Crystal structure of poly[[(μ3-hydroxido-κ3 O:O:O)(μ3-selenato-κ3 O 1:O 2:O 3)tris-[μ3-2-(1,2,4-triazol-4-yl)acetato-κ3 N 1:N 2:O]tricopper(II)] dihydrate].

The title coordination polymer, {[Cu3(C4H4N3O9)3(SeO4)(OH)]·2H2O} n or ([Cu3(μ3-OH)(trgly)3(SeO4)]·2H2O), crystallizes in the monoclinic space group P21/c. The three independent Cu2+ cations adopt distorted square-pyramidal geometries with {O2N2+O} polyhedra. The three copper centres are bridged by a μ3-OH anion, leading to a triangular [Cu3(μ3-OH)] core. 2-(1,2,4-Triazol-4-yl)acetic acid (trgly-H) acts in a deprotonated form as a μ3-κ3 N 1:N 2:O ligand. The three triazolyl groups bridge three copper centres of the hydroxo-cluster in an N 1:N 2 mode, thus supporting the triangular geometry. The [Cu3(μ3-OH)(tr)3] clusters serve as secondary building units (SBUs). Each SBU can be regarded as a six-connected node, which is linked to six neighbouring triangles through carboxyl-ate groups, generating a two-dimensional uninodal (3,6) coordination network. The selenate anion is bound in a μ3-κ3 O 1:O 2:O 3 fashion to the trinuclear copper platform. The [Cu3(OH)(trgly)3(SeO4)] coordination layers and guest water mol-ecules are linked together by numerous O-H⋯O and C-H⋯O hydrogen bonds, leading to a three-dimensional structure.

Chemical context

Extended coordination networks incorporating trinuclear 1,2,4-triazole (tr)-based hydroxo(oxo) clusters [Cu3(μ3-OH/or O)(tr)3] as secondary building units (SBUs) are a subject of high inter­est in many inter­disciplinary fields including gas storage and sorption (Lincke et al., 2012 ▸), magnetism (Ouellette et al., 2006 ▸), anion exchange and separation (Wang et al., 2007 ▸). In these clusters, the copper(II) cations display either distorted tetra­gonal–pyramidal (TP) or (and) octa­hedral coordination geometries, two of the most stable configurations in the OH−/tr ligand arrangement. Typically, the basal plane for a five-coordinate CuII atom (or the equatorial plane for six-coordinate CuII) consists of two nitro­gen atoms from two trans-coordinated tr groups, an oxygen atom from OH−/O2− and an O (N, or Cl−) donor atom (or anion) from an extra ligand, whereas the apical position is occupied by a water mol­ecule or anionic ligand (Lysenko et al., 2006 ▸; Naik et al., 2010 ▸). The alternative trigonal–bypiramidal (TBP) environment around the copper centres can not be realized in the specific ligand configuration. Addison et al. (1984 ▸) introduced a useful structural parameter, τ, as a criterion for distinguishing between TP and TBP polyhedra. This parameter, which varies from 0 (in TP) to 1 (in TBP), could perhaps be used to predict the anion binding affinity of closely related anions (e.g. SO4 2− versus SeO4 2−) toward the [Cu3(μ3-OH/or O)(tr)3] SBUs. The higher binding affinity might be associated with the lower τ parameter. As a matter of fact, the [Cu3(μ3-OH/or O)(tr)3] cationic clusters are perfectly suited for the binding of tetra­hedral anions through its three apical sites. In this context, it would be inter­esting to clarify how the size of the coordinating anions correlates with the τ value. In this paper, we report the crystal structure of the title Cu2+ complex, (I), which was prepared by reacting CuSeO4 and trgly-H in an aqueous solution under hydro­thermal conditions. The compound is isomorphous to the [Cu3(μ3-OH)(trgly)3(SO4)]·2H2O complex (Vasylevs’kyy et al., 2014 ▸).

Structural commentary

The title compound crystallizes in the centrosymmetric monoclinic space group P21/c. The asymmetric unit consists of three copper(II) cations, one selenate anion, one hydroxide anion, three deprotonated trgly− ligands and two water mol­ecules (Fig. 1 ▸ and Table 1 ▸). Each copper centre adopts a similar tetra­gonal–pyramidal coordination environment with the {O2N2+O} donor set. The basal plane of Cu1 is completed by atom O1 of the μ 3-bridging hydroxide group [Cu1—O1 = 2.022 (2) Å], atom N1 from one bridging tr-group [Cu1—N1 = 1.980 (3) Å], atom N8 from the other bridging tr-group [Cu1—N8, 1.993 (3) Å] and a carboxyl­ate O atom from the trgly ligand [Cu1—O8i = 1.935 (3) Å; symmetry code: (i) x, y, z − 1]. The basal planes of Cu2 and Cu3 cations consist four short bonds as follows: Cu2—N2 = 1.979 (3), Cu2—N4 = 1.986 (3), Cu2—O1 = 2.039 (3) and Cu2—O6ii 1.954 (3) Å and Cu3—N5 = 1.974 (3), Cu3—N7 = 1.982 (3), Cu3—O1 = 2.039 (2) and Cu3—O10iii 1.990 (3) Å for Cu2 and for Cu3, respectively [symmetry codes: (ii) x, −y − , z + ; (iii) x, −y + , z + ]. The basal planes of the three square pyramids share a common corner at the O1 atom of the OH− anion, forming a triangular [Cu3(μ3-OH)] core. The trinuclear motif is supported by a facially coordinating tripodal selenate anion [Cu1—O2 2.182 (3), Cu2—O3 = 2.146 (3) and Cu3—O4 = 2.182 (3) Å]. The value of the Addison structural parameter τ varies from 0.025 for Cu2 through 0.070 for Cu1 to 0.189 for Cu3, indicating the preference of a TP configuration (versus TBP) around the copper centres. A comparison of the τ values for (I) with the corresponding values for the isomorphous sulfate complex [Cu3(μ3-OH)(trgly)3(SO4)]·2H2O (τ = 0.021, 0.103, 0.211; Vasylevs’kyy et al., 2014 ▸) indicates a lower degree of TBP distortion for the selenate compound. This tendency is also observed for the other two isomorphous MOFs [{Cu3(μ3-OH)(X)}4{Cu2(H2O)2}3(trz-ia)12] [X = SO4 2− and SeO4 2−, trz-ia is the 5-(4H-1,2,4-triazol-4-yl)isophthalate anion], where the τ parameter values are 0.096 and 0.083 for the sulfate and selenate complexes, respectively (Lincke et al., 2012 ▸). Unlike [Cu3(μ3-OH)(trgly)3(SO4)]·2H2O, in which the highest τ value corresponds with the longest Cu—O axial bond, the τ parameter values for the title compound do not correlate with the Cu—O axial bond lengths. Atoms Cu1 and Cu3 with the lowest and highest τ values, respectively, have the same Cu—O axial bond lengths. For compound (I), the hydroxide oxygen atom O1 is displaced by 0.532 Å from the centroid of the Cu1–Cu2–Cu3 triangular fragment, whereas for [Cu3(μ3-OH)(trgly)3(SO4)]·2H2O, the O–centroid distance is 0.570 Å. Thus, the larger anion–anion repulsion (OH−/SO4 2− versus OH−/SeO4 2−) in the sulfate complex also confirms the higher TBP distortion. The trinuclear clusters function as SBUs (six-connected nodes), which self-assemble into a two-dimensional coordination network (Fig. 2 ▸) with all of the selenate anions on the same side of the coordination layer. The resultant 2D network topology can be rationalized as a (3,6) type. Inter­estingly, the selenate anions of two neighbouring layers point in opposite directions (Fig. 3 ▸).

Figure 1

A portion of the structure of (I), showing the atom-labelling scheme and the copper coordination environments. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, y, z − 1; (ii) x, −y − , z + ; (iii) x, −y + , z + ].

Table 1

Selected bond lengths (Å)

Cu1—O8i	1.935 (3)	Cu3—N5	1.974 (3)
Cu1—N1	1.980 (3)	Cu3—N7	1.982 (3)
Cu1—N8	1.993 (3)	Cu3—O10iii	1.990 (3)
Cu1—O1	2.022 (2)	Cu3—O1	2.039 (2)
Cu1—O2	2.182 (3)	Cu3—O4	2.182 (3)
Cu2—O6ii	1.954 (3)	Se1—O5	1.632 (3)
Cu2—N2	1.979 (3)	Se1—O2	1.637 (3)
Cu2—N4	1.986 (3)	Se1—O3	1.645 (3)
Cu2—O1	2.039 (3)	Se1—O4	1.649 (3)
Cu2—O3	2.146 (3)

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2

A single layer of the structure has the (3,6) topological type (view along the [0] direction, selenates shown as tetra­hedra).

Figure 3

Crystal packing of compound (I) (a) along the a axis, and (b) along the c axis. In (a), neighboring layers are shifted relative to one another while in (b) they are held together by O—H⋯O hydrogen bonds between hydroxide oxygen atoms and carboxyl­ate group oxygen atoms [O1⋯O10iv = 2.811 (4) Å, O1—H1O⋯O10iv = 156°; symmetry code: (iv) −x + 1, y − , −z + ].

Supra­molecular features

The trinuclear [Cu3(μ3-OH)(tr)3] clusters are involved in inter- and intra­molecular hydrogen-bonding inter­actions. Adjacent layers are linked together by hydrogen bonding between the hydroxide oxygen atoms (O1 as H-atom donor) and carboxyl­ate group oxygen atoms (O10 as H-atom acceptor) and are shifted with respect to each other, forming a H-bonded double layer (Fig. 3 ▸ a, Table 2 ▸). The guest water mol­ecules are trapped between neighboring double-layers, forming a set of hydrogen bonds to selenate oxygen atoms [O1W⋯O4 = 2.767 (4) Å, O1W—H2W⋯O4 = 168°], carboxyl­ate oxygen atoms [O1W⋯O11 = 2.940 (5) Å, O1W—H1W⋯O11 = 166°, and O2W⋯O9v = 2.798 (5) Å, O2W—H3W⋯O9v 178°, symmetry code: (v) −x + 1, y + , −z + ] and to one another [O2W⋯O1W = 2.812 (6) Å, O2W—H4W⋯O1W = 159°, Fig. 4 ▸]. Apparently, the presence of the hydrogen bond between the O1W water mol­ecule and the selenate oxygen atom O4 leads to an increase in the trigonal–bypiramidal distortion of the square-pyramidal coordination polyhedra of Cu3 (τ = 0.189 for Cu3, markedly higher than the values of 0.070 and 0.025 for Cu1 and for Cu2, respectively) in the trinuclear [Cu3(μ3-OH)(tr)3] core.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O10iv	0.85	2.01	2.811 (4)	156
O1W—H1W⋯O11	0.85	2.11	2.940 (5)	166
O1W—H2W⋯O4	0.85	1.93	2.767 (4)	168
O2W—H3W⋯O9v	0.85	1.95	2.798 (5)	178
O2W—H4W⋯O1W	0.85	2.00	2.812 (6)	159
C1—H1⋯O5vi	0.94	2.58	3.346 (5)	139
C2—H2⋯O5vii	0.94	2.28	2.955 (5)	128
C5—H5⋯O3viii	0.94	2.39	2.941 (5)	117
C6—H6⋯O2W iii	0.94	2.30	3.176 (6)	154
C7—H7A⋯O3viii	0.98	2.25	3.094 (6)	144
C7—H7B⋯O1W iii	0.98	2.38	3.338 (5)	164
C9—H9⋯O7ix	0.94	2.25	3.067 (6)	144

Symmetry codes: (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

Figure 4

Crystal packing pattern in (I) showing the O—H⋯O hydrogen-bonding inter­actions between neighboring layers.

The coordination polymeric network is reinforced by weak C—H⋯O hydrogen-bonding inter­actions (Desiraju & Steiner, 1999 ▸, Fig. 5 ▸, Table 2 ▸). These C—H hydrogen bonds with one acceptor oxygen atom [C⋯O distances ranging from 2.955 (5) to 3.440 (5) Å] help to stabilize the resulting three-dimensional hydrogen-bonded network.

Figure 5

Crystal packing patterns in (I) showing the presence of C—H⋯O hydrogen bonds.

Thus, the hydro­thermal reaction of CuSeO4 and trgly-H leads to a two-dimensional coordination network [Cu3(μ3-OH)(trgly)3(SeO4)] based on the trinuclear coordination clusters [Cu3(μ3-OH)]. The five-coordinate copper(II) centres in the [Cu3(μ3-OH)(tr)3] SBU display less-distorted square-pyramidal arrangements in comparison to those of the isomorphous complex [Cu3(μ3-OH)(trgly)3(SO4)]·2H2O.

Database survey

Among the known [Cu3(μ3-OH/or O)(tr)3] complexes (CSD version 5.39, update of May 2018; Groom et al., 2016 ▸), the highest possible value of τ (0.313) in the five-coordinate copper(II) cation was once observed for the copper(II)-polyoxomolybdate complex with 4-amino-1,2,4-triazole [Cu3(4-atrz)3(Mo8O27)(H2O)4]·6H2O (Wang et al., 2015 ▸). However, the authors described the trinuclear cationic core as [Cu3(μ3-H2O)(4-atrz)3]. They also inter­preted the five-coord­inate copper geometry as trigonal–bipyramidal, although the τ parameter is closer to 0 than to 1.

Synthesis and crystallization

1,2,4-Triazol-4-yl-acetic acid, (trgly-H) was prepared in a yield of 30% by reacting glycine and N,N-di­methyl­formamide azine in boiling toluene under acidic conditions (Vasylevs’kyy et al., 2014 ▸). Copper(II) selenate penta­hydrate was prepared by treating basic copper carbonate with selenic acid followed by crystallization. A solution of CuSeO4·5H2O (59.2 mg, 0.20 mmol) in 4 mL of water was added to a solution of trgly-H (27.2 mg, 0.20 mmol) in water (2 mL). The resulting solution was placed in a 20 mL Teflon-lined steel autoclave and heated at 393 K for 24 h. Cooling from to rt over 48 h afforded green–blue crystals of the product (yield 52%). Analysis calculated for C12H17Cu3N9O13Se (%): C, 18.84; H, 2.24; N, 16.48. Found: C, 18.79; H, 2.28; N, 16.40. Elemental analysis was carried out with a Vario EL-Heraeus microanalyzer.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All C-bound H atoms were placed at calculated positions [C—H = 0.94 Å (aromatic), C—H = 0.98 Å (aliphatic)] and refined using a riding model with U iso(H) = 1.2U eq(CH). All O-bound H atoms were located in a difference-Fourier map and then fixed at O—H = 0.85 Å and with U iso(H) =1.5U eq(O).

Table 3

Experimental details

Crystal data
Chemical formula	[Cu3(C4H4N3O9)3(SeO4)(OH)]·2H2O
M r	764.92
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	213
a, b, c (Å)	10.9403 (8), 17.5393 (15), 12.1289 (9)
β (°)	108.965 (8)
V (Å3)	2201.0 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	4.62
Crystal size (mm)	0.20 × 0.16 × 0.14
Data collection
Diffractometer	Stoe Image plate diffraction system
Absorption correction	Numerical [X-RED (Stoe & Cie, 2001 ▸) and X-SHAPE (Stoe & Cie, 1999 ▸)]
T min, T max	0.405, 0.569
No. of measured, independent and observed [I > 2σ(I)] reflections	16928, 4681, 3306
R int	0.057
(sin θ/λ)max (Å−1)	0.634
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.032, 0.072, 0.88
No. of reflections	4681
No. of parameters	343
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.99, −0.64

Computer programs: IPDS Software (Stoe & Cie, 2000 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2018 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019009812/lh5911sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009812/lh5911Isup2.hkl

CCDC reference: 1939397

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu3(C4H4N3O9)3(SeO4)(OH)]·2H2O	F(000) = 1508
Mr = 764.92	Dx = 2.308 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.9403 (8) Å	Cell parameters from 8000 reflections
b = 17.5393 (15) Å	θ = 2.0–26.8°
c = 12.1289 (9) Å	µ = 4.62 mm−1
β = 108.965 (8)°	T = 213 K
V = 2201.0 (3) Å3	Prism, blue
Z = 4	0.20 × 0.16 × 0.14 mm

Stoe Image plate diffraction system diffractometer	3306 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
φ oscillation scans	θmax = 26.8°, θmin = 2.0°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −13→13
Tmin = 0.405, Tmax = 0.569	k = −22→22
16928 measured reflections	l = −15→15
4681 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 0.88	w = 1/[σ2(Fo2) + (0.0392P)2] where P = (Fo2 + 2Fc2)/3
4681 reflections	(Δ/σ)max < 0.001
343 parameters	Δρmax = 0.99 e Å−3
0 restraints	Δρmin = −0.64 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.27623 (5)	0.00328 (2)	0.16661 (4)	0.01311 (11)
Cu2	0.17026 (5)	−0.07181 (2)	0.37617 (4)	0.01200 (11)
Cu3	0.39077 (5)	0.07288 (3)	0.44294 (4)	0.01223 (11)
Se1	0.08793 (4)	0.10530 (2)	0.27442 (3)	0.01415 (10)
O1	0.3177 (3)	−0.01857 (14)	0.3386 (2)	0.0113 (5)
H1O	0.378780	−0.050942	0.354877	0.017*
O2	0.1203 (3)	0.08350 (16)	0.1556 (2)	0.0237 (7)
O3	0.0502 (3)	0.02779 (15)	0.3325 (3)	0.0228 (7)
O4	0.2182 (3)	0.14261 (15)	0.3694 (3)	0.0218 (7)
O5	−0.0323 (3)	0.16534 (15)	0.2454 (3)	0.0231 (7)
O6	0.0419 (3)	−0.36472 (15)	−0.0871 (2)	0.0174 (6)
O7	0.2019 (3)	−0.28370 (17)	−0.0029 (3)	0.0301 (8)
O8	0.2547 (3)	0.02330 (16)	1.0045 (2)	0.0253 (7)
O9	0.3408 (4)	−0.0683 (2)	0.9233 (3)	0.0375 (9)
O10	0.5155 (3)	0.36051 (14)	0.0589 (2)	0.0160 (6)
O11	0.3676 (3)	0.28549 (17)	0.0946 (3)	0.0307 (8)
N1	0.1686 (4)	−0.09003 (18)	0.1341 (3)	0.0148 (7)
N2	0.1237 (4)	−0.11875 (18)	0.2195 (3)	0.0165 (7)
N3	0.0471 (3)	−0.18786 (17)	0.0647 (3)	0.0139 (7)
N4	0.2432 (3)	−0.03365 (18)	0.5386 (3)	0.0142 (7)
N5	0.3327 (3)	0.02449 (18)	0.5642 (3)	0.0152 (7)
N6	0.2564 (4)	0.01245 (19)	0.7085 (3)	0.0177 (8)
N7	0.4666 (3)	0.10867 (18)	0.3243 (3)	0.0135 (7)
N8	0.4102 (4)	0.08493 (17)	0.2103 (3)	0.0143 (7)
N9	0.5346 (3)	0.18128 (17)	0.2111 (3)	0.0146 (7)
C1	0.1208 (4)	−0.1327 (2)	0.0416 (4)	0.0174 (9)
H1	0.135662	−0.125898	−0.029885	0.021*
C2	0.0507 (4)	−0.1772 (2)	0.1748 (4)	0.0180 (9)
H2	0.007193	−0.207386	0.214252	0.022*
C3	−0.0143 (4)	−0.2514 (2)	−0.0127 (3)	0.0151 (8)
H3A	−0.070577	−0.231321	−0.087360	0.018*
H3B	−0.067585	−0.281162	0.022723	0.018*
C4	0.0885 (4)	−0.3024 (2)	−0.0333 (3)	0.0153 (8)
C5	0.1996 (4)	−0.0399 (2)	0.6262 (3)	0.0173 (9)
H5	0.137619	−0.075582	0.631377	0.021*
C6	0.3394 (5)	0.0504 (2)	0.6674 (4)	0.0209 (9)
H6	0.394363	0.089864	0.707040	0.025*
C7	0.2191 (5)	0.0356 (2)	0.8093 (3)	0.0196 (9)
H7A	0.124993	0.030830	0.788261	0.024*
H7B	0.240617	0.089592	0.824842	0.024*
C8	0.2803 (4)	−0.0084 (2)	0.9205 (4)	0.0202 (9)
C9	0.5423 (4)	0.1668 (2)	0.3220 (4)	0.0156 (8)
H9	0.593603	0.193848	0.387670	0.019*
C10	0.4526 (4)	0.1297 (2)	0.1453 (4)	0.0174 (9)
H10	0.429103	0.126325	0.063676	0.021*
C11	0.5883 (4)	0.2477 (2)	0.1676 (4)	0.0182 (9)
H11A	0.635122	0.230577	0.115612	0.022*
H11B	0.649085	0.275010	0.233175	0.022*
C12	0.4785 (4)	0.3008 (2)	0.1017 (3)	0.0159 (9)
O1W	0.3015 (4)	0.28114 (19)	0.3110 (4)	0.0441 (10)
H1W	0.309086	0.277778	0.243576	0.066*
H2W	0.264986	0.240868	0.323686	0.066*
O2W	0.5427 (4)	0.3544 (2)	0.3669 (3)	0.0408 (9)
H3W	0.576259	0.378437	0.430505	0.061*
H4W	0.471669	0.335127	0.367685	0.061*

	U11	U22	U33	U12	U13	U23
Cu1	0.0193 (3)	0.0112 (2)	0.0091 (2)	−0.00358 (19)	0.0050 (2)	−0.00138 (17)
Cu2	0.0176 (3)	0.0096 (2)	0.0093 (2)	−0.00239 (19)	0.0050 (2)	−0.00079 (17)
Cu3	0.0169 (3)	0.0109 (2)	0.0091 (2)	−0.00224 (19)	0.0045 (2)	−0.00038 (17)
Se1	0.0155 (2)	0.01058 (17)	0.01497 (19)	0.00218 (16)	0.00297 (17)	0.00008 (15)
O1	0.0139 (16)	0.0091 (12)	0.0104 (12)	−0.0007 (10)	0.0033 (12)	−0.0019 (10)
O2	0.0289 (19)	0.0285 (16)	0.0131 (14)	0.0102 (13)	0.0061 (14)	0.0027 (12)
O3	0.0225 (18)	0.0143 (13)	0.0333 (17)	0.0021 (12)	0.0114 (15)	0.0066 (12)
O4	0.0208 (18)	0.0158 (14)	0.0243 (15)	−0.0005 (12)	0.0013 (14)	−0.0001 (12)
O5	0.0201 (18)	0.0172 (14)	0.0275 (16)	0.0101 (12)	0.0014 (15)	0.0007 (12)
O6	0.0208 (17)	0.0165 (13)	0.0147 (14)	0.0032 (12)	0.0056 (13)	−0.0039 (11)
O7	0.021 (2)	0.0212 (15)	0.046 (2)	0.0001 (14)	0.0079 (17)	−0.0058 (15)
O8	0.045 (2)	0.0250 (15)	0.0092 (13)	−0.0068 (14)	0.0130 (15)	−0.0017 (12)
O9	0.046 (2)	0.045 (2)	0.0257 (17)	0.0226 (18)	0.0176 (18)	0.0120 (16)
O10	0.0215 (17)	0.0116 (13)	0.0151 (14)	0.0002 (11)	0.0063 (13)	0.0023 (10)
O11	0.023 (2)	0.0256 (17)	0.041 (2)	−0.0006 (14)	0.0068 (17)	0.0117 (15)
N1	0.020 (2)	0.0161 (16)	0.0088 (15)	−0.0036 (13)	0.0059 (15)	−0.0001 (12)
N2	0.026 (2)	0.0129 (16)	0.0124 (16)	−0.0029 (14)	0.0086 (16)	−0.0006 (12)
N3	0.018 (2)	0.0099 (15)	0.0123 (16)	−0.0009 (13)	0.0032 (15)	−0.0016 (12)
N4	0.014 (2)	0.0145 (15)	0.0123 (16)	−0.0019 (13)	0.0023 (15)	−0.0024 (13)
N5	0.020 (2)	0.0157 (16)	0.0104 (16)	−0.0047 (14)	0.0050 (15)	−0.0008 (12)
N6	0.023 (2)	0.0201 (17)	0.0100 (16)	−0.0050 (14)	0.0057 (16)	−0.0009 (13)
N7	0.0153 (19)	0.0140 (15)	0.0102 (15)	−0.0015 (14)	0.0028 (15)	0.0001 (12)
N8	0.0177 (19)	0.0147 (16)	0.0096 (15)	−0.0005 (13)	0.0034 (15)	0.0002 (12)
N9	0.019 (2)	0.0107 (15)	0.0165 (17)	−0.0012 (13)	0.0089 (16)	0.0008 (12)
C1	0.023 (3)	0.0138 (18)	0.0154 (19)	−0.0007 (16)	0.0069 (19)	0.0008 (15)
C2	0.026 (3)	0.0131 (18)	0.017 (2)	−0.0056 (16)	0.010 (2)	−0.0036 (15)
C3	0.017 (2)	0.0120 (17)	0.0123 (19)	−0.0029 (15)	0.0001 (18)	−0.0027 (14)
C4	0.021 (3)	0.0128 (18)	0.0108 (18)	−0.0008 (16)	0.0037 (18)	0.0023 (14)
C5	0.020 (3)	0.021 (2)	0.0123 (19)	−0.0051 (17)	0.0077 (19)	−0.0011 (15)
C6	0.027 (3)	0.022 (2)	0.0140 (19)	−0.0078 (18)	0.007 (2)	0.0000 (16)
C7	0.025 (3)	0.022 (2)	0.0127 (19)	−0.0013 (18)	0.0076 (19)	−0.0029 (16)
C8	0.019 (2)	0.023 (2)	0.018 (2)	−0.0069 (18)	0.004 (2)	−0.0012 (17)
C9	0.018 (2)	0.0141 (18)	0.0146 (19)	0.0023 (16)	0.0048 (18)	−0.0006 (15)
C10	0.023 (3)	0.0156 (18)	0.016 (2)	−0.0018 (16)	0.009 (2)	0.0009 (15)
C11	0.021 (3)	0.0146 (19)	0.021 (2)	−0.0025 (17)	0.010 (2)	0.0057 (16)
C12	0.023 (3)	0.0129 (17)	0.0122 (19)	−0.0027 (16)	0.0061 (19)	0.0006 (14)
O1W	0.053 (3)	0.0231 (17)	0.064 (3)	−0.0041 (17)	0.029 (2)	0.0046 (17)
O2W	0.037 (2)	0.054 (2)	0.0280 (19)	−0.0025 (18)	0.0055 (18)	−0.0045 (17)

Cu1—O8i	1.935 (3)	N4—C5	1.303 (5)
Cu1—N1	1.980 (3)	N4—N5	1.377 (4)
Cu1—N8	1.993 (3)	N5—C6	1.311 (5)
Cu1—O1	2.022 (2)	N6—C6	1.346 (5)
Cu1—O2	2.182 (3)	N6—C5	1.349 (5)
Cu2—O6ii	1.954 (3)	N6—C7	1.466 (5)
Cu2—N2	1.979 (3)	N7—C9	1.320 (5)
Cu2—N4	1.986 (3)	N7—N8	1.382 (4)
Cu2—O1	2.039 (3)	N8—C10	1.301 (5)
Cu2—O3	2.146 (3)	N9—C10	1.339 (5)
Cu3—N5	1.974 (3)	N9—C9	1.345 (5)
Cu3—N7	1.982 (3)	N9—C11	1.478 (5)
Cu3—O10iii	1.990 (3)	C1—H1	0.9400
Cu3—O1	2.039 (2)	C2—H2	0.9400
Cu3—O4	2.182 (3)	C3—C4	1.520 (6)
Se1—O5	1.632 (3)	C3—H3A	0.9800
Se1—O2	1.637 (3)	C3—H3B	0.9800
Se1—O3	1.645 (3)	C5—H5	0.9400
Se1—O4	1.649 (3)	C6—H6	0.9400
O1—H1O	0.8500	C7—C8	1.509 (6)
O6—C4	1.289 (5)	C7—H7A	0.9800
O7—C4	1.219 (5)	C7—H7B	0.9800
O8—C8	1.270 (5)	C9—H9	0.9400
O9—C8	1.235 (5)	C10—H10	0.9400
O10—C12	1.291 (4)	C11—C12	1.525 (6)
O11—C12	1.218 (5)	C11—H11A	0.9800
N1—C1	1.308 (5)	C11—H11B	0.9800
N1—N2	1.379 (4)	O1W—H1W	0.8500
N2—C2	1.304 (5)	O1W—H2W	0.8500
N3—C2	1.337 (5)	O2W—H3W	0.8500
N3—C1	1.346 (5)	O2W—H4W	0.8500
N3—C3	1.471 (5)
O8i—Cu1—N1	94.55 (13)	C6—N5—Cu3	129.1 (3)
O8i—Cu1—N8	88.65 (13)	N4—N5—Cu3	121.9 (2)
N1—Cu1—N8	170.10 (14)	C6—N6—C5	105.5 (3)
O8i—Cu1—O1	174.35 (13)	C6—N6—C7	125.2 (3)
N1—Cu1—O1	88.18 (11)	C5—N6—C7	128.2 (3)
N8—Cu1—O1	87.86 (12)	C9—N7—N8	107.0 (3)
O8i—Cu1—O2	89.20 (12)	C9—N7—Cu3	132.3 (3)
N1—Cu1—O2	96.79 (13)	N8—N7—Cu3	118.3 (2)
N8—Cu1—O2	92.62 (13)	C10—N8—N7	107.0 (3)
O1—Cu1—O2	95.40 (10)	C10—N8—Cu1	130.4 (3)
O6ii—Cu2—N2	90.12 (12)	N7—N8—Cu1	122.2 (2)
O6ii—Cu2—N4	93.00 (12)	C10—N9—C9	106.3 (3)
N2—Cu2—N4	170.93 (15)	C10—N9—C11	125.9 (3)
O6ii—Cu2—O1	172.41 (11)	C9—N9—C11	127.1 (3)
N2—Cu2—O1	87.23 (12)	N1—C1—N3	109.4 (3)
N4—Cu2—O1	88.59 (12)	N1—C1—H1	125.3
O6ii—Cu2—O3	95.29 (11)	N3—C1—H1	125.3
N2—Cu2—O3	98.97 (13)	N2—C2—N3	109.9 (3)
N4—Cu2—O3	89.24 (13)	N2—C2—H2	125.0
O1—Cu2—O3	92.15 (11)	N3—C2—H2	125.0
N5—Cu3—N7	171.64 (14)	N3—C3—C4	110.0 (3)
N5—Cu3—O10iii	92.21 (12)	N3—C3—H3A	109.7
N7—Cu3—O10iii	88.56 (12)	C4—C3—H3A	109.7
N5—Cu3—O1	88.15 (12)	N3—C3—H3B	109.7
N7—Cu3—O1	88.32 (12)	C4—C3—H3B	109.7
O10iii—Cu3—O1	160.30 (11)	H3A—C3—H3B	108.2
N5—Cu3—O4	95.76 (13)	O7—C4—O6	125.3 (4)
N7—Cu3—O4	92.07 (13)	O7—C4—C3	121.7 (3)
O10iii—Cu3—O4	105.28 (11)	O6—C4—C3	112.9 (4)
O1—Cu3—O4	94.27 (11)	N4—C5—N6	110.1 (4)
O5—Se1—O2	110.53 (15)	N4—C5—H5	125.0
O5—Se1—O3	109.17 (15)	N6—C5—H5	125.0
O2—Se1—O3	109.91 (15)	N5—C6—N6	110.3 (4)
O5—Se1—O4	110.35 (15)	N5—C6—H6	124.9
O2—Se1—O4	108.82 (16)	N6—C6—H6	124.9
O3—Se1—O4	108.01 (15)	N6—C7—C8	116.2 (4)
Cu1—O1—Cu3	113.72 (11)	N6—C7—H7A	108.2
Cu1—O1—Cu2	112.88 (13)	C8—C7—H7A	108.2
Cu3—O1—Cu2	113.63 (11)	N6—C7—H7B	108.2
Cu1—O1—H1O	105.2	C8—C7—H7B	108.2
Cu3—O1—H1O	105.1	H7A—C7—H7B	107.4
Cu2—O1—H1O	105.2	O9—C8—O8	127.3 (4)
Se1—O2—Cu1	119.02 (15)	O9—C8—C7	122.5 (4)
Se1—O3—Cu2	124.02 (16)	O8—C8—C7	110.1 (4)
Se1—O4—Cu3	119.98 (15)	N7—C9—N9	109.3 (4)
C4—O6—Cu2iv	113.7 (3)	N7—C9—H9	125.3
C8—O8—Cu1v	138.6 (3)	N9—C9—H9	125.3
C12—O10—Cu3vi	121.8 (3)	N8—C10—N9	110.4 (4)
C1—N1—N2	107.1 (3)	N8—C10—H10	124.8
C1—N1—Cu1	133.6 (3)	N9—C10—H10	124.8
N2—N1—Cu1	119.1 (2)	N9—C11—C12	109.4 (3)
C2—N2—N1	107.1 (3)	N9—C11—H11A	109.8
C2—N2—Cu2	131.1 (3)	C12—C11—H11A	109.8
N1—N2—Cu2	121.7 (2)	N9—C11—H11B	109.8
C2—N3—C1	106.4 (3)	C12—C11—H11B	109.8
C2—N3—C3	127.1 (3)	H11A—C11—H11B	108.2
C1—N3—C3	126.3 (3)	O11—C12—O10	125.9 (4)
C5—N4—N5	107.5 (3)	O11—C12—C11	120.0 (3)
C5—N4—Cu2	130.2 (3)	O10—C12—C11	114.1 (4)
N5—N4—Cu2	120.0 (2)	H1W—O1W—H2W	108.4
C6—N5—N4	106.7 (3)	H3W—O2W—H4W	108.4
O5—Se1—O2—Cu1	−179.53 (17)	Cu2iv—O6—C4—C3	176.2 (2)
O3—Se1—O2—Cu1	−59.0 (2)	N3—C3—C4—O7	−10.4 (5)
O4—Se1—O2—Cu1	59.1 (2)	N3—C3—C4—O6	170.9 (3)
O5—Se1—O3—Cu2	175.78 (18)	N5—N4—C5—N6	0.4 (5)
O2—Se1—O3—Cu2	54.4 (2)	Cu2—N4—C5—N6	−161.7 (3)
O4—Se1—O3—Cu2	−64.2 (2)	C6—N6—C5—N4	−1.1 (5)
O5—Se1—O4—Cu3	172.90 (16)	C7—N6—C5—N4	167.1 (4)
O2—Se1—O4—Cu3	−65.7 (2)	N4—N5—C6—N6	−1.2 (5)
O3—Se1—O4—Cu3	53.6 (2)	Cu3—N5—C6—N6	161.3 (3)
C1—N1—N2—C2	−0.1 (5)	C5—N6—C6—N5	1.4 (5)
Cu1—N1—N2—C2	176.8 (3)	C7—N6—C6—N5	−167.2 (4)
C1—N1—N2—Cu2	−179.7 (3)	C6—N6—C7—C8	−103.6 (5)
Cu1—N1—N2—Cu2	−2.8 (4)	C5—N6—C7—C8	90.4 (5)
C5—N4—N5—C6	0.4 (5)	Cu1v—O8—C8—O9	−4.3 (8)
Cu2—N4—N5—C6	164.7 (3)	Cu1v—O8—C8—C7	172.5 (3)
C5—N4—N5—Cu3	−163.6 (3)	N6—C7—C8—O9	−11.9 (6)
Cu2—N4—N5—Cu3	0.7 (4)	N6—C7—C8—O8	171.1 (4)
C9—N7—N8—C10	−0.7 (4)	N8—N7—C9—N9	0.8 (4)
Cu3—N7—N8—C10	163.8 (3)	Cu3—N7—C9—N9	−160.7 (3)
C9—N7—N8—Cu1	−175.1 (3)	C10—N9—C9—N7	−0.6 (5)
Cu3—N7—N8—Cu1	−10.5 (4)	C11—N9—C9—N7	170.5 (4)
N2—N1—C1—N3	−0.1 (5)	N7—N8—C10—N9	0.4 (5)
Cu1—N1—C1—N3	−176.4 (3)	Cu1—N8—C10—N9	174.1 (3)
C2—N3—C1—N1	0.4 (5)	C9—N9—C10—N8	0.1 (5)
C3—N3—C1—N1	−174.2 (4)	C11—N9—C10—N8	−171.1 (4)
N1—N2—C2—N3	0.4 (5)	C10—N9—C11—C12	62.3 (5)
Cu2—N2—C2—N3	179.8 (3)	C9—N9—C11—C12	−107.2 (4)
C1—N3—C2—N2	−0.4 (5)	Cu3vi—O10—C12—O11	−13.8 (6)
C3—N3—C2—N2	174.0 (4)	Cu3vi—O10—C12—C11	167.2 (2)
C2—N3—C3—C4	−110.0 (5)	N9—C11—C12—O11	1.7 (5)
C1—N3—C3—C4	63.4 (5)	N9—C11—C12—O10	−179.2 (3)
Cu2iv—O6—C4—O7	−2.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O10vii	0.85	2.01	2.811 (4)	156
O1W—H1W···O11	0.85	2.11	2.940 (5)	166
O1W—H2W···O4	0.85	1.93	2.767 (4)	168
O2W—H3W···O9viii	0.85	1.95	2.798 (5)	178
O2W—H4W···O1W	0.85	2.00	2.812 (6)	159
C1—H1···O5ix	0.94	2.58	3.346 (5)	139
C2—H2···O5x	0.94	2.28	2.955 (5)	128
C5—H5···O3xi	0.94	2.39	2.941 (5)	117
C6—H6···O2Wiii	0.94	2.30	3.176 (6)	154
C7—H7A···O3xi	0.98	2.25	3.094 (6)	144
C7—H7B···O1Wiii	0.98	2.38	3.338 (5)	164
C9—H9···O7xii	0.94	2.25	3.067 (6)	144