catena-Poly[[bis(1H-benzimidazole-[kappa]N³)(salicylato-[kappa]O)copper(II)]-[mu]-salicylato-O,O':O'']

The title compound, [Cu(C₇H₅O₃)₂(C₇H₆N₂)₂]_n, is a one-dimensional polymeric complex bridged by salicyl­ate anions. The Cu^II atom is surrounded by three salicyl­ate and two benz­imidazole ligands, with a tetragonally elongated octahedral coordination geometry. The Cu-O bond distances in the axial directions are 2.6092 (16) and 2.6834 (17) Å. [pi]-[pi] stacking interactions exist between the benz­imidazole rings of neighboring polymeric complex chains.

S1. Comment

As π–π stacking between aromatic rings is correlated with the electron transfer process in some biological systems (Deisenhofer & Michel, 1989), metal complexes incorporating aromatic ligands, such as phenanthroline, benzimidazole and bithiazole, have attracted our attention. A series of metal complexes with the benzimidazole (bzim) ligand have been prepared in our laboratory, and their structures have shown the existence of π–π stacking between the bzim rings (Chen et al., 2003). As a part of our ongoing investigations into π–π stacking, we report here the structure of the title compound, (I), [Cu(bzim)₂(sali)₂]_n. A search of the Cambridge Structural Database (November 2003 update; Allen, 2002) indicated that no [M(bzim)₂(sali)₂]_n compound has been reported before.

The structure of a fragment of (I) is illustrated in Fig. 1. The repeat unit of the polymeric complex includes one Cu^II atom, two salicylate (sali) anions and two bzim molecules. N atoms of the bzim ligands and carboxyl O atoms (O1 and O4) from two sali ligands form the equatorial coordination plane around the Cu atom, with bond distances of 1.9629 (16)–2.0061 (15) Å (Table 1).

The distances between the Cu atom and the other two carboxyl O atoms (O2 and O5) are appreciably different, and both are much longer than those in the equatorial plane. The Cu—O2 distance is longer than the average Cu—O distance in the equatorial plane [1.982 (2) Å] by 0.627 (3) Å, but the smaller Cu—O1—C1 angle [104.68 (14)°] suggests a bonding interaction between atoms Cu and O2 (as discussed below). On the other hand, the Cu···O5 distance [3.061 (2) Å] and the larger Cu—O4—C2 angle [120.94 (16)°] suggest no bonding interaction between atoms Cu and O5.

A comparison of the geometric parameters for carboxyl groups in some Cu^II complexes is listed in Table 3. The Cu—O1—C1 angles in these complexes fall into two distinct ranges, viz. either larger than 120° or close to 105°. The bond angle of 120° indicates normal sp² hybridization for atom O1 and corresponds to the long Cu···O2 distance in the complexes, suggesting a monodentate coordinate mode for the carboxyl group. Conversely, the smaller Cu—O1—C1 angle of 105° implies the existence of a bonding interaction between the Cu atom and the other O atom (O2) of the carboxyl group, suggesting a chelate coordination mode. A similar situation was also found in carboxylate–Mn^II complexes, in which the Mn—O—C angles of 120 and 95° correspond to the monodentate and chelate modes of the carboxyl group, respectively (Liu et al., 2004). Thus the metal—O—C angle may be an additional criterion of the coordination mode for the carboxyl group in transition metal complexes. According to this criterion, the two sali ligands in (I) coordinate to the Cu atom in different modes.

The C1-containing sali group also plays the role of bridging ligand in (I); hydroxy atom O3 coordinates to the Cu atom of the neighboring repeat unit to form a polymeric complex chain along the crystallographic a axis (Figs. 1 and 2). The Cu—O3ⁱ distance [symmetry code: (i) x − 1, y, z] is appreciably longer than the Cu—O2 distance (Table 1). The large Cu—O3ⁱ—C12ⁱ bond angle [143.93 (14)°], besides the Jahn–Teller effect, is a possible reason for the longer Cu—O3ⁱ bond. Thus each Cu^II atom is surrounded by three sali and two bzim ligands in a distorted octahedral coordination geometry.

The C2-containg sali group is not a bridging ligand. Carboxyl O5 atom is hydrogen bonded to the O3ⁱ hydroxy group of an adjacent sali ligand, resulting in there being a longer distance between atom O6 and the neighboring complex unit, the nearest distance between atom O6 and the non-H atoms of the neighboring complex unit being 3.684 (3) Å (O6···O4ⁱ; Fig. 1).

The packing of the polymeric chains is illustrated in Fig. 2. Neighboring polymeric chains are linked to one another via hydrogen bonds (Table 2) between the bzim and carboxyl groups. The nearly parallel arrangement of the bzim rings from neighboring polymeric chains is also shown in Fig. 2, a partial overlapping between the bzim rings being observed (Fig. 3). The dihedral angle between the bzim groups containing atoms N33 and N43ⁱⁱ is 7.64 (5)°, aso is the angle between the bzim groups containing atoms N33 and N43ⁱⁱⁱ [symmetry codes: (ii) 1/2 − x, y − 1/2, 1/2 − z; (iii) 3/2 − x, y − 1/2, 1/2 − z]. The distances of atoms N31 and C38 from the mean plane of the N43ⁱⁱ-containing bzim group are 3.344 (2) and 3.436 (3) Å, respectively; the distances of atoms C36 and C38 from the mean plane of the N43ⁱⁱⁱ-containing bzim grop are 3.467 (3) and 3.537 (3) Å, respectively. These distances are significantly shorter than that between uncoordinated parallel bzim rings in the Mn^II–bzim complex [3.600 (6) Å; Chen et al., 2003] and clearly suggest the existence of π–π stacking of bzim rings between polymeric complex chains in (I).

S2. Experimental

An ethanol solution (5 ml) of benzimidazole (0.24 g, 2 mmol) was mixed with an aqueous solution (8 ml) containing salicylic acid (0.28 g, 2 mmol), Na₂CO₃ (0.10 g, 1 mmol) and CuCl₂·2H₂O (0.17 g, 1 mmol). The mixture was refluxed for 4 h and filtered. Blue single crystals of (I) were obtained from the filtrate after 3 d.

S3. Refinement

H atoms on aromatic rings were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å, and were included in the final cycles of refinement in a riding model, with U_iso(H) values of 1.2U_eq(carrier atom). H atoms of hydroxy groups were located in difference Fourier maps and refined as riding in their as-found positions relative to the O atoms, with fixed isotropic displacement parameters of 0.05 Ų. The large anisotropy in the displacement parameters of atoms O6 and C24 may imply that the non-bridged sali ligand is disordered.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of a fragment of (I), with 30% probability displacement ellipsoids. Dashed lines indicate the hydrogen bonding. Symmetry code: (i) x − 1, y, z.
	Fig. 2. A crystal packing diagram, showing the nearly parallel arrangement of the bzim rings and hydrogen bonding (dashed lines) between neighboring polymeric complex chains.
	Fig. 3. π–π stacking between the bzim rings of neighboring molecules. [Symmetry code: (ii) 1/2 − x, y − 1/2, 1/2 − z.]

catena-Poly[[bis(benzimidazole)(salicylato-κO)copper(II)]- µ-salicylato-O,O':O'']

Crystal data

[Cu(C7H5O3)2(C7H6N2)2]	F(000) = 1180
Mr = 574.04	Dx = 1.538 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13793 reflections
a = 7.3032 (9) Å	θ = 2.0–24.0°
b = 14.0380 (12) Å	µ = 0.93 mm^−1
c = 24.1952 (18) Å	T = 295 K
β = 91.812 (4)°	Platelet, blue
V = 2479.3 (4) Å^3	0.32 × 0.22 × 0.08 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	4320 independent reflections
Radiation source: fine-focus sealed tube	3426 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 10.00 pixels mm^-1	θmax = 25.0°, θmin = 1.7°
ω scans	h = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
Tmin = 0.740, Tmax = 0.925	l = −28→28
18148 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0382P)^2 + 1.4329P] where P = (Fo^2 + 2Fc^2)/3
4320 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cu	0.49565 (4)	0.21655 (2)	0.250261 (12)	0.03035 (10)
O1	0.6207 (2)	0.16477 (12)	0.31890 (6)	0.0325 (4)
O2	0.8491 (2)	0.19458 (13)	0.26335 (7)	0.0388 (4)
O3	1.1837 (2)	0.17869 (13)	0.30168 (7)	0.0394 (4)
H3	1.0867	0.1989	0.2802	0.050*
O4	0.4135 (2)	0.26405 (13)	0.17731 (7)	0.0410 (4)
O5	0.1259 (3)	0.28394 (15)	0.20165 (8)	0.0530 (5)
O6	−0.1256 (3)	0.3192 (2)	0.12855 (13)	0.0955 (9)
H6	−0.0660	0.3031	0.1610	0.050*
N31	0.4673 (3)	−0.07259 (16)	0.22141 (9)	0.0452 (6)
H31	0.4457	−0.1289	0.2336	0.054*
N33	0.4931 (3)	0.08398 (15)	0.22048 (8)	0.0349 (5)
N41	0.5212 (3)	0.50478 (16)	0.27998 (9)	0.0420 (5)
H41	0.5402	0.5614	0.2678	0.050*
N43	0.4996 (3)	0.34802 (14)	0.28054 (8)	0.0331 (5)
C1	0.7884 (3)	0.16193 (16)	0.30773 (9)	0.0285 (5)
C2	0.2460 (4)	0.27998 (17)	0.16642 (10)	0.0347 (6)
C11	0.9198 (3)	0.11529 (17)	0.34758 (9)	0.0289 (5)
C12	1.1095 (3)	0.12609 (16)	0.34239 (9)	0.0301 (5)
C13	1.2298 (3)	0.08195 (19)	0.38008 (10)	0.0390 (6)
H13	1.3555	0.0907	0.3775	0.047*
C14	1.1627 (4)	0.0254 (2)	0.42109 (11)	0.0471 (7)
H14	1.2435	−0.0038	0.4463	0.057*
C15	0.9768 (4)	0.0115 (2)	0.42537 (11)	0.0513 (7)
H15	0.9327	−0.0282	0.4527	0.062*
C16	0.8572 (4)	0.0566 (2)	0.38917 (10)	0.0404 (6)
H16	0.7318	0.0477	0.3925	0.048*
C21	0.1901 (4)	0.29381 (18)	0.10707 (11)	0.0419 (6)
C22	0.0074 (5)	0.3131 (2)	0.09180 (15)	0.0642 (9)
C23	−0.0400 (7)	0.3254 (3)	0.0361 (2)	0.0959 (15)
H23	−0.1608	0.3388	0.0255	0.115*
C24	0.0879 (9)	0.3180 (3)	−0.00300 (18)	0.1025 (18)
H24	0.0536	0.3270	−0.0400	0.123*
C25	0.2663 (7)	0.2976 (3)	0.01085 (13)	0.0844 (13)
H25	0.3524	0.2913	−0.0164	0.101*
C26	0.3168 (5)	0.2864 (2)	0.06603 (11)	0.0590 (9)
H26	0.4386	0.2736	0.0757	0.071*
C32	0.4502 (4)	0.00860 (19)	0.24930 (11)	0.0412 (6)
H32	0.4117	0.0115	0.2855	0.049*
C34	0.6029 (3)	0.0958 (2)	0.12218 (11)	0.0439 (7)
H34	0.6187	0.1616	0.1216	0.053*
C35	0.6384 (4)	0.0400 (2)	0.07688 (12)	0.0549 (8)
H35	0.6755	0.0691	0.0446	0.066*
C36	0.6204 (4)	−0.0590 (2)	0.07795 (13)	0.0576 (8)
H36	0.6458	−0.0938	0.0464	0.069*
C37	0.5665 (4)	−0.1063 (2)	0.12417 (12)	0.0515 (7)
H37	0.5574	−0.1723	0.1252	0.062*
C38	0.5260 (3)	−0.04988 (19)	0.16937 (11)	0.0397 (6)
C39	0.5420 (3)	0.04869 (18)	0.16892 (10)	0.0350 (6)
C42	0.5371 (3)	0.42397 (19)	0.25137 (11)	0.0400 (6)
H42	0.5712	0.4218	0.2147	0.048*
C44	0.4115 (4)	0.3345 (2)	0.38109 (10)	0.0413 (6)
H44	0.4052	0.2683	0.3824	0.050*
C45	0.3755 (4)	0.3894 (2)	0.42652 (12)	0.0509 (7)
H45	0.3460	0.3594	0.4593	0.061*
C46	0.3818 (4)	0.4884 (2)	0.42507 (12)	0.0534 (8)
H46	0.3532	0.5228	0.4565	0.064*
C47	0.4292 (4)	0.5361 (2)	0.37842 (12)	0.0491 (7)
H47	0.4349	0.6023	0.3774	0.059*
C48	0.4685 (3)	0.48120 (18)	0.33261 (11)	0.0371 (6)
C49	0.4578 (3)	0.38193 (17)	0.33303 (10)	0.0318 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03097 (16)	0.03057 (16)	0.02933 (16)	0.00464 (13)	−0.00213 (12)	0.00162 (13)
O1	0.0268 (8)	0.0375 (10)	0.0333 (9)	0.0055 (7)	0.0016 (7)	0.0018 (7)
O2	0.0322 (9)	0.0491 (11)	0.0351 (9)	0.0047 (8)	0.0012 (8)	0.0126 (8)
O3	0.0280 (9)	0.0451 (11)	0.0450 (10)	−0.0025 (8)	−0.0005 (8)	0.0109 (8)
O4	0.0454 (11)	0.0459 (11)	0.0314 (9)	0.0117 (8)	−0.0026 (8)	0.0026 (8)
O5	0.0486 (11)	0.0657 (15)	0.0453 (11)	0.0022 (10)	0.0090 (10)	0.0037 (10)
O6	0.0495 (14)	0.121 (2)	0.115 (2)	0.0024 (15)	−0.0219 (16)	0.0344 (19)
N31	0.0534 (14)	0.0325 (13)	0.0496 (14)	−0.0081 (10)	−0.0008 (11)	0.0032 (11)
N33	0.0360 (11)	0.0350 (12)	0.0337 (11)	−0.0013 (9)	0.0006 (9)	−0.0005 (9)
N41	0.0504 (13)	0.0291 (12)	0.0464 (13)	−0.0022 (10)	−0.0005 (11)	0.0083 (10)
N43	0.0357 (11)	0.0303 (11)	0.0329 (11)	0.0013 (9)	−0.0015 (9)	0.0046 (9)
C1	0.0314 (12)	0.0252 (13)	0.0288 (12)	0.0031 (9)	0.0005 (10)	−0.0021 (10)
C2	0.0448 (15)	0.0253 (13)	0.0340 (13)	−0.0003 (11)	−0.0014 (12)	0.0020 (10)
C11	0.0311 (12)	0.0297 (13)	0.0257 (12)	0.0035 (10)	−0.0004 (10)	−0.0023 (9)
C12	0.0330 (12)	0.0280 (13)	0.0291 (12)	0.0012 (10)	−0.0005 (10)	−0.0016 (10)
C13	0.0329 (13)	0.0393 (15)	0.0442 (15)	0.0039 (11)	−0.0076 (12)	0.0004 (12)
C14	0.0499 (16)	0.0489 (18)	0.0417 (15)	0.0084 (13)	−0.0115 (13)	0.0086 (13)
C15	0.0544 (17)	0.059 (2)	0.0401 (15)	−0.0002 (15)	0.0000 (14)	0.0203 (14)
C16	0.0357 (13)	0.0490 (17)	0.0365 (14)	0.0005 (12)	0.0024 (12)	0.0067 (12)
C21	0.0588 (17)	0.0281 (14)	0.0379 (15)	−0.0007 (12)	−0.0111 (14)	0.0032 (11)
C22	0.067 (2)	0.051 (2)	0.073 (2)	−0.0118 (16)	−0.030 (2)	0.0125 (17)
C23	0.105 (3)	0.084 (3)	0.094 (3)	−0.021 (3)	−0.065 (3)	0.027 (3)
C24	0.177 (5)	0.070 (3)	0.056 (2)	−0.027 (3)	−0.060 (3)	0.010 (2)
C25	0.161 (4)	0.058 (2)	0.0344 (17)	0.007 (2)	−0.002 (2)	0.0002 (16)
C26	0.097 (2)	0.0452 (18)	0.0348 (16)	0.0126 (17)	−0.0038 (17)	0.0020 (13)
C32	0.0443 (15)	0.0410 (16)	0.0382 (14)	−0.0043 (11)	0.0001 (13)	0.0016 (12)
C34	0.0410 (15)	0.0444 (17)	0.0465 (16)	0.0061 (12)	0.0044 (13)	0.0023 (13)
C35	0.0546 (18)	0.065 (2)	0.0453 (17)	0.0084 (15)	0.0111 (14)	0.0032 (15)
C36	0.0583 (18)	0.062 (2)	0.0523 (19)	0.0097 (16)	0.0025 (15)	−0.0184 (16)
C37	0.0559 (18)	0.0405 (17)	0.0578 (19)	0.0031 (13)	−0.0034 (15)	−0.0124 (14)
C38	0.0360 (13)	0.0387 (16)	0.0441 (15)	−0.0026 (11)	−0.0023 (12)	−0.0032 (12)
C39	0.0298 (12)	0.0372 (15)	0.0379 (14)	0.0025 (10)	−0.0008 (11)	−0.0010 (11)
C42	0.0413 (15)	0.0426 (16)	0.0360 (14)	0.0005 (11)	0.0007 (12)	0.0061 (13)
C44	0.0481 (15)	0.0364 (16)	0.0397 (15)	−0.0011 (12)	0.0050 (12)	0.0047 (12)
C45	0.0580 (18)	0.056 (2)	0.0397 (16)	−0.0013 (14)	0.0107 (14)	0.0002 (13)
C46	0.0568 (18)	0.056 (2)	0.0476 (17)	0.0055 (15)	0.0065 (15)	−0.0138 (15)
C47	0.0499 (17)	0.0360 (16)	0.0613 (19)	0.0063 (13)	−0.0028 (15)	−0.0110 (14)
C48	0.0342 (13)	0.0328 (14)	0.0441 (15)	0.0026 (11)	−0.0042 (12)	0.0025 (11)
C49	0.0274 (12)	0.0322 (14)	0.0356 (13)	0.0017 (10)	−0.0041 (11)	0.0012 (10)

Geometric parameters (Å, º)

Cu—O1	2.0061 (15)	C15—H15	0.9300
Cu—O2	2.6092 (16)	C16—H16	0.9300
Cu—O3^i	2.6834 (17)	C21—C26	1.383 (4)
Cu—O4	1.9629 (16)	C21—C22	1.399 (4)
Cu—N33	1.996 (2)	C22—C23	1.393 (5)
Cu—N43	1.985 (2)	C23—C24	1.353 (7)
O1—C1	1.263 (3)	C23—H23	0.9300
O2—C1	1.261 (3)	C24—C25	1.366 (6)
O3—C12	1.357 (3)	C24—H24	0.9300
O3—H3	0.9103	C25—C26	1.383 (4)
O4—C2	1.263 (3)	C25—H25	0.9300
O5—C2	1.243 (3)	C26—H26	0.9300
O6—C22	1.340 (4)	C32—H32	0.9300
O6—H6	0.9126	C34—C35	1.379 (4)
N31—C32	1.332 (3)	C34—C39	1.395 (4)
N31—C38	1.380 (3)	C34—H34	0.9300
N31—H31	0.8600	C35—C36	1.396 (4)
N33—C32	1.311 (3)	C35—H35	0.9300
N33—C39	1.399 (3)	C36—C37	1.369 (4)
N41—C42	1.336 (3)	C36—H36	0.9300
N41—C48	1.382 (3)	C37—C38	1.389 (4)
N41—H41	0.8600	C37—H37	0.9300
N43—C42	1.312 (3)	C38—C39	1.389 (4)
N43—C49	1.399 (3)	C42—H42	0.9300
C1—C11	1.490 (3)	C44—C45	1.375 (4)
C2—C21	1.493 (3)	C44—C49	1.391 (3)
C11—C16	1.389 (3)	C44—H44	0.9300
C11—C12	1.403 (3)	C45—C46	1.390 (4)
C12—C13	1.391 (3)	C45—H45	0.9300
C13—C14	1.373 (4)	C46—C47	1.367 (4)
C13—H13	0.9300	C46—H46	0.9300
C14—C15	1.379 (4)	C47—C48	1.387 (4)
C14—H14	0.9300	C47—H47	0.9300
C15—C16	1.372 (4)	C48—C49	1.396 (3)
O4—Cu—N43	90.94 (8)	C22—C21—C2	120.6 (3)
O4—Cu—N33	89.60 (8)	O6—C22—C23	118.2 (4)
N43—Cu—N33	179.44 (8)	O6—C22—C21	122.8 (3)
O4—Cu—O1	170.28 (7)	C23—C22—C21	119.0 (4)
N43—Cu—O1	91.74 (7)	C24—C23—C22	120.7 (4)
N33—Cu—O1	87.70 (8)	C24—C23—H23	119.6
O2—Cu—O1	55.52 (6)	C22—C23—H23	119.6
O2—Cu—O3^i	140.50 (5)	C23—C24—C25	121.3 (4)
O2—Cu—O4	114.98 (7)	C23—C24—H24	119.4
O2—Cu—N31	87.04 (5)	C25—C24—H24	119.4
O2—Cu—N41	93.20 (5)	C24—C25—C26	119.0 (4)
O3^i—Cu—O1	85.15 (6)	C24—C25—H25	120.5
O3^i—Cu—O4	104.15 (6)	C26—C25—H25	120.5
O3^i—Cu—N31	81.06 (5)	C21—C26—C25	121.4 (4)
O3^i—Cu—N41	98.53 (5)	C21—C26—H26	119.3
C1—O1—Cu	104.68 (14)	C25—C26—H26	119.3
C2—O4—Cu	120.94 (16)	N33—C32—N31	113.2 (2)
Cu^ii—O3—C12	143.93 (14)	N33—C32—H32	123.4
C12—O3—H3	105.3	N31—C32—H32	123.4
C22—O6—H6	102.7	C35—C34—C39	116.6 (3)
C32—N31—C38	107.5 (2)	C35—C34—H34	121.7
C32—N31—H31	126.2	C39—C34—H34	121.7
C38—N31—H31	126.2	C34—C35—C36	122.1 (3)
C32—N33—C39	105.1 (2)	C34—C35—H35	119.0
C32—N33—Cu	124.09 (18)	C36—C35—H35	119.0
C39—N33—Cu	130.72 (17)	C37—C36—C35	121.8 (3)
C42—N41—C48	107.8 (2)	C37—C36—H36	119.1
C42—N41—H41	126.1	C35—C36—H36	119.1
C48—N41—H41	126.1	C36—C37—C38	116.2 (3)
C42—N43—C49	105.5 (2)	C36—C37—H37	121.9
C42—N43—Cu	123.90 (18)	C38—C37—H37	121.9
C49—N43—Cu	130.55 (16)	N31—C38—C39	105.4 (2)
O2—C1—O1	122.7 (2)	N31—C38—C37	131.8 (3)
O2—C1—C11	118.3 (2)	C39—C38—C37	122.8 (3)
O1—C1—C11	119.0 (2)	C38—C39—C34	120.5 (2)
O5—C2—O4	124.4 (2)	C38—C39—N33	108.8 (2)
O5—C2—C21	118.4 (2)	C34—C39—N33	130.7 (2)
O4—C2—C21	117.2 (2)	N43—C42—N41	112.8 (2)
C16—C11—C12	118.5 (2)	N43—C42—H42	123.6
C16—C11—C1	120.6 (2)	N41—C42—H42	123.6
C12—C11—C1	120.8 (2)	C45—C44—C49	117.2 (3)
O3—C12—C13	117.4 (2)	C45—C44—H44	121.4
O3—C12—C11	122.8 (2)	C49—C44—H44	121.4
C13—C12—C11	119.9 (2)	C44—C45—C46	122.2 (3)
C14—C13—C12	119.9 (2)	C44—C45—H45	118.9
C14—C13—H13	120.0	C46—C45—H45	118.9
C12—C13—H13	120.0	C47—C46—C45	121.3 (3)
C13—C14—C15	120.7 (2)	C47—C46—H46	119.3
C13—C14—H14	119.6	C45—C46—H46	119.3
C15—C14—H14	119.6	C46—C47—C48	116.9 (3)
C16—C15—C14	119.7 (3)	C46—C47—H47	121.6
C16—C15—H15	120.1	C48—C47—H47	121.6
C14—C15—H15	120.1	N41—C48—C47	132.3 (3)
C15—C16—C11	121.2 (2)	N41—C48—C49	105.3 (2)
C15—C16—H16	119.4	C47—C48—C49	122.4 (3)
C11—C16—H16	119.4	C44—C49—C48	120.0 (2)
C26—C21—C22	118.6 (3)	C44—C49—N43	131.4 (2)
C26—C21—C2	120.8 (3)	C48—C49—N43	108.6 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.91	1.77	2.596 (2)	149
O3—H3···O5^ii	0.91	2.27	2.856 (3)	122
O6—H6···O5	0.91	1.71	2.558 (3)	153
N31—H31···O5^iii	0.86	2.07	2.840 (3)	149
N41—H41···O2^iv	0.86	2.18	3.026 (3)	167
C34—H34···O4	0.93	2.50	3.064 (3)	119

Symmetry codes: (ii) x+1, y, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+3/2, y+1/2, −z+1/2.