A novel three-dimensional coordination polymer constructed from pyrazine and copper(I): poly[[copper(I)-di-[mu]₂-pyrazine-[kappa]⁴N:N'] 3,5-dicarboxy­benzene­sulfonate monohydrate]

In the title metal-organic framework complex, {[Cu(C₄H₄N₂)₂](C₈H₅O₇S)·H₂O}_n or {[Cu^I(pyz)₂](H₂SIP)·H₂O}_n (pyz is pyrazine and H₃SIP is 5-sulfoisophthalic acid or 3,5-di­carboxy­benzene­sulfonic acid), the asymmetric unit is composed of one copper(I) center, one whole pyrazine ligand, two half pyrazine ligands lying about inversion centres, one H₂SIP^- anion and one lattice water mol­ecule, wherein each Cu^I atom is in a slightly distorted tetra­hedral coordination environment completed by four pyrazine N atoms, with the Cu-N bond lengths in the range 2.017 (3)-2.061 (3) Å. The structure features a three-dimensional diamondoid network with one-dimensional channels occupied by H₂SIP^- anions and lattice water mol­ecules. Inter­estingly, the guest-water hydrogen-bonded network is also a diamondoid network, which inter­penetrates the metal-pyrazine network.

S1. Comment

The design and synthesis of porous coordination polymers is of great interest due to their intriguing topology architecture and significant potential applications in many fields, such as gas molecules, ion exchange, catalytic activity and polymer synthesis (Batten et al., 1998; Abrahams et al., 1999; Fang et al., 2007; Horike et al., 2008; Zhang et al., 2008; Vaqueiro, 2008; Nouar et al., 2008). Although these kinds of materials have promising applications, it would be a big challenge to achieve a major advance without understanding the structural aspects. Thereby, the synthesis of high-dimensional coordination polymers and analysis of the interesting topology become more important. The classification of structures by Wells (1986) and O'Keeffe (O'Keeffe et al., 2000) laid the foundation for our general understanding and the design of special inorganic compounds, as well as covalent organic frameworks. On the basis of the classification, a great number of such compounds are characterized by the prototype of mineral topologies, such as CdSO₄, NbO, Pt₃O₄, pyrite, quartz, rutile, halite, and sodalite (Luo et al.,2005; Chun et al., 2004). Pyrazine, as a normal rigid linear ligand, has been utilized to synthesize a number of orangic–inorganic hydrids thus far (MacGillivray et al., 1994; Kuhlman et al., 1999; Halasyamani et al., 1996; Amo-Ochoa et al., 2007). In order to enrich the coordination chemistry of the three-dimensional open framework constructed from this ligand with one-dimensional channels, in this communcation, we describe the synthsis and crystal structure of a novel three-dimensional porous coordination polymer constructed from pyrazine (pyz) and Cu^I, namely {[Cu^I(pyz)₂](H₂SIP).H₂O}_n (H₃SIP is 5-sulfoisophthalic acid), (I).

As shown in Fig. 1, the asymmetric unit of (I) consists of one Cu^I ion, one whole and two half pyrazine ligands, one H₂SIP^- anion and one lattice water molecule. The Cu^I centre is coordinated by four N atoms from pyrazine ligands to form a slightly distorted tetrahedral configuration, in which the four Cu—N bond lengths are 2.017 (3), 2.033 (3), 2.054 (3) and 2.061 (3)Å, and the N—Cu—N bond angles are in the range 98.21 (11)–123.27 (11)° (Table 1). The mean Cu—N bond length of 2.042Å is similar to that found in [Cu(2,5-Me₂-pyz)₂]PF₆ (2,5-Me₂-pyz is 2,5-dimethylpyrazine; Otieno et al., 1993).

The linear pyrazine ligands act as pillars along different directions and link Cu^I ions to form an extended three-dimensional porous coordination network (Fig. 2). As a consequence of this assembly, one-dimensional channels occupied by guest water and monodepronated H₂SIP^- anions are formed. As shown in Fig. 3, the one-dimensional porous channels in the three-dimensional open framework features a large hexagonal 26-membered ring with approximate dimensions 15.1 × 13.0Ų, which contains six Cu atoms and six pyrazine ligands. Although a good number of hexagonal-shaped metallacycles are known in coordination polymers, such nano-sized metallacycles constructed from Cu^I and simple linear ligands guested by H₂SIP^- anions and water molecules are still unprecedented.

A better insight into the nature of this intricate framework can be achieved by the application of a topological approach, i.e., reducing multidimensional structures to simple node and connection nets. As depicted in Fig. 4, each Cu^I site in (I) is coordinated by four pyrazine N atoms, while each pyrazine ligand serves as a two-connected node bridging two Cu^I atoms. Therefore, the Cu^I ion can be simplified to a four-connected node and, accordingly, each pyrazine ligand becomes a two-connected linker and the overall topology can thus be described as a diamondoid network.

Notably, the free water molecules and the H₂SIP^- anions are encapsulated in the channels and are further linked with each other through O—H···O hydrogen-bonding interactions into a three-dimensional supramolecular open framework, as shown in Fig. 5. There are three types of hydrogen bonds: (a) between the lattice water molecules and sulfonate O atoms [O1W···O3 = 2.790 (5)Å; O1W···O1 = 2.903 (4)Å]; (b) between a carboxyl O atom and lattice water [O5···O1W = 2.578 (5)Å]; (c) between a carboxyl O atom and a sulfonate O atom [O7···O1 = 2.767 (4)Å]. Thus, the guest molecules have a significant influence on the coordination geometry of the host metal ions. The guest–water hydrogen-bond network is also a diamondoid network, which interpenetrates the metal–pyrazine network.

Complex (I) is stable in air and insoluble in water and most organic solvents, so no additional measurements in solution could be performed. Interestingly, (I) shows strong photoluminescence in the solid state, with an emission maximum at 645 nm upon excitation at 385 nm at room temperature. According to the structural features of the compound, the emission band might be assigned to a combination of metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (LMCT). The compound appears to be a good candidate as a novel hybrid inorganic–organic photoactive material.

In summary, a new three-dimensional porous metal–organic framework with open channels featuring an unusual (2,4)-connected topology has been synthesized and characterized. The structure of (I) provides another valuable prototype of (2,4)-connected nets which may be important for the design of PCPS [Please define.

Related literature

For related literature, see: Abrahams et al. (1999); Amo-Ochoa, Givaja, Miguel, Sanz, Castillo & Zamora (2007); Batten et al. (1998); Chun et al. (2004); Fang et al. (2007); Halasyamani et al. (1996); Horike et al. (2008); Kuhlman et al. (1999); Luo et al. (2005); MacGillivray et al. (1994); Nouar et al. (2008); O'Keeffe et al. (2000); Otieno et al. (1993); Vaqueiro (2008); Wells (1986); Zhang et al. (2008).

S2. Experimental

A mixture of Cu(OH)₂ (19.5 mg, 0.2 mmol), NaH₂SIP (26.8 mg, 0.1 mmol), pyrazine (12.1 mg, 0.15 mmol) and water (15 ml) was heated at 448 K for 5 d. Black block-shaped crystals of (I) were obtained when the sample was cooled to room temperature at a rate of 5 K h^-1. The crystals were recovered by filtration, washed with distilled water and dried in air (yield 42.3% based on Cu). Analysis calculated for C₁₆H₁₅CuN₄O₈S: C 39.43, H 3.08, N 11.50%; found: C 40.02, H 3.56, N 11.71%. IR spectrum (KBr pellet, cm^-1): 3440 (ms), 1713 (s), 1478 (s), 1417 (s), 1241 (w), 1187 (ms), 1157 (m), 1101 (m), 1037 (s), 1000 (ms), 847 (w), 800 (s), 755 (ms), 721 (ms), 680 (w), 669 (ms), 653 (w), 622 (s), 574 (w), 485 (ms), 466 (w), 449 (ms).

S3. Refinement

H atoms attached to C atoms were positioned geometrically and refined using a riding model, with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C). The carboxyl H atoms were located in a difference Fourier map and were refined with O—H distance restraints of 0.86 (2)Å. Water H atoms were located in a difference map and refined with O—H and H···H distance restraints of 0.85 (2) and 1.39 (1)Å, respectively, and with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. [Symmetry codes: (i) x, -y+1/2, z+1/2; (ii) -x+2, -y, -z; (iii) -x+2, -y, -z; (iv) x, -y+1/2, z-1/2.]
	Fig. 2. A view of the three-dimensional network of (I) along the b axis.
	Fig. 3. A space-filling view of the three-dimensional framework of (I).
	Fig. 4. A topological view of the (2,4)-connected network for (I). Dark and light (purple and green in the electronic version of the paper) balls denote the Cu^I ions and pyrazine ligands, respectively.
	Fig. 5. A view of the hydrogen-bonded stacking along the a axis in the guest–water molecules for (I)

poly[[copper(I)-di-µ₂-pyrazine-κ⁴N:N'] 3,5-dicarboxybenzenesulfonate monohydrate]

Crystal data

[Cu(C4H4N2)2](C8H5O7S)·H2O	F(000) = 992
Mr = 486.94	Dx = 1.702 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17722 reflections
a = 11.124 (2) Å	θ = 3.2–27.4°
b = 15.709 (3) Å	µ = 1.32 mm^−1
c = 11.337 (2) Å	T = 293 K
β = 106.48 (3)°	Block, yellow
V = 1899.7 (6) Å^3	0.33 × 0.24 × 0.16 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	4323 independent reflections
Radiation source: fine-focus sealed tube	2960 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ω scans	θmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→14
Tmin = 0.692, Tmax = 0.810	k = −20→20
17404 measured reflections	l = −14→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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 1.528P] where P = (Fo^2 + 2Fc^2)/3
4323 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.36 e Å^−3
5 restraints	Δρmin = −0.30 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 > 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	0.76105 (4)	0.12696 (3)	0.03342 (4)	0.04321 (14)
S1	0.28990 (8)	0.22243 (5)	0.60633 (8)	0.0418 (2)
O1	0.3362 (2)	0.22587 (15)	0.7400 (2)	0.0562 (7)
O2	0.3744 (3)	0.26158 (16)	0.5475 (3)	0.0668 (8)
O3	0.1622 (2)	0.25185 (16)	0.5607 (3)	0.0612 (7)
O4	−0.0240 (2)	−0.00017 (17)	0.3174 (3)	0.0675 (8)
O5	0.0789 (2)	−0.12285 (16)	0.3329 (3)	0.0677 (8)
H5	0.0136	−0.1385	0.2832	0.102*
O6	0.5910 (3)	−0.04670 (18)	0.7356 (3)	0.0767 (9)
O7	0.4912 (2)	−0.15758 (16)	0.6277 (3)	0.0664 (8)
H7	0.5480	−0.1847	0.6745	0.100*
N1	0.7597 (2)	0.20714 (17)	−0.1100 (3)	0.0407 (6)
N2	0.7654 (2)	0.30509 (16)	−0.3145 (2)	0.0391 (6)
N3	0.9030 (2)	0.04938 (17)	0.0204 (3)	0.0405 (6)
N4	0.6042 (2)	0.05176 (16)	0.0094 (2)	0.0366 (6)
C1	0.2862 (3)	0.1122 (2)	0.5684 (3)	0.0372 (7)
C2	0.1839 (3)	0.0779 (2)	0.4828 (3)	0.0415 (8)
H2	0.1152	0.1120	0.4460	0.050*
C3	0.1832 (3)	−0.0077 (2)	0.4512 (3)	0.0411 (8)
C4	0.2868 (3)	−0.0588 (2)	0.5070 (3)	0.0423 (8)
H4	0.2871	−0.1160	0.4860	0.051*
C5	0.3892 (3)	−0.0240 (2)	0.5938 (3)	0.0387 (7)
C6	0.3876 (3)	0.0613 (2)	0.6237 (3)	0.0416 (8)
H6	0.4560	0.0846	0.6821	0.050*
C7	0.0687 (3)	−0.0425 (2)	0.3606 (3)	0.0464 (8)
C8	0.5009 (3)	−0.0761 (2)	0.6604 (3)	0.0485 (9)
C9	0.8485 (3)	0.2639 (2)	−0.1062 (3)	0.0486 (9)
H9A	0.9116	0.2713	−0.0330	0.058*
C10	0.6742 (4)	0.2008 (3)	−0.2189 (4)	0.0688 (13)
H10	0.6096	0.1616	−0.2274	0.083*
C11	0.8510 (4)	0.3122 (2)	−0.2063 (3)	0.0533 (9)
H11	0.9154	0.3516	−0.1980	0.064*
C12	0.6765 (3)	0.2488 (3)	−0.3185 (3)	0.0567 (10)
H12	0.6132	0.2416	−0.3916	0.068*
C13	1.0240 (3)	0.0668 (2)	0.0746 (3)	0.0450 (8)
H13	1.0442	0.1132	0.1273	0.054*
C14	0.8811 (3)	−0.0184 (2)	−0.0549 (3)	0.0461 (8)
H14	0.7986	−0.0330	−0.0951	0.055*
C15	0.6146 (3)	−0.0279 (2)	0.0527 (3)	0.0412 (8)
H15	0.6941	−0.0495	0.0906	0.049*
C16	0.4877 (3)	0.0788 (2)	−0.0430 (3)	0.0385 (7)
H16	0.4755	0.1339	−0.0740	0.046*
O1W	−0.1163 (3)	−0.1882 (3)	0.1797 (4)	0.1155 (16)
H1WA	−0.129 (5)	−0.205 (4)	0.108 (3)	0.139*
H1WB	−0.166 (5)	−0.208 (4)	0.215 (4)	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0416 (2)	0.0453 (2)	0.0441 (3)	−0.00452 (19)	0.01438 (19)	−0.00297 (19)
S1	0.0427 (5)	0.0354 (4)	0.0422 (5)	0.0001 (4)	0.0036 (4)	0.0007 (4)
O1	0.0679 (17)	0.0471 (14)	0.0416 (14)	0.0000 (12)	−0.0040 (12)	−0.0041 (11)
O2	0.0776 (19)	0.0490 (15)	0.082 (2)	−0.0124 (14)	0.0358 (17)	0.0062 (14)
O3	0.0507 (15)	0.0538 (15)	0.0700 (19)	0.0126 (12)	0.0022 (13)	−0.0063 (14)
O4	0.0486 (15)	0.0601 (17)	0.076 (2)	0.0076 (13)	−0.0106 (14)	−0.0085 (15)
O5	0.0510 (15)	0.0558 (16)	0.076 (2)	0.0006 (13)	−0.0143 (14)	−0.0209 (14)
O6	0.0555 (17)	0.0609 (18)	0.087 (2)	0.0020 (14)	−0.0224 (16)	−0.0077 (16)
O7	0.0582 (16)	0.0465 (15)	0.076 (2)	0.0068 (13)	−0.0114 (15)	−0.0006 (14)
N1	0.0388 (15)	0.0439 (16)	0.0368 (15)	−0.0069 (12)	0.0063 (13)	−0.0009 (12)
N2	0.0370 (15)	0.0404 (15)	0.0387 (16)	−0.0007 (12)	0.0089 (13)	−0.0001 (12)
N3	0.0369 (14)	0.0428 (15)	0.0433 (16)	−0.0023 (12)	0.0137 (13)	−0.0022 (13)
N4	0.0336 (14)	0.0363 (14)	0.0408 (15)	−0.0024 (11)	0.0119 (12)	−0.0006 (12)
C1	0.0362 (16)	0.0380 (17)	0.0341 (17)	−0.0005 (14)	0.0046 (14)	0.0011 (14)
C2	0.0352 (17)	0.0414 (19)	0.0420 (19)	0.0027 (14)	0.0015 (15)	0.0017 (15)
C3	0.0367 (17)	0.0420 (18)	0.0411 (19)	−0.0038 (14)	0.0055 (15)	−0.0031 (15)
C4	0.0403 (18)	0.0371 (17)	0.045 (2)	0.0016 (15)	0.0049 (16)	−0.0010 (15)
C5	0.0342 (16)	0.0399 (17)	0.0382 (18)	−0.0006 (14)	0.0040 (14)	0.0020 (14)
C6	0.0348 (17)	0.0427 (18)	0.0403 (19)	−0.0057 (15)	−0.0007 (15)	−0.0039 (15)
C7	0.0435 (19)	0.047 (2)	0.042 (2)	−0.0017 (17)	0.0012 (16)	−0.0044 (16)
C8	0.045 (2)	0.043 (2)	0.051 (2)	−0.0020 (16)	0.0029 (18)	−0.0019 (17)
C9	0.047 (2)	0.052 (2)	0.0375 (19)	−0.0166 (17)	−0.0024 (16)	0.0018 (16)
C10	0.058 (2)	0.096 (3)	0.045 (2)	−0.042 (2)	0.0021 (19)	0.010 (2)
C11	0.053 (2)	0.052 (2)	0.047 (2)	−0.0211 (18)	0.0014 (18)	0.0046 (18)
C12	0.045 (2)	0.080 (3)	0.038 (2)	−0.019 (2)	0.0003 (17)	0.0064 (19)
C13	0.0386 (19)	0.0452 (19)	0.050 (2)	−0.0093 (15)	0.0105 (16)	−0.0071 (16)
C14	0.0318 (17)	0.053 (2)	0.052 (2)	−0.0054 (16)	0.0092 (16)	−0.0041 (17)
C15	0.0316 (16)	0.0426 (18)	0.049 (2)	0.0060 (14)	0.0109 (15)	0.0048 (16)
C16	0.0392 (18)	0.0339 (16)	0.0451 (19)	0.0039 (14)	0.0163 (15)	0.0048 (14)
O1W	0.076 (2)	0.204 (4)	0.073 (2)	−0.068 (3)	0.032 (2)	−0.072 (3)

Geometric parameters (Å, º)

Cu1—N2^i	2.017 (3)	C2—C3	1.391 (4)
Cu1—N3	2.033 (3)	C2—H2	0.9300
Cu1—N1	2.054 (3)	C3—C4	1.400 (4)
Cu1—N4	2.061 (2)	C3—C7	1.494 (5)
S1—O2	1.437 (3)	C4—C5	1.389 (4)
S1—O3	1.443 (3)	C4—H4	0.9300
S1—O1	1.457 (3)	C5—C6	1.383 (4)
S1—C1	1.781 (3)	C5—C8	1.500 (5)
O4—C7	1.208 (4)	C6—H6	0.9300
O5—C7	1.313 (4)	C9—C11	1.372 (5)
O5—H5	0.8200	C9—H9A	0.9300
O6—C8	1.208 (4)	C10—C12	1.364 (5)
O7—C8	1.328 (4)	C10—H10	0.9300
O7—H7	0.8200	C11—H11	0.9300
N1—C9	1.322 (4)	C12—H12	0.9300
N1—C10	1.331 (5)	C13—C14^iii	1.369 (5)
N2—C12	1.318 (4)	C13—H13	0.9300
N2—C11	1.327 (4)	C14—C13^iii	1.369 (5)
N2—Cu1^ii	2.017 (3)	C14—H14	0.9300
N3—C13	1.340 (4)	C15—C16^iv	1.370 (4)
N3—C14	1.343 (4)	C15—H15	0.9300
N4—C16	1.332 (4)	C16—C15^iv	1.370 (4)
N4—C15	1.337 (4)	C16—H16	0.9300
C1—C2	1.380 (4)	O1W—H1WA	0.830 (19)
C1—C6	1.380 (4)	O1W—H1WB	0.829 (19)
N2^i—Cu1—N3	123.27 (11)	C6—C5—C4	119.3 (3)
N2^i—Cu1—N1	110.21 (11)	C6—C5—C8	118.1 (3)
N3—Cu1—N1	98.14 (11)	C4—C5—C8	122.5 (3)
N2^i—Cu1—N4	103.33 (11)	C1—C6—C5	121.1 (3)
N3—Cu1—N4	107.02 (11)	C1—C6—H6	119.5
N1—Cu1—N4	115.53 (11)	C5—C6—H6	119.5
O2—S1—O3	113.82 (18)	O4—C7—O5	123.6 (3)
O2—S1—O1	112.49 (18)	O4—C7—C3	122.7 (3)
O3—S1—O1	112.50 (17)	O5—C7—C3	113.7 (3)
O2—S1—C1	106.08 (16)	O6—C8—O7	123.4 (3)
O3—S1—C1	105.78 (15)	O6—C8—C5	123.3 (3)
O1—S1—C1	105.33 (15)	O7—C8—C5	113.3 (3)
C7—O5—H5	109.5	N1—C9—C11	122.4 (3)
C8—O7—H7	109.5	N1—C9—H9A	118.8
C9—N1—C10	114.3 (3)	C11—C9—H9A	118.8
C9—N1—Cu1	123.4 (2)	N1—C10—C12	123.3 (3)
C10—N1—Cu1	122.1 (2)	N1—C10—H10	118.3
C12—N2—C11	115.0 (3)	C12—C10—H10	118.3
C12—N2—Cu1^ii	119.3 (2)	N2—C11—C9	122.7 (3)
C11—N2—Cu1^ii	125.6 (2)	N2—C11—H11	118.7
C13—N3—C14	115.5 (3)	C9—C11—H11	118.7
C13—N3—Cu1	123.0 (2)	N2—C12—C10	122.2 (3)
C14—N3—Cu1	121.1 (2)	N2—C12—H12	118.9
C16—N4—C15	115.7 (3)	C10—C12—H12	118.9
C16—N4—Cu1	123.8 (2)	N3—C13—C14^iii	122.2 (3)
C15—N4—Cu1	120.4 (2)	N3—C13—H13	118.9
C2—C1—C6	119.8 (3)	C14^iii—C13—H13	118.9
C2—C1—S1	120.5 (2)	N3—C14—C13^iii	122.3 (3)
C6—C1—S1	119.6 (2)	N3—C14—H14	118.8
C1—C2—C3	120.2 (3)	C13^iii—C14—H14	118.8
C1—C2—H2	119.9	N4—C15—C16^iv	122.2 (3)
C3—C2—H2	119.9	N4—C15—H15	118.9
C2—C3—C4	119.6 (3)	C16^iv—C15—H15	118.9
C2—C3—C7	118.2 (3)	N4—C16—C15^iv	122.1 (3)
C4—C3—C7	122.2 (3)	N4—C16—H16	119.0
C5—C4—C3	120.0 (3)	C15^iv—C16—H16	119.0
C5—C4—H4	120.0	H1WA—O1W—H1WB	114 (3)
C3—C4—H4	120.0
N2^i—Cu1—N1—C9	58.4 (3)	C3—C4—C5—C8	177.6 (3)
N3—Cu1—N1—C9	−71.7 (3)	C2—C1—C6—C5	0.7 (5)
N4—Cu1—N1—C9	175.0 (3)	S1—C1—C6—C5	−178.2 (3)
N2^i—Cu1—N1—C10	−127.7 (3)	C4—C5—C6—C1	−0.3 (5)
N3—Cu1—N1—C10	102.3 (3)	C8—C5—C6—C1	−178.2 (3)
N4—Cu1—N1—C10	−11.1 (4)	C2—C3—C7—O4	−2.6 (5)
N2^i—Cu1—N3—C13	−34.8 (3)	C4—C3—C7—O4	175.5 (4)
N1—Cu1—N3—C13	86.0 (3)	C2—C3—C7—O5	177.4 (3)
N4—Cu1—N3—C13	−154.1 (3)	C4—C3—C7—O5	−4.5 (5)
N2^i—Cu1—N3—C14	152.6 (2)	C6—C5—C8—O6	−2.7 (6)
N1—Cu1—N3—C14	−86.6 (3)	C4—C5—C8—O6	179.5 (4)
N4—Cu1—N3—C14	33.3 (3)	C6—C5—C8—O7	177.9 (3)
N2^i—Cu1—N4—C16	80.6 (3)	C4—C5—C8—O7	0.1 (5)
N3—Cu1—N4—C16	−147.9 (2)	C10—N1—C9—C11	0.4 (6)
N1—Cu1—N4—C16	−39.8 (3)	Cu1—N1—C9—C11	174.8 (3)
N2^i—Cu1—N4—C15	−95.9 (3)	C9—N1—C10—C12	−0.4 (6)
N3—Cu1—N4—C15	35.6 (3)	Cu1—N1—C10—C12	−174.9 (4)
N1—Cu1—N4—C15	143.7 (2)	C12—N2—C11—C9	0.9 (6)
O2—S1—C1—C2	−105.3 (3)	Cu1^ii—N2—C11—C9	180.0 (3)
O3—S1—C1—C2	15.9 (3)	N1—C9—C11—N2	−0.7 (6)
O1—S1—C1—C2	135.3 (3)	C11—N2—C12—C10	−0.9 (6)
O2—S1—C1—C6	73.6 (3)	Cu1^ii—N2—C12—C10	179.9 (4)
O3—S1—C1—C6	−165.2 (3)	N1—C10—C12—N2	0.7 (7)
O1—S1—C1—C6	−45.8 (3)	C14—N3—C13—C14^iii	−0.3 (6)
C6—C1—C2—C3	−0.7 (5)	Cu1—N3—C13—C14^iii	−173.3 (3)
S1—C1—C2—C3	178.2 (3)	C13—N3—C14—C13^iii	0.3 (6)
C1—C2—C3—C4	0.1 (5)	Cu1—N3—C14—C13^iii	173.4 (3)
C1—C2—C3—C7	178.3 (3)	C16—N4—C15—C16^iv	0.5 (5)
C2—C3—C4—C5	0.3 (5)	Cu1—N4—C15—C16^iv	177.3 (2)
C7—C3—C4—C5	−177.8 (3)	C15—N4—C16—C15^iv	−0.5 (5)
C3—C4—C5—C6	−0.3 (5)	Cu1—N4—C16—C15^iv	−177.2 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3^v	0.83 (2)	1.96 (2)	2.790 (4)	178 (6)
O1W—H1WB···O1^vi	0.83 (2)	2.11 (3)	2.903 (4)	159 (6)
O5—H5···O1W	0.82	1.76	2.578 (4)	171
O7—H7···O1^vii	0.82	1.97	2.766 (4)	165

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