Synthesis and characterization of two novel bimetallic macrocyclic complexes generated from 1,2,4-triazole-containing semi-rigid ligands and M(NO₃)₂ units (M = Ni and Zn)

Bimetallic macrocyclic complexes have attracted the attention of chemists and various organic ligands have been used as mol­ecular building blocks, but supra­molecular complexes based on semi-rigid organic ligands containing 1,2,4-triazole have remained rare until recently. It is easier to obtain novel topologies by making use of asymmetric semi-rigid ligands in the self-assembly process than by making use of rigid ligands. A new semi-rigid ligand, 3-[(pyridin-4-yl­methyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine (L), has been synthesized and used to generate two novel bimetallic macrocycle complexes, namely bis­{μ-3-[(pyridin-4-yl­methyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-tri­azol-4-amine}­bis­[(methanol-κO)(nitrato-κ²O,O′)nickel(II)] dinitrate, [Ni₂(NO₃)₂(C₁₇H₁₄N₆S)₂(CH₃OH)₂](NO₃)₂, (I), and bis­{μ-3-[(pyridin-4-yl­methyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}­bis­[(methanol-κO)(nitrato-κ²O,O′)zinc(II)] di­nitrate, [Zn₂(NO₃)₂(C₁₇H₁₄N₆S)₂(CH₃OH)₂](NO₃)₂, (II), by solution reactions with the inorganic salts M(NO₃)₂ (M = Ni and Zn, respectively) in mixed solvents. In (I), two Ni^II cations with the same coordination environment are linked by L ligands through Ni—N bonds to form a bimetallic ring. Compound (I) is extended into a two-dimensional network in the crystallographic ac plane via N—H...O, O—H...N and O—H...O hydrogen bonds, and neighbouring two-dimensional planes are parallel and form a three-dimensional structure via π–π stacking. Compound (II) contains two bimetallic rings with the same coordination environment of the Zn^II cations. The Zn^II cations are bridged by L ligands through Zn—N bonds to form the bimetallic rings. One type of bimetallic ring constructs a one-dimensional nanotube via O—H...O and N—H...O hydrogen bonds along the crystallographic a direction, and the other constructs zero-dimensional mol­ecular cages via O—H...O and N—H...O hydrogen bonds. They are inter­linked into a two-dimensional network in the ac plane through extensive N—H...O hydrogen bonds, and a three-dimensional supra­molecular architecture is formed via π–π inter­actions between the centroids of the benzene rings of the quinoline ring systems.

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

(I) Bis{µ-3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-κO)(nitrato-κ²O,O') nickel(II)] dinitrate

Crystal data

[Ni2(NO3)2(C17H14N6S)2(CH4O)2](NO3)2	Z = 1
Mr = 1098.34	F(000) = 564
Triclinic, P1	Dx = 1.622 Mg m^−3
a = 9.4131 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9334 (7) Å	Cell parameters from 4292 reflections
c = 13.0829 (6) Å	θ = 3.9–28.5°
α = 77.650 (5)°	µ = 1.02 mm^−1
β = 83.824 (5)°	T = 100 K
γ = 70.284 (6)°	Block, clear light green
V = 1124.11 (12) Å^3	0.29 × 0.18 × 0.08 mm

Data collection

Agilent SuperNova Dual Source diffractometer with Eos detector	4594 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3976 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.023
Detector resolution: 16.0793 pixels mm^-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→12
Tmin = 0.907, Tmax = 1.000	l = −16→15
7894 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0247P)^2 + 0.6343P] where P = (Fo^2 + 2Fc^2)/3
4594 reflections	(Δ/σ)max = 0.001
317 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,16:31:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.4848 (2)	−0.0812 (2)	0.16190 (16)	0.0154 (5)
C2	0.5749 (2)	−0.2254 (2)	0.20181 (17)	0.0176 (5)
H2	0.5294	−0.2930	0.2368	0.021*
C3	0.7287 (2)	−0.2658 (3)	0.18920 (18)	0.0219 (5)
H3	0.7870	−0.3607	0.2162	0.026*
C4	0.7999 (3)	−0.1648 (3)	0.13556 (18)	0.0231 (5)
H4	0.9045	−0.1943	0.1263	0.028*
C5	0.7157 (2)	−0.0236 (3)	0.09716 (17)	0.0207 (5)
H5	0.7635	0.0422	0.0623	0.025*
C6	0.5570 (2)	0.0221 (3)	0.11040 (16)	0.0165 (5)
C7	0.4648 (2)	0.1677 (3)	0.07468 (16)	0.0182 (5)
H7	0.5086	0.2372	0.0408	0.022*
C8	0.3119 (2)	0.2055 (2)	0.09013 (16)	0.0171 (5)
H8	0.2505	0.3011	0.0685	0.021*
C9	0.2486 (2)	0.0973 (2)	0.13945 (16)	0.0141 (4)
C10	0.0869 (2)	0.1262 (2)	0.16618 (16)	0.0138 (4)
C11	−0.1536 (2)	0.2199 (2)	0.19911 (16)	0.0143 (4)
C12	−0.4301 (2)	0.2576 (3)	0.29624 (16)	0.0181 (5)
H12A	−0.5372	0.3120	0.2952	0.022*
H12B	−0.4173	0.1624	0.2816	0.022*
C13	−0.3757 (2)	0.2383 (2)	0.40446 (16)	0.0155 (5)
C14	−0.3585 (2)	0.3533 (3)	0.44177 (17)	0.0199 (5)
H14	−0.3799	0.4452	0.3994	0.024*
C15	−0.3097 (2)	0.3300 (2)	0.54162 (17)	0.0188 (5)
H15	−0.2992	0.4078	0.5654	0.023*
C16	−0.2939 (2)	0.0881 (2)	0.57046 (17)	0.0179 (5)
H16	−0.2723	−0.0028	0.6142	0.022*
C17	−0.3424 (2)	0.1040 (2)	0.47142 (17)	0.0186 (5)
H17	−0.3528	0.0248	0.4496	0.022*
C18	−0.0525 (3)	−0.2458 (3)	0.40587 (19)	0.0284 (6)
H18A	−0.0101	−0.3223	0.4636	0.043*
H18B	−0.1524	−0.2442	0.3952	0.043*
H18C	−0.0572	−0.1539	0.4210	0.043*
N1	0.32990 (19)	−0.04215 (19)	0.17446 (13)	0.0133 (4)
N2	0.03988 (19)	0.02663 (19)	0.22970 (13)	0.0143 (4)
N3	−0.11398 (19)	0.0846 (2)	0.25144 (14)	0.0155 (4)
N4	−0.03254 (19)	0.25038 (19)	0.14351 (13)	0.0137 (4)
N5	−0.0280 (2)	0.3818 (2)	0.07985 (14)	0.0197 (4)
H5A	−0.0308	0.4446	0.1200	0.030*
H5B	−0.1075	0.4183	0.0394	0.030*
N6	−0.27643 (19)	0.1986 (2)	0.60643 (14)	0.0158 (4)
N7	0.2698 (2)	−0.3583 (2)	0.12778 (14)	0.0174 (4)
N8	0.1402 (2)	0.3740 (2)	0.32742 (15)	0.0225 (4)
Ni1	0.19640 (3)	−0.17424 (3)	0.25010 (2)	0.01265 (8)
O2	0.17321 (16)	−0.23163 (16)	0.10154 (11)	0.0170 (3)
O3	0.33181 (16)	−0.38138 (16)	0.21469 (11)	0.0168 (3)
O4	0.30006 (18)	−0.45156 (18)	0.07358 (12)	0.0250 (4)
O5	0.04041 (16)	−0.27120 (17)	0.31305 (11)	0.0183 (3)
H5C	0.0540	−0.3556	0.3004	0.027*
O6	0.1513 (3)	0.2493 (2)	0.32338 (17)	0.0645 (8)
O7	0.21368 (18)	0.3999 (2)	0.38994 (13)	0.0283 (4)
O8	0.05204 (18)	0.47932 (18)	0.26555 (13)	0.0252 (4)
S1	−0.33258 (6)	0.35160 (6)	0.19261 (4)	0.01745 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0149 (11)	0.0214 (12)	0.0097 (10)	−0.0050 (9)	−0.0022 (8)	−0.0032 (9)
C2	0.0179 (12)	0.0187 (12)	0.0152 (11)	−0.0052 (9)	−0.0026 (8)	−0.0015 (9)
C3	0.0152 (12)	0.0259 (13)	0.0205 (12)	0.0006 (10)	−0.0058 (9)	−0.0053 (10)
C4	0.0125 (11)	0.0357 (15)	0.0215 (12)	−0.0062 (10)	−0.0006 (9)	−0.0089 (11)
C5	0.0203 (12)	0.0327 (14)	0.0153 (11)	−0.0150 (10)	−0.0007 (9)	−0.0070 (10)
C6	0.0212 (12)	0.0230 (12)	0.0093 (10)	−0.0108 (10)	−0.0015 (8)	−0.0047 (9)
C7	0.0241 (12)	0.0215 (12)	0.0126 (11)	−0.0126 (10)	−0.0009 (9)	−0.0026 (9)
C8	0.0225 (12)	0.0147 (11)	0.0144 (11)	−0.0067 (9)	−0.0040 (8)	−0.0004 (9)
C9	0.0152 (11)	0.0154 (11)	0.0111 (10)	−0.0038 (9)	−0.0023 (8)	−0.0026 (9)
C10	0.0162 (11)	0.0125 (11)	0.0118 (10)	−0.0030 (9)	−0.0022 (8)	−0.0024 (9)
C11	0.0142 (11)	0.0157 (11)	0.0126 (11)	−0.0037 (9)	−0.0021 (8)	−0.0029 (9)
C12	0.0131 (11)	0.0223 (12)	0.0171 (11)	−0.0038 (9)	−0.0004 (8)	−0.0035 (10)
C13	0.0106 (10)	0.0204 (12)	0.0137 (11)	−0.0031 (9)	0.0008 (8)	−0.0029 (9)
C14	0.0243 (12)	0.0134 (11)	0.0180 (12)	−0.0015 (9)	−0.0041 (9)	−0.0006 (9)
C15	0.0230 (12)	0.0133 (11)	0.0188 (12)	−0.0030 (9)	−0.0023 (9)	−0.0043 (9)
C16	0.0206 (12)	0.0127 (11)	0.0182 (12)	−0.0044 (9)	−0.0013 (9)	0.0005 (9)
C17	0.0192 (12)	0.0184 (12)	0.0206 (12)	−0.0077 (9)	−0.0001 (9)	−0.0062 (10)
C18	0.0265 (13)	0.0297 (15)	0.0261 (14)	−0.0091 (11)	0.0115 (10)	−0.0052 (11)
N1	0.0125 (9)	0.0154 (10)	0.0122 (9)	−0.0042 (7)	−0.0017 (7)	−0.0029 (7)
N2	0.0114 (9)	0.0147 (10)	0.0156 (9)	−0.0025 (7)	−0.0005 (7)	−0.0034 (8)
N3	0.0114 (9)	0.0157 (10)	0.0171 (9)	−0.0011 (7)	−0.0001 (7)	−0.0037 (8)
N4	0.0154 (9)	0.0098 (9)	0.0136 (9)	−0.0027 (7)	−0.0008 (7)	0.0005 (7)
N5	0.0225 (10)	0.0118 (10)	0.0198 (10)	−0.0028 (8)	−0.0023 (8)	0.0038 (8)
N6	0.0161 (9)	0.0131 (9)	0.0157 (9)	−0.0020 (7)	−0.0006 (7)	−0.0023 (8)
N7	0.0181 (10)	0.0165 (10)	0.0171 (10)	−0.0063 (8)	0.0030 (7)	−0.0031 (8)
N8	0.0293 (11)	0.0181 (11)	0.0171 (10)	−0.0047 (9)	0.0036 (8)	−0.0044 (8)
Ni1	0.01295 (15)	0.01106 (15)	0.01256 (15)	−0.00265 (11)	−0.00092 (10)	−0.00111 (11)
O2	0.0149 (8)	0.0150 (8)	0.0178 (8)	−0.0022 (6)	−0.0012 (6)	−0.0003 (6)
O3	0.0161 (8)	0.0159 (8)	0.0167 (8)	−0.0028 (6)	−0.0034 (6)	−0.0019 (6)
O4	0.0312 (10)	0.0224 (9)	0.0221 (9)	−0.0061 (7)	0.0037 (7)	−0.0118 (7)
O5	0.0202 (8)	0.0167 (8)	0.0186 (8)	−0.0080 (7)	0.0049 (6)	−0.0039 (7)
O6	0.128 (2)	0.0128 (10)	0.0513 (14)	−0.0079 (12)	−0.0434 (13)	−0.0069 (10)
O7	0.0277 (10)	0.0330 (11)	0.0253 (9)	−0.0126 (8)	−0.0054 (7)	−0.0008 (8)
O8	0.0235 (9)	0.0169 (9)	0.0319 (10)	−0.0030 (7)	−0.0098 (7)	0.0008 (7)
S1	0.0148 (3)	0.0165 (3)	0.0159 (3)	0.0007 (2)	−0.0015 (2)	−0.0011 (2)

Geometric parameters (Å, º)

C1—N1	1.377 (3)	C14—H14	0.9300
C1—C2	1.414 (3)	C15—N6	1.353 (3)
C1—C6	1.430 (3)	C15—H15	0.9300
C2—C3	1.367 (3)	C16—N6	1.346 (3)
C2—H2	0.9300	C16—C17	1.380 (3)
C3—C4	1.414 (3)	C16—H16	0.9300
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.372 (3)	C18—O5	1.434 (2)
C4—H4	0.9300	C18—H18A	0.9600
C5—C6	1.410 (3)	C18—H18B	0.9600
C5—H5	0.9300	C18—H18C	0.9600
C6—C7	1.419 (3)	N1—Ni1	2.1377 (18)
C7—C8	1.364 (3)	N2—N3	1.389 (2)
C7—H7	0.9300	N2—Ni1	2.0240 (17)
C8—C9	1.408 (3)	N4—N5	1.402 (2)
C8—H8	0.9300	N5—H5A	0.8900
C9—N1	1.342 (3)	N5—H5B	0.8900
C9—C10	1.467 (3)	N6—Ni1^i	2.0339 (18)
C10—N2	1.315 (3)	N7—O4	1.225 (2)
C10—N4	1.362 (3)	N7—O3	1.276 (2)
C11—N3	1.318 (3)	N7—O2	1.280 (2)
C11—N4	1.371 (3)	N8—O6	1.219 (3)
C11—S1	1.747 (2)	N8—O7	1.243 (3)
C12—C13	1.509 (3)	N8—O8	1.279 (2)
C12—S1	1.822 (2)	Ni1—O5	2.0290 (15)
C12—H12A	0.9700	Ni1—N6^i	2.0339 (18)
C12—H12B	0.9700	Ni1—O3	2.1411 (15)
C13—C17	1.386 (3)	Ni1—O2	2.1908 (15)
C13—C14	1.397 (3)	O5—H5C	0.8536
C14—C15	1.378 (3)
N1—C1—C2	119.7 (2)	C16—C17—H17	120.0
N1—C1—C6	121.26 (19)	C13—C17—H17	120.0
C2—C1—C6	119.04 (19)	O5—C18—H18A	109.5
C3—C2—C1	120.3 (2)	O5—C18—H18B	109.5
C3—C2—H2	119.9	H18A—C18—H18B	109.5
C1—C2—H2	119.9	O5—C18—H18C	109.5
C2—C3—C4	120.7 (2)	H18A—C18—H18C	109.5
C2—C3—H3	119.7	H18B—C18—H18C	109.5
C4—C3—H3	119.7	C9—N1—C1	117.91 (19)
C5—C4—C3	120.5 (2)	C9—N1—Ni1	113.71 (13)
C5—C4—H4	119.8	C1—N1—Ni1	128.32 (15)
C3—C4—H4	119.8	C10—N2—N3	109.34 (17)
C4—C5—C6	120.2 (2)	C10—N2—Ni1	113.40 (13)
C4—C5—H5	119.9	N3—N2—Ni1	136.25 (14)
C6—C5—H5	119.9	C11—N3—N2	105.29 (17)
C5—C6—C7	122.6 (2)	C10—N4—C11	105.28 (17)
C5—C6—C1	119.3 (2)	C10—N4—N5	126.26 (17)
C7—C6—C1	118.14 (19)	C11—N4—N5	128.41 (17)
C8—C7—C6	119.9 (2)	N4—N5—H5A	109.4
C8—C7—H7	120.1	N4—N5—H5B	109.2
C6—C7—H7	120.1	H5A—N5—H5B	109.5
C7—C8—C9	118.8 (2)	C16—N6—C15	117.49 (19)
C7—C8—H8	120.6	C16—N6—Ni1^i	123.11 (15)
C9—C8—H8	120.6	C15—N6—Ni1^i	119.37 (16)
N1—C9—C8	124.00 (19)	O4—N7—O3	122.17 (18)
N1—C9—C10	112.04 (19)	O4—N7—O2	122.40 (19)
C8—C9—C10	123.79 (19)	O3—N7—O2	115.43 (17)
N2—C10—N4	108.97 (18)	O6—N8—O7	121.1 (2)
N2—C10—C9	120.15 (18)	O6—N8—O8	119.1 (2)
N4—C10—C9	130.6 (2)	O7—N8—O8	119.8 (2)
N3—C11—N4	111.10 (17)	N2—Ni1—O5	92.37 (7)
N3—C11—S1	128.32 (16)	N2—Ni1—N6^i	103.63 (7)
N4—C11—S1	120.56 (16)	O5—Ni1—N6^i	91.55 (7)
C13—C12—S1	114.12 (16)	N2—Ni1—N1	78.70 (7)
C13—C12—H12A	108.7	O5—Ni1—N1	170.65 (6)
S1—C12—H12A	108.7	N6^i—Ni1—N1	93.23 (7)
C13—C12—H12B	108.7	N2—Ni1—O3	158.17 (7)
S1—C12—H12B	108.7	O5—Ni1—O3	86.66 (6)
H12A—C12—H12B	107.6	N6^i—Ni1—O3	98.20 (6)
C17—C13—C14	117.4 (2)	N1—Ni1—O3	100.58 (6)
C17—C13—C12	120.5 (2)	N2—Ni1—O2	98.34 (6)
C14—C13—C12	122.1 (2)	O5—Ni1—O2	87.30 (6)
C15—C14—C13	119.7 (2)	N6^i—Ni1—O2	158.03 (6)
C15—C14—H14	120.1	N1—Ni1—O2	91.24 (6)
C13—C14—H14	120.1	O3—Ni1—O2	59.83 (5)
N6—C15—C14	122.7 (2)	N7—O2—Ni1	91.08 (11)
N6—C15—H15	118.7	N7—O3—Ni1	93.48 (11)
C14—C15—H15	118.7	C18—O5—Ni1	126.36 (15)
N6—C16—C17	122.8 (2)	C18—O5—H5C	112.1
N6—C16—H16	118.6	Ni1—O5—H5C	116.8
C17—C16—H16	118.6	C11—S1—C12	98.93 (10)
C16—C17—C13	119.9 (2)
N1—C1—C2—C3	179.5 (2)	S1—C11—N4—C10	179.93 (15)
C6—C1—C2—C3	−1.4 (3)	N3—C11—N4—N5	−179.0 (2)
C1—C2—C3—C4	−0.5 (3)	S1—C11—N4—N5	2.3 (3)
C2—C3—C4—C5	1.3 (3)	C17—C16—N6—C15	0.5 (3)
C3—C4—C5—C6	−0.3 (3)	C17—C16—N6—Ni1^i	−177.29 (16)
C4—C5—C6—C7	178.3 (2)	C14—C15—N6—C16	−0.6 (3)
C4—C5—C6—C1	−1.5 (3)	C14—C15—N6—Ni1^i	177.32 (16)
N1—C1—C6—C5	−178.54 (19)	C10—N2—Ni1—O5	−164.80 (15)
C2—C1—C6—C5	2.4 (3)	N3—N2—Ni1—O5	2.0 (2)
N1—C1—C6—C7	1.6 (3)	C10—N2—Ni1—N6^i	103.02 (16)
C2—C1—C6—C7	−177.5 (2)	N3—N2—Ni1—N6^i	−90.1 (2)
C5—C6—C7—C8	−179.7 (2)	C10—N2—Ni1—N1	12.41 (15)
C1—C6—C7—C8	0.1 (3)	N3—N2—Ni1—N1	179.3 (2)
C6—C7—C8—C9	−1.5 (3)	C10—N2—Ni1—O3	−77.9 (2)
C7—C8—C9—N1	1.3 (3)	N3—N2—Ni1—O3	89.0 (2)
C7—C8—C9—C10	176.1 (2)	C10—N2—Ni1—O2	−77.19 (16)
N1—C9—C10—N2	8.7 (3)	N3—N2—Ni1—O2	89.7 (2)
C8—C9—C10—N2	−166.7 (2)	C9—N1—Ni1—N2	−8.05 (14)
N1—C9—C10—N4	−178.3 (2)	C1—N1—Ni1—N2	169.11 (18)
C8—C9—C10—N4	6.3 (4)	C9—N1—Ni1—O5	9.3 (5)
S1—C12—C13—C17	−132.14 (18)	C1—N1—Ni1—O5	−173.5 (3)
S1—C12—C13—C14	48.6 (2)	C9—N1—Ni1—N6^i	−111.31 (15)
C17—C13—C14—C15	0.2 (3)	C1—N1—Ni1—N6^i	65.85 (18)
C12—C13—C14—C15	179.45 (19)	C9—N1—Ni1—O3	149.72 (14)
C13—C14—C15—N6	0.2 (3)	C1—N1—Ni1—O3	−33.12 (18)
N6—C16—C17—C13	−0.1 (3)	C9—N1—Ni1—O2	90.21 (15)
C14—C13—C17—C16	−0.2 (3)	C1—N1—Ni1—O2	−92.63 (17)
C12—C13—C17—C16	−179.51 (19)	O4—N7—O2—Ni1	175.44 (18)
C8—C9—N1—C1	0.4 (3)	O3—N7—O2—Ni1	−4.15 (16)
C10—C9—N1—C1	−174.93 (17)	N2—Ni1—O2—N7	−177.13 (11)
C8—C9—N1—Ni1	177.91 (16)	O5—Ni1—O2—N7	−85.13 (11)
C10—C9—N1—Ni1	2.5 (2)	N6^i—Ni1—O2—N7	2.3 (2)
C2—C1—N1—C9	177.23 (19)	N1—Ni1—O2—N7	104.11 (11)
C6—C1—N1—C9	−1.9 (3)	O3—Ni1—O2—N7	2.58 (10)
C2—C1—N1—Ni1	0.2 (3)	O4—N7—O3—Ni1	−175.34 (17)
C6—C1—N1—Ni1	−178.92 (15)	O2—N7—O3—Ni1	4.26 (17)
N4—C10—N2—N3	−0.6 (2)	N2—Ni1—O3—N7	−1.8 (2)
C9—C10—N2—N3	173.82 (18)	O5—Ni1—O3—N7	86.21 (12)
N4—C10—N2—Ni1	169.81 (13)	N6^i—Ni1—O3—N7	177.30 (12)
C9—C10—N2—Ni1	−15.8 (3)	N1—Ni1—O3—N7	−87.83 (12)
N4—C11—N3—N2	1.0 (2)	O2—Ni1—O3—N7	−2.60 (10)
S1—C11—N3—N2	179.59 (16)	N2—Ni1—O5—C18	−60.18 (18)
C10—N2—N3—C11	−0.2 (2)	N6^i—Ni1—O5—C18	43.54 (18)
Ni1—N2—N3—C11	−167.45 (16)	N1—Ni1—O5—C18	−77.2 (4)
N2—C10—N4—C11	1.2 (2)	O3—Ni1—O5—C18	141.67 (17)
C9—C10—N4—C11	−172.5 (2)	O2—Ni1—O5—C18	−158.42 (17)
N2—C10—N4—N5	178.84 (19)	N3—C11—S1—C12	10.5 (2)
C9—C10—N4—N5	5.2 (4)	N4—C11—S1—C12	−171.04 (18)
N3—C11—N4—C10	−1.3 (2)	C13—C12—S1—C11	67.03 (18)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O8	0.89	2.27	3.050 (3)	147
N5—H5B···O4^ii	0.89	2.35	3.222 (3)	165
O5—H5C···O8^iii	0.85	1.80	2.646 (2)	171
O5—H5C···N8^iii	0.85	2.49	3.295 (3)	158
O5—H5C···O7^iii	0.85	2.50	3.114 (2)	130

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

(II) Bis{µ-3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-κO)(nitrato-κ²O,O') zinc(II)] dinitrate

Crystal data

[Zn2(NO3)2(C17H14N6S)2(CH4O)2](NO3)2	Z = 2
Mr = 1111.67	F(000) = 1136
Triclinic, P1	Dx = 1.669 Mg m^−3
a = 10.0414 (5) Å	Cu Kα radiation, λ = 1.54184 Å
b = 14.4893 (7) Å	Cell parameters from 6413 reflections
c = 15.6001 (8) Å	θ = 4.2–71.0°
α = 88.257 (4)°	µ = 2.97 mm^−1
β = 81.614 (4)°	T = 100 K
γ = 80.184 (4)°	Prism, colourless
V = 2212.53 (19) Å^3	0.21 × 0.07 × 0.04 mm

Data collection

Agilent SuperNova Dual Source diffractometer with Eos detector	7875 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	6746 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 16.0793 pixels mm^-1	θmax = 67.1°, θmin = 4.2°
ω scans	h = −11→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −17→17
Tmin = 0.784, Tmax = 1.000	l = −18→18
14520 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.060P)^2 + 1.4194P] where P = (Fo^2 + 2Fc^2)/3
7875 reflections	(Δ/σ)max = 0.001
633 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.82 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,16:31:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O9	0.0010 (2)	0.1910 (2)	0.05406 (15)	0.0528 (8)
C1	0.8354 (3)	0.32365 (18)	0.79060 (17)	0.0176 (6)
H1	0.9203	0.2853	0.7870	0.021*
C2	0.7678 (3)	0.35566 (19)	0.86972 (17)	0.0193 (6)
H2A	0.8072	0.3391	0.9196	0.023*
C3	0.6385 (3)	0.41373 (18)	0.87577 (17)	0.0189 (6)
H3A	0.5945	0.4365	0.9295	0.023*
C4	0.5777 (3)	0.43653 (18)	0.80385 (18)	0.0193 (6)
H4	0.4914	0.4732	0.8091	0.023*
C5	0.6444 (3)	0.40510 (18)	0.72091 (17)	0.0164 (6)
C6	0.7761 (3)	0.34889 (17)	0.71442 (17)	0.0149 (5)
C7	0.7882 (3)	0.34246 (17)	0.56490 (16)	0.0141 (5)
C8	0.6579 (3)	0.39678 (18)	0.56588 (18)	0.0180 (6)
H8A	0.6209	0.4114	0.5149	0.022*
C9	0.5870 (3)	0.42751 (18)	0.64442 (18)	0.0193 (6)
H9A	0.5004	0.4634	0.6471	0.023*
C10	0.8741 (3)	0.30341 (17)	0.48531 (17)	0.0140 (5)
C11	0.9589 (3)	0.25187 (17)	0.35641 (16)	0.0149 (5)
C12	1.1115 (3)	0.14148 (18)	0.23094 (17)	0.0170 (6)
H12A	1.1463	0.1344	0.1697	0.020*
H12B	1.1835	0.1572	0.2602	0.020*
C13	1.0732 (3)	0.05090 (18)	0.26652 (16)	0.0159 (5)
C14	1.1180 (3)	0.01082 (18)	0.34141 (17)	0.0168 (5)
H14A	1.1746	0.0395	0.3703	0.020*
C15	1.0782 (3)	−0.07191 (19)	0.37281 (17)	0.0184 (6)
H15	1.1096	−0.0980	0.4228	0.022*
C16	0.9520 (3)	−0.07797 (19)	0.26141 (17)	0.0198 (6)
H16	0.8950	−0.1079	0.2340	0.024*
C17	0.9884 (3)	0.00422 (19)	0.22601 (17)	0.0201 (6)
H17	0.9568	0.0285	0.1754	0.024*
C18	0.6390 (3)	−0.1720 (2)	0.4954 (2)	0.0360 (8)
H18A	0.6119	−0.2275	0.4763	0.054*
H18B	0.5630	−0.1215	0.4994	0.054*
H18C	0.6683	−0.1834	0.5512	0.054*
C19	0.3477 (3)	0.34179 (19)	0.27779 (18)	0.0197 (6)
H19	0.4335	0.3046	0.2736	0.024*
C20	0.2808 (3)	0.37392 (19)	0.35726 (18)	0.0219 (6)
H20	0.3224	0.3588	0.4065	0.026*
C21	0.1495 (3)	0.42958 (19)	0.36513 (18)	0.0236 (6)
H21	0.1051	0.4507	0.4193	0.028*
C22	0.0883 (3)	0.45210 (19)	0.29347 (18)	0.0221 (6)
H22	0.0017	0.4883	0.2991	0.026*
C23	0.1546 (3)	0.42135 (18)	0.20990 (18)	0.0187 (6)
C24	0.2858 (3)	0.36531 (17)	0.20217 (17)	0.0158 (5)
C25	0.2904 (3)	0.35376 (18)	0.05370 (17)	0.0156 (5)
C26	0.1614 (3)	0.40983 (19)	0.05595 (18)	0.0200 (6)
H26	0.1228	0.4240	0.0055	0.024*
C27	0.0938 (3)	0.44319 (19)	0.13474 (19)	0.0225 (6)
H27	0.0079	0.4802	0.1383	0.027*
C28	0.3671 (3)	0.30816 (18)	−0.02562 (16)	0.0147 (5)
C29	0.4354 (3)	0.24557 (17)	−0.15247 (16)	0.0155 (5)
C30	0.5747 (3)	0.12854 (18)	−0.28003 (17)	0.0186 (6)
H30A	0.6001	0.1191	−0.3419	0.022*
H30B	0.6514	0.1466	−0.2574	0.022*
C31	0.5434 (3)	0.03842 (18)	−0.23759 (17)	0.0158 (5)
C32	0.6022 (3)	0.00361 (18)	−0.16546 (17)	0.0169 (6)
H32	0.6623	0.0355	−0.1432	0.020*
C33	0.5710 (3)	−0.07837 (19)	−0.12699 (17)	0.0171 (6)
H33	0.6118	−0.1010	−0.0790	0.021*
C34	0.4268 (3)	−0.09315 (19)	−0.22595 (18)	0.0219 (6)
H34	0.3661	−0.1259	−0.2465	0.026*
C35	0.4543 (3)	−0.01180 (19)	−0.26837 (18)	0.0219 (6)
H35	0.4136	0.0090	−0.3169	0.026*
C62	0.7793 (4)	0.0800 (2)	0.0034 (2)	0.0449 (10)
H62A	0.8322	0.0392	0.0402	0.067*
H62B	0.8290	0.0795	−0.0540	0.067*
H62C	0.6942	0.0588	0.0018	0.067*
N1	0.9960 (2)	−0.11640 (15)	0.33417 (14)	0.0163 (5)
N2	1.0517 (2)	0.22035 (15)	0.40600 (14)	0.0158 (5)
N3	0.9955 (2)	0.25343 (15)	0.48816 (13)	0.0138 (4)
N4	0.8470 (2)	0.30474 (15)	0.40262 (14)	0.0148 (5)
N5	0.7219 (2)	0.34077 (17)	0.37356 (15)	0.0204 (5)
H5A	0.6797	0.2907	0.3638	0.024*
H5B	0.7402	0.3781	0.3257	0.024*
N6	0.8470 (2)	0.31887 (14)	0.63554 (14)	0.0136 (4)
N7	0.3530 (2)	0.33242 (15)	0.12322 (14)	0.0144 (5)
N8	0.4852 (2)	0.25269 (15)	−0.02394 (14)	0.0146 (5)
N9	0.5303 (2)	0.21180 (15)	−0.10474 (14)	0.0167 (5)
N10	0.3332 (2)	0.30683 (15)	−0.10648 (14)	0.0150 (5)
N11	0.2109 (2)	0.35226 (16)	−0.13419 (15)	0.0194 (5)
H11A	0.1625	0.3031	−0.1421	0.023*
H11B	0.2348	0.3792	−0.1865	0.023*
N12	0.4843 (2)	−0.12685 (15)	−0.15610 (14)	0.0163 (5)
N13	0.8108 (2)	−0.37585 (15)	0.35907 (14)	0.0171 (5)
N14	0.6875 (2)	0.37159 (16)	0.14884 (15)	0.0190 (5)
N15	0.0875 (3)	0.17909 (17)	−0.01357 (16)	0.0243 (5)
N16	0.7093 (2)	0.10437 (17)	0.46048 (15)	0.0202 (5)
O1	0.86417 (19)	−0.31119 (13)	0.31515 (12)	0.0191 (4)
O2	0.8159 (3)	−0.38048 (16)	0.43720 (13)	0.0353 (6)
O3	0.7588 (2)	−0.43063 (13)	0.32024 (13)	0.0218 (4)
O4	0.74837 (19)	−0.14797 (13)	0.43490 (12)	0.0205 (4)
H4A	0.7344	−0.0885	0.4102	0.025*
O5	0.7536 (2)	0.17212 (14)	0.03642 (14)	0.0282 (5)
H5	0.8277	0.2033	0.0340	0.034*
O6	0.6529 (2)	0.29791 (13)	0.18695 (13)	0.0235 (4)
O7	0.6601 (2)	0.38603 (17)	0.07346 (13)	0.0331 (5)
O8	0.7415 (2)	0.42477 (14)	0.18700 (13)	0.0232 (4)
O10	0.2092 (2)	0.15304 (16)	−0.00498 (16)	0.0360 (6)
O11	0.0502 (2)	0.19419 (16)	−0.08553 (13)	0.0312 (5)
O12	0.6843 (2)	0.17514 (14)	0.50813 (13)	0.0253 (5)
O13	0.7271 (3)	0.11297 (18)	0.38083 (14)	0.0413 (6)
O14	0.7157 (3)	0.02480 (14)	0.49573 (14)	0.0359 (6)
S1	0.96593 (7)	0.23574 (4)	0.24530 (4)	0.01697 (15)
S2	0.42808 (7)	0.22190 (4)	−0.26045 (4)	0.01849 (16)
Zn1	0.94009 (4)	−0.23344 (2)	0.39500 (2)	0.01448 (11)
Zn2	0.56310 (4)	0.24394 (2)	0.09007 (2)	0.01486 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O9	0.0269 (14)	0.112 (2)	0.0198 (12)	−0.0119 (14)	−0.0026 (10)	−0.0089 (13)
C1	0.0176 (15)	0.0160 (13)	0.0189 (13)	−0.0021 (11)	−0.0019 (11)	−0.0025 (10)
C2	0.0254 (16)	0.0162 (13)	0.0168 (13)	−0.0048 (11)	−0.0031 (11)	−0.0012 (10)
C3	0.0214 (15)	0.0167 (13)	0.0166 (13)	−0.0046 (11)	0.0061 (11)	−0.0058 (10)
C4	0.0172 (15)	0.0131 (13)	0.0248 (14)	−0.0010 (11)	0.0056 (11)	−0.0068 (11)
C5	0.0151 (14)	0.0119 (12)	0.0216 (14)	−0.0028 (10)	0.0012 (11)	−0.0054 (10)
C6	0.0173 (14)	0.0112 (12)	0.0162 (13)	−0.0044 (10)	0.0008 (10)	−0.0046 (10)
C7	0.0151 (14)	0.0121 (12)	0.0158 (13)	−0.0049 (10)	−0.0006 (10)	−0.0044 (10)
C8	0.0186 (15)	0.0169 (13)	0.0184 (13)	−0.0001 (11)	−0.0045 (11)	−0.0046 (10)
C9	0.0143 (14)	0.0155 (13)	0.0265 (15)	0.0010 (11)	−0.0009 (11)	−0.0051 (11)
C10	0.0154 (14)	0.0108 (12)	0.0166 (13)	−0.0023 (10)	−0.0039 (10)	−0.0030 (10)
C11	0.0173 (14)	0.0110 (12)	0.0154 (13)	−0.0024 (10)	0.0022 (10)	−0.0032 (10)
C12	0.0189 (15)	0.0164 (13)	0.0138 (12)	−0.0005 (11)	0.0013 (10)	−0.0017 (10)
C13	0.0142 (14)	0.0143 (13)	0.0155 (13)	0.0039 (10)	0.0042 (10)	−0.0052 (10)
C14	0.0122 (13)	0.0175 (13)	0.0208 (13)	−0.0022 (10)	−0.0021 (10)	−0.0051 (10)
C15	0.0192 (15)	0.0185 (14)	0.0170 (13)	0.0007 (11)	−0.0050 (11)	−0.0023 (10)
C16	0.0203 (15)	0.0204 (14)	0.0200 (14)	−0.0022 (11)	−0.0067 (11)	−0.0059 (11)
C17	0.0251 (16)	0.0184 (14)	0.0163 (13)	−0.0003 (11)	−0.0050 (11)	−0.0033 (10)
C18	0.0198 (17)	0.0251 (17)	0.058 (2)	−0.0014 (13)	0.0073 (15)	−0.0024 (15)
C19	0.0217 (15)	0.0159 (13)	0.0205 (14)	−0.0018 (11)	−0.0009 (11)	−0.0023 (10)
C20	0.0324 (17)	0.0161 (14)	0.0167 (13)	−0.0049 (12)	−0.0003 (12)	−0.0017 (10)
C21	0.0327 (18)	0.0171 (14)	0.0187 (14)	−0.0070 (12)	0.0088 (12)	−0.0073 (11)
C22	0.0248 (16)	0.0154 (14)	0.0238 (15)	−0.0031 (11)	0.0051 (12)	−0.0076 (11)
C23	0.0230 (15)	0.0118 (13)	0.0207 (14)	−0.0032 (11)	0.0000 (11)	−0.0055 (10)
C24	0.0187 (14)	0.0098 (12)	0.0184 (13)	−0.0035 (10)	0.0013 (11)	−0.0046 (10)
C25	0.0192 (15)	0.0116 (12)	0.0158 (13)	−0.0035 (10)	−0.0002 (11)	−0.0034 (10)
C26	0.0223 (15)	0.0180 (14)	0.0189 (14)	0.0017 (11)	−0.0052 (11)	−0.0049 (11)
C27	0.0181 (15)	0.0178 (14)	0.0289 (15)	0.0030 (11)	−0.0002 (12)	−0.0070 (11)
C28	0.0164 (14)	0.0124 (12)	0.0153 (13)	−0.0031 (10)	−0.0012 (10)	−0.0024 (10)
C29	0.0198 (15)	0.0114 (12)	0.0145 (12)	−0.0032 (10)	0.0020 (10)	−0.0053 (10)
C30	0.0241 (15)	0.0140 (13)	0.0156 (13)	0.0007 (11)	0.0006 (11)	−0.0030 (10)
C31	0.0132 (14)	0.0144 (13)	0.0167 (13)	0.0017 (10)	0.0044 (10)	−0.0064 (10)
C32	0.0131 (14)	0.0172 (13)	0.0201 (13)	−0.0022 (10)	−0.0003 (10)	−0.0054 (10)
C33	0.0135 (14)	0.0196 (14)	0.0180 (13)	0.0007 (11)	−0.0043 (10)	−0.0038 (10)
C34	0.0273 (16)	0.0175 (14)	0.0227 (14)	−0.0030 (12)	−0.0096 (12)	−0.0042 (11)
C35	0.0289 (17)	0.0181 (14)	0.0202 (14)	−0.0021 (12)	−0.0102 (12)	−0.0011 (11)
C62	0.039 (2)	0.041 (2)	0.054 (2)	0.0130 (16)	−0.0190 (18)	−0.0311 (18)
N1	0.0173 (12)	0.0131 (11)	0.0171 (11)	0.0011 (9)	−0.0009 (9)	−0.0046 (8)
N2	0.0173 (12)	0.0154 (11)	0.0139 (11)	−0.0024 (9)	0.0005 (9)	−0.0041 (8)
N3	0.0143 (12)	0.0141 (11)	0.0127 (10)	−0.0015 (9)	−0.0008 (8)	−0.0041 (8)
N4	0.0129 (12)	0.0160 (11)	0.0148 (11)	−0.0006 (9)	−0.0009 (9)	−0.0038 (8)
N5	0.0176 (13)	0.0231 (12)	0.0195 (12)	0.0028 (10)	−0.0065 (10)	−0.0024 (9)
N6	0.0121 (11)	0.0116 (10)	0.0166 (11)	−0.0017 (8)	0.0002 (9)	−0.0040 (8)
N7	0.0139 (12)	0.0123 (11)	0.0169 (11)	−0.0021 (9)	−0.0012 (9)	−0.0039 (8)
N8	0.0150 (12)	0.0140 (11)	0.0139 (11)	−0.0008 (9)	0.0004 (9)	−0.0054 (8)
N9	0.0201 (13)	0.0158 (11)	0.0135 (11)	−0.0014 (9)	−0.0008 (9)	−0.0049 (9)
N10	0.0158 (12)	0.0120 (11)	0.0162 (11)	0.0007 (9)	−0.0020 (9)	−0.0035 (8)
N11	0.0159 (12)	0.0235 (12)	0.0182 (11)	0.0007 (10)	−0.0050 (9)	−0.0033 (9)
N12	0.0170 (12)	0.0125 (11)	0.0185 (11)	0.0011 (9)	−0.0027 (9)	−0.0030 (9)
N13	0.0147 (12)	0.0166 (11)	0.0185 (12)	0.0009 (9)	−0.0009 (9)	−0.0053 (9)
N14	0.0135 (12)	0.0206 (12)	0.0211 (12)	0.0030 (9)	−0.0021 (9)	−0.0095 (9)
N15	0.0233 (14)	0.0261 (13)	0.0256 (13)	−0.0067 (10)	−0.0063 (11)	−0.0019 (10)
N16	0.0166 (12)	0.0244 (13)	0.0210 (12)	−0.0045 (10)	−0.0047 (9)	−0.0033 (10)
O1	0.0205 (11)	0.0182 (10)	0.0200 (10)	−0.0059 (8)	−0.0033 (8)	−0.0044 (8)
O2	0.0536 (16)	0.0397 (13)	0.0155 (11)	−0.0135 (11)	−0.0075 (10)	−0.0034 (9)
O3	0.0212 (11)	0.0193 (10)	0.0276 (11)	−0.0078 (8)	−0.0059 (8)	−0.0062 (8)
O4	0.0141 (10)	0.0195 (10)	0.0259 (10)	0.0010 (8)	0.0000 (8)	−0.0024 (8)
O5	0.0193 (11)	0.0252 (11)	0.0371 (12)	0.0000 (9)	0.0041 (9)	−0.0113 (9)
O6	0.0219 (11)	0.0187 (10)	0.0316 (11)	−0.0072 (8)	−0.0044 (9)	−0.0059 (8)
O7	0.0332 (13)	0.0488 (14)	0.0157 (10)	0.0027 (11)	−0.0077 (9)	−0.0070 (9)
O8	0.0249 (11)	0.0196 (10)	0.0277 (11)	−0.0054 (8)	−0.0093 (9)	−0.0048 (8)
O10	0.0177 (12)	0.0400 (14)	0.0524 (15)	−0.0051 (10)	−0.0133 (10)	0.0074 (11)
O11	0.0308 (13)	0.0442 (14)	0.0207 (11)	−0.0080 (10)	−0.0095 (9)	0.0010 (9)
O12	0.0281 (12)	0.0188 (10)	0.0289 (11)	−0.0043 (8)	−0.0017 (9)	−0.0064 (8)
O13	0.0585 (17)	0.0537 (16)	0.0175 (11)	−0.0257 (13)	−0.0051 (11)	−0.0031 (10)
O14	0.0570 (16)	0.0164 (11)	0.0367 (13)	−0.0047 (10)	−0.0157 (11)	−0.0015 (9)
S1	0.0219 (4)	0.0144 (3)	0.0127 (3)	0.0016 (3)	−0.0011 (2)	−0.0030 (2)
S2	0.0270 (4)	0.0139 (3)	0.0129 (3)	0.0019 (3)	−0.0028 (3)	−0.0040 (2)
Zn1	0.0147 (2)	0.01331 (19)	0.01557 (19)	−0.00140 (14)	−0.00285 (14)	−0.00415 (13)
Zn2	0.0161 (2)	0.01338 (19)	0.01497 (18)	−0.00124 (14)	−0.00262 (14)	−0.00371 (13)

Geometric parameters (Å, º)

O9—N15	1.261 (3)	C27—H27	0.9300
C1—C2	1.372 (4)	C28—N8	1.317 (3)
C1—C6	1.417 (4)	C28—N10	1.355 (3)
C1—H1	0.9300	C29—N9	1.315 (3)
C2—C3	1.414 (4)	C29—N10	1.367 (3)
C2—H2A	0.9300	C29—S2	1.744 (3)
C3—C4	1.359 (4)	C30—C31	1.506 (4)
C3—H3A	0.9300	C30—S2	1.818 (3)
C4—C5	1.417 (4)	C30—H30A	0.9700
C4—H4	0.9300	C30—H30B	0.9700
C5—C9	1.405 (4)	C31—C32	1.388 (4)
C5—C6	1.422 (4)	C31—C35	1.389 (4)
C6—N6	1.372 (3)	C32—C33	1.377 (4)
C7—N6	1.334 (3)	C32—H32	0.9300
C7—C8	1.406 (4)	C33—N12	1.343 (3)
C7—C10	1.473 (3)	C33—H33	0.9300
C8—C9	1.370 (4)	C34—N12	1.347 (4)
C8—H8A	0.9300	C34—C35	1.383 (4)
C9—H9A	0.9300	C34—H34	0.9300
C10—N3	1.313 (3)	C35—H35	0.9300
C10—N4	1.356 (3)	C62—O5	1.413 (4)
C11—N2	1.311 (3)	C62—H62A	0.9600
C11—N4	1.368 (3)	C62—H62B	0.9600
C11—S1	1.746 (3)	C62—H62C	0.9600
C12—C13	1.498 (4)	N1—Zn1	2.040 (2)
C12—S1	1.815 (3)	N2—N3	1.387 (3)
C12—H12A	0.9700	N3—Zn1^i	2.018 (2)
C12—H12B	0.9700	N4—N5	1.409 (3)
C13—C14	1.389 (4)	N5—H5A	0.9275
C13—C17	1.400 (4)	N5—H5B	0.9235
C14—C15	1.381 (4)	N6—Zn1^i	2.273 (2)
C14—H14A	0.9300	N7—Zn2	2.272 (2)
C15—N1	1.346 (4)	N8—N9	1.390 (3)
C15—H15	0.9300	N8—Zn2	2.037 (2)
C16—N1	1.348 (4)	N10—N11	1.411 (3)
C16—C17	1.381 (4)	N11—H11A	0.9485
C16—H16	0.9300	N11—H11B	0.9117
C17—H17	0.9300	N12—Zn2^ii	2.047 (2)
C18—O4	1.424 (4)	N13—O2	1.227 (3)
C18—H18A	0.9600	N13—O3	1.238 (3)
C18—H18B	0.9600	N13—O1	1.288 (3)
C18—H18C	0.9600	N14—O8	1.227 (3)
C19—C20	1.375 (4)	N14—O7	1.250 (3)
C19—C24	1.418 (4)	N14—O6	1.281 (3)
C19—H19	0.9300	N15—O11	1.236 (3)
C20—C21	1.414 (4)	N15—O10	1.241 (3)
C20—H20	0.9300	N16—O13	1.235 (3)
C21—C22	1.357 (4)	N16—O12	1.253 (3)
C21—H21	0.9300	N16—O14	1.258 (3)
C22—C23	1.422 (4)	O1—Zn1	2.0142 (18)
C22—H22	0.9300	O4—Zn1	2.1241 (18)
C23—C27	1.403 (4)	O4—H4A	0.9300
C23—C24	1.416 (4)	O5—Zn2	2.086 (2)
C24—N7	1.372 (3)	O5—H5	0.9300
C25—N7	1.334 (3)	O6—Zn2	2.102 (2)
C25—C26	1.403 (4)	O7—Zn2	2.415 (3)
C25—C28	1.470 (3)	Zn1—N3^i	2.018 (2)
C26—C27	1.373 (4)	Zn1—N6^i	2.273 (2)
C26—H26	0.9300	Zn2—N12^ii	2.047 (2)
C2—C1—C6	120.1 (3)	C32—C31—C30	120.6 (2)
C2—C1—H1	120.0	C35—C31—C30	121.4 (2)
C6—C1—H1	120.0	C33—C32—C31	119.7 (3)
C1—C2—C3	120.3 (3)	C33—C32—H32	120.1
C1—C2—H2A	119.9	C31—C32—H32	120.1
C3—C2—H2A	119.9	N12—C33—C32	122.6 (3)
C4—C3—C2	120.6 (2)	N12—C33—H33	118.7
C4—C3—H3A	119.7	C32—C33—H33	118.7
C2—C3—H3A	119.7	N12—C34—C35	122.7 (3)
C3—C4—C5	120.8 (3)	N12—C34—H34	118.6
C3—C4—H4	119.6	C35—C34—H34	118.6
C5—C4—H4	119.6	C34—C35—C31	119.2 (3)
C9—C5—C4	123.1 (3)	C34—C35—H35	120.4
C9—C5—C6	118.2 (2)	C31—C35—H35	120.4
C4—C5—C6	118.6 (2)	O5—C62—H62A	109.5
N6—C6—C1	119.4 (2)	O5—C62—H62B	109.5
N6—C6—C5	121.1 (2)	H62A—C62—H62B	109.5
C1—C6—C5	119.5 (2)	O5—C62—H62C	109.5
N6—C7—C8	124.2 (2)	H62A—C62—H62C	109.5
N6—C7—C10	112.3 (2)	H62B—C62—H62C	109.5
C8—C7—C10	123.5 (2)	C15—N1—C16	117.8 (2)
C9—C8—C7	117.8 (3)	C15—N1—Zn1	116.67 (18)
C9—C8—H8A	121.1	C16—N1—Zn1	125.39 (19)
C7—C8—H8A	121.1	C11—N2—N3	105.0 (2)
C8—C9—C5	120.4 (3)	C10—N3—N2	109.6 (2)
C8—C9—H9A	119.8	C10—N3—Zn1^i	117.57 (17)
C5—C9—H9A	119.8	N2—N3—Zn1^i	132.71 (17)
N3—C10—N4	108.6 (2)	C10—N4—C11	105.5 (2)
N3—C10—C7	120.9 (2)	C10—N4—N5	126.7 (2)
N4—C10—C7	130.4 (2)	C11—N4—N5	127.1 (2)
N2—C11—N4	111.3 (2)	N4—N5—H5A	108.0
N2—C11—S1	128.3 (2)	N4—N5—H5B	107.7
N4—C11—S1	120.4 (2)	H5A—N5—H5B	115.0
C13—C12—S1	111.22 (19)	C7—N6—C6	118.2 (2)
C13—C12—H12A	109.4	C7—N6—Zn1^i	112.87 (16)
S1—C12—H12A	109.4	C6—N6—Zn1^i	128.88 (18)
C13—C12—H12B	109.4	C25—N7—C24	118.0 (2)
S1—C12—H12B	109.4	C25—N7—Zn2	112.55 (16)
H12A—C12—H12B	108.0	C24—N7—Zn2	129.41 (18)
C14—C13—C17	117.4 (3)	C28—N8—N9	109.5 (2)
C14—C13—C12	121.6 (2)	C28—N8—Zn2	116.80 (17)
C17—C13—C12	121.0 (2)	N9—N8—Zn2	133.66 (17)
C15—C14—C13	119.6 (3)	C29—N9—N8	105.0 (2)
C15—C14—H14A	120.2	C28—N10—C29	105.7 (2)
C13—C14—H14A	120.2	C28—N10—N11	126.6 (2)
N1—C15—C14	122.9 (3)	C29—N10—N11	127.4 (2)
N1—C15—H15	118.6	N10—N11—H11A	104.5
C14—C15—H15	118.6	N10—N11—H11B	106.7
N1—C16—C17	122.4 (3)	H11A—N11—H11B	109.3
N1—C16—H16	118.8	C33—N12—C34	117.9 (2)
C17—C16—H16	118.8	C33—N12—Zn2^ii	119.40 (18)
C16—C17—C13	119.8 (3)	C34—N12—Zn2^ii	122.67 (19)
C16—C17—H17	120.1	O2—N13—O3	123.5 (2)
C13—C17—H17	120.1	O2—N13—O1	118.0 (2)
O4—C18—H18A	109.5	O3—N13—O1	118.5 (2)
O4—C18—H18B	109.5	O8—N14—O7	123.5 (3)
H18A—C18—H18B	109.5	O8—N14—O6	120.2 (2)
O4—C18—H18C	109.5	O7—N14—O6	116.4 (2)
H18A—C18—H18C	109.5	O11—N15—O10	122.1 (3)
H18B—C18—H18C	109.5	O11—N15—O9	120.0 (3)
C20—C19—C24	120.0 (3)	O10—N15—O9	117.9 (3)
C20—C19—H19	120.0	O13—N16—O12	120.5 (2)
C24—C19—H19	120.0	O13—N16—O14	121.0 (2)
C19—C20—C21	120.9 (3)	O12—N16—O14	118.4 (2)
C19—C20—H20	119.6	N13—O1—Zn1	109.55 (15)
C21—C20—H20	119.6	C18—O4—Zn1	126.92 (18)
C22—C21—C20	119.8 (3)	C18—O4—H4A	116.5
C22—C21—H21	120.1	Zn1—O4—H4A	116.5
C20—C21—H21	120.1	C62—O5—Zn2	125.4 (2)
C21—C22—C23	121.1 (3)	C62—O5—H5	117.3
C21—C22—H22	119.4	Zn2—O5—H5	117.3
C23—C22—H22	119.4	N14—O6—Zn2	100.56 (16)
C27—C23—C24	118.6 (2)	N14—O7—Zn2	86.72 (17)
C27—C23—C22	122.4 (3)	C11—S1—C12	97.95 (12)
C24—C23—C22	119.0 (3)	C29—S2—C30	99.36 (13)
N7—C24—C23	121.3 (2)	O1—Zn1—N3^i	135.43 (8)
N7—C24—C19	119.6 (2)	O1—Zn1—N1	111.59 (8)
C23—C24—C19	119.2 (2)	N3^i—Zn1—N1	111.92 (9)
N7—C25—C26	124.0 (2)	O1—Zn1—O4	93.77 (8)
N7—C25—C28	113.0 (2)	N3^i—Zn1—O4	98.42 (8)
C26—C25—C28	122.9 (2)	N1—Zn1—O4	85.96 (8)
C27—C26—C25	118.2 (3)	O1—Zn1—N6^i	92.05 (8)
C27—C26—H26	120.9	N3^i—Zn1—N6^i	76.25 (8)
C25—C26—H26	120.9	N1—Zn1—N6^i	93.36 (8)
C26—C27—C23	119.9 (3)	O4—Zn1—N6^i	173.96 (7)
C26—C27—H27	120.1	N8—Zn2—N12^ii	109.00 (9)
C23—C27—H27	120.1	N8—Zn2—O5	94.14 (9)
N8—C28—N10	108.6 (2)	N12^ii—Zn2—O5	91.60 (9)
N8—C28—C25	120.8 (2)	N8—Zn2—O6	153.19 (8)
N10—C28—C25	130.5 (2)	N12^ii—Zn2—O6	97.28 (8)
N9—C29—N10	111.2 (2)	O5—Zn2—O6	90.19 (8)
N9—C29—S2	128.6 (2)	N8—Zn2—N7	76.29 (8)
N10—C29—S2	120.2 (2)	N12^ii—Zn2—N7	95.83 (8)
C31—C30—S2	111.13 (19)	O5—Zn2—N7	169.39 (8)
C31—C30—H30A	109.4	O6—Zn2—N7	96.35 (8)
S2—C30—H30A	109.4	N8—Zn2—O7	97.34 (8)
C31—C30—H30B	109.4	N12^ii—Zn2—O7	153.63 (8)
S2—C30—H30B	109.4	O5—Zn2—O7	87.72 (8)
H30A—C30—H30B	108.0	O6—Zn2—O7	56.37 (7)
C32—C31—C35	117.9 (3)	N7—Zn2—O7	88.97 (8)
C6—C1—C2—C3	0.2 (4)	C23—C24—N7—C25	−0.9 (4)
C1—C2—C3—C4	1.8 (4)	C19—C24—N7—C25	178.3 (2)
C2—C3—C4—C5	−2.0 (4)	C23—C24—N7—Zn2	178.96 (18)
C3—C4—C5—C9	−179.2 (3)	C19—C24—N7—Zn2	−1.9 (4)
C3—C4—C5—C6	0.2 (4)	N10—C28—N8—N9	−1.2 (3)
C2—C1—C6—N6	177.9 (2)	C25—C28—N8—N9	174.4 (2)
C2—C1—C6—C5	−2.0 (4)	N10—C28—N8—Zn2	178.62 (16)
C9—C5—C6—N6	1.4 (4)	C25—C28—N8—Zn2	−5.7 (3)
C4—C5—C6—N6	−178.0 (2)	N10—C29—N9—N8	0.8 (3)
C9—C5—C6—C1	−178.8 (2)	S2—C29—N9—N8	−179.4 (2)
C4—C5—C6—C1	1.8 (4)	C28—N8—N9—C29	0.2 (3)
N6—C7—C8—C9	0.1 (4)	Zn2—N8—N9—C29	−179.54 (19)
C10—C7—C8—C9	178.7 (2)	N8—C28—N10—C29	1.6 (3)
C7—C8—C9—C5	0.2 (4)	C25—C28—N10—C29	−173.4 (3)
C4—C5—C9—C8	178.5 (3)	N8—C28—N10—N11	176.0 (2)
C6—C5—C9—C8	−0.9 (4)	C25—C28—N10—N11	0.9 (4)
N6—C7—C10—N3	−1.5 (4)	N9—C29—N10—C28	−1.6 (3)
C8—C7—C10—N3	179.7 (2)	S2—C29—N10—C28	178.64 (19)
N6—C7—C10—N4	174.0 (3)	N9—C29—N10—N11	−175.8 (2)
C8—C7—C10—N4	−4.8 (4)	S2—C29—N10—N11	4.4 (4)
S1—C12—C13—C14	−109.0 (3)	C32—C33—N12—C34	0.3 (4)
S1—C12—C13—C17	69.9 (3)	C32—C33—N12—Zn2^ii	−176.59 (19)
C17—C13—C14—C15	−0.1 (4)	C35—C34—N12—C33	0.4 (4)
C12—C13—C14—C15	178.8 (2)	C35—C34—N12—Zn2^ii	177.1 (2)
C13—C14—C15—N1	−0.4 (4)	O2—N13—O1—Zn1	−0.9 (3)
N1—C16—C17—C13	−0.5 (4)	O3—N13—O1—Zn1	179.97 (17)
C14—C13—C17—C16	0.5 (4)	O8—N14—O6—Zn2	177.93 (19)
C12—C13—C17—C16	−178.4 (2)	O7—N14—O6—Zn2	−0.3 (2)
C24—C19—C20—C21	0.7 (4)	O8—N14—O7—Zn2	−177.9 (2)
C19—C20—C21—C22	−0.2 (4)	O6—N14—O7—Zn2	0.3 (2)
C20—C21—C22—C23	−0.6 (4)	N2—C11—S1—C12	14.3 (3)
C21—C22—C23—C27	179.7 (3)	N4—C11—S1—C12	−167.1 (2)
C21—C22—C23—C24	0.8 (4)	C13—C12—S1—C11	74.5 (2)
C27—C23—C24—N7	−0.2 (4)	N9—C29—S2—C30	7.0 (3)
C22—C23—C24—N7	178.8 (2)	N10—C29—S2—C30	−173.3 (2)
C27—C23—C24—C19	−179.3 (3)	C31—C30—S2—C29	74.8 (2)
C22—C23—C24—C19	−0.3 (4)	N13—O1—Zn1—N3^i	23.2 (2)
C20—C19—C24—N7	−179.6 (2)	N13—O1—Zn1—N1	−170.02 (15)
C20—C19—C24—C23	−0.5 (4)	N13—O1—Zn1—O4	−82.87 (16)
N7—C25—C26—C27	−1.5 (4)	N13—O1—Zn1—N6^i	95.55 (16)
C28—C25—C26—C27	175.0 (3)	C15—N1—Zn1—O1	−163.84 (18)
C25—C26—C27—C23	0.4 (4)	C16—N1—Zn1—O1	19.6 (2)
C24—C23—C27—C26	0.4 (4)	C15—N1—Zn1—N3^i	6.2 (2)
C22—C23—C27—C26	−178.6 (3)	C16—N1—Zn1—N3^i	−170.3 (2)
N7—C25—C28—N8	−0.1 (4)	C15—N1—Zn1—O4	103.70 (19)
C26—C25—C28—N8	−176.9 (2)	C16—N1—Zn1—O4	−72.8 (2)
N7—C25—C28—N10	174.5 (3)	C15—N1—Zn1—N6^i	−70.29 (19)
C26—C25—C28—N10	−2.4 (4)	C16—N1—Zn1—N6^i	113.2 (2)
S2—C30—C31—C32	−108.9 (2)	C18—O4—Zn1—O1	77.4 (2)
S2—C30—C31—C35	70.4 (3)	C18—O4—Zn1—N3^i	−59.6 (2)
C35—C31—C32—C33	0.0 (4)	C18—O4—Zn1—N1	−171.2 (2)
C30—C31—C32—C33	179.3 (2)	C18—O4—Zn1—N6^i	−87.4 (8)
C31—C32—C33—N12	−0.5 (4)	C28—N8—Zn2—N12^ii	97.6 (2)
N12—C34—C35—C31	−0.8 (4)	N9—N8—Zn2—N12^ii	−82.6 (2)
C32—C31—C35—C34	0.6 (4)	C28—N8—Zn2—O5	−169.24 (19)
C30—C31—C35—C34	−178.7 (2)	N9—N8—Zn2—O5	10.5 (2)
C14—C15—N1—C16	0.4 (4)	C28—N8—Zn2—O6	−70.6 (3)
C14—C15—N1—Zn1	−176.4 (2)	N9—N8—Zn2—O6	109.2 (3)
C17—C16—N1—C15	0.1 (4)	C28—N8—Zn2—N7	6.12 (18)
C17—C16—N1—Zn1	176.6 (2)	N9—N8—Zn2—N7	−174.1 (2)
N4—C11—N2—N3	1.0 (3)	C28—N8—Zn2—O7	−81.01 (19)
S1—C11—N2—N3	179.68 (19)	N9—N8—Zn2—O7	98.7 (2)
N4—C10—N3—N2	0.0 (3)	C62—O5—Zn2—N8	−67.1 (3)
C7—C10—N3—N2	176.4 (2)	C62—O5—Zn2—N12^ii	42.1 (3)
N4—C10—N3—Zn1^i	−176.95 (16)	C62—O5—Zn2—O6	139.3 (3)
C7—C10—N3—Zn1^i	−0.6 (3)	C62—O5—Zn2—N7	−92.4 (5)
C11—N2—N3—C10	−0.6 (3)	C62—O5—Zn2—O7	−164.3 (3)
C11—N2—N3—Zn1^i	175.75 (18)	N14—O6—Zn2—N8	−12.3 (3)
N3—C10—N4—C11	0.5 (3)	N14—O6—Zn2—N12^ii	178.94 (15)
C7—C10—N4—C11	−175.4 (3)	N14—O6—Zn2—O5	87.31 (15)
N3—C10—N4—N5	171.8 (2)	N14—O6—Zn2—N7	−84.32 (15)
C7—C10—N4—N5	−4.1 (4)	N14—O6—Zn2—O7	0.18 (14)
N2—C11—N4—C10	−1.0 (3)	C25—N7—Zn2—N8	−6.14 (17)
S1—C11—N4—C10	−179.79 (19)	C24—N7—Zn2—N8	174.0 (2)
N2—C11—N4—N5	−172.2 (2)	C25—N7—Zn2—N12^ii	−114.32 (18)
S1—C11—N4—N5	9.0 (4)	C24—N7—Zn2—N12^ii	65.9 (2)
C8—C7—N6—C6	0.3 (4)	C25—N7—Zn2—O5	19.9 (5)
C10—C7—N6—C6	−178.4 (2)	C24—N7—Zn2—O5	−160.0 (4)
C8—C7—N6—Zn1^i	−178.7 (2)	C25—N7—Zn2—O6	147.65 (18)
C10—C7—N6—Zn1^i	2.6 (3)	C24—N7—Zn2—O6	−32.2 (2)
C1—C6—N6—C7	179.1 (2)	C25—N7—Zn2—O7	91.67 (18)
C5—C6—N6—C7	−1.1 (4)	C24—N7—Zn2—O7	−88.2 (2)
C1—C6—N6—Zn1^i	−2.1 (3)	N14—O7—Zn2—N8	174.19 (15)
C5—C6—N6—Zn1^i	177.72 (18)	N14—O7—Zn2—N12^ii	−2.9 (3)
C26—C25—N7—C24	1.7 (4)	N14—O7—Zn2—O5	−91.93 (15)
C28—C25—N7—C24	−175.1 (2)	N14—O7—Zn2—O6	−0.18 (14)
C26—C25—N7—Zn2	−178.1 (2)	N14—O7—Zn2—N7	98.15 (15)
C28—C25—N7—Zn2	5.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O1^ii	0.91	2.65	3.125 (3)	113
N11—H11B···O3^ii	0.91	2.19	3.077 (3)	164
O5—H5···N15^iii	0.93	2.57	3.348 (3)	141
O5—H5···O9^iii	0.93	1.79	2.600 (3)	144
N5—H5B···O8	0.92	2.25	3.113 (3)	156
N5—H5A···O13	0.93	2.55	3.291 (3)	137
N11—H11A···O11	0.95	2.18	3.037 (3)	149
O4—H4A···O14	0.93	2.11	2.655 (3)	116

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