41—C42—C47	−1.2 (3)
N1—C2—C27—O2	−9.8 (3)	N41—C42—C47—O4	−179.4 (2)
C3—C2—C27—O2	168.4 (3)	C43—C42—C47—O4	1.6 (4)
N1—C2—C27—N27	171.8 (2)	N41—C42—C47—N47	0.1 (3)
C3—C2—C27—N27	−10.0 (4)	C43—C42—C47—N47	−178.9 (2)
N27—C27—O2—Cu1	177.3 (2)	O4—C47—N47—C421	5.9 (4)
C2—C27—O2—Cu1	−1.0 (3)	C42—C47—N47—C421	−173.5 (2)
O3—Cu1—O2—C27	98.59 (18)	O4—C47—N47—Cu1	−179.5 (2)
N47—Cu1—O2—C27	−85.75 (18)	C42—C47—N47—Cu1	1.2 (3)
N41—Cu1—O2—C27	−165.66 (16)	N41—Cu1—N47—C47	−1.45 (19)
N1—Cu1—O2—C27	7.27 (17)	N1—Cu1—N47—C47	167.5 (2)
O2—C27—N27—C21	−10.1 (4)	O2—Cu1—N47—C47	−116.2 (2)
C2—C27—N27—C21	168.2 (2)	N41—Cu1—N47—C421	172.7 (2)
C27—N27—C21—C26	2.3 (5)	N1—Cu1—N47—C421	−18.3 (2)
C27—N27—C21—C22	−174.7 (3)	O2—Cu1—N47—C421	58.0 (2)
C26—C21—C22—C23	−1.1 (5)	C47—N47—C421—C422	−96.9 (3)
N27—C21—C22—C23	176.1 (3)	Cu1—N47—C421—C422	88.9 (3)
C21—C22—C23—C24	−1.1 (5)	C47—N47—C421—C426	85.4 (3)
C22—C23—C24—C25	3.0 (5)	Cu1—N47—C421—C426	−88.7 (3)
C23—C24—C25—C26	−2.9 (6)	C426—C421—C422—C423	−0.2 (5)
C22—C21—C26—C25	1.2 (5)	N47—C421—C422—C423	−177.8 (3)
N27—C21—C26—C25	−175.8 (3)	C421—C422—C423—C424	0.0 (6)
C24—C25—C26—C21	0.8 (6)	C422—C423—C424—C425	−0.1 (6)
N1—C2—C3—C4	−4.1 (4)	C423—C424—C425—C426	0.2 (5)
C27—C2—C3—C4	177.8 (3)	C424—C425—C426—C421	−0.3 (4)
C2—C3—C4—C5	−0.5 (5)	C422—C421—C426—C425	0.3 (4)
C3—C4—C5—C6	4.2 (5)	N47—C421—C426—C425	178.0 (2)
C2—N1—C6—C5	−1.0 (4)	N41—C42—C43—C44	−2.2 (4)
Cu1—N1—C6—C5	164.9 (2)	C47—C42—C43—C44	176.8 (3)
C4—C5—C6—N1	−3.5 (5)	C42—C43—C44—C45	1.0 (5)
N41—Cu1—O3—C31	84.9 (2)	C43—C44—C45—C46	0.0 (5)
N1—Cu1—O3—C31	−83.8 (2)	C42—N41—C46—C45	−1.1 (4)
O2—Cu1—O3—C31	−160.38 (19)	Cu1—N41—C46—C45	−176.0 (2)
Cu1—O3—C31—O31	−1.0 (4)	C44—C45—C46—N41	0.0 (5)
Cu1—O3—C31—C32	179.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N27—H27···O4^i	0.89	1.92	2.805 (3)	170
C3—H3···O4^i	0.95	2.32	3.095 (4)	138
C5—H5···O3^ii	0.95	2.55	3.401 (4)	150
C22—H22···O4^i	0.95	2.52	3.279 (4)	137
C45—H45···Cg5^iii	0.95	2.78	3.582 (3)	142

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