Preparation and characterization of two new Cu^II supra­molecular coordination polymers incorporating sulfobenzoate and flexible heterocyclic ligands

The assembly of Cu^II with the multifunctional ligand 2-amino-4-sulfo­benzoic acid (H₂asba) in the presence of the auxiliary flexible ligands 1,4-bis­(triazol-1-ylmeth­yl)benzene (bbtz) and 1,4-bis­(imidazol-1-ylmeth­yl)benzene (bix) under ambient conditions resulted in two new supra­molecular coordination polymers, namely poly[[(3-amino-4-carb­oxy­benzene­sulfonato-κO)aqua­bis­[μ₂-1,4-bis­(tri­az­ol-1-ylmeth­yl)benzene-κ²N⁴:N^4′]copper(II)] 3-amino-4-carb­oxy­benzene­sul­fon­ate tetrahydrate], {[Cu(C₇H₆NO₅S)(C₁₂H₁₂N₆)₂(H₂O)](C₇H₆NO₅S)·4H₂O}_n, (1), and poly[[bis­(μ₂-2-amino-4-sulfon­ato­benzoato-κ³O¹:N,O^1′)tetra­aqua­[μ₂-1,4-bis­(triazol-1-ylmeth­yl)benzene-κ²N⁴:N^4′]dicopper(II)] tetra­hydrate], {[Cu₂(C₇H₅NO₅S)₂(C₁₄H₁₄N₄)(H₂O)₄]·4H₂O}_n, (2). Single-crystal X-ray structure diffraction analysis of (1) reveals that the bbtz ligand acts as a bridge, linking adjacent Cu^II ions into a two-dimensional cationic (4,4) topological network, in which the coordinated 3-amino-4-carb­oxy­benzene­sulfonate (Hasba⁻) anion uses its sulfonate group to bind with the Cu^II ion in a monodentate fashion and the carboxyl­ate group remains protonated. The lattice Hasba⁻ anion resides in the two-dimensional layer and balances the charge. The carboxyl­ate group of the 2-amino-4-sulfon­ato­benzoate (asba²⁻) ligand in (2) is involved in bidentate coordination, connecting adjacent Cu^II ions into carboxyl­ate-bridged chains which are further bridged by the auxiliary flexible bix ligand in a trans–gauche (TG) mode, resulting in the formation of a two-dimensional network architecture. The amino group of the asba²⁻ ligand in (2) also takes part in the coordination with the central Cu^II ion. The six-coordinated Cu^II centres in (1) and (2) exhibit distorted octa­hedral coordination geometries. Extensive hydrogen bonding exists in both (1) and (2). The inter­layer hydrogen bonds in both compounds further extend adjacent two-dimensional layers into three-dimensional supra­molecular network architectures. Furthermore, a detailed analysis of the solid-state UV–Vis–NIR (NIR is near IR) diffuse reflectance data indicates that (1) and (2) may have potential as wide band gap indirect semiconductor materials. Compounds (1) and (2) show reversible and irreversible dehydration–rehydration behaviours, respectively.

Computing details

For both structures, data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008). Software used to prepare material for publication: SHELXTL for (1); SHELXTL (Sheldrick, 2008) for (2).

Poly[[(3-amino-4-carboxybenzenesulfonato-κO)aquabis[µ₂-1,4-bis(triazol-1-ylmethyl)benzene-κ²N⁴:N^4']copper(II)] 3-amino-4-carboxybenzenesulfonate 3.5-hydrate] (1)

Crystal data

[Cu(C7H6NO5S)(C12H12N6)2(H2O)](C7H6NO5S)·4H2O	F(000) = 2211
Mr = 1066.58	Dx = 1.534 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 9905 reflections
a = 24.390 (3) Å	θ = 2.3–26.1°
b = 11.8710 (15) Å	µ = 0.65 mm^−1
c = 16.048 (2) Å	T = 296 K
β = 96.325 (4)°	Block, green
V = 4618.2 (10) Å^3	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area detector diffractometer	10691 independent reflections
Radiation source: fine-focus sealed tube	7337 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
phi and ω scans	θmax = 27.7°, θmin = 0.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2002)	h = −31→29
Tmin = 0.824, Tmax = 0.879	k = −15→13
71401 measured reflections	l = −20→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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0891P)^2 + 5.1487P] where P = (Fo^2 + 2Fc^2)/3
10691 reflections	(Δ/σ)max = 0.001
631 parameters	Δρmax = 1.68 e Å^−3
22 restraints	Δρmin = −0.96 e Å^−3

Special details

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
C1	0.34850 (13)	0.6619 (3)	0.3632 (2)	0.0397 (8)
H1	0.3351	0.5912	0.3463	0.048*
C2	0.35841 (15)	0.8351 (3)	0.3822 (3)	0.0476 (9)
H2	0.3516	0.9122	0.3798	0.057*
C3	0.43344 (15)	0.5983 (4)	0.4532 (3)	0.0547 (11)
H3A	0.4208	0.5227	0.4384	0.066*
H3B	0.4343	0.6062	0.5135	0.066*
C4	0.49113 (14)	0.6137 (3)	0.4289 (2)	0.0422 (9)
C5	0.52669 (16)	0.6902 (4)	0.4715 (2)	0.0493 (10)
H5	0.5144	0.7346	0.5135	0.059*
C6	0.57999 (16)	0.7013 (3)	0.4524 (3)	0.0495 (10)
H6	0.6036	0.7524	0.4820	0.059*
C7	0.59880 (15)	0.6369 (3)	0.3893 (2)	0.0403 (8)
C8	0.56272 (16)	0.5609 (3)	0.3464 (2)	0.0434 (8)
H8	0.5747	0.5168	0.3040	0.052*
C9	0.50955 (15)	0.5502 (3)	0.3659 (2)	0.0437 (9)
H9	0.4858	0.4995	0.3362	0.052*
C10	0.65675 (16)	0.6515 (3)	0.3667 (3)	0.0535 (11)
H10A	0.6557	0.6937	0.3148	0.064*
H10B	0.6781	0.6944	0.4103	0.064*
C11	0.28567 (16)	0.8841 (4)	0.1117 (2)	0.0480 (9)
H11	0.2744	0.8198	0.0815	0.058*
C12	0.30100 (14)	0.9971 (3)	0.2124 (2)	0.0416 (8)
H12	0.3036	1.0316	0.2647	0.050*
C13	0.15408 (17)	0.6936 (4)	0.1511 (3)	0.0567 (11)
H13	0.1647	0.6187	0.1582	0.068*
C14	0.15330 (13)	0.8690 (3)	0.1636 (2)	0.0410 (8)
H14	0.1618	0.9429	0.1793	0.049*
C15	0.07192 (15)	0.9111 (4)	0.0598 (3)	0.0563 (12)
H15A	0.0738	0.8944	0.0011	0.068*
H15B	0.0830	0.9889	0.0692	0.068*
C16	0.01313 (13)	0.8986 (3)	0.0782 (2)	0.0392 (8)
C17	−0.02157 (15)	0.8195 (3)	0.0358 (2)	0.0456 (9)
H17	−0.0072	0.7672	0.0009	0.055*
C18	−0.07692 (15)	0.8181 (3)	0.0452 (2)	0.0409 (8)
H18	−0.0997	0.7652	0.0160	0.049*
C19	−0.09926 (13)	0.8943 (3)	0.09744 (19)	0.0304 (7)
C20	−0.06445 (14)	0.9691 (3)	0.1424 (2)	0.0386 (8)
H20	−0.0783	1.0185	0.1799	0.046*
C21	−0.00888 (15)	0.9710 (3)	0.1318 (2)	0.0427 (9)
H21	0.0141	1.0228	0.1619	0.051*
C22	−0.16053 (14)	0.8951 (3)	0.1009 (2)	0.0397 (8)
H22A	−0.1787	0.8633	0.0494	0.048*
H22B	−0.1693	0.8479	0.1470	0.048*
C23	0.19680 (16)	0.6778 (4)	0.4132 (2)	0.0471 (9)
H23	0.1979	0.7482	0.4388	0.057*
C24	0.20780 (13)	0.5495 (3)	0.3266 (2)	0.0362 (8)
H24	0.2175	0.5084	0.2811	0.043*
C25	0.49396 (15)	0.6618 (3)	0.1623 (2)	0.0448 (9)
C26	0.47822 (17)	0.5551 (4)	0.1322 (3)	0.0578 (11)
C27	0.42161 (17)	0.5280 (4)	0.1207 (3)	0.0576 (11)
H27	0.4106	0.4572	0.1005	0.069*
C28	0.38286 (15)	0.6040 (3)	0.1386 (2)	0.0411 (8)
C29	0.39860 (16)	0.7091 (3)	0.1713 (3)	0.0498 (10)
H29	0.3722	0.7603	0.1852	0.060*
C30	0.45393 (16)	0.7363 (3)	0.1828 (3)	0.0491 (9)
H30	0.4646	0.8064	0.2048	0.059*
C31	0.55234 (16)	0.6973 (4)	0.1728 (3)	0.0518 (10)
C32	0.00522 (18)	0.3657 (4)	0.1592 (2)	0.0517 (10)
C33	0.01680 (19)	0.2702 (4)	0.2103 (2)	0.0514 (10)
C34	0.07041 (19)	0.2273 (4)	0.2196 (3)	0.0528 (10)
H34	0.0784	0.1639	0.2528	0.063*
C35	0.11131 (18)	0.2767 (4)	0.1806 (3)	0.0522 (10)
C36	0.1008 (2)	0.3729 (4)	0.1319 (3)	0.0591 (11)
H36	0.1290	0.4076	0.1067	0.071*
C37	0.0482 (2)	0.4156 (4)	0.1216 (3)	0.0588 (11)
H37	0.0410	0.4794	0.0886	0.071*
C38	−0.0507 (2)	0.4146 (4)	0.1472 (3)	0.0644 (12)
Cu1	0.251700 (15)	0.77554 (4)	0.26931 (3)	0.03449 (14)
N1	0.32407 (11)	0.7587 (2)	0.34161 (18)	0.0349 (6)
N2	0.40203 (14)	0.7917 (3)	0.4251 (2)	0.0534 (9)
N3	0.39442 (11)	0.6801 (3)	0.41188 (19)	0.0407 (7)
N4	0.68359 (12)	0.5430 (3)	0.3567 (2)	0.0438 (7)
N5	0.69315 (14)	0.4715 (3)	0.4225 (2)	0.0523 (8)
N6	0.28142 (11)	0.8948 (2)	0.19525 (18)	0.0378 (7)
N7	0.18184 (11)	0.7794 (2)	0.1918 (2)	0.0395 (7)
N8	0.11029 (14)	0.7255 (3)	0.1001 (3)	0.0599 (10)
N9	0.11124 (11)	0.8385 (3)	0.11044 (19)	0.0409 (7)
N10	−0.18163 (11)	1.0086 (2)	0.11203 (17)	0.0355 (6)
N11	−0.17480 (14)	1.0901 (3)	0.0555 (2)	0.0498 (8)
N12	0.21812 (11)	0.6580 (3)	0.34008 (18)	0.0367 (7)
N13	0.51525 (19)	0.4748 (4)	0.1169 (4)	0.117 (2)
H13A	0.5500	0.4888	0.1259	0.140*
H13B	0.5041	0.4098	0.0986	0.140*
N14	−0.02227 (18)	0.2169 (3)	0.2508 (3)	0.0676 (11)
H14A	−0.0136	0.1583	0.2809	0.081*
H14B	−0.0556	0.2418	0.2462	0.081*
O1	0.28553 (11)	0.6187 (3)	0.18669 (17)	0.0522 (7)
O2	0.29177 (13)	0.6153 (3)	0.03856 (18)	0.0695 (9)
O3	0.31002 (13)	0.4468 (3)	0.1216 (2)	0.0697 (9)
O4	0.59033 (12)	0.6377 (3)	0.1552 (2)	0.0741 (10)
O5	0.56022 (12)	0.8002 (3)	0.2012 (2)	0.0686 (9)
H5A	0.5931	0.8159	0.2034	0.103*
O6	0.18671 (16)	0.1733 (4)	0.1099 (2)	0.0871 (11)
O7	0.17869 (17)	0.1274 (4)	0.2520 (3)	0.0951 (12)
O8	0.21547 (14)	0.3067 (3)	0.2196 (2)	0.0790 (10)
O9	−0.05383 (17)	0.5075 (4)	0.1018 (3)	0.0955 (12)
H9A	−0.0860	0.5285	0.0942	0.143*
O10	−0.09021 (16)	0.3757 (4)	0.1768 (3)	0.0929 (12)
O1W	0.23600 (15)	0.9190 (3)	0.3691 (2)	0.0744 (10)
H1WA	0.2087	0.9341	0.3324	0.089*
H1WB	0.2398	0.9718	0.4052	0.089*
O2W	0.34047 (14)	0.3855 (3)	0.2955 (2)	0.0794 (10)
H2WB	0.3202	0.3546	0.3285	0.095*
H2WA	0.3231	0.3921	0.2467	0.095*
O3W	0.23778 (15)	0.3237 (3)	0.0142 (2)	0.0838 (11)
H3WB	0.2605	0.3711	0.0388	0.101*
H3WA	0.2238	0.2848	0.0513	0.101*
O4W	0.15546 (16)	0.0847 (4)	0.4082 (3)	0.0989 (13)
H4WA	0.1592	0.1105	0.3591	0.119*
H4WB	0.1824	0.1092	0.4424	0.119*
O5W	0.2872 (4)	0.1836 (7)	0.3720 (6)	0.258 (4)
H5WA	0.3173	0.1780	0.3483	0.309*
H5WB	0.2960	0.1706	0.4248	0.309*
S1	0.31176 (4)	0.56852 (9)	0.11942 (6)	0.0449 (2)
S2	0.17878 (5)	0.21731 (10)	0.19082 (7)	0.0605 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0260 (17)	0.041 (2)	0.051 (2)	0.0019 (14)	−0.0009 (15)	0.0062 (16)
C2	0.0355 (19)	0.040 (2)	0.065 (3)	0.0002 (16)	−0.0043 (18)	−0.0001 (18)
C3	0.035 (2)	0.065 (3)	0.063 (3)	0.0107 (18)	0.0024 (18)	0.029 (2)
C4	0.0336 (18)	0.049 (2)	0.043 (2)	0.0103 (16)	−0.0018 (15)	0.0143 (17)
C5	0.038 (2)	0.064 (3)	0.046 (2)	0.0133 (18)	0.0039 (17)	−0.0117 (19)
C6	0.037 (2)	0.049 (2)	0.060 (2)	0.0070 (17)	−0.0030 (18)	−0.0164 (19)
C7	0.0363 (19)	0.0318 (18)	0.053 (2)	0.0046 (14)	0.0056 (16)	−0.0035 (16)
C8	0.047 (2)	0.039 (2)	0.046 (2)	0.0029 (16)	0.0076 (17)	−0.0032 (16)
C9	0.039 (2)	0.042 (2)	0.048 (2)	−0.0037 (16)	−0.0036 (16)	0.0044 (17)
C10	0.045 (2)	0.033 (2)	0.086 (3)	−0.0006 (16)	0.019 (2)	−0.011 (2)
C11	0.043 (2)	0.049 (2)	0.051 (2)	−0.0144 (17)	0.0003 (17)	0.0061 (18)
C12	0.0330 (18)	0.039 (2)	0.053 (2)	0.0027 (15)	0.0072 (16)	0.0044 (17)
C13	0.041 (2)	0.044 (2)	0.082 (3)	0.0048 (18)	−0.011 (2)	0.008 (2)
C14	0.0247 (16)	0.042 (2)	0.056 (2)	0.0026 (15)	0.0028 (15)	0.0124 (17)
C15	0.0311 (19)	0.077 (3)	0.061 (3)	0.0105 (19)	0.0026 (17)	0.038 (2)
C16	0.0267 (17)	0.051 (2)	0.0390 (19)	0.0089 (15)	0.0007 (14)	0.0194 (16)
C17	0.039 (2)	0.055 (2)	0.044 (2)	0.0139 (18)	0.0102 (16)	−0.0048 (18)
C18	0.0370 (19)	0.041 (2)	0.044 (2)	0.0019 (16)	0.0033 (15)	−0.0085 (16)
C19	0.0301 (16)	0.0311 (17)	0.0301 (16)	0.0053 (13)	0.0026 (13)	0.0050 (13)
C20	0.0384 (19)	0.042 (2)	0.0342 (18)	0.0039 (15)	−0.0003 (15)	−0.0039 (15)
C21	0.0355 (19)	0.049 (2)	0.040 (2)	−0.0028 (16)	−0.0088 (15)	0.0064 (17)
C22	0.0363 (19)	0.0388 (19)	0.045 (2)	0.0011 (15)	0.0105 (15)	−0.0066 (16)
C23	0.051 (2)	0.049 (2)	0.043 (2)	−0.0156 (18)	0.0130 (17)	−0.0068 (18)
C24	0.0292 (17)	0.043 (2)	0.0376 (18)	0.0020 (15)	0.0100 (14)	0.0042 (15)
C25	0.0366 (19)	0.049 (2)	0.050 (2)	0.0029 (16)	0.0059 (16)	0.0079 (18)
C26	0.041 (2)	0.059 (3)	0.074 (3)	0.0136 (19)	0.006 (2)	−0.008 (2)
C27	0.047 (2)	0.049 (2)	0.076 (3)	0.0044 (19)	0.005 (2)	−0.017 (2)
C28	0.0355 (19)	0.045 (2)	0.043 (2)	0.0000 (16)	0.0065 (15)	0.0010 (16)
C29	0.038 (2)	0.045 (2)	0.067 (3)	0.0011 (17)	0.0114 (19)	−0.0024 (19)
C30	0.039 (2)	0.043 (2)	0.065 (3)	−0.0023 (17)	0.0074 (18)	0.0013 (19)
C31	0.038 (2)	0.057 (3)	0.060 (3)	0.0059 (19)	0.0052 (18)	0.017 (2)
C32	0.063 (3)	0.051 (2)	0.043 (2)	−0.006 (2)	0.0139 (19)	−0.0127 (19)
C33	0.065 (3)	0.050 (2)	0.041 (2)	−0.018 (2)	0.0173 (19)	−0.0195 (18)
C34	0.067 (3)	0.047 (2)	0.045 (2)	−0.008 (2)	0.006 (2)	−0.0100 (18)
C35	0.059 (3)	0.049 (2)	0.049 (2)	−0.009 (2)	0.0066 (19)	−0.0161 (19)
C36	0.065 (3)	0.056 (3)	0.059 (3)	−0.014 (2)	0.018 (2)	−0.009 (2)
C37	0.074 (3)	0.054 (3)	0.050 (2)	−0.003 (2)	0.012 (2)	−0.005 (2)
C38	0.073 (3)	0.066 (3)	0.057 (3)	−0.006 (2)	0.016 (2)	−0.009 (2)
Cu1	0.0198 (2)	0.0387 (3)	0.0443 (3)	−0.00073 (16)	0.00056 (16)	0.01186 (18)
N1	0.0250 (13)	0.0371 (16)	0.0424 (16)	0.0029 (11)	0.0028 (12)	0.0033 (13)
N2	0.0390 (18)	0.052 (2)	0.066 (2)	0.0006 (15)	−0.0105 (16)	−0.0015 (17)
N3	0.0284 (15)	0.0474 (18)	0.0455 (17)	0.0063 (13)	0.0005 (13)	0.0104 (14)
N4	0.0333 (16)	0.0397 (17)	0.059 (2)	0.0016 (13)	0.0085 (14)	−0.0102 (15)
N5	0.0492 (19)	0.055 (2)	0.052 (2)	0.0105 (16)	0.0039 (16)	−0.0108 (17)
N6	0.0287 (14)	0.0404 (17)	0.0440 (17)	−0.0035 (12)	0.0027 (12)	0.0105 (13)
N7	0.0259 (14)	0.0397 (17)	0.0522 (18)	0.0005 (12)	0.0007 (13)	0.0125 (14)
N8	0.0402 (19)	0.062 (2)	0.072 (2)	0.0022 (16)	−0.0164 (17)	0.0041 (19)
N9	0.0251 (14)	0.0471 (19)	0.0503 (18)	0.0050 (12)	0.0034 (13)	0.0161 (14)
N10	0.0296 (14)	0.0401 (16)	0.0377 (15)	0.0016 (12)	0.0081 (12)	−0.0025 (13)
N11	0.055 (2)	0.055 (2)	0.0418 (18)	0.0151 (16)	0.0161 (15)	0.0057 (15)
N12	0.0266 (14)	0.0447 (18)	0.0391 (16)	−0.0030 (12)	0.0054 (12)	0.0067 (13)
N13	0.054 (3)	0.092 (4)	0.203 (6)	0.019 (3)	0.008 (3)	−0.067 (4)
N14	0.079 (3)	0.058 (2)	0.071 (3)	−0.014 (2)	0.030 (2)	−0.0065 (19)
O1	0.0378 (14)	0.0645 (18)	0.0556 (16)	−0.0028 (13)	0.0113 (12)	−0.0079 (14)
O2	0.0578 (19)	0.101 (3)	0.0478 (17)	−0.0080 (18)	−0.0037 (14)	0.0024 (17)
O3	0.0580 (19)	0.0498 (18)	0.101 (3)	−0.0112 (15)	0.0075 (17)	−0.0127 (17)
O4	0.0391 (16)	0.081 (2)	0.104 (3)	0.0074 (16)	0.0157 (17)	0.008 (2)
O5	0.0409 (16)	0.063 (2)	0.099 (3)	−0.0064 (14)	−0.0032 (16)	0.0110 (18)
O6	0.083 (3)	0.108 (3)	0.070 (2)	0.015 (2)	0.0084 (19)	−0.034 (2)
O7	0.085 (3)	0.092 (3)	0.109 (3)	0.010 (2)	0.012 (2)	0.023 (2)
O8	0.064 (2)	0.083 (2)	0.091 (3)	−0.0171 (18)	0.0101 (19)	−0.030 (2)
O9	0.077 (3)	0.098 (3)	0.114 (3)	0.015 (2)	0.021 (2)	0.030 (3)
O10	0.071 (2)	0.112 (3)	0.102 (3)	0.007 (2)	0.035 (2)	0.014 (2)
O1W	0.087 (2)	0.059 (2)	0.079 (2)	0.0216 (17)	0.0191 (19)	−0.0093 (17)
O2W	0.060 (2)	0.083 (2)	0.094 (3)	0.0173 (18)	0.0046 (18)	0.008 (2)
O3W	0.084 (3)	0.087 (3)	0.075 (2)	−0.012 (2)	−0.0109 (19)	−0.008 (2)
O4W	0.070 (2)	0.112 (3)	0.112 (3)	−0.002 (2)	−0.003 (2)	−0.017 (3)
O5W	0.220 (7)	0.338 (9)	0.224 (7)	−0.048 (7)	0.067 (6)	0.003 (7)
S1	0.0369 (5)	0.0504 (6)	0.0473 (5)	−0.0047 (4)	0.0049 (4)	−0.0049 (4)
S2	0.0609 (7)	0.0652 (7)	0.0555 (7)	−0.0041 (5)	0.0072 (5)	−0.0146 (5)

Geometric parameters (Å, º)

C1—N3	1.311 (4)	C26—C27	1.410 (6)
C1—N1	1.322 (4)	C27—C28	1.360 (5)
C1—H1	0.9300	C27—H27	0.9300
C2—N2	1.308 (5)	C28—C29	1.391 (5)
C2—N1	1.353 (5)	C28—S1	1.778 (4)
C2—H2	0.9300	C29—C30	1.380 (5)
C3—N3	1.466 (4)	C29—H29	0.9300
C3—C4	1.512 (5)	C30—H30	0.9300
C3—H3A	0.9700	C31—O4	1.224 (5)
C3—H3B	0.9700	C31—O5	1.310 (5)
C4—C9	1.376 (5)	C32—C37	1.399 (6)
C4—C5	1.384 (6)	C32—C33	1.409 (6)
C5—C6	1.375 (6)	C32—C38	1.475 (7)
C5—H5	0.9300	C33—N14	1.366 (5)
C6—C7	1.387 (5)	C33—C34	1.396 (6)
C6—H6	0.9300	C34—C35	1.366 (6)
C7—C8	1.389 (5)	C34—H34	0.9300
C7—C10	1.507 (5)	C35—C36	1.392 (6)
C8—C9	1.373 (5)	C35—S2	1.781 (5)
C8—H8	0.9300	C36—C37	1.373 (7)
C9—H9	0.9300	C36—H36	0.9300
C10—N4	1.461 (5)	C37—H37	0.9300
C10—H10A	0.9700	C38—O10	1.213 (6)
C10—H10B	0.9700	C38—O9	1.320 (6)
C11—N6	1.362 (5)	Cu1—N1	2.013 (3)
C11—H11	0.9300	Cu1—N6	2.033 (3)
C12—N6	1.324 (5)	Cu1—N7	1.997 (3)
C12—N4^i	1.326 (5)	Cu1—N12	2.028 (3)
C12—H12	0.9300	Cu1—O1W	2.397 (3)
C13—N8	1.327 (5)	Cu1—O1	2.479 (3)
C13—N7	1.351 (5)	C11—N5^i	1.307 (5)
C13—H13	0.9300	C24—N10^ii	1.323 (4)
C14—N9	1.311 (5)	N2—N3	1.352 (5)
C14—N7	1.323 (4)	N4—C12^iii	1.326 (5)
C14—H14	0.9300	N4—N5	1.355 (5)
C15—N9	1.467 (4)	N5—C11^iii	1.307 (5)
C15—C16	1.503 (5)	N8—N9	1.352 (5)
C15—H15A	0.9700	N10—C24^iv	1.323 (4)
C15—H15B	0.9700	N10—N11	1.348 (4)
C16—C21	1.366 (5)	N11—C23^iv	1.298 (5)
C16—C17	1.391 (5)	N13—H13A	0.8601
C17—C18	1.375 (5)	N13—H13B	0.8600
C17—H17	0.9300	N14—H14A	0.8600
C18—C19	1.385 (5)	N14—H14B	0.8599
C18—H18	0.9300	O1—S1	1.443 (3)
C19—C20	1.377 (5)	O2—S1	1.446 (3)
C19—C22	1.502 (5)	O3—S1	1.447 (3)
C20—C21	1.385 (5)	O5—H5A	0.8200
C20—H20	0.9300	O6—S2	1.432 (3)
C21—H21	0.9300	O7—S2	1.450 (4)
C22—N10	1.461 (4)	O8—S2	1.431 (3)
C22—H22A	0.9700	O9—H9A	0.8200
C22—H22B	0.9700	O1W—H1WA	0.8583
C23—N11^ii	1.298 (5)	O1W—H1WB	0.8515
C23—N12	1.356 (5)	O2W—H2WB	0.8466
C23—H23	0.9300	O2W—H2WA	0.8511
C24—N10^ii	1.323 (4)	O3W—H3WB	0.8561
C24—N12	1.325 (5)	O3W—H3WA	0.8550
C24—H24	0.9300	O4W—H4WA	0.8586
C25—C30	1.383 (5)	O4W—H4WB	0.8596
C25—C26	1.394 (6)	O5W—H5WA	0.8656
C25—C31	1.477 (5)	O5W—H5WB	0.8649
C26—N13	1.354 (6)
N3—C1—N1	110.1 (3)	C29—C30—C25	121.6 (4)
N3—C1—H1	124.9	C29—C30—H30	119.2
N1—C1—H1	124.9	C25—C30—H30	119.2
N2—C2—N1	114.4 (3)	O4—C31—O5	122.3 (4)
N2—C2—H2	122.8	O4—C31—C25	123.6 (4)
N1—C2—H2	122.8	O5—C31—C25	114.1 (4)
N3—C3—C4	112.3 (3)	C37—C32—C33	118.7 (4)
N3—C3—H3A	109.2	C37—C32—C38	120.2 (4)
C4—C3—H3A	109.2	C33—C32—C38	121.1 (4)
N3—C3—H3B	109.2	N14—C33—C34	118.3 (4)
C4—C3—H3B	109.2	N14—C33—C32	122.9 (4)
H3A—C3—H3B	107.9	C34—C33—C32	118.7 (4)
C9—C4—C5	119.1 (3)	C35—C34—C33	121.2 (4)
C9—C4—C3	120.8 (4)	C35—C34—H34	119.4
C5—C4—C3	120.1 (4)	C33—C34—H34	119.4
C6—C5—C4	120.6 (4)	C34—C35—C36	120.7 (4)
C6—C5—H5	119.7	C34—C35—S2	120.1 (4)
C4—C5—H5	119.7	C36—C35—S2	119.1 (3)
C5—C6—C7	120.5 (4)	C37—C36—C35	118.8 (4)
C5—C6—H6	119.7	C37—C36—H36	120.6
C7—C6—H6	119.7	C35—C36—H36	120.6
C6—C7—C8	118.5 (3)	C36—C37—C32	121.8 (4)
C6—C7—C10	120.5 (3)	C36—C37—H37	119.1
C8—C7—C10	121.0 (3)	C32—C37—H37	119.1
C9—C8—C7	120.7 (4)	O10—C38—O9	122.3 (5)
C9—C8—H8	119.7	O10—C38—C32	124.2 (5)
C7—C8—H8	119.7	O9—C38—C32	113.5 (4)
C8—C9—C4	120.6 (4)	N7—Cu1—N1	174.62 (13)
C8—C9—H9	119.7	N7—Cu1—N12	89.73 (11)
C4—C9—H9	119.7	N1—Cu1—N12	89.50 (11)
N4—C10—C7	111.6 (3)	N7—Cu1—N6	87.38 (11)
N4—C10—H10A	109.3	N1—Cu1—N6	93.43 (11)
C7—C10—H10A	109.3	N12—Cu1—N6	177.05 (11)
N4—C10—H10B	109.3	N7—Cu1—O1W	102.23 (13)
C7—C10—H10B	109.3	N1—Cu1—O1W	83.11 (12)
H10A—C10—H10B	108.0	N12—Cu1—O1W	90.60 (12)
N5^i—C11—N6	114.6 (4)	N6—Cu1—O1W	89.41 (12)
N5^i—C11—H11	122.7	N7—Cu1—O1	89.75 (11)
N6—C11—H11	122.7	N1—Cu1—O1	84.90 (10)
N6—C12—N4^i	109.4 (3)	N12—Cu1—O1	87.78 (11)
N6—C12—H12	125.3	N6—Cu1—O1	92.82 (11)
N4^i—C12—H12	125.3	O1W—Cu1—O1	167.91 (11)
N8—C13—N7	114.2 (4)	C1—N1—C2	102.7 (3)
N8—C13—H13	122.9	C1—N1—Cu1	125.4 (2)
N7—C13—H13	122.9	C2—N1—Cu1	131.9 (2)
N9—C14—N7	110.2 (3)	C2—N2—N3	102.4 (3)
N9—C14—H14	124.9	C1—N3—N2	110.4 (3)
N7—C14—H14	124.9	C1—N3—C3	129.1 (3)
N9—C15—C16	114.4 (3)	N2—N3—C3	120.5 (3)
N9—C15—H15A	108.7	C12^iii—N4—N5	110.7 (3)
C16—C15—H15A	108.7	C12^iii—N4—C10	128.7 (4)
N9—C15—H15B	108.7	N5—N4—C10	120.5 (3)
C16—C15—H15B	108.7	C11^iii—N5—N4	102.3 (3)
H15A—C15—H15B	107.6	C12—N6—C11	103.0 (3)
C21—C16—C17	118.2 (3)	C12—N6—Cu1	131.4 (3)
C21—C16—C15	120.7 (4)	C11—N6—Cu1	125.6 (3)
C17—C16—C15	120.8 (4)	C14—N7—C13	102.9 (3)
C18—C17—C16	120.4 (3)	C14—N7—Cu1	127.8 (3)
C18—C17—H17	119.8	C13—N7—Cu1	129.2 (3)
C16—C17—H17	119.8	C13—N8—N9	101.8 (3)
C17—C18—C19	121.0 (3)	C14—N9—N8	110.9 (3)
C17—C18—H18	119.5	C14—N9—C15	128.0 (4)
C19—C18—H18	119.5	N8—N9—C15	120.9 (3)
C20—C19—C18	118.5 (3)	C24^iv—N10—N11	110.1 (3)
C20—C19—C22	122.4 (3)	C24^iv—N10—C22	129.4 (3)
C18—C19—C22	119.1 (3)	N11—N10—C22	120.5 (3)
C19—C20—C21	120.1 (3)	C23^iv—N11—N10	103.2 (3)
C19—C20—H20	120.0	C24—N12—C23	103.1 (3)
C21—C20—H20	120.0	C24—N12—Cu1	131.2 (2)
C16—C21—C20	121.7 (3)	C23—N12—Cu1	125.6 (3)
C16—C21—H21	119.2	C26—N13—H13A	119.9
C20—C21—H21	119.2	C26—N13—H13B	120.1
N10—C22—C19	112.1 (3)	H13A—N13—H13B	120.0
N10—C22—H22A	109.2	C33—N14—H14A	120.0
C19—C22—H22A	109.2	C33—N14—H14B	120.0
N10—C22—H22B	109.2	H14A—N14—H14B	120.0
C19—C22—H22B	109.2	S1—O1—Cu1	155.67 (19)
H22A—C22—H22B	107.9	C31—O5—H5A	109.4
N11^ii—C23—N12	114.1 (4)	C38—O9—H9A	109.4
N11^ii—C23—H23	122.9	Cu1—O1W—H1WA	81.9
N12—C23—H23	122.9	Cu1—O1W—H1WB	164.6
N10^ii—C24—N12	109.5 (3)	H1WA—O1W—H1WB	109.3
N10^ii—C24—H24	125.3	H2WB—O2W—H2WA	110.4
N12—C24—H24	125.3	H3WB—O3W—H3WA	108.8
C30—C25—C26	119.2 (4)	H4WA—O4W—H4WB	108.5
C30—C25—C31	119.2 (4)	H5WA—O5W—H5WB	106.7
C26—C25—C31	121.6 (4)	O1—S1—O3	112.2 (2)
N13—C26—C25	122.6 (4)	O1—S1—O2	112.3 (2)
N13—C26—C27	118.7 (4)	O3—S1—O2	113.4 (2)
C25—C26—C27	118.7 (4)	O1—S1—C28	106.10 (17)
C28—C27—C26	121.0 (4)	O3—S1—C28	105.27 (18)
C28—C27—H27	119.5	O2—S1—C28	106.86 (18)
C26—C27—H27	119.5	O8—S2—O6	114.9 (2)
C27—C28—C29	120.3 (4)	O8—S2—O7	112.0 (3)
C27—C28—S1	119.6 (3)	O6—S2—O7	110.8 (3)
C29—C28—S1	120.1 (3)	O8—S2—C35	106.0 (2)
C30—C29—C28	119.0 (4)	O6—S2—C35	106.1 (2)
C30—C29—H29	120.5	O7—S2—C35	106.4 (2)
C28—C29—H29	120.5
N3—C3—C4—C9	−96.1 (4)	N1—C1—N3—C3	177.3 (3)
N3—C3—C4—C5	85.6 (5)	C2—N2—N3—C1	0.3 (4)
C9—C4—C5—C6	−1.2 (6)	C2—N2—N3—C3	−176.8 (3)
C3—C4—C5—C6	177.1 (4)	C4—C3—N3—C1	122.5 (4)
C4—C5—C6—C7	0.8 (6)	C4—C3—N3—N2	−61.1 (5)
C5—C6—C7—C8	−0.3 (6)	C7—C10—N4—C12^iii	113.0 (4)
C5—C6—C7—C10	178.2 (4)	C7—C10—N4—N5	−63.2 (5)
C6—C7—C8—C9	0.3 (6)	C12^iii—N4—N5—C11^iii	−0.1 (4)
C10—C7—C8—C9	−178.3 (4)	C10—N4—N5—C11^iii	176.7 (3)
C7—C8—C9—C4	−0.7 (6)	N4^i—C12—N6—C11	−0.7 (4)
C5—C4—C9—C8	1.1 (6)	N4^i—C12—N6—Cu1	179.0 (2)
C3—C4—C9—C8	−177.2 (3)	N5^i—C11—N6—C12	0.7 (4)
C6—C7—C10—N4	135.1 (4)	N5^i—C11—N6—Cu1	−179.0 (3)
C8—C7—C10—N4	−46.4 (5)	N7—Cu1—N6—C12	122.5 (3)
N9—C15—C16—C21	96.5 (5)	N1—Cu1—N6—C12	−62.9 (3)
N9—C15—C16—C17	−89.1 (5)	O1W—Cu1—N6—C12	20.2 (3)
C21—C16—C17—C18	2.8 (5)	O1—Cu1—N6—C12	−147.9 (3)
C15—C16—C17—C18	−171.8 (3)	N7—Cu1—N6—C11	−57.9 (3)
C16—C17—C18—C19	−0.7 (6)	N1—Cu1—N6—C11	116.8 (3)
C17—C18—C19—C20	−2.3 (5)	O1W—Cu1—N6—C11	−160.1 (3)
C17—C18—C19—C22	175.6 (3)	O1—Cu1—N6—C11	31.8 (3)
C18—C19—C20—C21	3.1 (5)	N9—C14—N7—C13	0.5 (4)
C22—C19—C20—C21	−174.7 (3)	N9—C14—N7—Cu1	176.7 (2)
C17—C16—C21—C20	−2.0 (5)	N8—C13—N7—C14	−0.2 (5)
C15—C16—C21—C20	172.6 (3)	N8—C13—N7—Cu1	−176.3 (3)
C19—C20—C21—C16	−1.0 (5)	N12—Cu1—N7—C14	130.9 (3)
C20—C19—C22—N10	33.1 (5)	N6—Cu1—N7—C14	−48.5 (3)
C18—C19—C22—N10	−144.7 (3)	O1W—Cu1—N7—C14	40.3 (3)
C30—C25—C26—N13	−174.9 (5)	O1—Cu1—N7—C14	−141.3 (3)
C31—C25—C26—N13	5.2 (7)	N12—Cu1—N7—C13	−53.9 (4)
C30—C25—C26—C27	2.4 (7)	N6—Cu1—N7—C13	126.7 (4)
C31—C25—C26—C27	−177.6 (4)	O1W—Cu1—N7—C13	−144.4 (4)
N13—C26—C27—C28	177.2 (5)	O1—Cu1—N7—C13	33.9 (4)
C25—C26—C27—C28	−0.2 (7)	N7—C13—N8—N9	−0.2 (5)
C26—C27—C28—C29	−2.1 (7)	N7—C14—N9—N8	−0.7 (4)
C26—C27—C28—S1	177.7 (4)	N7—C14—N9—C15	−174.7 (3)
C27—C28—C29—C30	2.1 (6)	C13—N8—N9—C14	0.5 (5)
S1—C28—C29—C30	−177.7 (3)	C13—N8—N9—C15	175.0 (4)
C28—C29—C30—C25	0.2 (6)	C16—C15—N9—C14	−118.3 (4)
C26—C25—C30—C29	−2.4 (6)	C16—C15—N9—N8	68.2 (5)
C31—C25—C30—C29	177.5 (4)	C19—C22—N10—C24^iv	−119.7 (4)
C30—C25—C31—O4	−179.0 (4)	C19—C22—N10—N11	59.2 (4)
C26—C25—C31—O4	1.0 (7)	C24^iv—N10—N11—C23^iv	1.0 (4)
C30—C25—C31—O5	−0.3 (6)	C22—N10—N11—C23^iv	−178.2 (3)
C26—C25—C31—O5	179.7 (4)	N10^ii—C24—N12—C23	0.4 (4)
C37—C32—C33—N14	179.0 (4)	N10^ii—C24—N12—Cu1	−175.3 (2)
C38—C32—C33—N14	0.6 (6)	N11^ii—C23—N12—C24	0.2 (4)
C37—C32—C33—C34	−1.7 (6)	N11^ii—C23—N12—Cu1	176.2 (3)
C38—C32—C33—C34	179.9 (4)	N7—Cu1—N12—C24	73.8 (3)
N14—C33—C34—C35	179.9 (4)	N1—Cu1—N12—C24	−100.9 (3)
C32—C33—C34—C35	0.5 (6)	O1W—Cu1—N12—C24	176.0 (3)
C33—C34—C35—C36	1.3 (6)	O1—Cu1—N12—C24	−15.9 (3)
C33—C34—C35—S2	−178.0 (3)	N7—Cu1—N12—C23	−101.1 (3)
C34—C35—C36—C37	−1.8 (6)	N1—Cu1—N12—C23	84.3 (3)
S2—C35—C36—C37	177.4 (3)	O1W—Cu1—N12—C23	1.2 (3)
C35—C36—C37—C32	0.6 (6)	O1—Cu1—N12—C23	169.2 (3)
C33—C32—C37—C36	1.2 (6)	N7—Cu1—O1—S1	85.2 (4)
C38—C32—C37—C36	179.5 (4)	N1—Cu1—O1—S1	−95.4 (4)
C37—C32—C38—O10	179.1 (5)	N12—Cu1—O1—S1	174.9 (4)
C33—C32—C38—O10	−2.6 (7)	N6—Cu1—O1—S1	−2.2 (4)
C37—C32—C38—O9	−2.2 (6)	O1W—Cu1—O1—S1	−102.6 (6)
C33—C32—C38—O9	176.1 (4)	Cu1—O1—S1—O3	−177.4 (4)
N3—C1—N1—C2	−1.0 (4)	Cu1—O1—S1—O2	−48.3 (5)
N3—C1—N1—Cu1	−178.8 (2)	Cu1—O1—S1—C28	68.1 (4)
N2—C2—N1—C1	1.2 (5)	C27—C28—S1—O1	143.4 (3)
N2—C2—N1—Cu1	178.8 (3)	C29—C28—S1—O1	−36.9 (4)
N12—Cu1—N1—C1	48.4 (3)	C27—C28—S1—O3	24.3 (4)
N6—Cu1—N1—C1	−131.9 (3)	C29—C28—S1—O3	−156.0 (3)
O1W—Cu1—N1—C1	139.1 (3)	C27—C28—S1—O2	−96.6 (4)
O1—Cu1—N1—C1	−39.4 (3)	C29—C28—S1—O2	83.1 (4)
N12—Cu1—N1—C2	−128.7 (3)	C34—C35—S2—O8	−126.5 (4)
N6—Cu1—N1—C2	51.0 (4)	C36—C35—S2—O8	54.2 (4)
O1W—Cu1—N1—C2	−38.0 (3)	C34—C35—S2—O6	111.0 (4)
O1—Cu1—N1—C2	143.5 (3)	C36—C35—S2—O6	−68.3 (4)
N1—C2—N2—N3	−1.0 (5)	C34—C35—S2—O7	−7.1 (4)
N1—C1—N3—N2	0.5 (4)	C36—C35—S2—O7	173.6 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2^v	0.85	2.58	2.931 (5)	106
O1W—H1WB···O4W^vi	0.85	2.46	2.897 (5)	113
O2W—H2WA···O3	0.85	2.10	2.900 (5)	156
O3W—H3WA···O6	0.85	1.91	2.743 (6)	165
O4W—H4WA···O7	0.86	1.84	2.678 (6)	163
O3W—H3WB···O3	0.86	1.92	2.746 (5)	163
O4W—H4WB···O3W^vii	0.86	1.86	2.712 (5)	174
O5W—H5WB···O3W^vii	0.86	2.13	2.697 (10)	123
O5—H5A···O2W^i	0.82	1.82	2.620 (4)	166
O9—H9A···O4W^iv	0.82	1.82	2.631 (6)	172

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

Poly[[bis(µ₂-2-amino-4-sulfonatobenzoato-κ³O⁴:N,O^4')tetraaqua[µ₂-1,4-bis(triazol-1-ylmethyl)benzene-κ²N¹:N^1']dicopper(II)] tetrahydrate] (2)

Crystal data

[Cu2(C7H5NO5S)2(C14H14N4)(H2O)4]·4H2O	F(000) = 968
Mr = 939.90	Dx = 1.679 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 6621 reflections
a = 13.4947 (16) Å	θ = 2.5–27.2°
b = 10.1948 (11) Å	µ = 1.34 mm^−1
c = 18.8909 (16) Å	T = 293 K
β = 134.327 (5)°	Massive, blue
V = 1859.2 (3) Å^3	0.25 × 0.2 × 0.15 mm
Z = 2

Data collection

CCD area detector diffractometer	4280 independent reflections
Radiation source: fine-focus sealed tube	3100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
phi and ω scans	θmax = 27.6°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2002)	h = −17→16
Tmin = 0.732, Tmax = 0.818	k = −13→10
18121 measured reflections	l = −23→24

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0391P)^2 + 1.7411P] where P = (Fo^2 + 2Fc^2)/3
4280 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.49 e Å^−3
65 restraints	Δρmin = −0.52 e Å^−3

Special details

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	Occ. (<1)
C1	0.1985 (3)	0.5704 (2)	0.42966 (19)	0.0196 (6)
C2	0.1768 (3)	0.4342 (2)	0.41821 (19)	0.0186 (6)
C3	0.2835 (3)	0.3511 (3)	0.4905 (2)	0.0231 (6)
H3	0.2701	0.2609	0.4825	0.028*
C4	0.4106 (3)	0.4013 (3)	0.5751 (2)	0.0272 (7)
C5	0.4283 (3)	0.5346 (3)	0.5898 (2)	0.0353 (8)
H5	0.5113	0.5685	0.6483	0.042*
C6	0.3228 (3)	0.6176 (3)	0.5178 (2)	0.0305 (7)
H6	0.3353	0.7077	0.5286	0.037*
C7	0.0970 (3)	0.6657 (2)	0.3481 (2)	0.0197 (6)
C8	−0.0010 (3)	0.6057 (3)	0.0859 (2)	0.0273 (7)
H8	0.0903	0.6270	0.1422	0.033*
C9	−0.1982 (3)	0.5938 (3)	−0.0677 (2)	0.0363 (8)
H9	−0.2679	0.6043	−0.1360	0.044*
C10	−0.2064 (3)	0.5263 (3)	−0.0104 (2)	0.0307 (7)
H10	−0.2843	0.4818	−0.0331	0.037*
C11	−0.0069 (4)	0.7210 (3)	−0.0331 (3)	0.0414 (9)
H11A	−0.0605	0.7065	−0.1025	0.050*
H11B	0.0868	0.6908	0.0049	0.050*
C12	−0.0035 (3)	0.8664 (3)	−0.0155 (2)	0.0303 (7)
C13	−0.1150 (4)	0.9446 (3)	−0.0888 (2)	0.0386 (8)
H13	−0.1927	0.9078	−0.1488	0.046*
C14	0.1114 (4)	0.9226 (3)	0.0730 (2)	0.0379 (8)
H14	0.1871	0.8704	0.1225	0.046*
Cu1	−0.02625 (4)	0.44961 (3)	0.20296 (2)	0.02237 (12)
N1	0.0468 (3)	0.3814 (2)	0.33106 (17)	0.0206 (5)
H1A	0.045 (3)	0.2981 (11)	0.326 (2)	0.040 (10)*
H1B	−0.020 (2)	0.399 (3)	0.325 (2)	0.037 (10)*
N2	−0.0830 (3)	0.5336 (2)	0.08566 (16)	0.0236 (5)
N3	−0.0672 (3)	0.6433 (2)	−0.00532 (18)	0.0294 (6)
O1	0.0110 (2)	0.62843 (17)	0.25905 (14)	0.0273 (5)
O2	0.1070 (2)	0.78215 (17)	0.37282 (13)	0.0261 (5)
O3	0.5439 (4)	0.1980 (4)	0.6018 (2)	0.0878 (14)	0.883 (3)
O3'	0.6475 (19)	0.313 (2)	0.6538 (16)	0.0878 (14)	0.117 (3)
O4	0.5192 (3)	0.2285 (4)	0.7126 (2)	0.0778 (12)	0.883 (3)
O4'	0.506 (2)	0.1579 (12)	0.6447 (15)	0.0778 (12)	0.117 (3)
O5	0.6716 (3)	0.3674 (3)	0.7240 (2)	0.0785 (13)	0.883 (3)
O5'	0.611 (2)	0.3358 (19)	0.7596 (9)	0.0785 (13)	0.117 (3)
O1W	−0.2376 (3)	0.4630 (2)	0.1641 (2)	0.0653 (9)
H1WA	−0.3012	0.4090	0.1424	0.078*
H1WB	−0.2589	0.5391	0.1667	0.078*
O2W	0.2022 (2)	0.4086 (2)	0.26747 (16)	0.0427 (6)
H2WA	0.2514	0.4765	0.2883	0.051*
H2WB	0.2215	0.3377	0.2556	0.051*
O3W	0.3816 (3)	0.2988 (2)	0.89294 (19)	0.0548 (7)
H3WA	0.4423	0.2929	0.9556	0.066*
H3WB	0.4184	0.3294	0.8739	0.066*
O4W	0.4732 (3)	0.4025 (3)	0.8134 (2)	0.0777 (9)
H4WA	0.4857	0.3511	0.7848	0.093*
H4WB	0.4910	0.4805	0.8102	0.093*
S1	0.54915 (8)	0.29130 (8)	0.66184 (6)	0.0379 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0221 (14)	0.0144 (13)	0.0211 (14)	0.0016 (11)	0.0146 (12)	0.0011 (10)
C2	0.0211 (14)	0.0153 (13)	0.0181 (13)	−0.0014 (11)	0.0132 (12)	−0.0007 (10)
C3	0.0280 (16)	0.0129 (13)	0.0263 (15)	0.0012 (12)	0.0182 (13)	0.0031 (11)
C4	0.0226 (15)	0.0239 (15)	0.0239 (15)	0.0038 (13)	0.0121 (13)	0.0057 (12)
C5	0.0227 (16)	0.0270 (17)	0.0279 (16)	−0.0014 (14)	0.0073 (14)	−0.0019 (13)
C6	0.0290 (17)	0.0142 (14)	0.0315 (16)	−0.0036 (13)	0.0149 (14)	−0.0037 (12)
C7	0.0243 (15)	0.0132 (12)	0.0247 (15)	0.0007 (12)	0.0183 (13)	0.0015 (11)
C8	0.0316 (17)	0.0176 (14)	0.0255 (16)	−0.0003 (13)	0.0173 (14)	0.0000 (12)
C9	0.041 (2)	0.0290 (16)	0.0247 (16)	0.0023 (15)	0.0176 (15)	0.0030 (13)
C10	0.0278 (17)	0.0260 (16)	0.0276 (16)	−0.0029 (13)	0.0155 (14)	−0.0017 (13)
C11	0.073 (3)	0.0239 (16)	0.060 (2)	−0.0012 (17)	0.059 (2)	0.0009 (15)
C12	0.046 (2)	0.0230 (15)	0.0409 (18)	0.0006 (15)	0.0375 (17)	0.0046 (14)
C13	0.0383 (19)	0.0333 (18)	0.0333 (17)	−0.0029 (16)	0.0211 (16)	−0.0003 (15)
C14	0.0390 (19)	0.0302 (17)	0.0386 (19)	0.0090 (15)	0.0249 (17)	0.0111 (14)
Cu1	0.0317 (2)	0.01008 (16)	0.01832 (18)	−0.00197 (15)	0.01493 (16)	−0.00001 (13)
N1	0.0217 (13)	0.0127 (12)	0.0219 (12)	−0.0020 (10)	0.0133 (11)	0.0002 (10)
N2	0.0331 (14)	0.0118 (11)	0.0212 (12)	−0.0010 (10)	0.0173 (11)	0.0009 (9)
N3	0.0458 (17)	0.0176 (12)	0.0337 (14)	0.0010 (12)	0.0311 (14)	0.0019 (11)
O1	0.0347 (12)	0.0122 (9)	0.0186 (10)	0.0002 (9)	0.0126 (9)	−0.0008 (8)
O2	0.0368 (12)	0.0110 (9)	0.0231 (10)	0.0043 (9)	0.0182 (10)	0.0003 (8)
O3	0.068 (2)	0.084 (3)	0.056 (2)	0.053 (2)	0.0232 (17)	0.0026 (18)
O3'	0.068 (2)	0.084 (3)	0.056 (2)	0.053 (2)	0.0232 (17)	0.0026 (18)
O4	0.059 (2)	0.085 (3)	0.077 (2)	0.0279 (19)	0.0430 (19)	0.056 (2)
O4'	0.059 (2)	0.085 (3)	0.077 (2)	0.0279 (19)	0.0430 (19)	0.056 (2)
O5	0.0245 (15)	0.0466 (18)	0.075 (2)	−0.0029 (14)	0.0020 (14)	0.0232 (17)
O5'	0.0245 (15)	0.0466 (18)	0.075 (2)	−0.0029 (14)	0.0020 (14)	0.0232 (17)
O1W	0.0418 (16)	0.0402 (15)	0.110 (2)	−0.0015 (13)	0.0518 (17)	−0.0052 (15)
O2W	0.0397 (14)	0.0419 (13)	0.0473 (14)	−0.0006 (12)	0.0306 (12)	0.0008 (11)
O3W	0.0521 (16)	0.0493 (16)	0.0603 (17)	0.0007 (13)	0.0383 (15)	0.0008 (13)
O4W	0.072 (2)	0.086 (2)	0.079 (2)	−0.0112 (19)	0.0541 (19)	−0.0051 (19)
S1	0.0252 (4)	0.0271 (4)	0.0350 (4)	0.0069 (3)	0.0114 (4)	0.0092 (3)

Geometric parameters (Å, º)

C1—C6	1.384 (4)	C13—C14^i	1.380 (4)
C1—C2	1.404 (3)	C13—H13	0.9300
C1—C7	1.498 (4)	C14—C13^i	1.380 (4)
C2—C3	1.381 (4)	C14—H14	0.9300
C2—N1	1.429 (3)	Cu1—N1	1.994 (2)
C3—C4	1.388 (4)	Cu1—N2	1.964 (2)
C3—H3	0.9300	Cu1—O1	1.9885 (18)
C4—C5	1.374 (4)	Cu1—O2^ii	1.9929 (18)
C4—S1	1.776 (3)	Cu1—O1W	2.402 (3)
C5—C6	1.374 (4)	Cu1—O2W	2.431 (2)
C5—H5	0.9300	Cu1—H1B	2.32 (3)
C6—H6	0.9300	N1—H1A	0.854 (10)
C7—O2	1.248 (3)	N1—H1B	0.857 (10)
C7—O1	1.262 (3)	O2—Cu1^iii	1.9929 (18)
C8—N2	1.326 (4)	O3—S1	1.444 (3)
C8—N3	1.328 (4)	O3'—S1	1.455 (9)
C8—H8	0.9300	O4—S1	1.427 (3)
C9—C10	1.351 (4)	O4'—S1	1.427 (9)
C9—N3	1.363 (4)	O5—S1	1.414 (3)
C9—H9	0.9300	O5'—S1	1.472 (9)
C10—N2	1.360 (4)	O1W—H1WA	0.8457
C10—H10	0.9300	O1W—H1WB	0.8401
C11—N3	1.469 (4)	O2W—H2WA	0.8423
C11—C12	1.512 (4)	O2W—H2WB	0.8500
C11—H11A	0.9700	O3W—H3WA	0.8483
C11—H11B	0.9700	O3W—H3WB	0.8500
C12—C14	1.380 (4)	O4W—H4WA	0.8501
C12—C13	1.381 (4)	O4W—H4WB	0.8454
C6—C1—C2	118.4 (2)	O1—Cu1—O1W	85.11 (9)
C6—C1—C7	118.7 (2)	O2^ii—Cu1—O1W	83.85 (9)
C2—C1—C7	122.7 (2)	N1—Cu1—O1W	82.27 (10)
C3—C2—C1	119.5 (2)	N2—Cu1—O2W	89.93 (9)
C3—C2—N1	120.0 (2)	O1—Cu1—O2W	97.50 (8)
C1—C2—N1	120.4 (2)	O2^ii—Cu1—O2W	94.47 (8)
C2—C3—C4	120.6 (3)	N1—Cu1—O2W	87.31 (9)
C2—C3—H3	119.7	O1W—Cu1—O2W	169.12 (9)
C4—C3—H3	119.7	C2—N1—Cu1	115.74 (17)
C5—C4—C3	119.8 (3)	C2—N1—H1A	115 (2)
C5—C4—S1	121.1 (2)	Cu1—N1—H1A	105 (2)
C3—C4—S1	119.1 (2)	C2—N1—H1B	114 (2)
C6—C5—C4	119.7 (3)	Cu1—N1—H1B	101 (2)
C6—C5—H5	120.1	H1A—N1—H1B	105 (3)
C4—C5—H5	120.1	C8—N2—C10	106.0 (2)
C5—C6—C1	121.6 (3)	C8—N2—Cu1	124.82 (19)
C5—C6—H6	119.2	C10—N2—Cu1	129.1 (2)
C1—C6—H6	119.2	C8—N3—C9	107.7 (3)
O2—C7—O1	122.9 (2)	C8—N3—C11	125.5 (3)
O2—C7—C1	116.7 (2)	C9—N3—C11	126.7 (3)
O1—C7—C1	120.3 (2)	C7—O1—Cu1	129.86 (17)
N2—C8—N3	110.7 (3)	C7—O2—Cu1^iii	133.14 (18)
N2—C8—H8	124.7	Cu1—O1W—H1WA	134.1
N3—C8—H8	124.7	Cu1—O1W—H1WB	114.6
C10—C9—N3	106.2 (3)	H1WA—O1W—H1WB	110.9
C10—C9—H9	126.9	Cu1—O2W—H2WA	113.8
N3—C9—H9	126.9	Cu1—O2W—H2WB	121.9
C9—C10—N2	109.4 (3)	H2WA—O2W—H2WB	122.3
C9—C10—H10	125.3	H3WA—O3W—H3WB	109.7
N2—C10—H10	125.3	H4WA—O4W—H4WB	109.9
N3—C11—C12	112.9 (3)	O5—S1—O4	113.8 (2)
N3—C11—H11A	109.0	O5—S1—O4'	140.3 (9)
C12—C11—H11A	109.0	O4—S1—O4'	57.3 (9)
N3—C11—H11B	109.0	O5—S1—O3	113.6 (2)
C12—C11—H11B	109.0	O4—S1—O3	110.6 (2)
H11A—C11—H11B	107.8	O4'—S1—O3	53.7 (9)
C14—C12—C13	119.3 (3)	O5—S1—O3'	51.7 (8)
C14—C12—C11	120.6 (3)	O4—S1—O3'	147.9 (9)
C13—C12—C11	120.1 (3)	O4'—S1—O3'	112.6 (8)
C14^i—C13—C12	120.1 (3)	O3—S1—O3'	64.3 (8)
C14^i—C13—H13	119.9	O5—S1—O5'	58.8 (8)
C12—C13—H13	119.9	O4—S1—O5'	58.0 (8)
C13^i—C14—C12	120.6 (3)	O4'—S1—O5'	111.1 (8)
C13^i—C14—H14	119.7	O3—S1—O5'	149.9 (8)
C12—C14—H14	119.7	O3'—S1—O5'	109.2 (8)
N2—Cu1—O1	87.45 (8)	O5—S1—C4	106.57 (16)
N2—Cu1—O2^ii	88.65 (8)	O4—S1—C4	107.04 (17)
O1—Cu1—O2^ii	167.40 (8)	O4'—S1—C4	113.0 (9)
N2—Cu1—N1	173.38 (10)	O3—S1—C4	104.42 (16)
O1—Cu1—N1	86.94 (9)	O3'—S1—C4	104.9 (9)
O2^ii—Cu1—N1	97.56 (8)	O5'—S1—C4	105.6 (8)
N2—Cu1—O1W	100.76 (10)
C6—C1—C2—C3	−5.9 (4)	O2^ii—Cu1—N2—C8	−129.9 (2)
C7—C1—C2—C3	169.7 (2)	O1W—Cu1—N2—C8	146.6 (2)
C6—C1—C2—N1	176.0 (3)	O2W—Cu1—N2—C8	−35.5 (2)
C7—C1—C2—N1	−8.4 (4)	O1—Cu1—N2—C10	−121.7 (3)
C1—C2—C3—C4	1.4 (4)	O2^ii—Cu1—N2—C10	46.3 (2)
N1—C2—C3—C4	179.5 (3)	O1W—Cu1—N2—C10	−37.1 (3)
C2—C3—C4—C5	3.7 (5)	O2W—Cu1—N2—C10	140.8 (2)
C2—C3—C4—S1	−175.2 (2)	N2—C8—N3—C9	0.1 (3)
C3—C4—C5—C6	−4.1 (5)	N2—C8—N3—C11	−178.1 (2)
S1—C4—C5—C6	174.8 (3)	C10—C9—N3—C8	0.0 (4)
C4—C5—C6—C1	−0.6 (5)	C10—C9—N3—C11	178.2 (3)
C2—C1—C6—C5	5.5 (5)	C12—C11—N3—C8	−81.0 (4)
C7—C1—C6—C5	−170.2 (3)	C12—C11—N3—C9	101.1 (4)
C6—C1—C7—O2	−23.2 (4)	O2—C7—O1—Cu1	−178.2 (2)
C2—C1—C7—O2	161.2 (3)	C1—C7—O1—Cu1	5.0 (4)
C6—C1—C7—O1	153.8 (3)	N2—Cu1—O1—C7	−151.0 (3)
C2—C1—C7—O1	−21.8 (4)	O2^ii—Cu1—O1—C7	136.8 (3)
N3—C9—C10—N2	−0.1 (4)	N1—Cu1—O1—C7	25.4 (3)
N3—C11—C12—C14	91.9 (4)	O1W—Cu1—O1—C7	107.9 (3)
N3—C11—C12—C13	−89.0 (4)	O2W—Cu1—O1—C7	−61.4 (3)
C14—C12—C13—C14^i	−0.4 (5)	O1—C7—O2—Cu1^iii	−9.9 (4)
C11—C12—C13—C14^i	−179.5 (3)	C1—C7—O2—Cu1^iii	166.97 (19)
C13—C12—C14—C13^i	0.4 (5)	C5—C4—S1—O5	−14.5 (4)
C11—C12—C14—C13^i	179.5 (3)	C3—C4—S1—O5	164.3 (3)
C3—C2—N1—Cu1	−128.6 (2)	C5—C4—S1—O4	107.6 (3)
C1—C2—N1—Cu1	49.5 (3)	C3—C4—S1—O4	−73.6 (3)
O1—Cu1—N1—C2	−49.3 (2)	C5—C4—S1—O4'	168.6 (10)
O2^ii—Cu1—N1—C2	142.48 (19)	C3—C4—S1—O4'	−12.5 (10)
O1W—Cu1—N1—C2	−134.8 (2)	C5—C4—S1—O3	−135.1 (3)
O2W—Cu1—N1—C2	48.33 (19)	C3—C4—S1—O3	43.7 (3)
N3—C8—N2—C10	−0.2 (3)	C5—C4—S1—O3'	−68.4 (9)
N3—C8—N2—Cu1	176.82 (18)	C3—C4—S1—O3'	110.5 (9)
C9—C10—N2—C8	0.1 (3)	C5—C4—S1—O5'	46.9 (9)
C9—C10—N2—Cu1	−176.7 (2)	C3—C4—S1—O5'	−134.2 (9)
O1—Cu1—N2—C8	62.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3^iv	0.85	1.98	2.814 (4)	171
O1W—H1WB···O3W^v	0.84	2.03	2.812 (4)	154
O2W—H2WA···O5^vi	0.84	2.00	2.785 (4)	155
O2W—H2WB···O3W^vii	0.85	2.35	2.817 (3)	115
O3W—H3WA···O3^viii	0.85	2.06	2.879 (4)	163
O3W—H3WB···O4W	0.85	1.89	2.737 (4)	172
O4W—H4WA···O4	0.85	2.12	2.968 (5)	178
N1—H1A···O1^ii	0.85 (1)	2.11 (2)	2.881 (3)	151 (3)

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