μ-Acetato-1:2κ²O:O′-diacetato-1κ²O,O′;2κO-bis(di-2-pyridylamine)-1κ²N,N′;2κ²N,N′-isothiocyanato-2κN-dicopper(II)

In the title dinuclear acetate-bridged complex, [Cu₂(C₂H₃O₂)₃(NCS)(C₁₀H₉N₃)₂], the two Cu atoms are five-coordinated, with a basal plane consisting of two N atoms of a di-2-pyridylamine (dpyam) ligand and two O atoms of two different acetate ligands. The axial positions of these Cu atoms are coordinated to N and O atoms from thio­cyanate and acetate mol­ecules, respectively, leading to a distorted square-pyramidal geometry with τ values of 0.30 and 0.22. Both Cu^II ions are linked by an acetate group in the equatorial–equatorial positions and have syn–anti bridging configurations. Hydrogen-bond inter­actions between the amine H atom and the coordinated and uncoordinated O atoms of the acetate anions generate an infinite one-dimensional chain.

S1. Comment

The coordination chemistry of copper(II) complexes with various carboxylates has been investigated for many years. Carboxylate chemistry is interesting for two reasons. Firstly, carboxylates play a vital role as ligands in biochemical systems involving mono-, di- or polymetallic active sites, and secondly, polynuclear carboxylates are very good probes for exchange-coupling interactions between adjacent metal ions. Carboxylate groups are known to assume different bridging conformations and the important types are syn–syn, anti–anti and syn–anti (Colacio et al., 1993). It may be noted that structurally characterized examples of syn–anti configuration are far less numerous than those with the syn–syn configuration (Sen et al., 1998). We report here the synthesis and crystal structure of a new syn–anti configuration acetate-bridged complex, [Cu₂(dpyam)₂(µ-O₂CCH₃)(O₂CCH₃)₂(NCS)], (I).

The structure of (I) consists of a dinuclear [Cu₂(dpyam)₂(µ-O₂CCH₃)(O₂CCH₃)₂(NCS)] unit. The Cu atoms are bridged unsymmetrically by an acetate group in a syn–anti arrangement (Fig. 1). Atoms Cu1 and Cu2 are five-coordinated, with a basal plane consisting of two N atoms of the dpyam ligand and two O atoms of two different acetate ligands. The axial positions of Cu1 and Cu2 are coordinated by N and O atoms from thiocyanate and acetate molecules, respectively (Table 1), leading to a square-pyramidal geometry. The square bases of the copper chromophores are non-planar, with tetrahedral twists of 25.7 (1) and 43.7 (1)° for Cu1 and Cu2, respectively. The Cu atoms lie above the basal plane, at 0.280 (1) Å towards N7 for Cu1 and 0.112 (1) Å towards O6 for Cu2.

The distortion of a square pyramid can be best described by the structural parameter τ (τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid; Addison et al., 1984), which in this case has values of 0.30 and 0.22 for Cu1 and Cu2, respectively. The copper chromophores can be described as having a distorted square-pyramidal geometry, with a high tetrahedral twist of the square bases. The Cu···Cu distance is 4.800 (3) Å. The dihedral angles between the pyridine rings of the dpyam ligands are 20.9 (1)° for Cu1 and 12.0 (1)° for Cu2. The molecular structure and bridging configuration of (I) are very similar to those of the closely related complexes [Cu(dpyam)(µ-O₂CH)(OH₂)]_n(NO₃)_n (Youngme et al., 2005) and {[Cu(dpa)(µ-O₂CCH₃)](ClO₄)·0.5THF}_n with a single carboxylate bridge (Tanase et al., 2005).

Analysis of the crystal packing of (I) shows hydrogen-bonding interactions between the N—H of the amide and the coordinated and uncoordinated O atoms of the acetate anions, with N—H···O contacts of 2.915 (3) and 2.862 (3) Å. A plot of the hydrogen-bond system forming a one-dimensional structure is given in Fig. 2 and details are given in Table 2. Classical N3—H5···O2ⁱ [symmetry code: (i) -x + 2, -y + 1, -z + 1] and N6—H15···O1ⁱⁱ [symmetry code: (ii) -x + 1, -y + 1, -z] intermolecular hydrogen bonds between adjacent dimeric units link them into a one-dimensional chain. The resulting motifs, A and B, in the formalism of graph-set analysis of hydrogen-bond patterns (Etter et al., 1990), are characterized as R₂²(15) [N3, H5, O2ⁱ, C21ⁱ, O1ⁱ, Cu1ⁱ, N1ⁱ, C5ⁱ, N3ⁱ, H5ⁱ, O2, C21, Cu1, N1 and C5] and R₂²(20) [N6, H15, O1ⁱⁱ, Cu1ⁱⁱ, O3ⁱⁱ, C23ⁱⁱ, O4ⁱⁱ, Cu2ⁱⁱ, N4ⁱⁱ, C15ⁱⁱ, N6ⁱⁱ, H15ⁱⁱ, O1, Cu1, O3, C23, O4, Cu2, N4 and C15], respectively.

Related literature

For related literature, see: Addison et al. (1984); Colacio et al. (1993); Etter et al. (1990); Sen et al. (1998); Sheldrick (2000b); Tanase et al. (2005); Youngme et al. (2005).

S2. Experimental

The title complex was obtained as a by-product in the preparation of [Cu₃(dpyam)₂(µ-NCS)₂(µ-OOCCH₃)₄] by adding Cu(O₂CCH₃)₂.nH₂O (1.5 mmol) to a warm solution of dpyam (1.0 mmol) in dimethylformamide (DMF) (10.0 ml). A solution of NaNCS (1.0 mmol) in DMF (5.0 ml) was then added and the resulting green solution was allowed to evaporate slowly at room temperature. After several days, green crystals of (I) were formed. The crystals were filtered off, washed with mother liquor and dried in air. IR data (KBr, ν, cm^-1): 2084 (vs), 1654 (s), 1589 (s), 1556 (s), 1486 (vs), 1424 (s), 1237 (m), 1160 (m), 1019 (m), 784 (m).

S3. Refinement

H atoms attached to atoms N3 and N6 were located in difference Fourier maps and refined with a DFIX (SHELXTL; Sheldrick, 2000b) restraint of N—H = 0.86 (1) Å. All H atoms attached to C atoms were fixed geometrically and treated as riding, with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl), and with U_iso(H) = 1.2U_eq(aromatic) or 1.5U_eq(methyl).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL (Sheldrick 2000b) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are represented as spheres of arbitrary radii.
	Fig. 2. A view of the packing structure of (I), showing the hydrogen-bonding interactions (dashed lines). The hydrogen-bonded rings A and B are defined in the Comment. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) 2 - x, 1 - y, 1 - z; (ii) 1 - x, 1 - y, -z].

[(Acetato-κ²O,O')(di-2-pyridylamine-κ²N²,N^2')copper(II)]-µ-acetato- κ²O:O'-[(acetato-κO)(di-2-pyridylamine-κ²N²,N^2')(isothiocyanato- κN)copper(II)]

Crystal data

[Cu2(C2H3O2)3(NCS)(C10H9N3)2]	V = 1505.09 (4) Å^3
Mr = 704.70	Z = 2
Triclinic, P1	F(000) = 720
Hall symbol: -P 1	Dx = 1.555 Mg m^−3
a = 9.6949 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4915 (2) Å	θ = 1.3–30.4°
c = 16.9001 (2) Å	µ = 1.54 mm^−1
α = 97.645 (1)°	T = 273 K
β = 101.458 (1)°	Polygon, green
γ = 113.215 (1)°	0.30 × 0.18 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5440 independent reflections
Radiation source: fine-focus sealed tube	4510 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 25.4°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a)	h = −11→11
Tmin = 0.732, Tmax = 0.891	k = −12→8
8178 measured reflections	l = −19→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0423P)^2 + 1.2895P] where P = (Fo^2 + 2Fc^2)/3
5440 reflections	(Δ/σ)max = 0.001
399 parameters	Δρmax = 0.34 e Å^−3
2 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
Cu1	0.65426 (4)	0.43795 (4)	0.31247 (2)	0.02719 (11)
Cu2	0.49437 (5)	0.71429 (4)	0.14258 (2)	0.03208 (12)
S1	0.11020 (11)	0.07683 (10)	0.21812 (7)	0.0524 (3)
O1	0.7660 (2)	0.3883 (2)	0.23370 (13)	0.0326 (5)
O2	0.9782 (3)	0.4853 (3)	0.34124 (14)	0.0432 (6)
O3	0.6492 (3)	0.5871 (2)	0.25150 (13)	0.0344 (5)
O4	0.7010 (3)	0.8018 (2)	0.22820 (13)	0.0344 (5)
O5	0.3752 (3)	0.6718 (3)	0.22647 (15)	0.0406 (6)
O6	0.4062 (4)	0.8763 (3)	0.19568 (17)	0.0546 (7)
N1	0.6402 (3)	0.5470 (3)	0.41686 (15)	0.0289 (6)
N2	0.6877 (3)	0.3020 (3)	0.37880 (16)	0.0309 (6)
N3	0.8092 (3)	0.4802 (3)	0.50463 (16)	0.0316 (6)
N4	0.3479 (3)	0.5391 (3)	0.05710 (16)	0.0321 (6)
N5	0.5758 (3)	0.8142 (3)	0.05899 (16)	0.0302 (6)
N6	0.3664 (3)	0.6495 (3)	−0.05682 (17)	0.0368 (7)
N7	0.4131 (3)	0.2952 (3)	0.25318 (18)	0.0409 (7)
C1	0.5591 (4)	0.6271 (4)	0.4093 (2)	0.0361 (8)
H1	0.4898	0.6104	0.3582	0.043*
C2	0.5748 (5)	0.7317 (4)	0.4736 (2)	0.0443 (9)
H2	0.5165	0.7837	0.4664	0.053*
C3	0.6804 (5)	0.7577 (4)	0.5499 (2)	0.0486 (9)
H3	0.6965	0.8304	0.5938	0.058*
C4	0.7600 (4)	0.6758 (4)	0.5599 (2)	0.0419 (8)
H4	0.8298	0.6914	0.6107	0.050*
C5	0.7346 (4)	0.5671 (3)	0.49191 (19)	0.0287 (7)
C6	0.7732 (4)	0.3457 (3)	0.45805 (19)	0.0284 (7)
C7	0.8302 (4)	0.2590 (4)	0.4971 (2)	0.0386 (8)
H7	0.8892	0.2912	0.5523	0.046*
C8	0.7977 (5)	0.1273 (4)	0.4528 (3)	0.0552 (11)
H8	0.8370	0.0698	0.4774	0.066*
C9	0.7054 (5)	0.0788 (4)	0.3707 (2)	0.0529 (10)
H9	0.6810	−0.0113	0.3398	0.063*
C10	0.6516 (4)	0.1679 (3)	0.3367 (2)	0.0414 (8)
H10	0.5876	0.1352	0.2825	0.050*
C11	0.2836 (4)	0.4185 (4)	0.0848 (2)	0.0384 (8)
H11	0.3168	0.4230	0.1411	0.046*
C12	0.1726 (4)	0.2913 (4)	0.0339 (2)	0.0443 (9)
H12	0.1322	0.2108	0.0549	0.053*
C13	0.1218 (5)	0.2856 (4)	−0.0500 (2)	0.0478 (9)
H13	0.0444	0.2012	−0.0857	0.057*
C14	0.1859 (4)	0.4046 (4)	−0.0804 (2)	0.0425 (8)
H14	0.1532	0.4014	−0.1365	0.051*
C15	0.3021 (4)	0.5317 (3)	−0.02479 (19)	0.0305 (7)
C16	0.4981 (4)	0.7779 (3)	−0.02211 (18)	0.0288 (7)
C17	0.5478 (4)	0.8682 (4)	−0.0755 (2)	0.0367 (8)
H17	0.4918	0.8422	−0.1311	0.044*
C18	0.6791 (4)	0.9945 (4)	−0.0449 (2)	0.0407 (8)
H18	0.7138	1.0550	−0.0795	0.049*
C19	0.7603 (4)	1.0312 (4)	0.0388 (2)	0.0434 (9)
H19	0.8504	1.1162	0.0608	0.052*
C20	0.7057 (4)	0.9410 (4)	0.0879 (2)	0.0393 (8)
H20	0.7597	0.9671	0.1439	0.047*
C21	0.9122 (4)	0.4239 (3)	0.2670 (2)	0.0319 (7)
C22	1.0019 (5)	0.3883 (5)	0.2110 (3)	0.0545 (10)
H22A	1.1090	0.4577	0.2297	0.082*
H22B	0.9572	0.3891	0.1551	0.082*
H22C	0.9963	0.2953	0.2126	0.082*
C23	0.7351 (4)	0.7197 (3)	0.26862 (19)	0.0294 (7)
C24	0.8841 (4)	0.7883 (4)	0.3382 (2)	0.0485 (10)
H24A	0.8607	0.8061	0.3900	0.073*
H24B	0.9524	0.8768	0.3288	0.073*
H24C	0.9343	0.7256	0.3401	0.073*
C25	0.3538 (4)	0.7851 (4)	0.2360 (2)	0.0387 (8)
C26	0.2705 (6)	0.8090 (5)	0.2987 (3)	0.0678 (13)
H26A	0.3458	0.8719	0.3493	0.102*
H26B	0.2090	0.7194	0.3096	0.102*
H26C	0.2035	0.8510	0.2772	0.102*
C27	0.2882 (4)	0.2042 (3)	0.2387 (2)	0.0343 (7)
H5	0.866 (4)	0.497 (4)	0.5537 (13)	0.034 (9)*
H15	0.329 (4)	0.637 (4)	−0.1093 (12)	0.042 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0318 (2)	0.0273 (2)	0.0202 (2)	0.01257 (16)	0.00274 (15)	0.00595 (15)
Cu2	0.0356 (2)	0.0328 (2)	0.0199 (2)	0.00848 (17)	0.00413 (16)	0.00678 (16)
S1	0.0348 (5)	0.0399 (5)	0.0647 (7)	0.0051 (4)	0.0030 (5)	0.0071 (5)
O1	0.0327 (12)	0.0411 (13)	0.0209 (11)	0.0168 (10)	0.0009 (9)	0.0045 (9)
O2	0.0363 (13)	0.0502 (15)	0.0295 (14)	0.0127 (11)	−0.0020 (11)	0.0016 (11)
O3	0.0451 (13)	0.0329 (12)	0.0269 (12)	0.0196 (11)	0.0060 (10)	0.0098 (9)
O4	0.0380 (13)	0.0321 (12)	0.0282 (12)	0.0140 (10)	−0.0002 (10)	0.0098 (9)
O5	0.0509 (15)	0.0411 (14)	0.0349 (13)	0.0212 (12)	0.0165 (11)	0.0139 (11)
O6	0.080 (2)	0.0583 (17)	0.0510 (17)	0.0435 (16)	0.0320 (15)	0.0291 (14)
N1	0.0311 (14)	0.0293 (13)	0.0237 (13)	0.0111 (11)	0.0065 (11)	0.0068 (11)
N2	0.0354 (14)	0.0272 (13)	0.0250 (14)	0.0116 (11)	0.0025 (11)	0.0048 (11)
N3	0.0349 (15)	0.0307 (14)	0.0218 (14)	0.0132 (12)	−0.0024 (12)	0.0012 (11)
N4	0.0341 (14)	0.0337 (14)	0.0265 (14)	0.0138 (12)	0.0064 (11)	0.0065 (11)
N5	0.0296 (14)	0.0337 (14)	0.0230 (13)	0.0112 (12)	0.0037 (11)	0.0065 (11)
N6	0.0381 (16)	0.0397 (16)	0.0181 (14)	0.0071 (13)	−0.0016 (12)	0.0052 (12)
N7	0.0339 (16)	0.0429 (17)	0.0335 (16)	0.0097 (14)	−0.0013 (13)	0.0073 (13)
C1	0.0361 (18)	0.045 (2)	0.0341 (18)	0.0224 (16)	0.0103 (15)	0.0169 (15)
C2	0.058 (2)	0.045 (2)	0.046 (2)	0.0335 (19)	0.0222 (19)	0.0151 (17)
C3	0.068 (3)	0.042 (2)	0.037 (2)	0.026 (2)	0.0155 (19)	0.0039 (16)
C4	0.055 (2)	0.0406 (19)	0.0245 (17)	0.0196 (17)	0.0046 (16)	0.0026 (14)
C5	0.0321 (16)	0.0277 (16)	0.0236 (16)	0.0103 (13)	0.0073 (13)	0.0064 (12)
C6	0.0295 (16)	0.0296 (16)	0.0253 (16)	0.0126 (13)	0.0053 (13)	0.0078 (13)
C7	0.045 (2)	0.0383 (19)	0.0296 (18)	0.0195 (16)	−0.0006 (15)	0.0090 (14)
C8	0.070 (3)	0.044 (2)	0.054 (3)	0.034 (2)	0.000 (2)	0.0138 (19)
C9	0.074 (3)	0.036 (2)	0.041 (2)	0.027 (2)	−0.001 (2)	0.0024 (16)
C10	0.055 (2)	0.0267 (17)	0.0316 (19)	0.0135 (16)	0.0015 (16)	0.0030 (14)
C11	0.043 (2)	0.0360 (18)	0.0357 (19)	0.0161 (16)	0.0093 (16)	0.0143 (15)
C12	0.047 (2)	0.0331 (19)	0.051 (2)	0.0133 (16)	0.0177 (18)	0.0123 (16)
C13	0.044 (2)	0.0352 (19)	0.047 (2)	0.0076 (16)	0.0071 (18)	−0.0046 (16)
C14	0.044 (2)	0.040 (2)	0.0291 (18)	0.0123 (17)	0.0005 (16)	−0.0018 (15)
C15	0.0316 (17)	0.0344 (17)	0.0235 (16)	0.0141 (14)	0.0053 (13)	0.0042 (13)
C16	0.0292 (16)	0.0361 (17)	0.0214 (15)	0.0164 (14)	0.0031 (13)	0.0060 (13)
C17	0.0415 (19)	0.047 (2)	0.0233 (17)	0.0202 (16)	0.0069 (14)	0.0128 (14)
C18	0.045 (2)	0.045 (2)	0.038 (2)	0.0187 (17)	0.0159 (16)	0.0215 (16)
C19	0.041 (2)	0.0381 (19)	0.042 (2)	0.0081 (16)	0.0065 (16)	0.0146 (16)
C20	0.0340 (18)	0.0404 (19)	0.0299 (18)	0.0073 (15)	−0.0006 (14)	0.0071 (15)
C21	0.0349 (18)	0.0288 (16)	0.0296 (18)	0.0145 (14)	0.0036 (14)	0.0049 (13)
C22	0.046 (2)	0.064 (3)	0.050 (2)	0.025 (2)	0.0117 (19)	−0.002 (2)
C23	0.0313 (16)	0.0365 (18)	0.0240 (16)	0.0169 (14)	0.0091 (13)	0.0095 (13)
C24	0.0320 (19)	0.053 (2)	0.051 (2)	0.0122 (17)	−0.0021 (17)	0.0221 (19)
C25	0.0403 (19)	0.053 (2)	0.0294 (18)	0.0251 (17)	0.0107 (15)	0.0132 (16)
C26	0.085 (3)	0.082 (3)	0.073 (3)	0.056 (3)	0.049 (3)	0.032 (3)
C27	0.0353 (19)	0.0348 (18)	0.0282 (17)	0.0144 (16)	0.0011 (14)	0.0060 (14)

Geometric parameters (Å, º)

Cu1—O3	1.996 (2)	C4—C5	1.414 (4)
Cu1—N2	2.011 (3)	C4—H4	0.9300
Cu1—O1	2.013 (2)	C6—C7	1.406 (4)
Cu1—N1	2.030 (3)	C7—C8	1.363 (5)
Cu1—N7	2.150 (3)	C7—H7	0.9300
Cu2—N4	1.976 (3)	C8—C9	1.395 (6)
Cu2—N5	1.976 (3)	C8—H8	0.9300
Cu2—O5	1.989 (2)	C9—C10	1.372 (5)
Cu2—O4	1.999 (2)	C9—H9	0.9300
Cu2—O6	2.339 (3)	C10—H10	0.9300
S1—C27	1.645 (3)	C11—C12	1.370 (5)
O1—C21	1.295 (4)	C11—H11	0.9300
O2—C21	1.240 (4)	C12—C13	1.391 (5)
O3—C23	1.264 (4)	C12—H12	0.9300
O4—C23	1.268 (4)	C13—C14	1.377 (5)
O5—C25	1.280 (4)	C13—H13	0.9300
O6—C25	1.250 (4)	C14—C15	1.412 (4)
N1—C5	1.344 (4)	C14—H14	0.9300
N1—C1	1.360 (4)	C16—C17	1.409 (4)
N2—C6	1.337 (4)	C17—C18	1.367 (5)
N2—C10	1.362 (4)	C17—H17	0.9300
N3—C5	1.382 (4)	C18—C19	1.394 (5)
N3—C6	1.393 (4)	C18—H18	0.9300
N3—H5	0.852 (18)	C19—C20	1.362 (5)
N4—C15	1.349 (4)	C19—H19	0.9300
N4—C11	1.364 (4)	C20—H20	0.9300
N5—C16	1.348 (4)	C21—C22	1.510 (5)
N5—C20	1.362 (4)	C22—H22A	0.9600
N6—C15	1.383 (4)	C22—H22B	0.9600
N6—C16	1.387 (4)	C22—H22C	0.9600
N6—H15	0.860 (18)	C23—C24	1.506 (5)
N7—C27	1.160 (4)	C24—H24A	0.9600
C1—C2	1.377 (5)	C24—H24B	0.9600
C1—H1	0.9300	C24—H24C	0.9600
C2—C3	1.395 (5)	C25—C26	1.507 (5)
C2—H2	0.9300	C26—H26A	0.9600
C3—C4	1.369 (5)	C26—H26B	0.9600
C3—H3	0.9300	C26—H26C	0.9600
O3—Cu1—N2	173.03 (10)	C7—C8—H8	120.1
O3—Cu1—O1	86.58 (9)	C9—C8—H8	120.1
N2—Cu1—O1	90.75 (10)	C10—C9—C8	118.1 (3)
O3—Cu1—N1	91.91 (10)	C10—C9—H9	121.0
N2—Cu1—N1	87.77 (10)	C8—C9—H9	121.0
O1—Cu1—N1	154.89 (10)	N2—C10—C9	123.0 (3)
O3—Cu1—N7	93.57 (11)	N2—C10—H10	118.5
N2—Cu1—N7	93.31 (11)	C9—C10—H10	118.5
O1—Cu1—N7	103.31 (10)	N4—C11—C12	123.2 (3)
N1—Cu1—N7	101.80 (11)	N4—C11—H11	118.4
N4—Cu2—N5	92.41 (11)	C12—C11—H11	118.4
N4—Cu2—O5	95.05 (11)	C11—C12—C13	118.2 (3)
N5—Cu2—O5	156.16 (11)	C11—C12—H12	120.9
N4—Cu2—O4	142.76 (10)	C13—C12—H12	120.9
N5—Cu2—O4	94.46 (10)	C14—C13—C12	120.1 (3)
O5—Cu2—O4	93.21 (10)	C14—C13—H13	119.9
N4—Cu2—O6	120.17 (11)	C12—C13—H13	119.9
N5—Cu2—O6	96.50 (10)	C13—C14—C15	118.8 (3)
O5—Cu2—O6	60.28 (9)	C13—C14—H14	120.6
O4—Cu2—O6	95.34 (10)	C15—C14—H14	120.6
C21—O1—Cu1	114.53 (19)	N4—C15—N6	120.9 (3)
C23—O3—Cu1	131.0 (2)	N4—C15—C14	121.3 (3)
C23—O4—Cu2	116.6 (2)	N6—C15—C14	117.8 (3)
C25—O5—Cu2	97.3 (2)	N5—C16—N6	121.5 (3)
C25—O6—Cu2	82.2 (2)	N5—C16—C17	121.4 (3)
C5—N1—C1	118.1 (3)	N6—C16—C17	117.1 (3)
C5—N1—Cu1	121.4 (2)	C18—C17—C16	119.5 (3)
C1—N1—Cu1	118.9 (2)	C18—C17—H17	120.3
C6—N2—C10	118.2 (3)	C16—C17—H17	120.3
C6—N2—Cu1	122.3 (2)	C17—C18—C19	119.1 (3)
C10—N2—Cu1	117.8 (2)	C17—C18—H18	120.5
C5—N3—C6	129.1 (3)	C19—C18—H18	120.5
C5—N3—H5	116 (2)	C20—C19—C18	119.1 (3)
C6—N3—H5	112 (2)	C20—C19—H19	120.5
C15—N4—C11	118.3 (3)	C18—C19—H19	120.5
C15—N4—Cu2	125.2 (2)	N5—C20—C19	123.1 (3)
C11—N4—Cu2	116.4 (2)	N5—C20—H20	118.4
C16—N5—C20	117.9 (3)	C19—C20—H20	118.4
C16—N5—Cu2	124.2 (2)	O2—C21—O1	122.6 (3)
C20—N5—Cu2	117.0 (2)	O2—C21—C22	120.5 (3)
C15—N6—C16	130.8 (3)	O1—C21—C22	116.9 (3)
C15—N6—H15	115 (2)	C21—C22—H22A	109.5
C16—N6—H15	113 (2)	C21—C22—H22B	109.5
C27—N7—Cu1	162.6 (3)	H22A—C22—H22B	109.5
N1—C1—C2	123.1 (3)	C21—C22—H22C	109.5
N1—C1—H1	118.4	H22A—C22—H22C	109.5
C2—C1—H1	118.4	H22B—C22—H22C	109.5
C1—C2—C3	118.3 (3)	O3—C23—O4	122.0 (3)
C1—C2—H2	120.8	O3—C23—C24	121.4 (3)
C3—C2—H2	120.8	O4—C23—C24	116.6 (3)
C4—C3—C2	119.7 (3)	C23—C24—H24A	109.5
C4—C3—H3	120.1	C23—C24—H24B	109.5
C2—C3—H3	120.1	H24A—C24—H24B	109.5
C3—C4—C5	118.9 (3)	C23—C24—H24C	109.5
C3—C4—H4	120.5	H24A—C24—H24C	109.5
C5—C4—H4	120.5	H24B—C24—H24C	109.5
N1—C5—N3	120.3 (3)	O6—C25—O5	120.2 (3)
N1—C5—C4	121.6 (3)	O6—C25—C26	120.9 (3)
N3—C5—C4	118.1 (3)	O5—C25—C26	118.8 (3)
N2—C6—N3	120.5 (3)	C25—C26—H26A	109.5
N2—C6—C7	121.7 (3)	C25—C26—H26B	109.5
N3—C6—C7	117.8 (3)	H26A—C26—H26B	109.5
C8—C7—C6	119.1 (3)	C25—C26—H26C	109.5
C8—C7—H7	120.5	H26A—C26—H26C	109.5
C6—C7—H7	120.5	H26B—C26—H26C	109.5
C7—C8—C9	119.8 (3)	N7—C27—S1	179.2 (3)
O3—Cu1—O1—C21	109.1 (2)	C1—N1—C5—N3	174.5 (3)
N2—Cu1—O1—C21	−64.5 (2)	Cu1—N1—C5—N3	−19.9 (4)
N1—Cu1—O1—C21	21.9 (4)	C1—N1—C5—C4	−5.2 (5)
N7—Cu1—O1—C21	−158.1 (2)	Cu1—N1—C5—C4	160.5 (3)
O1—Cu1—O3—C23	−99.2 (3)	C6—N3—C5—N1	−19.5 (5)
N1—Cu1—O3—C23	55.7 (3)	C6—N3—C5—C4	160.1 (3)
N7—Cu1—O3—C23	157.7 (3)	C3—C4—C5—N1	3.3 (5)
N4—Cu2—O4—C23	−38.1 (3)	C3—C4—C5—N3	−176.3 (3)
N5—Cu2—O4—C23	−138.0 (2)	C10—N2—C6—N3	−178.0 (3)
O5—Cu2—O4—C23	64.6 (2)	Cu1—N2—C6—N3	16.9 (4)
O6—Cu2—O4—C23	125.0 (2)	C10—N2—C6—C7	2.2 (5)
N4—Cu2—O5—C25	−122.1 (2)	Cu1—N2—C6—C7	−162.9 (3)
N5—Cu2—O5—C25	−14.3 (4)	C5—N3—C6—N2	21.5 (5)
O4—Cu2—O5—C25	94.3 (2)	C5—N3—C6—C7	−158.7 (3)
O6—Cu2—O5—C25	0.0 (2)	N2—C6—C7—C8	0.2 (5)
N4—Cu2—O6—C25	77.6 (2)	N3—C6—C7—C8	−179.6 (4)
N5—Cu2—O6—C25	174.2 (2)	C6—C7—C8—C9	−1.8 (6)
O5—Cu2—O6—C25	0.0 (2)	C7—C8—C9—C10	0.8 (7)
O4—Cu2—O6—C25	−90.6 (2)	C6—N2—C10—C9	−3.3 (6)
O3—Cu1—N1—C5	−133.4 (2)	Cu1—N2—C10—C9	162.6 (3)
N2—Cu1—N1—C5	39.6 (2)	C8—C9—C10—N2	1.8 (7)
O1—Cu1—N1—C5	−47.4 (4)	C15—N4—C11—C12	−1.4 (5)
N7—Cu1—N1—C5	132.5 (2)	Cu2—N4—C11—C12	175.6 (3)
O3—Cu1—N1—C1	32.1 (2)	N4—C11—C12—C13	−0.8 (6)
N2—Cu1—N1—C1	−154.8 (2)	C11—C12—C13—C14	1.8 (6)
O1—Cu1—N1—C1	118.1 (3)	C12—C13—C14—C15	−0.6 (6)
N7—Cu1—N1—C1	−61.9 (3)	C11—N4—C15—N6	−178.2 (3)
O1—Cu1—N2—C6	116.8 (3)	Cu2—N4—C15—N6	5.1 (4)
N1—Cu1—N2—C6	−38.1 (3)	C11—N4—C15—C14	2.6 (5)
N7—Cu1—N2—C6	−139.8 (3)	Cu2—N4—C15—C14	−174.0 (3)
O1—Cu1—N2—C10	−48.4 (3)	C16—N6—C15—N4	13.8 (5)
N1—Cu1—N2—C10	156.7 (3)	C16—N6—C15—C14	−167.0 (3)
N7—Cu1—N2—C10	55.0 (3)	C13—C14—C15—N4	−1.6 (5)
N5—Cu2—N4—C15	−18.2 (3)	C13—C14—C15—N6	179.2 (3)
O5—Cu2—N4—C15	139.1 (3)	C20—N5—C16—N6	178.8 (3)
O4—Cu2—N4—C15	−118.8 (3)	Cu2—N5—C16—N6	−12.7 (4)
O6—Cu2—N4—C15	80.7 (3)	C20—N5—C16—C17	−0.7 (5)
N5—Cu2—N4—C11	165.1 (2)	Cu2—N5—C16—C17	167.8 (2)
O5—Cu2—N4—C11	−37.6 (3)	C15—N6—C16—N5	−9.7 (5)
O4—Cu2—N4—C11	64.5 (3)	C15—N6—C16—C17	169.9 (3)
O6—Cu2—N4—C11	−95.9 (2)	N5—C16—C17—C18	1.1 (5)
N4—Cu2—N5—C16	21.9 (3)	N6—C16—C17—C18	−178.5 (3)
O5—Cu2—N5—C16	−86.4 (4)	C16—C17—C18—C19	−0.4 (5)
O4—Cu2—N5—C16	165.2 (3)	C17—C18—C19—C20	−0.6 (6)
O6—Cu2—N5—C16	−98.9 (3)	C16—N5—C20—C19	−0.3 (5)
N4—Cu2—N5—C20	−169.6 (3)	Cu2—N5—C20—C19	−169.6 (3)
O5—Cu2—N5—C20	82.2 (4)	C18—C19—C20—N5	1.0 (6)
O4—Cu2—N5—C20	−26.2 (3)	Cu1—O1—C21—O2	−0.9 (4)
O6—Cu2—N5—C20	69.7 (3)	Cu1—O1—C21—C22	179.5 (3)
O3—Cu1—N7—C27	−159.3 (10)	Cu1—O3—C23—O4	−169.8 (2)
N2—Cu1—N7—C27	21.8 (10)	Cu1—O3—C23—C24	10.4 (5)
O1—Cu1—N7—C27	113.4 (10)	Cu2—O4—C23—O3	5.5 (4)
N1—Cu1—N7—C27	−66.6 (10)	Cu2—O4—C23—C24	−174.8 (2)
C5—N1—C1—C2	3.1 (5)	Cu2—O6—C25—O5	0.0 (3)
Cu1—N1—C1—C2	−162.9 (3)	Cu2—O6—C25—C26	177.5 (4)
N1—C1—C2—C3	0.8 (6)	Cu2—O5—C25—O6	0.0 (4)
C1—C2—C3—C4	−2.7 (6)	Cu2—O5—C25—C26	−177.5 (3)
C2—C3—C4—C5	0.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H5···O2^i	0.85 (2)	2.02 (2)	2.862 (3)	168
N6—H15···O1^ii	0.86 (2)	2.06 (2)	2.915 (3)	178

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