Bis(pyridine-2,6-dimethanol-N,O,O')cobalt(II) and -copper(II) disacchar­inate dihydrate: three-dimensional structures with extensive hydrogen bonds and aromatic [pi]-[pi]-stacking interactions

Bis­(pyridine-2,6-di­methanol-N,O,O')­cobalt(II) disaccharinate dihydrate, [Co(C₇H₉NO₂)₂](C₇H₄NO₃S)₂·2H₂O, (I), and bis­(pyridine-2,6-di­methanol-N,O,O')copper(II) disaccharinate dihydrate, [Cu(C₇H₉NO₂)₂](C₇H₄NO₃S)₂·2H₂O, (II), collectively [M(dmpy)₂](sac)₂·2H₂O (where M is Co^II or Cu^II, sac is the saccharinate anion and dmpy is pyridine-2,6-di­methanol), are isostructural. The [M(dmpy)₂]²⁺ cations exhibit distorted octahedral geometry in which the two neutral dmpy species act as tripodal N,O,O'-tridentate ligands. The crystal packing is determined by hydrogen bonding, as well as by weak pyridine-saccharinate [pi]-[pi]-stacking interactions.

S1. Comment

The artificial sweetener saccharin (also known as 1,2-benzisothiazol-3(2H)-one 1,1-dioxide or o-benzosulfimide) is readily deprotonated to form the corresponding saccharinate anion (sac). The coordination behaviour of sac to metal ions depends on the presence of other co-ligands. Bulky ligands such as 1,10-phenathroline (phen; Deng et al., 2000, 2001; Williams et al., 2000; Yilmaz et al., 2001) and triethanolamine (tea; Topcu et al., 2001; Andac et al., 2001) prevent the coordination of sac to metal ions and so sac is present as a counter-ion in such complexes. The present study is part of our continuing research into the preparation and characterization of a series of mixed-ligand complexes of sac with N and O donor ligands and here we report the crystal structures of the pyridine-2,6-dimethanol (dmpy) complexes with cobalt and copper saccharinates, [Co(dmpy)₂](sac)₂·2H₂O, (I), and [Cu(dmpy)₂](sac)₂·2H₂O, (II). \sch

The structures of (I) and (II) are shown in Figs. 1 and 2, respectively. Tables 1–4 list selected geometrical data. These isostructural phases consist of a complex cation, two sac ions and two lattice water molecules. In the complex cations, the Co^II or Cu^II ions are octahedrally coordinated by a pair of neutral dmpy ligands with no sac in the primary coordination sphere. Each dmpy ligand behaves as a tridentate ligand using all donor atoms, the amino N atom and both hydroxyl O atoms, and forms two five-membered metallocyclic chelate rings. The M—N bond lengths of the Co^II complex, (I), are noticeably longer than those of the Cu^II complex, (II), while the M—O bond distances of (I) are somewhat shorter than those of (II).

The M—N bond distances in (II) are somewhat longer than those found in [Cu(dmpy)₂](nif)₂, where nif is the niflumate anion (Koman & Melnik, 1997), and similar to the corresponding distances in [Cu(pydca)(dmpy)], where pydca is pyridine-2,6-dicarboxylate (Koman et al., 2000), while the M—O bond distances are comparable with those observed in [Cu(dmpy)₂](nif)₂ and shorter than those found in [Cu(pydca)(dmpy)]. The larger deviations from regular octahedral geometry for the Cu phase are characteristic of the Jahn-Teller effect. The four M—O bonds forming the plane of the MO₄N₂ core are longer than the two M—N bonds occupying the axial positions, resulting in a `compressed' distorted octahedron around the metal ions.

Both dmpy ligands are essentially planar, with an average r.m.s. deviation of 0.057 Å in (I) and 0.065 Å in (II). Both hydroxyl O atoms deviate slightly from the dmpy planes. The planes of the two dmpy ligands are nearly perpendicular to each other, and the dihedral angles between the corresponding planes are 83.73 (3)° for both (I) and (II). The sac anions are also planar, with average r.m.s. deviations of 0.029 and 0.031 Å for (I) and (II), respectively.

In both complexes, the sac ions adopt a parallel alignment with each other and the dihedral angles between the corresponding planes are 16.02 (5) and 13.95 (6)° for (I) and (II), respectively. One of the pyridine rings (ring A = N2/C8—C12) is located between the phenyl rings (ring B = C16—C21 and ring C = C23—C28) of the two sac ions. The planes of rings A, B and C also adopt a parallel alignment and the dihedral angles between A and B, and A and C are 6.92 (12) and 11.39 (11)°, respectively, for (I), and 6.59 (14) and 9.36 (13)°, respectively, for (II). Additionally, the angle of the line passing through the centres of C—A—B to the plane of A is 159.86° for the both complexes. As a result, the phenyl rings of the sac ions and pyridine rings are connected by weak π–π interactions: A···B 3.6349 (11) and A···C 3.6093 (11) Å for (I), and A···B 3.6299 (13) and A···C 3.5844 (12) Å for (II).

The crystals exhibit a number of hydrogen bonds (Fig. 3). The packing and hydrogen-bonding schemes of compounds (I) and (II) are very similar. The H atoms of the hydroxyl groups of the dmpy ligands are involved in intermolecular hydrogen bonding with the water molecules and the carbonyl O atoms of the neighbouring sac ions, while the H atoms of the two water molecules form bifurcated hydrogen bonds with the negatively charged amine N atom and carbonyl and sulfonyl O atoms of the sac ions. Additionally, there are weak C—H···O interactions between phenyl H atoms and hydroxyl and sulfonyl O atoms. The crystal structures are stabilized by an infinite three-dimensional network of extensive hydrogen bonds and other intermolecular interactions.

S2. Experimental

Previously prepared tetraaquabis(saccharinato)cobalt(II) and copper(II) dihydrates, [M(H₂O)₄(sac)₂]·2H₂O (1 mmol), were dissolved in a mixture of methanol-2-propanol (1:1 v:v; 30 ml) and mixed with the dmpy ligand (2 mmol) dissolved in methanol (15 ml) at room temperature. The resulting solutions were left to stand at room temperature and allowed to evaporate slowly over a few days for crystallization. Crystals of (I) and (II), suitable for X-ray diffraction analysis, were collected by suction filtration, washed with acetone and dried in air.

S3. Refinement

Hydroxyl and water H atoms were found in difference maps and were positionally refined with geometric restraints (O—H = 0.82 Å for both hydroxyl and water H atoms, and H···H = 1.30 Å for the water H atoms) and with U_iso(H) = 1.5U_eq of the parent atom. The remaining H atoms were placed in calculated positions 0.93 Å from their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (I) with the atom-numbering scheme and 40% displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecular structure of (II) with the atom-numbering scheme and 40% displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A packing diagram for (II).

(I) Bis(pyridine-2,6-dimethanol)cobalt(II) disaccharinate dihydrate

Crystal data

[Co(C7H9NO2)2]·2C7H4O3S·2H2O	Z = 2
Mr = 737.61	F(000) = 762
Triclinic, P1	Dx = 1.559 Mg m^−3
a = 8.1365 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5177 (6) Å	Cell parameters from 4198 reflections
c = 15.7558 (8) Å	θ = 2.7–29.9°
α = 93.054 (1)°	µ = 0.75 mm^−1
β = 97.494 (1)°	T = 298 K
γ = 98.030 (1)°	Block, pale purple
V = 1571.24 (13) Å^3	0.46 × 0.42 × 0.21 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	9108 independent reflections
Radiation source: fine-focus sealed tube	6843 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 30.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −11→10
Tmin = 0.716, Tmax = 0.854	k = −17→17
19456 measured reflections	l = −22→22

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)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0533P)^2] where P = (Fo^2 + 2Fc^2)/3
9108 reflections	(Δ/σ)max = 0.001
448 parameters	Δρmax = 0.30 e Å^−3
10 restraints	Δρmin = −0.41 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
Co1	−0.26131 (3)	0.312977 (16)	0.669785 (13)	0.03018 (6)
O1	−0.13859 (16)	0.45647 (9)	0.74000 (8)	0.0440 (3)
H1	−0.055 (2)	0.4479 (18)	0.7757 (13)	0.066*
O2	−0.39229 (16)	0.22318 (9)	0.55628 (8)	0.0453 (3)
H2	−0.473 (2)	0.1752 (16)	0.5595 (15)	0.068*
O3	−0.03683 (17)	0.25103 (11)	0.65113 (9)	0.0476 (3)
H3	−0.034 (3)	0.2138 (18)	0.6080 (12)	0.071*
O4	−0.48982 (16)	0.31145 (11)	0.72428 (8)	0.0479 (3)
H4	−0.493 (3)	0.3712 (14)	0.7463 (15)	0.072*
O1W	1.0330 (2)	0.14679 (13)	0.51538 (10)	0.0589 (4)
H1W1	0.973 (3)	0.109 (2)	0.4788 (15)	0.088*
H2W1	1.118 (3)	0.119 (2)	0.5258 (17)	0.088*
O2W	0.42923 (19)	0.49401 (12)	0.78286 (9)	0.0548 (3)
H1W2	0.496 (3)	0.530 (2)	0.8191 (14)	0.082*
H2W2	0.350 (2)	0.482 (2)	0.8080 (15)	0.082*
N1	−0.25932 (17)	0.42389 (10)	0.57963 (8)	0.0359 (3)
N2	−0.23706 (17)	0.20888 (10)	0.76391 (8)	0.0336 (3)
C1	−0.1776 (2)	0.52398 (13)	0.60092 (11)	0.0444 (4)
C2	−0.1637 (3)	0.59950 (16)	0.54034 (14)	0.0647 (6)
H2A	−0.1076	0.6692	0.5555	0.078*
C3	−0.2351 (3)	0.56873 (18)	0.45678 (14)	0.0725 (7)
H3A	−0.2263	0.6180	0.4149	0.087*
C4	−0.3194 (3)	0.46575 (17)	0.43494 (12)	0.0614 (6)
H4A	−0.3683	0.4446	0.3788	0.074*
C5	−0.3292 (2)	0.39471 (13)	0.49877 (10)	0.0416 (4)
C6	−0.1028 (3)	0.54806 (15)	0.69364 (13)	0.0621 (6)
H6A	0.0176	0.5683	0.6977	0.075*
H6B	−0.1486	0.6083	0.7181	0.075*
C7	−0.4141 (3)	0.28008 (15)	0.48207 (12)	0.0578 (6)
H7A	−0.5328	0.2792	0.4637	0.069*
H7B	−0.3679	0.2447	0.4363	0.069*
C8	−0.0933 (2)	0.16691 (13)	0.77976 (11)	0.0427 (4)
C9	−0.0680 (3)	0.09946 (17)	0.84518 (14)	0.0655 (6)
H9	0.0325	0.0720	0.8564	0.079*
C10	−0.1961 (4)	0.07378 (18)	0.89356 (15)	0.0774 (8)
H10	−0.1822	0.0283	0.9379	0.093*
C11	−0.3427 (3)	0.11469 (17)	0.87659 (13)	0.0655 (6)
H11	−0.4297	0.0963	0.9084	0.079*
C12	−0.3606 (2)	0.18428 (13)	0.81102 (11)	0.0423 (4)
C13	0.0338 (2)	0.19815 (16)	0.72152 (13)	0.0505 (5)
H13A	0.1284	0.2460	0.7534	0.061*
H13B	0.0744	0.1339	0.7003	0.061*
C14	−0.5151 (2)	0.23407 (16)	0.78673 (13)	0.0513 (5)
H14A	−0.6069	0.1778	0.7636	0.062*
H14B	−0.5455	0.2694	0.8375	0.062*
S1	0.23536 (5)	0.28997 (4)	1.03158 (3)	0.04249 (11)
O5	0.12446 (15)	0.43468 (10)	0.84277 (7)	0.0432 (3)
O6	0.2541 (2)	0.17818 (12)	1.02295 (11)	0.0700 (4)
O7	0.33430 (17)	0.35034 (12)	1.10592 (9)	0.0580 (4)
N3	0.26807 (17)	0.34909 (13)	0.94508 (9)	0.0428 (3)
C15	0.13097 (19)	0.38640 (12)	0.91082 (10)	0.0333 (3)
C16	−0.01603 (18)	0.36521 (12)	0.95909 (9)	0.0314 (3)
C17	−0.1731 (2)	0.39595 (14)	0.94256 (11)	0.0394 (4)
H17	−0.2011	0.4353	0.8957	0.047*
C18	−0.2881 (2)	0.36609 (17)	0.99832 (13)	0.0521 (5)
H18	−0.3945	0.3861	0.9889	0.063*
C19	−0.2463 (3)	0.30749 (19)	1.06696 (14)	0.0615 (6)
H19	−0.3262	0.2874	1.1026	0.074*
C20	−0.0892 (2)	0.27735 (17)	1.08474 (12)	0.0537 (5)
H20	−0.0610	0.2382	1.1317	0.064*
C21	0.0242 (2)	0.30835 (13)	1.02924 (11)	0.0379 (3)
S2	−0.77230 (5)	−0.12073 (3)	0.71436 (3)	0.03969 (10)
O8	−0.65563 (14)	0.07947 (9)	0.56422 (7)	0.0415 (3)
O9	−0.86006 (17)	−0.22643 (11)	0.68565 (11)	0.0652 (4)
O10	−0.8028 (2)	−0.07784 (13)	0.79610 (10)	0.0655 (4)
N4	−0.80667 (16)	−0.03621 (11)	0.64162 (9)	0.0395 (3)
C22	−0.66303 (18)	0.00737 (11)	0.61621 (10)	0.0305 (3)
C23	−0.51292 (17)	−0.04062 (11)	0.65306 (9)	0.0283 (3)
C24	−0.35072 (19)	−0.02258 (13)	0.63412 (11)	0.0376 (3)
H24	−0.3198	0.0277	0.5956	0.045*
C25	−0.2355 (2)	−0.08199 (16)	0.67445 (12)	0.0480 (4)
H25	−0.1256	−0.0713	0.6626	0.058*
C26	−0.2808 (2)	−0.15674 (17)	0.73191 (13)	0.0526 (5)
H26	−0.2008	−0.1954	0.7578	0.063*
C27	−0.4424 (2)	−0.17522 (15)	0.75165 (11)	0.0439 (4)
H27	−0.4731	−0.2250	0.7906	0.053*
C28	−0.55623 (19)	−0.11605 (12)	0.71061 (10)	0.0317 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02952 (11)	0.02995 (10)	0.03102 (11)	0.00422 (8)	0.00297 (8)	0.00550 (8)
O1	0.0479 (7)	0.0396 (6)	0.0379 (6)	−0.0022 (5)	−0.0096 (5)	0.0050 (5)
O2	0.0502 (8)	0.0369 (6)	0.0419 (6)	−0.0099 (5)	−0.0029 (6)	0.0069 (5)
O3	0.0421 (7)	0.0530 (8)	0.0523 (8)	0.0160 (6)	0.0141 (6)	0.0043 (6)
O4	0.0374 (7)	0.0644 (8)	0.0452 (7)	0.0156 (6)	0.0089 (5)	0.0042 (6)
O1W	0.0588 (10)	0.0696 (10)	0.0503 (8)	0.0310 (8)	−0.0040 (7)	−0.0038 (7)
O2W	0.0490 (8)	0.0627 (9)	0.0547 (8)	0.0052 (7)	0.0178 (7)	0.0046 (7)
N1	0.0406 (8)	0.0309 (6)	0.0337 (7)	0.0006 (5)	−0.0005 (6)	0.0056 (5)
N2	0.0382 (7)	0.0280 (6)	0.0332 (6)	0.0038 (5)	0.0021 (5)	0.0006 (5)
C1	0.0521 (10)	0.0317 (8)	0.0436 (9)	−0.0033 (7)	−0.0069 (8)	0.0095 (7)
C2	0.0805 (16)	0.0386 (10)	0.0643 (13)	−0.0138 (9)	−0.0119 (11)	0.0202 (9)
C3	0.0963 (18)	0.0580 (12)	0.0551 (12)	−0.0138 (12)	−0.0038 (12)	0.0322 (10)
C4	0.0795 (15)	0.0600 (12)	0.0373 (10)	−0.0092 (11)	−0.0038 (10)	0.0184 (9)
C5	0.0502 (10)	0.0394 (8)	0.0317 (8)	−0.0033 (7)	0.0026 (7)	0.0053 (7)
C6	0.0868 (16)	0.0329 (9)	0.0531 (11)	−0.0098 (9)	−0.0226 (11)	0.0074 (8)
C7	0.0833 (15)	0.0448 (10)	0.0344 (9)	−0.0168 (10)	−0.0042 (9)	0.0037 (8)
C8	0.0529 (11)	0.0336 (8)	0.0394 (9)	0.0143 (7)	−0.0082 (8)	−0.0037 (7)
C9	0.0967 (18)	0.0503 (11)	0.0500 (11)	0.0345 (12)	−0.0137 (12)	0.0034 (9)
C10	0.134 (2)	0.0467 (11)	0.0541 (13)	0.0251 (13)	0.0025 (14)	0.0199 (10)
C11	0.1007 (19)	0.0483 (11)	0.0462 (11)	−0.0067 (11)	0.0206 (12)	0.0114 (9)
C12	0.0538 (11)	0.0335 (8)	0.0370 (8)	−0.0057 (7)	0.0100 (8)	0.0006 (7)
C13	0.0380 (10)	0.0590 (11)	0.0541 (11)	0.0228 (8)	−0.0062 (8)	−0.0113 (9)
C14	0.0434 (10)	0.0562 (11)	0.0534 (11)	−0.0056 (8)	0.0191 (9)	−0.0010 (9)
S1	0.0353 (2)	0.0483 (2)	0.0445 (2)	0.01009 (17)	−0.00064 (17)	0.01368 (19)
O5	0.0363 (6)	0.0557 (7)	0.0371 (6)	0.0026 (5)	0.0033 (5)	0.0144 (5)
O6	0.0735 (11)	0.0510 (8)	0.0906 (12)	0.0266 (7)	0.0059 (9)	0.0185 (8)
O7	0.0466 (8)	0.0735 (9)	0.0481 (7)	0.0033 (7)	−0.0124 (6)	0.0131 (7)
N3	0.0290 (7)	0.0575 (9)	0.0445 (8)	0.0098 (6)	0.0071 (6)	0.0125 (7)
C15	0.0283 (7)	0.0381 (8)	0.0321 (7)	0.0019 (6)	0.0027 (6)	0.0018 (6)
C16	0.0265 (7)	0.0348 (7)	0.0309 (7)	0.0008 (6)	0.0025 (6)	−0.0012 (6)
C17	0.0307 (8)	0.0459 (9)	0.0397 (8)	0.0056 (7)	−0.0003 (7)	−0.0024 (7)
C18	0.0304 (9)	0.0692 (12)	0.0549 (11)	0.0042 (8)	0.0085 (8)	−0.0098 (10)
C19	0.0441 (11)	0.0879 (16)	0.0532 (12)	−0.0034 (10)	0.0230 (9)	0.0064 (11)
C20	0.0477 (11)	0.0692 (13)	0.0449 (10)	−0.0002 (9)	0.0128 (8)	0.0177 (9)
C21	0.0329 (8)	0.0423 (8)	0.0375 (8)	0.0021 (6)	0.0032 (6)	0.0062 (7)
S2	0.02830 (19)	0.0427 (2)	0.0519 (2)	0.00645 (15)	0.01251 (17)	0.01875 (18)
O8	0.0358 (6)	0.0416 (6)	0.0470 (7)	0.0018 (5)	0.0033 (5)	0.0182 (5)
O9	0.0427 (8)	0.0483 (7)	0.1003 (12)	−0.0110 (6)	0.0042 (8)	0.0254 (8)
O10	0.0685 (10)	0.0848 (10)	0.0587 (9)	0.0316 (8)	0.0367 (8)	0.0240 (8)
N4	0.0253 (6)	0.0438 (7)	0.0518 (8)	0.0067 (5)	0.0061 (6)	0.0186 (6)
C22	0.0262 (7)	0.0306 (7)	0.0337 (7)	0.0020 (5)	0.0018 (6)	0.0037 (6)
C23	0.0229 (7)	0.0303 (7)	0.0303 (7)	0.0026 (5)	0.0015 (5)	−0.0007 (5)
C24	0.0268 (7)	0.0436 (8)	0.0414 (9)	−0.0001 (6)	0.0077 (6)	−0.0002 (7)
C25	0.0252 (8)	0.0634 (11)	0.0553 (11)	0.0097 (7)	0.0049 (7)	−0.0022 (9)
C26	0.0374 (10)	0.0647 (12)	0.0577 (11)	0.0248 (9)	−0.0054 (8)	0.0067 (9)
C27	0.0417 (9)	0.0496 (9)	0.0431 (9)	0.0153 (8)	0.0027 (7)	0.0131 (8)
C28	0.0275 (7)	0.0348 (7)	0.0331 (7)	0.0056 (6)	0.0038 (6)	0.0029 (6)

Geometric parameters (Å, º)

Co1—N2	2.0341 (12)	C11—C12	1.393 (3)
Co1—N1	2.0385 (12)	C11—H11	0.9300
Co1—O1	2.1086 (12)	C12—C14	1.494 (3)
Co1—O3	2.1295 (13)	C13—H13A	0.9700
Co1—O2	2.1334 (12)	C13—H13B	0.9700
Co1—O4	2.1455 (13)	C14—H14A	0.9700
O1—C6	1.409 (2)	C14—H14B	0.9700
O1—H1	0.846 (16)	S1—O6	1.4300 (15)
O2—C7	1.406 (2)	S1—O7	1.4425 (15)
O2—H2	0.835 (15)	S1—N3	1.6196 (14)
O3—C13	1.420 (2)	S1—C21	1.7606 (17)
O3—H3	0.808 (16)	O5—C15	1.2573 (18)
O4—C14	1.431 (2)	N3—C15	1.330 (2)
O4—H4	0.812 (16)	C15—C16	1.500 (2)
O1W—H1W1	0.793 (16)	C16—C21	1.375 (2)
O1W—H2W1	0.821 (16)	C16—C17	1.383 (2)
O2W—H1W2	0.805 (16)	C17—C18	1.392 (2)
O2W—H2W2	0.802 (16)	C17—H17	0.9300
N1—C5	1.335 (2)	C18—C19	1.372 (3)
N1—C1	1.337 (2)	C18—H18	0.9300
N2—C12	1.338 (2)	C19—C20	1.381 (3)
N2—C8	1.348 (2)	C19—H19	0.9300
C1—C2	1.383 (2)	C20—C21	1.383 (2)
C1—C6	1.505 (3)	C20—H20	0.9300
C2—C3	1.380 (3)	S2—O9	1.4329 (14)
C2—H2A	0.9300	S2—O10	1.4336 (15)
C3—C4	1.376 (3)	S2—N4	1.6247 (13)
C3—H3A	0.9300	S2—C28	1.7597 (15)
C4—C5	1.380 (2)	O8—C22	1.2511 (17)
C4—H4A	0.9300	N4—C22	1.3383 (19)
C5—C7	1.497 (2)	C22—C23	1.499 (2)
C6—H6A	0.9700	C23—C24	1.381 (2)
C6—H6B	0.9700	C23—C28	1.3855 (19)
C7—H7A	0.9700	C24—C25	1.388 (2)
C7—H7B	0.9700	C24—H24	0.9300
C8—C9	1.380 (2)	C25—C26	1.383 (3)
C8—C13	1.496 (3)	C25—H25	0.9300
C9—C10	1.382 (4)	C26—C27	1.381 (3)
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.363 (4)	C27—C28	1.383 (2)
C10—H10	0.9300	C27—H27	0.9300
N2—Co1—N1	173.86 (5)	C12—C11—H11	120.4
N2—Co1—O1	98.82 (5)	N2—C12—C11	120.49 (19)
N1—Co1—O1	76.85 (5)	N2—C12—C14	115.53 (14)
N2—Co1—O3	76.87 (5)	C11—C12—C14	123.96 (18)
N1—Co1—O3	99.01 (5)	O3—C13—C8	110.81 (14)
O1—Co1—O3	95.06 (5)	O3—C13—H13A	109.5
N2—Co1—O2	108.04 (5)	C8—C13—H13A	109.5
N1—Co1—O2	76.36 (5)	O3—C13—H13B	109.5
O1—Co1—O2	153.14 (4)	C8—C13—H13B	109.5
O3—Co1—O2	91.06 (5)	H13A—C13—H13B	108.1
N2—Co1—O4	76.86 (5)	O4—C14—C12	111.27 (14)
N1—Co1—O4	107.66 (5)	O4—C14—H14A	109.4
O1—Co1—O4	95.02 (5)	C12—C14—H14A	109.4
O3—Co1—O4	152.99 (5)	O4—C14—H14B	109.4
O2—Co1—O4	91.15 (5)	C12—C14—H14B	109.4
C6—O1—Co1	117.35 (10)	H14A—C14—H14B	108.0
C6—O1—H1	111.5 (16)	O6—S1—O7	114.91 (9)
Co1—O1—H1	114.2 (16)	O6—S1—N3	111.20 (9)
C7—O2—Co1	116.80 (10)	O7—S1—N3	110.62 (8)
C7—O2—H2	113.0 (16)	O6—S1—C21	112.19 (9)
Co1—O2—H2	120.0 (16)	O7—S1—C21	109.40 (9)
C13—O3—Co1	114.65 (11)	N3—S1—C21	97.12 (7)
C13—O3—H3	107.3 (18)	C15—N3—S1	110.60 (11)
Co1—O3—H3	119.7 (18)	O5—C15—N3	122.65 (14)
C14—O4—Co1	115.06 (11)	O5—C15—C16	122.56 (14)
C14—O4—H4	108.5 (17)	N3—C15—C16	114.79 (13)
Co1—O4—H4	109.4 (18)	C21—C16—C17	120.42 (15)
H1W1—O1W—H2W1	106 (2)	C21—C16—C15	110.29 (13)
H1W2—O2W—H2W2	101 (2)	C17—C16—C15	129.28 (14)
C5—N1—C1	120.36 (13)	C16—C17—C18	117.83 (16)
C5—N1—Co1	120.18 (10)	C16—C17—H17	121.1
C1—N1—Co1	119.30 (11)	C18—C17—H17	121.1
C12—N2—C8	120.24 (14)	C19—C18—C17	120.75 (18)
C12—N2—Co1	120.49 (11)	C19—C18—H18	119.6
C8—N2—Co1	119.24 (11)	C17—C18—H18	119.6
N1—C1—C2	121.13 (16)	C18—C19—C20	121.98 (17)
N1—C1—C6	115.98 (14)	C18—C19—H19	119.0
C2—C1—C6	122.88 (16)	C20—C19—H19	119.0
C3—C2—C1	118.27 (17)	C19—C20—C21	116.63 (17)
C3—C2—H2A	120.9	C19—C20—H20	121.7
C1—C2—H2A	120.9	C21—C20—H20	121.7
C4—C3—C2	120.55 (17)	C16—C21—C20	122.37 (16)
C4—C3—H3A	119.7	C16—C21—S1	107.17 (11)
C2—C3—H3A	119.7	C20—C21—S1	130.45 (14)
C3—C4—C5	118.09 (18)	O9—S2—O10	115.95 (10)
C3—C4—H4A	121.0	O9—S2—N4	110.27 (8)
C5—C4—H4A	121.0	O10—S2—N4	110.37 (8)
N1—C5—C4	121.58 (16)	O9—S2—C28	110.42 (8)
N1—C5—C7	115.67 (14)	O10—S2—C28	111.16 (9)
C4—C5—C7	122.73 (16)	N4—S2—C28	97.07 (7)
O1—C6—C1	110.11 (14)	C22—N4—S2	110.85 (10)
O1—C6—H6A	109.6	O8—C22—N4	122.91 (14)
C1—C6—H6A	109.6	O8—C22—C23	122.99 (13)
O1—C6—H6B	109.6	N4—C22—C23	114.06 (12)
C1—C6—H6B	109.6	C24—C23—C28	120.08 (14)
H6A—C6—H6B	108.2	C24—C23—C22	129.11 (13)
O2—C7—C5	110.86 (14)	C28—C23—C22	110.73 (12)
O2—C7—H7A	109.5	C23—C24—C25	117.83 (15)
C5—C7—H7A	109.5	C23—C24—H24	121.1
O2—C7—H7B	109.5	C25—C24—H24	121.1
C5—C7—H7B	109.5	C26—C25—C24	121.31 (16)
H7A—C7—H7B	108.1	C26—C25—H25	119.3
N2—C8—C9	121.47 (19)	C24—C25—H25	119.3
N2—C8—C13	115.33 (14)	C27—C26—C25	121.42 (16)
C9—C8—C13	123.20 (18)	C27—C26—H26	119.3
C8—C9—C10	118.2 (2)	C25—C26—H26	119.3
C8—C9—H9	120.9	C26—C27—C28	116.70 (15)
C10—C9—H9	120.9	C26—C27—H27	121.6
C11—C10—C9	120.36 (19)	C28—C27—H27	121.6
C11—C10—H10	119.8	C27—C28—C23	122.65 (15)
C9—C10—H10	119.8	C27—C28—S2	130.37 (12)
C10—C11—C12	119.2 (2)	C23—C28—S2	106.94 (11)
C10—C11—H11	120.4
N2—Co1—O1—C6	169.81 (15)	C8—N2—C12—C11	−0.4 (2)
N1—Co1—O1—C6	−5.75 (15)	Co1—N2—C12—C11	−178.72 (14)
O3—Co1—O1—C6	92.35 (15)	C8—N2—C12—C14	−179.04 (15)
O2—Co1—O1—C6	−10.1 (2)	Co1—N2—C12—C14	2.6 (2)
O4—Co1—O1—C6	−112.74 (15)	C10—C11—C12—N2	1.5 (3)
N2—Co1—O2—C7	−176.76 (14)	C10—C11—C12—C14	−179.9 (2)
N1—Co1—O2—C7	−1.21 (15)	Co1—O3—C13—C8	18.54 (19)
O1—Co1—O2—C7	3.2 (2)	N2—C8—C13—O3	−10.5 (2)
O3—Co1—O2—C7	−100.23 (15)	C9—C8—C13—O3	169.15 (17)
O4—Co1—O2—C7	106.69 (15)	Co1—O4—C14—C12	9.89 (19)
N2—Co1—O3—C13	−15.86 (12)	N2—C12—C14—O4	−8.2 (2)
N1—Co1—O3—C13	159.49 (12)	C11—C12—C14—O4	173.17 (17)
O1—Co1—O3—C13	82.04 (13)	O6—S1—N3—C15	118.12 (14)
O2—Co1—O3—C13	−124.14 (13)	O7—S1—N3—C15	−112.92 (13)
O4—Co1—O3—C13	−29.5 (2)	C21—S1—N3—C15	0.95 (14)
N2—Co1—O4—C14	−6.86 (12)	S1—N3—C15—O5	−179.33 (13)
N1—Co1—O4—C14	177.46 (12)	S1—N3—C15—C16	−0.05 (18)
O1—Co1—O4—C14	−104.76 (12)	O5—C15—C16—C21	178.09 (15)
O3—Co1—O4—C14	6.80 (19)	N3—C15—C16—C21	−1.2 (2)
O2—Co1—O4—C14	101.41 (12)	O5—C15—C16—C17	−3.1 (3)
O1—Co1—N1—C5	−179.19 (15)	N3—C15—C16—C17	177.64 (16)
O3—Co1—N1—C5	87.68 (14)	C21—C16—C17—C18	−0.9 (2)
O2—Co1—N1—C5	−1.22 (13)	C15—C16—C17—C18	−179.63 (16)
O4—Co1—N1—C5	−88.04 (14)	C16—C17—C18—C19	−0.4 (3)
O1—Co1—N1—C1	5.35 (14)	C17—C18—C19—C20	1.2 (3)
O3—Co1—N1—C1	−87.78 (15)	C18—C19—C20—C21	−0.6 (3)
O2—Co1—N1—C1	−176.69 (15)	C17—C16—C21—C20	1.5 (3)
O4—Co1—N1—C1	96.50 (15)	C15—C16—C21—C20	−179.55 (17)
O1—Co1—N2—C12	95.39 (12)	C17—C16—C21—S1	−177.24 (13)
O3—Co1—N2—C12	−171.43 (13)	C15—C16—C21—S1	1.72 (16)
O2—Co1—N2—C12	−84.64 (13)	C19—C20—C21—C16	−0.7 (3)
O4—Co1—N2—C12	2.25 (12)	C19—C20—C21—S1	177.68 (16)
O1—Co1—N2—C8	−82.99 (12)	O6—S1—C21—C16	−118.01 (13)
O3—Co1—N2—C8	10.19 (12)	O7—S1—C21—C16	113.24 (12)
O2—Co1—N2—C8	96.98 (12)	N3—S1—C21—C16	−1.61 (13)
O4—Co1—N2—C8	−176.13 (13)	O6—S1—C21—C20	63.4 (2)
C5—N1—C1—C2	0.2 (3)	O7—S1—C21—C20	−65.4 (2)
Co1—N1—C1—C2	175.66 (17)	N3—S1—C21—C20	179.79 (19)
C5—N1—C1—C6	−179.65 (18)	O9—S2—N4—C22	−120.44 (13)
Co1—N1—C1—C6	−4.2 (2)	O10—S2—N4—C22	110.15 (14)
N1—C1—C2—C3	−0.6 (4)	C28—S2—N4—C22	−5.57 (13)
C6—C1—C2—C3	179.2 (2)	S2—N4—C22—O8	−175.79 (13)
C1—C2—C3—C4	0.7 (4)	S2—N4—C22—C23	6.30 (18)
C2—C3—C4—C5	−0.3 (4)	O8—C22—C23—C24	−4.9 (3)
C1—N1—C5—C4	0.2 (3)	N4—C22—C23—C24	172.98 (16)
Co1—N1—C5—C4	−175.25 (17)	O8—C22—C23—C28	178.18 (14)
C1—N1—C5—C7	178.71 (18)	N4—C22—C23—C28	−3.91 (19)
Co1—N1—C5—C7	3.3 (2)	C28—C23—C24—C25	0.0 (2)
C3—C4—C5—N1	−0.1 (4)	C22—C23—C24—C25	−176.68 (16)
C3—C4—C5—C7	−178.5 (2)	C23—C24—C25—C26	−0.1 (3)
Co1—O1—C6—C1	5.2 (2)	C24—C25—C26—C27	−0.1 (3)
N1—C1—C6—O1	−0.8 (3)	C25—C26—C27—C28	0.5 (3)
C2—C1—C6—O1	179.4 (2)	C26—C27—C28—C23	−0.7 (3)
Co1—O2—C7—C5	3.1 (2)	C26—C27—C28—S2	176.60 (15)
N1—C5—C7—O2	−4.0 (3)	C24—C23—C28—C27	0.5 (2)
C4—C5—C7—O2	174.5 (2)	C22—C23—C28—C27	177.70 (15)
C12—N2—C8—C9	−1.1 (3)	C24—C23—C28—S2	−177.38 (12)
Co1—N2—C8—C9	177.32 (14)	C22—C23—C28—S2	−0.17 (15)
C12—N2—C8—C13	178.57 (15)	O9—S2—C28—C27	−59.69 (19)
Co1—N2—C8—C13	−3.05 (19)	O10—S2—C28—C27	70.47 (19)
N2—C8—C9—C10	1.3 (3)	N4—S2—C28—C27	−174.44 (17)
C13—C8—C9—C10	−178.3 (2)	O9—S2—C28—C23	117.96 (12)
C8—C9—C10—C11	−0.1 (3)	O10—S2—C28—C23	−111.89 (12)
C9—C10—C11—C12	−1.2 (4)	N4—S2—C28—C23	3.21 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.85 (2)	1.72 (2)	2.5658 (17)	175 (2)
O2—H2···O8	0.84 (2)	1.79 (2)	2.6192 (16)	176 (2)
O3—H3···O1W^i	0.81 (2)	1.83 (2)	2.613 (2)	164 (3)
O4—H4···O2W^i	0.81 (2)	1.84 (2)	2.620 (2)	162 (3)
O1W—H2W1···O8^ii	0.82 (2)	2.00 (2)	2.8064 (18)	168 (3)
O1W—H1W1···N4^iii	0.79 (2)	2.25 (2)	3.027 (2)	166 (3)
O2W—H2W2···O5	0.80 (2)	2.00 (2)	2.7861 (18)	166 (3)
O2W—H1W2···O7^iv	0.81 (2)	2.09 (2)	2.877 (2)	168 (3)
C17—H17···O1	0.93	2.59	3.357 (2)	140
C20—H20···O10^v	0.93	2.55	3.294 (2)	137
C27—H27···O7^vi	0.93	2.58	3.341 (2)	139

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

(II) Bis(pyridine-2,6-dimethanol)copper(II) disaccharinate dihydrate

Crystal data

[Cu(C7H9NO2)2]·2C7H4O3S·2H2O	Z = 2
Mr = 742.22	F(000) = 766
Triclinic, P1	Dx = 1.570 Mg m^−3
a = 8.1544 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4805 (5) Å	Cell parameters from 5581 reflections
c = 15.7510 (7) Å	θ = 2.2–29.3°
α = 93.195 (1)°	µ = 0.90 mm^−1
β = 97.501 (1)°	T = 298 K
γ = 97.877 (1)°	Rod, blue
V = 1569.85 (12) Å^3	0.52 × 0.30 × 0.19 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	8915 independent reflections
Radiation source: fine-focus sealed tube	6477 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→11
Tmin = 0.731, Tmax = 0.843	k = −17→16
13441 measured reflections	l = −22→14

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)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0497P)^2] where P = (Fo^2 + 2Fc^2)/3
8915 reflections	(Δ/σ)max = 0.001
448 parameters	Δρmax = 0.36 e Å^−3
10 restraints	Δρmin = −0.30 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	−0.25895 (2)	0.318117 (16)	0.668457 (13)	0.02893 (6)
O1	−0.13777 (17)	0.46034 (11)	0.74270 (9)	0.0428 (3)
H1	−0.054 (2)	0.454 (2)	0.7753 (14)	0.064*
O2	−0.38258 (17)	0.21909 (11)	0.55525 (9)	0.0433 (3)
H2	−0.461 (3)	0.1733 (17)	0.5609 (16)	0.065*
O3	−0.02534 (18)	0.25759 (12)	0.65292 (11)	0.0493 (4)
H3	−0.019 (3)	0.223 (2)	0.6096 (13)	0.074*
O4	−0.49689 (19)	0.32511 (14)	0.71615 (10)	0.0513 (4)
H4	−0.496 (4)	0.3828 (16)	0.7394 (17)	0.077*
O1W	1.0341 (2)	0.14736 (15)	0.51569 (11)	0.0611 (4)
H1W1	1.117 (3)	0.121 (2)	0.525 (2)	0.092*
H2W1	0.969 (3)	0.106 (2)	0.4825 (17)	0.092*
O2W	0.4287 (2)	0.50642 (14)	0.78407 (11)	0.0567 (4)
H1W2	0.348 (3)	0.487 (2)	0.8082 (17)	0.085*
H2W2	0.492 (3)	0.537 (2)	0.8243 (15)	0.085*
N1	−0.25646 (18)	0.42281 (11)	0.58145 (9)	0.0331 (3)
N2	−0.24859 (18)	0.21529 (11)	0.75653 (9)	0.0332 (3)
C1	−0.1757 (3)	0.52393 (14)	0.60190 (13)	0.0431 (5)
C2	−0.1626 (3)	0.59844 (17)	0.54111 (16)	0.0610 (7)
H2A	−0.1057	0.6681	0.5559	0.073*
C3	−0.2355 (3)	0.5677 (2)	0.45776 (16)	0.0649 (7)
H3A	−0.2289	0.6170	0.4157	0.078*
C4	−0.3184 (3)	0.46383 (18)	0.43682 (14)	0.0547 (6)
H4A	−0.3676	0.4421	0.3808	0.066*
C5	−0.3269 (2)	0.39301 (15)	0.50049 (12)	0.0385 (4)
C6	−0.0989 (3)	0.54927 (17)	0.69462 (15)	0.0654 (7)
H6A	0.0215	0.5668	0.6980	0.079*
H6B	−0.1408	0.6119	0.7183	0.079*
C7	−0.4134 (3)	0.27830 (17)	0.48323 (14)	0.0585 (6)
H7A	−0.5328	0.2782	0.4690	0.070*
H7B	−0.3738	0.2441	0.4345	0.070*
C8	−0.1087 (3)	0.16958 (15)	0.77560 (13)	0.0458 (5)
C9	−0.0944 (4)	0.1005 (2)	0.84053 (17)	0.0729 (8)
H9	0.0039	0.0712	0.8540	0.087*
C10	−0.2253 (5)	0.0754 (2)	0.88473 (18)	0.0869 (10)
H10	−0.2176	0.0280	0.9281	0.104*
C11	−0.3677 (4)	0.1199 (2)	0.86536 (16)	0.0751 (9)
H11	−0.4580	0.1025	0.8950	0.090*
C12	−0.3773 (3)	0.19193 (16)	0.80049 (13)	0.0454 (5)
C13	0.0276 (3)	0.19918 (19)	0.72276 (15)	0.0551 (6)
H13A	0.1217	0.2427	0.7586	0.066*
H13B	0.0650	0.1336	0.7014	0.066*
C14	−0.5285 (3)	0.24455 (19)	0.77488 (16)	0.0568 (6)
H14A	−0.6197	0.1897	0.7485	0.068*
H14B	−0.5625	0.2777	0.8257	0.068*
S1	0.23480 (6)	0.28538 (4)	1.02792 (3)	0.04502 (12)
O5	0.12665 (16)	0.43827 (11)	0.84374 (9)	0.0442 (3)
O6	0.2531 (2)	0.17314 (14)	1.01633 (13)	0.0751 (5)
O7	0.33249 (19)	0.34340 (14)	1.10364 (10)	0.0621 (4)
N3	0.26849 (19)	0.34809 (15)	0.94349 (11)	0.0441 (4)
C15	0.1320 (2)	0.38717 (14)	0.91010 (12)	0.0342 (4)
C16	−0.0148 (2)	0.36355 (14)	0.95781 (11)	0.0319 (4)
C17	−0.1718 (2)	0.39502 (16)	0.94205 (13)	0.0396 (4)
H17	−0.1991	0.4368	0.8966	0.047*
C18	−0.2869 (3)	0.3621 (2)	0.99638 (15)	0.0529 (5)
H18	−0.3929	0.3826	0.9875	0.064*
C19	−0.2466 (3)	0.2996 (2)	1.06335 (16)	0.0654 (7)
H19	−0.3270	0.2770	1.0979	0.079*
C20	−0.0896 (3)	0.2698 (2)	1.08022 (14)	0.0560 (6)
H20	−0.0614	0.2287	1.1259	0.067*
C21	0.0238 (2)	0.30393 (15)	1.02609 (12)	0.0385 (4)
S2	−0.77522 (6)	−0.11871 (4)	0.71413 (3)	0.04053 (12)
O8	−0.65194 (16)	0.08107 (11)	0.56522 (9)	0.0420 (3)
O9	−0.86538 (19)	−0.22355 (13)	0.68494 (13)	0.0669 (5)
O10	−0.8053 (2)	−0.07535 (15)	0.79606 (11)	0.0673 (5)
N4	−0.80581 (17)	−0.03337 (13)	0.64174 (11)	0.0398 (4)
C22	−0.6623 (2)	0.00806 (13)	0.61650 (11)	0.0304 (3)
C23	−0.51412 (19)	−0.04219 (13)	0.65345 (11)	0.0280 (3)
C24	−0.3528 (2)	−0.02618 (15)	0.63426 (12)	0.0365 (4)
H24	−0.3205	0.0239	0.5959	0.044*
C25	−0.2401 (2)	−0.08810 (18)	0.67469 (14)	0.0473 (5)
H25	−0.1306	−0.0794	0.6626	0.057*
C26	−0.2872 (2)	−0.16185 (18)	0.73207 (15)	0.0505 (5)
H26	−0.2089	−0.2017	0.7581	0.061*
C27	−0.4484 (2)	−0.17771 (16)	0.75161 (13)	0.0438 (5)
H27	−0.4806	−0.2272	0.7905	0.053*
C28	−0.5600 (2)	−0.11663 (14)	0.71068 (11)	0.0311 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02817 (11)	0.02750 (10)	0.03069 (11)	0.00306 (7)	0.00258 (8)	0.00444 (8)
O1	0.0463 (8)	0.0368 (7)	0.0398 (8)	−0.0007 (6)	−0.0089 (6)	0.0051 (6)
O2	0.0460 (8)	0.0348 (7)	0.0448 (8)	−0.0074 (6)	0.0006 (6)	0.0099 (6)
O3	0.0413 (8)	0.0466 (8)	0.0622 (10)	0.0097 (6)	0.0138 (7)	−0.0009 (7)
O4	0.0403 (8)	0.0667 (10)	0.0482 (9)	0.0151 (7)	0.0064 (6)	−0.0030 (7)
O1W	0.0609 (11)	0.0703 (11)	0.0547 (10)	0.0318 (9)	−0.0041 (8)	−0.0005 (8)
O2W	0.0512 (9)	0.0635 (10)	0.0561 (10)	0.0026 (8)	0.0165 (8)	0.0035 (8)
N1	0.0365 (8)	0.0277 (7)	0.0332 (8)	0.0014 (6)	0.0004 (6)	0.0046 (6)
N2	0.0400 (8)	0.0271 (7)	0.0305 (8)	0.0021 (6)	0.0018 (6)	−0.0001 (6)
C1	0.0505 (11)	0.0284 (9)	0.0454 (11)	−0.0017 (8)	−0.0059 (9)	0.0085 (8)
C2	0.0742 (16)	0.0353 (10)	0.0644 (15)	−0.0108 (10)	−0.0107 (12)	0.0179 (10)
C3	0.0799 (17)	0.0532 (13)	0.0563 (15)	−0.0106 (12)	−0.0003 (12)	0.0304 (11)
C4	0.0717 (15)	0.0542 (13)	0.0332 (11)	−0.0039 (11)	−0.0026 (10)	0.0139 (9)
C5	0.0448 (10)	0.0363 (9)	0.0318 (9)	−0.0014 (8)	0.0021 (8)	0.0044 (7)
C6	0.0938 (19)	0.0315 (10)	0.0560 (14)	−0.0112 (11)	−0.0260 (13)	0.0081 (10)
C7	0.0889 (17)	0.0410 (11)	0.0348 (11)	−0.0163 (11)	−0.0054 (11)	0.0048 (9)
C8	0.0619 (13)	0.0332 (9)	0.0392 (11)	0.0164 (9)	−0.0109 (9)	−0.0047 (8)
C9	0.120 (2)	0.0489 (14)	0.0489 (14)	0.0346 (14)	−0.0175 (15)	0.0053 (11)
C10	0.161 (3)	0.0493 (15)	0.0500 (16)	0.0199 (18)	0.0040 (19)	0.0180 (12)
C11	0.124 (3)	0.0504 (14)	0.0475 (14)	−0.0185 (15)	0.0301 (15)	0.0059 (11)
C12	0.0609 (13)	0.0344 (10)	0.0380 (11)	−0.0087 (9)	0.0148 (9)	−0.0031 (8)
C13	0.0417 (11)	0.0622 (14)	0.0596 (14)	0.0256 (10)	−0.0101 (10)	−0.0149 (11)
C14	0.0451 (12)	0.0599 (14)	0.0628 (15)	−0.0126 (10)	0.0247 (11)	−0.0093 (11)
S1	0.0386 (3)	0.0511 (3)	0.0461 (3)	0.0110 (2)	−0.0006 (2)	0.0155 (2)
O5	0.0368 (7)	0.0566 (8)	0.0384 (7)	0.0012 (6)	0.0033 (6)	0.0159 (6)
O6	0.0818 (13)	0.0533 (10)	0.0959 (15)	0.0295 (9)	0.0067 (11)	0.0208 (10)
O7	0.0503 (9)	0.0800 (11)	0.0498 (9)	0.0034 (8)	−0.0146 (7)	0.0179 (8)
N3	0.0295 (8)	0.0612 (11)	0.0443 (10)	0.0103 (7)	0.0074 (7)	0.0140 (8)
C15	0.0294 (8)	0.0383 (9)	0.0334 (9)	0.0013 (7)	0.0032 (7)	0.0023 (7)
C16	0.0284 (8)	0.0346 (9)	0.0308 (9)	0.0004 (7)	0.0033 (7)	−0.0010 (7)
C17	0.0316 (9)	0.0462 (10)	0.0393 (10)	0.0058 (8)	0.0012 (8)	−0.0022 (8)
C18	0.0321 (10)	0.0717 (15)	0.0540 (13)	0.0057 (10)	0.0089 (9)	−0.0067 (11)
C19	0.0488 (13)	0.0915 (19)	0.0560 (15)	−0.0062 (13)	0.0244 (11)	0.0060 (13)
C20	0.0530 (13)	0.0725 (15)	0.0421 (12)	−0.0024 (11)	0.0118 (10)	0.0177 (11)
C21	0.0347 (9)	0.0420 (10)	0.0370 (10)	−0.0005 (7)	0.0037 (7)	0.0057 (8)
S2	0.0297 (2)	0.0421 (3)	0.0535 (3)	0.00588 (18)	0.0123 (2)	0.0196 (2)
O8	0.0383 (7)	0.0417 (7)	0.0463 (8)	0.0033 (6)	0.0035 (6)	0.0194 (6)
O9	0.0431 (8)	0.0493 (9)	0.1040 (14)	−0.0104 (7)	0.0030 (9)	0.0273 (9)
O10	0.0701 (11)	0.0868 (12)	0.0616 (11)	0.0334 (9)	0.0382 (9)	0.0282 (9)
N4	0.0250 (7)	0.0444 (9)	0.0520 (10)	0.0068 (6)	0.0042 (7)	0.0192 (7)
C22	0.0278 (8)	0.0300 (8)	0.0323 (9)	0.0028 (6)	0.0014 (6)	0.0030 (7)
C23	0.0250 (7)	0.0278 (8)	0.0299 (8)	0.0028 (6)	0.0015 (6)	−0.0004 (6)
C24	0.0289 (8)	0.0406 (10)	0.0393 (10)	0.0016 (7)	0.0063 (7)	0.0005 (8)
C25	0.0275 (9)	0.0588 (13)	0.0561 (13)	0.0114 (8)	0.0042 (8)	−0.0006 (10)
C26	0.0396 (11)	0.0588 (13)	0.0556 (13)	0.0247 (9)	−0.0035 (9)	0.0066 (10)
C27	0.0450 (11)	0.0438 (11)	0.0449 (11)	0.0149 (8)	0.0017 (9)	0.0135 (9)
C28	0.0282 (8)	0.0318 (8)	0.0334 (9)	0.0052 (6)	0.0031 (7)	0.0037 (7)

Geometric parameters (Å, º)

Cu1—N1	1.9455 (14)	C11—C12	1.400 (3)
Cu1—N2	1.9432 (15)	C11—H11	0.9300
Cu1—O1	2.1168 (13)	C12—C14	1.495 (3)
Cu1—O2	2.1603 (14)	C13—H13A	0.9700
Cu1—O3	2.1806 (14)	C13—H13B	0.9700
Cu1—O4	2.1809 (15)	C14—H14A	0.9700
O1—C6	1.402 (2)	C14—H14B	0.9700
O1—H1	0.819 (16)	S1—O6	1.4331 (17)
O2—C7	1.402 (2)	S1—O7	1.4418 (17)
O2—H2	0.812 (16)	S1—N3	1.6153 (17)
O3—C13	1.407 (3)	S1—C21	1.7638 (19)
O3—H3	0.797 (16)	O5—C15	1.253 (2)
O4—C14	1.424 (3)	N3—C15	1.333 (2)
O4—H4	0.788 (16)	C15—C16	1.499 (2)
O1W—H1W1	0.796 (16)	C16—C21	1.369 (2)
O1W—H2W1	0.801 (17)	C16—C17	1.386 (2)
O2W—H1W2	0.818 (17)	C17—C18	1.388 (3)
O2W—H2W2	0.809 (17)	C17—H17	0.9300
N1—C5	1.338 (2)	C18—C19	1.379 (3)
N1—C1	1.342 (2)	C18—H18	0.9300
N2—C12	1.339 (3)	C19—C20	1.379 (3)
N2—C8	1.351 (2)	C19—H19	0.9300
C1—C2	1.375 (3)	C20—C21	1.379 (3)
C1—C6	1.510 (3)	C20—H20	0.9300
C2—C3	1.379 (3)	S2—O9	1.4300 (16)
C2—H2A	0.9300	S2—O10	1.4349 (17)
C3—C4	1.378 (3)	S2—N4	1.6219 (15)
C3—H3A	0.9300	S2—C28	1.7595 (17)
C4—C5	1.376 (3)	O8—C22	1.252 (2)
C4—H4A	0.9300	N4—C22	1.332 (2)
C5—C7	1.500 (3)	C22—C23	1.502 (2)
C6—H6A	0.9700	C23—C24	1.378 (2)
C6—H6B	0.9700	C23—C28	1.379 (2)
C7—H7A	0.9700	C24—C25	1.395 (3)
C7—H7B	0.9700	C24—H24	0.9300
C8—C9	1.378 (3)	C25—C26	1.378 (3)
C8—C13	1.492 (3)	C25—H25	0.9300
C9—C10	1.360 (4)	C26—C27	1.379 (3)
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.360 (4)	C27—C28	1.385 (2)
C10—H10	0.9300	C27—H27	0.9300
N2—Cu1—N1	176.96 (6)	C12—C11—H11	120.2
N2—Cu1—O1	99.30 (6)	N2—C12—C11	120.3 (2)
N1—Cu1—O1	79.10 (6)	N2—C12—C14	116.48 (18)
N2—Cu1—O2	103.30 (5)	C11—C12—C14	123.2 (2)
N1—Cu1—O2	78.30 (5)	O3—C13—C8	111.98 (16)
O1—Cu1—O2	157.40 (5)	O3—C13—H13A	109.2
N2—Cu1—O3	78.66 (6)	C8—C13—H13A	109.2
N1—Cu1—O3	98.82 (6)	O3—C13—H13B	109.2
O1—Cu1—O3	93.62 (6)	C8—C13—H13B	109.2
O2—Cu1—O3	90.16 (6)	H13A—C13—H13B	107.9
N2—Cu1—O4	78.92 (6)	O4—C14—C12	111.57 (17)
N1—Cu1—O4	103.70 (6)	O4—C14—H14A	109.3
O1—Cu1—O4	93.78 (6)	C12—C14—H14A	109.3
O2—Cu1—O4	91.22 (6)	O4—C14—H14B	109.3
O3—Cu1—O4	157.25 (6)	C12—C14—H14B	109.3
C6—O1—Cu1	114.32 (12)	H14A—C14—H14B	108.0
C6—O1—H1	107.8 (18)	O6—S1—O7	115.18 (10)
Cu1—O1—H1	116.2 (18)	O6—S1—N3	111.26 (11)
C7—O2—Cu1	113.55 (11)	O7—S1—N3	110.51 (10)
C7—O2—H2	113.2 (18)	O6—S1—C21	112.10 (10)
Cu1—O2—H2	117.7 (18)	O7—S1—C21	109.17 (10)
C13—O3—Cu1	111.30 (12)	N3—S1—C21	97.19 (8)
C13—O3—H3	109 (2)	C15—N3—S1	110.69 (13)
Cu1—O3—H3	119 (2)	O5—C15—N3	122.64 (17)
C14—O4—Cu1	111.55 (12)	O5—C15—C16	122.93 (15)
C14—O4—H4	109 (2)	N3—C15—C16	114.42 (16)
Cu1—O4—H4	109 (2)	C21—C16—C17	120.20 (17)
H1W1—O1W—H2W1	108 (3)	C21—C16—C15	110.73 (15)
H1W2—O2W—H2W2	100 (2)	C17—C16—C15	129.06 (17)
C5—N1—C1	119.88 (16)	C16—C17—C18	117.73 (19)
C5—N1—Cu1	120.43 (12)	C16—C17—H17	121.1
C1—N1—Cu1	119.59 (12)	C18—C17—H17	121.1
C12—N2—C8	119.64 (18)	C19—C18—C17	121.0 (2)
C12—N2—Cu1	120.45 (13)	C19—C18—H18	119.5
C8—N2—Cu1	119.88 (14)	C17—C18—H18	119.5
N1—C1—C2	121.39 (19)	C20—C19—C18	121.4 (2)
N1—C1—C6	115.88 (16)	C20—C19—H19	119.3
C2—C1—C6	122.72 (18)	C18—C19—H19	119.3
C1—C2—C3	118.7 (2)	C19—C20—C21	116.8 (2)
C1—C2—H2A	120.7	C19—C20—H20	121.6
C3—C2—H2A	120.7	C21—C20—H20	121.6
C4—C3—C2	119.9 (2)	C16—C21—C20	122.76 (19)
C4—C3—H3A	120.0	C16—C21—S1	106.93 (13)
C2—C3—H3A	120.0	C20—C21—S1	130.30 (17)
C5—C4—C3	118.7 (2)	O9—S2—O10	115.82 (12)
C5—C4—H4A	120.7	O9—S2—N4	110.27 (10)
C3—C4—H4A	120.7	O10—S2—N4	110.54 (10)
N1—C5—C4	121.50 (17)	O9—S2—C28	110.59 (9)
N1—C5—C7	116.32 (16)	O10—S2—C28	111.20 (10)
C4—C5—C7	122.17 (18)	N4—S2—C28	96.82 (8)
O1—C6—C1	110.48 (16)	C22—N4—S2	111.07 (11)
O1—C6—H6A	109.6	O8—C22—N4	123.08 (15)
C1—C6—H6A	109.6	O8—C22—C23	122.82 (15)
O1—C6—H6B	109.6	N4—C22—C23	114.09 (15)
C1—C6—H6B	109.6	C24—C23—C28	120.61 (15)
H6A—C6—H6B	108.1	C24—C23—C22	128.85 (16)
O2—C7—C5	110.67 (16)	C28—C23—C22	110.47 (14)
O2—C7—H7A	109.5	C23—C24—C25	117.36 (18)
C5—C7—H7A	109.5	C23—C24—H24	121.3
O2—C7—H7B	109.5	C25—C24—H24	121.3
C5—C7—H7B	109.5	C26—C25—C24	121.48 (18)
H7A—C7—H7B	108.1	C26—C25—H25	119.3
N2—C8—C9	121.3 (2)	C24—C25—H25	119.3
N2—C8—C13	116.00 (18)	C25—C26—C27	121.26 (17)
C9—C8—C13	122.7 (2)	C25—C26—H26	119.4
C10—C9—C8	119.4 (3)	C27—C26—H26	119.4
C10—C9—H9	120.3	C26—C27—C28	116.94 (19)
C8—C9—H9	120.3	C26—C27—H27	121.5
C9—C10—C11	119.9 (2)	C28—C27—H27	121.5
C9—C10—H10	120.1	C23—C28—C27	122.35 (17)
C11—C10—H10	120.1	C23—C28—S2	107.22 (12)
C10—C11—C12	119.6 (3)	C27—C28—S2	130.37 (15)
C10—C11—H11	120.2
N2—Cu1—O1—C6	170.01 (16)	C8—N2—C12—C11	−0.5 (3)
N1—Cu1—O1—C6	−7.37 (16)	Cu1—N2—C12—C11	−178.41 (15)
O2—Cu1—O1—C6	−8.2 (2)	C8—N2—C12—C14	−179.23 (17)
O3—Cu1—O1—C6	90.92 (16)	Cu1—N2—C12—C14	2.9 (2)
O4—Cu1—O1—C6	−110.61 (16)	C10—C11—C12—N2	1.4 (3)
N2—Cu1—O2—C7	176.33 (15)	C10—C11—C12—C14	180.0 (2)
N1—Cu1—O2—C7	−6.32 (15)	Cu1—O3—C13—C8	15.1 (2)
O1—Cu1—O2—C7	−5.5 (2)	N2—C8—C13—O3	−9.1 (3)
O3—Cu1—O2—C7	−105.29 (15)	C9—C8—C13—O3	171.28 (19)
O4—Cu1—O2—C7	97.42 (16)	Cu1—O4—C14—C12	10.9 (2)
N2—Cu1—O3—C13	−13.15 (13)	N2—C12—C14—O4	−9.5 (3)
N1—Cu1—O3—C13	165.13 (13)	C11—C12—C14—O4	171.8 (2)
O1—Cu1—O3—C13	85.61 (13)	O6—S1—N3—C15	118.08 (16)
O2—Cu1—O3—C13	−116.69 (13)	O7—S1—N3—C15	−112.65 (15)
O4—Cu1—O3—C13	−23.2 (2)	C21—S1—N3—C15	0.96 (16)
N2—Cu1—O4—C14	−7.69 (13)	S1—N3—C15—O5	−179.35 (15)
N1—Cu1—O4—C14	173.88 (13)	S1—N3—C15—C16	−0.1 (2)
O1—Cu1—O4—C14	−106.44 (13)	O5—C15—C16—C21	178.15 (17)
O2—Cu1—O4—C14	95.62 (14)	N3—C15—C16—C21	−1.0 (2)
O3—Cu1—O4—C14	2.3 (2)	O5—C15—C16—C17	−3.1 (3)
O1—Cu1—N1—C5	−178.06 (15)	N3—C15—C16—C17	177.74 (18)
O2—Cu1—N1—C5	1.60 (14)	C21—C16—C17—C18	−1.3 (3)
O3—Cu1—N1—C5	89.92 (15)	C15—C16—C17—C18	−179.99 (18)
O4—Cu1—N1—C5	−86.79 (15)	C16—C17—C18—C19	−0.5 (3)
O1—Cu1—N1—C1	5.55 (15)	C17—C18—C19—C20	1.7 (4)
O2—Cu1—N1—C1	−174.79 (16)	C18—C19—C20—C21	−1.1 (4)
O3—Cu1—N1—C1	−86.47 (15)	C17—C16—C21—C20	1.9 (3)
O4—Cu1—N1—C1	96.82 (15)	C15—C16—C21—C20	−179.15 (19)
O1—Cu1—N2—C12	94.68 (14)	C17—C16—C21—S1	−177.32 (14)
O2—Cu1—N2—C12	−86.02 (14)	C15—C16—C21—S1	1.59 (18)
O3—Cu1—N2—C12	−173.46 (15)	C19—C20—C21—C16	−0.7 (3)
O4—Cu1—N2—C12	2.61 (13)	C19—C20—C21—S1	178.37 (18)
O1—Cu1—N2—C8	−83.19 (14)	O6—S1—C21—C16	−118.01 (15)
O2—Cu1—N2—C8	96.12 (14)	O7—S1—C21—C16	113.15 (14)
O3—Cu1—N2—C8	8.68 (13)	N3—S1—C21—C16	−1.54 (15)
O4—Cu1—N2—C8	−175.25 (14)	O6—S1—C21—C20	62.8 (2)
C5—N1—C1—C2	−0.3 (3)	O7—S1—C21—C20	−66.0 (2)
Cu1—N1—C1—C2	176.13 (18)	N3—S1—C21—C20	179.3 (2)
C5—N1—C1—C6	−179.33 (19)	O9—S2—N4—C22	−120.21 (15)
Cu1—N1—C1—C6	−2.9 (3)	O10—S2—N4—C22	110.44 (15)
N1—C1—C2—C3	0.4 (4)	C28—S2—N4—C22	−5.26 (15)
C6—C1—C2—C3	179.4 (2)	S2—N4—C22—O8	−175.19 (15)
C1—C2—C3—C4	−0.5 (4)	S2—N4—C22—C23	6.1 (2)
C2—C3—C4—C5	0.3 (4)	O8—C22—C23—C24	−5.8 (3)
C1—N1—C5—C4	0.1 (3)	N4—C22—C23—C24	172.93 (17)
Cu1—N1—C5—C4	−176.23 (16)	O8—C22—C23—C28	177.35 (16)
C1—N1—C5—C7	179.55 (19)	N4—C22—C23—C28	−3.9 (2)
Cu1—N1—C5—C7	3.2 (2)	C28—C23—C24—C25	0.2 (3)
C3—C4—C5—N1	−0.2 (3)	C22—C23—C24—C25	−176.42 (17)
C3—C4—C5—C7	−179.5 (2)	C23—C24—C25—C26	−0.5 (3)
Cu1—O1—C6—C1	7.7 (3)	C24—C25—C26—C27	0.3 (3)
N1—C1—C6—O1	−3.5 (3)	C25—C26—C27—C28	0.3 (3)
C2—C1—C6—O1	177.5 (2)	C24—C23—C28—C27	0.4 (3)
Cu1—O2—C7—C5	9.2 (2)	C22—C23—C28—C27	177.56 (17)
N1—C5—C7—O2	−8.3 (3)	C24—C23—C28—S2	−177.10 (13)
C4—C5—C7—O2	171.1 (2)	C22—C23—C28—S2	0.06 (17)
C12—N2—C8—C9	−1.1 (3)	C26—C27—C28—C23	−0.6 (3)
Cu1—N2—C8—C9	176.81 (16)	C26—C27—C28—S2	176.25 (16)
C12—N2—C8—C13	179.33 (17)	O9—S2—C28—C23	117.57 (14)
Cu1—N2—C8—C13	−2.8 (2)	O10—S2—C28—C23	−112.29 (14)
N2—C8—C9—C10	1.8 (3)	N4—S2—C28—C23	2.88 (14)
C13—C8—C9—C10	−178.6 (2)	O9—S2—C28—C27	−59.7 (2)
C8—C9—C10—C11	−0.9 (4)	O10—S2—C28—C27	70.5 (2)
C9—C10—C11—C12	−0.6 (4)	N4—S2—C28—C27	−174.34 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.82 (2)	1.75 (2)	2.5639 (18)	179 (3)
O2—H2···O8	0.81 (2)	1.82 (2)	2.6267 (18)	173 (3)
O3—H3···O1W^i	0.80 (2)	1.84 (2)	2.631 (2)	171 (3)
O4—H4···O2W^i	0.79 (2)	1.87 (2)	2.629 (2)	160 (3)
O1W—H1W1···O8^ii	0.80 (2)	2.04 (2)	2.825 (2)	168 (3)
O1W—H2W1···N4^iii	0.80 (2)	2.28 (2)	3.052 (2)	161 (3)
O2W—H1W2···O5	0.82 (2)	1.99 (2)	2.791 (2)	169 (3)
O2W—H2W2···O7^iv	0.81 (2)	2.08 (2)	2.858 (2)	160 (3)
C17—H17···O1	0.93	2.56	3.324 (2)	139
C20—H20···O10^v	0.93	2.53	3.289 (3)	139
C27—H27···O7^vi	0.93	2.56	3.296 (2)	136

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