A mixed-valence Cu^II/Cu^I anion-cation complex: bis­[[mu]-5-sulfosali­cylato(3-)]bis­[(di-2-pyridylamine)­copper(II)] bis­[bis­(di-2-pyridyl­amine)copper(I)] dihydrate

The title compound, [Cu(C₇H₃O₆S)₂(C₁₀H₉N₃)₂][Cu^I(C₁₀H₉N₃)₂]₂·2H₂O, consists of anionic Cu^II moieties, cationic Cu^I species and uncoordinated water mol­ecules. The anionic dimeric unit consists of one crystallographically independent fully deprotonated 5-sulfosalicylate (2-oxido-5-sulfonatobenzoate) anion, a di-2-pyridylamine group and a Cu^II atom. Each Cu^II atom is five-coordinate within a square-pyramidal geometry. The anion lies on a special position of site symmetry. In the cationic monomer, the Cu^I atom adopts tetra­hedral geometry. The cations and anions are connected by O-H...O and N-H...O hydrogen bonds.

S1. Comment

It is well known that Cu^II ions can be reduced to Cu^I by N-heterocyclic ligands under hydrothermal conditions, such as 4,4'-bipyridine or pyridine derivatives (Wen et al., 2004). Interesting reactions and novel structures can be achieved when Cu^II is reduced. Mixed-valence Cu^I,II complexes are of great importance in structural topology and functional materials (Zhang & Chen, 2003). In general, mixed-valence copper complexes exist as polynuclear species or ion pairs (Pawlowski et al., 2004). Although numerous complexes with Cu^II cationic and Cu^I anionic components have been prepared, complexes containing Cu^I cationic and Cu^II anionic motifs have been apparently ignored. In our recent report on metal 5-sulfosalicylates, a copper salt was reacted with 5-sulfosalicylic acid (H₃ssal) and 2,2'-dipyridylamine (dpa), and [Cu₃(dpa)₃(ssal)₂]·3H₂O was obtained (Fan & Zhu, 2005). Without an abstracting reagent, a similar synthesis but addition of NaOH yielded the mixed-valence compound with Cu^I cationic components, [Cu^II₂(ssal)₂(dpa)₂]·2[Cu^I(dpa)₂]·2H₂O, (I).

The molecular structure consists of [Cu₂(dpa)₂(ssal)₂]²⁻ anions, [Cu(dpa)₂]⁺ cations and uncoordinated water molecules (Figs. 1 and 2, and Table 1). The anionic dimer [Cu₂(dpa)₂(ssal)₂]²⁻ consists of two centrosymmetrically related five-coordinate Cu^II centers, with a Cu···Cuⁱ distance of 3.225 (1) Å [symmetry code: (i) 1 − x, 1 − y, 2 − z]. The basal plane of the square-pyramidal geometry of the Cu^II center is occupied by two N atoms of a dpa ligand and two O atoms of the fully deprotonated ssal³⁻ ligand, while the apical position is taken by the phenoxo O atom of a second centrosymmetrically imposed ssal³⁻ ligand. A four-membered bridging unit, Cu₂O₂, is formed between the Cu^II atoms via phenoxo atoms O3 and O3ⁱ. Only one carboxylate O atom from the ssal³⁻ ligand is directly bonded to the Cu^II atom, and the coordination mode of the carboxylate moiety is obviously anti monodentate. As expected, in the anion, the C11—O1 bond is significantly longer than the C11—O2 distance, indicating a more keto character in the latter. The dihedral angle between the planes of the ring (atoms C2–C7) and its carboxyl group is 11.0 (4)°. The structure of the anion is closely related to that of the ternary dimeric compound [Cu^II₂(dpa)₂(salal)₂(ClO₄)₂] (Garland et al., 1987), in which the Cu^II atom is coordinated by a sixth O atom from a ClO₄⁻ anion and the Cu···Cu distance is longer than that in the title compound.

The cation consists of a Cu^I atom and two dpa ligands (Fig. 2). The Cu^I center adopts tetrahedral geometry. The Cu^I—N bond lengths are similar to those in the anion, and the conformations of the three dpa ligands in the asymmetric unit differ slightly. The dihedral angle between the two pyridyl rings of the dpa ligand in the anion is 19.2 (2)°, while the corresponding angles in the cation are 23.9 (3) and 15.3 (4)°. The N1···N3, N4···N6 and N7···N9 distances are 2.855 (5), 2.891 (6) and 2.955 (6) Å, respectively.

The anions and water molecules form one-dimensional hydrogen-bonded chain through N—H···O1W and O1W—H···O(SO₃⁻) interactions (Fig. 3 and Table 2). These chains are linked into a two-dimensional hydrogen-bonded network by the cations through N—H···O(–COO⁻) and N—H···O(SO₃⁻) interactions (Fig. 4). Therefore, in the solid state, the stability of (I) is enhanced by hydrogen-bonding interactions.

S2. Experimental

A mixture of Cu(CH₃COO)₂·H₂O (0.040 g, 0.20 mmol), 5-sulfosalicylic acid dihydrate (0.026 g, 0.10 mmol), 2,2'-dipyridylamine (0.035 g, 0.20 mmol), NaOH (0.019 g, 0.5 mmol) and water (10 ml) was heated at 413 K for 72 h in a 20 ml Teflon-lined stainless steel autoclave. After cooling, green block-shaped crystals of (I) were obtained by filtration.

S3. Refinement

The aromatic H atoms were generated geometrically, and were included in the refinements in the riding model approximation (C—H 0.93 Å, U 1.2U_eqC). The water and amine H atoms were located from a difference Fourier map and were refined with distance restraints of O—H 0.85 (1) and N—H 0.82 (1) and with fixed isotropic displacement parameters of U_iso(H)=0.08 and 0.05 Ų, respectively. The crystals were dried and stored in air. Data collection was directly done using such a crystal without a protective oil at room temperature. PLATON analysis (Spek, 2003) suggests that the structure contains a solvent accessible void which is capable to accommodate an additional water molecule in the region around (1/2, 0, 0), while under present treated procedure, the additional water molecule is not located. Although the crystal was measured to a 2θ limit of 56.7 °, only the intensities below 50.1 ° were used in the refinement; the use of all reflections gave a much lower data completeness (90.5%). In present refinement, there are 55 reflections missing from the dataset.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. An ORTEP-3 view of the anionic dimer. Displacement ellipsoids are drawn at the 50% probability level, and H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 2 − z.]
	Fig. 2. An ORTEP-3 view of the cationic monomer. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. A view of the one-dimensional hydrogen-bonding chain constructed from anions and water molecules. Hydrogen bonds are shown as dashed lines and H atoms have been omitted for clarity.
	Fig. 4. A view of the two-dimensional hydrogen-bonding network of (I), parrallel to (010). Hydrogen bonds are shown as dashed lines and H atoms have been omitted for clarity.

bis[µ-5-sulfosalicylato(3-)]bis[(di-2-pyridylamine)copper(II)] bis[bis(di-2-pyridylamine)copper(I)] dihydrate

Crystal data

[Cu2(C7H3O6S)2(C10H9N3)2][Cu(C10H9N3)2]2·2H2O	Z = 1
Mr = 1747.71	F(000) = 894
Triclinic, P1	Dx = 1.549 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.258 (2) Å	Cell parameters from 4694 reflections
b = 14.422 (4) Å	θ = 2.5–26.2°
c = 18.312 (5) Å	µ = 1.25 mm^−1
α = 82.428 (4)°	T = 295 K
β = 80.697 (4)°	Block, green
γ = 86.409 (4)°	0.28 × 0.19 × 0.14 mm
V = 1873.5 (9) Å^3

Data collection

Bruker SMART APEX area-detector diffractometer	6582 independent reflections
Radiation source: fine-focus sealed tube	6078 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
Tmin = 0.759, Tmax = 0.844	k = −17→16
13648 measured reflections	l = −21→21

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.23	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 3.6691P] where P = (Fo^2 + 2Fc^2)/3
6582 reflections	(Δ/σ)max < 0.001
514 parameters	Δρmax = 0.65 e Å^−3
5 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
Cu1	0.68516 (8)	0.45186 (4)	0.95670 (3)	0.02985 (17)
Cu2	0.18868 (10)	0.75470 (5)	0.41661 (4)	0.0536 (2)
S1	0.71032 (18)	0.92243 (8)	0.76677 (6)	0.0375 (3)
O1	0.6209 (5)	0.4850 (2)	0.85829 (16)	0.0366 (8)
O2	0.5829 (5)	0.5723 (2)	0.75380 (18)	0.0427 (8)
O3	0.6158 (4)	0.5776 (2)	0.97907 (16)	0.0329 (7)
O4	0.8609 (6)	0.9702 (3)	0.7852 (2)	0.0618 (11)
O5	0.7470 (7)	0.8950 (3)	0.6930 (2)	0.0634 (12)
O6	0.5349 (6)	0.9744 (3)	0.7804 (3)	0.0740 (14)
O7	0.1860 (6)	0.9049 (3)	0.8444 (3)	0.0935 (17)
N1	0.8028 (5)	0.4254 (3)	1.0503 (2)	0.0313 (8)
N2	0.7951 (6)	0.2611 (3)	1.0568 (2)	0.0411 (10)
N3	0.7608 (6)	0.3196 (3)	0.9333 (2)	0.0365 (9)
N4	−0.0029 (6)	0.8607 (3)	0.4300 (2)	0.0418 (10)
N5	−0.0302 (6)	0.8319 (3)	0.5614 (2)	0.0426 (10)
N6	0.2612 (6)	0.7623 (3)	0.5182 (2)	0.0432 (10)
N7	0.0631 (6)	0.6361 (3)	0.4063 (3)	0.0523 (12)
N8	0.3240 (6)	0.5820 (3)	0.3260 (2)	0.0454 (11)
N9	0.3973 (6)	0.7387 (3)	0.3337 (2)	0.0429 (10)
C1	0.8459 (7)	0.4984 (4)	1.0828 (3)	0.0394 (11)
H1	0.8345	0.5584	1.0576	0.047*
C2	0.9053 (7)	0.4890 (4)	1.1509 (3)	0.0462 (13)
H2	0.9367	0.5410	1.1706	0.055*
C3	0.9173 (7)	0.4009 (4)	1.1892 (3)	0.0499 (14)
H3	0.9521	0.3926	1.2365	0.060*
C4	0.8782 (7)	0.3264 (4)	1.1578 (3)	0.0453 (13)
H4	0.8866	0.2664	1.1831	0.054*
C5	0.8248 (6)	0.3398 (3)	1.0868 (3)	0.0347 (10)
C6	0.7879 (7)	0.2477 (3)	0.9849 (3)	0.0377 (11)
C7	0.8082 (10)	0.1558 (4)	0.9676 (3)	0.0615 (17)
H7	0.8210	0.1065	1.0049	0.074*
C8	0.8093 (11)	0.1382 (4)	0.8970 (4)	0.078 (2)
H8	0.8236	0.0771	0.8853	0.094*
C9	0.7891 (10)	0.2118 (4)	0.8425 (4)	0.0675 (18)
H9	0.7920	0.2016	0.7932	0.081*
C10	0.7646 (8)	0.3001 (4)	0.8627 (3)	0.0522 (14)
H10	0.7497	0.3497	0.8258	0.063*
C11	0.6120 (6)	0.5651 (3)	0.8197 (2)	0.0287 (9)
C12	0.6384 (6)	0.6514 (3)	0.8522 (2)	0.0278 (9)
C13	0.6421 (6)	0.6523 (3)	0.9290 (2)	0.0282 (9)
C14	0.6713 (7)	0.7381 (3)	0.9532 (3)	0.0358 (11)
H14	0.6758	0.7398	1.0035	0.043*
C15	0.6933 (7)	0.8191 (3)	0.9051 (3)	0.0389 (11)
H15	0.7113	0.8749	0.9227	0.047*
C16	0.6884 (6)	0.8175 (3)	0.8292 (2)	0.0318 (10)
C17	0.6620 (6)	0.7344 (3)	0.8044 (2)	0.0291 (10)
H17	0.6599	0.7336	0.7538	0.035*
C18	−0.0624 (9)	0.9107 (4)	0.3696 (3)	0.0542 (14)
H18	−0.0038	0.8987	0.3226	0.065*
C19	−0.2019 (8)	0.9769 (4)	0.3740 (3)	0.0533 (14)
H19	−0.2403	1.0086	0.3311	0.064*
C20	−0.2859 (7)	0.9963 (4)	0.4432 (3)	0.0473 (13)
H20	−0.3829	1.0415	0.4476	0.057*
C21	−0.2272 (7)	0.9493 (3)	0.5056 (3)	0.0405 (12)
H21	−0.2809	0.9629	0.5528	0.049*
C22	−0.0846 (6)	0.8803 (3)	0.4968 (3)	0.0341 (10)
C23	0.1413 (7)	0.7916 (3)	0.5739 (3)	0.0379 (11)
C24	0.1803 (8)	0.7821 (4)	0.6462 (3)	0.0522 (14)
H24	0.0921	0.8013	0.6846	0.063*
C25	0.3492 (9)	0.7444 (5)	0.6602 (4)	0.0673 (18)
H25	0.3776	0.7371	0.7084	0.081*
C26	0.4779 (9)	0.7170 (5)	0.6024 (4)	0.072 (2)
H26	0.5952	0.6919	0.6104	0.086*
C27	0.4288 (8)	0.7277 (4)	0.5335 (4)	0.0615 (16)
H27	0.5165	0.7101	0.4943	0.074*
C28	−0.1097 (9)	0.6207 (5)	0.4427 (4)	0.077 (2)
H28	−0.1667	0.6651	0.4725	0.093*
C29	−0.2065 (10)	0.5451 (5)	0.4391 (5)	0.091 (3)
H29	−0.3278	0.5387	0.4643	0.109*
C30	−0.1202 (10)	0.4775 (5)	0.3970 (4)	0.081 (2)
H30	−0.1824	0.4241	0.3938	0.097*
C31	0.0560 (9)	0.4897 (4)	0.3604 (3)	0.0589 (16)
H31	0.1169	0.4442	0.3325	0.071*
C32	0.1454 (7)	0.5717 (3)	0.3649 (3)	0.0413 (12)
C33	0.4361 (7)	0.6581 (3)	0.3048 (3)	0.0402 (11)
C34	0.5887 (8)	0.6470 (4)	0.2497 (4)	0.0630 (17)
H34	0.6144	0.5901	0.2307	0.076*
C35	0.7005 (10)	0.7209 (5)	0.2239 (4)	0.083 (2)
H35	0.8031	0.7148	0.1869	0.100*
C36	0.6600 (10)	0.8044 (5)	0.2531 (4)	0.081 (2)
H36	0.7343	0.8555	0.2363	0.098*
C37	0.5102 (9)	0.8102 (4)	0.3065 (4)	0.0633 (17)
H37	0.4830	0.8669	0.3258	0.076*
H8A	0.360 (7)	0.540 (3)	0.300 (3)	0.050*
H5A	−0.096 (6)	0.850 (4)	0.5980 (19)	0.050*
H2A	0.794 (8)	0.213 (2)	1.086 (2)	0.050*
H7A	0.0918	0.9366	0.8294	0.080*
H7B	0.2740	0.9337	0.8175	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0385 (3)	0.0239 (3)	0.0268 (3)	0.0013 (2)	−0.0048 (2)	−0.0034 (2)
Cu2	0.0559 (4)	0.0516 (4)	0.0563 (4)	0.0036 (3)	−0.0011 (3)	−0.0308 (3)
S1	0.0503 (7)	0.0265 (6)	0.0321 (6)	−0.0030 (5)	0.0019 (5)	0.0003 (5)
O1	0.057 (2)	0.0263 (17)	0.0291 (17)	−0.0025 (15)	−0.0139 (15)	−0.0049 (13)
O2	0.069 (2)	0.0292 (17)	0.0321 (18)	0.0016 (16)	−0.0134 (16)	−0.0077 (14)
O3	0.0478 (19)	0.0224 (15)	0.0261 (16)	0.0017 (13)	0.0008 (14)	−0.0034 (13)
O4	0.085 (3)	0.043 (2)	0.056 (2)	−0.027 (2)	−0.015 (2)	0.0112 (18)
O5	0.106 (3)	0.047 (2)	0.032 (2)	−0.010 (2)	0.004 (2)	−0.0013 (17)
O6	0.070 (3)	0.050 (2)	0.083 (3)	0.016 (2)	0.014 (2)	0.023 (2)
O7	0.072 (3)	0.086 (3)	0.107 (4)	−0.006 (3)	−0.016 (3)	0.052 (3)
N1	0.033 (2)	0.030 (2)	0.030 (2)	0.0009 (16)	−0.0052 (16)	−0.0027 (16)
N2	0.052 (3)	0.033 (2)	0.036 (2)	0.002 (2)	−0.008 (2)	0.0023 (18)
N3	0.044 (2)	0.031 (2)	0.035 (2)	0.0050 (17)	−0.0033 (18)	−0.0118 (17)
N4	0.050 (3)	0.038 (2)	0.037 (2)	0.0027 (19)	−0.0029 (19)	−0.0115 (19)
N5	0.045 (3)	0.053 (3)	0.030 (2)	0.010 (2)	−0.0047 (18)	−0.0100 (19)
N6	0.039 (2)	0.042 (2)	0.049 (3)	0.0040 (19)	−0.006 (2)	−0.012 (2)
N7	0.042 (3)	0.053 (3)	0.065 (3)	−0.006 (2)	0.000 (2)	−0.027 (2)
N8	0.051 (3)	0.039 (2)	0.047 (3)	−0.003 (2)	0.004 (2)	−0.021 (2)
N9	0.046 (3)	0.038 (2)	0.046 (2)	−0.0016 (19)	−0.002 (2)	−0.0166 (19)
C1	0.035 (3)	0.042 (3)	0.042 (3)	−0.001 (2)	−0.006 (2)	−0.011 (2)
C2	0.034 (3)	0.063 (4)	0.046 (3)	0.001 (2)	−0.007 (2)	−0.025 (3)
C3	0.040 (3)	0.072 (4)	0.041 (3)	0.006 (3)	−0.012 (2)	−0.015 (3)
C4	0.042 (3)	0.055 (3)	0.036 (3)	0.009 (2)	−0.009 (2)	0.002 (2)
C5	0.027 (2)	0.039 (3)	0.036 (3)	0.002 (2)	−0.0004 (19)	−0.007 (2)
C6	0.040 (3)	0.031 (2)	0.041 (3)	0.005 (2)	−0.006 (2)	−0.002 (2)
C7	0.095 (5)	0.032 (3)	0.059 (4)	0.010 (3)	−0.019 (3)	−0.005 (3)
C8	0.131 (7)	0.035 (3)	0.075 (5)	0.018 (4)	−0.035 (4)	−0.023 (3)
C9	0.106 (5)	0.050 (4)	0.054 (4)	0.020 (3)	−0.025 (4)	−0.028 (3)
C10	0.075 (4)	0.042 (3)	0.042 (3)	0.012 (3)	−0.015 (3)	−0.014 (2)
C11	0.027 (2)	0.031 (2)	0.027 (2)	0.0016 (18)	−0.0021 (18)	−0.0038 (19)
C12	0.025 (2)	0.028 (2)	0.030 (2)	0.0030 (17)	0.0001 (18)	−0.0070 (18)
C13	0.028 (2)	0.026 (2)	0.029 (2)	0.0043 (18)	0.0008 (18)	−0.0070 (18)
C14	0.047 (3)	0.036 (3)	0.025 (2)	−0.005 (2)	−0.002 (2)	−0.0073 (19)
C15	0.054 (3)	0.025 (2)	0.038 (3)	−0.008 (2)	−0.002 (2)	−0.007 (2)
C16	0.039 (3)	0.024 (2)	0.030 (2)	−0.0028 (19)	−0.0013 (19)	0.0013 (18)
C17	0.033 (2)	0.030 (2)	0.024 (2)	0.0014 (19)	−0.0029 (18)	−0.0054 (18)
C18	0.072 (4)	0.057 (4)	0.033 (3)	−0.002 (3)	−0.003 (3)	−0.007 (3)
C19	0.058 (4)	0.056 (4)	0.043 (3)	−0.001 (3)	−0.010 (3)	0.007 (3)
C20	0.038 (3)	0.045 (3)	0.054 (3)	0.000 (2)	−0.003 (2)	0.004 (3)
C21	0.036 (3)	0.046 (3)	0.038 (3)	0.002 (2)	−0.001 (2)	−0.009 (2)
C22	0.031 (2)	0.036 (3)	0.036 (3)	−0.006 (2)	−0.001 (2)	−0.006 (2)
C23	0.042 (3)	0.031 (2)	0.041 (3)	−0.003 (2)	−0.006 (2)	−0.002 (2)
C24	0.048 (3)	0.063 (4)	0.041 (3)	0.000 (3)	−0.008 (2)	0.007 (3)
C25	0.056 (4)	0.092 (5)	0.050 (4)	−0.004 (3)	−0.017 (3)	0.018 (3)
C26	0.038 (3)	0.088 (5)	0.083 (5)	0.007 (3)	−0.017 (3)	0.016 (4)
C27	0.046 (3)	0.069 (4)	0.066 (4)	0.008 (3)	−0.002 (3)	−0.007 (3)
C28	0.047 (4)	0.072 (4)	0.112 (6)	−0.014 (3)	0.019 (4)	−0.043 (4)
C29	0.057 (4)	0.083 (5)	0.125 (7)	−0.023 (4)	0.032 (4)	−0.034 (5)
C30	0.075 (5)	0.067 (4)	0.099 (6)	−0.030 (4)	0.012 (4)	−0.022 (4)
C31	0.068 (4)	0.047 (3)	0.062 (4)	−0.015 (3)	0.005 (3)	−0.019 (3)
C32	0.048 (3)	0.039 (3)	0.039 (3)	−0.004 (2)	−0.008 (2)	−0.012 (2)
C33	0.041 (3)	0.040 (3)	0.042 (3)	0.000 (2)	−0.003 (2)	−0.017 (2)
C34	0.055 (4)	0.052 (4)	0.083 (5)	−0.008 (3)	0.007 (3)	−0.033 (3)
C35	0.060 (4)	0.075 (5)	0.110 (6)	−0.020 (4)	0.031 (4)	−0.043 (4)
C36	0.074 (5)	0.062 (4)	0.105 (6)	−0.031 (4)	0.020 (4)	−0.028 (4)
C37	0.065 (4)	0.046 (3)	0.081 (5)	−0.010 (3)	0.000 (3)	−0.028 (3)

Geometric parameters (Å, º)

Cu1—O1	1.926 (3)	C7—C8	1.349 (8)
Cu1—O3	1.930 (3)	C7—H7	0.9300
Cu1—N1	2.019 (4)	C8—C9	1.375 (9)
Cu1—N3	2.033 (4)	C8—H8	0.9300
Cu1—O3^i	2.343 (3)	C9—C10	1.366 (7)
Cu2—N9	1.989 (4)	C9—H9	0.9300
Cu2—N4	2.013 (4)	C10—H10	0.9300
Cu2—N6	2.031 (4)	C11—C12	1.484 (6)
Cu2—N7	2.032 (4)	C12—C17	1.389 (6)
S1—O4	1.435 (4)	C12—C13	1.411 (6)
S1—O5	1.436 (4)	C13—C14	1.408 (6)
S1—O6	1.440 (4)	C14—C15	1.369 (6)
S1—C16	1.772 (4)	C14—H14	0.9300
O1—C11	1.276 (5)	C15—C16	1.398 (6)
O2—C11	1.249 (5)	C15—H15	0.9300
O3—C13	1.321 (5)	C16—C17	1.371 (6)
O3—Cu1^i	2.343 (3)	C17—H17	0.9300
O7—H7A	0.86	C18—C19	1.348 (8)
O7—H7B	0.84	C18—H18	0.9300
N1—C5	1.338 (6)	C19—C20	1.369 (8)
N1—C1	1.352 (6)	C19—H19	0.9300
N2—C6	1.365 (6)	C20—C21	1.366 (7)
N2—C5	1.367 (6)	C20—H20	0.9300
N2—H2A	0.82 (3)	C21—C22	1.394 (7)
N3—C6	1.336 (6)	C21—H21	0.9300
N3—C10	1.354 (6)	C23—C24	1.386 (7)
N4—C22	1.328 (6)	C24—C25	1.359 (8)
N4—C18	1.354 (7)	C24—H24	0.9300
N5—C23	1.381 (6)	C25—C26	1.376 (9)
N5—C22	1.394 (6)	C25—H25	0.9300
N5—H5A	0.82 (4)	C26—C27	1.352 (9)
N6—C23	1.326 (6)	C26—H26	0.9300
N6—C27	1.343 (7)	C27—H27	0.9300
N7—C32	1.327 (6)	C28—C29	1.347 (9)
N7—C28	1.339 (7)	C28—H28	0.9300
N8—C32	1.382 (7)	C29—C30	1.379 (10)
N8—C33	1.383 (6)	C29—H29	0.9300
N8—H8A	0.82 (5)	C30—C31	1.355 (9)
N9—C33	1.336 (6)	C30—H30	0.9300
N9—C37	1.350 (7)	C31—C32	1.402 (7)
C1—C2	1.371 (7)	C31—H31	0.9300
C1—H1	0.9300	C33—C34	1.389 (7)
C2—C3	1.374 (8)	C34—C35	1.367 (9)
C2—H2	0.9300	C34—H34	0.9300
C3—C4	1.350 (8)	C35—C36	1.377 (9)
C3—H3	0.9300	C35—H35	0.9300
C4—C5	1.401 (7)	C36—C37	1.346 (9)
C4—H4	0.9300	C36—H36	0.9300
C6—C7	1.396 (7)	C37—H37	0.9300
O1—Cu1—O3	89.89 (13)	C9—C10—H10	118.2
O1—Cu1—N1	168.73 (15)	O2—C11—O1	120.7 (4)
O3—Cu1—N1	90.05 (14)	O2—C11—C12	118.8 (4)
O1—Cu1—N3	90.36 (14)	O1—C11—C12	120.5 (4)
O3—Cu1—N3	179.45 (16)	C17—C12—C13	119.1 (4)
N1—Cu1—N3	89.61 (15)	C17—C12—C11	118.0 (4)
O1—Cu1—O3^i	98.07 (13)	C13—C12—C11	122.9 (4)
O3—Cu1—O3^i	82.45 (12)	O3—C13—C14	118.6 (4)
N1—Cu1—O3^i	93.09 (13)	O3—C13—C12	123.6 (4)
N3—Cu1—O3^i	97.99 (14)	C14—C13—C12	117.8 (4)
N9—Cu2—N4	130.02 (18)	C15—C14—C13	122.0 (4)
N9—Cu2—N6	116.50 (18)	C15—C14—H14	119.0
N4—Cu2—N6	91.23 (16)	C13—C14—H14	119.0
N9—Cu2—N7	94.58 (17)	C14—C15—C16	119.6 (4)
N4—Cu2—N7	110.31 (18)	C14—C15—H15	120.2
N6—Cu2—N7	115.75 (19)	C16—C15—H15	120.2
O4—S1—O5	113.4 (3)	C17—C16—C15	119.3 (4)
O4—S1—O6	111.7 (3)	C17—C16—S1	120.7 (3)
O5—S1—O6	112.4 (3)	C15—C16—S1	120.1 (3)
O4—S1—C16	106.3 (2)	C16—C17—C12	122.1 (4)
O5—S1—C16	106.3 (2)	C16—C17—H17	118.9
O6—S1—C16	106.2 (2)	C12—C17—H17	118.9
C11—O1—Cu1	129.8 (3)	C19—C18—N4	123.5 (5)
C13—O3—Cu1	123.1 (3)	C19—C18—H18	118.2
C13—O3—Cu1^i	119.6 (3)	N4—C18—H18	118.2
Cu1—O3—Cu1^i	97.55 (12)	C18—C19—C20	118.5 (5)
H7A—O7—H7B	100.00	C18—C19—H19	120.7
C5—N1—C1	117.1 (4)	C20—C19—H19	120.7
C5—N1—Cu1	123.9 (3)	C21—C20—C19	119.9 (5)
C1—N1—Cu1	118.7 (3)	C21—C20—H20	120.0
C6—N2—C5	130.9 (4)	C19—C20—H20	120.0
C6—N2—H2A	115 (4)	C20—C21—C22	118.4 (5)
C5—N2—H2A	113 (4)	C20—C21—H21	120.8
C6—N3—C10	117.2 (4)	C22—C21—H21	120.8
C6—N3—Cu1	123.8 (3)	N4—C22—N5	120.7 (4)
C10—N3—Cu1	118.5 (3)	N4—C22—C21	122.1 (4)
C22—N4—C18	117.5 (4)	N5—C22—C21	117.2 (4)
C22—N4—Cu2	122.4 (3)	N6—C23—N5	120.3 (4)
C18—N4—Cu2	119.9 (3)	N6—C23—C24	122.1 (5)
C23—N5—C22	130.1 (4)	N5—C23—C24	117.6 (5)
C23—N5—H5A	115 (4)	C25—C24—C23	119.1 (6)
C22—N5—H5A	110 (4)	C25—C24—H24	120.5
C23—N6—C27	117.2 (5)	C23—C24—H24	120.5
C23—N6—Cu2	122.3 (3)	C24—C25—C26	119.4 (6)
C27—N6—Cu2	120.2 (4)	C24—C25—H25	120.3
C32—N7—C28	117.6 (5)	C26—C25—H25	120.3
C32—N7—Cu2	122.9 (4)	C27—C26—C25	118.0 (6)
C28—N7—Cu2	119.5 (4)	C27—C26—H26	121.0
C32—N8—C33	133.1 (4)	C25—C26—H26	121.0
C32—N8—H8A	114 (4)	N6—C27—C26	124.1 (6)
C33—N8—H8A	110 (4)	N6—C27—H27	118.0
C33—N9—C37	117.6 (5)	C26—C27—H27	118.0
C33—N9—Cu2	122.6 (3)	N7—C28—C29	124.4 (6)
C37—N9—Cu2	119.7 (4)	N7—C28—H28	117.8
N1—C1—C2	123.6 (5)	C29—C28—H28	117.8
N1—C1—H1	118.2	C28—C29—C30	118.0 (6)
C2—C1—H1	118.2	C28—C29—H29	121.0
C1—C2—C3	118.4 (5)	C30—C29—H29	121.0
C1—C2—H2	120.8	C31—C30—C29	119.4 (6)
C3—C2—H2	120.8	C31—C30—H30	120.3
C4—C3—C2	119.3 (5)	C29—C30—H30	120.3
C4—C3—H3	120.3	C30—C31—C32	119.2 (6)
C2—C3—H3	120.3	C30—C31—H31	120.4
C3—C4—C5	119.8 (5)	C32—C31—H31	120.4
C3—C4—H4	120.1	N7—C32—N8	121.3 (4)
C5—C4—H4	120.1	N7—C32—C31	121.3 (5)
N1—C5—N2	121.6 (4)	N8—C32—C31	117.4 (5)
N1—C5—C4	121.6 (4)	N9—C33—N8	122.3 (4)
N2—C5—C4	116.8 (4)	N9—C33—C34	121.6 (5)
N3—C6—N2	121.3 (4)	N8—C33—C34	116.1 (4)
N3—C6—C7	121.3 (5)	C35—C34—C33	119.1 (5)
N2—C6—C7	117.4 (5)	C35—C34—H34	120.5
C8—C7—C6	120.2 (5)	C33—C34—H34	120.5
C8—C7—H7	119.9	C34—C35—C36	119.4 (6)
C6—C7—H7	119.9	C34—C35—H35	120.3
C7—C8—C9	119.2 (5)	C36—C35—H35	120.3
C7—C8—H8	120.4	C37—C36—C35	118.4 (6)
C9—C8—H8	120.4	C37—C36—H36	120.8
C10—C9—C8	118.3 (6)	C35—C36—H36	120.8
C10—C9—H9	120.9	C36—C37—N9	123.9 (5)
C8—C9—H9	120.9	C36—C37—H37	118.1
N3—C10—C9	123.7 (5)	N9—C37—H37	118.1
N3—C10—H10	118.2

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7^i	0.82 (3)	2.00 (3)	2.814 (6)	175 (6)
N5—H5A···O5^ii	0.82 (4)	2.08 (4)	2.896 (5)	178 (5)
N8—H8A···O2^iii	0.82 (5)	1.99 (5)	2.809 (5)	172 (5)
O7—H7A···O4^ii	0.86	1.98	2.813 (6)	162
O7—H7B···O6	0.84	2.00	2.801 (6)	159

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