A novel one-dimensional zigzag coordination polymer of copper(II) with di­methyl­glyoxime

A novel metal-organic based polymeric complex, namely catena-poly­[[bis([mu]₄-di­methyl­glyoximato)­bis([mu]₂-di­methyl­gly­oxi­mato)­bis­(di­methyl­glyoxime)­tetracopper(II)] diperchlorate dihydrate], {[Cu₄(dmg)₂(Hdmg)₂(H₂dmg)₂](ClO₄)₂·2H₂O}_[infinity] (H₂dmg is di­methyl­glyoxime, C₂H₈N₂O₂), has been synthesized and characterized by single-crystal X-ray diffraction methods. The complex is a one-dimensional zigzag chain coordination polymer, in which the tetranuclear repeat unit is a centrosymmetric Cu₄ moiety coordinated to di­methyl­glyoxime ligands only. These units are linked by double Cu-O-Cu bridges in a centrosymmetric rectangular ­junction.

S1. Comment

Self-assembly processes involving metal ions have attracted much attention in the past few years because a metal ion together with its ligand contains a variety of structural information to guide the self-assembly reaction (Lehn, 1995). Recent attention has particularly been focused on the construction of various supramolecular structures. In these structures, the very simple topological types of coordination arrays are one-dimensional architectures, such as one-dimensional zigzag chains (Mimura et al., 1998; Colacio et al., 1999) and a one-dimensional helix (Ranford et al., 1999). The most commonly used strategy to obtain these extended structures is to employ appropriate bridging ligands, which are capable of linking to several metal centers through direct bond formation.

It is well known that the oximate group (=N—O–) can function as a bridging ligand to link two metal ions through the imine N atom and the deprotonated O atom, and this group can coordinate with metal ions in versatile ways. Dimethylglyoxime (H₂dmg) has four potential donor sites. Framework molecular models show that it is more likely to act as a bridging ligand between two metal ions than as a terminal ligand (Cervera et al., 1997; Ruiz et al., 1997). Recently, several groups, including our own, have reported the syntheses, X-ray crystal structure analyses and SQUID (superconducting quantum interference device) measurements of complicated complexes of transition metals using this bridging ligand (Chen et al., 2003; Li et al., 2002; Liu et al., 2002; Zhang et al., 2003). In this present contribution, we have extended our work using this ligand to form one-dimensional zigzag chains containing multidentate dimethylglyoxime. In this paper, we report the synthesis, structure and spectroscopic properties of the title compound, {[Cu₄(dmg)₂(Hdmg)₂(H₂dmg)₂](ClO₄)₂·2H₂O}_∞, (I).

The principal feature of the structure of (I) is polymeric chains extending along [110]. The translationally repeating unit of these chains is a centrosymmetric sequence of four square-pyramidally coordinated Cu^II ions (Fig. 1). Cu1 and Cu1ⁱ [symmetry code: (i) −x, 2 − y, 1 − z] are at the 1,4-positions of a centrosymmetric six-membered ring that is in a chair conformation. The two unique Cu atoms (Cu1 and Cu2) are also bridged in a six-membered ring but in the half-chair conformation. This tetranuclear unit is repeated by lattice translation, incorporating another centre of symmetry, this time involving an oxo bridge (O3) between atoms Cu2 and Cu2ⁱⁱ [symmetry code: (ii) 1 − x, 1 − y, 1 − z] giving a four-membered ring. This linking style forms an interesting Cu₂O₂ quadrangular junction. To our knowledge, it is rare for metal coordination polymers to be connected through double bridges in a quadrangular junction.

A remarkable feature of this coordination environment is that all ligands are either H₂dmg or one of its ions, and there are no coordinated water molecules; in this respect, compound (I) differs from all previously reported complexes containing dimethylglyoxime ligands. Among the six ligands in each tetranuclear moiety, two (H₂dmg) are bidentate terminal ligands, two (Hdmg⁻) are tridentate bridging ligands within the moiety, and the other two (dmg²⁻) are tetradentate but are bound to five different Cu atoms because atom O3 bridges two Cu atoms.

As can be seen from Fig. 2, the entire polymer is a one-dimensional zigzag chain, which is built from Cu₄ moieties. In order to form double Cu—O—Cu bonding bridges, the symmetrical dinuclear Cu^II unit in the Cu₄ moiety adopts a chair form. The zigzag chain is further stabilized by intrachain hydrogen bonding by all three OH groups (Fig. 1 and Table 2). Both bonds of the bifurcated O6—H hydrogen bonds are intrachain, as is the O5—H hydrogen bond. The other component of the latter is to the uncoordinated water molecule (O11).

There are weak and ill-defined interactions between O atoms of the disordered perchlorate ion and both Cu atoms near the sixth (vacant) octahedral coordination site of the Cu atoms. The uncoordinated water molecule is located in the interchain region.

The crystal structure of (I) exhibits some characteristics that differ from those of previously reported structures, viz. all coordination sites are occupied by dimethylglyoxime ligands and double Cu—O—Cu bridges are connected in a quadrangular form. This polymeric structure shows the amazing bridging ability and the fantastic coordinating versatility of the dimethylglyoxime ligand, which can play an important role in the direct assembly of coordination polymers. Further investigation is in progress.

S2. Experimental

To prepare (I), H₂dmg (0.058 g, 0.5 mmol) and Cu(ClO₄)₂6H₂O (0.270 g, 0.75 mmol) were dissolved in methanol (10 ml) and a 0.5M NaOH aqueous solution (1 ml) was added in order to deprotonate the oximate groups. The resulting mixture was stirred for 1 h at room temperature and then filtered and evaporated at room temperature. After 4 d, dark-red crystals of the complex suitable for X-ray single-crystal analysis were obtained. These were collected by filter suction and air-dried. All chemicals used in this experiment were purchased commercially and used without further purification. Yield: 60%. Analysis found: C 25.56, H 3.77, N 14.10%; calcualted: C 24.43, H 3.90, N 14.25%. IR (cm⁻¹): ν 1589 (s, C=N), 1201 (s, N—O), 1090 (s, Cl=O). The room-temperature value of C_MT for (I) (C_M, the molar magnetic susceptibility for a one-dimensional copper chain; ca 0.454 cm³ K mol⁻¹) is higher than the expected value for a one-dimensional chain of copper(II) ions (ca 0.374 cm³ K mol⁻¹), so the C_MT value of (I) reveals a ferromagnetic coupling between the copper(II) ions.

Table 2. Intra-chain hydrogen-bonding geometry of (I).

S3. Refinement

The O atoms of the perchlorate ion occupy two positions. They were refined freely but with a parameter constraining their populations to 1.0. Consequently, the U_eq(max)/U_eq(min) ratio for the perchlorate group is larger than usual. Hydroxy H atoms were positioned geometrically (O—H = 0.82 Å), and the coordinates of water H atoms were calculated using HYDROGEN (Nardelli, 1999) (O—H = 0.8498 and 0.8501 Å). All of these H atoms were allowed to ride on their parent atoms in the final refinement. H atoms attached to C atoms were placed in calculated positions (C—H = 0.93 Å) and allowed to ride on the parent atoms. For all H atoms, U_iso(H) values were constrained to 1.5U_eq of the parent atom??.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SMART and SAINT? (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEPII? (Johnson, 1976); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The centrosymmetric tetranuclear unit of (I), also showing one quadrangular junction. Intrachain hydrogen-bond interactions (O6—H... O1^ii omitted) are shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level and the atom-numbering scheme is shown. Methyl group H atoms, the perchlorate ion and the uncoordinated water molecule have been omitted. [Symmetry codes: (i) −x, 2 − y, 1 − z; (ii) 1 − x, 1 − y, 1 − z.]

Fig. 2. An extended view of the polymeric chain. The quadrangular junctions are one lattice repeat apart along [110].

catena-poly[bis(µ₄-dimethylglyoximato)bis(µ₂– dimethylglyoximato)bis(dimethylglyoxime)tetracopper(II) diperchlorate dihydrate

Crystal data

[Cu4(C2H6N2O2)2(C2H7N2O2)2(C2H8N2O2)2](ClO4)2·2H2O	Z = 1
Mr = 1179.78	F(000) = 600
Triclinic, P1	Dx = 1.817 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.458 (3) Å	Cell parameters from 1006 reflections
b = 10.381 (3) Å	θ = 2.5–26.4°
c = 12.838 (3) Å	µ = 2.16 mm^−1
α = 88.402 (5)°	T = 293 K
β = 74.831 (4)°	Prism, red
γ = 63.064 (4)°	0.12 × 0.10 × 0.06 mm
V = 1078.5 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4356 independent reflections
Radiation source: fine-focus sealed tube	3341 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −11→11
Tmin = 0.762, Tmax = 0.878	k = −9→12
6254 measured reflections	l = −14→16

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.005P)^2 + 2.5P] where P = (Fo^2 + 2Fc^2)/3
4356 reflections	(Δ/σ)max = 0.001
305 parameters	Δρmax = 0.66 e Å^−3
20 restraints	Δρmin = −0.66 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	Occ. (<1)
Cu1	0.21477 (6)	0.84447 (5)	0.40438 (4)	0.03069 (15)
Cu2	0.57969 (6)	0.50808 (5)	0.36959 (4)	0.03108 (15)
O1	0.3943 (3)	0.5293 (3)	0.3196 (2)	0.0353 (7)
O2	0.0076 (4)	1.0770 (3)	0.2912 (3)	0.0487 (9)
H2	0.0014	1.1212	0.3455	0.073*
O3	0.4705 (3)	0.6399 (3)	0.5042 (2)	0.0318 (7)
O4	0.0220 (4)	1.1577 (3)	0.4702 (2)	0.0395 (7)
O5	0.7110 (4)	0.3426 (4)	0.1435 (3)	0.0559 (10)
H5	0.6170	0.3515	0.1616	0.084*
O6	0.8202 (4)	0.5035 (4)	0.4873 (2)	0.0442 (8)
H6	0.7391	0.5204	0.5385	0.066*
N1	0.2934 (4)	0.6683 (3)	0.3046 (3)	0.0289 (8)
N2	0.1065 (4)	0.9319 (4)	0.2908 (3)	0.0338 (8)
N3	0.3637 (4)	0.7798 (4)	0.4987 (3)	0.0289 (8)
N4	0.1493 (4)	1.0321 (4)	0.4820 (3)	0.0331 (8)
N5	0.7439 (4)	0.3853 (4)	0.2313 (3)	0.0370 (9)
N6	0.7962 (4)	0.4657 (4)	0.3937 (3)	0.0333 (8)
C1	0.2949 (7)	0.5778 (5)	0.1285 (4)	0.0510 (13)
H1A	0.3726	0.5860	0.0669	0.077*
H1B	0.1988	0.5908	0.1083	0.077*
H1C	0.3447	0.4834	0.1528	0.077*
C2	0.2464 (5)	0.6907 (4)	0.2170 (3)	0.0305 (9)
C3	0.1379 (5)	0.8461 (5)	0.2085 (3)	0.0342 (10)
C4	0.0714 (7)	0.8958 (6)	0.1127 (4)	0.0624 (16)
H4A	0.0058	0.9995	0.1227	0.094*
H4B	0.0043	0.8511	0.1062	0.094*
H4C	0.1616	0.8685	0.0480	0.094*
C5	0.4545 (6)	0.8564 (5)	0.6385 (4)	0.0492 (13)
H5A	0.3837	0.8753	0.7111	0.074*
H5B	0.5042	0.9202	0.6288	0.074*
H5C	0.5394	0.7574	0.6262	0.074*
C6	0.3553 (5)	0.8820 (5)	0.5596 (3)	0.0302 (9)
C7	0.2315 (5)	1.0298 (4)	0.5488 (3)	0.0331 (10)
C8	0.2034 (6)	1.1613 (5)	0.6113 (4)	0.0491 (13)
H8A	0.1124	1.2448	0.5972	0.074*
H8B	0.3010	1.1741	0.5898	0.074*
H8C	0.1785	1.1502	0.6874	0.074*
C9	1.0227 (7)	0.3097 (7)	0.1085 (4)	0.0620 (16)
H9A	0.9991	0.2510	0.0662	0.093*
H9B	1.1279	0.2518	0.1217	0.093*
H9C	1.0253	0.3893	0.0695	0.093*
C10	0.8916 (6)	0.3673 (5)	0.2141 (3)	0.0384 (11)
C11	0.9252 (5)	0.4105 (5)	0.3118 (3)	0.0348 (10)
C12	1.0920 (6)	0.3852 (6)	0.3141 (4)	0.0553 (14)
H12A	1.1037	0.4713	0.2976	0.083*
H12B	1.1746	0.3058	0.2612	0.083*
H12C	1.1056	0.3623	0.3849	0.083*
Cl1	0.6308 (3)	0.7722 (2)	0.16147 (12)	0.0894 (6)
O7	0.549 (2)	0.764 (4)	0.2676 (10)	0.083 (4)	0.596 (7)
O8	0.583 (3)	0.705 (4)	0.0945 (19)	0.115 (6)	0.596 (7)
O9	0.620 (2)	0.9028 (11)	0.1315 (13)	0.157 (6)	0.596 (7)
O10	0.8153 (9)	0.6862 (10)	0.1513 (6)	0.101 (3)	0.596 (7)
O7'	0.597 (4)	0.738 (5)	0.2688 (16)	0.083 (4)	0.404 (7)
O8'	0.638 (5)	0.685 (5)	0.077 (3)	0.115 (6)	0.404 (7)
O9'	0.4807 (16)	0.9083 (12)	0.1730 (17)	0.157 (6)	0.404 (7)
O10'	0.702 (2)	0.8646 (18)	0.1335 (12)	0.101 (3)	0.404 (7)
O11	0.5060 (7)	0.2079 (5)	0.1070 (4)	0.0998 (16)
H11A	0.5060	0.2152	0.0409	0.150*
H11B	0.5444	0.1193	0.1194	0.150*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0351 (3)	0.0231 (3)	0.0298 (3)	−0.0056 (2)	−0.0170 (2)	0.0006 (2)
Cu2	0.0280 (3)	0.0297 (3)	0.0269 (3)	−0.0055 (2)	−0.0083 (2)	−0.0005 (2)
O1	0.0357 (16)	0.0261 (15)	0.0397 (17)	−0.0056 (13)	−0.0194 (13)	0.0002 (13)
O2	0.061 (2)	0.0290 (17)	0.0393 (19)	−0.0021 (16)	−0.0225 (17)	0.0032 (14)
O3	0.0294 (15)	0.0278 (15)	0.0264 (15)	−0.0029 (12)	−0.0089 (12)	0.0024 (12)
O4	0.0420 (17)	0.0227 (15)	0.0431 (18)	−0.0040 (13)	−0.0155 (14)	0.0026 (13)
O5	0.052 (2)	0.081 (3)	0.0385 (19)	−0.031 (2)	−0.0166 (16)	−0.0048 (18)
O6	0.0436 (19)	0.056 (2)	0.0332 (17)	−0.0228 (17)	−0.0096 (14)	−0.0054 (16)
N1	0.0269 (17)	0.0259 (18)	0.0295 (18)	−0.0070 (15)	−0.0108 (14)	0.0041 (14)
N2	0.0352 (19)	0.0254 (18)	0.0308 (19)	−0.0032 (15)	−0.0139 (15)	0.0047 (15)
N3	0.0282 (18)	0.0258 (18)	0.0270 (18)	−0.0072 (15)	−0.0084 (14)	0.0021 (14)
N4	0.037 (2)	0.0258 (18)	0.0318 (19)	−0.0096 (16)	−0.0103 (16)	0.0018 (15)
N5	0.036 (2)	0.040 (2)	0.0284 (19)	−0.0109 (17)	−0.0109 (16)	−0.0001 (16)
N6	0.0338 (19)	0.034 (2)	0.0301 (19)	−0.0132 (16)	−0.0097 (16)	0.0008 (15)
C1	0.066 (3)	0.043 (3)	0.036 (3)	−0.015 (3)	−0.020 (2)	−0.003 (2)
C2	0.031 (2)	0.032 (2)	0.026 (2)	−0.0124 (18)	−0.0090 (17)	0.0003 (17)
C3	0.036 (2)	0.037 (2)	0.027 (2)	−0.0125 (19)	−0.0126 (18)	0.0054 (18)
C4	0.082 (4)	0.050 (3)	0.043 (3)	−0.008 (3)	−0.039 (3)	0.006 (2)
C5	0.051 (3)	0.044 (3)	0.053 (3)	−0.015 (2)	−0.027 (3)	−0.003 (2)
C6	0.030 (2)	0.034 (2)	0.024 (2)	−0.0136 (18)	−0.0062 (17)	−0.0034 (17)
C7	0.035 (2)	0.029 (2)	0.031 (2)	−0.0135 (19)	−0.0043 (18)	−0.0037 (17)
C8	0.055 (3)	0.037 (3)	0.055 (3)	−0.018 (2)	−0.019 (3)	−0.008 (2)
C9	0.053 (3)	0.088 (4)	0.039 (3)	−0.034 (3)	0.003 (2)	−0.011 (3)
C10	0.041 (3)	0.037 (2)	0.030 (2)	−0.015 (2)	−0.007 (2)	0.0032 (19)
C11	0.034 (2)	0.034 (2)	0.036 (2)	−0.017 (2)	−0.0074 (19)	0.0061 (19)
C12	0.037 (3)	0.079 (4)	0.051 (3)	−0.030 (3)	−0.007 (2)	0.000 (3)
Cl1	0.1526 (19)	0.1262 (16)	0.0440 (9)	−0.1128 (16)	−0.0227 (10)	0.0113 (9)
O7	0.078 (12)	0.150 (12)	0.052 (3)	−0.076 (11)	−0.020 (4)	0.010 (3)
O8	0.185 (19)	0.172 (10)	0.055 (8)	−0.137 (13)	−0.034 (10)	0.005 (5)
O9	0.213 (17)	0.109 (7)	0.215 (13)	−0.118 (11)	−0.082 (13)	0.043 (8)
O10	0.096 (6)	0.162 (8)	0.065 (4)	−0.088 (6)	0.002 (4)	−0.001 (5)
O7'	0.078 (12)	0.150 (12)	0.052 (3)	−0.076 (11)	−0.020 (4)	0.010 (3)
O8'	0.185 (19)	0.172 (10)	0.055 (8)	−0.137 (13)	−0.034 (10)	0.005 (5)
O9'	0.213 (17)	0.109 (7)	0.215 (13)	−0.118 (11)	−0.082 (13)	0.043 (8)
O10'	0.096 (6)	0.162 (8)	0.065 (4)	−0.088 (6)	0.002 (4)	−0.001 (5)
O11	0.145 (5)	0.072 (3)	0.094 (4)	−0.046 (3)	−0.059 (3)	0.017 (3)

Geometric parameters (Å, º)

Cu1—N4	1.965 (3)	C3—C4	1.499 (6)
Cu1—N2	1.966 (3)	C4—H4A	0.9600
Cu1—N3	1.973 (3)	C4—H4B	0.9600
Cu1—N1	1.984 (3)	C4—H4C	0.9600
Cu1—O4^i	2.400 (3)	C5—C6	1.494 (6)
Cu2—O1	1.941 (3)	C5—H5A	0.9600
Cu2—O3	1.961 (3)	C5—H5B	0.9600
Cu2—N6	1.997 (4)	C5—H5C	0.9600
Cu2—N5	2.019 (4)	C6—C7	1.480 (6)
Cu2—O3^ii	2.308 (3)	C7—C8	1.483 (6)
O1—N1	1.365 (4)	C8—H8A	0.9600
O2—N2	1.366 (4)	C8—H8B	0.9600
O2—H2	0.8200	C8—H8C	0.9600
O3—N3	1.355 (4)	C9—C10	1.493 (6)
O3—Cu2^ii	2.308 (3)	C9—H9A	0.9600
O4—N4	1.355 (4)	C9—H9B	0.9600
O4—Cu1^i	2.400 (3)	C9—H9C	0.9600
O5—N5	1.379 (5)	C10—C11	1.498 (6)
O5—H5	0.8200	C11—C12	1.486 (6)
O6—N6	1.379 (4)	C12—H12A	0.9600
O6—H6	0.8200	C12—H12B	0.9600
N1—C2	1.292 (5)	C12—H12C	0.9600
N2—C3	1.283 (5)	Cl1—O9	1.363 (8)
N3—C6	1.296 (5)	Cl1—O10'	1.397 (9)
N4—C7	1.292 (5)	Cl1—O8	1.401 (8)
N5—C10	1.281 (6)	Cl1—O8'	1.401 (10)
N6—C11	1.284 (5)	Cl1—O7'	1.402 (9)
C1—C2	1.481 (6)	Cl1—O7	1.404 (8)
C1—H1A	0.9600	Cl1—O9'	1.455 (9)
C1—H1B	0.9600	Cl1—O10	1.528 (7)
C1—H1C	0.9600	O11—H11A	0.85
C2—C3	1.488 (6)	O11—H11B	0.85
N4—Cu1—N2	94.38 (14)	C2—C3—C4	122.7 (4)
N4—Cu1—N3	79.96 (14)	C3—C4—H4A	109.5
N2—Cu1—N3	164.17 (15)	C3—C4—H4B	109.5
N4—Cu1—N1	170.67 (14)	H4A—C4—H4B	109.5
N2—Cu1—N1	79.64 (14)	C3—C4—H4C	109.5
N3—Cu1—N1	103.92 (13)	H4A—C4—H4C	109.5
N4—Cu1—O4^i	87.32 (13)	H4B—C4—H4C	109.5
N2—Cu1—O4^i	96.35 (13)	C6—C5—H5A	109.5
N3—Cu1—O4^i	98.12 (12)	C6—C5—H5B	109.5
N1—Cu1—O4^i	100.38 (12)	H5A—C5—H5B	109.5
O1—Cu2—O3	102.47 (12)	C6—C5—H5C	109.5
O1—Cu2—N6	169.22 (13)	H5A—C5—H5C	109.5
O3—Cu2—N6	88.16 (13)	H5B—C5—H5C	109.5
O1—Cu2—N5	91.93 (14)	N3—C6—C7	114.2 (4)
O3—Cu2—N5	163.92 (14)	N3—C6—C5	124.3 (4)
N6—Cu2—N5	77.30 (14)	C7—C6—C5	121.4 (4)
O1—Cu2—O3^ii	89.98 (12)	N4—C7—C6	113.6 (4)
N6—Cu2—O3^ii	94.10 (13)	N4—C7—C8	123.9 (4)
N5—Cu2—O3^ii	109.59 (13)	C6—C7—C8	122.5 (4)
N1—O1—Cu2	114.4 (2)	C7—C8—H8A	109.5
N2—O2—H2	109.5	C7—C8—H8B	109.5
N3—O3—Cu2	117.6 (2)	H8A—C8—H8B	109.5
N3—O3—Cu2^ii	125.7 (2)	C7—C8—H8C	109.5
Cu2—O3—Cu2^ii	102.07 (12)	H8A—C8—H8C	109.5
N4—O4—Cu1^i	103.4 (2)	H8B—C8—H8C	109.5
N5—O5—H5	109.5	C10—C9—H9A	109.5
N6—O6—H6	109.5	C10—C9—H9B	109.5
C2—N1—O1	118.5 (3)	H9A—C9—H9B	109.5
C2—N1—Cu1	115.6 (3)	C10—C9—H9C	109.5
O1—N1—Cu1	125.8 (2)	H9A—C9—H9C	109.5
C3—N2—O2	118.3 (3)	H9B—C9—H9C	109.5
C3—N2—Cu1	116.9 (3)	N5—C10—C9	125.2 (4)
O2—N2—Cu1	124.7 (3)	N5—C10—C11	113.7 (4)
C6—N3—O3	119.0 (3)	C9—C10—C11	121.1 (4)
C6—N3—Cu1	115.7 (3)	N6—C11—C12	124.2 (4)
O3—N3—Cu1	125.3 (2)	N6—C11—C10	112.7 (4)
C7—N4—O4	120.7 (3)	C12—C11—C10	123.1 (4)
C7—N4—Cu1	116.4 (3)	C11—C12—H12A	109.5
O4—N4—Cu1	122.8 (3)	C11—C12—H12B	109.5
C10—N5—O5	114.9 (4)	H12A—C12—H12B	109.5
C10—N5—Cu2	116.1 (3)	C11—C12—H12C	109.5
O5—N5—Cu2	127.6 (3)	H12A—C12—H12C	109.5
C11—N6—O6	115.5 (4)	H12B—C12—H12C	109.5
C11—N6—Cu2	117.7 (3)	O9—Cl1—O8	113.8 (16)
O6—N6—Cu2	126.4 (3)	O10'—Cl1—O8'	117 (2)
C2—C1—H1A	109.5	O10'—Cl1—O7'	120 (2)
C2—C1—H1B	109.5	O8'—Cl1—O7'	120 (3)
H1A—C1—H1B	109.5	O9—Cl1—O7	119.5 (15)
C2—C1—H1C	109.5	O8—Cl1—O7	104.8 (14)
H1A—C1—H1C	109.5	O10'—Cl1—O9'	81.3 (9)
H1B—C1—H1C	109.5	O8'—Cl1—O9'	106 (2)
N1—C2—C1	125.6 (4)	O7'—Cl1—O9'	98.1 (18)
N1—C2—C3	114.1 (4)	O9—Cl1—O10	101.0 (8)
C1—C2—C3	120.3 (4)	O8—Cl1—O10	111.3 (12)
N2—C3—C2	113.6 (3)	O7—Cl1—O10	106.1 (8)
N2—C3—C4	123.8 (4)	H11A—O11—H11B	110.3

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	0.82	1.73	2.525 (5)	161
O5—H5···O1	0.82	2.53	3.046 (4)	122
O5—H5···O11	0.82	2.38	2.984 (9)	131
O6—H6···O3	0.82	2.43	2.897 (4)	117
O6—H6···O1^ii	0.82	2.12	2.885 (4)	154
O11—H11A···O8^iii	0.85	2.11	2.92 (3)	159
O11—H11B···O9^iv	0.85	2.04	2.885 (12)	171

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