catena-Poly[[[aqua­(ethyl­enediamine-κ²N,N′)(nitrato-κO)copper(II)]-μ-4,4′-dithio­dipyridine-κ²N:N′] nitrate mono­hydrate]

The title compound, {[Cu(NO₃)(C₂H₄N₂)(C₁₀H₈N₂S₂)(H₂O)]NO₃·H₂O}_n, is composed of a one-dimensional linear coordination polymer involving cis-protected copper(II) ions and a 4,4′-dithio­dipyridine bridging ligand. The polymeric chains run along the c-axis direction. N—H...O and O—H...O hydrogen bonds involving the coordinating amine groups, nitrate ions and water mol­ecules, as well as cocrystallized noncoordinating nitrate ions and water mol­ecules, generate a three-dimensional structure.

S1. Comment

Since Fujita's pioneering work on the molecular square with M₄L₄ topology, derived from Pd(en)(NO₃)₂ (en is 1,2-diaminoethane) and 4,4'-bipyridine (Fujita et al., 1990), 1,2-diaminoethane has frequently been used to protect cis-coordination sites at Pd²⁺ and Pt²⁺ metal corners in discrete two- and three-dimensional metallosupramolecular assemblies, in particular with pyridine-based monodentate ligands (Fujita, 1998; Navarro & Lippert, 2001; Fujita et al. 2005; Fujita & Yoshizawa, 2008). Not surprisingly, a related chemistry based on 1,2-diaminoethane complexes of divalent metal ions from the first transition metal row is much less developed with respect to the lability of these metal ions. Two coordination polymers based on Cu(en)²⁺ and 4,4'-bipyridine were reported by Chawla et al. (2001), but the solid-state structures were not determined. To the best of our knowledge the title compound, {[Cu(en)(µ₂-dtdp)(NO₃)(H₂O)]NO₃.H₂O}_n, (I) (dtdp is 4,4'-dithiodipyridine), is the first structurally studied coordination polymer comprising Cu(en)²⁺ units and a bridging ligand of the 4,4'-bipyridine type. The dtdp ligand has, inevitably, an ideal 90° bent structure and exhibits axial chirality. Because the barrier of rotation is relatively low, it exists as an equilibrium mixture of both enantiomeric conformers in solution (Kessler & Rundel, 1968).

The dtdp ligand has frequently been used in metallosupramolecular assemblies. A wide variety of coordination polymers are known in the literature, including double chains (Kondo et al., 2000; Luo et al., 2003; Horikoshi & Mikuriya, 2005a; Suen et al., 2005; Manna et al.,2005; Gosh et al., 2006; Suen & Wang, 2006; Carballo et al., 2007), zigzag chains (Horikoshi et al., 2001, 2002, 2005; Ng et al., 2004; Horikoshi & Mikuriya, 2005b), helices (Tabellion et al., 2001; Horikoshi et al., 2001, 2002), arched chains (Lai & Tiekink, 2004; Carballo et al., 2006; Manna et al., 2007) and two-dimensional networks (Luo et al., 2003). Achiral (Tabellion et al., 2001) and chiral (Yu et al., 2002; Horikoshi et al., 2005) metallamacrocycles with M₂L₂ topology have also been reported. The coordination chemistry of the dtdp ligand was reviewed by Horikoshi & Mochida (2006). Essentially, three different products of self-assembly can be expected from the 1:1 combination of µ₂-bridging dtdp and cis-configured square-planar or octahedrally coordinated metal ions, namely infinite chiral helices or arched chains and discrete M₂L₂ metallamacrocycles (Fig. 1).

Compound (I) crystallizes in the monoclinic space group P2₁/c with all atoms on general positions, and exhibits the arched chain motif as depicted in Fig. 1(c). A diagram of the repeat unit is shown in Fig. 2. The coordination polymer is generated by translational symmetry in the [001] direction (Fig. 3), with a period corresponding to the crystallographic c axis [11.092 (5) Å]. In each polymeric chain there is only one crystallographically independent Cu²⁺ ion. The dtdp ligand connects the Cu²⁺ ions in a µ₂-bridging mode. The coordination environment about the Cu²⁺ ion is essentially an elongated octahedron with some deviations of the angles. Two equatorial cis coordination sites are occupied by 1,2-diaminoethane. The two remaining equatorial cis sites are occupied by pyridine moieties of dtdp. The coordination geometry parameters about the Cu²⁺ ion and the equatorial N donors exhibit typical values. A water molecule is in an axial position, with a Cu1—O3 distance of 2.532 (2) Å. The coordination environment is completed by a weaker κO-bonded NO₃^- anion with a considerably longer bond length of 2.751 (2) Å. In contrast, in trans-Cu(en)₂(NO₃)₂ this distance is 2.566 (4) Å (Manríquez et al., 1996). A known example for Cu²⁺ with trans-configured H₂O and NO₃^- in an equatorial four N-ligand donor set is Cu(dien)(nic)(NO₃^-)(H₂O) [dien is bis(2-aminoethyl)amine and nic is 3-pyridinecarboxylate; Palicová et al., 2008]. Interestingly, in this complex the bonding situation of the axial ligands is quite different from that observed in (I); the Cu—O distances are 2.716 (2) and 2,457 (2) Å for H₂O and NO₃^-, respectively. The molecular geometry parameters of the dtdp ligand in (I) are within the expected ranges [Standard reference?]. The S—S bond length is 2.032 (1) Å. The C—S—S—C torsion angle is considerably larger than the ideal value of 90°, at 98.4 (1)°.

The coordinated NO₃^- anion accepts an intrachain hydrogen bond from an amino group of the 1,2-diaminoethane ligand with a graph-set motif of S(6) (Bernstein et al., 1995). The asymmetric unit comprises a non-coordinating NO₃^- anion and a co-crystallized water molecule. The crystal packing is achieved via hydrogen bonds of N—H···O and O—H···O types (Table 1), which link the coordination polymer chains into a three-dimensional framework structure, in which adjacent chains form a centrosymmetric R²₂(8) motif by means of N—H···O hydrogen-bonding interactions between atoms N1 and O3.

The polymeric chains in compound (I)are composed of only one enantiomeric conformer of the dtdp ligand and the Cu(en)²⁺ unit, respectively. The right-handed P form of dtdp forms a chain with the right-handed δ conformer of the Cu(en)²⁺ unit and vice versa. Thus, the chains exhibit chirality, although the crystal structure contains both enantiomeric forms with respect to the centrosymmetric space group. The compact arrangement is achieved by the interlocking of chains of opposite chirality.

It is notable that compound (I) was obtained from a mixture which contained Cu²⁺, 1,2-diaminoethane and dtdp in 1:2:1 molar ratio. This means that Cu(en)₂²⁺ was the precursor in solution from which the title coordination polymer has self-assembled. Indeed, the major product in the crystallization vessel was trans-Cu(en)₂(NO₃)₂. Attempts to allow the components to react in a 1:1:1 molar ratio under the same conditions led immediately to a light-blue powder, the elemental analysis and powder X-ray diffraction analysis of which were not consistent with the calculated ones for the structure of (I).

In summary, this work has shown that the Cu(en)²⁺ unit can be principally functionalized as a cis metal corner in metallosupramolecular chemistry, although its reactivity is difficult to control.

S2. Experimental

Cu(NO₃)₂.3H₂O (22 mg, 0.091 mmol) was dissolved in methanol (3 ml), followed by 1,2-diaminoethane (12 µl, 0.182 mmol) and dtdp (20 mg, 0.091 mmol). The solution was allowed to evaporate slowly to dryness at ambient temperature. Blue crystals of the title compound were formed, accompanied by a major component of violet crystals of trans-Cu(en)₂(NO₃)₂ which were identified from the dimensions of the unit cell (Komiyama & Lingafelter, 1964; Manríquez et al., 1996).

S3. Refinement

H atoms attached to C or N atoms were treated as riding atoms in geometrically calculated positions, with C—H = 0.93–0.97 and N—H = 0.90 Å, and with U_iso(H) = 1.2U_eq(C,N). The water H atoms were located in difference maps and then refined subject to restraints, with U_iso(H) = 1.2U_eq(O), giving O—H distances in the range 0.82 (3)–0.85 (3)Å.

Computing details

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS (Bruker, 1999); data reduction: XSCANS (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. Topological isomers in the self-assembly of dtdp with cis-configured square-planar or octahedrally coordinated metal ions (large grey spheres) in a 1:1 molar ratio. (a) Discrete metallamacrocycle, (b) infinite helix and (c) infinite arched chain.
	Fig. 2. The asymmetric unit of compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are represented by dashed lines. [Symmetry code: (iv) x, y, -1 + z.]
	Fig. 3. The compact arrangement of two polymeric chains of opposite chirality in the crystal structure of (I). H atoms and non-coordinating nitrate anions and water molecules have been omitted for clarity.

catena-Poly[[[aqua(ethylenediamine-κ²N,N')(nitrato- κO)copper(II)]-µ₂-4,4'-dithiodipyridine-κ²N:N'] nitrate monohydrate]

Crystal data

[Cu(NO3)(C2H4N2)(C10H8N2S2)(H2O)]NO3·H2O	F(000) = 1036
Mr = 504.00	Dx = 1.720 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.5762 (11) Å	θ = 4.7–12.6°
b = 21.844 (2) Å	µ = 1.39 mm^−1
c = 11.092 (5) Å	T = 294 K
β = 110.512 (17)°	Prism, blue
V = 1946.2 (10) Å^3	0.49 × 0.20 × 0.20 mm
Z = 4

Data collection

Siemens P4 four-circle diffractometer	2847 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scans	h = −1→10
Absorption correction: ψ scan ABSPsiScan in PLATON (Spek, 2009)	k = −1→25
Tmin = 0.543, Tmax = 0.761	l = −13→12
4383 measured reflections	3 standard reflections every 97 reflections
3419 independent reflections	intensity decay: none

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 1.0178P] where P = (Fo^2 + 2Fc^2)/3
3419 reflections	(Δ/σ)max = 0.001
274 parameters	Δρmax = 0.35 e Å^−3
4 restraints	Δρmin = −0.28 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	0.24379 (4)	0.461038 (14)	0.24673 (3)	0.02842 (12)
O3	−0.0708 (3)	0.45702 (10)	0.1497 (2)	0.0400 (5)
H3A	−0.132 (4)	0.4806 (13)	0.174 (3)	0.048*
H3B	−0.111 (4)	0.4241 (11)	0.159 (3)	0.048*
S14	0.40293 (8)	0.27120 (3)	0.73399 (6)	0.03066 (17)
S24	0.19734 (9)	0.26502 (3)	0.78428 (6)	0.03153 (17)
N11	0.2736 (3)	0.39907 (9)	0.3873 (2)	0.0270 (5)
C12	0.1641 (3)	0.39047 (12)	0.4462 (3)	0.0306 (6)
H12	0.0630	0.4111	0.4149	0.037*
C13	0.1928 (3)	0.35245 (12)	0.5517 (3)	0.0311 (6)
H13	0.1126	0.3475	0.5896	0.037*
C14	0.3427 (3)	0.32212 (11)	0.5992 (2)	0.0251 (5)
C15	0.4581 (3)	0.32988 (12)	0.5384 (2)	0.0285 (6)
H15	0.5596	0.3094	0.5677	0.034*
C16	0.4196 (3)	0.36847 (12)	0.4340 (2)	0.0295 (6)
H16	0.4973	0.3737	0.3938	0.035*
N21	0.2573 (3)	0.39560 (10)	1.1180 (2)	0.0299 (5)
C22	0.1310 (3)	0.35579 (12)	1.0737 (3)	0.0311 (6)
H22	0.0514	0.3549	1.1129	0.037*
C23	0.1129 (3)	0.31611 (12)	0.9730 (3)	0.0294 (6)
H23	0.0227	0.2895	0.9447	0.035*
C24	0.2326 (3)	0.31680 (11)	0.9145 (2)	0.0259 (5)
C25	0.3667 (4)	0.35592 (13)	0.9626 (3)	0.0361 (6)
H25	0.4508	0.3564	0.9277	0.043*
C26	0.3740 (4)	0.39432 (13)	1.0632 (3)	0.0372 (7)
H26	0.4645	0.4207	1.0946	0.045*
N1	0.2688 (3)	0.52854 (10)	0.1321 (2)	0.0326 (5)
H1A	0.3647	0.5237	0.1172	0.039*
H1B	0.1842	0.5271	0.0560	0.039*
N2	0.2014 (3)	0.52970 (10)	0.3525 (2)	0.0369 (6)
H2A	0.1188	0.5194	0.3811	0.044*
H2B	0.2937	0.5373	0.4210	0.044*
C1	0.2690 (4)	0.58823 (13)	0.1946 (3)	0.0413 (7)
H1C	0.2323	0.6202	0.1300	0.050*
H1D	0.3808	0.5981	0.2518	0.050*
C2	0.1540 (4)	0.58458 (13)	0.2694 (3)	0.0408 (7)
H2C	0.1644	0.6210	0.3216	0.049*
H2D	0.0396	0.5813	0.2113	0.049*
O31	0.5762 (3)	0.48905 (11)	0.3603 (2)	0.0508 (6)
O32	0.6431 (3)	0.51406 (11)	0.1955 (2)	0.0538 (6)
O33	0.8345 (3)	0.49563 (11)	0.3795 (2)	0.0518 (6)
N31	0.6850 (3)	0.49950 (11)	0.3125 (2)	0.0361 (6)
O41	−0.2220 (3)	0.25313 (11)	0.2215 (2)	0.0600 (7)
O42	−0.2319 (4)	0.29728 (14)	0.0443 (3)	0.0731 (8)
O43	−0.1948 (4)	0.35034 (13)	0.2144 (3)	0.0855 (9)
N41	−0.2174 (3)	0.29968 (14)	0.1599 (3)	0.0510 (7)
O4	−0.2045 (4)	0.33030 (16)	0.4708 (3)	0.0753 (8)
H4A	−0.200 (6)	0.2944 (12)	0.501 (4)	0.090*
H4B	−0.205 (6)	0.328 (2)	0.395 (2)	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0390 (2)	0.02378 (18)	0.02399 (19)	0.00294 (13)	0.01298 (14)	0.00162 (12)
O3	0.0429 (12)	0.0413 (12)	0.0388 (12)	0.0027 (10)	0.0179 (10)	−0.0029 (10)
S14	0.0369 (4)	0.0307 (4)	0.0261 (3)	0.0075 (3)	0.0132 (3)	0.0040 (3)
S24	0.0413 (4)	0.0287 (4)	0.0279 (4)	−0.0051 (3)	0.0164 (3)	−0.0029 (3)
N11	0.0322 (12)	0.0234 (11)	0.0261 (11)	0.0022 (9)	0.0109 (9)	0.0021 (9)
C12	0.0293 (14)	0.0314 (14)	0.0313 (14)	0.0062 (11)	0.0110 (11)	0.0041 (11)
C13	0.0305 (14)	0.0349 (15)	0.0317 (14)	0.0032 (12)	0.0155 (12)	0.0027 (12)
C14	0.0308 (14)	0.0204 (12)	0.0237 (13)	0.0003 (10)	0.0089 (10)	−0.0019 (10)
C15	0.0240 (13)	0.0301 (14)	0.0305 (14)	0.0032 (11)	0.0085 (11)	0.0018 (11)
C16	0.0306 (14)	0.0303 (14)	0.0318 (14)	−0.0011 (11)	0.0162 (12)	0.0012 (11)
N21	0.0370 (13)	0.0258 (11)	0.0296 (12)	0.0009 (10)	0.0151 (10)	0.0003 (9)
C22	0.0344 (15)	0.0296 (14)	0.0348 (15)	0.0024 (12)	0.0190 (12)	0.0003 (12)
C23	0.0311 (14)	0.0254 (13)	0.0345 (15)	−0.0002 (11)	0.0149 (12)	0.0021 (11)
C24	0.0341 (14)	0.0213 (12)	0.0219 (13)	0.0034 (11)	0.0094 (11)	0.0017 (10)
C25	0.0371 (16)	0.0389 (16)	0.0413 (16)	−0.0085 (13)	0.0249 (13)	−0.0065 (13)
C26	0.0362 (16)	0.0384 (16)	0.0411 (17)	−0.0109 (13)	0.0187 (13)	−0.0080 (13)
N1	0.0326 (12)	0.0334 (13)	0.0299 (12)	−0.0006 (10)	0.0085 (10)	0.0043 (10)
N2	0.0486 (15)	0.0322 (13)	0.0290 (13)	0.0042 (11)	0.0124 (11)	−0.0014 (10)
C1	0.0475 (18)	0.0284 (15)	0.0437 (18)	−0.0039 (13)	0.0107 (14)	0.0032 (13)
C2	0.0504 (19)	0.0259 (14)	0.0437 (18)	0.0034 (13)	0.0133 (15)	−0.0015 (12)
O31	0.0361 (12)	0.0738 (16)	0.0443 (13)	0.0009 (11)	0.0163 (10)	0.0129 (11)
O32	0.0575 (14)	0.0644 (15)	0.0432 (14)	0.0040 (12)	0.0220 (11)	0.0124 (11)
O33	0.0310 (12)	0.0609 (15)	0.0602 (15)	0.0013 (10)	0.0119 (11)	−0.0111 (12)
N31	0.0342 (14)	0.0340 (13)	0.0402 (14)	−0.0012 (10)	0.0132 (11)	−0.0009 (11)
O41	0.0672 (17)	0.0542 (15)	0.0586 (16)	−0.0161 (12)	0.0221 (13)	0.0075 (12)
O42	0.0804 (19)	0.091 (2)	0.0488 (16)	−0.0092 (16)	0.0241 (14)	0.0083 (14)
O43	0.125 (3)	0.0579 (18)	0.083 (2)	−0.0290 (18)	0.049 (2)	−0.0115 (16)
N41	0.0369 (15)	0.0604 (19)	0.0558 (19)	−0.0148 (13)	0.0163 (13)	−0.0016 (15)
O4	0.0636 (18)	0.101 (2)	0.071 (2)	−0.0045 (17)	0.0361 (16)	−0.0134 (18)

Geometric parameters (Å, º)

Cu1—N1	2.007 (2)	C23—C24	1.394 (4)
Cu1—N11	2.012 (2)	C23—H23	0.9300
Cu1—N2	2.014 (2)	C24—C25	1.381 (4)
Cu1—N21^i	2.052 (2)	C25—C26	1.380 (4)
Cu1—O3	2.532 (2)	C25—H25	0.9300
Cu1—O31	2.751 (2)	C26—H26	0.9300
O3—H3A	0.84 (3)	N1—C1	1.477 (4)
O3—H3B	0.82 (3)	N1—H1A	0.9000
S14—C14	1.788 (3)	N1—H1B	0.9000
S14—S24	2.032 (1)	N2—C2	1.480 (4)
S24—C24	1.775 (3)	N2—H2A	0.9000
N11—C12	1.332 (3)	N2—H2B	0.9000
N11—C16	1.352 (3)	C1—C2	1.497 (5)
C12—C13	1.385 (4)	C1—H1C	0.9700
C12—H12	0.9300	C1—H1D	0.9700
C13—C14	1.376 (4)	C2—H2C	0.9700
C13—H13	0.9300	C2—H2D	0.9700
C14—C15	1.390 (4)	O31—N31	1.245 (3)
C15—C16	1.376 (4)	O32—N31	1.260 (3)
C15—H15	0.9300	O33—N31	1.239 (3)
C16—H16	0.9300	O41—N41	1.233 (4)
N21—C22	1.341 (4)	O42—N41	1.245 (4)
N21—C26	1.341 (4)	O43—N41	1.243 (4)
N21—Cu1^ii	2.052 (2)	O4—H4A	0.85 (3)
C22—C23	1.379 (4)	O4—H4B	0.84 (3)
C22—H22	0.9300
N1—Cu1—N11	166.48 (9)	C22—C23—C24	118.6 (2)
N1—Cu1—N2	84.45 (10)	C22—C23—H23	120.7
N11—Cu1—N2	92.84 (9)	C24—C23—H23	120.7
N1—Cu1—N21^i	91.49 (10)	C25—C24—C23	118.5 (2)
N11—Cu1—N21^i	92.74 (9)	C25—C24—S24	126.2 (2)
N2—Cu1—N21^i	171.75 (9)	C23—C24—S24	115.4 (2)
N1—Cu1—O3	95.21 (9)	C26—C25—C24	118.9 (2)
N11—Cu1—O3	97.66 (8)	C26—C25—H25	120.5
N2—Cu1—O3	83.71 (9)	C24—C25—H25	120.5
N21^i—Cu1—O3	89.51 (8)	N21—C26—C25	123.4 (3)
N1—Cu1—O31	78.64 (8)	N21—C26—H26	118.3
N11—Cu1—O31	87.99 (8)	C25—C26—H26	118.3
N2—Cu1—O31	86.41 (9)	C1—N1—Cu1	109.49 (18)
N21^i—Cu1—O31	99.87 (8)	C1—N1—H1A	109.8
O3—Cu1—O31	168.84 (7)	Cu1—N1—H1A	109.8
Cu1—O3—H3A	122 (2)	C1—N1—H1B	109.8
Cu1—O3—H3B	114 (2)	Cu1—N1—H1B	109.8
H3A—O3—H3B	99 (3)	H1A—N1—H1B	108.2
C14—S14—S24	104.29 (9)	C2—N2—Cu1	107.86 (18)
C24—S24—S14	105.31 (9)	C2—N2—H2A	110.1
C12—N11—C16	117.3 (2)	Cu1—N2—H2A	110.1
C12—N11—Cu1	123.72 (18)	C2—N2—H2B	110.1
C16—N11—Cu1	118.61 (17)	Cu1—N2—H2B	110.1
N11—C12—C13	123.5 (2)	H2A—N2—H2B	108.4
N11—C12—H12	118.2	N1—C1—C2	108.7 (2)
C13—C12—H12	118.2	N1—C1—H1C	109.9
C14—C13—C12	118.5 (2)	C2—C1—H1C	109.9
C14—C13—H13	120.7	N1—C1—H1D	109.9
C12—C13—H13	120.7	C2—C1—H1D	109.9
C13—C14—C15	119.0 (2)	H1C—C1—H1D	108.3
C13—C14—S14	125.2 (2)	N2—C2—C1	107.3 (2)
C15—C14—S14	115.82 (19)	N2—C2—H2C	110.2
C16—C15—C14	118.8 (2)	C1—C2—H2C	110.2
C16—C15—H15	120.6	N2—C2—H2D	110.2
C14—C15—H15	120.6	C1—C2—H2D	110.2
N11—C16—C15	122.9 (2)	H2C—C2—H2D	108.5
N11—C16—H16	118.6	N31—O31—Cu1	131.06 (18)
C15—C16—H16	118.6	O33—N31—O31	120.3 (3)
C22—N21—C26	117.1 (2)	O33—N31—O32	119.8 (3)
C22—N21—Cu1^ii	118.13 (18)	O31—N31—O32	119.9 (2)
C26—N21—Cu1^ii	124.27 (19)	O41—N41—O43	119.6 (3)
N21—C22—C23	123.5 (2)	O41—N41—O42	121.6 (3)
N21—C22—H22	118.3	O43—N41—O42	118.7 (3)
C23—C22—H22	118.3	H4A—O4—H4B	108 (5)
C14—S14—S24—C24	−98.35 (12)	N1—C1—C2—N2	51.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O32	0.90	2.25	3.052 (4)	149
N1—H1B···O3^iii	0.90	2.17	3.006 (3)	154
N2—H2B···O31^iv	0.90	2.36	3.114 (3)	141
N2—H2A···O33^iv	0.90	2.56	3.143 (4)	123
N2—H2A···O33^v	0.90	2.49	3.347 (4)	160
O3—H3A···O32^v	0.84 (3)	2.15 (4)	2.950 (4)	158 (3)
O3—H3A···O33^v	0.84 (3)	2.42 (3)	3.053 (4)	133 (3)
O3—H3B···O43	0.82 (3)	1.95 (3)	2.759 (4)	169 (3)
O4—H4A···O42^vi	0.85 (3)	2.10 (3)	2.936 (5)	169 (5)
O4—H4B···O43	0.84 (3)	2.09 (3)	2.907 (5)	163 (4)

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