Diacetonitrile-1κN,3κN-bis­{μ-trans-N-[3-(dimethyl­amino)prop­yl]-N′-(2-hydroxy­ethyl)oxamidato(2–)}-1:2κ⁵N,N′,O:O′,N′′;2:3κ⁵O′,N′′:N,N′,O-dithio­cyanato-1κN,3κN-tricopper(II)

The title compound, [Cu₃(C₉H₁₇N₃O₃)₂(NCS)₂(CH₃CN)₂], contains two square-pyramidal Cu^II units chelated by a transoid asymmetrical N-[3-(dimethyl­amino)­propyl]-N′-(2-hy­droxy­ethyl)­oxamidate (dmapheoxd) dianion {H₂dmapheoxd is N-[3-(dimethyl­amino)­propyl]-N′-(2-hydroxy­ethyl)­ox­am­ide}, which coordinates to another Cu^II ion in a square-planar environment lying on a crystallographic inversion center. Thus, the trans-oxamide ligand bridges two Cu^II ions with different coordination numbers, and this is the first instance of such a zero-dimensional oxamide-bridged complex. The activated methyl group in the coordinated acetonitrile mol­ecule is involved in a strong nonclassical C—H...O hydrogen bond, which contributes to a one-dimensional chain extending in the b direction. Considering the presence of weak bonding between the Cu atom and the uncoordinated hydroxyl O atoms, a two-dimensional structure is formed parallel to the ab plane.

S1. Comment

Symmetrical N,N'-bis(substituent)oxamides have been fully studied and are known to be versatile organic ligands which can both chelate and bridge metal ions to construct discrete and extended structures (Bencini et al., 1986; Dominguez-Vera et al., 1996; Real et al., 1994; Sanz et al., 1996). Compared with the large number of complexes bridged by symmetrical N,N'-bis(substituted)oxamides, only 11 complexes bridged by asymmetrical N,N'-bis(substituted)oxamides have been characterized to date by single-crystal X-ray diffraction (Table 3) [Cambridge Structural Database (CSD), Version 5.28; Allen, 2002]. In these complexes, all the asymmetrical ligands contain aromatic structure moieties as terminal groups, while no asymmetrical N,N'-bis(aminoalkyl)oxamide has been found. Taking the above facts into account, we synthesized a novel asymmetrical ligand, N-[3-(dimethylamino)propyl]-N'-(2-hydroxyethyl)oxamide (H₂dmapheoxd), and its tricopper complex, the title compound, [Cu₃(dmapheoxd)₂(MeCN)₂(NCS)₂] (I), and report the crystal structure of the complex here.

The molecular structure of complex (I) is illustrated in Fig. 1. Selected bond lengths and angles are listed in Table 1. Compound (I), a trinuclear Cu^II complex, is formed by two trans-oxamidate-chelated [Cu(dmapheoxd)(MeCN)(NCS)]^- units as ligands coordinating another Cu^II ion (Cu1) sitting on a crystallographic inversion center. The central Cu^II atom (Cu1) is in a square-planar environment, while in the complex ligand the Cu^II ion (Cu2) has a slightly distorted [CuN₄O] square-pyramidal coordination geometry. The basal plane is defined by the atom N4 of the SCN^- ligand and three atoms (O2, N2 and N3) from the dmapheoxd ligand, with a maximum deviation of 0.013 (3) Å for atom O2 from the least-squares plane. The apical position is occupied by atom N5 of a coordinated acetonitrile molecule. In the basal plane, the Cu2—N2(amide) bond [1.972 (6) Å] is shorter than the Cu2—N3(amine) bond [2.052 (9) Å], which is consistent with the stronger donor ability of the deprotonated amide N atom compared with the amine N atom (Jubert et al., 2002). The axial Cu—N bond length [Cu2—N5 = 2.390 (9) Å] is significantly longer than those in the basal plane, from which atom Cu2 is displaced by 0.177 (3) Å towards the apex. The Cu1···Cu2 distance is 5.248 (3) Å.

Although several examples have been observed of cis-oxamide bridging ligands chelating two metal ions with different coordination numbers (Cronin et al., 1999; Sun et al., 2007; Tao, Zang, Cheng et al., 2003), for transoid ligands the metal ions usually have equal ligancy, such as both five or four in general (denoted [5 + 5] or [4 + 4], respectively). Among the reported crystal structures of trans-oxamide bridging complexes, only two two-dimensional complexes have the styles of [4 + 5] (Chen et al., 1998) and [5 + 6] (Chen et al., 1994). The title compound also has the style of [4 + 5], and this is the first instance of this for a zero-dimensional complex with different ligancies. The hydroxyl group in the dmapheoxd ligand acts as a donor of the intramolecular hydrogen bond O1—H1···O3ⁱ [symmetry code: (i) -x, -y, -z; Table 2] and a seven-membered hydrogen-bonding circuit is formed (Fig. 1), folding at C2—O3ⁱ with a dihedral angle of 59.2 (3)°.

The distances C3—N1 [1.307 (9) Å] and C4—N2 [1.275 (9) Å] have typical values for C═N. Whereas the bond lengths of C3—O2 [1.262 (9) Å] and C4—O3 [1.291 (8) Å] are well in accordance with those of (O═)C—O^- fragments in many complexes (Berg et al., 2002; Delgado et al., 2006; Nash & Schaefer, 1969), the oximade fragment is best described as N═ C—O^- rather than delocalized.

The dimethylaminopropyl group in the dmapheoxd ligand is disordered over two positions (C6A–C9A and C6B–C9B), with occupancy factors of 0.55 and 0.45, respectively (Fig. 2). The puckering parameters (Cremer & Pople, 1975) of the corresponding six-membered chelating rings around Cu2 are Q = 0.575 (19) Å, θ = 142.7 (14)° and ϕ = 26 (2)°, and Q = 0.698 (15) Å, θ = 68.5 (10)° and ϕ = 196.5 (11)°, respectively.

In the crystal structure, only one classical hydrogen bond is observed, as noted above (Table 2). For all that, due to the activation of the methyl group by the cyano group of the acetonitrile ligand, the methyl interacts with the O atom of the hydroxyl group of a neighboring molecule, forming a non-classical C—H···O hydrogen bond (Fig. 3), via which a one-dimensional chain extending in the b direction is formed.

Related literature

For related literature, see: Allen (2002); Bencini et al. (1986); Berg et al. (2002); Chen et al. (1994, 1998); Cremer & Pople (1975); Cronin et al. (1999); Delgado et al. (2006); Dominguez-Vera, Gulvez, Colacio, Cuesta, Costes & Laurent (1996); Jubert et al. (2002); Nash & Schaefer (1969); Real et al. (1994); Sanz et al. (1996); Sun et al. (2007); Tao, Zang, Cheng, Wang, Hu, Niu & Liao (2003).

S2. Experimental

All reagents were of AR grade and were used without further purification. The H₂dmapheoxd ligand was synthesized as follows. An ethanol solution (10 ml) of 3-dimethylamino-1-propylamine (1.26 ml, 10 mmol) was added very slowly, via a dropping funnel, to an ethanol solution (10 ml) of diethyl oxalate (1.36 ml, 10 mmol) with continuous stirring. The mixture was stirred quickly for 30 min, and then an ethanol solution (10 ml) containing enthanolamine (0.60 ml) was added dropwise. The reaction solution was kept at room temperature with stirring for 3 h. The resulting solution was concentrated under vacuum and H₂dmapheoxd precipitated as a white powder (yield 78%).

[Cu₃(dmapheoxd)₂(MeCN)₂(NCS)₂] was obtained according to the following procedure. To a solution of H₂dmapheoxd (0.0217 g, 0.1 mmol) in acetonitrile (5 ml) were added successively piperidine (0.2 mmol) and a solution of CuCl₂·2H₂O (0.0256 g, 0.15 mmol) in acetonitrile (5 ml). The mixture was stirred quickly for 30 min, and then an acetonitrile solution (5 ml) containing KSCN (0.0098 g, 0.1 mmol) was added dropwise. The reaction solution was stirred continuously at 333 K for a further 5 h. Green crystals of the title complex suitable for X-ray analysis were obtained from the solution by slow evaporation at room temperature for 7 d (yield 70%). Elemental analysis for C₂₄H₄₀Cu₃N₁₀O₆S₂, calculated: C 35.18, H 4.92, N 17.09%; found: C 35.28, H 4.99, N 17.04%.

S3. Refinement

The hydroxyl H atom was located in a difference Fourier map and treated as riding, with O—H = 0.85 Å and with a fixed U_iso(H) = 0.08 Ų. The remaining H atoms were placed in calculated positions, with C—H distances of 0.96 (methyl) or 0.97 Å (methylene), and refined in riding mode, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The CH₃ groups were allowed to rotate freely around the C—N or C—C bond. Atoms C6, C7, C8 and C9 in the N-[3-(dimethylamino)propyl] moiety appeared to be disordered, and were refined as two parts (occupancy factors 0.55 and 0.45).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dotted lines. Disordered atoms C6B–C9B and C6B^i–C9B^i have been omitted for clarity. [Symmetry code: (i) -x, -y, -z.]
	Fig. 2. The positional disorder of the dimethylaminopropyl group in the dmapheoxd ligand. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 3. The one-dimensional chain extending in the b direction. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x, -y, -z; (ii) -x, -y + 1, -z.]

Diacetonitrile-1κN,3κN-bis{µ-trans-N-[3-(dimethylamino)propyl]-N'- (2-hydroxyethyl)oxamidato(2-)}-1:2κ⁵N,N',O:O',N'';2:3κ⁵O',N'':N,N',O- dithiocyanato-1κN,3κN-tricopper(II)

Crystal data

[Cu3(C9H17N3O3)2(NCS)2(C2H3N)2]	Z = 1
Mr = 819.45	F(000) = 421
Triclinic, P1	Dx = 1.606 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.040 (5) Å	Cell parameters from 1007 reflections
b = 8.262 (6) Å	θ = 2.4–25.2°
c = 17.256 (13) Å	µ = 2.04 mm^−1
α = 91.999 (10)°	T = 298 K
β = 97.831 (10)°	Prism, green
γ = 96.185 (10)°	0.19 × 0.12 × 0.08 mm
V = 847.1 (11) Å^3

Data collection

Bruker APEX area-detector diffractometer	2987 independent reflections
Radiation source: fine-focus sealed tube	1649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ϕ and ω scans	θmax = 25.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −6→7
Tmin = 0.698, Tmax = 0.854	k = −9→9
4458 measured reflections	l = −18→20

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.175	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0826P)^2] where P = (Fo^2 + 2Fc^2)/3
2987 reflections	(Δ/σ)max < 0.001
247 parameters	Δρmax = 0.63 e Å^−3
19 restraints	Δρmin = −0.49 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	0.0000	0.0000	0.0000	0.0445 (4)
Cu2	0.26972 (16)	0.31187 (12)	0.27230 (6)	0.0438 (4)
S1	0.0488 (5)	0.7658 (3)	0.40289 (15)	0.0693 (8)
O1	−0.5675 (10)	0.1578 (7)	−0.0271 (4)	0.0637 (17)
H1	−0.4716	0.1249	−0.0540	0.080*
O2	0.0379 (9)	0.3276 (6)	0.1780 (3)	0.0516 (15)
O3	0.1903 (9)	−0.0347 (6)	0.0983 (3)	0.0455 (14)
N1	−0.0662 (10)	0.1953 (7)	0.0556 (4)	0.0392 (15)
N2	0.3151 (10)	0.1090 (8)	0.2160 (4)	0.0406 (16)
N3	0.4609 (10)	0.2646 (7)	0.3749 (4)	0.0506 (18)
N4	0.1577 (12)	0.4950 (9)	0.3228 (4)	0.0522 (18)
N5	0.5423 (14)	0.4881 (10)	0.2179 (5)	0.071 (2)
C1	−0.4541 (14)	0.2754 (10)	0.0318 (5)	0.053 (2)
H1A	−0.4672	0.2327	0.0829	0.064*
H1B	−0.5293	0.3734	0.0283	0.064*
C2	−0.2050 (13)	0.3211 (9)	0.0260 (5)	0.046 (2)
H2A	−0.1873	0.3376	−0.0283	0.055*
H2B	−0.1528	0.4231	0.0557	0.055*
C3	0.0407 (13)	0.2147 (9)	0.1270 (5)	0.0389 (18)
C4	0.1922 (13)	0.0833 (9)	0.1496 (5)	0.0388 (19)
C5	0.4874 (16)	−0.0004 (11)	0.2370 (5)	0.065 (3)
H5A	0.6241	0.0397	0.2168	0.078*	0.454 (18)
H5B	0.4358	−0.1080	0.2127	0.078*	0.454 (18)
H5C	0.4183	−0.1010	0.2551	0.078*	0.546 (18)
H5D	0.5553	−0.0271	0.1911	0.078*	0.546 (18)
C6A	0.539 (4)	−0.013 (2)	0.3246 (7)	0.058 (7)	0.454 (18)
H6A	0.4014	−0.0491	0.3456	0.070*	0.454 (18)
H6B	0.6437	−0.0927	0.3363	0.070*	0.454 (18)
C6B	0.669 (2)	0.080 (2)	0.3005 (7)	0.056 (6)	0.546 (18)
H6C	0.7901	0.0122	0.3099	0.067*	0.546 (18)
H6D	0.7302	0.1848	0.2841	0.067*	0.546 (18)
C7A	0.638 (3)	0.1507 (19)	0.3619 (18)	0.059 (9)	0.454 (18)
H7A	0.7398	0.2024	0.3289	0.070*	0.454 (18)
H7B	0.7256	0.1348	0.4120	0.070*	0.454 (18)
C7B	0.566 (4)	0.1034 (19)	0.3741 (12)	0.056 (7)	0.546 (18)
H7C	0.6813	0.1037	0.4193	0.067*	0.546 (18)
H7D	0.4516	0.0133	0.3777	0.067*	0.546 (18)
C8A	0.338 (6)	0.201 (4)	0.439 (2)	0.044 (7)	0.454 (18)
H8A	0.2653	0.2871	0.4604	0.066*	0.454 (18)
H8B	0.4422	0.1635	0.4795	0.066*	0.454 (18)
H8C	0.2267	0.1130	0.4184	0.066*	0.454 (18)
C8B	0.301 (5)	0.251 (3)	0.4347 (17)	0.045 (6)	0.546 (18)
H8D	0.3822	0.2340	0.4850	0.067*	0.546 (18)
H8E	0.1869	0.1615	0.4197	0.067*	0.546 (18)
H8F	0.2319	0.3504	0.4377	0.067*	0.546 (18)
C9A	0.585 (3)	0.425 (2)	0.406 (2)	0.039 (7)	0.454 (18)
H9A	0.6854	0.4097	0.4530	0.059*	0.454 (18)
H9B	0.4796	0.4981	0.4185	0.059*	0.454 (18)
H9C	0.6703	0.4716	0.3678	0.059*	0.454 (18)
C9B	0.648 (3)	0.398 (2)	0.400 (2)	0.049 (7)	0.546 (18)
H9D	0.7329	0.3710	0.4483	0.073*	0.546 (18)
H9E	0.5854	0.4983	0.4084	0.073*	0.546 (18)
H9F	0.7439	0.4099	0.3605	0.073*	0.546 (18)
C10	0.1182 (14)	0.6088 (10)	0.3561 (5)	0.047 (2)
C11	0.6791 (16)	0.5777 (11)	0.1996 (5)	0.053 (2)
C12	0.8580 (16)	0.6906 (10)	0.1797 (6)	0.063 (2)
H12A	0.9814	0.6326	0.1696	0.094*
H12B	0.9073	0.7695	0.2224	0.094*
H12C	0.8050	0.7452	0.1337	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0654 (10)	0.0367 (8)	0.0301 (9)	0.0107 (7)	0.0001 (7)	−0.0075 (6)
Cu2	0.0410 (6)	0.0498 (6)	0.0389 (7)	0.0093 (4)	0.0004 (5)	−0.0146 (5)
S1	0.0906 (19)	0.0505 (14)	0.0660 (18)	0.0188 (13)	0.0055 (15)	−0.0176 (12)
O1	0.061 (4)	0.071 (4)	0.056 (4)	0.005 (3)	0.002 (3)	−0.012 (3)
O2	0.052 (4)	0.057 (3)	0.045 (4)	0.022 (3)	−0.004 (3)	−0.022 (3)
O3	0.058 (4)	0.042 (3)	0.036 (3)	0.012 (3)	0.004 (3)	−0.008 (3)
N1	0.045 (4)	0.042 (4)	0.031 (4)	0.011 (3)	0.002 (3)	0.000 (3)
N2	0.039 (4)	0.052 (4)	0.028 (4)	0.010 (3)	−0.007 (3)	−0.007 (3)
N3	0.052 (4)	0.054 (4)	0.045 (5)	0.009 (4)	0.005 (4)	−0.011 (3)
N4	0.056 (5)	0.060 (5)	0.038 (5)	0.008 (4)	0.002 (4)	−0.016 (4)
N5	0.073 (6)	0.069 (5)	0.070 (6)	−0.003 (5)	0.020 (5)	−0.005 (4)
C1	0.059 (6)	0.057 (5)	0.046 (6)	0.017 (4)	0.011 (4)	−0.005 (4)
C2	0.049 (5)	0.040 (4)	0.046 (6)	0.002 (4)	0.003 (4)	−0.006 (4)
C3	0.035 (4)	0.046 (5)	0.036 (5)	0.004 (4)	0.006 (4)	0.001 (4)
C4	0.037 (5)	0.037 (4)	0.043 (5)	0.003 (4)	0.013 (4)	−0.006 (4)
C5	0.089 (7)	0.066 (6)	0.039 (6)	0.036 (6)	−0.009 (5)	−0.018 (5)
C6A	0.065 (15)	0.063 (14)	0.051 (15)	0.034 (12)	0.004 (11)	0.009 (11)
C6B	0.067 (12)	0.078 (13)	0.022 (10)	0.028 (10)	−0.011 (8)	−0.006 (9)
C7A	0.050 (15)	0.066 (17)	0.05 (2)	0.009 (14)	−0.011 (13)	−0.010 (14)
C7B	0.069 (16)	0.047 (11)	0.047 (13)	0.012 (11)	−0.014 (11)	0.002 (11)
C8A	0.056 (15)	0.019 (16)	0.060 (18)	0.015 (11)	0.012 (13)	0.009 (11)
C8B	0.068 (16)	0.029 (15)	0.037 (11)	0.008 (10)	0.001 (10)	0.017 (11)
C9A	0.008 (10)	0.064 (14)	0.044 (13)	0.003 (10)	0.007 (12)	−0.027 (12)
C9B	0.027 (11)	0.071 (13)	0.052 (13)	0.016 (10)	0.013 (12)	−0.011 (10)
C10	0.051 (5)	0.050 (5)	0.035 (5)	0.004 (4)	−0.009 (4)	−0.012 (4)
C11	0.060 (6)	0.057 (5)	0.046 (6)	0.017 (5)	0.008 (5)	0.006 (4)
C12	0.073 (6)	0.050 (5)	0.064 (7)	0.002 (5)	0.008 (5)	0.005 (5)

Geometric parameters (Å, º)

Cu1—N1	1.954 (6)	C5—C6A	1.511 (11)
Cu1—N1^i	1.954 (6)	C5—C6B	1.520 (11)
Cu1—O3	1.964 (5)	C5—H5A	0.9700
Cu1—O3^i	1.964 (5)	C5—H5B	0.9700
Cu2—N2	1.972 (6)	C5—H5C	0.9700
Cu2—N3	2.052 (7)	C5—H5D	0.9700
Cu2—N4	1.948 (7)	C6A—C7A	1.506 (11)
Cu2—N5	2.390 (9)	C6A—H6A	0.9700
Cu2—O2	2.015 (6)	C6A—H6B	0.9700
S1—C10	1.626 (8)	C7A—H7A	0.9700
O1—C1	1.430 (9)	C7A—H7B	0.9700
O1—H1	0.8499	C8A—H8A	0.9600
O2—C3	1.262 (9)	C8A—H8B	0.9600
O3—C4	1.291 (8)	C8A—H8C	0.9600
N1—C3	1.307 (9)	C9A—H9A	0.9600
N1—C2	1.467 (9)	C9A—H9B	0.9600
N2—C4	1.275 (9)	C9A—H9C	0.9600
N2—C5	1.467 (10)	C6B—C7B	1.502 (11)
N3—C7A	1.533 (14)	C6B—H6C	0.9700
N3—C7B	1.537 (13)	C6B—H6D	0.9700
N3—C8A	1.494 (10)	C7B—H7C	0.9700
N3—C8B	1.506 (9)	C7B—H7D	0.9700
N3—C9A	1.500 (10)	C8B—H8D	0.9600
N3—C9B	1.496 (10)	C8B—H8E	0.9600
N4—C10	1.148 (9)	C8B—H8F	0.9600
N5—C11	1.134 (11)	C9B—H9D	0.9600
C1—C2	1.529 (11)	C9B—H9E	0.9600
C1—H1A	0.9700	C9B—H9F	0.9600
C1—H1B	0.9700	C11—C12	1.436 (13)
C2—H2A	0.9700	C12—H12A	0.9600
C2—H2B	0.9700	C12—H12B	0.9600
C3—C4	1.522 (10)	C12—H12C	0.9600
O3—Cu1—O3^i	180	N2—C5—H5D	109.4
N1^i—Cu1—N1	180	C6A—C5—C6B	45.4 (9)
N1^i—Cu1—O3	95.2 (2)	C6A—C5—H5A	109.2
N1—Cu1—O3	84.8 (2)	C6A—C5—H5B	109.2
N1^i—Cu1—O3^i	84.8 (2)	C6A—C5—H5C	67.0
N1—Cu1—O3^i	95.2 (2)	C6A—C5—H5D	137.4
O2—Cu2—N3	169.2 (2)	C6B—C5—H5A	67.3
O2—Cu2—N5	91.4 (3)	C6B—C5—H5B	139.0
N2—Cu2—N3	95.0 (3)	C6B—C5—H5C	109.8
N2—Cu2—N5	97.0 (3)	C6B—C5—H5D	109.2
N2—Cu2—O2	82.7 (2)	H5A—C5—H5B	107.9
N3—Cu2—N5	99.3 (3)	H5A—C5—H5C	138.9
N4—Cu2—N2	167.9 (3)	H5A—C5—H5D	45.3
N4—Cu2—N3	91.5 (3)	H5B—C5—H5C	45.8
N4—Cu2—N5	92.1 (3)	H5B—C5—H5D	65.2
N4—Cu2—O2	89.1 (2)	H5C—C5—H5D	108.1
N4—Cu2—N3	91.5 (3)	C5—C6A—H6A	109.8
C1—O1—H1	108.8	C5—C6A—H6B	109.8
C3—O2—Cu2	111.5 (5)	C7A—C6A—C5	109.5 (18)
C4—O3—Cu1	111.4 (5)	C7A—C6A—H6A	109.8
C2—N1—Cu1	128.6 (5)	C7A—C6A—H6B	109.8
C3—N1—C2	118.6 (6)	C7A—C6A—H5C	146.2
C3—N1—Cu1	112.7 (5)	H5C—C6A—H6A	82.1
C4—N2—C5	118.0 (6)	H5C—C6A—H6B	95.2
C4—N2—Cu2	113.6 (5)	H6A—C6A—H6B	108.2
C5—N2—Cu2	127.9 (5)	N3—C7A—H7A	108.9
C7A—N3—Cu2	112.5 (12)	N3—C7A—H7B	108.9
C7B—N3—Cu2	115.4 (9)	C6A—C7A—N3	113.3 (13)
C8A—N3—C7A	108.3 (8)	C6A—C7A—H7A	108.9
C8A—N3—C7B	87.7 (12)	C6A—C7A—H7B	108.9
C8A—N3—C9A	106 (2)	H7A—C7A—H7B	107.7
C8A—N3—C9B	115 (2)	N3—C8A—H8A	109.5
C8A—N3—Cu2	117.0 (18)	N3—C8A—H8B	109.5
C8B—N3—C7A	127.2 (13)	N3—C8A—H8C	109.5
C8B—N3—C7B	106.5 (7)	N3—C9A—H9A	109.5
C8B—N3—Cu2	105.4 (14)	N3—C9A—H9B	109.5
C9A—N3—C7A	107.1 (8)	N3—C9A—H9C	109.5
C9A—N3—C7B	124.4 (15)	C5—C6B—H6C	110.0
C9A—N3—C8B	96.1 (19)	C5—C6B—H6D	110.0
C9A—N3—Cu2	105.7 (17)	C6B—C7B—N3	110.8 (12)
C9B—N3—C7A	88.7 (12)	C6B—C7B—H7C	109.5
C9B—N3—C7B	107.3 (8)	C6B—C7B—H7D	109.5
C9B—N3—C8B	109.9 (19)	C7B—C6B—C5	108.6 (15)
C9B—N3—Cu2	112.1 (15)	C7B—C6B—H6C	110.0
C10—N4—Cu2	171.7 (7)	C7B—C6B—H6D	110.0
C11—N5—Cu2	173.1 (8)	H6C—C6B—H6D	108.3
O1—C1—C2	114.3 (6)	N3—C7B—H7C	109.5
O1—C1—H1A	108.7	N3—C7B—H7D	109.5
O1—C1—H1B	108.7	H7C—C7B—H7D	108.1
C2—C1—H1A	108.7	N3—C8B—H8D	109.5
C2—C1—H1B	108.7	N3—C8B—H8E	109.5
H1A—C1—H1B	107.6	N3—C8B—H8F	109.5
N1—C2—C1	112.2 (7)	H8D—C8B—H8E	109.5
N1—C2—H2A	109.2	H8D—C8B—H8F	109.5
N1—C2—H2B	109.2	H8E—C8B—H8F	109.5
C1—C2—H2A	109.2	N3—C9B—H9D	109.5
C1—C2—H2B	109.2	N3—C9B—H9E	109.5
H2A—C2—H2B	107.9	N3—C9B—H9F	109.5
O2—C3—N1	129.0 (7)	H9D—C9B—H9E	109.5
O2—C3—C4	116.8 (7)	H9D—C9B—H9F	109.5
N1—C3—C4	114.2 (6)	H9E—C9B—H9F	109.5
O3—C4—C3	116.9 (7)	N4—C10—S1	177.0 (8)
N2—C4—O3	128.0 (7)	N5—C11—C12	177.5 (10)
N2—C4—C3	115.0 (6)	C11—C12—H12A	109.5
N2—C5—C6A	111.8 (9)	C11—C12—H12B	109.5
N2—C5—C6B	110.6 (8)	C11—C12—H12C	109.5
N2—C5—H5A	109.2	H12A—C12—H12B	109.5
N2—C5—H5B	109.2	H12A—C12—H12C	109.5
N2—C5—H5C	109.7	H12B—C12—H12C	109.5
N2—Cu2—O2—C3	−4.9 (5)	C3—N1—C2—C1	−98.3 (8)
N3—Cu2—O2—C3	−82.7 (13)	Cu1—N1—C2—C1	85.7 (8)
N4—Cu2—O2—C3	−175.9 (5)	O1—C1—C2—N1	−77.0 (9)
N5—Cu2—O2—C3	92.0 (5)	Cu2—O2—C3—N1	−171.8 (6)
N1^i—Cu1—O3—C4	177.2 (5)	Cu2—O2—C3—C4	6.7 (8)
N1—Cu1—O3—C4	−2.8 (5)	C2—N1—C3—O2	2.6 (12)
O3—Cu1—N1—C3	1.1 (5)	Cu1—N1—C3—O2	179.2 (7)
O3^i—Cu1—N1—C3	−178.9 (5)	C2—N1—C3—C4	−175.9 (6)
O3—Cu1—N1—C2	177.3 (6)	Cu1—N1—C3—C4	0.7 (8)
O3^i—Cu1—N1—C2	−2.7 (6)	C5—N2—C4—O3	4.2 (12)
N4—Cu2—N2—C4	49.5 (16)	Cu2—N2—C4—O3	177.0 (6)
O2—Cu2—N2—C4	1.8 (5)	C5—N2—C4—C3	−171.7 (7)
N3—Cu2—N2—C4	171.2 (5)	Cu2—N2—C4—C3	1.1 (8)
N5—Cu2—N2—C4	−88.7 (6)	Cu1—O3—C4—N2	−171.9 (7)
N4—Cu2—N2—C5	−138.5 (13)	Cu1—O3—C4—C3	3.9 (8)
O2—Cu2—N2—C5	173.8 (7)	O2—C3—C4—N2	−5.6 (10)
N3—Cu2—N2—C5	−16.8 (7)	N1—C3—C4—N2	173.2 (6)
N5—Cu2—N2—C5	83.3 (7)	O2—C3—C4—O3	178.1 (6)
N4—Cu2—N3—C8A	68.7 (15)	N1—C3—C4—O3	−3.2 (10)
N2—Cu2—N3—C8A	−101.0 (15)	C4—N2—C5—C6A	−152.1 (10)
O2—Cu2—N3—C8A	−24 (2)	Cu2—N2—C5—C6A	36.2 (13)
N5—Cu2—N3—C8A	161.0 (15)	C4—N2—C5—C6B	159.0 (9)
N4—Cu2—N3—C9B	−66.9 (10)	Cu2—N2—C5—C6B	−12.7 (12)
N2—Cu2—N3—C9B	123.4 (10)	N2—C5—C6A—C7A	−63.9 (16)
O2—Cu2—N3—C9B	−159.8 (13)	C6B—C5—C6A—C7A	33.9 (11)
N5—Cu2—N3—C9B	25.5 (10)	C5—C6A—C7A—N3	82 (2)
N4—Cu2—N3—C9A	−48.5 (11)	C8A—N3—C7A—C6A	71 (3)
N2—Cu2—N3—C9A	141.8 (11)	C9B—N3—C7A—C6A	−173 (2)
O2—Cu2—N3—C9A	−141.4 (14)	C9A—N3—C7A—C6A	−176 (3)
N5—Cu2—N3—C9A	43.8 (11)	C8B—N3—C7A—C6A	72 (3)
N4—Cu2—N3—C8B	52.6 (12)	C7B—N3—C7A—C6A	42 (3)
N2—Cu2—N3—C8B	−117.1 (12)	Cu2—N3—C7A—C6A	−60 (2)
O2—Cu2—N3—C8B	−40.3 (18)	N2—C5—C6B—C7B	65.9 (14)
N5—Cu2—N3—C8B	145.0 (12)	C6A—C5—C6B—C7B	−34.9 (11)
N4—Cu2—N3—C7A	−165.0 (8)	C5—C6B—C7B—N3	−86.4 (18)
N2—Cu2—N3—C7A	25.3 (8)	C8A—N3—C7B—C6B	164 (2)
O2—Cu2—N3—C7A	102.0 (14)	C9B—N3—C7B—C6B	−80.6 (19)
N5—Cu2—N3—C7A	−72.7 (8)	C9A—N3—C7B—C6B	−88 (3)
N4—Cu2—N3—C7B	169.8 (8)	C8B—N3—C7B—C6B	162 (2)
N2—Cu2—N3—C7B	0.1 (8)	C7A—N3—C7B—C6B	−43 (3)
O2—Cu2—N3—C7B	76.9 (15)	Cu2—N3—C7B—C6B	45.2 (18)
N5—Cu2—N3—C7B	−97.8 (8)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.85	2.15	2.985 (8)	168
C12—H12C···O1^ii	0.96	2.39	3.320 (11)	163

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