Poly[diaqua­bis­([mu]-4,4'-bipyridine-[kappa]²N:N')bis­(ethane-1,2-diol)di-[mu]-sulfato-dicopper(II)]

The title compound, [Cu₂(SO₄)₂(C₁₀H₈N₂)₂(C₂H₆O₂)₂(H₂O)₂]_n, contains two crystallographically unique Cu^II centres, each lying on a twofold axis and having a slightly distorted octa­hedral environment. One Cu^II centre is coordinated by two bridging 4,4'-bipyridine (4,4'-bipy) ligands, two sulfate anions and two aqua ligands. The second is surrounded by two 4,4'-bipy N atoms and four O atoms, two from bridging sulfate anions and two from ethane-1,2-diol ligands. The sulfate anion bridges adjacent Cu^II centres, leading to the formation of linear ...Cu1-Cu2-Cu1-Cu2... chains. Adjacent chains are further bridged by 4,4'-bipy ligands, which are also located on the twofold axis, resulting in a two-dimensional layered polymer. In the crystal structure, extensive O-H...O hydrogen-bonding inter­actions between water mol­ecules, ethane-1,2-diol mol­ecules and sulfate anions lead to the formation of a three-dimensional supra­molecular network structure.

S1. Comment

The self-assembly of coordination polymers and the crystal engineering of metal–organic coordination frameworks have recently received much attention because of their interesting molecular topologies and potential applications as functional materials (Batten & Robson, 1998; Eddaoudi et al., 2001; Li et al., 2003; Dietzel et al., 2005; Liu et al., 2007; Zhang et al., 2010). It is still challenging to construct metal–organic coordination frameworks of mixed ligands with metal salts in crystal engineering. 4,4'-Bipyridine (4,4'-bipy) has been used as a bridging ligand, owing to its rod-like rigidity and length, and has been widely applied in constructing interesting coordination polymers (Tong et al., 1998; Lu et al., 1998; Kondo et al., 1999; Greve et al., 2003; Lah & Leban, 2006; Díaz de Vivar et al., 2007; Bo et al., 2008; Li et al., 2009; Xu et al., 2010; Wang et al., 2010; Guo et al., 2010). It is well known that hydrothermal (solvothermal) synthesis is an effective method for the construction of new metal–organic coordination polymers because it can provide ideal conditions for crystal growth, owing to the enhanced transport ability of solvents in superheated systems. We have focused on the synthesis of complexes with 4,4'-bipy as an auxiliary ligand, while retaining some of the solvent molecules capable of hydrogen bonding to form higher-dimensional supramolecular networks. The title compound, (I), a new three-dimensional supramolecular network with two-dimensional layers, was obtained via a solvothermal reaction.

Part of the layer structure of (I) is shown in Fig. 1. There are two types of crystallographically independent Cu^II centres, both on symmetry 2 with a slightly distorted octahedral CuN₂O₄ environment. Atom Cu1 is coordinated by two N atoms from bridging 4,4'-bipy ligands occupying the axial positions [Cu1—N3 = 2.016 (3) Å and Cu1—N4 = 1.986 (3) Å], two O atoms from two bridging sulfate anions [Cu1—O2 = 2.0640 (19) Å] and two O atoms from water molecules [Cu1—O1W = 2.323 (2) Å] occupying the equatorial sites (Table 1). Atoms Cu1, O2, O2A, O1W and O1Wⁱ [symmetry code: (i) -x, y, -z + 3/2] are almost coplanar, the mean deviation from the plane being 0.0416 Å. The bond angles around each Cu1 centre are in the range 87.37 (5)–92.63 (5)° (Table 1). The coordination environment of each Cu2 centre is very similar to that of Cu1, with ethane-1,2-diol ligands replacing the water ligands. The corresponding bond angles around Cu2 lie in the range 84.67 (6)–95.33 (6)° (Table 1).

The sulfate anion acts as an O—S—O bridging link between two different Cu^II cations, giving rise to the formation of linear ···Cu1–O–SO₂–O–Cu2–O–SO₂–O··· chains running parallel to the a axis, the Cu1···Cu2 and Cu1···Cu1^v [symmetry code: (v) -x + 1, y - 1, z] distances are 5.530 (1) and 11.060 (2) Å, respectively (Fig. 1). The dihedral angles between the two half-bipy rings coordinated to Cu1 and Cu2 are 82.254 (65) and 74.334 (80)°, respectively. The Cu1 and Cu2 centres of adjacent ···Cu1–O–SO₂–O–Cu2–O–SO₂–O··· chains are further cross-linked by the bridging 4,4'-bipy ligands, leading to the formation of linear ···Cu1–bipy–Cu2–bipy··· chains along the b axis, in which the Cu1···Cu2^viii and Cu1···Cu^vi [symmetry codes: (vi) x - 1/2, y - 1/2, z; (viii) x - 1/2, y + 1/2, z] separations are 11.093 (2) and 11.127 (2) Å, respectively (Fig. 2). Each bridging 4,4'-bipy ligand lies on a two-fold axis, with dihedral angles between the two pyridine rings of two adjacent independent 4,4'-bipy ligands of 7.94 (7) [4,4'-bipy A] and 15.47 (8)° [4,4'-bipy B] (Fig. 2). The ···M–O–SO₂–O–M··· and ···M–bipy–M··· chains are almost orthogonal, leading to a layered structure (Fig. 2). Intermolecular O1W—H5C···O7 and O6—H6···O2 hydrogen bonds help to further stabilize the layered structure (Table 2).

In the crystal structure of (I), the two-dimensional polymeric layers are linked by classical hydrogen-bonding, namely O—H···O interactions involving the water molecules, sulfate anions and 1,2-ethanediol molecules, resulting in a three-dimensional supramolecular network (Table 2 and Fig. 3).

Related literature

For related literature, see: Batten & Robson (1998); Bo et al. (2008); Díaz de Vivar, Baggio, Garland & Baggio (2007); Dietzel et al. (2005); Eddaoudi et al. (2001); Greve et al. (2003); Guo et al. (2010); Kondo et al. (1999); Lah & Leban (2006); Li et al. (2003, 2009); Liu et al. (2007); Lu et al. (1998); Tong et al. (1998); Wang et al. (2010); Xu et al. (2010); Zhang et al. (2010).

S2. Experimental

4,4'-Bipyridine (0.2 mmol), CuSO₄.5H₂O (0.1 mmol), ethane-1,2-diol (2.0 ml) and water (1.0 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 383 K for 72 h. After this time, the tube was allowed to cool to room temperature and blue prisms of (I) were obtained. Analysis found: C 36.41, H 4.05, N 7.08%; calculated for C₂₄H₃₂Cu₂N₄O₁₄S₂: C 36.32, H 3.93, N 6.74%.

S3. Refinement

The aromatic and methylene H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 and 0.97 Å, respectively, and with U_iso(H) = 1.2U_eq(C). The hydroxy and water H atoms were located in a difference Fourier map and their positions were refined freely, but with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Part of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 35% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x, y, -z + 3/2; (ii) -x + 1, y, -z + 3/2; (iii) x - 1, y, z; (iv) x + 1, y, z.]
	Fig. 2. The crystal structure of (I), viewed along the c axis. The C and uncoordinated O atoms of the ethane-1,2-diol ligands and H atoms have been omitted for clarity. [Symmetry codes: (v) x, y - 1, z; (vi) x - 1/2, y - 1/2, z; (viii) x - 1/2, y + 1/2, z.]
	Fig. 3. Hydrogen-bonding interactions between adjacent layers of (I), viewed along the a axis. Hydrogen bonds are represented by dashed lines and H atoms not involved in hydrogen bonds have been omitted for clarity.

Poly[diaquabis(µ-4,4'-bipyridine-κ²N:N')bis(ethane-1,2- diol)-di-µ-sulfato-dicopper(II)]

Crystal data

[Cu2(SO4)2(C10H8N2)2(C2H6O2)2(H2O)2]	F(000) = 1624
Mr = 791.74	Dx = 1.762 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 6932 reflections
a = 11.060 (2) Å	θ = 3.3–27.5°
b = 22.220 (4) Å	µ = 1.64 mm^−1
c = 12.208 (2) Å	T = 223 K
β = 95.87 (3)°	Prism, blue
V = 2984.5 (10) Å^3	0.65 × 0.20 × 0.18 mm
Z = 4

Data collection

Rigaku Mercury CCD area-detector diffractometer	3390 independent reflections
Radiation source: fine-focus sealed tube	2730 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 28.5714 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −14→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −28→25
Tmin = 0.823, Tmax = 1.000	l = −15→15
8511 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 1.4943P] where P = (Fo^2 + 2Fc^2)/3
3390 reflections	(Δ/σ)max = 0.002
225 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

Experimental. Collected data with 0.8 mm caliber collimator tube.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.0000	0.626444 (15)	0.7500	0.01634 (12)
Cu2	0.5000	0.627198 (16)	0.7500	0.01783 (12)
S1	0.26518 (6)	0.60462 (3)	0.88780 (5)	0.02182 (15)
N1	0.5000	0.53688 (12)	0.7500	0.0184 (6)
N2	0.5000	0.71808 (12)	0.7500	0.0198 (6)
N3	0.0000	0.71719 (12)	0.7500	0.0178 (6)
N4	0.0000	0.53708 (12)	0.7500	0.0174 (6)
C8	0.0623 (2)	0.81057 (10)	0.8353 (2)	0.0227 (5)
H8A	0.1047	0.8305	0.8943	0.027*
C3	0.4288 (2)	0.50574 (11)	0.6752 (2)	0.0273 (6)
H3A	0.3789	0.5268	0.6225	0.033*
C6	0.5000	0.84460 (14)	0.7500	0.0197 (7)
C9	0.0608 (2)	0.74843 (10)	0.8322 (2)	0.0225 (5)
H9A	0.1038	0.7273	0.8893	0.027*
C10	0.0764 (2)	0.50599 (10)	0.6931 (2)	0.0219 (5)
H10A	0.1304	0.5271	0.6538	0.026*
C5	0.4051 (3)	0.81159 (11)	0.7864 (2)	0.0302 (6)
H5A	0.3395	0.8314	0.8120	0.036*
C1	0.5000	0.41052 (14)	0.7500	0.0180 (7)
C2	0.4262 (2)	0.44350 (11)	0.6730 (2)	0.0257 (6)
H2A	0.3749	0.4237	0.6196	0.031*
C4	0.4081 (2)	0.74948 (11)	0.7847 (2)	0.0306 (6)
H4A	0.3430	0.7285	0.8088	0.037*
C11	0.0784 (2)	0.44386 (10)	0.6904 (2)	0.0223 (5)
H11A	0.1320	0.4239	0.6489	0.027*
C7	0.0000	0.84347 (14)	0.7500	0.0182 (7)
C12	0.0000	0.41118 (14)	0.7500	0.0186 (7)
C14	0.2969 (3)	0.60414 (14)	0.4427 (2)	0.0360 (7)
H14A	0.2817	0.6180	0.3672	0.043*
H14B	0.3719	0.5812	0.4497	0.043*
C13	0.3081 (3)	0.65679 (12)	0.5193 (3)	0.0383 (7)
H13A	0.3728	0.6830	0.5002	0.046*
H13B	0.2329	0.6796	0.5121	0.046*
O2	0.18604 (16)	0.62764 (7)	0.78866 (14)	0.0225 (4)
O1	0.38961 (17)	0.62756 (7)	0.87965 (16)	0.0255 (4)
O3	0.26430 (19)	0.53917 (8)	0.88790 (18)	0.0407 (5)
O1W	0.0269 (2)	0.63123 (9)	0.56389 (16)	0.0301 (4)
H5C	0.072 (3)	0.6098 (15)	0.531 (3)	0.045*
H5B	−0.044 (3)	0.6278 (14)	0.532 (3)	0.045*
O4	0.22028 (18)	0.62951 (9)	0.98674 (16)	0.0330 (5)
O7	0.19940 (19)	0.56732 (9)	0.46951 (18)	0.0379 (5)
H7A	0.205 (3)	0.5346 (16)	0.443 (3)	0.057*
O6	0.3337 (2)	0.63657 (10)	0.62979 (18)	0.0379 (5)
H6	0.271 (4)	0.6373 (17)	0.654 (3)	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0162 (2)	0.0099 (2)	0.0228 (2)	0.000	0.00125 (16)	0.000
Cu2	0.0189 (2)	0.0099 (2)	0.0246 (2)	0.000	0.00234 (16)	0.000
S1	0.0209 (3)	0.0173 (3)	0.0267 (3)	−0.0019 (2)	−0.0005 (2)	0.0041 (2)
N4	0.0182 (14)	0.0121 (13)	0.0215 (14)	0.000	−0.0001 (11)	0.000
N2	0.0203 (15)	0.0128 (13)	0.0267 (15)	0.000	0.0036 (12)	0.000
N3	0.0200 (15)	0.0117 (12)	0.0217 (14)	0.000	0.0017 (11)	0.000
N1	0.0209 (15)	0.0114 (13)	0.0234 (14)	0.000	0.0038 (12)	0.000
C8	0.0271 (14)	0.0177 (12)	0.0219 (12)	−0.0017 (10)	−0.0054 (10)	0.0014 (10)
C3	0.0328 (15)	0.0184 (12)	0.0284 (13)	0.0007 (11)	−0.0081 (11)	0.0028 (11)
C6	0.0230 (18)	0.0132 (15)	0.0224 (17)	0.000	−0.0001 (14)	0.000
C9	0.0251 (13)	0.0169 (11)	0.0243 (12)	−0.0004 (10)	−0.0036 (10)	0.0023 (10)
C10	0.0210 (13)	0.0174 (11)	0.0280 (13)	−0.0005 (9)	0.0058 (10)	0.0013 (10)
C5	0.0282 (15)	0.0163 (12)	0.0491 (17)	0.0017 (10)	0.0183 (13)	−0.0002 (11)
C1	0.0198 (17)	0.0135 (15)	0.0208 (16)	0.000	0.0033 (13)	0.000
C2	0.0307 (15)	0.0184 (12)	0.0260 (13)	0.0004 (10)	−0.0068 (11)	−0.0009 (10)
C4	0.0281 (15)	0.0164 (12)	0.0497 (17)	−0.0019 (10)	0.0161 (13)	0.0001 (12)
C11	0.0246 (13)	0.0169 (12)	0.0263 (13)	0.0019 (9)	0.0076 (10)	−0.0016 (10)
C7	0.0215 (18)	0.0107 (15)	0.0229 (17)	0.000	0.0057 (13)	0.000
C12	0.0201 (17)	0.0158 (15)	0.0198 (16)	0.000	0.0016 (13)	0.000
C14	0.0358 (17)	0.0429 (16)	0.0307 (15)	0.0051 (14)	0.0104 (12)	0.0041 (13)
C13	0.0341 (17)	0.0277 (14)	0.0551 (19)	−0.0028 (12)	0.0139 (14)	0.0080 (14)
O2	0.0200 (9)	0.0223 (9)	0.0250 (9)	−0.0015 (7)	0.0014 (7)	0.0042 (7)
O1	0.0206 (9)	0.0213 (9)	0.0343 (10)	−0.0012 (7)	0.0005 (8)	−0.0029 (7)
O3	0.0403 (12)	0.0181 (9)	0.0613 (14)	−0.0056 (8)	−0.0066 (10)	0.0107 (9)
O1W	0.0283 (11)	0.0319 (10)	0.0298 (11)	0.0038 (8)	0.0023 (9)	−0.0066 (8)
O4	0.0253 (10)	0.0499 (13)	0.0234 (9)	−0.0033 (8)	0.0007 (8)	−0.0013 (8)
O7	0.0378 (12)	0.0308 (10)	0.0467 (12)	−0.0016 (9)	0.0116 (10)	−0.0146 (9)
O6	0.0259 (11)	0.0503 (12)	0.0392 (12)	−0.0070 (10)	0.0111 (9)	−0.0131 (10)

Geometric parameters (Å, º)

Cu1—N3	2.016 (3)	C6—C5^ii	1.390 (3)
Cu1—N4	1.986 (3)	C6—C12^iii	1.479 (5)
Cu1—O1W	2.324 (2)	C9—H9A	0.9300
Cu1—O2	2.0637 (18)	C10—C11	1.381 (3)
Cu1—O2^i	2.0637 (18)	C10—H10A	0.9300
Cu2—N1	2.007 (3)	C5—C4	1.381 (3)
Cu2—N2	2.019 (3)	C5—H5A	0.9300
Cu2—O1	2.095 (2)	C1—C2^ii	1.389 (3)
Cu2—O6	2.242 (2)	C1—C2	1.389 (3)
Cu1—O1W^i	2.324 (2)	C1—C7^iv	1.490 (5)
Cu2—O1^ii	2.095 (2)	C2—H2A	0.9300
Cu2—O6^ii	2.242 (2)	C4—H4A	0.9300
S1—O1	1.4805 (19)	C11—C12	1.392 (3)
S1—O2	1.5085 (19)	C11—H11A	0.9300
S1—O3	1.4544 (19)	C7—C8^i	1.395 (3)
S1—O4	1.461 (2)	C7—C1^v	1.490 (5)
N4—C10^i	1.340 (3)	C12—C11^i	1.392 (3)
N4—C10	1.340 (3)	C12—C6^vi	1.479 (5)
N2—C4	1.337 (3)	C14—O7	1.418 (4)
N2—C4^ii	1.337 (3)	C14—C13	1.495 (4)
N3—C9	1.343 (3)	C14—H14A	0.9700
N3—C9^i	1.343 (3)	C14—H14B	0.9700
N1—C3^ii	1.336 (3)	C13—O6	1.423 (4)
N1—C3	1.336 (3)	C13—H13A	0.9700
C8—C9	1.381 (3)	C13—H13B	0.9700
C8—C7	1.395 (3)	O1W—H5C	0.83 (3)
C8—H8A	0.9300	O1W—H5B	0.84 (4)
C3—C2	1.383 (3)	O7—H7A	0.80 (4)
C3—H3A	0.9300	O6—H6	0.78 (4)
C6—C5	1.390 (3)
N3—Cu1—N4	180.000 (1)	C2—C3—H3A	118.6
N3—Cu1—O1W	87.37 (5)	C5—C6—C5^ii	116.3 (3)
N3—Cu1—O2	89.26 (4)	C5—C6—C12^iii	121.85 (15)
N4—Cu1—O1W	92.63 (5)	C5^ii—C6—C12^iii	121.85 (15)
N4—Cu1—O2	90.74 (4)	N3—C9—C8	122.8 (2)
O1W^i—Cu1—O1W	174.75 (10)	N3—C9—H9A	118.6
O1W—Cu1—O2	89.91 (8)	C8—C9—H9A	118.6
O2^i—Cu1—O2	178.53 (9)	N4—C10—C11	122.7 (2)
N1—Cu2—N2	180.000 (1)	N4—C10—H10A	118.6
N1—Cu2—O1	90.22 (4)	C11—C10—H10A	118.6
N1—Cu2—O6	95.33 (6)	C4—C5—C6	120.2 (2)
N2—Cu2—O1	89.78 (4)	C4—C5—H5A	119.9
N2—Cu2—O6	84.67 (6)	C6—C5—H5A	119.9
O1—Cu2—O1^ii	179.55 (9)	C2^ii—C1—C2	116.3 (3)
O1—Cu2—O6	89.53 (8)	C2^ii—C1—C7^iv	121.83 (15)
O6^ii—Cu2—O6	169.34 (12)	C2—C1—C7^iv	121.83 (15)
N4—Cu1—O2^i	90.74 (4)	C3—C2—C1	120.3 (2)
N3—Cu1—O2^i	89.26 (4)	C3—C2—H2A	119.9
N4—Cu1—O1W^i	92.63 (5)	C1—C2—H2A	119.9
N3—Cu1—O1W^i	87.37 (5)	N2—C4—C5	123.1 (2)
O2^i—Cu1—O1W^i	89.91 (8)	N2—C4—H4A	118.5
O2—Cu1—O1W^i	90.02 (8)	C5—C4—H4A	118.5
O2^i—Cu1—O1W	90.02 (8)	C10—C11—C12	119.8 (2)
N1—Cu2—O1^ii	90.22 (4)	C10—C11—H11A	120.1
N2—Cu2—O1^ii	89.78 (4)	C12—C11—H11A	120.1
N1—Cu2—O6^ii	95.33 (6)	C8^i—C7—C8	116.8 (3)
N2—Cu2—O6^ii	84.67 (6)	C8^i—C7—C1^v	121.60 (15)
O1—Cu2—O6^ii	90.43 (8)	C8—C7—C1^v	121.60 (15)
O1^ii—Cu2—O6^ii	89.53 (8)	C11^i—C12—C11	117.1 (3)
O1^ii—Cu2—O6	90.43 (8)	C11^i—C12—C6^vi	121.44 (15)
O3—S1—O4	112.03 (13)	C11—C12—C6^vi	121.44 (15)
O3—S1—O1	110.54 (11)	O7—C14—C13	108.9 (2)
O4—S1—O1	108.79 (11)	O7—C14—H14A	109.9
O3—S1—O2	109.66 (11)	C13—C14—H14A	109.9
O4—S1—O2	108.45 (11)	O7—C14—H14B	109.9
O1—S1—O2	107.24 (11)	C13—C14—H14B	109.9
C10^i—N4—C10	117.9 (3)	H14A—C14—H14B	108.3
C10^i—N4—Cu1	121.04 (14)	O6—C13—C14	110.0 (2)
C10—N4—Cu1	121.04 (14)	O6—C13—H13A	109.7
C4—N2—C4^ii	117.1 (3)	C14—C13—H13A	109.7
C4—N2—Cu2	121.45 (15)	O6—C13—H13B	109.7
C4^ii—N2—Cu2	121.45 (15)	C14—C13—H13B	109.7
C9—N3—C9^i	117.7 (3)	H13A—C13—H13B	108.2
C9—N3—Cu1	121.13 (14)	S1—O2—Cu1	131.47 (11)
C9^i—N3—Cu1	121.13 (14)	S1—O1—Cu2	131.82 (11)
C3^ii—N1—C3	117.6 (3)	Cu1—O1W—H5C	127 (2)
C3^ii—N1—Cu2	121.20 (14)	Cu1—O1W—H5B	104 (2)
C3—N1—Cu2	121.20 (14)	H5C—O1W—H5B	108 (3)
C9—C8—C7	120.0 (2)	C14—O7—H7A	110 (3)
C9—C8—H8A	120.0	C13—O6—Cu2	136.10 (18)
C7—C8—H8A	120.0	C13—O6—H6	104 (3)
N1—C3—C2	122.8 (2)	Cu2—O6—H6	117 (3)
N1—C3—H3A	118.6
O2^i—Cu1—N4—C10^i	−50.16 (13)	C10^i—N4—C10—C11	0.53 (18)
O2—Cu1—N4—C10^i	129.84 (13)	Cu1—N4—C10—C11	−179.47 (18)
O1W^i—Cu1—N4—C10^i	39.78 (13)	C5^ii—C6—C5—C4	−0.3 (2)
O1W—Cu1—N4—C10^i	−140.22 (13)	C12^iii—C6—C5—C4	179.7 (2)
O2^i—Cu1—N4—C10	129.84 (13)	N1—C3—C2—C1	−0.4 (4)
O2—Cu1—N4—C10	−50.16 (13)	C2^ii—C1—C2—C3	0.17 (19)
O1W^i—Cu1—N4—C10	−140.22 (13)	C7^iv—C1—C2—C3	−179.83 (19)
O1W—Cu1—N4—C10	39.78 (13)	C4^ii—N2—C4—C5	−0.3 (2)
O1—Cu2—N2—C4	−27.03 (16)	Cu2—N2—C4—C5	179.7 (2)
O1^ii—Cu2—N2—C4	152.97 (16)	C6—C5—C4—N2	0.7 (4)
O6^ii—Cu2—N2—C4	−117.49 (16)	N4—C10—C11—C12	−1.1 (3)
O6—Cu2—N2—C4	62.51 (16)	C9—C8—C7—C8^i	0.41 (17)
O1—Cu2—N2—C4^ii	152.97 (16)	C9—C8—C7—C1^v	−179.59 (18)
O1^ii—Cu2—N2—C4^ii	−27.03 (16)	C10—C11—C12—C11^i	0.50 (16)
O6^ii—Cu2—N2—C4^ii	62.51 (16)	C10—C11—C12—C6^vi	−179.50 (17)
O6—Cu2—N2—C4^ii	−117.49 (16)	O7—C14—C13—O6	61.2 (3)
O2^i—Cu1—N3—C9	132.91 (14)	O3—S1—O2—Cu1	69.94 (17)
O2—Cu1—N3—C9	−47.09 (14)	O4—S1—O2—Cu1	−52.68 (16)
O1W^i—Cu1—N3—C9	42.96 (14)	O1—S1—O2—Cu1	−170.00 (12)
O1W—Cu1—N3—C9	−137.04 (14)	N4—Cu1—O2—S1	−62.36 (13)
O2^i—Cu1—N3—C9^i	−47.09 (14)	N3—Cu1—O2—S1	117.64 (13)
O2—Cu1—N3—C9^i	132.91 (14)	O1W^i—Cu1—O2—S1	30.27 (14)
O1W^i—Cu1—N3—C9^i	−137.04 (14)	O1W—Cu1—O2—S1	−154.98 (14)
O1W—Cu1—N3—C9^i	42.96 (14)	O3—S1—O1—Cu2	70.52 (17)
O1—Cu2—N1—C3^ii	−78.68 (15)	O4—S1—O1—Cu2	−166.08 (13)
O1^ii—Cu2—N1—C3^ii	101.32 (15)	O2—S1—O1—Cu2	−48.97 (16)
O6^ii—Cu2—N1—C3^ii	11.77 (16)	N1—Cu2—O1—S1	−62.25 (13)
O6—Cu2—N1—C3^ii	−168.23 (16)	N2—Cu2—O1—S1	117.75 (13)
O1—Cu2—N1—C3	101.32 (15)	O6^ii—Cu2—O1—S1	−157.58 (14)
O1^ii—Cu2—N1—C3	−78.68 (15)	O6—Cu2—O1—S1	33.08 (14)
O6^ii—Cu2—N1—C3	−168.23 (16)	C14—C13—O6—Cu2	98.9 (3)
O6—Cu2—N1—C3	11.77 (16)	N1—Cu2—O6—C13	−111.1 (3)
C3^ii—N1—C3—C2	0.2 (2)	N2—Cu2—O6—C13	68.9 (3)
Cu2—N1—C3—C2	−179.8 (2)	O1—Cu2—O6—C13	158.7 (3)
C9^i—N3—C9—C8	0.43 (19)	O1^ii—Cu2—O6—C13	−20.9 (3)
Cu1—N3—C9—C8	−179.57 (19)	O6^ii—Cu2—O6—C13	68.9 (3)
C7—C8—C9—N3	−0.9 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H5B···O4^i	0.84 (4)	1.94 (4)	2.741 (3)	159 (3)
O7—H7A···O3^vii	0.80 (4)	1.92 (4)	2.693 (3)	164 (4)
O1W—H5C···O7	0.83 (3)	1.91 (4)	2.726 (3)	170 (3)
O6—H6···O2	0.78 (4)	1.99 (4)	2.668 (3)	145 (4)

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