catena-Poly[[[tetra­aqua­zinc(II)]-[mu]-4-amino-3,5-di-3-pyridyl-4H-1,2,4-triazole] sulfate monohydrate] and poly[[bis([mu]-4-amino-3,5-di-4-pyridyl-4H-1,2,4-triazole)diaqua­copper(II)] dinitrate octa­hydrate]

The isomeric bent triazole-containing ligands 4-amino-3,5-di-3-pyridyl-4H-1,2,4-triazole (L1) and 4-amino-3,5-di-4-pyridyl-4H-1,2,4-triazole (L2) have been used to create the two novel title complexes catena-poly[[[tetra­aqua­zinc(II)]-[mu]-4-amino-3,5-di-3-pyridyl-4H-1,2,4-triazole] sulfate monohydrate], {[Zn(C₁₂H₁₀N₆)(H₂O)₄]SO₄·H₂O}_n, (I), and poly[[diaqua­bis([mu]-4-amino-3,5-di-4-pyridyl-4H-1,2,4-triazole)copper(II)] dinitrate octa­hydrate], {[Cu(C₁₂H₁₀N₆)₂(H₂O)₂](NO₃)₂·8H₂O}_n, (II). The Zn^II and Cu^II atoms are all six-coordinated in approximately octa­hedral environments. Compound (I) presents a sinusoidal chain generated by ZnO₄ cores which are bridged by L1 ligands in a cisoid conformation. These sinusoidal chains are bound to each other by O-H...O hydrogen bonds between coordinated water mol­ecules of neighboring chains into a two-dimensional network. These layers stack in an ...ABAB... sequence and are further linked into a three-dimensional framework through O-H...N hydrogen bonds between coordinated water mol­ecules and the N atoms of the triazole rings. In (II), the Cu^II centers are bridged by the L2 ligands to form a two-dimensional network with square grids. All of the two-dimensional nets also stack alternately along the crystallographic a axis. Neighboring layers are further linked into a three-dimensional framework via inter­layer N-H...N hydrogen bonds between -NH₂ groups of the triazole rings and the N atoms in the triazole rings.

S1. Comment

Intelligent ligand design and the proper choice of a metal center are the main keys to the design of intriguing and functional coordination polymers (Gardner et al., 2003; Natarajan et al., 2005). It is well known that the relative orientations of the nitrogen donors and the different bridging space may result in unusual building blocks, which can lead to the construction of supramolecular motifs that have not been achieved using normal rigid linear organic ligands. As part of our continuing study of coordination polymers with bridging nitrogen donor ligands (Dong et al., 2003), we report here two novel coordination polymers, namely, tetraaqua[4-amino-3,5-di-3-pyridyl- 1,2,4-triazole]zinc(II) sulfate monohydrate, (I), and diaquabis[4-amino-3,5-di-4-pyridyl-1,2,4-triazole]copper(II) nitrate octahydrate (2), generated from the isomeric bent ligands 4-amino-3,5-di-3-pyridyl-1,2,4-triazole (L1) and 4-amino-3,5-di-4-pyridyl-1,2,4-triazole L2, respectively.

Compound (I) crystallizes with only one type of crystallographic Zn^II center, six-coordinated in an approximately octahedral environment with two pyridyl nitrogen donors of two L1 ligands in the axial sites and four O atoms of coordinated water molecules in the equatorial plane (Fig. 1). The corresponding Zn—N distances are 2.162 (3) Å for N6ⁱⁱ [symmetry code: (ii) x - 1, -y + 1/2 , z - 1/2] and 2.172 (3) Å for N1, which are slightly longer than the Zn—N bond (2.078 Å) in [Zn(H₂O)₄(L3)Zn(L4)₂].H₂O [L3 is N-(3-pyridyl)isonicotinamide and L4 is isonicotinic acid; Kumar et al., 2006]. The Zn—O bond lengths range from 2.038 (3) to 2.162 (2) Å, being very close to the Zn—O bond lengths found in [Zn₃(4,4'-bipy)₄(OAc)₄](ClO₄)₂.2H₂O (Woodward et al., 2006).

The asymmetric unit in (I) contains one Zn^II ion, one L1 ligand, one sulfate anion, four coordinated water molecules and one water molecule of crystallization. Each L1 ligand is bound to two Zn^II centers and is bent with a cisoid conformation; the two terminal pyridyl groups and the bridging triazole heterocycle ring do not lie in the same plane. The torsion angles for the two pyridyl rings are -29.8 (6) (C9—C8—C7—N2) and 5.5 (6)° (N3—C6—C4—C3). The corresponding dihedral angles between the planes of the three rings are 72.48° (between N1/C8–C12 and N2–N4/C6/C7), 7.40° (N2–N4/C6/C7 and N6/C1–C5) and 24.17° (N1/C8–C12 and N6/C1–C5) [please provide s.u. values]. The coordinating N1 and N6 atoms are on the same side of the molecule and the N—Zn—N angle [171.54 (11)°] is close to 180°, so that the ZnO₄ units are bridged by the L1 ligands through the pyridyl N atoms into a one-dimensional sinusoidal chain along the crystallographic a axis with a Zn···Zn separation of ca 9.64 Å. These sinusoidal chains are bound to each other by interpolymer O—H···O hydrogen bonds between coordinated water molecules to generate a two-dimensional network parallel to the ac plane (Table 1 and Fig. 2). These layers stack in an –ABAB– sequence along the b axis to form a three-dimensional framework linked through O—H···N hydrogen bonds between coordinated water molecules and the N atoms on the triazole rings (Fig. 3). When viewed down the crystallographic c axis, honeycomb-like channels are evident, in which the uncoordinated sulfate counter-ions and water molecule are located. All the amine groups on the triazole rings project into these channels and interact with the framework through hydrogen bonds.

The asymmetric unit in (II) contains one Cu^II ion, two L2 ligands, two nitrate anions, two coordinated water molecules and eight water molecules of crystallization. Each L2 ligand is bound to two Cu^II atoms. The Cu^II atoms are again six-coordinated in an approximately octahedral environment, in a similar manner to Zn^II in (I) except that the octahedral Cu^II coordination in (II) is built up of four N atoms (N1, N7, N6^viii and N12^ix) [symmetry codes: (viii) x, -y + 1/2, z + 1/2; (ix) x, -y + 5/2, z + 1/2] from four L2 ligands in the equatorial plane and two O atoms of water molecules in the axial sites (Fig. 4). The Cu^II centers are bridged by L2 ligands to form a two-dimensional network parallel to the bc plane and consisting of an essentially square grid (Fig. 5). The dimensions of the squares are ca 14 × 14 Å, which is significantly larger than the corresponding dimensions (ca 8 × 8 Å) in [Cu(4,4'-bipy)₂(H₂O)₂].SiF₆ (4,4'-bipy is 4,4'-bipyridine; Noro et al., 2002). When viewed down the crystallographic a axis, the NO₃^- anions and eight crystallization water molecules are seen to be located in the voids in the grid. The shortest intralayer Cu···Cu distance is 14.369 (1) Å, ca 5 Å longer than the shortest interlayer Cu···Cu distance [9.250 (1) Å]. These two-dimensional layers are arranged alternately along the a axis and are further linked into a three-dimensional framework through interlayer N—H···N hydrogen bonds. The hydrogen-bonding system involves uncoordinated N atoms of the triazole ring and H atoms of the –NH₂ group of the triazole ring of a neighboring layer (Table 2 and Fig. 6). The NO₃^- anions and crystallization water molecules are located between the layers and interact with the framework via O—H···O and N—H···O hydrogen bonds (Table 2).

The ligands in (I) and (II) are both bent triazole-bridged ligands, and the essential difference between L1 and L2 is the relative orientation of the donor N atoms on the pyridyl rings. L1 is a 3,3'-bipyridyl-type ligand, while L2 is a 4,4'-bipyridyl-type ligand. Both ligands act as bidentate bridging ligands; however, in (I), each Zn^II center is linked two other Zn atoms via two axially-bound ligands, while in (II), each Cu^II center is linked to four others via four equatorially-bound ligands. Thus the polymer in (I) exhibits a sinusoidal chain and the polymer in (II) presents a two-dimensional network with a square grid. This study clearly demonstrates that the relative orientations of the nitrogen donors on the pyridyl rings causes the ligands to act as distinct building blocks, leading to different frameworks. We expect ligands of this type to be viable agents for the creation of more new complexes with interesting topology and physical properties.

Related literature

For related literature, see: Dong et al. (2003); Kumar et al. (2006); Natarajan et al. (2005); Noro et al. (2002); Traisnel et al. (1999); Woodward et al. (2006).

S2. Experimental

All the solvents and reagents were commercially available and used as received. L1 and L2 were prepared according to the literature method (Traisnel et al., 1999). L1 (12 mg, 0.05 mmol) and ZnSO₄.7H₂O (14 mg, 0.05 mmol) were dissolved in water (2 ml). Upon slow evaporation, colourless block-shaped crystals were obtained in 61% yield based on L1. L2 (12 mg, 0.05 mmol) and Cu(NO₃)₂.3H₂O (12 mg, 0.05 mmol) were mixed in water (2 ml). After ca one week, blue block-shaped crystals were obtained in 63% yield based on L2. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

S3. Refinement

H atoms attached to carbon were placed in geometrically idealized positions [C_arene—H = 0.93 Å for (I) and C_arene—H = 0.95 Å for (II)] and refined using a riding model with isotropic displacement parameters [U_iso(H) = 1.2U_eq(C)]. The NH₂ group and aqua H atoms were located by Fourier difference synthesis and refined as riding atoms, with N—H distances of 0.86–92 Å and O—H distances of 0.84–0.86 Å and with isotropic displacement parameters [U_iso(H) = 1.2U_eq(N) and 1.5U_eq(O)].

Computing details

For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. : A view of (I), showing the coordination around Zn. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (ii) x - 1, -y + 1/2 , z - 1/2; (vi) x + 1, -y + 1/2, z + 1/2.]
	Fig. 2. : A perspective view of the hydrogen-bonded two-dimensional network in (I). Hydrogen bonds are indicated by dashed lines.
	Fig. 3. : A perspective view of the three-dimensional network of (I), along the crystallographic c axis. S, O and H atoms in sulfate anions, and water molecules of crystallization in the channels, are shown as spheres.
	Fig. 4. : A view of (II), showing the coordination around Cu. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) x, -y + 1/2, z + 1/2; (ii): x, -y + 5/2, z + 1/2.]
	Fig. 5. : A perspective view of the two-dimensional network in (II), along the a axis.
	Fig. 6. : A view of the stacking of the sheets in (II), along the a axis. H atoms have been omitted for clarity. Hydrogen bonds are indicated by dashed lines.

(I) catena-poly[[[tetraaquazinc(II)]-µ- 4-amino-3,5-di-3-pyridyl-4H-1,2,4-triazole] sulfate monohydrate]

Crystal data

[Zn(C12H10N6)(H2O)4]SO4·H2O	F(000) = 1008
Mr = 489.77	Dx = 1.711 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.3593 (19) Å	Cell parameters from 2449 reflections
b = 17.437 (3) Å	θ = 2.3–25.6°
c = 11.532 (2) Å	µ = 1.46 mm^−1
β = 114.121 (3)°	T = 298 K
V = 1901.2 (6) Å^3	Block, colourless
Z = 4	0.27 × 0.12 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3346 independent reflections
Radiation source: fine-focus sealed tube	2790 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
phi and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→10
Tmin = 0.694, Tmax = 0.856	k = −20→20
9776 measured reflections	l = −10→13

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 2.2894P] where P = (Fo^2 + 2Fc^2)/3
3346 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.93 e Å^−3
0 restraints	Δρmin = −0.67 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
Zn1	0.26366 (4)	0.21853 (2)	0.74913 (4)	0.02350 (16)
N1	0.3530 (3)	0.10537 (17)	0.7530 (3)	0.0274 (7)
N2	0.7373 (3)	−0.05578 (16)	1.0121 (3)	0.0299 (7)
N3	0.8732 (3)	−0.04492 (17)	1.1017 (3)	0.0296 (7)
N4	0.8002 (3)	0.06156 (15)	0.9967 (3)	0.0225 (6)
N5	0.8098 (3)	0.13528 (17)	0.9516 (3)	0.0349 (8)
H1N5	0.7661	0.1706	0.9786	0.042*
H2N5	0.7713	0.1328	0.8669	0.042*
N6	1.2057 (3)	0.16409 (17)	1.2651 (3)	0.0277 (7)
C1	1.2938 (4)	0.1166 (2)	1.3522 (4)	0.0347 (9)
H1	1.3768	0.1367	1.4136	0.042*
C2	1.2681 (4)	0.0398 (2)	1.3555 (4)	0.0393 (10)
H2	1.3340	0.0082	1.4158	0.047*
C3	1.1428 (4)	0.0100 (2)	1.2680 (4)	0.0362 (10)
H3	1.1230	−0.0419	1.2686	0.043*
C4	1.0465 (4)	0.0585 (2)	1.1791 (3)	0.0243 (8)
C5	1.0829 (4)	0.1351 (2)	1.1805 (3)	0.0266 (8)
H5	1.0197	0.1679	1.1204	0.032*
C6	0.9097 (4)	0.02558 (19)	1.0913 (3)	0.0230 (8)
C7	0.6940 (4)	0.00896 (19)	0.9507 (3)	0.0228 (8)
C8	0.5503 (4)	0.02109 (19)	0.8528 (3)	0.0242 (8)
C9	0.4735 (4)	−0.0394 (2)	0.7786 (4)	0.0390 (10)
H9	0.5132	−0.0880	0.7869	0.047*
C10	0.3366 (5)	−0.0257 (3)	0.6919 (5)	0.0515 (13)
H10	0.2827	−0.0652	0.6408	0.062*
C11	0.2809 (4)	0.0464 (2)	0.6819 (4)	0.0391 (10)
H11	0.1887	0.0547	0.6230	0.047*
C12	0.4853 (4)	0.0916 (2)	0.8377 (3)	0.0250 (8)
H12	0.5360	0.1318	0.8893	0.030*
O1	0.3374 (3)	0.20504 (13)	0.9525 (2)	0.0253 (6)
H1O1	0.3176	0.1593	0.9652	0.038*
H2O1	0.4252	0.2152	0.9884	0.038*
O2	0.0758 (3)	0.16974 (16)	0.7372 (3)	0.0399 (7)
H1O2	0.0852	0.1336	0.7894	0.060*
H2O2	−0.0034	0.1924	0.7098	0.060*
O3	0.1772 (3)	0.21948 (16)	0.5555 (3)	0.0394 (7)
H1O3	0.2208	0.2431	0.5179	0.059*
H2O3	0.0922	0.2084	0.5072	0.059*
O4	0.4617 (3)	0.26488 (15)	0.7665 (2)	0.0311 (6)
H1O4	0.5242	0.2780	0.8393	0.047*
H2O4	0.4981	0.2445	0.7206	0.047*
S1	0.69152 (10)	0.21222 (6)	0.60764 (9)	0.0321 (3)
O5	0.6345 (8)	0.1609 (3)	0.6680 (5)	0.154 (3)
O6	0.6053 (5)	0.2790 (3)	0.5864 (5)	0.122 (2)
O7	0.6815 (4)	0.1868 (3)	0.4860 (3)	0.0868 (14)
O8	0.8314 (4)	0.2356 (3)	0.6891 (4)	0.1004 (17)
O9	0.9140 (3)	0.3226 (2)	0.9111 (3)	0.0545 (9)
H1O9	0.8814	0.3083	0.8345	0.082*
H2O9	0.8576	0.3208	0.9474	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0184 (2)	0.0230 (2)	0.0267 (3)	0.00238 (16)	0.00684 (18)	0.00278 (17)
N1	0.0219 (16)	0.0273 (16)	0.0284 (17)	0.0025 (13)	0.0056 (13)	−0.0041 (13)
N2	0.0221 (16)	0.0210 (15)	0.0403 (19)	−0.0024 (13)	0.0063 (14)	0.0058 (14)
N3	0.0206 (16)	0.0238 (16)	0.0379 (19)	−0.0022 (13)	0.0054 (14)	0.0053 (14)
N4	0.0227 (15)	0.0166 (14)	0.0261 (16)	0.0011 (12)	0.0079 (13)	0.0021 (12)
N5	0.0368 (19)	0.0182 (15)	0.039 (2)	−0.0036 (14)	0.0050 (15)	0.0073 (14)
N6	0.0222 (15)	0.0253 (16)	0.0334 (18)	−0.0017 (13)	0.0091 (14)	−0.0033 (13)
C1	0.027 (2)	0.038 (2)	0.032 (2)	−0.0016 (17)	0.0053 (17)	−0.0008 (18)
C2	0.027 (2)	0.038 (2)	0.040 (3)	0.0028 (18)	0.0000 (18)	0.0080 (19)
C3	0.033 (2)	0.026 (2)	0.043 (3)	−0.0046 (17)	0.0078 (19)	0.0049 (18)
C4	0.0193 (18)	0.0234 (18)	0.029 (2)	0.0010 (14)	0.0092 (15)	0.0010 (15)
C5	0.0226 (18)	0.0224 (18)	0.032 (2)	−0.0012 (15)	0.0078 (16)	−0.0007 (15)
C6	0.0220 (18)	0.0211 (18)	0.026 (2)	0.0019 (14)	0.0102 (15)	0.0027 (15)
C7	0.0219 (18)	0.0190 (17)	0.028 (2)	−0.0007 (14)	0.0111 (15)	−0.0029 (15)
C8	0.0221 (18)	0.0214 (18)	0.029 (2)	0.0003 (14)	0.0106 (15)	−0.0011 (15)
C9	0.035 (2)	0.022 (2)	0.049 (3)	0.0016 (17)	0.0054 (19)	−0.0084 (18)
C10	0.035 (2)	0.036 (2)	0.063 (3)	−0.004 (2)	−0.001 (2)	−0.023 (2)
C11	0.026 (2)	0.041 (2)	0.038 (2)	0.0010 (18)	−0.0002 (18)	−0.0110 (19)
C12	0.0208 (18)	0.0218 (18)	0.030 (2)	−0.0014 (15)	0.0079 (15)	−0.0059 (15)
O1	0.0243 (13)	0.0239 (13)	0.0262 (14)	−0.0014 (10)	0.0090 (11)	0.0005 (10)
O2	0.0180 (13)	0.0411 (16)	0.0560 (19)	0.0047 (12)	0.0105 (12)	0.0263 (14)
O3	0.0277 (15)	0.0590 (19)	0.0268 (15)	−0.0117 (13)	0.0063 (12)	0.0047 (13)
O4	0.0252 (14)	0.0360 (15)	0.0329 (15)	−0.0024 (11)	0.0127 (12)	−0.0011 (12)
S1	0.0252 (5)	0.0431 (6)	0.0266 (5)	0.0066 (4)	0.0094 (4)	0.0070 (4)
O5	0.263 (8)	0.123 (4)	0.089 (4)	−0.100 (5)	0.084 (5)	0.002 (3)
O6	0.072 (3)	0.112 (4)	0.122 (4)	0.058 (3)	−0.022 (3)	−0.024 (3)
O7	0.058 (2)	0.159 (4)	0.050 (2)	0.002 (3)	0.0277 (19)	−0.030 (3)
O8	0.0297 (19)	0.172 (5)	0.079 (3)	0.022 (2)	0.0017 (19)	−0.051 (3)
O9	0.0365 (17)	0.080 (2)	0.0429 (19)	0.0109 (16)	0.0116 (15)	−0.0009 (17)

Geometric parameters (Å, º)

Zn1—O3	2.038 (3)	C4—C6	1.480 (5)
Zn1—O2	2.076 (3)	C5—H5	0.9300
Zn1—O4	2.136 (3)	C7—C8	1.470 (5)
Zn1—N6^i	2.162 (3)	C8—C12	1.378 (5)
Zn1—O1	2.162 (2)	C8—C9	1.386 (5)
Zn1—N1	2.172 (3)	C9—C10	1.381 (6)
N1—C11	1.337 (5)	C9—H9	0.9300
N1—C12	1.341 (4)	C10—C11	1.367 (6)
N2—C7	1.310 (4)	C10—H10	0.9300
N2—N3	1.378 (4)	C11—H11	0.9300
N3—C6	1.306 (4)	C12—H12	0.9300
N4—C7	1.363 (4)	O1—H1O1	0.8507
N4—C6	1.363 (4)	O1—H2O1	0.8501
N4—N5	1.405 (4)	O2—H1O2	0.8489
N5—H1N5	0.8931	O2—H2O2	0.8473
N5—H2N5	0.8921	O3—H1O3	0.8493
N6—C1	1.333 (5)	O3—H2O3	0.8498
N6—C5	1.345 (4)	O4—H1O4	0.8556
N6—Zn1^ii	2.162 (3)	O4—H2O4	0.8447
C1—C2	1.369 (6)	S1—O5	1.404 (5)
C1—H1	0.9300	S1—O6	1.427 (4)
C2—C3	1.379 (5)	S1—O8	1.427 (4)
C2—H2	0.9300	S1—O7	1.434 (4)
C3—C4	1.387 (5)	O9—H1O9	0.8444
C3—H3	0.9300	O9—H2O9	0.8469
C4—C5	1.387 (5)
O3—Zn1—O2	87.15 (11)	N6—C5—H5	118.6
O3—Zn1—O4	94.31 (10)	C4—C5—H5	118.6
O2—Zn1—O4	177.59 (10)	N3—C6—N4	109.3 (3)
O3—Zn1—N6^i	94.16 (12)	N3—C6—C4	122.3 (3)
O2—Zn1—N6^i	96.21 (11)	N4—C6—C4	128.3 (3)
O4—Zn1—N6^i	85.60 (11)	N2—C7—N4	109.0 (3)
O3—Zn1—O1	172.53 (10)	N2—C7—C8	123.7 (3)
O2—Zn1—O1	86.18 (10)	N4—C7—C8	127.3 (3)
O4—Zn1—O1	92.26 (10)	C12—C8—C9	118.2 (3)
N6^i—Zn1—O1	89.89 (10)	C12—C8—C7	121.0 (3)
O3—Zn1—N1	91.28 (11)	C9—C8—C7	120.7 (3)
O2—Zn1—N1	90.52 (11)	C10—C9—C8	118.4 (4)
O4—Zn1—N1	87.54 (11)	C10—C9—H9	120.8
N6^i—Zn1—N1	171.54 (11)	C8—C9—H9	120.8
O1—Zn1—N1	85.44 (10)	C11—C10—C9	119.6 (4)
C11—N1—C12	117.2 (3)	C11—C10—H10	120.2
C11—N1—Zn1	124.1 (2)	C9—C10—H10	120.2
C12—N1—Zn1	118.6 (2)	N1—C11—C10	123.0 (4)
C7—N2—N3	107.8 (3)	N1—C11—H11	118.5
C6—N3—N2	107.8 (3)	C10—C11—H11	118.5
C7—N4—C6	106.1 (3)	N1—C12—C8	123.6 (3)
C7—N4—N5	129.8 (3)	N1—C12—H12	118.2
C6—N4—N5	123.8 (3)	C8—C12—H12	118.2
N4—N5—H1N5	112.3	Zn1—O1—H1O1	106.6
N4—N5—H2N5	107.0	Zn1—O1—H2O1	109.8
H1N5—N5—H2N5	110.5	H1O1—O1—H2O1	113.3
C1—N6—C5	117.8 (3)	Zn1—O2—H1O2	115.1
C1—N6—Zn1^ii	121.5 (2)	Zn1—O2—H2O2	124.9
C5—N6—Zn1^ii	120.5 (2)	H1O2—O2—H2O2	115.0
N6—C1—C2	123.2 (4)	Zn1—O3—H1O3	118.4
N6—C1—H1	118.4	Zn1—O3—H2O3	126.1
C2—C1—H1	118.4	H1O3—O3—H2O3	113.7
C1—C2—C3	118.9 (4)	Zn1—O4—H1O4	120.4
C1—C2—H2	120.5	Zn1—O4—H2O4	116.1
C3—C2—H2	120.5	H1O4—O4—H2O4	112.0
C2—C3—C4	119.3 (4)	O5—S1—O6	104.2 (4)
C2—C3—H3	120.4	O5—S1—O8	112.0 (4)
C4—C3—H3	120.4	O6—S1—O8	106.0 (3)
C5—C4—C3	117.9 (3)	O5—S1—O7	114.3 (3)
C5—C4—C6	124.2 (3)	O6—S1—O7	107.1 (3)
C3—C4—C6	117.9 (3)	O8—S1—O7	112.4 (2)
N6—C5—C4	122.8 (3)	H1O9—O9—H2O9	116.4
O3—Zn1—N1—C11	−47.2 (3)	N5—N4—C6—C4	11.7 (6)
O2—Zn1—N1—C11	40.0 (3)	C5—C4—C6—N3	−172.5 (4)
O4—Zn1—N1—C11	−141.4 (3)	C3—C4—C6—N3	5.5 (6)
N6^i—Zn1—N1—C11	−177.2 (7)	C5—C4—C6—N4	2.4 (6)
O1—Zn1—N1—C11	126.1 (3)	C3—C4—C6—N4	−179.6 (4)
O3—Zn1—N1—C12	137.8 (3)	N3—N2—C7—N4	1.3 (4)
O2—Zn1—N1—C12	−135.0 (3)	N3—N2—C7—C8	−176.1 (3)
O4—Zn1—N1—C12	43.5 (3)	C6—N4—C7—N2	−1.2 (4)
N6^i—Zn1—N1—C12	7.7 (10)	N5—N4—C7—N2	171.7 (3)
O1—Zn1—N1—C12	−48.9 (3)	C6—N4—C7—C8	176.0 (3)
C7—N2—N3—C6	−0.9 (4)	N5—N4—C7—C8	−11.0 (6)
C5—N6—C1—C2	3.1 (6)	N2—C7—C8—C12	146.2 (4)
Zn1^ii—N6—C1—C2	−171.9 (3)	N4—C7—C8—C12	−30.7 (6)
N6—C1—C2—C3	−2.6 (7)	N2—C7—C8—C9	−29.8 (6)
C1—C2—C3—C4	0.1 (7)	N4—C7—C8—C9	153.4 (4)
C2—C3—C4—C5	1.6 (6)	C12—C8—C9—C10	1.0 (6)
C2—C3—C4—C6	−176.6 (4)	C7—C8—C9—C10	177.1 (4)
C1—N6—C5—C4	−1.3 (6)	C8—C9—C10—C11	−0.1 (8)
Zn1^ii—N6—C5—C4	173.8 (3)	C12—N1—C11—C10	−0.5 (6)
C3—C4—C5—N6	−1.0 (6)	Zn1—N1—C11—C10	−175.6 (4)
C6—C4—C5—N6	177.0 (3)	C9—C10—C11—N1	−0.2 (8)
N2—N3—C6—N4	0.2 (4)	C11—N1—C12—C8	1.5 (6)
N2—N3—C6—C4	175.9 (3)	Zn1—N1—C12—C8	176.9 (3)
C7—N4—C6—N3	0.6 (4)	C9—C8—C12—N1	−1.8 (6)
N5—N4—C6—N3	−172.8 (3)	C7—C8—C12—N1	−177.8 (3)
C7—N4—C6—C4	−174.8 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H2N5···O5	0.89	2.20	3.056 (6)	160
O4—H1O4···O7^iii	0.86	1.91	2.755 (5)	170
O3—H2O3···O9^i	0.85	1.80	2.652 (4)	175
O1—H1O1···N2^iv	0.85	1.94	2.792 (4)	177
O9—H1O9···O8	0.84	1.99	2.793 (5)	157
O9—H2O9···O7^iii	0.85	2.05	2.876 (5)	165
O2—H2O2···O8^v	0.85	1.79	2.625 (4)	166
O1—H2O1···O6^iii	0.85	1.75	2.581 (5)	167
O4—H2O4···O5	0.84	2.28	3.074 (8)	157
O3—H1O3···O1^vi	0.85	1.89	2.740 (4)	173

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

(II) poly[[bis(µ-4-amino-3,5-di-4-pyridyl-4H-1,2,4-triazole)diaquacopper(II)] dinitrate octahydrate]

Crystal data

[Cu(C12H10N6)2(H2O)2](NO3)2·8H2O	Dx = 1.489 Mg m^−3
Mr = 844.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9843 reflections
a = 18.2543 (17) Å	θ = 2.5–27.8°
b = 19.8942 (18) Å	µ = 0.67 mm^−1
c = 20.7455 (19) Å	T = 173 K
V = 7533.8 (12) Å^3	Block, blue
Z = 8	0.48 × 0.47 × 0.16 mm
F(000) = 3512

Data collection

Bruker SMART CCD area-detector diffractometer	6994 independent reflections
Radiation source: fine-focus sealed tube	5639 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
phi and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→22
Tmin = 0.740, Tmax = 0.901	k = −21→24
37726 measured reflections	l = −25→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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0513P)^2 + 3.4143P] where P = (Fo^2 + 2Fc^2)/3
6994 reflections	(Δ/σ)max = 0.001
496 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.24 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 > 2sigma(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
C1	0.03814 (12)	1.45108 (10)	0.40372 (9)	0.0188 (4)
H1	0.0086	1.4899	0.3979	0.023*
C2	0.02960 (12)	1.41370 (10)	0.45914 (9)	0.0190 (4)
H2	−0.0056	1.4263	0.4906	0.023*
C3	0.07335 (11)	1.35724 (9)	0.46820 (9)	0.0159 (4)
C4	0.12041 (11)	1.33820 (10)	0.41932 (9)	0.0187 (4)
H4	0.1490	1.2985	0.4231	0.022*
C5	0.12514 (12)	1.37785 (10)	0.36491 (10)	0.0180 (4)
H5	0.1571	1.3643	0.3312	0.022*
C6	0.07320 (11)	1.32420 (9)	0.53133 (9)	0.0155 (4)
C7	0.08362 (11)	1.25229 (10)	0.60866 (9)	0.0170 (4)
C8	0.09141 (11)	1.18984 (10)	0.64589 (9)	0.0172 (4)
C9	0.03614 (12)	1.17318 (10)	0.68838 (9)	0.0192 (4)
H9	−0.0063	1.2005	0.6920	0.023*
C10	0.04372 (12)	1.11608 (10)	0.72540 (9)	0.0184 (4)
H10	0.0053	1.1043	0.7542	0.022*
C11	0.15584 (12)	1.09283 (10)	0.68094 (10)	0.0218 (5)
H11	0.1978	1.0648	0.6784	0.026*
C12	0.15217 (12)	1.14871 (11)	0.64157 (10)	0.0247 (5)
H12	0.1906	1.1586	0.6122	0.030*
C13	0.17644 (12)	0.55832 (10)	0.40304 (9)	0.0209 (5)
H13	0.1981	0.5150	0.4054	0.025*
C14	0.19387 (12)	0.60465 (10)	0.44960 (10)	0.0214 (5)
H14	0.2272	0.5935	0.4831	0.026*
C15	0.16213 (11)	0.66802 (10)	0.44715 (9)	0.0155 (4)
C16	0.11299 (11)	0.68124 (10)	0.39820 (9)	0.0190 (4)
H16	0.0891	0.7236	0.3958	0.023*
C17	0.09903 (11)	0.63227 (10)	0.35278 (9)	0.0179 (4)
H17	0.0658	0.6422	0.3188	0.021*
C18	0.18631 (11)	0.71877 (9)	0.49405 (9)	0.0160 (4)
C19	0.18983 (11)	0.79716 (9)	0.56638 (9)	0.0157 (4)
C20	0.17015 (11)	0.84622 (9)	0.61627 (9)	0.0149 (4)
C21	0.21553 (11)	0.85189 (10)	0.66980 (9)	0.0183 (4)
H21	0.2583	0.8249	0.6733	0.022*
C22	0.19779 (12)	0.89703 (10)	0.71775 (9)	0.0182 (4)
H22	0.2290	0.9005	0.7542	0.022*
C23	0.09537 (12)	0.93193 (10)	0.66237 (9)	0.0187 (4)
H23	0.0537	0.9604	0.6595	0.022*
C24	0.10931 (11)	0.88796 (10)	0.61251 (9)	0.0190 (4)
H24	0.0778	0.8862	0.5761	0.023*
Cu1	0.111754 (14)	1.000092 (11)	0.786239 (11)	0.01541 (9)
N1	0.13800 (10)	0.93625 (8)	0.71476 (7)	0.0159 (4)
N2	0.25722 (10)	0.78018 (9)	0.55393 (8)	0.0230 (4)
N3	0.25528 (10)	0.73007 (9)	0.50767 (8)	0.0237 (4)
N4	0.14296 (9)	0.76013 (8)	0.52906 (7)	0.0143 (3)
N5	0.06663 (9)	0.75337 (9)	0.53160 (8)	0.0226 (4)
H5A	0.0477	0.7483	0.5713	0.027*
H5B	0.0464	0.7913	0.5150	0.027*
N6	0.13023 (9)	0.57140 (8)	0.35439 (7)	0.0157 (4)
N7	0.10276 (9)	1.07661 (8)	0.72250 (7)	0.0155 (4)
N8	0.07376 (10)	1.31174 (8)	0.63508 (8)	0.0211 (4)
N9	0.06776 (10)	1.35775 (8)	0.58570 (8)	0.0194 (4)
N10	0.08334 (9)	1.25789 (8)	0.54343 (7)	0.0144 (3)
N11	0.08842 (10)	1.20664 (8)	0.49674 (8)	0.0177 (4)
H11A	0.0671	1.1717	0.5117	0.021*
H11B	0.1377	1.1979	0.4926	0.021*
N12	0.08662 (9)	1.43471 (8)	0.35765 (7)	0.0161 (4)
N13	0.09541 (12)	0.72449 (10)	0.69924 (10)	0.0327 (5)
N14	0.02183 (12)	0.92460 (11)	0.42487 (10)	0.0354 (5)
O1	−0.01320 (8)	0.97267 (7)	0.77501 (7)	0.0251 (3)
H1A	−0.0244	0.9352	0.7587	0.038*
H1B	−0.0496	0.9978	0.7821	0.038*
O2	0.04409 (12)	0.87038 (10)	0.44588 (10)	0.0583 (6)
O3	0.05720 (13)	0.95418 (11)	0.38301 (9)	0.0636 (7)
O4	−0.03675 (14)	0.94661 (14)	0.44356 (12)	0.0812 (8)
O5	0.13899 (13)	0.68917 (10)	0.66869 (10)	0.0573 (6)
O6	0.10954 (11)	0.74474 (10)	0.75427 (9)	0.0478 (5)
O7	0.03617 (11)	0.74168 (10)	0.67374 (8)	0.0453 (5)
O8	−0.25289 (11)	0.72629 (10)	0.68106 (10)	0.0541 (5)
H8A	−0.2892	0.7314	0.7058	0.081*
H8B	−0.2354	0.7654	0.6756	0.081*
O9	0.20172 (10)	0.87781 (10)	0.39427 (9)	0.0486 (5)
H9A	0.2123	0.8413	0.3753	0.073*
H9B	0.1555	0.8786	0.3975	0.073*
O10	0.23169 (11)	0.95657 (10)	0.50439 (9)	0.0501 (5)
H10A	0.2011	0.9865	0.4934	0.075*
H10B	0.2273	0.9245	0.4779	0.075*
O11	0.35238 (13)	0.98404 (9)	0.58233 (10)	0.0567 (6)
H11C	0.3106	0.9762	0.5651	0.085*
H11D	0.3774	0.9479	0.5861	0.085*
O12	0.25017 (10)	1.02966 (8)	0.79681 (8)	0.0359 (4)
H12A	0.2809	1.0298	0.7659	0.054*
H12B	0.2668	1.0532	0.8276	0.054*
O13	0.35624 (10)	1.04739 (8)	0.69674 (8)	0.0361 (4)
H13A	0.3489	1.0279	0.6610	0.054*
H13B	0.3566	1.0898	0.6938	0.054*
O14	−0.13054 (12)	0.94301 (10)	0.55042 (11)	0.0618 (6)
H14A	−0.1073	0.9441	0.5148	0.093*
H14B	−0.1138	0.9689	0.5797	0.093*
O15	−0.05069 (9)	0.84292 (7)	0.73373 (7)	0.0292 (4)
H15A	−0.0622	0.8324	0.7721	0.044*
H15B	−0.0232	0.8135	0.7168	0.044*
O16	−0.17915 (11)	0.84615 (11)	0.65950 (9)	0.0546 (5)
H16B	−0.1717	0.8755	0.6305	0.082*
H16A	−0.1383	0.8428	0.6787	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0267 (12)	0.0138 (10)	0.0159 (10)	0.0052 (9)	0.0012 (8)	0.0016 (8)
C2	0.0257 (12)	0.0163 (10)	0.0151 (10)	0.0029 (9)	0.0034 (8)	0.0014 (8)
C3	0.0184 (11)	0.0141 (9)	0.0153 (10)	−0.0028 (8)	−0.0011 (8)	0.0016 (8)
C4	0.0240 (11)	0.0151 (10)	0.0171 (10)	0.0029 (9)	0.0006 (8)	0.0025 (8)
C5	0.0232 (11)	0.0159 (10)	0.0150 (10)	−0.0003 (9)	0.0034 (8)	0.0005 (8)
C6	0.0154 (10)	0.0144 (10)	0.0168 (10)	−0.0002 (8)	−0.0003 (8)	0.0029 (8)
C7	0.0160 (10)	0.0199 (10)	0.0151 (10)	0.0002 (9)	0.0007 (8)	0.0053 (8)
C8	0.0227 (11)	0.0164 (10)	0.0126 (9)	0.0000 (9)	−0.0011 (8)	0.0015 (8)
C9	0.0226 (11)	0.0178 (10)	0.0171 (10)	0.0048 (9)	0.0021 (8)	0.0030 (8)
C10	0.0215 (11)	0.0176 (10)	0.0162 (10)	0.0008 (9)	0.0033 (8)	0.0023 (8)
C11	0.0230 (12)	0.0204 (11)	0.0221 (11)	0.0072 (9)	0.0036 (9)	0.0041 (8)
C12	0.0238 (12)	0.0271 (12)	0.0230 (11)	0.0042 (10)	0.0075 (9)	0.0093 (9)
C13	0.0316 (13)	0.0135 (10)	0.0177 (10)	0.0047 (9)	−0.0051 (9)	−0.0025 (8)
C14	0.0275 (12)	0.0199 (11)	0.0166 (10)	0.0048 (9)	−0.0068 (9)	−0.0032 (8)
C15	0.0163 (10)	0.0174 (10)	0.0127 (9)	−0.0020 (8)	0.0024 (8)	−0.0027 (8)
C16	0.0245 (12)	0.0146 (10)	0.0180 (10)	0.0045 (8)	−0.0020 (8)	−0.0028 (8)
C17	0.0219 (11)	0.0178 (10)	0.0139 (10)	0.0019 (9)	−0.0047 (8)	−0.0001 (8)
C18	0.0194 (11)	0.0157 (10)	0.0127 (9)	0.0026 (8)	−0.0013 (8)	−0.0017 (8)
C19	0.0185 (11)	0.0143 (9)	0.0143 (10)	−0.0004 (8)	−0.0023 (8)	−0.0024 (8)
C20	0.0192 (11)	0.0125 (9)	0.0130 (9)	−0.0030 (8)	0.0015 (8)	−0.0029 (7)
C21	0.0191 (11)	0.0172 (10)	0.0184 (10)	0.0027 (9)	−0.0016 (8)	−0.0032 (8)
C22	0.0243 (12)	0.0177 (10)	0.0126 (10)	0.0005 (9)	−0.0030 (8)	−0.0017 (8)
C23	0.0237 (12)	0.0172 (10)	0.0153 (10)	0.0033 (9)	−0.0009 (8)	0.0007 (8)
C24	0.0237 (12)	0.0196 (10)	0.0137 (10)	0.0009 (9)	−0.0033 (8)	−0.0028 (8)
Cu1	0.02865 (17)	0.00974 (14)	0.00785 (14)	0.00303 (10)	0.00027 (10)	0.00001 (8)
N1	0.0240 (10)	0.0120 (8)	0.0118 (8)	0.0010 (7)	−0.0002 (7)	0.0000 (6)
N2	0.0197 (10)	0.0259 (10)	0.0235 (9)	0.0012 (8)	−0.0014 (8)	−0.0136 (8)
N3	0.0189 (10)	0.0267 (10)	0.0254 (10)	0.0027 (8)	−0.0018 (8)	−0.0158 (8)
N4	0.0142 (9)	0.0146 (8)	0.0142 (8)	0.0000 (7)	−0.0001 (7)	−0.0035 (6)
N5	0.0139 (9)	0.0303 (10)	0.0235 (9)	0.0002 (8)	0.0006 (7)	−0.0095 (8)
N6	0.0239 (9)	0.0122 (8)	0.0111 (8)	−0.0007 (7)	0.0004 (7)	−0.0009 (6)
N7	0.0221 (10)	0.0131 (8)	0.0112 (8)	0.0022 (7)	−0.0002 (7)	0.0000 (6)
N8	0.0309 (10)	0.0177 (9)	0.0147 (8)	0.0022 (8)	0.0030 (8)	0.0049 (7)
N9	0.0282 (10)	0.0157 (8)	0.0143 (8)	0.0019 (7)	0.0022 (7)	0.0054 (7)
N10	0.0158 (9)	0.0144 (8)	0.0132 (8)	0.0002 (7)	−0.0002 (7)	0.0018 (6)
N11	0.0185 (9)	0.0145 (8)	0.0202 (9)	−0.0020 (7)	0.0007 (7)	−0.0016 (7)
N12	0.0244 (10)	0.0122 (8)	0.0115 (8)	−0.0012 (7)	−0.0007 (7)	0.0001 (6)
N13	0.0412 (13)	0.0256 (11)	0.0312 (11)	−0.0069 (10)	0.0119 (10)	0.0049 (9)
N14	0.0348 (13)	0.0403 (13)	0.0310 (11)	−0.0124 (10)	−0.0086 (10)	0.0035 (10)
O1	0.0267 (9)	0.0198 (8)	0.0288 (8)	−0.0002 (7)	−0.0008 (7)	−0.0045 (6)
O2	0.0674 (15)	0.0489 (12)	0.0585 (13)	−0.0036 (11)	−0.0185 (11)	0.0247 (10)
O3	0.0803 (16)	0.0719 (15)	0.0385 (11)	−0.0458 (13)	−0.0069 (11)	0.0179 (10)
O4	0.0648 (17)	0.111 (2)	0.0681 (16)	0.0302 (15)	0.0060 (13)	−0.0141 (15)
O5	0.0739 (15)	0.0366 (11)	0.0615 (13)	0.0151 (10)	0.0298 (12)	0.0036 (10)
O6	0.0460 (12)	0.0690 (13)	0.0284 (10)	−0.0157 (10)	0.0026 (8)	−0.0042 (9)
O7	0.0461 (12)	0.0601 (12)	0.0297 (10)	−0.0004 (10)	−0.0002 (9)	−0.0020 (9)
O8	0.0478 (12)	0.0448 (11)	0.0697 (14)	0.0051 (9)	0.0157 (11)	−0.0116 (10)
O9	0.0351 (11)	0.0593 (12)	0.0515 (11)	0.0003 (9)	0.0016 (9)	−0.0056 (10)
O10	0.0603 (14)	0.0425 (11)	0.0475 (12)	−0.0051 (10)	−0.0027 (10)	0.0042 (9)
O11	0.0785 (16)	0.0356 (10)	0.0561 (13)	0.0208 (10)	−0.0221 (12)	−0.0149 (9)
O12	0.0419 (11)	0.0376 (10)	0.0282 (9)	−0.0060 (8)	0.0062 (8)	−0.0015 (7)
O13	0.0440 (11)	0.0297 (9)	0.0348 (9)	0.0049 (8)	0.0001 (8)	−0.0017 (7)
O14	0.0592 (14)	0.0421 (12)	0.0840 (16)	−0.0117 (10)	0.0029 (12)	−0.0052 (11)
O15	0.0404 (10)	0.0259 (8)	0.0212 (8)	−0.0014 (7)	0.0022 (7)	0.0014 (6)
O16	0.0420 (12)	0.0689 (14)	0.0530 (12)	−0.0053 (10)	−0.0097 (9)	0.0126 (10)

Geometric parameters (Å, º)

C1—N12	1.343 (3)	C22—H22	0.9500
C1—C2	1.378 (3)	C23—N1	1.340 (3)
C1—H1	0.9500	C23—C24	1.378 (3)
C2—C3	1.391 (3)	C23—H23	0.9500
C2—H2	0.9500	C24—H24	0.9500
C3—C4	1.382 (3)	Cu1—N1	2.0104 (16)
C3—C6	1.465 (3)	Cu1—N12^i	2.0219 (16)
C4—C5	1.380 (3)	Cu1—N7	2.0231 (16)
C4—H4	0.9500	Cu1—N6^ii	2.0337 (16)
C5—N12	1.340 (3)	Cu1—O1	2.3569 (16)
C5—H5	0.9500	Cu1—O12	2.6034 (18)
C6—N9	1.314 (3)	N2—N3	1.384 (2)
C6—N10	1.355 (2)	N4—N5	1.401 (2)
C7—N8	1.316 (3)	N5—H5A	0.8988
C7—N10	1.358 (2)	N5—H5B	0.9083
C7—C8	1.470 (3)	N6—Cu1^iii	2.0337 (16)
C8—C9	1.380 (3)	N8—N9	1.378 (2)
C8—C12	1.381 (3)	N10—N11	1.410 (2)
C9—C10	1.378 (3)	N11—H11A	0.8550
C9—H9	0.9500	N11—H11B	0.9191
C10—N7	1.335 (3)	N12—Cu1^iv	2.0219 (16)
C10—H10	0.9500	N13—O5	1.236 (3)
C11—N7	1.337 (3)	N13—O6	1.238 (3)
C11—C12	1.381 (3)	N13—O7	1.252 (3)
C11—H11	0.9500	N14—O4	1.219 (3)
C12—H12	0.9500	N14—O3	1.232 (3)
C13—N6	1.341 (3)	N14—O2	1.232 (3)
C13—C14	1.372 (3)	O1—H1A	0.8439
C13—H13	0.9500	O1—H1B	0.8448
C14—C15	1.388 (3)	O8—H8A	0.8448
C14—H14	0.9500	O8—H8B	0.8485
C15—C16	1.380 (3)	O9—H9A	0.8477
C15—C18	1.470 (3)	O9—H9B	0.8456
C16—C17	1.379 (3)	O10—H10A	0.8481
C16—H16	0.9500	O10—H10B	0.8464
C17—N6	1.339 (3)	O11—H11C	0.8572
C17—H17	0.9500	O11—H11D	0.8552
C18—N3	1.310 (3)	O12—H12A	0.8518
C18—N4	1.353 (2)	O12—H12B	0.8484
C19—N2	1.302 (3)	O13—H13A	0.8482
C19—N4	1.369 (2)	O13—H13B	0.8470
C19—C20	1.467 (3)	O14—H14A	0.8526
C20—C24	1.389 (3)	O14—H14B	0.8522
C20—C21	1.390 (3)	O15—H15A	0.8500
C21—C22	1.379 (3)	O15—H15B	0.8463
C21—H21	0.9500	O16—H16B	0.8506
C22—N1	1.343 (3)	O16—H16A	0.8486
N12—C1—C2	122.52 (18)	C23—C24—C20	119.00 (18)
N12—C1—H1	118.7	C23—C24—H24	120.5
C2—C1—H1	118.7	C20—C24—H24	120.5
C1—C2—C3	118.91 (19)	N1—Cu1—N12^i	179.10 (7)
C1—C2—H2	120.5	N1—Cu1—N7	90.72 (7)
C3—C2—H2	120.5	N12^i—Cu1—N7	88.73 (6)
C4—C3—C2	118.62 (18)	N1—Cu1—N6^ii	91.80 (6)
C4—C3—C6	122.28 (18)	N12^i—Cu1—N6^ii	88.68 (7)
C2—C3—C6	118.81 (18)	N7—Cu1—N6^ii	173.79 (7)
C5—C4—C3	118.85 (18)	N1—Cu1—O1	90.66 (6)
C5—C4—H4	120.6	N12^i—Cu1—O1	90.08 (6)
C3—C4—H4	120.6	N7—Cu1—O1	91.78 (6)
N12—C5—C4	122.79 (19)	N6^ii—Cu1—O1	93.86 (6)
N12—C5—H5	118.6	N1—Cu1—O12	88.48 (6)
C4—C5—H5	118.6	N12^i—Cu1—O12	90.78 (6)
N9—C6—N10	110.21 (16)	N7—Cu1—O12	87.92 (6)
N9—C6—C3	122.64 (17)	N6^ii—Cu1—O12	86.47 (6)
N10—C6—C3	127.00 (17)	O1—Cu1—O12	179.09 (5)
N8—C7—N10	109.92 (17)	C23—N1—C22	118.19 (16)
N8—C7—C8	123.65 (17)	C23—N1—Cu1	120.04 (14)
N10—C7—C8	126.41 (18)	C22—N1—Cu1	121.78 (13)
C9—C8—C12	119.10 (18)	C19—N2—N3	107.46 (16)
C9—C8—C7	117.90 (18)	C18—N3—N2	107.32 (16)
C12—C8—C7	122.97 (18)	C18—N4—C19	105.38 (16)
C10—C9—C8	118.71 (19)	C18—N4—N5	122.93 (16)
C10—C9—H9	120.6	C19—N4—N5	130.69 (16)
C8—C9—H9	120.6	N4—N5—H5A	115.3
N7—C10—C9	122.74 (19)	N4—N5—H5B	108.1
N7—C10—H10	118.6	H5A—N5—H5B	106.5
C9—C10—H10	118.6	C17—N6—C13	117.52 (17)
N7—C11—C12	122.73 (19)	C17—N6—Cu1^iii	123.01 (13)
N7—C11—H11	118.6	C13—N6—Cu1^iii	119.47 (13)
C12—C11—H11	118.6	C10—N7—C11	118.19 (17)
C11—C12—C8	118.52 (19)	C10—N7—Cu1	118.60 (13)
C11—C12—H12	120.7	C11—N7—Cu1	122.99 (14)
C8—C12—H12	120.7	C7—N8—N9	107.35 (15)
N6—C13—C14	123.04 (18)	C6—N9—N8	107.14 (15)
N6—C13—H13	118.5	C6—N10—C7	105.37 (16)
C14—C13—H13	118.5	C6—N10—N11	125.85 (15)
C13—C14—C15	119.16 (19)	C7—N10—N11	128.70 (16)
C13—C14—H14	120.4	N10—N11—H11A	107.9
C15—C14—H14	120.4	N10—N11—H11B	105.3
C16—C15—C14	118.11 (18)	H11A—N11—H11B	109.1
C16—C15—C18	123.45 (18)	C5—N12—C1	118.07 (17)
C14—C15—C18	118.31 (18)	C5—N12—Cu1^iv	120.31 (14)
C17—C16—C15	119.22 (18)	C1—N12—Cu1^iv	121.03 (13)
C17—C16—H16	120.4	O5—N13—O6	121.6 (2)
C15—C16—H16	120.4	O5—N13—O7	119.6 (2)
N6—C17—C16	122.91 (19)	O6—N13—O7	118.7 (2)
N6—C17—H17	118.5	O4—N14—O3	120.8 (3)
C16—C17—H17	118.5	O4—N14—O2	119.4 (2)
N3—C18—N4	110.01 (17)	O3—N14—O2	119.6 (3)
N3—C18—C15	123.31 (17)	Cu1—O1—H1A	118.6
N4—C18—C15	126.68 (18)	Cu1—O1—H1B	127.3
N2—C19—N4	109.81 (17)	H1A—O1—H1B	113.8
N2—C19—C20	122.95 (18)	N13—O7—H5A	110.6
N4—C19—C20	127.15 (18)	H15B—O7—H5A	116.9
C24—C20—C21	118.22 (17)	H8A—O8—H8B	105.4
C24—C20—C19	123.63 (17)	H9A—O9—H9B	106.2
C21—C20—C19	118.15 (17)	H10A—O10—H10B	107.1
C22—C21—C20	119.30 (19)	H11C—O11—H11D	111.1
C22—C21—H21	120.4	Cu1—O12—H12A	125.2
C20—C21—H21	120.4	Cu1—O12—H12B	122.3
N1—C22—C21	122.41 (18)	H12A—O12—H12B	109.2
N1—C22—H22	118.8	H13A—O13—H13B	113.2
C21—C22—H22	118.8	H14A—O14—H14B	115.0
N1—C23—C24	122.85 (19)	H1A—O15—H15B	127.5
N1—C23—H23	118.6	H15A—O15—H15B	111.3
C24—C23—H23	118.6	H16B—O16—H16A	104.2
N12—C1—C2—C3	0.7 (3)	N4—C18—N3—N2	0.7 (2)
C1—C2—C3—C4	−4.2 (3)	C15—C18—N3—N2	−179.31 (17)
C1—C2—C3—C6	169.81 (19)	C19—N2—N3—C18	−0.1 (2)
C2—C3—C4—C5	3.5 (3)	N3—C18—N4—C19	−1.1 (2)
C6—C3—C4—C5	−170.34 (19)	C15—C18—N4—C19	178.95 (18)
C3—C4—C5—N12	0.8 (3)	N3—C18—N4—N5	−170.79 (17)
C4—C3—C6—N9	137.9 (2)	C15—C18—N4—N5	9.3 (3)
C2—C3—C6—N9	−35.9 (3)	N2—C19—N4—C18	1.1 (2)
C4—C3—C6—N10	−37.3 (3)	C20—C19—N4—C18	−175.49 (18)
C2—C3—C6—N10	148.9 (2)	N2—C19—N4—N5	169.64 (19)
N8—C7—C8—C9	56.2 (3)	C20—C19—N4—N5	−6.9 (3)
N10—C7—C8—C9	−121.9 (2)	C16—C17—N6—C13	0.6 (3)
N8—C7—C8—C12	−121.8 (2)	C16—C17—N6—Cu1^iii	−178.40 (15)
N10—C7—C8—C12	60.2 (3)	C14—C13—N6—C17	−1.5 (3)
C12—C8—C9—C10	0.3 (3)	C14—C13—N6—Cu1^iii	177.57 (17)
C7—C8—C9—C10	−177.69 (18)	C9—C10—N7—C11	−1.3 (3)
C8—C9—C10—N7	0.9 (3)	C9—C10—N7—Cu1	173.46 (15)
N7—C11—C12—C8	0.7 (3)	C12—C11—N7—C10	0.5 (3)
C9—C8—C12—C11	−1.1 (3)	C12—C11—N7—Cu1	−174.01 (16)
C7—C8—C12—C11	176.85 (19)	N1—Cu1—N7—C10	132.34 (15)
N6—C13—C14—C15	0.6 (3)	N12^i—Cu1—N7—C10	−48.38 (15)
C13—C14—C15—C16	1.2 (3)	O1—Cu1—N7—C10	41.66 (15)
C13—C14—C15—C18	−174.76 (19)	O12—Cu1—N7—C10	−139.20 (15)
C14—C15—C16—C17	−2.0 (3)	N1—Cu1—N7—C11	−53.15 (17)
C18—C15—C16—C17	173.73 (19)	N12^i—Cu1—N7—C11	126.13 (17)
C15—C16—C17—N6	1.1 (3)	O1—Cu1—N7—C11	−143.83 (16)
C16—C15—C18—N3	−130.0 (2)	O12—Cu1—N7—C11	35.30 (16)
C14—C15—C18—N3	45.7 (3)	N10—C7—N8—N9	−0.8 (2)
C16—C15—C18—N4	50.0 (3)	C8—C7—N8—N9	−179.11 (18)
C14—C15—C18—N4	−134.3 (2)	N10—C6—N9—N8	−0.6 (2)
N2—C19—C20—C24	149.0 (2)	C3—C6—N9—N8	−176.52 (18)
N4—C19—C20—C24	−34.9 (3)	C7—N8—N9—C6	0.9 (2)
N2—C19—C20—C21	−30.1 (3)	N9—C6—N10—C7	0.2 (2)
N4—C19—C20—C21	146.1 (2)	C3—C6—N10—C7	175.8 (2)
C24—C20—C21—C22	1.7 (3)	N9—C6—N10—N11	177.25 (17)
C19—C20—C21—C22	−179.22 (18)	C3—C6—N10—N11	−7.1 (3)
C20—C21—C22—N1	−0.2 (3)	N8—C7—N10—C6	0.4 (2)
N1—C23—C24—C20	−0.1 (3)	C8—C7—N10—C6	178.66 (19)
C21—C20—C24—C23	−1.6 (3)	N8—C7—N10—N11	−176.58 (18)
C19—C20—C24—C23	179.42 (18)	C8—C7—N10—N11	1.7 (3)
C24—C23—N1—C22	1.7 (3)	C4—C5—N12—C1	−4.3 (3)
C24—C23—N1—Cu1	−178.28 (15)	C4—C5—N12—Cu1^iv	166.99 (16)
C21—C22—N1—C23	−1.5 (3)	C2—C1—N12—C5	3.5 (3)
C21—C22—N1—Cu1	178.44 (15)	C2—C1—N12—Cu1^iv	−167.74 (16)
N7—Cu1—N1—C23	−51.78 (15)	O4—N14—O2—H5B	−20.6
N6^ii—Cu1—N1—C23	133.89 (15)	O3—N14—O2—H5B	162.9
O1—Cu1—N1—C23	40.00 (15)	O4—N14—O3—H9B	173.5
O12—Cu1—N1—C23	−139.69 (15)	O2—N14—O3—H9B	−10.1
N7—Cu1—N1—C22	128.28 (16)	O3—N14—O4—H14A	−159.2
N6^ii—Cu1—N1—C22	−46.05 (16)	O2—N14—O4—H14A	24.4
O1—Cu1—N1—C22	−139.93 (16)	O5—N13—O7—H15B	−167.7
O12—Cu1—N1—C22	40.38 (16)	O6—N13—O7—H15B	10.7
N4—C19—N2—N3	−0.6 (2)	O5—N13—O7—H5A	−29.0
C20—C19—N2—N3	176.08 (17)	O6—N13—O7—H5A	149.4

Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+5/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12B···O9^v	0.85	2.03	2.872 (3)	171
O13—H13B···O5^vi	0.85	2.04	2.881 (3)	169
O13—H13A···O11	0.85	1.85	2.688 (2)	169
O12—H12A···O13	0.85	2.02	2.861 (2)	170
O14—H14B···O3^vii	0.85	2.00	2.808 (3)	157
O8—H8B···O16	0.85	1.94	2.774 (3)	170
O8—H8A···O6^viii	0.84	2.04	2.871 (3)	166
O10—H10A···O14^vii	0.85	2.11	2.948 (3)	170
O9—H9A···O8^ix	0.85	1.89	2.724 (3)	166
O10—H10B···O9	0.85	2.02	2.824 (3)	158
O11—H11D···N9^x	0.86	2.05	2.906 (2)	174
O11—H11C···O10	0.86	1.95	2.787 (3)	164
N5—H5A···O7	0.90	2.14	3.010 (2)	163
O16—H16A···O15	0.85	1.96	2.806 (2)	171
O1—H1B···O13^viii	0.84	2.03	2.869 (2)	173
N5—H5B···O2	0.91	2.13	2.958 (3)	151
O15—H15B···O7	0.85	2.00	2.849 (2)	176
N11—H11B···N3^vi	0.92	2.08	2.900 (3)	148
O1—H1A···O15	0.84	1.97	2.804 (2)	172
O16—H16B···O14	0.85	2.26	3.102 (3)	169
O15—H15A···N8^xi	0.85	1.98	2.823 (2)	171
O14—H14A···O4	0.85	1.96	2.802 (3)	169

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