catena-Poly[[aqua­(1,10-phenanthroline-κ²N,N′)copper(II)]-μ-1,3,4-thia­diazol-2,5-diyldithio­diacetato]

In the title one-dimensional coordination polymer, [Cu(tdzdta)(phen)(H₂O)]_n [where tdzdta²⁻ is the 1,3,4-thia­diazole-2,5-diyldithio­diacetate dianion (C₆H₄N₂O₄S₃²⁻) and phen is 1,10-phenanthroline (C₁₂H₈N₂)], the Cu^II atom displays an elongated square-pyramidal coordination geometry with the base capped by one very long semicoordinate Cu—O_{carbox­ylate} bond [2.842 (2) Å]. The Cu^II ions are bridged by tdzdta²⁻ groups, resulting in a one-dimensional chain structure. The intra­chain Cu...Cu separation is 9.112 (4) Å. Furthermore, the chains are linked into a three-dimensional supramolecular network via hydrogen bonds and π–π stacking inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.048
• wR factor = 0.171
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

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Alert level C
PLAT322_ALERT_2_C Check Hybridisation of  S2     in Main Residue .          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

We have studied metal complexes of dicarboxylic acids having two –X—CH₂CO₂H arms (where X is O or S) on a aromatic unit, such as benzenedioxyacetatic acid (Gao et al., 2004a,b) and 4-(carboxymethoxy)phenylsulfanylacetic acid (Gao, Su et al., 2005; Huo et al., 2005). 1,3,4-Thiadiazolyl-2,5-dithioacetic acid (tdzdtaH₂) is also a multidentate flexible aromatic carboxylate having two –S—CH₂CO₂H arms, and it can be considered as an potential candidate for the construction of supramolecular complexes. Recently, we reported the crystal structure of a mononuclear Cu^II complex based on the tdzdtaH⁻ ligand, namely [Cu(tdzdtaH)(C₁₀H₈N₂)₂](tdzdtaH)·2H₂O (Gao, Huo et al., 2005), in which the tdzdtaH⁻ ligand shows monodentate coordination. We have now synthesized the title new one-dimensional chain Cu^II coordination polymer, [Cu((tdzdta)(phen)(H₂O)]_n, (I), and report its crystal structure here.

The Cu^II atom in (I) is coordinated by three carboxyl O atoms from two different tdzdta²⁻ groups, two N donors from the phen ligand and one water molecule, displaying an elongated square-pyramidal coordination geometry, with the base capped by one very long semicoordinate Cu1—O2 bond distance of 2.842 (2) Å (Sieroń et al., 2002) (Fig. 1). Atoms N1, N2, O1 and O3_i [symmetry code: (i) x, −y + 3/2, z + 1/2] define the basal plane [r.m.s. deviation 0.053 (3) Å]. The Cu^II atom is displaced from the mean basal plane by 0.19 (4) Å. Atom O1W occupies the apical site, with the Cu—O1W bond distance being 2.210 (3) Å. Both thioacetate groups are twisted out of the 1,3,4-thiadiazole ring plane, with torsion angles of 64.8 (3)° (C15—S1—C14—C13) and 64.5 (3)° (C16—S2—C17—C18), respectively. This demonstrates their obvious conformational flexibility.

The O1—C13 [1.277 (4) Å] and O3—C18 distances [1.257 (4) Å] are longer than those of O2—C13 [1.228 (4) Å] and O4—C18 [1.225 (4) Å], in agreement with the greater double-bond character of the latter bonds. Each tdzdta²⁻ ligand serves as a bis-monodentate bridging group to link two Cu^II ions, giving rise to a one-dimensional chain structure (Fig. 2). The antiparallel phen ligands lie on alternate sides of the chain. The polymeric chains run along the c axis of the unit cell and show a corrugated arrangement. The shortest adjacent intrachain Cu···Cu distance is 9.112 (4) Å.

The polymeric chains are connected via hydrogen bonds between the carboxylate O atoms and the water molecule (Table 2), leading to a two-dimensional hydrogen-bonding layer architecture along the crystallographic ac plane. Individual layers are stacked in an offset manner through π–π stacking interactions between adjacent phen molecules at 3.432 (3) Å. With the help of the hydrogen-bonding and π–π stacking interactions, a three-dimensional supramolecular network structure is constructed, as shown in Fig. 3.

S2. Experimental

1,3,4-Thiadiazolyl-2,5-dithioacetic acid (tdzdtaH₂) was prepared from 2,5-dimercapto-1,3,4-thiadiazole, using the method for synthesis of benzene-1,4-dioxyacetic acid reported by Liu et al. (2004). The copper complex was obtained from the reaction of copper dinitrate hexahydrate (1.43 g, 5 mmol), 1,10-phenanthroline (1.99 g, 10 mmol) and tdzdtaH₂ (2.66 g, 10 mmol) in water (Volume?), and then the pH was raised to about 6 with 0.2 M sodium hydroxide. The hot solution (heating temperature and time?) was filtered and yielded blue crystals of (I) when left aside for several days. CHN analysis, calculated for C₁₈H₁₄N₄O₅S₃Cu: C 41.10, H 2.68, N 10.65%; found: C 41.13, H 2.71, N 10.69%.

S3. Refinement

C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å and U_iso(H) = 1.2U_eq(C), and were refined in the riding-model approximation. The H atoms of the water molecule were located in a difference Fourier map and refined with O—H and H···H distance restraints of 0.85 (1) and 1.39 (1) Å, respectively, and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); 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 plot of the title complex, with 30% probability displacement ellipsoids. The semicoordinate bond is shown as a dashed line. [Symmetry codes: (i) x, −y + 3/2, z + 1/2; (A) x, −y + 3/2, z − 1/2.]
	Fig. 2. The 1-D chain structure of the title complex. The semicoordinate bond is shown as a dashed line.
	Fig. 3. A packing diagram of the title complex, viewed along the a axis. Hydrogen bonds and the semicoordinate bond are shown as dashed lines (the H atoms on C atoms have been omitted).

catena-Poly[[aqua(1,10-phenanthroline-κ²N,N')copper(II)]- µ-1,3,4-thiadiazol-2,5-diyldithiodiacetato]

Crystal data

[Cu(C6H4N2O4S3)(C12H8N2)(H2O)]	F(000) = 1068
Mr = 526.09	Dx = 1.744 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16825 reflections
a = 7.226 (1) Å	θ = 3.3–27.5°
b = 15.230 (3) Å	µ = 1.44 mm^−1
c = 18.222 (4) Å	T = 295 K
β = 92.19 (3)°	Prism, blue
V = 2003.9 (7) Å^3	0.39 × 0.28 × 0.21 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	4590 independent reflections
Radiation source: fine-focus sealed tube	4016 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −8→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −19→19
Tmin = 0.623, Tmax = 0.737	l = −23→23
17853 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.119P)^2 + 1.1283P] where P = (Fo^2 + 2Fc^2)/3
4590 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.55 e Å^−3
3 restraints	Δρmin = −0.50 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	0.43020 (5)	0.75499 (2)	0.48148 (2)	0.03130 (16)
S1	0.98859 (12)	0.84555 (6)	0.29926 (5)	0.0418 (2)
S2	1.02624 (13)	0.70449 (7)	0.18212 (6)	0.0480 (3)
S3	0.84385 (12)	0.54647 (6)	0.10634 (5)	0.0402 (2)
O1	0.5230 (3)	0.81527 (15)	0.39541 (13)	0.0356 (5)
O1W	0.1509 (4)	0.8140 (3)	0.4827 (2)	0.0795 (12)
H1W1	0.041 (3)	0.801 (5)	0.469 (4)	0.119*
H1W2	0.151 (9)	0.853 (4)	0.516 (3)	0.119*
O2	0.8001 (3)	0.76688 (16)	0.43470 (14)	0.0396 (5)
N1	0.3515 (4)	0.64695 (18)	0.42210 (15)	0.0365 (6)
N2	0.3902 (4)	0.66975 (18)	0.56652 (15)	0.0353 (6)
N3	0.7377 (4)	0.7219 (2)	0.25759 (17)	0.0448 (7)
N4	0.7040 (4)	0.6491 (2)	0.21182 (16)	0.0437 (7)
C1	0.3382 (5)	0.6378 (2)	0.3495 (2)	0.0443 (8)
H1	0.3726	0.6842	0.3198	0.053*
C2	0.2730 (6)	0.5591 (3)	0.3163 (2)	0.0523 (9)
H2	0.2644	0.5543	0.2654	0.063*
C3	0.2223 (6)	0.4898 (3)	0.3596 (3)	0.0523 (9)
H3	0.1778	0.4382	0.3380	0.063*
C4	0.2381 (4)	0.4972 (2)	0.4368 (2)	0.0423 (8)
C5	0.1963 (5)	0.4279 (2)	0.4881 (3)	0.0527 (10)
H5	0.1573	0.3735	0.4702	0.063*
C6	0.2125 (5)	0.4405 (2)	0.5611 (3)	0.0506 (9)
H6	0.1820	0.3951	0.5926	0.061*
C7	0.2762 (5)	0.5228 (2)	0.5915 (2)	0.0422 (8)
C8	0.2988 (5)	0.5409 (3)	0.6678 (2)	0.0514 (9)
H8	0.2684	0.4987	0.7022	0.062*
C9	0.3664 (5)	0.6217 (3)	0.6906 (2)	0.0472 (8)
H9	0.3810	0.6343	0.7404	0.057*
C10	0.4129 (5)	0.6845 (3)	0.63819 (19)	0.0407 (7)
H10	0.4610	0.7382	0.6540	0.049*
C11	0.3234 (4)	0.5908 (2)	0.54331 (19)	0.0355 (6)
C12	0.3032 (4)	0.5781 (2)	0.46514 (19)	0.0367 (7)
C13	0.6996 (4)	0.81329 (19)	0.39506 (16)	0.0310 (6)
C14	0.7788 (5)	0.8793 (2)	0.34144 (18)	0.0362 (7)
H14A	0.8027	0.9340	0.3674	0.043*
H14B	0.6856	0.8910	0.3030	0.043*
C15	0.8990 (5)	0.7557 (2)	0.24900 (19)	0.0354 (7)
C16	0.8412 (4)	0.6322 (2)	0.17009 (17)	0.0346 (6)
C17	0.6030 (5)	0.5183 (2)	0.10691 (19)	0.0371 (7)
H17A	0.5833	0.4659	0.0774	0.045*
H17B	0.5724	0.5038	0.1569	0.045*
C18	0.4682 (5)	0.5897 (2)	0.07819 (17)	0.0350 (6)
O3	0.5378 (3)	0.65280 (16)	0.04436 (14)	0.0413 (5)
O4	0.3041 (4)	0.5791 (2)	0.0903 (2)	0.0687 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0306 (2)	0.0283 (2)	0.0353 (2)	−0.00449 (13)	0.00505 (17)	−0.00281 (13)
S1	0.0356 (4)	0.0480 (5)	0.0425 (4)	−0.0129 (3)	0.0104 (3)	−0.0094 (3)
S2	0.0381 (4)	0.0500 (5)	0.0571 (5)	−0.0089 (4)	0.0159 (4)	−0.0156 (4)
S3	0.0387 (4)	0.0324 (4)	0.0494 (5)	0.0061 (3)	0.0004 (3)	−0.0051 (3)
O1	0.0316 (10)	0.0327 (11)	0.0429 (11)	−0.0030 (9)	0.0068 (9)	0.0006 (9)
O1W	0.0313 (13)	0.120 (3)	0.086 (2)	0.0195 (17)	−0.0125 (14)	−0.056 (2)
O2	0.0362 (12)	0.0376 (12)	0.0451 (13)	0.0023 (10)	0.0049 (10)	0.0035 (10)
N1	0.0325 (13)	0.0344 (13)	0.0428 (14)	−0.0022 (11)	0.0021 (11)	−0.0040 (11)
N2	0.0342 (13)	0.0328 (13)	0.0392 (13)	−0.0005 (10)	0.0068 (11)	0.0004 (11)
N3	0.0414 (16)	0.0535 (18)	0.0401 (15)	−0.0093 (14)	0.0094 (12)	−0.0110 (13)
N4	0.0426 (15)	0.0476 (17)	0.0413 (14)	−0.0133 (13)	0.0054 (12)	−0.0077 (13)
C1	0.0473 (19)	0.0398 (18)	0.0459 (18)	−0.0012 (15)	0.0001 (15)	−0.0048 (15)
C2	0.052 (2)	0.052 (2)	0.053 (2)	0.0065 (17)	−0.0026 (17)	−0.0147 (17)
C3	0.0431 (19)	0.0413 (19)	0.072 (2)	0.0004 (16)	−0.0031 (18)	−0.0224 (18)
C4	0.0290 (14)	0.0302 (16)	0.068 (2)	−0.0006 (12)	0.0024 (14)	−0.0064 (15)
C5	0.0366 (17)	0.0278 (16)	0.094 (3)	−0.0050 (13)	0.0083 (19)	−0.0056 (18)
C6	0.0403 (18)	0.0311 (17)	0.081 (3)	0.0018 (14)	0.0143 (18)	0.0124 (17)
C7	0.0296 (15)	0.0362 (17)	0.061 (2)	0.0032 (12)	0.0104 (14)	0.0107 (15)
C8	0.0429 (19)	0.053 (2)	0.059 (2)	0.0076 (16)	0.0130 (17)	0.0213 (18)
C9	0.0370 (17)	0.061 (2)	0.0445 (18)	0.0083 (16)	0.0073 (14)	0.0096 (16)
C10	0.0350 (16)	0.0476 (19)	0.0396 (16)	0.0030 (14)	0.0039 (13)	0.0024 (14)
C11	0.0266 (13)	0.0296 (15)	0.0507 (17)	0.0026 (11)	0.0068 (12)	0.0046 (13)
C12	0.0262 (13)	0.0295 (15)	0.0546 (19)	0.0006 (12)	0.0055 (13)	−0.0018 (13)
C13	0.0332 (14)	0.0245 (13)	0.0357 (14)	−0.0024 (11)	0.0069 (11)	−0.0041 (11)
C14	0.0381 (16)	0.0295 (15)	0.0413 (15)	−0.0053 (12)	0.0082 (13)	−0.0003 (12)
C15	0.0336 (16)	0.0388 (17)	0.0341 (15)	−0.0031 (12)	0.0056 (13)	−0.0005 (12)
C16	0.0330 (14)	0.0333 (15)	0.0377 (14)	−0.0002 (12)	0.0015 (12)	0.0014 (12)
C17	0.0409 (16)	0.0262 (14)	0.0438 (16)	−0.0008 (12)	−0.0045 (13)	0.0006 (12)
C18	0.0377 (15)	0.0286 (14)	0.0386 (15)	−0.0005 (12)	0.0018 (12)	0.0012 (12)
O3	0.0364 (12)	0.0379 (12)	0.0496 (13)	0.0032 (10)	0.0030 (10)	0.0143 (10)
O4	0.0409 (14)	0.0585 (18)	0.107 (3)	−0.0028 (13)	0.0105 (16)	0.0342 (18)

Geometric parameters (Å, º)

Cu1—O3^i	1.955 (2)	C1—H1	0.9300
Cu1—O1	1.958 (2)	C2—C3	1.376 (6)
Cu1—O2	2.842 (2)	C2—H2	0.9300
Cu1—N1	2.038 (3)	C3—C4	1.412 (6)
Cu1—N2	2.051 (3)	C3—H3	0.9300
Cu1—O1W	2.210 (3)	C4—C12	1.410 (5)
O1—C13	1.277 (4)	C4—C5	1.450 (6)
O2—C13	1.228 (4)	C5—C6	1.345 (7)
C18—O4	1.225 (4)	C5—H5	0.9300
C18—O3	1.257 (4)	C6—C7	1.439 (6)
S1—C15	1.756 (3)	C6—H6	0.9300
S1—C14	1.801 (3)	C7—C11	1.409 (5)
S2—C15	1.739 (4)	C7—C8	1.420 (6)
S2—C16	1.739 (3)	C8—C9	1.382 (6)
S3—C16	1.748 (3)	C8—H8	0.9300
S3—C17	1.793 (4)	C9—C10	1.402 (5)
O1W—H1W1	0.85 (3)	C9—H9	0.9300
O1W—H1W2	0.85 (6)	C10—H10	0.9300
N1—C1	1.330 (5)	C11—C12	1.440 (5)
N1—C12	1.363 (4)	C13—C14	1.529 (4)
N2—C10	1.329 (4)	C14—H14A	0.9700
N2—C11	1.357 (4)	C14—H14B	0.9700
N3—C15	1.289 (5)	C17—C18	1.539 (4)
N3—N4	1.403 (4)	C17—H17A	0.9700
N4—C16	1.298 (4)	C17—H17B	0.9700
C1—C2	1.415 (5)	O3—Cu1^ii	1.955 (2)
O3^i—Cu1—O1	89.54 (10)	C5—C6—H6	119.3
O3^i—Cu1—N1	171.01 (11)	C7—C6—H6	119.3
O1—Cu1—N1	92.89 (11)	C11—C7—C8	116.5 (3)
O3^i—Cu1—N2	94.37 (11)	C11—C7—C6	118.8 (4)
O1—Cu1—N2	164.76 (10)	C8—C7—C6	124.7 (3)
N1—Cu1—N2	81.12 (12)	C9—C8—C7	119.6 (3)
O3^i—Cu1—O1W	92.59 (12)	C9—C8—H8	120.2
O1—Cu1—O1W	99.11 (15)	C7—C8—H8	120.2
N1—Cu1—O1W	95.57 (13)	C8—C9—C10	119.6 (4)
N2—Cu1—O1W	95.42 (16)	C8—C9—H9	120.2
O2—Cu1—O1	51.39 (11)	C10—C9—H9	120.2
O2—Cu1—O1W	147.86 (12)	N2—C10—C9	122.0 (4)
O2—Cu1—N1	97.97 (10)	N2—C10—H10	119.0
O2—Cu1—N2	115.36 (10)	C9—C10—H10	119.0
O2—Cu1—O3^i	76.89 (11)	N2—C11—C7	123.3 (3)
C15—S1—C14	98.37 (16)	N2—C11—C12	116.7 (3)
C15—S2—C16	87.02 (16)	C7—C11—C12	120.0 (3)
C16—S3—C17	98.02 (15)	N1—C12—C4	123.4 (3)
C13—O1—Cu1	111.5 (2)	N1—C12—C11	116.6 (3)
Cu1—O1W—H1W1	139 (5)	C4—C12—C11	120.0 (3)
Cu1—O1W—H1W2	108 (4)	O2—C13—O1	125.4 (3)
H1W1—O1W—H1W2	111 (7)	O2—C13—C14	121.8 (3)
C1—N1—C12	118.7 (3)	O1—C13—C14	112.7 (3)
C1—N1—Cu1	128.4 (2)	C13—C14—S1	115.3 (2)
C12—N1—Cu1	112.8 (2)	C13—C14—H14A	108.5
C10—N2—C11	119.0 (3)	S1—C14—H14A	108.5
C10—N2—Cu1	128.3 (2)	C13—C14—H14B	108.5
C11—N2—Cu1	112.6 (2)	S1—C14—H14B	108.5
C15—N3—N4	112.4 (3)	H14A—C14—H14B	107.5
C16—N4—N3	112.7 (3)	N3—C15—S2	114.2 (3)
N1—C1—C2	121.7 (4)	N3—C15—S1	124.4 (3)
N1—C1—H1	119.2	S2—C15—S1	121.4 (2)
C2—C1—H1	119.2	N4—C16—S2	113.7 (3)
C3—C2—C1	119.7 (4)	N4—C16—S3	124.4 (3)
C3—C2—H2	120.1	S2—C16—S3	121.90 (19)
C1—C2—H2	120.1	C18—C17—S3	115.5 (2)
C2—C3—C4	119.8 (3)	C18—C17—H17A	108.4
C2—C3—H3	120.1	S3—C17—H17A	108.4
C4—C3—H3	120.1	C18—C17—H17B	108.4
C12—C4—C3	116.6 (3)	S3—C17—H17B	108.4
C12—C4—C5	118.3 (4)	H17A—C17—H17B	107.5
C3—C4—C5	125.1 (3)	O4—C18—O3	126.8 (3)
C6—C5—C4	121.5 (3)	O4—C18—C17	116.7 (3)
C6—C5—H5	119.3	O3—C18—C17	116.5 (3)
C4—C5—H5	119.3	C18—O3—Cu1^ii	132.7 (2)
C5—C6—C7	121.3 (3)
C15—S1—C14—C13	64.8 (3)	Cu1—N2—C11—C7	−176.8 (2)
C16—S3—C17—C18	64.5 (3)	C10—N2—C11—C12	−179.5 (3)
O3^i—Cu1—O1—C13	67.7 (2)	Cu1—N2—C11—C12	3.7 (3)
N1—Cu1—O1—C13	−103.6 (2)	C8—C7—C11—N2	1.0 (5)
N2—Cu1—O1—C13	−37.4 (5)	C6—C7—C11—N2	−177.9 (3)
O1W—Cu1—O1—C13	160.3 (2)	C8—C7—C11—C12	−179.5 (3)
O1—Cu1—N1—C1	−12.3 (3)	C6—C7—C11—C12	1.6 (5)
N2—Cu1—N1—C1	−178.2 (3)	C1—N1—C12—C4	−0.5 (5)
O1W—Cu1—N1—C1	87.1 (3)	Cu1—N1—C12—C4	177.8 (2)
O1—Cu1—N1—C12	169.6 (2)	C1—N1—C12—C11	178.9 (3)
N2—Cu1—N1—C12	3.7 (2)	Cu1—N1—C12—C11	−2.8 (3)
O1W—Cu1—N1—C12	−91.0 (2)	C3—C4—C12—N1	−0.6 (5)
O3^i—Cu1—N2—C10	7.4 (3)	C5—C4—C12—N1	178.2 (3)
O1—Cu1—N2—C10	111.8 (4)	C3—C4—C12—C11	−179.9 (3)
N1—Cu1—N2—C10	179.5 (3)	C5—C4—C12—C11	−1.1 (5)
O1W—Cu1—N2—C10	−85.7 (3)	N2—C11—C12—N1	−0.6 (4)
O3^i—Cu1—N2—C11	−176.2 (2)	C7—C11—C12—N1	179.9 (3)
O1—Cu1—N2—C11	−71.7 (5)	N2—C11—C12—C4	178.7 (3)
N1—Cu1—N2—C11	−4.0 (2)	C7—C11—C12—C4	−0.7 (5)
O1W—Cu1—N2—C11	90.8 (2)	Cu1—O1—C13—O2	12.7 (4)
C15—N3—N4—C16	−0.8 (5)	Cu1—O1—C13—C14	−164.55 (19)
C12—N1—C1—C2	0.9 (5)	O2—C13—C14—S1	35.4 (4)
Cu1—N1—C1—C2	−177.1 (3)	O1—C13—C14—S1	−147.3 (2)
N1—C1—C2—C3	−0.3 (6)	N4—N3—C15—S2	1.7 (4)
C1—C2—C3—C4	−0.9 (6)	N4—N3—C15—S1	−178.2 (3)
C2—C3—C4—C12	1.3 (5)	C16—S2—C15—N3	−1.6 (3)
C2—C3—C4—C5	−177.5 (4)	C16—S2—C15—S1	178.3 (2)
C12—C4—C5—C6	2.2 (5)	C14—S1—C15—N3	−11.6 (4)
C3—C4—C5—C6	−179.1 (4)	C14—S1—C15—S2	168.5 (2)
C4—C5—C6—C7	−1.4 (6)	N3—N4—C16—S2	−0.4 (4)
C5—C6—C7—C11	−0.5 (5)	N3—N4—C16—S3	−179.6 (3)
C5—C6—C7—C8	−179.3 (4)	C15—S2—C16—N4	1.1 (3)
C11—C7—C8—C9	−0.8 (5)	C15—S2—C16—S3	−179.7 (2)
C6—C7—C8—C9	178.1 (3)	C17—S3—C16—N4	12.3 (3)
C7—C8—C9—C10	−0.4 (5)	C17—S3—C16—S2	−166.9 (2)
C11—N2—C10—C9	−1.3 (5)	S3—C17—C18—O4	−167.0 (3)
Cu1—N2—C10—C9	175.0 (2)	S3—C17—C18—O3	13.4 (4)
C8—C9—C10—N2	1.5 (5)	O4—C18—O3—Cu1^ii	−14.0 (6)
C10—N2—C11—C7	0.0 (5)	C17—C18—O3—Cu1^ii	165.6 (2)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2^iii	0.85 (3)	1.90 (4)	2.745 (4)	176 (6)
O1W—H1W2···O4^i	0.85 (6)	2.00 (4)	2.749 (5)	146 (6)

Symmetry codes: (i) x, −y+3/2, z+1/2; (iii) x−1, y, z.