Chloro(L-glutamato-[kappa]²N,O)(1,10-phenanthroline-[kappa]²N,N')copper(II) monohydrate

The crystal structure of the title compound, [CuCl(C₅H₈­NO₄)(C₁₂H₈N₂)]·H₂O or [CuCl(L-Glu)(phen)]·H₂O (where phen is 1,10-phenanthroline and L-Glu is L-glutamate), shows that the ternary complex consists of two neutral mol­ecules, in which the Cu^II ions each have a distorted square-pyramidal coordination geometry comprised of one bidentate phenanthroline ligand, one O,N-bidentate L-glutamate anion and an apical Cl^- anion. The angles between the planes of the Cu-phenanthroline and the Cu-amino­carboxyl­ate chelate rings are 6.1 (5) and 11.8 (5)° in the two mol­ecules. The Cu-Cl bond lengths are 2.608 (3) and 2.590 (3) Å in the two mol­ecules, slightly longer than the value of 2.546 Å observed for the Cu-Cl bond in the analogous chloro(L-glycin­ato)(1,10-phenanthroline)copper complex [Solans, Ruiz-Ramírez, Martinez, Gasque & Briansó (1983). Acta Cryst. C44, 628-631]. Additionally, the Cu ion is weakly coordinated at a sixth position by an [alpha]-carboxyl O atom from a neighbouring complex. A number of intra- and intermolecular hydrogen bonds stabilize the crystal structure.

S1. Comment

In recent years, ternary copper(II) complexes have attracted significant attention due to their range of properties, which include interactions with DNA (Chikira et al., 2002), anticonvulsant activity (Viossat et al., 2003), nuclease activity (Garcýa-Raso et al., 2003), and interactions of copper(II) with nucleotides and nucleosides (Gasowska, 2003; Lomozik & Jastrzáb, 2003). A variety of ternary complexes involving copper, 1,10-phenanthroline (phen) and α-amino acids have been described (Anitolini et al., 1983, 1985; Moreno-Esparza et al., 1995; Solans et al., 1988; Venkatraman et al., 1999). Here, we report the crystal structure of the title novel copper, phenanthroline and α-amino acid ternary complex, (I). \sch

Some features of the molecular geometry of (I) are listed in Table 1. The molecular conformation and crystal packing are illustrated in Figs. 1 and 2, respectively. In this ternary complex, there are two neutral molecules in the asymmetric unit. The Cu ions in each complex have distorted square-pyramidal coordination geometry, with one bidentate phenanthroline ligand, one O,N-bidentate L-glutamic acid monovalent anion (with protonated γ-carboxylate) and an apical Cl⁻ anion, in contrast with the structure of [Cu(phen)(L-glu)(H₂O)] (Anitolini et al., 1985), in which the Cu ions also have distorted square-pyramidal coordination geometry with a bidentate phenanthroline ligand, but an O,N-bidentate L-glutamic acid divalent anion (with ionized γ-carboxyl) and an apical coordinating water O atom.

The four equatorial donor atoms in (I) (N1, N2, N3 and O1, or N4, N5, N6 and O5) are nearly coplanar, with respective r.m.s. deviations of 0.0347 and 0.0526 Å in the two independent molecules, and the displacements of the Cu atoms toward the apical Cl⁻ ligand are 0.191 (5) and 0.151 (5) Å, respectively. The angles between the planes of the Cu-phenanthroline (atoms C1—C12/N1/N2/Cu1 or C18–29/N4/N5/Cu2) and the aminocarboxylate chelation ring (atoms C13/C14/Cu1/O1/N3 or C30/C31/Cu2/O5/N6) are 6.1 (5) and 11.8 (5)°, respectively, i.e. somewhat different in the two molecules. This variability in the angles between planes defined by chelation rings is also observed in ternary copper complexes with phenanthroline and other amino acids (Anitolini et al. 1985; Moreno-Esparza et al., 1995).

The Cu coordination distances are listed in Table 1. The Cu—N coordination bond lengths to the phenanthroline ligand are in the range 1.986 (11)–2.057 (9) Å; these and the other Cu coordination distances are typically observed in many other related structures (Anitolini et al., 1983, 1985; Moreno-Esparza et al., 1995; Solans et al., 1988; Venkatraman et al., 1999). The Cu—Cl bond lengths are 2.608 (3) and 2.590 (3) Å in the two molecules, slightly longer than the value of 2.546 Å observed for the Cu—Cl bond in the analogous chloro(glycinato)(1,10-phenanthroline)copper complex (Solans et al., 1988), but similar to that (2.602 Å) observed in the complex [Cu₂(phen)₂(OH)₂(H₂O)₂][Cu₂(phen)₂(OH)₂Cl₂]Cl₂·6H₂O (Lu et al., 2003). In addition, Fig.2 shows that the Cu ions are coordinated by the O atom of an α-carboxylate group from a neighbouring asymmetric unit, forming a weak sixth coordination ligand, with Cu2—O2ⁱ and Cu1—O6ⁱⁱ distances of 3.275 and 3.215 Å, respectively [symmetry codes: (i) x, y − 1, z; x, y + 1, z]. Therefore, the overall coordination geometry is actually octahedral. This octahedral coordination geometry is also found in a similar L-proline ternary complex (Venkatraman et al., 1999), in which the weak sixth coordinating α-carboxyl O atom is from another ternary complex in same asymmetric unit.

The hydrogen-bonding geometry in (I) is listed in Table 2. As illustrated in Figs. 1 and 2 and Table 2, a number of intra- and intermolecular hydrogen bonds stabilize the crystal structure of (I). These hydrogen bonds are formed mainly between water molecules and α-amino N atoms, α-carboxyl and γ-carboxyl O atoms, and O atoms and the coordinating Cl⁻ anions. Hydrogen bonds also exist between α-amino N atoms and the Cl⁻ ligands. It is worthy of mention that atom H10B is involved in an intermolecular three-centred hydrogen bond with atoms O1 and O2. Furthermore, the weak coordination by the sixth ligand also contributes to the intermolecular interactions observed in the crystal packing. The Cl⁻ and carboxylate ligands together contribute to the extension of the intermolecular packing interactions throughout the crystal. Additionally, the complex molecules are arranged in such a way that symmetry-related phenanthroline planes of neighbouring complexes [the plane containing atoms C1—C12/N1/N2 and that containing atoms C18ⁱⁱⁱ—C31ⁱⁱⁱ/N4ⁱⁱⁱ/N5ⁱⁱⁱ; symmetry code: (iii) x, y + 1, z − 1] are orientated in parallel planes with phen-phen separations of about 3.42 Å, indicating siginificant π–π stacking interactions.

S2. Experimental

All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. CuCl₂·2H₂O (1.705 g, 10.0 mmol) was dissolved in water (80 ml), and 1,10-phenanthroline (1.98 g, 10 mmol) was dissolved in water (20 ml) with a few drops of HCl. L-glutamic acid (1,47 g, 10.0 mmol) was then added to the copper(II) chloride solution with stirring at 333 K until all the L-glutamic acid had dissolved. The two solutions were then mixed, the pH adjusted to 3 with HCl and the solution stirred at room temperature for 2 h. The blue solution was filtered and the filtrate left at 277 K. Blue crystals of (I) appeared from the solution after several weeks, by slow evaporation of the aqueous solvent. Elemental analysis, calculated for C₁₇H₁₆ClCuN₃O₄·H₂O: C 46.06, H 4.09, N 9.48%; found: C 45.98, H 4.17, N 9.35%.

S3. Refinement

H atoms attached to C and N atoms were placed in geometrically idealized positions, with Csp³—H = 0.99, Csp²—H = 0.95, α-Csp³—H = 1.000 and Nsp³—H = 0.92 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C,N). H atoms attached to O atoms (L-glutamic acid and solvent water) were located from difference Fourier maps and their global U_iso value was refined. The O—H distances are in the range 0.81 (5)–0.90 (5) Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The hydrogen-bonding network and octahedral coordination geometry of (I). Atoms labelled with the suffices A, B, C or E are at the symmetry positions (x, y − 1, z), (x, y + 1, z), (x + 1, y − 1, z) and (x + 1, y, z), respectively.

Chloro(L-glutamato-κ²N,O)(1,10-phenanthroline-κ²N,N')copper(II) monohydrate

Crystal data

[CuCl(C5H8NO4)(C12H8N2)]·H2O	Z = 2
Mr = 443.33	F(000) = 454
Triclinic, P1	Dx = 1.693 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3022 (14) Å	Cell parameters from 3499 reflections
b = 10.0591 (17) Å	θ = 2.3–27.2°
c = 12.393 (2) Å	µ = 1.45 mm^−1
α = 66.730 (2)°	T = 183 K
β = 72.047 (2)°	Block, blue
γ = 68.828 (2)°	0.55 × 0.40 × 0.40 mm
V = 869.9 (3) Å^3

Data collection

Bruker SMART 1K CCD area-detector diffractometer	3578 independent reflections
Radiation source: fine-focus sealed tube	3455 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −9→9
Tmin = 0.474, Tmax = 0.561	k = −11→8
4229 measured reflections	l = −14→14

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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 2.5194P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3578 reflections	Δρmax = 0.52 e Å^−3
506 parameters	Δρmin = −0.75 e Å^−3
9 restraints	Absolute structure: Flack (1983), with x Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (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
Cu1	0.27011 (10)	0.95620 (8)	0.66301 (7)	0.0258 (3)
Cu2	0.48343 (10)	0.28453 (9)	0.85224 (7)	0.0257 (3)
Cl1	0.6759 (3)	0.4730 (3)	0.7447 (2)	0.0296 (6)
Cl2	0.0761 (3)	0.7714 (3)	0.7697 (2)	0.0293 (6)
N1	0.1037 (13)	1.1118 (11)	0.5554 (9)	0.023 (2)
N2	0.3848 (12)	0.8895 (12)	0.5133 (8)	0.024 (2)
N3	0.4529 (14)	0.8288 (11)	0.7609 (10)	0.028 (2)
H3A	0.4804	0.7302	0.7644	0.033*
H3B	0.5535	0.8606	0.7278	0.033*
N4	0.3802 (12)	0.3553 (10)	0.9945 (9)	0.026 (2)
N5	0.6526 (14)	0.1349 (12)	0.9559 (9)	0.026 (2)
N6	0.3012 (13)	0.4185 (12)	0.7519 (8)	0.027 (2)
H6A	0.1911	0.4278	0.8001	0.033*
H6B	0.3191	0.5127	0.7155	0.033*
C1	−0.0297 (17)	1.2233 (15)	0.5803 (12)	0.033 (3)
H1	−0.0535	1.2378	0.6556	0.040*
C2	−0.1355 (14)	1.3200 (14)	0.4962 (11)	0.031 (3)
H2	−0.2301	1.4006	0.5146	0.038*
C3	−0.1052 (16)	1.3005 (15)	0.3875 (11)	0.032 (3)
H3	−0.1786	1.3661	0.3311	0.038*
C4	0.0328 (17)	1.1846 (14)	0.3617 (11)	0.028 (3)
C5	0.1366 (15)	1.0922 (13)	0.4512 (11)	0.025 (2)
C6	0.2869 (17)	0.9733 (14)	0.4251 (10)	0.028 (2)
C7	0.0847 (16)	1.1484 (14)	0.2519 (11)	0.029 (2)
H7	0.0168	1.2080	0.1913	0.035*
C8	0.2252 (17)	1.0338 (15)	0.2308 (11)	0.035 (3)
H8	0.2529	1.0146	0.1571	0.042*
C9	0.3331 (16)	0.9406 (14)	0.3199 (11)	0.031 (3)
C10	0.4810 (19)	0.8257 (16)	0.3017 (12)	0.039 (3)
H10	0.5141	0.8013	0.2298	0.047*
C11	0.5796 (17)	0.7469 (15)	0.3902 (12)	0.035 (3)
H11	0.6822	0.6677	0.3794	0.042*
C12	0.5287 (16)	0.7836 (14)	0.4958 (12)	0.033 (3)
H12	0.5992	0.7312	0.5555	0.040*
C13	0.2543 (13)	1.0017 (12)	0.8710 (10)	0.023 (2)
C14	0.3798 (11)	0.8427 (9)	0.8834 (7)	0.0235 (17)
H14	0.3037	0.7723	0.9253	0.028*
C15	0.5145 (15)	0.7928 (13)	0.9585 (11)	0.035 (3)
H15A	0.5840	0.8669	0.9249	0.042*
H15B	0.4519	0.7960	1.0400	0.042*
C16	0.6398 (15)	0.6399 (14)	0.9697 (10)	0.026 (2)
H16A	0.5743	0.5709	0.9769	0.031*
H16B	0.7297	0.6455	0.8950	0.031*
C17	0.7274 (16)	0.5769 (14)	1.0683 (12)	0.040 (3)
C18	0.2381 (15)	0.4686 (13)	1.0153 (11)	0.029 (2)
H18	0.1683	0.5260	0.9556	0.035*
C19	0.1901 (17)	0.5046 (14)	1.1201 (12)	0.035 (3)
H19	0.0876	0.5841	1.1306	0.042*
C20	0.2856 (18)	0.4294 (14)	1.2072 (12)	0.035 (3)
H20	0.2523	0.4566	1.2778	0.042*
C21	0.4366 (16)	0.3090 (15)	1.1919 (11)	0.029 (3)
C22	0.4730 (15)	0.2814 (13)	1.0815 (11)	0.024 (2)
C23	0.6195 (17)	0.1588 (14)	1.0654 (10)	0.025 (2)
C24	0.5470 (16)	0.2163 (15)	1.2781 (11)	0.032 (3)
H24	0.5197	0.2359	1.3516	0.039*
C25	0.689 (2)	0.1018 (17)	1.2592 (13)	0.041 (3)
H25	0.7617	0.0441	1.3169	0.049*
C26	0.7254 (15)	0.0699 (13)	1.1502 (11)	0.027 (2)
C27	0.8694 (15)	−0.0539 (14)	1.1234 (12)	0.031 (3)
H27	0.9439	−0.1189	1.1792	0.038*
C28	0.8962 (16)	−0.0756 (14)	1.0166 (11)	0.031 (3)
H28	0.9894	−0.1568	0.9978	0.038*
C29	0.7874 (15)	0.0207 (13)	0.9358 (11)	0.026 (2)
H29	0.8108	0.0040	0.8615	0.031*
C30	0.4791 (16)	0.2286 (13)	0.6536 (10)	0.027 (3)
C31	0.3098 (11)	0.3566 (9)	0.6597 (8)	0.0259 (18)
H31	0.2100	0.3099	0.6888	0.031*
C32	0.2859 (15)	0.4708 (13)	0.5397 (11)	0.034 (2)
H32A	0.2881	0.4205	0.4848	0.041*
H32B	0.3845	0.5178	0.5059	0.041*
C33	0.1101 (18)	0.5936 (14)	0.5495 (12)	0.035 (3)
H33A	0.0155	0.5447	0.5992	0.042*
H33B	0.1184	0.6565	0.5910	0.042*
C34	0.0593 (17)	0.6951 (12)	0.4290 (11)	0.037 (3)
O1	0.1805 (10)	1.0619 (9)	0.7796 (7)	0.0263 (18)
O2	0.2261 (12)	1.0633 (10)	0.9466 (8)	0.035 (2)
O3	0.7081 (11)	0.6263 (9)	1.1466 (8)	0.060 (3)
O4	0.8524 (13)	0.4391 (10)	1.0784 (9)	0.044 (2)
H4A	0.867 (12)	0.438 (10)	1.011 (5)	0.020 (8)*
O5	0.5650 (11)	0.1780 (9)	0.7368 (7)	0.0275 (18)
O6	0.5196 (12)	0.1761 (10)	0.5703 (7)	0.035 (2)
O7	0.1283 (12)	0.6655 (8)	0.3374 (7)	0.056 (2)
O8	−0.0643 (12)	0.8215 (11)	0.4284 (9)	0.044 (2)
H8A	−0.076 (11)	0.846 (9)	0.488 (6)	0.020 (8)*
O9	0.7884 (11)	0.9109 (10)	0.6139 (9)	0.034 (2)
H9A	0.861 (10)	0.897 (9)	0.661 (7)	0.020 (8)*
H9B	0.763 (11)	1.004 (6)	0.569 (6)	0.020 (8)*
O10	0.9680 (12)	0.3349 (11)	0.8998 (9)	0.038 (2)
H10A	0.922 (11)	0.377 (9)	0.840 (6)	0.020 (8)*
H10B	1.051 (9)	0.250 (7)	0.896 (7)	0.020 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0257 (7)	0.0265 (8)	0.0245 (7)	−0.0012 (6)	−0.0083 (6)	−0.0103 (6)
Cu2	0.0260 (7)	0.0268 (7)	0.0220 (7)	0.0010 (6)	−0.0090 (5)	−0.0098 (6)
Cl1	0.0300 (14)	0.0275 (15)	0.0300 (15)	−0.0051 (12)	−0.0061 (12)	−0.0102 (12)
Cl2	0.0325 (14)	0.0244 (14)	0.0314 (15)	−0.0058 (11)	−0.0103 (12)	−0.0083 (12)
N1	0.025 (5)	0.019 (5)	0.022 (5)	−0.005 (4)	−0.009 (4)	−0.001 (4)
N2	0.022 (4)	0.037 (5)	0.018 (4)	−0.008 (4)	0.000 (3)	−0.015 (4)
N3	0.032 (5)	0.021 (5)	0.042 (6)	−0.005 (4)	−0.014 (4)	−0.018 (4)
N4	0.020 (4)	0.017 (4)	0.032 (5)	0.004 (3)	−0.013 (4)	−0.002 (4)
N5	0.026 (5)	0.034 (6)	0.018 (5)	−0.006 (4)	−0.003 (4)	−0.013 (4)
N6	0.027 (5)	0.030 (5)	0.013 (5)	0.002 (4)	−0.008 (4)	−0.002 (4)
C1	0.033 (7)	0.037 (7)	0.026 (7)	−0.009 (6)	−0.002 (5)	−0.011 (6)
C2	0.018 (5)	0.034 (7)	0.033 (7)	0.003 (5)	−0.007 (5)	−0.009 (5)
C3	0.028 (6)	0.040 (7)	0.021 (6)	−0.007 (5)	−0.014 (5)	0.002 (5)
C4	0.033 (6)	0.029 (6)	0.025 (6)	−0.016 (5)	−0.012 (5)	−0.001 (5)
C5	0.019 (5)	0.019 (5)	0.031 (6)	0.000 (4)	−0.007 (4)	−0.005 (4)
C6	0.035 (6)	0.030 (5)	0.016 (5)	−0.006 (4)	−0.011 (4)	−0.001 (4)
C7	0.028 (5)	0.035 (6)	0.023 (5)	−0.003 (4)	−0.016 (4)	−0.005 (4)
C8	0.044 (7)	0.042 (7)	0.016 (5)	−0.008 (5)	−0.013 (5)	−0.006 (5)
C9	0.030 (5)	0.027 (6)	0.031 (6)	0.000 (4)	−0.010 (5)	−0.008 (4)
C10	0.051 (7)	0.044 (7)	0.020 (6)	−0.013 (6)	−0.003 (5)	−0.012 (5)
C11	0.033 (6)	0.030 (6)	0.032 (7)	0.001 (5)	−0.002 (5)	−0.010 (5)
C12	0.036 (6)	0.029 (6)	0.038 (7)	−0.003 (5)	−0.017 (5)	−0.011 (5)
C13	0.016 (5)	0.022 (5)	0.028 (6)	0.000 (4)	0.001 (4)	−0.014 (4)
C14	0.026 (4)	0.028 (5)	0.020 (4)	−0.003 (3)	−0.010 (3)	−0.011 (3)
C15	0.039 (6)	0.035 (5)	0.034 (6)	0.003 (4)	−0.021 (5)	−0.014 (5)
C16	0.023 (6)	0.031 (6)	0.026 (6)	0.004 (5)	−0.010 (5)	−0.017 (5)
C17	0.035 (5)	0.042 (7)	0.044 (7)	0.000 (5)	−0.002 (5)	−0.029 (5)
C18	0.023 (5)	0.029 (6)	0.025 (6)	−0.003 (4)	−0.002 (4)	−0.005 (4)
C19	0.041 (6)	0.025 (6)	0.036 (7)	0.002 (5)	−0.011 (5)	−0.013 (5)
C20	0.043 (7)	0.026 (6)	0.027 (6)	−0.001 (5)	−0.005 (5)	−0.008 (5)
C21	0.030 (5)	0.041 (7)	0.025 (6)	−0.016 (5)	0.003 (4)	−0.020 (5)
C22	0.019 (5)	0.029 (5)	0.026 (6)	−0.006 (4)	−0.002 (4)	−0.012 (4)
C23	0.036 (6)	0.033 (6)	0.010 (5)	−0.014 (5)	−0.007 (4)	−0.004 (4)
C24	0.036 (6)	0.040 (7)	0.032 (6)	−0.010 (5)	−0.010 (5)	−0.020 (5)
C25	0.043 (7)	0.044 (7)	0.039 (7)	−0.012 (6)	−0.019 (5)	−0.008 (5)
C26	0.020 (5)	0.023 (5)	0.033 (6)	0.001 (4)	−0.006 (4)	−0.009 (4)
C27	0.019 (5)	0.027 (6)	0.039 (7)	0.002 (4)	−0.009 (5)	−0.005 (5)
C28	0.029 (6)	0.024 (6)	0.037 (7)	−0.008 (5)	0.002 (5)	−0.011 (5)
C29	0.027 (6)	0.022 (6)	0.028 (6)	−0.008 (5)	−0.005 (5)	−0.007 (5)
C30	0.034 (6)	0.027 (6)	0.019 (5)	−0.010 (5)	−0.009 (4)	−0.001 (4)
C31	0.024 (4)	0.022 (4)	0.035 (5)	−0.002 (3)	−0.010 (4)	−0.014 (4)
C32	0.031 (5)	0.034 (5)	0.028 (5)	0.003 (4)	−0.009 (4)	−0.010 (4)
C33	0.041 (7)	0.027 (7)	0.032 (7)	0.002 (5)	−0.016 (6)	−0.009 (5)
C34	0.057 (7)	0.024 (5)	0.030 (6)	0.005 (4)	−0.028 (5)	−0.008 (4)
O1	0.023 (4)	0.029 (4)	0.029 (5)	−0.003 (3)	−0.005 (3)	−0.015 (4)
O2	0.037 (5)	0.029 (5)	0.043 (6)	0.005 (4)	−0.020 (4)	−0.017 (4)
O3	0.070 (6)	0.056 (5)	0.052 (5)	0.023 (4)	−0.039 (4)	−0.031 (4)
O4	0.049 (5)	0.039 (5)	0.035 (4)	0.014 (3)	−0.024 (4)	−0.014 (3)
O5	0.033 (4)	0.023 (4)	0.024 (5)	0.002 (3)	−0.019 (4)	−0.004 (3)
O6	0.036 (5)	0.041 (5)	0.020 (5)	0.009 (4)	−0.008 (4)	−0.017 (4)
O7	0.076 (6)	0.043 (4)	0.031 (4)	0.023 (4)	−0.024 (4)	−0.017 (3)
O8	0.051 (5)	0.040 (4)	0.034 (5)	0.016 (4)	−0.025 (4)	−0.017 (4)
O9	0.028 (4)	0.031 (5)	0.044 (6)	0.000 (4)	−0.009 (4)	−0.019 (4)
O10	0.033 (5)	0.037 (5)	0.039 (5)	0.007 (4)	−0.016 (4)	−0.015 (4)

Geometric parameters (Å, º)

Cu1—O1	1.937 (8)	C14—H14	1.0000
Cu1—N3	1.979 (11)	C15—C16	1.494 (16)
Cu1—N1	2.016 (10)	C15—H15A	0.9900
Cu1—N2	2.057 (9)	C15—H15B	0.9900
Cu1—Cl2	2.590 (3)	C16—C17	1.423 (17)
Cu2—O5	1.934 (8)	C16—H16A	0.9900
Cu2—N5	1.986 (11)	C16—H16B	0.9900
Cu2—N4	1.993 (10)	C17—O3	1.202 (14)
Cu2—N6	2.004 (10)	C17—O4	1.385 (15)
Cu2—Cl1	2.608 (3)	C18—C19	1.387 (17)
N1—C5	1.313 (15)	C18—H18	0.9500
N1—C1	1.321 (17)	C19—C20	1.348 (18)
N2—C12	1.308 (17)	C19—H19	0.9500
N2—C6	1.374 (16)	C20—C21	1.418 (18)
N3—C14	1.495 (12)	C20—H20	0.9500
N3—H3A	0.9200	C21—C22	1.424 (16)
N3—H3B	0.9200	C21—C24	1.432 (18)
N4—C22	1.331 (15)	C22—C23	1.415 (17)
N4—C18	1.353 (16)	C23—C26	1.392 (18)
N5—C29	1.327 (16)	C24—C25	1.35 (2)
N5—C23	1.398 (14)	C24—H24	0.9500
N6—C31	1.475 (12)	C25—C26	1.427 (18)
N6—H6A	0.9200	C25—H25	0.9500
N6—H6B	0.9200	C26—C27	1.448 (16)
C1—C2	1.397 (18)	C27—C28	1.363 (17)
C1—H1	0.9500	C27—H27	0.9500
C2—C3	1.372 (17)	C28—C29	1.384 (18)
C2—H2	0.9500	C28—H28	0.9500
C3—C4	1.371 (19)	C29—H29	0.9500
C3—H3	0.9500	C30—O6	1.243 (14)
C4—C5	1.426 (17)	C30—O5	1.269 (13)
C4—C7	1.444 (17)	C30—C31	1.531 (15)
C5—C6	1.439 (17)	C31—C32	1.496 (15)
C6—C9	1.377 (17)	C31—H31	1.0000
C7—C8	1.355 (18)	C32—C33	1.542 (17)
C7—H7	0.9500	C32—H32A	0.9900
C8—C9	1.444 (17)	C32—H32B	0.9900
C8—H8	0.9500	C33—C34	1.524 (16)
C9—C10	1.380 (19)	C33—H33A	0.9900
C10—C11	1.378 (19)	C33—H33B	0.9900
C10—H10	0.9500	C34—O7	1.204 (14)
C11—C12	1.399 (17)	C34—O8	1.313 (14)
C11—H11	0.9500	O4—H4A	0.81 (5)
C12—H12	0.9500	O8—H8A	0.84 (4)
C13—O2	1.239 (13)	O9—H9A	0.90 (5)
C13—O1	1.281 (13)	O9—H9B	0.87 (5)
C13—C14	1.539 (13)	O10—H10A	0.83 (5)
C14—C15	1.495 (13)	O10—H10B	0.89 (5)
O1—Cu1—N3	84.6 (4)	C15—C14—C13	116.0 (8)
O1—Cu1—N1	92.4 (4)	N3—C14—H14	105.8
N3—Cu1—N1	170.8 (4)	C15—C14—H14	105.8
O1—Cu1—N2	166.2 (4)	C13—C14—H14	105.8
N3—Cu1—N2	99.2 (4)	C16—C15—C14	116.8 (9)
N1—Cu1—N2	81.8 (4)	C16—C15—H15A	108.1
O1—Cu1—Cl2	95.9 (3)	C14—C15—H15A	108.1
N3—Cu1—Cl2	93.1 (3)	C16—C15—H15B	108.1
N1—Cu1—Cl2	95.9 (3)	C14—C15—H15B	108.1
N2—Cu1—Cl2	97.2 (3)	H15A—C15—H15B	107.3
O5—Cu2—N5	93.4 (3)	C17—C16—C15	115.2 (9)
O5—Cu2—N4	167.4 (4)	C17—C16—H16A	108.5
N5—Cu2—N4	81.9 (4)	C15—C16—H16A	108.5
O5—Cu2—N6	84.1 (4)	C17—C16—H16B	108.5
N5—Cu2—N6	174.1 (4)	C15—C16—H16B	108.5
N4—Cu2—N6	99.3 (4)	H16A—C16—H16B	107.5
O5—Cu2—Cl1	97.8 (3)	O3—C17—O4	113.7 (12)
N5—Cu2—Cl1	94.6 (3)	O3—C17—C16	129.0 (11)
N4—Cu2—Cl1	94.2 (3)	O4—C17—C16	117.3 (10)
N6—Cu2—Cl1	91.0 (3)	N4—C18—C19	122.8 (11)
C5—N1—C1	119.8 (11)	N4—C18—H18	118.6
C5—N1—Cu1	113.0 (8)	C19—C18—H18	118.6
C1—N1—Cu1	127.2 (9)	C20—C19—C18	121.4 (12)
C12—N2—C6	120.7 (10)	C20—C19—H19	119.3
C12—N2—Cu1	128.8 (9)	C18—C19—H19	119.3
C6—N2—Cu1	110.5 (8)	C19—C20—C21	119.0 (11)
C14—N3—Cu1	107.3 (6)	C19—C20—H20	120.5
C14—N3—H3A	110.3	C21—C20—H20	120.5
Cu1—N3—H3A	110.2	C20—C21—C22	114.8 (12)
C14—N3—H3B	110.3	C20—C21—C24	125.2 (10)
Cu1—N3—H3B	110.3	C22—C21—C24	120.0 (11)
H3A—N3—H3B	108.5	N4—C22—C23	117.2 (10)
C22—N4—C18	115.1 (10)	N4—C22—C21	126.8 (11)
C22—N4—Cu2	113.5 (8)	C23—C22—C21	116.0 (11)
C18—N4—Cu2	131.3 (9)	C26—C23—N5	122.1 (12)
C29—N5—C23	117.6 (11)	C26—C23—C22	123.2 (10)
C29—N5—Cu2	129.9 (9)	N5—C23—C22	114.7 (11)
C23—N5—Cu2	112.5 (9)	C25—C24—C21	122.7 (11)
C31—N6—Cu2	110.8 (7)	C25—C24—H24	118.7
C31—N6—H6A	109.5	C21—C24—H24	118.7
Cu2—N6—H6A	109.5	C24—C25—C26	118.3 (13)
C31—N6—H6B	109.5	C24—C25—H25	120.8
Cu2—N6—H6B	109.5	C26—C25—H25	120.8
H6A—N6—H6B	108.1	C23—C26—C25	119.8 (12)
N1—C1—C2	120.1 (12)	C23—C26—C27	117.5 (11)
N1—C1—H1	119.9	C25—C26—C27	122.7 (12)
C2—C1—H1	119.9	C28—C27—C26	118.9 (12)
C3—C2—C1	121.1 (12)	C28—C27—H27	120.6
C3—C2—H2	119.4	C26—C27—H27	120.6
C1—C2—H2	119.4	C27—C28—C29	119.9 (11)
C4—C3—C2	118.8 (12)	C27—C28—H28	120.0
C4—C3—H3	120.6	C29—C28—H28	120.0
C2—C3—H3	120.6	N5—C29—C28	123.9 (11)
C3—C4—C5	116.8 (11)	N5—C29—H29	118.0
C3—C4—C7	126.3 (12)	C28—C29—H29	118.0
C5—C4—C7	116.9 (12)	O6—C30—O5	124.0 (11)
N1—C5—C4	123.4 (11)	O6—C30—C31	118.0 (10)
N1—C5—C6	118.4 (11)	O5—C30—C31	117.9 (9)
C4—C5—C6	118.2 (11)	N6—C31—C32	114.8 (8)
N2—C6—C9	120.3 (11)	N6—C31—C30	109.2 (8)
N2—C6—C5	116.0 (10)	C32—C31—C30	112.8 (8)
C9—C6—C5	123.7 (11)	N6—C31—H31	106.5
C8—C7—C4	123.4 (11)	C32—C31—H31	106.5
C8—C7—H7	118.3	C30—C31—H31	106.5
C4—C7—H7	118.3	C31—C32—C33	111.0 (9)
C7—C8—C9	120.3 (11)	C31—C32—H32A	109.4
C7—C8—H8	119.8	C33—C32—H32A	109.4
C9—C8—H8	119.8	C31—C32—H32B	109.4
C6—C9—C10	119.8 (12)	C33—C32—H32B	109.4
C6—C9—C8	117.4 (11)	H32A—C32—H32B	108.0
C10—C9—C8	122.8 (11)	C34—C33—C32	113.8 (11)
C11—C10—C9	118.5 (11)	C34—C33—H33A	108.8
C11—C10—H10	120.7	C32—C33—H33A	108.8
C9—C10—H10	120.7	C34—C33—H33B	108.8
C10—C11—C12	120.1 (12)	C32—C33—H33B	108.8
C10—C11—H11	120.0	H33A—C33—H33B	107.7
C12—C11—H11	120.0	O7—C34—O8	120.3 (10)
N2—C12—C11	120.6 (12)	O7—C34—C33	123.3 (11)
N2—C12—H12	119.7	O8—C34—C33	116.4 (11)
C11—C12—H12	119.7	C13—O1—Cu1	115.7 (7)
O2—C13—O1	123.6 (10)	C17—O4—H4A	99 (6)
O2—C13—C14	121.2 (10)	C30—O5—Cu2	116.6 (8)
O1—C13—C14	115.2 (8)	C34—O8—H8A	112 (6)
N3—C14—C15	114.6 (8)	H9A—O9—H9B	109 (8)
N3—C14—C13	108.0 (8)	H10A—O10—H10B	112 (8)
O1—Cu1—N1—C5	171.7 (8)	Cu1—N3—C14—C15	−162.6 (7)
N2—Cu1—N1—C5	4.3 (8)	Cu1—N3—C14—C13	−31.5 (9)
Cl2—Cu1—N1—C5	−92.2 (7)	O2—C13—C14—N3	−153.3 (10)
O1—Cu1—N1—C1	−9.6 (10)	O1—C13—C14—N3	28.1 (12)
N2—Cu1—N1—C1	−177.0 (10)	O2—C13—C14—C15	−23.1 (14)
Cl2—Cu1—N1—C1	86.6 (10)	O1—C13—C14—C15	158.3 (9)
O1—Cu1—N2—C12	110.1 (18)	N3—C14—C15—C16	−51.8 (13)
N3—Cu1—N2—C12	5.4 (11)	C13—C14—C15—C16	−178.8 (10)
N1—Cu1—N2—C12	176.2 (11)	C14—C15—C16—C17	−161.1 (10)
Cl2—Cu1—N2—C12	−88.9 (11)	C15—C16—C17—O3	4 (2)
O1—Cu1—N2—C6	−70.4 (18)	C15—C16—C17—O4	−176.3 (10)
N3—Cu1—N2—C6	−175.1 (7)	C22—N4—C18—C19	−0.9 (16)
N1—Cu1—N2—C6	−4.3 (7)	Cu2—N4—C18—C19	−177.5 (9)
Cl2—Cu1—N2—C6	90.6 (7)	N4—C18—C19—C20	1.3 (18)
O1—Cu1—N3—C14	22.5 (6)	C18—C19—C20—C21	−1.2 (18)
N2—Cu1—N3—C14	−171.0 (6)	C19—C20—C21—C22	0.8 (16)
Cl2—Cu1—N3—C14	−73.1 (6)	C19—C20—C21—C24	−177.9 (12)
O5—Cu2—N4—C22	73 (2)	C18—N4—C22—C23	178.0 (10)
N5—Cu2—N4—C22	4.0 (8)	Cu2—N4—C22—C23	−4.8 (12)
N6—Cu2—N4—C22	178.2 (8)	C18—N4—C22—C21	0.6 (16)
Cl1—Cu2—N4—C22	−90.1 (7)	Cu2—N4—C22—C21	177.8 (9)
O5—Cu2—N4—C18	−110.2 (18)	C20—C21—C22—N4	−0.5 (17)
N5—Cu2—N4—C18	−179.3 (11)	C24—C21—C22—N4	178.3 (11)
N6—Cu2—N4—C18	−5.2 (11)	C20—C21—C22—C23	−178.0 (10)
Cl1—Cu2—N4—C18	86.6 (10)	C24—C21—C22—C23	0.8 (15)
O5—Cu2—N5—C29	9.5 (10)	C29—N5—C23—C26	1.7 (15)
N4—Cu2—N5—C29	177.8 (11)	Cu2—N5—C23—C26	−178.0 (9)
Cl1—Cu2—N5—C29	−88.6 (10)	C29—N5—C23—C22	−179.4 (10)
O5—Cu2—N5—C23	−170.9 (8)	Cu2—N5—C23—C22	0.9 (12)
N4—Cu2—N5—C23	−2.6 (7)	N4—C22—C23—C26	−178.5 (10)
Cl1—Cu2—N5—C23	91.0 (7)	C21—C22—C23—C26	−0.8 (16)
O5—Cu2—N6—C31	7.5 (7)	N4—C22—C23—N5	2.6 (15)
N4—Cu2—N6—C31	−160.3 (7)	C21—C22—C23—N5	−179.7 (10)
Cl1—Cu2—N6—C31	105.3 (7)	C20—C21—C24—C25	179.3 (13)
C5—N1—C1—C2	0.1 (17)	C22—C21—C24—C25	0.6 (18)
Cu1—N1—C1—C2	−178.5 (8)	C21—C24—C25—C26	−2.0 (19)
N1—C1—C2—C3	0.8 (18)	N5—C23—C26—C25	178.3 (11)
C1—C2—C3—C4	−0.7 (18)	C22—C23—C26—C25	−0.5 (17)
C2—C3—C4—C5	−0.4 (17)	N5—C23—C26—C27	−2.3 (16)
C2—C3—C4—C7	−179.4 (10)	C22—C23—C26—C27	178.9 (11)
C1—N1—C5—C4	−1.2 (17)	C24—C25—C26—C23	1.9 (18)
Cu1—N1—C5—C4	177.6 (8)	C24—C25—C26—C27	−177.4 (12)
C1—N1—C5—C6	177.6 (11)	C23—C26—C27—C28	1.2 (16)
Cu1—N1—C5—C6	−3.5 (13)	C25—C26—C27—C28	−179.4 (11)
C3—C4—C5—N1	1.3 (17)	C26—C27—C28—C29	0.5 (16)
C7—C4—C5—N1	−179.5 (10)	C23—N5—C29—C28	0.2 (16)
C3—C4—C5—C6	−177.5 (12)	Cu2—N5—C29—C28	179.8 (8)
C7—C4—C5—C6	1.6 (15)	C27—C28—C29—N5	−1.3 (17)
C12—N2—C6—C9	4.0 (17)	Cu2—N6—C31—C32	−139.7 (7)
Cu1—N2—C6—C9	−175.6 (10)	Cu2—N6—C31—C30	−11.8 (10)
C12—N2—C6—C5	−176.7 (11)	O6—C30—C31—N6	−170.9 (10)
Cu1—N2—C6—C5	3.8 (12)	O5—C30—C31—N6	12.3 (13)
N1—C5—C6—N2	−0.3 (16)	O6—C30—C31—C32	−41.9 (13)
C4—C5—C6—N2	178.6 (9)	O5—C30—C31—C32	141.3 (10)
N1—C5—C6—C9	179.0 (11)	N6—C31—C32—C33	−56.5 (12)
C4—C5—C6—C9	−2.0 (18)	C30—C31—C32—C33	177.5 (9)
C3—C4—C7—C8	178.6 (13)	C31—C32—C33—C34	−168.2 (10)
C5—C4—C7—C8	−0.5 (17)	C32—C33—C34—O7	14.4 (17)
C4—C7—C8—C9	−0.4 (19)	C32—C33—C34—O8	−164.4 (11)
N2—C6—C9—C10	−1.6 (18)	O2—C13—O1—Cu1	171.7 (9)
C5—C6—C9—C10	179.1 (12)	C14—C13—O1—Cu1	−9.7 (11)
N2—C6—C9—C8	−179.6 (10)	N3—Cu1—O1—C13	−7.7 (8)
C5—C6—C9—C8	1.1 (18)	N1—Cu1—O1—C13	−179.0 (8)
C7—C8—C9—C6	0.1 (18)	N2—Cu1—O1—C13	−114.0 (17)
C7—C8—C9—C10	−177.8 (13)	Cl2—Cu1—O1—C13	84.9 (7)
C6—C9—C10—C11	−0.5 (18)	O6—C30—O5—Cu2	177.0 (9)
C8—C9—C10—C11	177.4 (12)	C31—C30—O5—Cu2	−6.4 (12)
C9—C10—C11—C12	0.3 (19)	N5—Cu2—O5—C30	173.9 (8)
C6—N2—C12—C11	−4.2 (17)	N4—Cu2—O5—C30	106.0 (18)
Cu1—N2—C12—C11	175.3 (8)	N6—Cu2—O5—C30	−0.7 (8)
C10—C11—C12—N2	2.0 (18)	Cl1—Cu2—O5—C30	−90.9 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10B···O1^i	0.89 (5)	2.56 (6)	3.313 (12)	143 (6)
O10—H10B···O2^i	0.89 (5)	1.92 (5)	2.771 (13)	159 (7)
O9—H9B···O6^ii	0.87 (5)	2.13 (7)	2.774 (12)	130 (7)
O8—H8A···O9^iii	0.84 (4)	1.82 (6)	2.587 (12)	152 (8)
O4—H4A···O10	0.81 (5)	1.86 (6)	2.592 (13)	149 (9)
O10—H10A···Cl1	0.83 (5)	2.38 (6)	3.136 (10)	153 (8)
O9—H9A···Cl2^iv	0.90 (5)	2.26 (6)	3.112 (10)	157 (7)
N6—H6B···Cl2	0.92	2.84	3.423 (11)	123
N6—H6A···O10^iii	0.92	2.18	3.009 (14)	149
N3—H3B···O9	0.92	2.12	3.017 (14)	164
N3—H3A···Cl1	0.92	2.57	3.440 (10)	158

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