Bis[bis­(methoxy­carbimido)amine-κ²N,N′]bis­(perchlorato-κO)copper(II) bis­[bis­(methoxy­carbimido)amine-κ²N,N′]bis­(methanol-κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square-planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen-bonding network.

S1. Comment

Copper(II) complexes of the bis(methoxycarbimido)amine ligand HN[C(NH)OCH₃]₂, (L), though relatively uncommon, are interesting because (L) is usually formed in situ from reactions of Cu^II salts with sodium dicyanamide (dca) in methanol or mixed solvents (Kozisek et al., 1990; Boca et al., 1996; Bishop et al., 2000; Atkinson et al., 2002; Tong et al., 2003). The formation of (L) involves a nucleophilic addition of the methanol molecule on the dca anion. This reaction is promoted by a coordinative activation of the C β-site of the nonlinear dca anion. Under activation, it is susceptible to bending of the linear pseudohalide (sp-hybridized C) via N-coordination, which alters the Cβ site to sp²-hybridized, with an unsaturated valency and susceptibility to a nucleophilic attack. Ligand (L) when coordinated to Cu^II exists in its anionic and/or neutral form. For example, the neutral complex [Cu{N[C(NH)OCH₃]₂}₂], (II), contains two anionic N[C(NH)OCH₃]₂⁻ species (Kozisek et al., 1990; Boca et al., 1996; Tong et al., 2003), whereas in [Cu{HN[C(NH)OCH₃]₂}₂(C₂H₅N₃O₂)₂]Br₂·2C₂H₅N₃O₂·2CH₃OH·0.8CH₃CN (C₂H₅N₃O₂ is biuret), (III), the central Cu^II atom is coordinated by two neutral HN[C(NH)OCH₃]₂ ligands to form [Cu{HN[C(NH)OCH₃]₂}₂]²⁺ dications (Bishop et al., 2000). However, a monocationic complex, [Cu{HN[C(NH)OCH₃]₂}{N[C(NH)OCH₃]₂}](PF₆), has also been isolated by heating (II) with excess NH₄PF₆ in a CH₃OH and CH₃CN mixture (Atkinson et al., 2002). This consists of a neutral HN[C(NH)OCH₃]₂ ligand (L) and an anionic N[C(NH)OCH₃]₂⁻ ligand bonded to Cu^II. Recently, we have reacted Cu(ClO₄)₂ with Na(dca) in methanol and isolated a dicationic complex with methanol solvent molecules, [Cu{HN[C(NH)OCH₃]₂}₂](ClO₄)₂·2CH₃OH, (I); we report here the crystal structure of (I).

The asymmetric unit of (I) consists of two halves of the [Cu{HN[C(NH)OCH₃]₂}₂]²⁺ species, two ClO₄⁻ anions and two methanol molecules. The existence of two distinct Cu^II systems in the asymmetric unit is uncommon and only two examples (Curtis & Puschmann, 2004; Suksangpanya et al. 2003) were found on the Cambridge Structural Database (Allen, 2002). In (I), the Cu^II complexes lie with the Cu centre on different inversion centers and with each Cu^II atom coordinated by four N atoms in a basic square-planar geometry, forming two six-membered metallorings (Figs. 1 and 2). The (H)N═C bonds are typical double bonds [the average bond length is 1.276 (2) Å], while the average bond length for the (H)N—C bonds is 1.365 (2) Å, indicating a weak delocalized π-bonding system. The average Cu—N bond length of 1.970 (2) Å (Table 1) is slightly longer than in (II) [1.948 (1) Å] but close to the corresponding length in (III) [1.965 (3) Å].

In one complex, two ClO₄ ions weakly bind to Cu forming a distorted octahedral [Cu{HN[C(NH)OCH₃]₂}₂(ClO₄)₂] species. The Cu—O bond length [2.701 (2) Å] is longer than in [Cu(L')(ClO₄)₂]·H₂O [2.543 (3) Å] and [Cu(HL)(ClO₄)₂](ClO₄)·H₂O [2.590 (4) Å; L' is 3-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5,8,12-pentaazacyclotetradecane; Comba et al., 2002]. In the other complex, two methanol molecules are coordinated to atom Cu2 to form the [Cu{(HN[C(NH)OCH₃]₂}₂(CH₃OH)₂]²⁺ octahedral species. The Cu2—O distance [2.719 (2) Å] is much longer than those found in [CuL₂(CH₃OH)₂](NO₃)₂ [2.298 (4) Å; L is 1-(2-pyridyl)benzotriazole; Richardson & Steel, 2003] and [CuL₂(CH₃OH)₂](SiF₆)₂ [2.481 (5) Å; L is 2,2'-dipyridylamine; Casellas et al., 2005].

The crystal structure of (I) is stabilized by extensive N—H···O, O—H···N and O—H···O hydrogen-bonding interactions (Table 2). The O atoms of the coordinated ClO₄ anions in the [Cu{HN[C(NH)OCH₃]₂}₂(ClO₄)₂] species interact with the imide groups of neighbouring species to afford intermolecular N—H···O hydrogen bonding interactions, thereby forming one-dimensional chains along the a-axis direction. The [Cu{HN[C(NH)OCH₃]₂}₂(CH₃OH)₂]²⁺ complexes are also linked via intermolecular interactions between O atoms of the coordinated CH₃OH molecules and amine groups to form another one-dimensional chain. Between the two chains are sandwiched free ClO₄⁻ anions and CH₃OH molecules. In addition, the O atoms from the free ClO₄⁻ ions and methanol solvent molecules interact with the imide and amine groups of the adjacent species of the two chains to afford a two-dimensional network along the (012) plane (Fig. 3). Furthermore, the O atoms of the coordinated ClO₄ anions interact with the coordinated methanol molecules of adjacent layers to afford hydrogen bonds [O14···O11ⁱ and O14···O12ⁱ; symmetry code: (i) −x, −y + 1, −z + 1], affording a three-dimensional structure.

S2. Experimental

To a solution of Cu(ClO₄)₂·6H₂O (370 mg, 1.0 mmol) in 15 ml of methanol was added a solution containing sodium dicyanamide (100 mg, 1.12 mmol) in 10 ml of methanol. The mixture was stirred for 2 h at 323 K to form a green solution. Slow diffusion of diethyl ether into the filtrate gave rise to purple crystals of (I) (yield 48%). Analysis, found: C 20.23, H 4.38, N 14.15%; calculated for C₂₀H₅₂C1₄Cu₂N₁₂O₂₈: C 20.40, H 4.45, N 14.27%. IR (KBr, ν, cm⁻¹): 3008 (w), 2942 (w), 2920 (w), 1633 (m), 1558 (m), 1465 (m), 1427 (m).

S3. Refinement

The methyl H atoms were included in the refinement in the riding model approximation [C—H = 0.98 Å, with U_iso(H) = 1.5U_eq(C)]; the groups were rotated to fit the electron density. The N– and O-bound H atoms were located in difference Fourier maps and were refined with distance restraints [N—H = O—H = 0.85 (1) Å]; their displacement parameters were freely refined.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the ClO4-coordinated species in (I). Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as spheres of arbitrary radii. The dashed lines represent the Cu···O bonds. [Symmetry code (i) −x + 1, −y + 1, −z + 1.]
	Fig. 2. A view of the CH3OH-coordinated species in (I). Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as spheres of arbitrary radii. The dashed lines represent the Cu···O bonds. [Symmetry code: (ii) −x, −y + 1, −z + 2.]
	Fig. 3. The layer structure of (I) parallel to (012). The dashed lines indicate N—H···O and O—H···O interactions.

Bis[bis(methoxycarbimido)amine-κ²N,N']bis(perchlorato-κO)copper(II) bis[bis(methoxycarbimido)amine-κ²N,N']bis(methanol-κO)copper(II) bis(perchlorate) methanol disolvate

Crystal data

[Cu(C4H9N3O2)2(CH4O)2][Cu(ClO4)2(C4H9N3O2)2](ClO4)2·2CH4O	Z = 1
Mr = 1177.64	F(000) = 606
Triclinic, P1	Dx = 1.734 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.444 (2) Å	Cell parameters from 4658 reflections
b = 10.067 (2) Å	θ = 3.1–25.3°
c = 15.330 (3) Å	µ = 1.28 mm^−1
α = 85.06 (3)°	T = 153 K
β = 89.91 (3)°	Block, purple
γ = 80.20 (3)°	0.32 × 0.30 × 0.26 mm
V = 1127.7 (5) Å^3

Data collection

Rigaku Mercury diffractometer	4082 independent reflections
Radiation source: fine-focus sealed tube	3857 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω scans	θmax = 25.3°, θmin = 3.1°
Absorption correction: multi-scan (Jacobson, 1998)	h = −8→8
Tmin = 0.684, Tmax = 0.731	k = −10→12
10868 measured reflections	l = −18→18

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.6301P] where P = (Fo^2 + 2Fc^2)/3
4082 reflections	(Δ/σ)max = 0.001
339 parameters	Δρmax = 0.72 e Å^−3
8 restraints	Δρmin = −0.37 e Å^−3

Special details

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	0.5000	0.5000	0.5000	0.01507 (10)
Cu2	0.0000	0.5000	1.0000	0.01631 (10)
Cl1	0.18124 (6)	1.04408 (4)	0.83609 (3)	0.01955 (12)
Cl2	0.14635 (6)	0.52414 (5)	0.32136 (3)	0.01933 (12)
O1	0.7581 (2)	0.8397 (1)	0.5062 (1)	0.0224 (3)
O2	0.2572 (2)	0.8186 (1)	0.6446 (1)	0.0267 (3)
O3	0.3757 (2)	0.7624 (1)	1.0162 (1)	0.0212 (3)
O4	0.4330 (2)	0.4668 (1)	0.8236 (1)	0.0221 (3)
O5	0.1613 (2)	1.1485 (2)	0.8957 (1)	0.0321 (4)
O6	0.3712 (2)	1.0089 (2)	0.8156 (1)	0.0407 (4)
O7	0.0787 (3)	1.0912 (2)	0.7580 (1)	0.0460 (4)
O8	0.1167 (2)	0.9285 (2)	0.8764 (1)	0.0389 (4)
O9	0.2577 (2)	0.5968 (1)	0.3693 (1)	0.0241 (3)
O10	−0.0193 (2)	0.5153 (2)	0.3695 (1)	0.0358 (4)
O11	0.2410 (2)	0.3899 (2)	0.3112 (1)	0.0315 (4)
O12	0.1025 (2)	0.5933 (2)	0.2365 (1)	0.0431 (4)
O13	0.5092 (2)	1.0392 (2)	0.6440 (1)	0.0278 (3)
O14	−0.2687 (2)	0.6330 (1)	0.8890 (1)	0.0233 (3)
N1	0.4975 (2)	0.8058 (2)	0.5618 (1)	0.0204 (3)
N2	0.3445 (2)	0.6211 (2)	0.5745 (1)	0.0179 (3)
N3	0.6511 (2)	0.6426 (2)	0.4763 (1)	0.0177 (3)
N4	0.1191 (2)	0.6565 (2)	1.0166 (1)	0.0182 (3)
N5	0.1679 (2)	0.4566 (2)	0.9038 (1)	0.0191 (3)
N6	0.3733 (2)	0.5994 (2)	0.9302 (1)	0.0193 (3)
C1	0.9120 (3)	0.8108 (2)	0.4500 (2)	0.0308 (5)
C2	0.6389 (3)	0.7547 (2)	0.5111 (1)	0.0174 (4)
C3	0.3627 (3)	0.7392 (2)	0.5932 (1)	0.0181 (4)
C4	0.1113 (3)	0.7657 (2)	0.6899 (1)	0.0282 (5)
C5	0.2908 (3)	0.8584 (2)	1.0751 (1)	0.0258 (4)
C6	0.2768 (2)	0.6740 (2)	0.9906 (1)	0.0164 (4)
C7	0.3145 (2)	0.5022 (2)	0.8863 (1)	0.0168 (4)
C8	0.3994 (3)	0.3589 (2)	0.7725 (1)	0.0251 (4)
C9	0.6860 (3)	1.0633 (2)	0.6661 (2)	0.0357 (5)
C10	−0.2537 (3)	0.7728 (2)	0.8764 (2)	0.0359 (5)
H13	0.451 (4)	1.033 (3)	0.690 (1)	0.050 (8)*
H14	−0.250 (4)	0.601 (3)	0.841 (1)	0.057 (9)*
H1	0.507 (3)	0.8812 (13)	0.580 (1)	0.018 (5)*
H2	0.254 (2)	0.593 (2)	0.598 (1)	0.024 (6)*
H3	0.747 (2)	0.625 (2)	0.447 (1)	0.020 (6)*
H4	0.070 (3)	0.710 (2)	1.053 (1)	0.023 (6)*
H5	0.150 (3)	0.398 (2)	0.870 (1)	0.028 (6)*
H6	0.475 (2)	0.620 (2)	0.919 (1)	0.022 (6)*
H1A	0.9857	0.8826	0.4507	0.046*
H1B	0.8691	0.8061	0.3902	0.046*
H1C	0.9862	0.7239	0.4710	0.046*
H4A	0.0487	0.8330	0.7271	0.042*
H4B	0.1615	0.6829	0.7263	0.042*
H4C	0.0246	0.7452	0.6471	0.042*
H5A	0.3786	0.9146	1.0915	0.039*
H5B	0.2516	0.8095	1.1279	0.039*
H5C	0.1847	0.9161	1.0460	0.039*
H8A	0.4927	0.3447	0.7276	0.038*
H8B	0.2788	0.3835	0.7445	0.038*
H8C	0.4040	0.2755	0.8111	0.038*
H9A	0.6893	1.1604	0.6565	0.053*
H9b	0.7768	1.0137	0.6291	0.053*
H9c	0.7136	1.0325	0.7277	0.053*
H10a	−0.2807	0.8149	0.9313	0.054*
H10B	−0.3406	0.8181	0.8308	0.054*
H10C	−0.1296	0.7814	0.8584	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01667 (17)	0.01458 (17)	0.01526 (17)	−0.00464 (12)	0.00425 (12)	−0.00484 (12)
Cu2	0.01504 (17)	0.01686 (17)	0.01950 (18)	−0.00718 (12)	0.00692 (12)	−0.00686 (12)
Cl1	0.0215 (2)	0.0186 (2)	0.0198 (2)	−0.00558 (18)	0.00294 (18)	−0.00484 (17)
Cl2	0.0160 (2)	0.0250 (2)	0.0185 (2)	−0.00595 (18)	0.00243 (17)	−0.00583 (18)
O1	0.0218 (7)	0.0219 (7)	0.0267 (7)	−0.0101 (6)	0.0089 (6)	−0.0086 (6)
O2	0.0243 (7)	0.0226 (7)	0.0373 (8)	−0.0094 (6)	0.0159 (6)	−0.0157 (6)
O3	0.0179 (7)	0.0225 (7)	0.0263 (7)	−0.0091 (5)	0.0027 (5)	−0.0087 (6)
O4	0.0195 (7)	0.0250 (7)	0.0251 (7)	−0.0094 (6)	0.0111 (6)	−0.0100 (6)
O5	0.0358 (9)	0.0296 (8)	0.0359 (9)	−0.0117 (7)	0.0120 (7)	−0.0191 (7)
O6	0.0248 (8)	0.0505 (10)	0.0500 (10)	−0.0063 (7)	0.0108 (7)	−0.0227 (8)
O7	0.0581 (12)	0.0448 (10)	0.0311 (9)	0.0005 (9)	−0.0151 (8)	0.0011 (8)
O8	0.0567 (11)	0.0296 (8)	0.0358 (9)	−0.0236 (8)	0.0053 (8)	−0.0016 (7)
O9	0.0247 (7)	0.0275 (8)	0.0229 (7)	−0.0109 (6)	−0.0012 (6)	−0.0043 (6)
O10	0.0260 (8)	0.0358 (9)	0.0529 (10)	−0.0163 (7)	0.0222 (7)	−0.0234 (8)
O11	0.0266 (8)	0.0291 (8)	0.0405 (9)	−0.0028 (6)	0.0063 (7)	−0.0168 (7)
O12	0.0482 (10)	0.0557 (11)	0.0254 (8)	−0.0138 (8)	−0.0146 (7)	0.0070 (7)
O13	0.0282 (8)	0.0288 (8)	0.0298 (8)	−0.0114 (6)	0.0071 (7)	−0.0087 (6)
O14	0.0224 (7)	0.0261 (7)	0.0244 (8)	−0.0085 (6)	0.0066 (6)	−0.0098 (6)
N1	0.0214 (8)	0.0156 (8)	0.0265 (9)	−0.0066 (6)	0.0065 (7)	−0.0080 (7)
N2	0.0160 (8)	0.0202 (8)	0.0196 (8)	−0.0069 (6)	0.0042 (6)	−0.0054 (6)
N3	0.0165 (8)	0.0198 (8)	0.0182 (8)	−0.0050 (6)	0.0058 (6)	−0.0049 (6)
N4	0.0176 (8)	0.0172 (8)	0.0217 (8)	−0.0059 (6)	0.0062 (6)	−0.0068 (6)
N5	0.0180 (8)	0.0209 (8)	0.0217 (8)	−0.0087 (7)	0.0059 (6)	−0.0095 (7)
N6	0.0135 (8)	0.0212 (8)	0.0255 (9)	−0.0079 (6)	0.0053 (6)	−0.0060 (7)
C1	0.0293 (11)	0.0324 (11)	0.0360 (12)	−0.0159 (9)	0.0176 (9)	−0.0126 (9)
C2	0.0187 (9)	0.0177 (9)	0.0167 (9)	−0.0055 (7)	0.0016 (7)	−0.0011 (7)
C3	0.0169 (9)	0.0189 (9)	0.0189 (9)	−0.0028 (7)	0.0019 (7)	−0.0050 (7)
C4	0.0262 (11)	0.0299 (11)	0.0323 (11)	−0.0096 (9)	0.0150 (9)	−0.0146 (9)
C5	0.0265 (11)	0.0258 (10)	0.0285 (11)	−0.0095 (8)	0.0020 (8)	−0.0123 (8)
C6	0.0186 (9)	0.0137 (8)	0.0172 (9)	−0.0040 (7)	−0.0006 (7)	−0.0007 (7)
C7	0.0166 (9)	0.0168 (9)	0.0162 (9)	−0.0013 (7)	0.0019 (7)	−0.0012 (7)
C8	0.0242 (10)	0.0280 (11)	0.0261 (11)	−0.0079 (8)	0.0103 (8)	−0.0119 (8)
C9	0.0307 (12)	0.0339 (12)	0.0469 (14)	−0.0120 (10)	0.0079 (10)	−0.0164 (10)
C10	0.0339 (12)	0.0286 (12)	0.0467 (14)	−0.0132 (10)	0.0000 (10)	0.0039 (10)

Geometric parameters (Å, º)

Cu1—N2	1.971 (2)	N3—C2	1.279 (2)
Cu1—N2^i	1.971 (2)	N4—C6	1.275 (2)
Cu1—N3	1.979 (2)	N5—C7	1.274 (2)
Cu1—N3^i	1.979 (2)	N6—C7	1.364 (2)
Cu1—O9	2.701 (2)	N6—C6	1.367 (2)
Cu2—N4	1.969 (2)	O13—H13	0.83 (1)
Cu2—N4^ii	1.969 (2)	O14—H14	0.83 (1)
Cu2—N5	1.961 (2)	N1—H1	0.84 (1)
Cu2—N5^ii	1.961 (2)	N2—H2	0.84 (1)
Cu2—O14	2.719 (2)	N3—H3	0.84 (1)
Cl1—O7	1.423 (2)	N4—H4	0.84 (1)
Cl1—O8	1.426 (2)	N5—H5	0.84 (1)
Cl1—O6	1.439 (2)	N6—H6	0.84 (1)
Cl1—O5	1.441 (2)	C1—H1A	0.98
Cl2—O12	1.432 (2)	C1—H1B	0.98
Cl2—O11	1.435 (2)	C1—H1C	0.98
Cl2—O9	1.436 (1)	C4—H4A	0.98
Cl2—O10	1.448 (2)	C4—H4B	0.98
O1—C2	1.331 (2)	C4—H4C	0.98
O1—C1	1.437 (2)	C5—H5A	0.98
O2—C3	1.330 (2)	C5—H5B	0.98
O2—C4	1.441 (2)	C5—H5C	0.98
O3—C6	1.332 (2)	C8—H8A	0.98
O3—C5	1.446 (2)	C8—H8B	0.98
O4—C7	1.335 (2)	C8—H8C	0.98
O4—C8	1.446 (2)	C9—H9A	0.98
O13—C9	1.425 (3)	C9—H9B	0.98
O14—C10	1.427 (3)	C9—H9C	0.98
N1—C3	1.364 (2)	C10—H10A	0.98
N1—C2	1.364 (3)	C10—H10B	0.98
N2—C3	1.276 (2)	C10—H10C	0.98
N2—Cu1—N2^i	180	N5—C7—N6	123.8 (2)
N2—Cu1—N3	88.70 (7)	O4—C7—N6	108.9 (2)
N2—Cu1—N3^i	91.30 (7)	C9—O13—H13	108 (2)
N2^i—Cu1—N3^i	88.70 (7)	C10—O14—H14	107 (2)
N2^i—Cu1—N3	91.30 (7)	Cu2—O14—H14	107 (2)
N3—Cu1—N3^i	180	C3—N1—H1	120 (2)
N2—Cu1—O9	86.69 (6)	C2—N1—H1	114 (2)
N2^i—Cu1—O9	93.31 (6)	C3—N2—H2	114 (2)
N3^i—Cu1—O9	85.32 (6)	Cu1—N2—H2	118 (2)
N3—Cu1—O9	94.68 (6)	C2—N3—H3	112 (2)
N4—Cu2—N4^ii	180	Cu1—N3—H3	119 (2)
N4—Cu2—N5	88.51 (7)	C6—N4—H4	116 (2)
N4—Cu2—N5^ii	91.49 (7)	Cu2—N4—H4	116 (2)
N4^ii—Cu2—N5	91.49 (7)	C7—N5—H5	112 (2)
N4^ii—Cu2—N5^ii	88.51 (7)	Cu2—N5—H5	120 (2)
N5—Cu2—N5^ii	180	C7—N6—H6	119 (2)
N5—Cu2—O14	92.66 (6)	C6—N6—H6	114 (2)
N5^ii—Cu2—O14	87.34 (6)	O1—C1—H1A	109.5
N4^ii—Cu2—O14	83.17 (6)	O1—C1—H1B	109.5
N4—Cu2—O14	96.83 (6)	H1A—C1—H1B	109.5
O7—Cl1—O8	109.2 (1)	O1—C1—H1C	109.5
O7—Cl1—O6	109.7 (1)	H1A—C1—H1C	109.5
O8—Cl1—O6	109.9 (1)	H1B—C1—H1C	109.5
O7—Cl1—O5	110.1 (1)	O2—C4—H4A	109.5
O8—Cl1—O5	109.3 (1)	O2—C4—H4B	109.5
O6—Cl1—O5	108.6 (1)	H4A—C4—H4B	109.5
O12—Cl2—O11	109.0 (1)	O2—C4—H4C	109.5
O12—Cl2—O9	109.9 (1)	H4A—C4—H4C	109.5
O11—Cl2—O9	110.4 (1)	H4B—C4—H4C	109.5
O12—Cl2—O10	109.8 (1)	O3—C5—H5A	109.5
O11—Cl2—O10	109.0 (1)	O3—C5—H5B	109.5
O9—Cl2—O10	108.9 (1)	H5A—C5—H5B	109.5
C2—O1—C1	117.8 (2)	O3—C5—H5C	109.5
C3—O2—C4	118.2 (2)	H5A—C5—H5C	109.5
C6—O3—C5	117.1 (2)	H5B—C5—H5C	109.5
C7—O4—C8	117.3 (1)	O4—C8—H8A	109.5
Cl2—O9—Cu1	128.4 (1)	O4—C8—H8B	109.5
C10—O14—Cu2	109.7 (1)	H8A—C8—H8B	109.5
C3—N1—C2	125.9 (2)	O4—C8—H8C	109.5
C3—N2—Cu1	128.4 (1)	H8A—C8—H8C	109.5
C2—N3—Cu1	127.8 (1)	H8B—C8—H8C	109.5
C7—N5—Cu2	127.6 (1)	O13—C9—H9A	109.5
C6—N4—Cu2	126.9 (1)	O13—C9—H9B	109.5
C7—N6—C6	126.2 (2)	H9A—C9—H9B	109.5
N3—C2—O1	127.5 (2)	O13—C9—H9C	109.5
N3—C2—N1	124.2 (2)	H9A—C9—H9C	109.5
O1—C2—N1	108.4 (2)	H9B—C9—H9C	109.5
N2—C3—O2	127.4 (2)	O14—C10—H10A	109.5
N2—C3—N1	124.3 (2)	O14—C10—H10B	109.5
O2—C3—N1	108.3 (2)	H10A—C10—H10B	109.5
N4—C6—O3	127.8 (2)	O14—C10—H10C	109.5
N4—C6—N6	123.5 (2)	H10A—C10—H10C	109.5
O3—C6—N6	108.8 (2)	H10B—C10—H10C	109.5
N5—C7—O4	127.2 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O13	0.84 (1)	1.95 (1)	2.774 (2)	168 (2)
N2—H2···O10^iii	0.84 (1)	2.25 (1)	3.067 (2)	165 (2)
N3—H3···O10^iv	0.84 (1)	2.29 (1)	3.102 (2)	163 (2)
N4—H4···O5^v	0.84 (1)	2.23 (1)	3.011 (2)	154 (2)
N5—H5···O5^vi	0.84 (1)	2.50 (2)	3.123 (2)	132 (2)
N5—H5···O12^iii	0.84 (1)	2.48 (2)	3.078 (2)	129 (2)
N6—H6···O14^iv	0.84 (1)	1.98 (1)	2.808 (2)	169 (2)
O13—H13···O6	0.83 (1)	2.02 (1)	2.833 (2)	166 (3)
O14—H14···O11^iii	0.83 (1)	2.33 (2)	3.101 (2)	155 (3)
O14—H14···O12^iii	0.83 (1)	2.47 (2)	3.196 (3)	146 (3)

Symmetry codes: (iii) −x, −y+1, −z+1; (iv) x+1, y, z; (v) −x, −y+2, −z+2; (vi) x, y−1, z.