catena-Poly[[[tetra-kis-(4-methyl-pyridine-κN)copper(II)]-μ-sulfato-κO:O'] 4.393-hydrate].

The structure of the title compound, {[Cu(SO(4))(C(6)H(7)N)(4)]·4.393H(2)O}(n), consists of Cu(2+) ions surrounded in a square-planar fashion by 4-methyl-pyridine ligands, forming two crystallographically independent Cu{H(3)C(C(5)H(4)N)}(4) units that are both located on crystallographic inversion centers. The Cu(4-methyl-pyridine)(4) units are, in turn, connected with each other via bridging sulfate anions, leading to the formation of infinite [Cu{H(3)C(C(5)H(4)N)}(4)SO(4)](n) zigzag chains along [001]. The completed coordination spheres of the Cu(2+) ions are slightly distorted octa-hedral. The axial Cu-O bonds are elongated [average length = 2.42 (4) Å] compared to the equatorial Cu-N bonds [average length = 2.043 (2) Å]. The inter-stitial space between the chains is filled with uncoordinated water mol-ecules that consolidate the structure through O-H⋯O hydrogen bonding. One of the five crystallographically independent solvent water mol-ecules is partially occupied with an occupancy factor of 0.396 (4). Due to hydrogen bonding between symmetry-equivalent water mol-ecules across inversion centers, several of the water H atoms are disordered in 1:1 ratios over mutually exclusive positions. The crystal under investigation was found to be non-merohedrally twinned in a 0.789 (1):0.211 (1) ratio by a 180° rotation around the reciprocal b axis.

Related literature

For the structures of related binuclear copper(II) complexes, see: Shahid et al. (2008 ▶, 2009 ▶).

Experimental

Crystal data

[Cu(SO4)(C6H7N)4]·4.393H2O

M = 611.27

Triclinic,

a = 10.4688 (12) Å

b = 11.6327 (14) Å

c = 12.8300 (15) Å

α = 78.672 (3)°

β = 87.609 (3)°

γ = 67.571 (3)°

V = 1415.2 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.90 mm−1

T = 100 K

0.60 × 0.45 × 0.40 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (TWINABS; Bruker, 2008 ▶) T min = 0.607, T max = 0.746

16814 measured reflections

6963 independent reflections

6170 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.118

S = 1.06

6963 reflections

361 parameters

H-atom parameters constrained

Δρmax = 0.68 e Å−3

Δρmin = −0.61 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: CELL NOW (Bruker, 2009 ▶) and SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006325/wm2458sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006325/wm2458Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(SO4)(C6H7N)4]·4.393H2O	Z = 2
Mr = 611.27	F(000) = 642
Triclinic, P1	Dx = 1.434 Mg m−3
Hall symbol: -P 1	Melting point: 373 K
a = 10.4688 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6327 (14) Å	Cell parameters from 4676 reflections
c = 12.8300 (15) Å	θ = 2.3–30.4°
α = 78.672 (3)°	µ = 0.90 mm−1
β = 87.609 (3)°	T = 100 K
γ = 67.571 (3)°	Block, blue
V = 1415.2 (3) Å3	0.60 × 0.45 × 0.40 mm

Bruker SMART APEX CCD diffractometer	6963 independent reflections
Radiation source: fine-focus sealed tube	6170 reflections with I > 2σ(I)
graphite	Rint = 0.033
ω scans	θmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (TWINABS; Bruker, 2008)	h = −13→13
Tmin = 0.607, Tmax = 0.746	k = −15→15
16814 measured reflections	l = 0→17

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0573P)2 + 1.4896P] where P = (Fo2 + 2Fc2)/3
6963 reflections	(Δ/σ)max < 0.001
361 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7599 (3)	1.0000 (3)	0.5809 (2)	0.0204 (5)
H1	0.7594	0.9263	0.6281	0.024*
C2	0.8641 (3)	1.0426 (3)	0.5935 (2)	0.0231 (5)
H2	0.9329	0.9984	0.6488	0.028*
C3	0.8680 (3)	1.1497 (3)	0.5255 (2)	0.0230 (5)
C4	0.7680 (3)	1.2070 (3)	0.4436 (2)	0.0254 (6)
H4	0.7692	1.2784	0.3932	0.030*
C5	0.6665 (3)	1.1597 (3)	0.4355 (2)	0.0242 (6)
H5	0.5990	1.1999	0.3789	0.029*
C6	0.9755 (3)	1.2030 (3)	0.5399 (3)	0.0313 (6)
H6F	0.9338	1.2775	0.5729	0.047*
H6E	1.0100	1.2278	0.4704	0.047*
H6D	1.0523	1.1385	0.5856	0.047*
C7	0.6771 (3)	0.7248 (3)	0.5052 (2)	0.0259 (6)
H7	0.6453	0.7125	0.5754	0.031*
C8	0.7656 (4)	0.6209 (3)	0.4678 (2)	0.0318 (7)
H8	0.7943	0.5392	0.5123	0.038*
C9	0.8136 (3)	0.6346 (3)	0.3647 (2)	0.0272 (6)
C10	0.9073 (4)	0.5230 (3)	0.3195 (3)	0.0451 (9)
H10A	0.8548	0.4736	0.3050	0.068*
H10B	0.9834	0.4695	0.3709	0.068*
H10C	0.9449	0.5532	0.2533	0.068*
C11	0.7700 (3)	0.7568 (3)	0.3053 (2)	0.0224 (5)
H11	0.8015	0.7715	0.2353	0.027*
C12	0.6808 (3)	0.8575 (3)	0.3476 (2)	0.0212 (5)
H12	0.6517	0.9402	0.3048	0.025*
C13	0.4334 (3)	0.8651 (3)	0.2020 (2)	0.0216 (5)
H13	0.3870	0.9490	0.2138	0.026*
C14	0.4296 (3)	0.7646 (3)	0.2792 (2)	0.0208 (5)
H14	0.3811	0.7806	0.3424	0.025*
C15	0.4963 (3)	0.6413 (3)	0.2645 (2)	0.0253 (6)
C16	0.5674 (4)	0.6247 (3)	0.1714 (2)	0.0341 (7)
H16	0.6166	0.5416	0.1585	0.041*
C17	0.5667 (3)	0.7287 (3)	0.0975 (2)	0.0310 (6)
H17	0.6156	0.7150	0.0342	0.037*
C18	0.4934 (4)	0.5303 (3)	0.3466 (2)	0.0371 (8)
H18A	0.5735	0.5000	0.3960	0.056*
H18B	0.4967	0.4620	0.3112	0.056*
H18C	0.4082	0.5569	0.3860	0.056*
C19	0.7394 (3)	1.0233 (3)	0.0928 (2)	0.0228 (5)
H19	0.6692	1.0967	0.1105	0.027*
C20	0.8748 (3)	0.9916 (3)	0.1272 (2)	0.0258 (6)
H20	0.8958	1.0428	0.1676	0.031*
C21	0.9792 (3)	0.8852 (3)	0.1023 (2)	0.0256 (6)
C22	0.9428 (3)	0.8158 (3)	0.0406 (2)	0.0291 (6)
H22	1.0113	0.7430	0.0207	0.035*
C23	0.8054 (3)	0.8539 (3)	0.0084 (2)	0.0272 (6)
H23	0.7822	0.8067	−0.0349	0.033*
C24	1.1264 (3)	0.8448 (3)	0.1420 (2)	0.0328 (7)
H24A	1.1478	0.9201	0.1405	0.049*
H24B	1.1893	0.7918	0.0962	0.049*
H24C	1.1378	0.7964	0.2150	0.049*
Cu1	0.5000	1.0000	0.5000	0.01857 (11)
Cu2	0.5000	1.0000	0.0000	0.02031 (11)
N1	0.6596 (2)	1.0589 (2)	0.50462 (17)	0.0197 (4)
N2	0.6332 (2)	0.8438 (2)	0.44667 (17)	0.0196 (4)
N3	0.5002 (2)	0.8479 (2)	0.11114 (17)	0.0204 (4)
N4	0.7039 (2)	0.9544 (2)	0.03565 (17)	0.0208 (4)
O1	0.4432 (2)	1.11465 (19)	0.32076 (14)	0.0241 (4)
O2	0.4297 (2)	1.1372 (2)	0.13099 (15)	0.0257 (4)
O3	0.2438 (2)	1.2743 (2)	0.21897 (18)	0.0387 (6)
O4	0.4641 (3)	1.2969 (2)	0.20710 (19)	0.0389 (6)
O5	0.7247 (3)	0.3043 (2)	0.1438 (2)	0.0501 (7)
H5A	0.7007	0.3519	0.0826	0.075*
H5B	0.6529	0.2956	0.1714	0.075*
O6	0.3674 (3)	0.5172 (3)	0.0548 (2)	0.0568 (7)
H6A	0.4103	0.5011	−0.0008	0.085*	0.50
H6B	0.4034	0.4467	0.0972	0.085*
H6C	0.2905	0.5147	0.0399	0.085*	0.50
O7	0.9960 (3)	0.2146 (3)	0.2479 (2)	0.0567 (8)
H7A	0.9293	0.2632	0.2054	0.085*
H7B	1.0552	0.2449	0.2228	0.085*
O8	0.1306 (4)	0.4630 (4)	0.0397 (4)	0.0971 (15)
H8A	0.1109	0.4722	0.1027	0.146*
H8B	0.1842	0.5027	0.0261	0.146*	0.50
H8C	0.0507	0.4844	0.0125	0.146*	0.50
O9	0.2000 (7)	0.5327 (6)	0.2704 (5)	0.045 (2)	0.393 (8)
H9A	0.2311	0.5640	0.2151	0.067*	0.393 (8)
H9B	0.2166	0.4593	0.2590	0.067*	0.393 (8)
S3	0.39467 (7)	1.20521 (6)	0.21937 (5)	0.01904 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0229 (13)	0.0205 (12)	0.0186 (12)	−0.0087 (11)	−0.0004 (9)	−0.0046 (10)
C2	0.0201 (12)	0.0294 (14)	0.0220 (13)	−0.0095 (11)	−0.0012 (10)	−0.0099 (11)
C3	0.0187 (12)	0.0275 (14)	0.0274 (14)	−0.0106 (11)	0.0047 (10)	−0.0131 (11)
C4	0.0276 (14)	0.0269 (14)	0.0247 (14)	−0.0145 (12)	0.0019 (11)	−0.0035 (11)
C5	0.0278 (14)	0.0285 (14)	0.0198 (13)	−0.0162 (12)	−0.0028 (10)	−0.0002 (10)
C6	0.0259 (14)	0.0341 (16)	0.0411 (17)	−0.0166 (13)	0.0008 (12)	−0.0126 (13)
C7	0.0371 (16)	0.0245 (14)	0.0176 (12)	−0.0145 (12)	−0.0017 (11)	−0.0015 (10)
C8	0.0478 (19)	0.0231 (14)	0.0235 (14)	−0.0138 (14)	−0.0010 (13)	−0.0013 (11)
C9	0.0316 (15)	0.0267 (15)	0.0241 (14)	−0.0111 (12)	−0.0026 (11)	−0.0056 (11)
C10	0.062 (2)	0.0287 (17)	0.0363 (19)	−0.0067 (17)	0.0047 (17)	−0.0091 (14)
C11	0.0238 (13)	0.0278 (14)	0.0184 (12)	−0.0128 (11)	0.0005 (10)	−0.0046 (10)
C12	0.0202 (12)	0.0258 (13)	0.0190 (12)	−0.0118 (11)	−0.0009 (10)	−0.0014 (10)
C13	0.0212 (13)	0.0235 (13)	0.0222 (13)	−0.0106 (11)	−0.0007 (10)	−0.0044 (10)
C14	0.0221 (12)	0.0275 (14)	0.0178 (12)	−0.0145 (11)	0.0002 (10)	−0.0051 (10)
C15	0.0333 (15)	0.0262 (14)	0.0187 (13)	−0.0148 (12)	−0.0032 (11)	−0.0017 (10)
C16	0.053 (2)	0.0220 (14)	0.0234 (14)	−0.0103 (14)	0.0054 (13)	−0.0057 (11)
C17	0.0429 (18)	0.0297 (15)	0.0183 (13)	−0.0117 (14)	0.0062 (12)	−0.0053 (11)
C18	0.062 (2)	0.0293 (16)	0.0227 (15)	−0.0231 (16)	0.0065 (14)	−0.0013 (12)
C19	0.0259 (13)	0.0262 (14)	0.0201 (12)	−0.0157 (11)	−0.0012 (10)	−0.0010 (10)
C20	0.0290 (14)	0.0341 (15)	0.0208 (13)	−0.0211 (13)	−0.0035 (10)	−0.0006 (11)
C21	0.0212 (13)	0.0377 (16)	0.0175 (12)	−0.0147 (12)	−0.0016 (10)	0.0032 (11)
C22	0.0232 (14)	0.0358 (16)	0.0252 (14)	−0.0078 (12)	−0.0004 (11)	−0.0059 (12)
C23	0.0280 (14)	0.0338 (15)	0.0223 (13)	−0.0134 (13)	−0.0044 (11)	−0.0065 (12)
C24	0.0235 (14)	0.0469 (18)	0.0278 (15)	−0.0162 (14)	−0.0024 (11)	−0.0009 (13)
Cu1	0.0212 (2)	0.0220 (2)	0.0169 (2)	−0.01266 (19)	−0.00015 (16)	−0.00454 (18)
Cu2	0.0198 (2)	0.0240 (2)	0.0176 (2)	−0.0110 (2)	−0.00355 (16)	0.00135 (18)
N1	0.0229 (11)	0.0248 (11)	0.0158 (10)	−0.0127 (9)	0.0005 (8)	−0.0060 (8)
N2	0.0237 (11)	0.0233 (11)	0.0163 (10)	−0.0141 (9)	−0.0028 (8)	−0.0025 (8)
N3	0.0213 (11)	0.0236 (11)	0.0178 (10)	−0.0103 (9)	−0.0041 (8)	−0.0027 (9)
N4	0.0221 (11)	0.0242 (11)	0.0172 (10)	−0.0119 (9)	−0.0015 (8)	0.0003 (8)
O1	0.0311 (10)	0.0295 (10)	0.0130 (8)	−0.0145 (9)	−0.0030 (7)	−0.0002 (7)
O2	0.0331 (11)	0.0319 (11)	0.0149 (9)	−0.0143 (9)	0.0015 (8)	−0.0069 (8)
O3	0.0250 (11)	0.0461 (14)	0.0315 (12)	−0.0004 (10)	0.0011 (9)	−0.0046 (10)
O4	0.0571 (15)	0.0289 (11)	0.0373 (13)	−0.0282 (11)	−0.0223 (11)	0.0077 (9)
O5	0.0516 (16)	0.0386 (14)	0.0540 (16)	−0.0131 (12)	−0.0121 (13)	−0.0011 (12)
O6	0.077 (2)	0.0500 (17)	0.0409 (15)	−0.0260 (16)	−0.0023 (14)	0.0007 (13)
O7	0.0577 (17)	0.0562 (17)	0.0492 (16)	−0.0260 (15)	−0.0123 (13)	0.0174 (14)
O8	0.066 (2)	0.089 (3)	0.123 (3)	−0.044 (2)	−0.044 (2)	0.050 (2)
O9	0.049 (4)	0.044 (4)	0.045 (4)	−0.017 (3)	0.001 (3)	−0.017 (3)
S3	0.0231 (3)	0.0207 (3)	0.0147 (3)	−0.0099 (2)	−0.0032 (2)	−0.0026 (2)

C1—N1	1.343 (3)	C19—N4	1.342 (3)
C1—C2	1.386 (4)	C19—C20	1.388 (4)
C1—H1	0.9500	C19—H19	0.9500
C2—C3	1.387 (4)	C20—C21	1.386 (4)
C2—H2	0.9500	C20—H20	0.9500
C3—C4	1.389 (4)	C21—C22	1.391 (4)
C3—C6	1.509 (4)	C21—C24	1.508 (4)
C4—C5	1.386 (4)	C22—C23	1.388 (4)
C4—H4	0.9500	C22—H22	0.9500
C5—N1	1.348 (4)	C23—N4	1.341 (4)
C5—H5	0.9500	C23—H23	0.9500
C6—H6F	0.9800	C24—H24A	0.9800
C6—H6E	0.9800	C24—H24B	0.9800
C6—H6D	0.9800	C24—H24C	0.9800
C7—N2	1.352 (4)	Cu1—N1i	2.041 (2)
C7—C8	1.373 (4)	Cu1—N1	2.041 (2)
C7—H7	0.9500	Cu1—N2	2.046 (2)
C8—C9	1.397 (4)	Cu1—N2i	2.046 (2)
C8—H8	0.9500	Cu1—O1	2.3926 (18)
C9—C11	1.385 (4)	Cu1—O1i	2.3926 (18)
C9—C10	1.503 (4)	Cu2—N4ii	2.042 (2)
C10—H10A	0.9800	Cu2—N4	2.042 (2)
C10—H10B	0.9800	Cu2—N3	2.042 (2)
C10—H10C	0.9800	Cu2—N3ii	2.042 (2)
C11—C12	1.382 (4)	Cu2—O2ii	2.443 (2)
C11—H11	0.9500	Cu2—O2	2.443 (2)
C12—N2	1.348 (3)	O1—S3	1.4726 (19)
C12—H12	0.9500	O2—S3	1.464 (2)
C13—N3	1.344 (3)	O3—S3	1.473 (2)
C13—C14	1.387 (4)	O4—S3	1.485 (2)
C13—H13	0.9500	O5—H5A	0.8515
C14—C15	1.382 (4)	O5—H5B	0.8498
C14—H14	0.9500	O6—H6A	0.8408
C15—C16	1.388 (4)	O6—H6B	0.8470
C15—C18	1.507 (4)	O6—H6C	0.8472
C16—C17	1.381 (4)	O7—H7A	0.8445
C16—H16	0.9500	O7—H7B	0.8477
C17—N3	1.336 (4)	O8—H8A	0.8431
C17—H17	0.9500	O8—H8B	0.8459
C18—H18A	0.9800	O8—H8C	0.8456
C18—H18B	0.9800	O9—H9A	0.8436
C18—H18C	0.9800	O9—H9B	0.8448
N1—C1—C2	122.6 (3)	C22—C21—C24	121.1 (3)
N1—C1—H1	118.7	C23—C22—C21	119.3 (3)
C2—C1—H1	118.7	C23—C22—H22	120.3
C1—C2—C3	120.0 (3)	C21—C22—H22	120.3
C1—C2—H2	120.0	N4—C23—C22	123.0 (3)
C3—C2—H2	120.0	N4—C23—H23	118.5
C2—C3—C4	117.3 (2)	C22—C23—H23	118.5
C2—C3—C6	121.7 (3)	C21—C24—H24A	109.5
C4—C3—C6	121.0 (3)	C21—C24—H24B	109.5
C5—C4—C3	119.7 (3)	H24A—C24—H24B	109.5
C5—C4—H4	120.1	C21—C24—H24C	109.5
C3—C4—H4	120.1	H24A—C24—H24C	109.5
N1—C5—C4	122.7 (3)	H24B—C24—H24C	109.5
N1—C5—H5	118.7	N1i—Cu1—N1	180.00 (11)
C4—C5—H5	118.7	N1i—Cu1—N2	91.28 (9)
C3—C6—H6F	109.5	N1—Cu1—N2	88.72 (9)
C3—C6—H6E	109.5	N1i—Cu1—N2i	88.72 (9)
H6F—C6—H6E	109.5	N1—Cu1—N2i	91.28 (9)
C3—C6—H6D	109.5	N2—Cu1—N2i	179.999 (1)
H6F—C6—H6D	109.5	N1i—Cu1—O1	90.27 (8)
H6E—C6—H6D	109.5	N1—Cu1—O1	89.73 (8)
N2—C7—C8	122.9 (3)	N2—Cu1—O1	90.38 (8)
N2—C7—H7	118.5	N2i—Cu1—O1	89.62 (8)
C8—C7—H7	118.5	N1i—Cu1—O1i	89.73 (8)
C7—C8—C9	120.4 (3)	N1—Cu1—O1i	90.27 (8)
C7—C8—H8	119.8	N2—Cu1—O1i	89.62 (8)
C9—C8—H8	119.8	N2i—Cu1—O1i	90.38 (8)
C11—C9—C8	116.6 (3)	O1—Cu1—O1i	180.0
C11—C9—C10	121.3 (3)	N4ii—Cu2—N4	180.0
C8—C9—C10	122.1 (3)	N4ii—Cu2—N3	89.63 (9)
C9—C10—H10A	109.5	N4—Cu2—N3	90.37 (9)
C9—C10—H10B	109.5	N4ii—Cu2—N3ii	90.37 (9)
H10A—C10—H10B	109.5	N4—Cu2—N3ii	89.63 (9)
C9—C10—H10C	109.5	N3—Cu2—N3ii	179.999 (1)
H10A—C10—H10C	109.5	N4—Cu2—O2ii	88.90 (8)
H10B—C10—H10C	109.5	N4ii—Cu2—O2ii	91.11 (8)
C12—C11—C9	120.2 (3)	N3—Cu2—O2ii	88.72 (8)
C12—C11—H11	119.9	N3ii—Cu2—O2ii	91.28 (8)
C9—C11—H11	119.9	N4—Cu2—O2	91.11 (8)
N2—C12—C11	123.1 (3)	N4ii—Cu2—O2	88.90 (8)
N2—C12—H12	118.5	N3—Cu2—O2	91.28 (8)
C11—C12—H12	118.5	N3ii—Cu2—O2	88.72 (8)
N3—C13—C14	122.4 (3)	O2ii—Cu2—O2	180.000 (1)
N3—C13—H13	118.8	C1—N1—C5	117.5 (2)
C14—C13—H13	118.8	C1—N1—Cu1	120.11 (18)
C15—C14—C13	120.2 (3)	C5—N1—Cu1	122.30 (18)
C15—C14—H14	119.9	C12—N2—C7	116.8 (2)
C13—C14—H14	119.9	C12—N2—Cu1	119.50 (19)
C14—C15—C16	116.9 (3)	C7—N2—Cu1	123.72 (19)
C14—C15—C18	121.5 (3)	C17—N3—C13	117.5 (2)
C16—C15—C18	121.7 (3)	C17—N3—Cu2	122.05 (19)
C17—C16—C15	120.1 (3)	C13—N3—Cu2	120.41 (19)
C17—C16—H16	120.0	C23—N4—C19	117.7 (2)
C15—C16—H16	120.0	C23—N4—Cu2	122.75 (19)
N3—C17—C16	122.9 (3)	C19—N4—Cu2	119.52 (19)
N3—C17—H17	118.5	S3—O1—Cu1	169.60 (13)
C16—C17—H17	118.5	H5A—O5—H5B	107.6
C15—C18—H18A	109.5	H6A—O6—H6B	101.2
C15—C18—H18B	109.5	H6A—O6—H6C	101.0
H18A—C18—H18B	109.5	H6B—O6—H6C	100.4
C15—C18—H18C	109.5	H7A—O7—H7B	97.7
H18A—C18—H18C	109.5	H8A—O8—H8B	100.6
H18B—C18—H18C	109.5	H8A—O8—H8C	100.5
N4—C19—C20	122.5 (3)	H8B—O8—H8C	126.9
N4—C19—H19	118.7	H9A—O9—H9B	100.6
C20—C19—H19	118.7	O2—S3—O1	109.72 (12)
C21—C20—C19	119.9 (3)	O2—S3—O3	109.57 (13)
C21—C20—H20	120.0	O1—S3—O3	110.06 (13)
C19—C20—H20	120.0	O2—S3—O4	109.34 (14)
C20—C21—C22	117.5 (3)	O1—S3—O4	108.76 (12)
C20—C21—C24	121.4 (3)	O3—S3—O4	109.37 (15)
N1—C1—C2—C3	−0.3 (4)	C11—C12—N2—C7	0.1 (4)
C1—C2—C3—C4	−2.6 (4)	C11—C12—N2—Cu1	−179.4 (2)
C1—C2—C3—C6	176.9 (3)	C8—C7—N2—C12	−0.1 (4)
C2—C3—C4—C5	2.7 (4)	C8—C7—N2—Cu1	179.4 (2)
C6—C3—C4—C5	−176.8 (3)	N1i—Cu1—N2—C12	109.81 (19)
C3—C4—C5—N1	0.1 (5)	N1—Cu1—N2—C12	−70.19 (19)
N2—C7—C8—C9	−0.7 (5)	O1—Cu1—N2—C12	19.53 (19)
C7—C8—C9—C11	1.5 (4)	O1i—Cu1—N2—C12	−160.47 (19)
C7—C8—C9—C10	−178.2 (3)	N1i—Cu1—N2—C7	−69.7 (2)
C8—C9—C11—C12	−1.5 (4)	N1—Cu1—N2—C7	110.3 (2)
C10—C9—C11—C12	178.3 (3)	O1—Cu1—N2—C7	−160.0 (2)
C9—C11—C12—N2	0.7 (4)	O1i—Cu1—N2—C7	20.0 (2)
N3—C13—C14—C15	0.1 (4)	C16—C17—N3—C13	1.0 (5)
C13—C14—C15—C16	1.2 (4)	C16—C17—N3—Cu2	−179.6 (3)
C13—C14—C15—C18	−179.7 (3)	C14—C13—N3—C17	−1.2 (4)
C14—C15—C16—C17	−1.4 (5)	C14—C13—N3—Cu2	179.34 (19)
C18—C15—C16—C17	179.4 (3)	N4ii—Cu2—N3—C17	109.5 (2)
C15—C16—C17—N3	0.4 (5)	N4—Cu2—N3—C17	−70.5 (2)
N4—C19—C20—C21	0.1 (4)	N4ii—Cu2—N3—C13	−71.1 (2)
C19—C20—C21—C22	1.6 (4)	N4—Cu2—N3—C13	108.9 (2)
C19—C20—C21—C24	−177.5 (3)	C22—C23—N4—C19	2.9 (4)
C20—C21—C22—C23	−1.1 (4)	C22—C23—N4—Cu2	−174.0 (2)
C24—C21—C22—C23	178.1 (3)	C20—C19—N4—C23	−2.3 (4)
C21—C22—C23—N4	−1.2 (5)	C20—C19—N4—Cu2	174.7 (2)
C2—C1—N1—C5	3.2 (4)	N3—Cu2—N4—C23	71.8 (2)
C2—C1—N1—Cu1	−174.3 (2)	N3ii—Cu2—N4—C23	−108.2 (2)
C4—C5—N1—C1	−3.1 (4)	N3—Cu2—N4—C19	−105.1 (2)
C4—C5—N1—Cu1	174.3 (2)	N3ii—Cu2—N4—C19	74.9 (2)
N2—Cu1—N1—C1	−73.2 (2)	N1i—Cu1—O1—S3	97.0 (7)
N2i—Cu1—N1—C1	106.8 (2)	N1—Cu1—O1—S3	−83.0 (7)
O1—Cu1—N1—C1	−163.6 (2)	N2—Cu1—O1—S3	−171.7 (7)
O1i—Cu1—N1—C1	16.4 (2)	N2i—Cu1—O1—S3	8.3 (7)
N2—Cu1—N1—C5	109.4 (2)	Cu1—O1—S3—O2	−173.0 (7)
N2i—Cu1—N1—C5	−70.6 (2)	Cu1—O1—S3—O3	−52.3 (7)
O1—Cu1—N1—C5	19.1 (2)	Cu1—O1—S3—O4	67.4 (7)
O1i—Cu1—N1—C5	−160.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6iii	0.85	2.04	2.887 (4)	173
O5—H5B···O4iv	0.85	2.01	2.843 (4)	168
O6—H6A···O6iii	0.84	2.34	2.983 (6)	133
O6—H6B···O4iv	0.85	1.92	2.762 (4)	172
O6—H6C···O8	0.85	1.98	2.804 (5)	163
O7—H7A···O5	0.84	2.16	2.906 (4)	148
O7—H7B···O3v	0.85	2.13	2.923 (4)	157
O8—H8A···O3iv	0.84	2.42	2.788 (4)	107
O8—H8B···O6	0.85	2.04	2.804 (5)	149
O8—H8C···O8vi	0.85	1.87	2.710 (7)	176
O9—H9A···O6	0.84	2.48	3.210 (7)	145
O9—H9B···O3iv	0.84	2.22	3.063 (7)	175
O9—H9B···O4iv	0.84	2.71	3.275 (7)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6i	0.85	2.04	2.887 (4)	173
O5—H5B⋯O4ii	0.85	2.01	2.843 (4)	168
O6—H6A⋯O6i	0.84	2.34	2.983 (6)	133
O6—H6B⋯O4ii	0.85	1.92	2.762 (4)	172
O6—H6C⋯O8	0.85	1.98	2.804 (5)	163
O7—H7A⋯O5	0.84	2.16	2.906 (4)	148
O7—H7B⋯O3iii	0.85	2.13	2.923 (4)	157
O8—H8A⋯O3ii	0.84	2.42	2.788 (4)	107
O8—H8B⋯O6	0.85	2.04	2.804 (5)	149
O8—H8C⋯O8iv	0.85	1.87	2.710 (7)	176
O9—H9A⋯O6	0.84	2.48	3.210 (7)	145
O9—H9B⋯O3ii	0.84	2.22	3.063 (7)	175
O9—H9B⋯O4ii	0.84	2.71	3.275 (7)	126

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .