Synthesis, crystal structures and luminescence properties of seven mononuclear zinc(II), cadmium(II), cobalt(II) and nickel(II) complexes with 5-(4-methyl­phenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole

Due to their versatile coordination modes and metal-binding conformations, triazolyl ligands can provide a wide range of possibilities for the construction of supra­molecular structures. Seven mononuclear transition metal complexes with different structural forms, namely aquabis­[3-(4-methyl­phenyl)-5-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(H₂O)], (I), bis­[5-(4-methyl­phenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N³,N⁴]bis(nitrato-κO)zinc(II), [Zn(NO₃)₂(C₁₄H₁₂N₄)₂], (II), bis(methanol-κO)bis­[3-(4-methyl­phenyl)-5-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(CH₄O)₂], (III), di­io­dido­bis­[5-(4-methyl­phenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N³,N⁴]cadmium(II), [CdI₂(C₁₄H₁₂N₄)₂], (IV), bis­[5-(4-methyl­phenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N³,N⁴]bis(nitrato-κO)cadmium(II), [Cd(NO₃)₂(C₁₄H₁₂N₄)₂], (V), aquabis­[3-(4-methyl­phenyl)-5-(pyridin-2-yl)-1H-1,2,4-tria­zol­ato-κ²N¹,N⁵]co­balt(II), [Co(C₁₄H₁₁N₄)₂(H₂O)], (VI), and diaquabis­[3-(4-methyl­phenyl)-5-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]nickel(II), [Ni(C₁₄H₁₁N₄)₂(H₂O)₂], (VII), have been prepared by the reaction of transition metal salts (Zn^II, Cd^II, Co^II and Ni^II) with 3-(4-methyl­phenyl)-5-(pyridin-2-yl)-1H-1,2,4-triazole (pymphtzH) under either ambient or hydro­thermal conditions. These compounds have been characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. All the complexes form three-dimensional supra­molecular structures through hydrogen bonds or through π–π stacking inter­actions between the centroids of the pyridyl or arene rings. The pymphtzH and pymphtz⁻ entities act as bidentate coordinating ligands in each structure. Moreover, all the pyridyl N atoms are coordinated to metal atoms (Zn, Cd, Co or Ni). The N atom in the 4-position of the triazole group is coordinated to the Zn and Cd atoms in the crystal structures of (II), (IV) and (V), while the N atom in the 1-position of the triazolate group is coordinated to the Zn, Co and Ni atoms in (I), (III), (VI) and (VII).

Computing details

For all compounds, data collection: CrystalStructure (Rigaku/MSC, 2006); cell refinement: CrystalStructure (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXL2014/7 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXL2014/7 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

(I) Aquabis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]zinc(II)

Crystal data

[Zn(C14H11N4)2(H2O)]	F(000) = 1144
Mr = 553.94	Dx = 1.473 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 28.730 (6) Å	Cell parameters from 11889 reflections
b = 7.5129 (15) Å	θ = 3.1–25.0°
c = 12.476 (3) Å	µ = 1.02 mm^−1
β = 111.97 (3)°	T = 293 K
V = 2497.3 (11) Å^3	Block, colourless
Z = 4	0.30 × 0.27 × 0.25 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1422 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.098
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan ABSCOR	h = −34→34
Tmin = 0.743, Tmax = 0.774	k = −8→8
9211 measured reflections	l = −14→14
2194 independent 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0716P)^2] where P = (Fo^2 + 2Fc^2)/3
2194 reflections	(Δ/σ)max < 0.001
177 parameters	Δρmax = 0.42 e Å^−3
1 restraint	Δρmin = −0.63 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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.0000	0.38474 (10)	0.7500	0.0521 (3)
N1	0.03174 (14)	0.2829 (5)	0.9088 (3)	0.0512 (10)
N2	0.08020 (14)	0.2435 (5)	0.9822 (3)	0.0540 (10)
N3	0.06436 (14)	0.3620 (5)	0.6965 (3)	0.0485 (9)
N4	0.02756 (14)	0.2102 (5)	1.0789 (3)	0.0487 (10)
O1W	0.0000	0.6501 (6)	0.7500	0.0698 (14)
H1WA	−0.0090 (15)	0.721 (4)	0.788 (3)	0.105*
C1	0.00230 (17)	0.2630 (6)	0.9692 (4)	0.0464 (11)
C2	0.07519 (17)	0.2014 (6)	1.0818 (4)	0.0468 (11)
C3	0.05145 (17)	0.2975 (6)	0.5873 (4)	0.0456 (11)
C4	0.08626 (18)	0.2672 (6)	0.5381 (4)	0.0564 (13)
H4	0.0766	0.2229	0.4633	0.068*
C5	0.13637 (19)	0.3045 (7)	0.6031 (4)	0.0660 (14)
H5	0.1608	0.2845	0.5724	0.079*
C6	0.14941 (19)	0.3710 (7)	0.7130 (4)	0.0624 (13)
H6	0.1826	0.3995	0.7571	0.075*
C7	0.11251 (19)	0.3946 (6)	0.7561 (4)	0.0572 (13)
H7	0.1217	0.4358	0.8315	0.069*
C8	0.11915 (17)	0.1484 (6)	1.1852 (4)	0.0478 (11)
C9	0.11328 (18)	0.0706 (6)	1.2800 (4)	0.0524 (12)
H9	0.0812	0.0509	1.2793	0.063*
C10	0.15490 (19)	0.0218 (6)	1.3759 (4)	0.0573 (13)
H10	0.1501	−0.0325	1.4381	0.069*
C11	0.2029 (2)	0.0514 (6)	1.3816 (4)	0.0569 (13)
C12	0.20898 (19)	0.1295 (7)	1.2867 (4)	0.0629 (13)
H12	0.2411	0.1503	1.2881	0.076*
C13	0.16755 (19)	0.1769 (6)	1.1899 (4)	0.0568 (13)
H13	0.1723	0.2286	1.1271	0.068*
C14	0.2483 (2)	0.0004 (7)	1.4868 (4)	0.0767 (17)
H14A	0.2375	−0.0516	1.5439	0.115*
H14B	0.2680	0.1046	1.5183	0.115*
H14C	0.2682	−0.0842	1.4650	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0514 (6)	0.0692 (5)	0.0403 (5)	0.000	0.0225 (4)	0.000
N1	0.046 (3)	0.070 (2)	0.043 (2)	0.000 (2)	0.022 (2)	−0.0003 (18)
N2	0.046 (3)	0.075 (3)	0.046 (2)	0.004 (2)	0.022 (2)	0.0030 (19)
N3	0.049 (3)	0.057 (2)	0.038 (2)	−0.0004 (19)	0.0139 (18)	−0.0031 (17)
N4	0.049 (3)	0.060 (2)	0.042 (2)	−0.0015 (18)	0.0230 (19)	−0.0022 (17)
O1W	0.106 (4)	0.062 (3)	0.065 (3)	0.000	0.060 (3)	0.000
C1	0.045 (3)	0.057 (3)	0.043 (3)	−0.003 (2)	0.022 (2)	−0.006 (2)
C2	0.047 (3)	0.057 (3)	0.041 (3)	0.000 (2)	0.021 (2)	−0.004 (2)
C3	0.046 (3)	0.050 (3)	0.043 (3)	0.002 (2)	0.020 (2)	0.003 (2)
C4	0.047 (3)	0.079 (3)	0.048 (3)	0.001 (3)	0.023 (2)	−0.007 (2)
C5	0.049 (3)	0.089 (4)	0.070 (4)	0.005 (3)	0.034 (3)	0.001 (3)
C6	0.047 (3)	0.085 (4)	0.053 (3)	−0.003 (3)	0.015 (3)	−0.003 (3)
C7	0.058 (4)	0.074 (3)	0.039 (3)	−0.001 (3)	0.019 (3)	−0.003 (2)
C8	0.050 (3)	0.057 (3)	0.041 (3)	0.002 (2)	0.022 (2)	−0.003 (2)
C9	0.047 (3)	0.064 (3)	0.050 (3)	0.001 (2)	0.022 (2)	−0.001 (2)
C10	0.060 (4)	0.064 (3)	0.047 (3)	0.004 (3)	0.018 (3)	0.003 (2)
C11	0.056 (3)	0.058 (3)	0.051 (3)	0.006 (2)	0.013 (3)	−0.002 (2)
C12	0.044 (3)	0.088 (4)	0.059 (3)	−0.003 (3)	0.021 (3)	0.002 (3)
C13	0.059 (3)	0.070 (3)	0.046 (3)	−0.002 (3)	0.025 (3)	−0.001 (2)
C14	0.070 (4)	0.078 (4)	0.069 (4)	0.006 (3)	0.010 (3)	0.009 (3)

Geometric parameters (Å, º)

Zn1—O1W	1.994 (5)	C5—C6	1.373 (6)
Zn1—N1	1.997 (4)	C5—H5	0.9300
Zn1—N1^i	1.997 (4)	C6—C7	1.368 (7)
Zn1—N3^i	2.195 (4)	C6—H6	0.9300
Zn1—N3	2.195 (4)	C7—H7	0.9300
N1—C1	1.335 (5)	C8—C9	1.385 (6)
N1—N2	1.382 (5)	C8—C13	1.386 (6)
N2—C2	1.341 (5)	C9—C10	1.388 (6)
N3—C7	1.325 (6)	C9—H9	0.9300
N3—C3	1.360 (5)	C10—C11	1.372 (7)
N4—C1	1.347 (5)	C10—H10	0.9300
N4—C2	1.357 (6)	C11—C12	1.390 (7)
O1W—H1WA	0.8200 (11)	C11—C14	1.514 (6)
C1—C3^i	1.461 (6)	C12—C13	1.388 (6)
C2—C8	1.483 (6)	C12—H12	0.9300
C3—C4	1.374 (6)	C13—H13	0.9300
C3—C1^i	1.461 (6)	C14—H14A	0.9600
C4—C5	1.391 (6)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
O1W—Zn1—N1	112.52 (11)	C6—C5—H5	120.3
O1W—Zn1—N1^i	112.52 (11)	C4—C5—H5	120.3
N1—Zn1—N1^i	135.0 (2)	C7—C6—C5	118.5 (5)
O1W—Zn1—N3^i	94.47 (9)	C7—C6—H6	120.7
N1—Zn1—N3^i	78.01 (15)	C5—C6—H6	120.7
N1^i—Zn1—N3^i	98.51 (14)	N3—C7—C6	123.7 (4)
O1W—Zn1—N3	94.47 (9)	N3—C7—H7	118.1
N1—Zn1—N3	98.51 (14)	C6—C7—H7	118.1
N1^i—Zn1—N3	78.02 (14)	C9—C8—C13	118.0 (4)
N3^i—Zn1—N3	171.06 (19)	C9—C8—C2	121.3 (4)
C1—N1—N2	107.2 (3)	C13—C8—C2	120.6 (4)
C1—N1—Zn1	116.9 (3)	C8—C9—C10	120.5 (5)
N2—N1—Zn1	135.4 (3)	C8—C9—H9	119.8
C2—N2—N1	103.5 (4)	C10—C9—H9	119.8
C7—N3—C3	117.7 (4)	C11—C10—C9	121.8 (5)
C7—N3—Zn1	129.5 (3)	C11—C10—H10	119.1
C3—N3—Zn1	112.8 (3)	C9—C10—H10	119.1
C1—N4—C2	101.3 (4)	C10—C11—C12	118.0 (4)
Zn1—O1W—H1WA	131 (3)	C10—C11—C14	121.8 (5)
N1—C1—N4	113.1 (4)	C12—C11—C14	120.2 (5)
N1—C1—C3^i	119.1 (4)	C13—C12—C11	120.6 (5)
N4—C1—C3^i	127.8 (4)	C13—C12—H12	119.7
N2—C2—N4	114.9 (4)	C11—C12—H12	119.7
N2—C2—C8	121.2 (4)	C8—C13—C12	121.2 (4)
N4—C2—C8	123.9 (4)	C8—C13—H13	119.4
N3—C3—C4	122.3 (4)	C12—C13—H13	119.4
N3—C3—C1^i	112.9 (4)	C11—C14—H14A	109.5
C4—C3—C1^i	124.7 (4)	C11—C14—H14B	109.5
C3—C4—C5	118.3 (4)	H14A—C14—H14B	109.5
C3—C4—H4	120.9	C11—C14—H14C	109.5
C5—C4—H4	120.9	H14A—C14—H14C	109.5
C6—C5—C4	119.4 (5)	H14B—C14—H14C	109.5
C1—N1—N2—C2	0.4 (5)	C4—C5—C6—C7	1.5 (8)
Zn1—N1—N2—C2	171.6 (3)	C3—N3—C7—C6	1.6 (7)
N2—N1—C1—N4	−0.8 (5)	Zn1—N3—C7—C6	178.5 (4)
Zn1—N1—C1—N4	−173.9 (3)	C5—C6—C7—N3	−2.2 (8)
N2—N1—C1—C3^i	179.6 (4)	N2—C2—C8—C9	−166.7 (4)
Zn1—N1—C1—C3^i	6.5 (5)	N4—C2—C8—C9	12.8 (7)
C2—N4—C1—N1	0.8 (5)	N2—C2—C8—C13	13.8 (6)
C2—N4—C1—C3^i	−179.7 (4)	N4—C2—C8—C13	−166.7 (4)
N1—N2—C2—N4	0.0 (5)	C13—C8—C9—C10	−0.5 (7)
N1—N2—C2—C8	179.5 (4)	C2—C8—C9—C10	179.9 (4)
C1—N4—C2—N2	−0.5 (5)	C8—C9—C10—C11	1.3 (7)
C1—N4—C2—C8	−180.0 (4)	C9—C10—C11—C12	−1.2 (7)
C7—N3—C3—C4	−0.5 (6)	C9—C10—C11—C14	179.2 (4)
Zn1—N3—C3—C4	−177.8 (3)	C10—C11—C12—C13	0.4 (7)
C7—N3—C3—C1^i	178.8 (4)	C14—C11—C12—C13	−179.9 (4)
Zn1—N3—C3—C1^i	1.4 (4)	C9—C8—C13—C12	−0.2 (7)
N3—C3—C4—C5	−0.1 (7)	C2—C8—C13—C12	179.3 (4)
C1^i—C3—C4—C5	−179.2 (4)	C11—C12—C13—C8	0.3 (7)
C3—C4—C5—C6	−0.5 (7)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···N4^ii	0.82 (1)	1.99 (2)	2.748 (4)	153 (4)

Symmetry code: (ii) −x, −y+1, −z+2.

(II) Bis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N³,N⁴]bis(nitrato-κO)zinc(II)

Crystal data

[Zn(NO3)2(C14H12N4)2]	F(000) = 1360
Mr = 661.94	Dx = 1.574 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.869 (3) Å	Cell parameters from 12787 reflections
b = 12.488 (3) Å	θ = 3.1–25.0°
c = 14.626 (3) Å	µ = 0.94 mm^−1
β = 114.98 (3)°	T = 293 K
V = 2792.9 (11) Å^3	Block, colourless
Z = 4	0.29 × 0.25 × 0.23 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	2247 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.031
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan ABSCOR	h = −20→19
Tmin = 0.761, Tmax = 0.805	k = −14→14
10060 measured reflections	l = −15→17
2451 independent 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.041P)^2 + 1.7059P] where P = (Fo^2 + 2Fc^2)/3
2451 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.26 e Å^−3
1 restraint	Δρmin = −0.34 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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.88204 (2)	0.7500	0.03176 (12)
N1	0.61243 (10)	1.15005 (13)	0.66917 (12)	0.0386 (4)
N2	0.53227 (10)	1.17340 (13)	0.59492 (12)	0.0378 (4)
H2	0.5261 (14)	1.2282 (12)	0.5558 (14)	0.045*
N3	0.63825 (10)	0.89979 (12)	0.80187 (11)	0.0314 (3)
N4	0.51444 (9)	1.02035 (12)	0.65421 (11)	0.0298 (3)
N5	0.52104 (10)	0.69679 (12)	0.62964 (12)	0.0362 (4)
O1	0.47666 (9)	0.78093 (10)	0.62533 (10)	0.0403 (3)
O2	0.57618 (11)	0.66514 (14)	0.71065 (12)	0.0625 (5)
O3	0.50665 (10)	0.65091 (12)	0.54813 (11)	0.0464 (3)
C1	0.59807 (11)	1.05699 (14)	0.70195 (13)	0.0306 (4)
C2	0.66656 (11)	0.99222 (14)	0.77859 (13)	0.0319 (4)
C3	0.75421 (12)	1.02048 (17)	0.81933 (15)	0.0404 (5)
H3A	0.7718	1.0851	0.8021	0.049*
C4	0.81500 (12)	0.95106 (18)	0.88586 (15)	0.0442 (5)
H4	0.8740	0.9693	0.9161	0.053*
C5	0.78687 (13)	0.85418 (18)	0.90685 (16)	0.0445 (5)
H5	0.8268	0.8047	0.9491	0.053*
C6	0.69831 (12)	0.83199 (16)	0.86391 (15)	0.0379 (4)
H6	0.6796	0.7670	0.8788	0.046*
C7	0.47423 (12)	1.09556 (14)	0.58526 (13)	0.0312 (4)
C8	0.38316 (12)	1.09571 (15)	0.51027 (14)	0.0337 (4)
C9	0.34081 (13)	1.19056 (17)	0.46581 (17)	0.0469 (5)
H9	0.3712	1.2551	0.4814	0.056*
C10	0.25363 (13)	1.18846 (19)	0.39845 (18)	0.0529 (6)
H10	0.2261	1.2521	0.3689	0.063*
C11	0.20634 (13)	1.09440 (18)	0.37388 (16)	0.0454 (5)
C12	0.25005 (13)	1.00015 (18)	0.41521 (15)	0.0442 (5)
H12	0.2201	0.9355	0.3976	0.053*
C13	0.33736 (12)	1.00033 (16)	0.48215 (14)	0.0378 (4)
H13	0.3655	0.9360	0.5085	0.045*
C14	0.10968 (15)	1.0948 (2)	0.3065 (2)	0.0658 (7)
H14A	0.0776	1.0852	0.3467	0.099*
H14B	0.0961	1.0375	0.2585	0.099*
H14C	0.0938	1.1619	0.2714	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02389 (17)	0.03534 (19)	0.03164 (18)	0.000	0.00743 (13)	0.000
N1	0.0295 (8)	0.0411 (9)	0.0378 (9)	−0.0020 (7)	0.0070 (7)	0.0059 (7)
N2	0.0311 (8)	0.0387 (9)	0.0373 (9)	0.0002 (7)	0.0084 (7)	0.0096 (7)
N3	0.0251 (7)	0.0358 (8)	0.0311 (8)	0.0037 (6)	0.0098 (7)	0.0026 (6)
N4	0.0251 (7)	0.0341 (8)	0.0287 (8)	0.0013 (6)	0.0099 (6)	0.0024 (6)
N5	0.0324 (8)	0.0338 (8)	0.0380 (9)	0.0018 (7)	0.0107 (7)	0.0016 (7)
O1	0.0390 (7)	0.0374 (7)	0.0385 (7)	0.0096 (6)	0.0104 (6)	−0.0019 (6)
O2	0.0639 (10)	0.0598 (10)	0.0432 (9)	0.0252 (8)	0.0025 (8)	0.0055 (8)
O3	0.0497 (8)	0.0418 (8)	0.0433 (8)	0.0016 (6)	0.0154 (7)	−0.0107 (7)
C1	0.0276 (9)	0.0348 (10)	0.0287 (9)	−0.0007 (7)	0.0113 (8)	0.0002 (7)
C2	0.0277 (9)	0.0370 (10)	0.0290 (9)	0.0018 (7)	0.0100 (8)	0.0015 (8)
C3	0.0291 (9)	0.0485 (12)	0.0402 (11)	−0.0037 (8)	0.0113 (9)	0.0022 (9)
C4	0.0241 (9)	0.0617 (14)	0.0410 (11)	0.0019 (9)	0.0081 (9)	0.0001 (10)
C5	0.0326 (10)	0.0567 (13)	0.0392 (11)	0.0141 (9)	0.0104 (9)	0.0060 (10)
C6	0.0322 (10)	0.0391 (10)	0.0385 (10)	0.0082 (8)	0.0110 (9)	0.0067 (8)
C7	0.0281 (9)	0.0350 (10)	0.0298 (9)	0.0026 (7)	0.0115 (8)	0.0010 (7)
C8	0.0285 (9)	0.0408 (10)	0.0303 (9)	0.0040 (8)	0.0109 (8)	0.0036 (8)
C9	0.0309 (10)	0.0425 (12)	0.0587 (14)	0.0020 (9)	0.0105 (10)	0.0088 (10)
C10	0.0338 (11)	0.0496 (13)	0.0627 (15)	0.0096 (9)	0.0083 (11)	0.0143 (11)
C11	0.0302 (10)	0.0603 (14)	0.0396 (11)	0.0019 (9)	0.0088 (9)	0.0015 (10)
C12	0.0382 (11)	0.0483 (12)	0.0375 (11)	−0.0083 (9)	0.0077 (9)	−0.0026 (9)
C13	0.0373 (10)	0.0400 (11)	0.0308 (10)	0.0018 (8)	0.0091 (9)	0.0028 (8)
C14	0.0329 (12)	0.0810 (18)	0.0656 (17)	0.0003 (11)	0.0033 (12)	0.0021 (13)

Geometric parameters (Å, º)

Zn1—O1	2.1138 (13)	C4—C5	1.381 (3)
Zn1—O1^i	2.1138 (13)	C4—H4	0.9300
Zn1—N3^i	2.1376 (16)	C5—C6	1.382 (3)
Zn1—N3	2.1376 (16)	C5—H5	0.9300
Zn1—N4^i	2.3007 (15)	C6—H6	0.9300
Zn1—N4	2.3007 (15)	C7—C8	1.463 (3)
N1—C1	1.318 (2)	C8—C13	1.384 (3)
N1—N2	1.361 (2)	C8—C9	1.394 (3)
N2—C7	1.344 (2)	C9—C10	1.382 (3)
N2—H2	0.870 (10)	C9—H9	0.9300
N3—C6	1.338 (2)	C10—C11	1.380 (3)
N3—C2	1.347 (2)	C10—H10	0.9300
N4—C7	1.335 (2)	C11—C12	1.385 (3)
N4—C1	1.362 (2)	C11—C14	1.508 (3)
N5—O2	1.223 (2)	C12—C13	1.382 (3)
N5—O3	1.251 (2)	C12—H12	0.9300
N5—O1	1.276 (2)	C13—H13	0.9300
C1—C2	1.467 (3)	C14—H14A	0.9600
C2—C3	1.386 (3)	C14—H14B	0.9600
C3—C4	1.381 (3)	C14—H14C	0.9600
C3—H3A	0.9300
O1—Zn1—O1^i	106.64 (8)	C2—C3—H3A	120.6
O1—Zn1—N3^i	88.73 (6)	C5—C4—C3	118.95 (18)
O1^i—Zn1—N3^i	98.39 (6)	C5—C4—H4	120.5
O1—Zn1—N3	98.39 (6)	C3—C4—H4	120.5
O1^i—Zn1—N3	88.73 (6)	C4—C5—C6	118.79 (19)
N3^i—Zn1—N3	168.10 (8)	C4—C5—H5	120.6
O1—Zn1—N4^i	160.86 (5)	C6—C5—H5	120.6
O1^i—Zn1—N4^i	87.26 (5)	N3—C6—C5	123.02 (19)
N3^i—Zn1—N4^i	76.00 (6)	N3—C6—H6	118.5
N3—Zn1—N4^i	94.95 (6)	C5—C6—H6	118.5
O1—Zn1—N4	87.26 (5)	N4—C7—N2	108.32 (16)
O1^i—Zn1—N4	160.86 (5)	N4—C7—C8	127.23 (17)
N3^i—Zn1—N4	94.95 (6)	N2—C7—C8	124.45 (16)
N3—Zn1—N4	76.00 (6)	C13—C8—C9	118.73 (18)
N4^i—Zn1—N4	82.70 (7)	C13—C8—C7	119.95 (17)
C1—N1—N2	101.88 (15)	C9—C8—C7	121.32 (18)
C7—N2—N1	111.29 (15)	C10—C9—C8	119.8 (2)
C7—N2—H2	128.3 (15)	C10—C9—H9	120.1
N1—N2—H2	119.8 (15)	C8—C9—H9	120.1
C6—N3—C2	117.78 (16)	C11—C10—C9	121.7 (2)
C6—N3—Zn1	125.12 (13)	C11—C10—H10	119.1
C2—N3—Zn1	116.70 (11)	C9—C10—H10	119.1
C7—N4—C1	103.70 (15)	C10—C11—C12	117.85 (19)
C7—N4—Zn1	146.90 (12)	C10—C11—C14	121.0 (2)
C1—N4—Zn1	107.04 (11)	C12—C11—C14	121.2 (2)
O2—N5—O3	122.53 (16)	C13—C12—C11	121.3 (2)
O2—N5—O1	120.29 (16)	C13—C12—H12	119.4
O3—N5—O1	117.16 (15)	C11—C12—H12	119.4
N5—O1—Zn1	123.89 (11)	C12—C13—C8	120.40 (19)
N1—C1—N4	114.79 (16)	C12—C13—H13	119.8
N1—C1—C2	123.90 (16)	C8—C13—H13	119.8
N4—C1—C2	121.17 (16)	C11—C14—H14A	109.5
N3—C2—C3	122.50 (17)	C11—C14—H14B	109.5
N3—C2—C1	114.64 (15)	H14A—C14—H14B	109.5
C3—C2—C1	122.75 (17)	C11—C14—H14C	109.5
C4—C3—C2	118.88 (19)	H14A—C14—H14C	109.5
C4—C3—H3A	120.6	H14B—C14—H14C	109.5
C1—N1—N2—C7	−0.5 (2)	Zn1—N3—C6—C5	−170.49 (15)
O2—N5—O1—Zn1	6.3 (2)	C4—C5—C6—N3	0.7 (3)
O3—N5—O1—Zn1	−172.31 (12)	C1—N4—C7—N2	−1.39 (19)
N2—N1—C1—N4	−0.5 (2)	Zn1—N4—C7—N2	156.45 (17)
N2—N1—C1—C2	175.30 (17)	C1—N4—C7—C8	178.10 (17)
C7—N4—C1—N1	1.2 (2)	Zn1—N4—C7—C8	−24.1 (3)
Zn1—N4—C1—N1	−166.37 (13)	N1—N2—C7—N4	1.2 (2)
C7—N4—C1—C2	−174.71 (16)	N1—N2—C7—C8	−178.28 (17)
Zn1—N4—C1—C2	17.74 (19)	N4—C7—C8—C13	−21.6 (3)
C6—N3—C2—C3	−2.5 (3)	N2—C7—C8—C13	157.78 (18)
Zn1—N3—C2—C3	170.59 (14)	N4—C7—C8—C9	158.42 (19)
C6—N3—C2—C1	173.69 (16)	N2—C7—C8—C9	−22.2 (3)
Zn1—N3—C2—C1	−13.21 (19)	C13—C8—C9—C10	2.8 (3)
N1—C1—C2—N3	179.79 (17)	C7—C8—C9—C10	−177.2 (2)
N4—C1—C2—N3	−4.7 (2)	C8—C9—C10—C11	0.4 (4)
N1—C1—C2—C3	−4.0 (3)	C9—C10—C11—C12	−3.1 (4)
N4—C1—C2—C3	171.49 (17)	C9—C10—C11—C14	175.3 (2)
N3—C2—C3—C4	0.4 (3)	C10—C11—C12—C13	2.6 (3)
C1—C2—C3—C4	−175.49 (18)	C14—C11—C12—C13	−175.8 (2)
C2—C3—C4—C5	2.3 (3)	C11—C12—C13—C8	0.6 (3)
C3—C4—C5—C6	−2.8 (3)	C9—C8—C13—C12	−3.3 (3)
C2—N3—C6—C5	2.0 (3)	C7—C8—C13—C12	176.73 (18)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N5^ii	0.87 (1)	2.65 (1)	3.425 (2)	148 (2)
N2—H2···O1^ii	0.87 (1)	2.63 (2)	3.212 (2)	125 (2)
N2—H2···O3^ii	0.87 (1)	2.05 (1)	2.909 (2)	172 (2)
C6—H6···O1^i	0.93	2.62	3.088 (2)	112

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

(III) Bis(methanol-κO)bis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]zinc(II)

Crystal data

[Zn(C14H11N4)2(CH4O)2]	F(000) = 624
Mr = 599.99	Dx = 1.377 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.297 (3) Å	Cell parameters from 14234 reflections
b = 12.663 (3) Å	θ = 3.2–25.0°
c = 9.990 (2) Å	µ = 0.89 mm^−1
β = 111.58 (3)°	T = 293 K
V = 1446.6 (6) Å^3	Block, colourless
Z = 2	0.31 × 0.28 × 0.26 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1625 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.083
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan ABSCOR	h = −14→14
Tmin = 0.759, Tmax = 0.793	k = −15→14
11056 measured reflections	l = −11→11
2526 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0582P)^2] where P = (Fo^2 + 2Fc^2)/3
2526 reflections	(Δ/σ)max = 0.003
197 parameters	Δρmax = 0.35 e Å^−3
2 restraints	Δρmin = −0.69 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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	1.0000	0.0000	0.5000	0.0377 (2)
N1	0.9038 (2)	0.0748 (2)	0.3088 (3)	0.0371 (7)
N2	0.8097 (2)	0.0535 (2)	0.1852 (3)	0.0380 (7)
N3	1.0890 (2)	0.1492 (2)	0.5249 (3)	0.0350 (7)
N4	0.8768 (2)	0.2179 (2)	0.1694 (3)	0.0336 (7)
O1	0.8864 (2)	0.07444 (18)	0.6045 (3)	0.0446 (6)
H1	0.885 (3)	0.1387 (4)	0.613 (4)	0.067*
C1	0.9404 (3)	0.1715 (2)	0.2957 (3)	0.0327 (8)
C2	1.0392 (3)	0.2174 (2)	0.4146 (3)	0.0328 (8)
C3	1.0791 (3)	0.3191 (3)	0.4186 (4)	0.0450 (9)
H3	1.0440	0.3650	0.3421	0.054*
C4	1.1724 (3)	0.3520 (3)	0.5380 (4)	0.0544 (11)
H4	1.2003	0.4208	0.5430	0.065*
C5	1.2239 (3)	0.2828 (3)	0.6498 (4)	0.0499 (10)
H5	1.2874	0.3036	0.7304	0.060*
C6	1.1793 (3)	0.1819 (3)	0.6394 (4)	0.0425 (9)
H6	1.2134	0.1350	0.7149	0.051*
C7	0.7965 (3)	0.1408 (2)	0.1050 (3)	0.0337 (8)
C8	0.7024 (3)	0.1505 (3)	−0.0373 (3)	0.0380 (8)
C9	0.6950 (3)	0.2383 (3)	−0.1237 (4)	0.0458 (9)
H9	0.7482	0.2933	−0.0895	0.055*
C10	0.6090 (3)	0.2449 (3)	−0.2610 (4)	0.0548 (11)
H10	0.6051	0.3047	−0.3166	0.066*
C11	0.5295 (3)	0.1644 (4)	−0.3161 (4)	0.0560 (11)
C12	0.5339 (3)	0.0787 (4)	−0.2280 (4)	0.0600 (11)
H2	0.4796	0.0245	−0.2619	0.072*
C13	0.6182 (3)	0.0723 (3)	−0.0896 (4)	0.0501 (10)
H13	0.6181	0.0149	−0.0316	0.060*
C14	0.4431 (4)	0.1677 (4)	−0.4705 (4)	0.0841 (16)
H14A	0.4305	0.2396	−0.5028	0.126*
H14B	0.3703	0.1370	−0.4756	0.126*
H14C	0.4739	0.1284	−0.5308	0.126*
C15	0.8322 (10)	0.0210 (7)	0.6900 (13)	0.064 (2)	0.637 (15)
H15A	0.8049	−0.0469	0.6487	0.096*	0.637 (15)
H15B	0.7673	0.0621	0.6924	0.096*	0.637 (15)
H15C	0.8880	0.0122	0.7861	0.096*	0.637 (15)
C15B	0.7833 (12)	0.0312 (15)	0.616 (2)	0.064 (2)	0.363 (15)
H15D	0.7174	0.0463	0.5298	0.096*	0.363 (15)
H15E	0.7710	0.0620	0.6971	0.096*	0.363 (15)
H15F	0.7919	−0.0439	0.6289	0.096*	0.363 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0479 (4)	0.0262 (3)	0.0298 (3)	−0.0032 (3)	0.0033 (2)	0.0033 (2)
N1	0.0448 (16)	0.0292 (16)	0.0309 (16)	−0.0026 (13)	0.0065 (13)	−0.0028 (12)
N2	0.0452 (17)	0.0313 (16)	0.0285 (15)	−0.0032 (13)	0.0031 (13)	0.0012 (13)
N3	0.0407 (16)	0.0340 (16)	0.0262 (15)	−0.0002 (13)	0.0074 (12)	0.0025 (12)
N4	0.0400 (16)	0.0282 (15)	0.0266 (15)	0.0024 (13)	0.0052 (12)	0.0042 (12)
O1	0.0561 (15)	0.0317 (14)	0.0464 (15)	−0.0001 (13)	0.0193 (12)	−0.0029 (12)
C1	0.0406 (19)	0.0262 (18)	0.0290 (18)	−0.0006 (15)	0.0102 (15)	−0.0006 (15)
C2	0.0371 (18)	0.0294 (18)	0.0286 (18)	0.0020 (15)	0.0084 (15)	0.0000 (15)
C3	0.058 (2)	0.033 (2)	0.036 (2)	−0.0034 (18)	0.0081 (18)	0.0067 (16)
C4	0.070 (3)	0.038 (2)	0.046 (2)	−0.019 (2)	0.010 (2)	−0.0013 (18)
C5	0.055 (2)	0.045 (2)	0.034 (2)	−0.0153 (19)	−0.0022 (17)	0.0003 (18)
C6	0.051 (2)	0.041 (2)	0.0290 (19)	−0.0002 (18)	0.0067 (17)	0.0025 (16)
C7	0.0393 (19)	0.0289 (19)	0.0295 (18)	0.0036 (16)	0.0087 (15)	0.0017 (15)
C8	0.0382 (19)	0.041 (2)	0.0307 (19)	0.0015 (17)	0.0079 (15)	−0.0037 (16)
C9	0.047 (2)	0.050 (2)	0.037 (2)	−0.0026 (18)	0.0107 (17)	0.0053 (18)
C10	0.048 (2)	0.075 (3)	0.035 (2)	0.004 (2)	0.0082 (18)	0.016 (2)
C11	0.045 (2)	0.085 (3)	0.031 (2)	0.008 (2)	0.0052 (17)	0.002 (2)
C12	0.047 (2)	0.071 (3)	0.049 (3)	−0.012 (2)	0.0015 (19)	−0.015 (2)
C13	0.047 (2)	0.049 (2)	0.045 (2)	−0.0021 (19)	0.0059 (18)	−0.0008 (19)
C14	0.062 (3)	0.136 (5)	0.035 (2)	0.004 (3)	−0.005 (2)	0.000 (3)
C15	0.063 (6)	0.056 (4)	0.081 (7)	−0.012 (5)	0.037 (5)	−0.008 (5)
C15B	0.063 (6)	0.056 (4)	0.081 (7)	−0.012 (5)	0.037 (5)	−0.008 (5)

Geometric parameters (Å, º)

Zn1—N1^i	2.070 (3)	C5—H5	0.9300
Zn1—N1	2.070 (3)	C6—H6	0.9300
Zn1—N3^i	2.151 (3)	C7—C8	1.472 (4)
Zn1—N3	2.151 (3)	C8—C13	1.389 (5)
Zn1—O1	2.236 (2)	C8—C9	1.390 (5)
Zn1—O1^i	2.236 (2)	C9—C10	1.393 (5)
N1—C1	1.328 (4)	C9—H9	0.9300
N1—N2	1.373 (3)	C10—C11	1.379 (5)
N2—C7	1.340 (4)	C10—H10	0.9300
N3—C6	1.333 (4)	C11—C12	1.386 (6)
N3—C2	1.356 (4)	C11—C14	1.518 (5)
N4—C1	1.350 (4)	C12—C13	1.392 (5)
N4—C7	1.368 (4)	C12—H2	0.9300
O1—C15B	1.425 (8)	C13—H13	0.9300
O1—C15	1.432 (6)	C14—H14A	0.9600
O1—H1	0.8200 (11)	C14—H14B	0.9600
C1—C2	1.471 (4)	C14—H14C	0.9600
C2—C3	1.374 (4)	C15—H15A	0.9600
C3—C4	1.381 (5)	C15—H15B	0.9600
C3—H3	0.9300	C15—H15C	0.9600
C4—C5	1.377 (5)	C15B—H15D	0.9600
C4—H4	0.9300	C15B—H15E	0.9600
C5—C6	1.379 (5)	C15B—H15F	0.9600
N1^i—Zn1—N1	180.00 (15)	N3—C6—C5	122.3 (3)
N1^i—Zn1—N3^i	78.40 (10)	N3—C6—H6	118.8
N1—Zn1—N3^i	101.60 (10)	C5—C6—H6	118.8
N1^i—Zn1—N3	101.60 (10)	N2—C7—N4	113.6 (3)
N1—Zn1—N3	78.40 (10)	N2—C7—C8	121.7 (3)
N3^i—Zn1—N3	180.0	N4—C7—C8	124.7 (3)
N1^i—Zn1—O1	90.31 (10)	C13—C8—C9	117.9 (3)
N1—Zn1—O1	89.69 (10)	C13—C8—C7	121.1 (3)
N3^i—Zn1—O1	92.61 (10)	C9—C8—C7	121.0 (3)
N3—Zn1—O1	87.39 (10)	C8—C9—C10	120.8 (4)
N1^i—Zn1—O1^i	89.69 (10)	C8—C9—H9	119.6
N1—Zn1—O1^i	90.31 (10)	C10—C9—H9	119.6
N3^i—Zn1—O1^i	87.39 (10)	C11—C10—C9	121.3 (4)
N3—Zn1—O1^i	92.61 (10)	C11—C10—H10	119.3
O1—Zn1—O1^i	180.0	C9—C10—H10	119.3
C1—N1—N2	107.3 (3)	C10—C11—C12	117.9 (3)
C1—N1—Zn1	114.4 (2)	C10—C11—C14	120.9 (4)
N2—N1—Zn1	138.3 (2)	C12—C11—C14	121.1 (4)
C7—N2—N1	104.6 (2)	C11—C12—C13	121.2 (4)
C6—N3—C2	118.9 (3)	C11—C12—H2	119.4
C6—N3—Zn1	126.8 (2)	C13—C12—H2	119.4
C2—N3—Zn1	114.0 (2)	C8—C13—C12	120.8 (4)
C1—N4—C7	101.5 (3)	C8—C13—H13	119.6
C15B—O1—Zn1	127.1 (8)	C12—C13—H13	119.6
C15—O1—Zn1	126.0 (4)	C11—C14—H14A	109.5
C15B—O1—H1	108 (3)	C11—C14—H14B	109.5
C15—O1—H1	112 (3)	H14A—C14—H14B	109.5
Zn1—O1—H1	121 (3)	C11—C14—H14C	109.5
N1—C1—N4	113.1 (3)	H14A—C14—H14C	109.5
N1—C1—C2	119.6 (3)	H14B—C14—H14C	109.5
N4—C1—C2	127.2 (3)	O1—C15—H15A	109.5
N3—C2—C3	121.6 (3)	O1—C15—H15B	109.5
N3—C2—C1	113.3 (3)	H15A—C15—H15B	109.5
C3—C2—C1	125.1 (3)	O1—C15—H15C	109.5
C2—C3—C4	118.9 (3)	H15A—C15—H15C	109.5
C2—C3—H3	120.6	H15B—C15—H15C	109.5
C4—C3—H3	120.6	O1—C15B—H15D	109.5
C5—C4—C3	119.8 (3)	O1—C15B—H15E	109.5
C5—C4—H4	120.1	H15D—C15B—H15E	109.5
C3—C4—H4	120.1	O1—C15B—H15F	109.5
C4—C5—C6	118.5 (3)	H15D—C15B—H15F	109.5
C4—C5—H5	120.7	H15E—C15B—H15F	109.5
C6—C5—H5	120.7
C1—N1—N2—C7	0.1 (4)	Zn1—N3—C6—C5	−174.2 (3)
Zn1—N1—N2—C7	−179.3 (3)	C4—C5—C6—N3	0.5 (6)
N2—N1—C1—N4	−0.2 (4)	N1—N2—C7—N4	0.0 (4)
Zn1—N1—C1—N4	179.4 (2)	N1—N2—C7—C8	−179.1 (3)
N2—N1—C1—C2	178.3 (3)	C1—N4—C7—N2	−0.1 (4)
Zn1—N1—C1—C2	−2.1 (4)	C1—N4—C7—C8	178.9 (3)
C7—N4—C1—N1	0.2 (4)	N2—C7—C8—C13	4.8 (5)
C7—N4—C1—C2	−178.2 (3)	N4—C7—C8—C13	−174.2 (3)
C6—N3—C2—C3	−0.3 (5)	N2—C7—C8—C9	−175.2 (3)
Zn1—N3—C2—C3	174.7 (3)	N4—C7—C8—C9	5.8 (5)
C6—N3—C2—C1	−179.8 (3)	C13—C8—C9—C10	−2.9 (5)
Zn1—N3—C2—C1	−4.8 (4)	C7—C8—C9—C10	177.0 (3)
N1—C1—C2—N3	4.8 (5)	C8—C9—C10—C11	−0.7 (6)
N4—C1—C2—N3	−177.0 (3)	C9—C10—C11—C12	3.1 (6)
N1—C1—C2—C3	−174.7 (3)	C9—C10—C11—C14	−174.4 (4)
N4—C1—C2—C3	3.5 (6)	C10—C11—C12—C13	−1.9 (6)
N3—C2—C3—C4	0.0 (6)	C14—C11—C12—C13	175.6 (4)
C1—C2—C3—C4	179.5 (3)	C9—C8—C13—C12	4.1 (5)
C2—C3—C4—C5	0.5 (6)	C7—C8—C13—C12	−175.8 (3)
C3—C4—C5—C6	−0.8 (6)	C11—C12—C13—C8	−1.8 (6)
C2—N3—C6—C5	0.0 (5)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4^ii	0.82 (1)	1.91 (1)	2.722 (3)	169 (4)
C3—H3···O1^iii	0.93	2.57	3.437 (4)	156
C6—H6···N2^i	0.93	2.64	3.435 (5)	144

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

(IV) Diiodidobis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N³,N⁴]cadmium(II)

Crystal data

[CdI2(C14H12N4)2]	F(000) = 1608
Mr = 838.75	Dx = 1.920 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.848 (4) Å	Cell parameters from 14086 reflections
b = 11.254 (2) Å	θ = 3.2–25.0°
c = 15.707 (3) Å	µ = 2.91 mm^−1
β = 119.44 (3)°	T = 293 K
V = 2901.4 (13) Å^3	Block, colourless
Z = 4	0.27 × 0.26 × 0.24 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	2414 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.061
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan ABSCOR	h = −22→22
Tmin = 0.474, Tmax = 0.497	k = −13→13
10864 measured reflections	l = −18→18
2528 independent 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) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0693P)^2 + 1.7102P] where P = (Fo^2 + 2Fc^2)/3
2528 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 1.10 e Å^−3
1 restraint	Δρmin = −1.67 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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.5000	0.67530 (4)	0.2500	0.03911 (16)
I1	0.48448 (2)	0.85102 (2)	0.10686 (2)	0.04451 (16)
N1	0.5146 (2)	0.3485 (3)	0.0663 (3)	0.0452 (8)
H1	0.501 (3)	0.301 (3)	0.0169 (17)	0.054*
N2	0.59155 (19)	0.3833 (4)	0.1292 (3)	0.0483 (8)
N3	0.36863 (17)	0.6357 (3)	0.2137 (2)	0.0376 (7)
N4	0.49983 (16)	0.4984 (3)	0.14289 (19)	0.0360 (7)
C1	0.5804 (2)	0.4726 (3)	0.1743 (2)	0.0360 (7)
C2	0.4599 (2)	0.4178 (3)	0.0730 (2)	0.0343 (7)
C3	0.3720 (2)	0.4008 (3)	0.0105 (2)	0.0371 (8)
C4	0.3408 (2)	0.2979 (4)	−0.0444 (3)	0.0448 (9)
H4	0.3763	0.2379	−0.0403	0.054*
C5	0.2574 (2)	0.2831 (4)	−0.1052 (3)	0.0497 (10)
H5	0.2380	0.2135	−0.1414	0.060*
C6	0.2029 (2)	0.3708 (4)	−0.1126 (3)	0.0436 (9)
C7	0.2339 (2)	0.4724 (4)	−0.0566 (3)	0.0467 (9)
H7	0.1983	0.5310	−0.0587	0.056*
C8	0.3169 (2)	0.4883 (4)	0.0024 (3)	0.0439 (9)
H8	0.3362	0.5587	0.0373	0.053*
C9	0.35142 (19)	0.5430 (3)	0.2527 (2)	0.0360 (8)
C10	0.2705 (2)	0.5147 (4)	0.2278 (3)	0.0485 (10)
H10	0.2591	0.4494	0.2554	0.058*
C11	0.2095 (2)	0.5857 (5)	0.1623 (3)	0.0557 (12)
H11	0.1555	0.5667	0.1423	0.067*
C12	0.2273 (2)	0.6860 (5)	0.1251 (3)	0.0548 (11)
H12	0.1862	0.7371	0.0830	0.066*
C13	0.3078 (2)	0.7078 (4)	0.1525 (3)	0.0486 (9)
H13	0.3204	0.7747	0.1278	0.058*
C14	0.1119 (3)	0.3549 (4)	−0.1785 (4)	0.0619 (13)
H14A	0.0847	0.3645	−0.1408	0.093*
H14B	0.1012	0.2769	−0.2068	0.093*
H14C	0.0922	0.4134	−0.2296	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0264 (2)	0.0459 (3)	0.0431 (3)	0.000	0.01552 (18)	0.000
I1	0.0496 (2)	0.0469 (2)	0.0385 (2)	0.00765 (10)	0.02279 (16)	0.00098 (9)
N1	0.0426 (18)	0.048 (2)	0.0496 (19)	0.0016 (13)	0.0258 (16)	−0.0142 (14)
N2	0.0402 (17)	0.053 (2)	0.0542 (18)	0.0058 (15)	0.0255 (15)	−0.0035 (17)
N3	0.0271 (14)	0.0418 (18)	0.0423 (16)	0.0025 (11)	0.0158 (13)	−0.0034 (13)
N4	0.0338 (14)	0.0409 (19)	0.0355 (15)	0.0043 (12)	0.0187 (12)	0.0025 (13)
C1	0.0368 (17)	0.038 (2)	0.0374 (16)	0.0057 (14)	0.0215 (15)	0.0069 (15)
C2	0.0388 (17)	0.0335 (19)	0.0337 (16)	0.0045 (14)	0.0202 (15)	0.0018 (14)
C3	0.0420 (18)	0.038 (2)	0.0356 (16)	0.0010 (15)	0.0223 (15)	0.0005 (15)
C4	0.045 (2)	0.038 (2)	0.050 (2)	0.0017 (16)	0.0229 (18)	−0.0044 (17)
C5	0.049 (2)	0.046 (2)	0.050 (2)	−0.0048 (18)	0.0206 (18)	−0.0107 (18)
C6	0.041 (2)	0.050 (2)	0.0386 (18)	−0.0026 (16)	0.0191 (17)	0.0024 (16)
C7	0.043 (2)	0.045 (2)	0.048 (2)	0.0066 (16)	0.0187 (18)	0.0000 (18)
C8	0.046 (2)	0.039 (2)	0.0418 (18)	0.0053 (16)	0.0177 (16)	−0.0061 (16)
C9	0.0336 (17)	0.040 (2)	0.0374 (17)	−0.0046 (14)	0.0199 (15)	−0.0099 (15)
C10	0.0390 (19)	0.061 (3)	0.053 (2)	−0.0077 (18)	0.0280 (18)	−0.0104 (19)
C11	0.0307 (19)	0.082 (3)	0.056 (2)	−0.003 (2)	0.0225 (18)	−0.017 (2)
C12	0.035 (2)	0.067 (3)	0.059 (2)	0.0131 (19)	0.0197 (19)	−0.003 (2)
C13	0.0365 (19)	0.049 (2)	0.055 (2)	0.0077 (17)	0.0181 (17)	0.0006 (18)
C14	0.049 (3)	0.065 (3)	0.056 (3)	0.000 (2)	0.014 (2)	−0.005 (2)

Geometric parameters (Å, º)

Cd1—N3^i	2.295 (3)	C5—C6	1.388 (6)
Cd1—N3	2.295 (3)	C5—H5	0.9300
Cd1—N4^i	2.605 (3)	C6—C7	1.385 (6)
Cd1—N4	2.605 (3)	C6—C14	1.517 (6)
Cd1—I1^i	2.8990 (6)	C7—C8	1.382 (5)
Cd1—I1	2.8990 (6)	C7—H7	0.9300
N1—C2	1.337 (5)	C8—H8	0.9300
N1—N2	1.351 (5)	C9—C10	1.413 (5)
N1—H1	0.8700 (11)	C9—C1^i	1.465 (5)
N2—C1	1.305 (5)	C10—C11	1.362 (7)
N3—C9	1.329 (5)	C10—H10	0.9300
N3—C13	1.347 (5)	C11—C12	1.385 (7)
N4—C2	1.334 (5)	C11—H11	0.9300
N4—C1	1.377 (4)	C12—C13	1.381 (6)
C1—C9^i	1.465 (5)	C12—H12	0.9300
C2—C3	1.465 (5)	C13—H13	0.9300
C3—C4	1.390 (6)	C14—H14A	0.9600
C3—C8	1.391 (5)	C14—H14B	0.9600
C4—C5	1.391 (6)	C14—H14C	0.9600
C4—H4	0.9300
N3^i—Cd1—N3	157.63 (16)	C3—C4—H4	119.5
N3^i—Cd1—N4^i	91.87 (10)	C5—C4—H4	119.5
N3—Cd1—N4^i	70.79 (10)	C6—C5—C4	120.8 (4)
N3^i—Cd1—N4	70.79 (10)	C6—C5—H5	119.6
N3—Cd1—N4	91.87 (10)	C4—C5—H5	119.6
N4^i—Cd1—N4	80.36 (13)	C7—C6—C5	118.0 (4)
N3^i—Cd1—I1^i	104.74 (9)	C7—C6—C14	120.9 (4)
N3—Cd1—I1^i	90.59 (8)	C5—C6—C14	121.0 (4)
N4^i—Cd1—I1^i	93.02 (6)	C8—C7—C6	121.2 (4)
N4—Cd1—I1^i	171.74 (6)	C8—C7—H7	119.4
N3^i—Cd1—I1	90.59 (8)	C6—C7—H7	119.4
N3—Cd1—I1	104.74 (9)	C7—C8—C3	121.2 (4)
N4^i—Cd1—I1	171.74 (6)	C7—C8—H8	119.4
N4—Cd1—I1	93.02 (6)	C3—C8—H8	119.4
I1^i—Cd1—I1	93.98 (2)	N3—C9—C10	121.6 (3)
C2—N1—N2	111.4 (3)	N3—C9—C1^i	117.8 (3)
C2—N1—H1	121 (3)	C10—C9—C1^i	120.5 (4)
N2—N1—H1	125 (3)	C11—C10—C9	118.2 (4)
C1—N2—N1	102.6 (3)	C11—C10—H10	120.9
C9—N3—C13	119.1 (3)	C9—C10—H10	120.9
C9—N3—Cd1	121.1 (2)	C10—C11—C12	120.4 (4)
C13—N3—Cd1	119.8 (3)	C10—C11—H11	119.8
C2—N4—C1	103.2 (3)	C12—C11—H11	119.8
C2—N4—Cd1	150.6 (2)	C13—C12—C11	118.1 (4)
C1—N4—Cd1	106.2 (2)	C13—C12—H12	121.0
N2—C1—N4	114.3 (3)	C11—C12—H12	121.0
N2—C1—C9^i	121.8 (3)	N3—C13—C12	122.3 (4)
N4—C1—C9^i	123.7 (3)	N3—C13—H13	118.8
N4—C2—N1	108.5 (3)	C12—C13—H13	118.8
N4—C2—C3	129.4 (3)	C6—C14—H14A	109.5
N1—C2—C3	122.1 (3)	C6—C14—H14B	109.5
C4—C3—C8	117.6 (3)	H14A—C14—H14B	109.5
C4—C3—C2	121.2 (3)	C6—C14—H14C	109.5
C8—C3—C2	121.1 (3)	H14A—C14—H14C	109.5
C3—C4—C5	121.1 (4)	H14B—C14—H14C	109.5
C2—N1—N2—C1	1.5 (5)	C3—C4—C5—C6	−0.2 (6)
N1—N2—C1—N4	−0.7 (4)	C4—C5—C6—C7	−0.9 (6)
N1—N2—C1—C9^i	−176.9 (3)	C4—C5—C6—C14	−179.7 (4)
C2—N4—C1—N2	−0.3 (4)	C5—C6—C7—C8	2.3 (6)
Cd1—N4—C1—N2	178.6 (3)	C14—C6—C7—C8	−178.9 (4)
C2—N4—C1—C9^i	175.8 (3)	C6—C7—C8—C3	−2.5 (7)
Cd1—N4—C1—C9^i	−5.3 (4)	C4—C3—C8—C7	1.2 (6)
C1—N4—C2—N1	1.2 (4)	C2—C3—C8—C7	180.0 (4)
Cd1—N4—C2—N1	−176.5 (4)	C13—N3—C9—C10	3.3 (5)
C1—N4—C2—C3	−178.7 (4)	Cd1—N3—C9—C10	−177.2 (3)
Cd1—N4—C2—C3	3.5 (7)	C13—N3—C9—C1^i	−174.6 (3)
N2—N1—C2—N4	−1.8 (5)	Cd1—N3—C9—C1^i	4.9 (4)
N2—N1—C2—C3	178.2 (3)	N3—C9—C10—C11	−0.3 (6)
N4—C2—C3—C4	−166.5 (4)	C1^i—C9—C10—C11	177.5 (3)
N1—C2—C3—C4	13.5 (6)	C9—C10—C11—C12	−3.1 (6)
N4—C2—C3—C8	14.8 (6)	C10—C11—C12—C13	3.3 (7)
N1—C2—C3—C8	−165.2 (4)	C9—N3—C13—C12	−3.0 (6)
C8—C3—C4—C5	0.1 (6)	Cd1—N3—C13—C12	177.5 (3)
C2—C3—C4—C5	−178.7 (4)	C11—C12—C13—N3	−0.3 (7)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I1^ii	0.87 (1)	2.71 (2)	3.534 (3)	159 (4)
C12—H12···I1^iii	0.93	3.29	3.884 (5)	124

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

(V) Bis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N³,N⁴]bis(nitrato-κO)cadmium(II)

Crystal data

[Cd(NO3)2(C14H12N4)2]	F(000) = 1432
Mr = 708.98	Dx = 1.649 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.113 (3) Å	Cell parameters from 12693 reflections
b = 12.603 (3) Å	θ = 3.1–25.0°
c = 14.708 (3) Å	µ = 0.83 mm^−1
β = 115.80 (3)°	T = 293 K
V = 2855.9 (12) Å^3	Block, colourless
Z = 4	0.31 × 0.28 × 0.26 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	2336 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.048
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan ABSCOR	h = −20→20
Tmin = 0.774, Tmax = 0.807	k = −14→14
9965 measured reflections	l = −17→17
2495 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0348P)^2 + 0.6811P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2495 reflections	Δρmax = 0.40 e Å^−3
209 parameters	Δρmin = −0.48 e Å^−3
1 restraint	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.5000	0.37028 (2)	0.2500	0.02761 (12)
N1	0.53288 (14)	0.67516 (17)	0.10020 (15)	0.0379 (5)
H1	0.5261 (19)	0.7278 (13)	0.0592 (15)	0.057*
N2	0.61303 (14)	0.65221 (17)	0.17397 (16)	0.0392 (5)
N3	0.64694 (12)	0.40041 (15)	0.30256 (14)	0.0303 (4)
N4	0.51837 (12)	0.51949 (15)	0.15311 (13)	0.0282 (4)
N5	0.51830 (12)	0.19354 (16)	0.12028 (15)	0.0354 (5)
O1	0.46517 (11)	0.26928 (13)	0.10618 (12)	0.0412 (4)
O2	0.51257 (13)	0.14472 (14)	0.04362 (15)	0.0476 (5)
O3	0.57316 (14)	0.17370 (18)	0.20563 (15)	0.0623 (6)
C1	0.47705 (15)	0.59533 (19)	0.08706 (16)	0.0298 (5)
C2	0.60083 (14)	0.55744 (18)	0.20319 (16)	0.0297 (5)
C3	0.67073 (14)	0.49398 (18)	0.27933 (16)	0.0291 (5)
C4	0.75733 (15)	0.5262 (2)	0.32137 (18)	0.0379 (6)
H4A	0.7726	0.5918	0.3049	0.045*
C5	0.81950 (15)	0.4598 (2)	0.38722 (19)	0.0420 (6)
H5	0.8775	0.4804	0.4170	0.050*
C6	0.79557 (17)	0.3622 (2)	0.4091 (2)	0.0412 (6)
H6	0.8371	0.3152	0.4520	0.049*
C7	0.70863 (16)	0.3359 (2)	0.36583 (19)	0.0380 (6)
H7	0.6923	0.2705	0.3814	0.046*
C8	0.38581 (15)	0.5943 (2)	0.01227 (16)	0.0319 (5)
C9	0.34220 (16)	0.6877 (2)	−0.0315 (2)	0.0461 (7)
H9	0.3715	0.7522	−0.0158	0.055*
C10	0.25472 (17)	0.6842 (2)	−0.0988 (2)	0.0527 (7)
H10	0.2262	0.7469	−0.1280	0.063*
C11	0.20923 (17)	0.5900 (2)	−0.1233 (2)	0.0435 (6)
C12	0.25412 (16)	0.4973 (2)	−0.08254 (19)	0.0431 (6)
H12	0.2251	0.4327	−0.1002	0.052*
C13	0.34168 (16)	0.49901 (19)	−0.01579 (17)	0.0362 (5)
H13	0.3708	0.4357	0.0102	0.043*
C14	0.11312 (19)	0.5877 (3)	−0.1908 (2)	0.0637 (9)
H14A	0.0833	0.5584	−0.1545	0.095*
H14B	0.1021	0.5447	−0.2490	0.095*
H14C	0.0928	0.6586	−0.2120	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02055 (15)	0.02801 (17)	0.02983 (17)	0.000	0.00685 (11)	0.000
N1	0.0343 (11)	0.0332 (12)	0.0385 (12)	−0.0011 (9)	0.0087 (10)	0.0090 (9)
N2	0.0316 (11)	0.0372 (12)	0.0405 (13)	−0.0031 (9)	0.0079 (10)	0.0069 (9)
N3	0.0224 (9)	0.0304 (11)	0.0342 (11)	0.0016 (8)	0.0088 (8)	0.0018 (8)
N4	0.0239 (9)	0.0301 (11)	0.0284 (10)	0.0006 (8)	0.0093 (8)	0.0025 (7)
N5	0.0298 (10)	0.0294 (11)	0.0407 (12)	−0.0010 (8)	0.0096 (10)	−0.0034 (9)
O1	0.0407 (9)	0.0346 (10)	0.0411 (10)	0.0096 (8)	0.0110 (8)	−0.0058 (7)
O2	0.0464 (11)	0.0398 (11)	0.0542 (13)	0.0022 (8)	0.0196 (10)	−0.0151 (8)
O3	0.0526 (12)	0.0643 (14)	0.0485 (13)	0.0177 (11)	0.0019 (10)	0.0046 (10)
C1	0.0289 (12)	0.0306 (12)	0.0306 (12)	0.0016 (10)	0.0136 (10)	0.0010 (9)
C2	0.0287 (12)	0.0285 (12)	0.0319 (12)	−0.0004 (9)	0.0134 (10)	0.0002 (9)
C3	0.0252 (11)	0.0310 (13)	0.0289 (12)	0.0008 (9)	0.0096 (10)	−0.0014 (9)
C4	0.0271 (12)	0.0390 (14)	0.0435 (14)	−0.0057 (10)	0.0115 (11)	0.0022 (10)
C5	0.0213 (11)	0.0554 (17)	0.0429 (15)	−0.0014 (11)	0.0081 (11)	0.0005 (11)
C6	0.0246 (12)	0.0467 (17)	0.0431 (16)	0.0090 (10)	0.0061 (12)	0.0038 (10)
C7	0.0288 (12)	0.0351 (14)	0.0446 (15)	0.0047 (10)	0.0109 (11)	0.0074 (11)
C8	0.0289 (12)	0.0370 (13)	0.0280 (13)	0.0038 (10)	0.0106 (10)	0.0042 (9)
C9	0.0322 (13)	0.0365 (15)	0.0610 (18)	0.0039 (11)	0.0122 (13)	0.0102 (12)
C10	0.0340 (14)	0.0458 (18)	0.0644 (19)	0.0121 (12)	0.0085 (13)	0.0163 (13)
C11	0.0303 (13)	0.0557 (17)	0.0378 (14)	0.0024 (12)	0.0085 (11)	0.0024 (12)
C12	0.0382 (14)	0.0454 (16)	0.0362 (14)	−0.0055 (11)	0.0072 (12)	−0.0017 (11)
C13	0.0368 (13)	0.0350 (14)	0.0291 (13)	0.0055 (10)	0.0073 (11)	0.0031 (9)
C14	0.0323 (15)	0.077 (2)	0.064 (2)	0.0014 (15)	0.0048 (14)	0.0021 (17)

Geometric parameters (Å, º)

Cd1—O1^i	2.3135 (17)	C4—H4A	0.9300
Cd1—O1	2.3136 (17)	C5—C6	1.377 (4)
Cd1—N3	2.3179 (19)	C5—H5	0.9300
Cd1—N3^i	2.3180 (19)	C6—C7	1.380 (4)
Cd1—N4^i	2.4609 (18)	C6—H6	0.9300
Cd1—N4	2.4609 (18)	C7—H7	0.9300
N1—C1	1.342 (3)	C8—C13	1.383 (3)
N1—N2	1.359 (3)	C8—C9	1.392 (3)
N1—H1	0.8700 (11)	C9—C10	1.390 (4)
N2—C2	1.316 (3)	C9—H9	0.9300
N3—C7	1.336 (3)	C10—C11	1.379 (4)
N3—C3	1.339 (3)	C10—H10	0.9300
N4—C1	1.326 (3)	C11—C12	1.383 (4)
N4—C2	1.363 (3)	C11—C14	1.507 (4)
N5—O3	1.222 (3)	C12—C13	1.389 (3)
N5—O2	1.250 (3)	C12—H12	0.9300
N5—O1	1.271 (3)	C13—H13	0.9300
C1—C8	1.467 (3)	C14—H14A	0.9600
C2—C3	1.469 (3)	C14—H14B	0.9600
C3—C4	1.395 (3)	C14—H14C	0.9600
C4—C5	1.369 (4)
O1^i—Cd1—O1	113.24 (9)	C4—C3—C2	122.3 (2)
O1^i—Cd1—N3	88.56 (7)	C5—C4—C3	119.0 (2)
O1—Cd1—N3	101.86 (7)	C5—C4—H4A	120.5
O1^i—Cd1—N3^i	101.86 (7)	C3—C4—H4A	120.5
O1—Cd1—N3^i	88.56 (7)	C4—C5—C6	119.5 (2)
N3—Cd1—N3^i	161.14 (10)	C4—C5—H5	120.3
O1^i—Cd1—N4^i	86.44 (6)	C6—C5—H5	120.3
O1—Cd1—N4^i	154.54 (6)	C5—C6—C7	118.5 (2)
N3—Cd1—N4^i	94.31 (7)	C5—C6—H6	120.7
N3^i—Cd1—N4^i	71.00 (7)	C7—C6—H6	120.7
O1^i—Cd1—N4	154.54 (6)	N3—C7—C6	122.7 (2)
O1—Cd1—N4	86.44 (6)	N3—C7—H7	118.6
N3—Cd1—N4	71.00 (7)	C6—C7—H7	118.6
N3^i—Cd1—N4	94.31 (7)	C13—C8—C9	118.9 (2)
N4^i—Cd1—N4	80.34 (9)	C13—C8—C1	119.7 (2)
C1—N1—N2	111.30 (19)	C9—C8—C1	121.4 (2)
C1—N1—H1	126.9 (19)	C10—C9—C8	119.8 (3)
N2—N1—H1	120 (2)	C10—C9—H9	120.1
C2—N2—N1	101.85 (19)	C8—C9—H9	120.1
C7—N3—C3	118.5 (2)	C11—C10—C9	121.6 (3)
C7—N3—Cd1	123.10 (16)	C11—C10—H10	119.2
C3—N3—Cd1	117.72 (14)	C9—C10—H10	119.2
C1—N4—C2	103.85 (19)	C10—C11—C12	118.0 (2)
C1—N4—Cd1	144.39 (15)	C10—C11—C14	121.2 (3)
C2—N4—Cd1	108.56 (14)	C12—C11—C14	120.7 (3)
O3—N5—O2	123.3 (2)	C11—C12—C13	121.2 (2)
O3—N5—O1	119.7 (2)	C11—C12—H12	119.4
O2—N5—O1	116.91 (19)	C13—C12—H12	119.4
N5—O1—Cd1	112.49 (13)	C8—C13—C12	120.3 (2)
N4—C1—N1	108.4 (2)	C8—C13—H13	119.8
N4—C1—C8	126.7 (2)	C12—C13—H13	119.8
N1—C1—C8	124.9 (2)	C11—C14—H14A	109.5
N2—C2—N4	114.6 (2)	C11—C14—H14B	109.5
N2—C2—C3	123.4 (2)	H14A—C14—H14B	109.5
N4—C2—C3	121.9 (2)	C11—C14—H14C	109.5
N3—C3—C4	121.7 (2)	H14A—C14—H14C	109.5
N3—C3—C2	115.89 (19)	H14B—C14—H14C	109.5
C1—N1—N2—C2	−0.7 (3)	N4—C2—C3—C4	171.4 (2)
O3—N5—O1—Cd1	8.5 (3)	N3—C3—C4—C5	0.7 (4)
O2—N5—O1—Cd1	−169.48 (15)	C2—C3—C4—C5	−176.0 (2)
C2—N4—C1—N1	−1.5 (2)	C3—C4—C5—C6	1.2 (4)
Cd1—N4—C1—N1	153.7 (2)	C4—C5—C6—C7	−2.0 (4)
C2—N4—C1—C8	179.0 (2)	C3—N3—C7—C6	0.8 (4)
Cd1—N4—C1—C8	−25.9 (4)	Cd1—N3—C7—C6	−169.7 (2)
N2—N1—C1—N4	1.4 (3)	C5—C6—C7—N3	1.0 (4)
N2—N1—C1—C8	−179.0 (2)	N4—C1—C8—C13	−19.8 (4)
N1—N2—C2—N4	−0.3 (3)	N1—C1—C8—C13	160.8 (2)
N1—N2—C2—C3	176.3 (2)	N4—C1—C8—C9	160.2 (2)
C1—N4—C2—N2	1.1 (3)	N1—C1—C8—C9	−19.2 (4)
Cd1—N4—C2—N2	−163.91 (16)	C13—C8—C9—C10	2.8 (4)
C1—N4—C2—C3	−175.6 (2)	C1—C8—C9—C10	−177.2 (2)
Cd1—N4—C2—C3	19.4 (2)	C8—C9—C10—C11	0.4 (4)
C7—N3—C3—C4	−1.7 (3)	C9—C10—C11—C12	−3.0 (4)
Cd1—N3—C3—C4	169.32 (17)	C9—C10—C11—C14	175.9 (3)
C7—N3—C3—C2	175.2 (2)	C10—C11—C12—C13	2.4 (4)
Cd1—N3—C3—C2	−13.8 (3)	C14—C11—C12—C13	−176.4 (3)
N2—C2—C3—N3	178.2 (2)	C9—C8—C13—C12	−3.3 (4)
N4—C2—C3—N3	−5.4 (3)	C1—C8—C13—C12	176.7 (2)
N2—C2—C3—C4	−5.0 (4)	C11—C12—C13—C8	0.7 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5^ii	0.87 (1)	2.60 (1)	3.398 (3)	152 (2)
N1—H1···O1^ii	0.87 (1)	2.50 (2)	3.129 (3)	130 (2)
N1—H1···O2^ii	0.87 (1)	2.11 (1)	2.967 (3)	170 (3)
C6—H6···O1^iii	0.93	2.60	3.500 (3)	164

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

(VI) Aquabis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]cobalt(II)

Crystal data

[Co(C14H11N4)2(H2O)]	F(000) = 1132
Mr = 547.48	Dx = 1.471 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 28.735 (6) Å	Cell parameters from 12169 reflections
b = 7.4617 (15) Å	θ = 3.1–25.0°
c = 12.421 (3) Å	µ = 0.73 mm^−1
β = 111.79 (3)°	T = 293 K
V = 2472.9 (10) Å^3	Block, red
Z = 4	0.31 × 0.27 × 0.25 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1866 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.032
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan ABSCOR	h = −34→34
Tmin = 0.796, Tmax = 0.832	k = −8→8
9301 measured reflections	l = −14→14
2177 independent 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0315P)^2 + 1.7253P] where P = (Fo^2 + 2Fc^2)/3
2177 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.23 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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.88006 (5)	0.2500	0.03214 (13)
O1W	0.0000	1.1468 (3)	0.2500	0.0430 (5)
H1	0.0088	1.2041	0.2045	0.065*
N1	−0.03312 (6)	0.7797 (2)	0.08970 (12)	0.0342 (4)
N2	−0.08111 (6)	0.7396 (2)	0.01684 (13)	0.0365 (4)
N3	0.06247 (6)	0.8606 (2)	0.19489 (13)	0.0322 (4)
N4	−0.02919 (6)	0.7113 (2)	−0.08164 (12)	0.0306 (4)
C1	−0.07690 (7)	0.6996 (3)	−0.08404 (15)	0.0302 (4)
C2	−0.00365 (7)	0.7615 (2)	0.02813 (14)	0.0291 (4)
C3	0.04983 (7)	0.7986 (3)	0.08521 (15)	0.0297 (4)
C4	0.08522 (7)	0.7711 (3)	0.03616 (17)	0.0393 (5)
H4	0.0758	0.7282	−0.0393	0.047*
C5	0.13471 (8)	0.8083 (3)	0.10114 (19)	0.0465 (5)
H5	0.1592	0.7910	0.0698	0.056*
C6	0.14772 (8)	0.8712 (3)	0.21247 (18)	0.0439 (5)
H6	0.1809	0.8972	0.2574	0.053*
C7	0.11054 (7)	0.8950 (3)	0.25617 (17)	0.0390 (5)
H7	0.1194	0.9369	0.3317	0.047*
C8	−0.12048 (7)	0.6482 (3)	−0.18666 (15)	0.0319 (4)
C9	−0.11495 (8)	0.5704 (3)	−0.28298 (16)	0.0367 (5)
H9	−0.0830	0.5504	−0.2830	0.044*
C10	−0.15641 (8)	0.5224 (3)	−0.37867 (17)	0.0403 (5)
H10	−0.1518	0.4703	−0.4420	0.048*
C11	−0.20464 (8)	0.5500 (3)	−0.38274 (17)	0.0401 (5)
C12	−0.21000 (8)	0.6271 (3)	−0.28589 (18)	0.0451 (5)
H12	−0.2420	0.6465	−0.2859	0.054*
C13	−0.16890 (8)	0.6752 (3)	−0.19002 (17)	0.0412 (5)
H13	−0.1736	0.7266	−0.1266	0.049*
C14	−0.24995 (9)	0.4998 (3)	−0.4882 (2)	0.0572 (6)
H14A	−0.2392	0.4464	−0.5453	0.086*
H14B	−0.2693	0.6054	−0.5199	0.086*
H14C	−0.2702	0.4159	−0.4663	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0335 (2)	0.0426 (2)	0.02309 (19)	0.000	0.01376 (16)	0.000
O1W	0.0610 (14)	0.0456 (12)	0.0366 (10)	0.000	0.0344 (10)	0.000
N1	0.0304 (9)	0.0483 (10)	0.0271 (8)	−0.0022 (8)	0.0145 (7)	−0.0019 (7)
N2	0.0317 (9)	0.0521 (11)	0.0282 (8)	−0.0058 (8)	0.0141 (7)	−0.0039 (8)
N3	0.0314 (9)	0.0391 (9)	0.0271 (7)	0.0019 (7)	0.0121 (7)	0.0006 (7)
N4	0.0326 (9)	0.0373 (9)	0.0253 (7)	−0.0001 (7)	0.0147 (7)	0.0016 (7)
C1	0.0320 (10)	0.0341 (10)	0.0269 (9)	−0.0006 (8)	0.0137 (8)	0.0035 (8)
C2	0.0312 (10)	0.0336 (10)	0.0256 (9)	0.0023 (8)	0.0143 (8)	0.0032 (8)
C3	0.0333 (10)	0.0323 (10)	0.0261 (9)	0.0027 (8)	0.0138 (8)	0.0040 (8)
C4	0.0359 (11)	0.0535 (13)	0.0325 (10)	0.0005 (10)	0.0174 (9)	−0.0034 (9)
C5	0.0341 (12)	0.0631 (15)	0.0494 (12)	0.0008 (11)	0.0237 (11)	−0.0002 (11)
C6	0.0298 (11)	0.0554 (14)	0.0453 (12)	−0.0026 (10)	0.0125 (10)	−0.0011 (11)
C7	0.0349 (12)	0.0481 (13)	0.0317 (10)	−0.0013 (10)	0.0095 (9)	−0.0032 (9)
C8	0.0344 (11)	0.0344 (11)	0.0286 (9)	−0.0017 (9)	0.0137 (9)	0.0044 (8)
C9	0.0354 (11)	0.0433 (12)	0.0340 (10)	0.0002 (9)	0.0161 (9)	−0.0005 (9)
C10	0.0458 (13)	0.0428 (12)	0.0321 (10)	−0.0008 (10)	0.0141 (10)	−0.0049 (9)
C11	0.0396 (12)	0.0388 (11)	0.0354 (10)	−0.0019 (10)	0.0063 (9)	0.0030 (9)
C12	0.0302 (11)	0.0587 (14)	0.0460 (12)	0.0020 (10)	0.0139 (10)	0.0006 (11)
C13	0.0399 (12)	0.0538 (13)	0.0338 (10)	0.0009 (10)	0.0181 (10)	−0.0020 (10)
C14	0.0498 (14)	0.0558 (16)	0.0522 (13)	−0.0024 (12)	0.0031 (12)	−0.0059 (12)

Geometric parameters (Å, º)

Co1—O1W	1.990 (2)	C5—H5	0.9300
Co1—N1	2.0061 (16)	C6—C7	1.378 (3)
Co1—N1^i	2.0062 (16)	C6—H6	0.9300
Co1—N3^i	2.1504 (15)	C7—H7	0.9300
Co1—N3	2.1505 (15)	C8—C9	1.391 (3)
O1W—H1	0.8199	C8—C13	1.391 (3)
N1—C2	1.342 (2)	C9—C10	1.382 (3)
N1—N2	1.372 (2)	C9—H9	0.9300
N2—C1	1.337 (2)	C10—C11	1.383 (3)
N3—C7	1.331 (3)	C10—H10	0.9300
N3—C3	1.355 (2)	C11—C12	1.393 (3)
N4—C2	1.340 (2)	C11—C14	1.511 (3)
N4—C1	1.363 (2)	C12—C13	1.378 (3)
C1—C8	1.468 (3)	C12—H12	0.9300
C2—C3	1.460 (3)	C13—H13	0.9300
C3—C4	1.381 (3)	C14—H14A	0.9600
C4—C5	1.378 (3)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C5—C6	1.374 (3)
O1W—Co1—N1	111.93 (5)	C6—C5—H5	120.2
O1W—Co1—N1^i	111.93 (5)	C4—C5—H5	120.2
N1—Co1—N1^i	136.14 (10)	C5—C6—C7	118.65 (19)
O1W—Co1—N3^i	93.86 (4)	C5—C6—H6	120.7
N1—Co1—N3^i	98.41 (6)	C7—C6—H6	120.7
N1^i—Co1—N3^i	78.66 (6)	N3—C7—C6	122.79 (18)
O1W—Co1—N3	93.86 (4)	N3—C7—H7	118.6
N1—Co1—N3	78.66 (6)	C6—C7—H7	118.6
N1^i—Co1—N3	98.41 (6)	C9—C8—C13	117.85 (18)
N3^i—Co1—N3	172.28 (9)	C9—C8—C1	121.54 (17)
Co1—O1W—H1	121.4	C13—C8—C1	120.62 (16)
C2—N1—N2	107.11 (14)	C10—C9—C8	120.71 (18)
C2—N1—Co1	115.86 (12)	C10—C9—H9	119.6
N2—N1—Co1	136.57 (12)	C8—C9—H9	119.6
C1—N2—N1	104.38 (15)	C9—C10—C11	121.69 (18)
C7—N3—C3	118.35 (16)	C9—C10—H10	119.2
C7—N3—Co1	128.06 (13)	C11—C10—H10	119.2
C3—N3—Co1	113.53 (12)	C10—C11—C12	117.41 (19)
C2—N4—C1	101.93 (14)	C10—C11—C14	121.61 (19)
N2—C1—N4	113.92 (16)	C12—C11—C14	121.0 (2)
N2—C1—C8	121.84 (16)	C13—C12—C11	121.3 (2)
N4—C1—C8	124.24 (15)	C13—C12—H12	119.3
N4—C2—N1	112.66 (16)	C11—C12—H12	119.3
N4—C2—C3	128.84 (15)	C12—C13—C8	120.99 (18)
N1—C2—C3	118.50 (15)	C12—C13—H13	119.5
N3—C3—C4	121.87 (17)	C8—C13—H13	119.5
N3—C3—C2	113.22 (15)	C11—C14—H14A	109.5
C4—C3—C2	124.90 (17)	C11—C14—H14B	109.5
C5—C4—C3	118.71 (18)	H14A—C14—H14B	109.5
C5—C4—H4	120.6	C11—C14—H14C	109.5
C3—C4—H4	120.6	H14A—C14—H14C	109.5
C6—C5—C4	119.63 (19)	H14B—C14—H14C	109.5
C2—N1—N2—C1	0.1 (2)	C2—C3—C4—C5	−178.56 (19)
Co1—N1—N2—C1	171.60 (15)	C3—C4—C5—C6	0.1 (3)
N1—N2—C1—N4	−0.1 (2)	C4—C5—C6—C7	0.1 (3)
N1—N2—C1—C8	179.93 (17)	C3—N3—C7—C6	0.4 (3)
C2—N4—C1—N2	0.1 (2)	Co1—N3—C7—C6	177.52 (15)
C2—N4—C1—C8	−179.97 (18)	C5—C6—C7—N3	−0.4 (3)
C1—N4—C2—N1	0.0 (2)	N2—C1—C8—C9	−166.02 (19)
C1—N4—C2—C3	−179.29 (19)	N4—C1—C8—C9	14.0 (3)
N2—N1—C2—N4	−0.1 (2)	N2—C1—C8—C13	13.6 (3)
Co1—N1—C2—N4	−173.59 (12)	N4—C1—C8—C13	−166.38 (18)
N2—N1—C2—C3	179.31 (16)	C13—C8—C9—C10	0.2 (3)
Co1—N1—C2—C3	5.8 (2)	C1—C8—C9—C10	179.83 (18)
C7—N3—C3—C4	−0.2 (3)	C8—C9—C10—C11	0.2 (3)
Co1—N3—C3—C4	−177.68 (15)	C9—C10—C11—C12	−0.5 (3)
C7—N3—C3—C2	178.45 (17)	C9—C10—C11—C14	179.1 (2)
Co1—N3—C3—C2	1.0 (2)	C10—C11—C12—C13	0.4 (3)
N4—C2—C3—N3	174.89 (18)	C14—C11—C12—C13	−179.2 (2)
N1—C2—C3—N3	−4.4 (3)	C11—C12—C13—C8	−0.1 (3)
N4—C2—C3—C4	−6.5 (3)	C9—C8—C13—C12	−0.3 (3)
N1—C2—C3—C4	174.20 (18)	C1—C8—C13—C12	−179.89 (19)
N3—C3—C4—C5	−0.1 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···N4^ii	0.82	1.93	2.7386 (17)	167

Symmetry code: (ii) −x, −y+2, −z.

(VII) Diaquabis[5-(4-methylphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazolato-κ²N¹,N⁵]nickel(II)

Crystal data

[Ni(C14H11N4)2(H2O)2]	F(000) = 1176
Mr = 565.28	Dx = 1.504 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 26.778 (5) Å	Cell parameters from 12342 reflections
b = 7.4858 (15) Å	θ = 3.1–25.0°
c = 12.472 (3) Å	µ = 0.82 mm^−1
β = 92.91 (3)°	T = 293 K
V = 2496.8 (9) Å^3	Block, purple
Z = 4	0.32 × 0.28 × 0.26 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	2016 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.023
ω scans at fixed χ = 45°	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan ABSCOR	h = −31→31
Tmin = 0.769, Tmax = 0.808	k = −8→8
9388 measured reflections	l = −13→14
2186 independent 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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 1.0824P] where P = (Fo^2 + 2Fc^2)/3
2186 reflections	(Δ/σ)max < 0.001
185 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.21 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. SHELXL-2014/7 (Sheldrick, 2015)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.2500	−0.03344 (4)	0.0000	0.02241 (11)
N1	0.21155 (5)	−0.01668 (17)	0.13760 (10)	0.0262 (3)
N2	0.16365 (5)	0.01555 (18)	0.16472 (11)	0.0287 (3)
N3	0.19172 (5)	−0.04746 (16)	−0.11687 (10)	0.0250 (3)
N4	0.21437 (5)	0.02969 (17)	0.31469 (10)	0.0269 (3)
O1	0.2500	−0.3149 (2)	0.0000	0.0385 (4)
H1WA	0.2384 (9)	−0.372 (3)	−0.0472 (17)	0.058*
O2	0.2500	0.2501 (2)	0.0000	0.0351 (4)
H2WA	0.2441 (9)	0.306 (3)	−0.0535 (16)	0.053*
C1	0.16687 (6)	0.0426 (2)	0.27055 (12)	0.0255 (3)
C2	0.24037 (6)	−0.0064 (2)	0.22750 (12)	0.0244 (3)
C3	0.20562 (6)	−0.0326 (2)	−0.21889 (12)	0.0251 (3)
C4	0.17112 (7)	−0.0449 (3)	−0.30512 (13)	0.0390 (4)
H4	0.1811	−0.0328	−0.3751	0.047*
C5	0.12170 (7)	−0.0755 (3)	−0.28513 (15)	0.0454 (5)
H5	0.0979	−0.0839	−0.3419	0.055*
C6	0.10769 (6)	−0.0936 (3)	−0.18138 (14)	0.0393 (4)
H6	0.0745	−0.1157	−0.1669	0.047*
C7	0.14384 (6)	−0.0783 (2)	−0.09896 (13)	0.0316 (4)
H7	0.1345	−0.0899	−0.0285	0.038*
C8	0.12222 (6)	0.0883 (2)	0.32949 (12)	0.0271 (3)
C9	0.12556 (6)	0.1509 (2)	0.43446 (12)	0.0337 (4)
H9	0.1566	0.1575	0.4711	0.040*
C10	0.08310 (6)	0.2036 (2)	0.48518 (13)	0.0370 (4)
H10	0.0863	0.2441	0.5557	0.044*
C11	0.03630 (6)	0.1978 (2)	0.43428 (14)	0.0355 (4)
C12	0.03294 (7)	0.1337 (3)	0.32928 (15)	0.0446 (5)
H12	0.0018	0.1273	0.2929	0.054*
C13	0.07497 (7)	0.0794 (3)	0.27817 (13)	0.0395 (4)
H13	0.0716	0.0363	0.2083	0.047*
C14	−0.00982 (7)	0.2557 (3)	0.49021 (17)	0.0494 (5)
H14A	−0.0001	0.3085	0.5582	0.074*
H14B	−0.0307	0.1537	0.5014	0.074*
H14C	−0.0280	0.3416	0.4465	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02456 (17)	0.02787 (17)	0.01480 (15)	0.000	0.00105 (11)	0.000
N1	0.0261 (7)	0.0337 (7)	0.0187 (7)	0.0002 (5)	0.0015 (5)	−0.0007 (5)
N2	0.0253 (7)	0.0401 (8)	0.0209 (7)	0.0005 (6)	0.0025 (5)	−0.0017 (5)
N3	0.0273 (7)	0.0278 (7)	0.0198 (6)	−0.0006 (5)	0.0017 (5)	−0.0002 (5)
N4	0.0270 (7)	0.0358 (7)	0.0179 (6)	0.0015 (5)	0.0012 (5)	0.0001 (5)
O1	0.0656 (13)	0.0273 (9)	0.0215 (8)	0.000	−0.0073 (8)	0.000
O2	0.0497 (10)	0.0274 (9)	0.0269 (8)	0.000	−0.0100 (8)	0.000
C1	0.0281 (8)	0.0278 (8)	0.0207 (7)	−0.0003 (6)	0.0016 (6)	0.0018 (6)
C2	0.0271 (8)	0.0271 (8)	0.0189 (8)	−0.0005 (6)	0.0014 (6)	0.0008 (6)
C3	0.0282 (8)	0.0272 (8)	0.0199 (7)	−0.0002 (6)	0.0022 (6)	0.0000 (6)
C4	0.0332 (10)	0.0640 (12)	0.0197 (8)	−0.0039 (8)	0.0002 (7)	0.0002 (8)
C5	0.0302 (9)	0.0745 (13)	0.0307 (9)	−0.0064 (9)	−0.0069 (7)	−0.0029 (9)
C6	0.0259 (9)	0.0563 (11)	0.0357 (9)	−0.0070 (8)	0.0025 (7)	−0.0009 (8)
C7	0.0299 (9)	0.0412 (9)	0.0242 (8)	−0.0038 (7)	0.0051 (6)	0.0000 (7)
C8	0.0285 (8)	0.0304 (8)	0.0225 (7)	−0.0003 (7)	0.0039 (6)	0.0025 (6)
C9	0.0285 (9)	0.0463 (10)	0.0263 (8)	−0.0006 (7)	0.0009 (7)	−0.0031 (7)
C10	0.0373 (10)	0.0451 (10)	0.0291 (8)	−0.0014 (8)	0.0077 (7)	−0.0065 (7)
C11	0.0319 (9)	0.0363 (9)	0.0391 (9)	−0.0009 (7)	0.0110 (7)	0.0014 (7)
C12	0.0254 (9)	0.0689 (13)	0.0393 (10)	0.0000 (9)	−0.0016 (7)	−0.0010 (9)
C13	0.0340 (9)	0.0595 (11)	0.0246 (8)	−0.0018 (9)	−0.0004 (7)	−0.0040 (8)
C14	0.0371 (10)	0.0518 (11)	0.0608 (12)	0.0021 (9)	0.0172 (9)	−0.0043 (10)

Geometric parameters (Å, º)

Ni1—N1^i	2.0495 (14)	C4—H4	0.9300
Ni1—N1	2.0495 (14)	C5—C6	1.372 (3)
Ni1—N3	2.0834 (14)	C5—H5	0.9300
Ni1—N3^i	2.0834 (14)	C6—C7	1.380 (2)
Ni1—O1	2.1066 (17)	C6—H6	0.9300
Ni1—O2	2.1223 (17)	C7—H7	0.9300
N1—C2	1.331 (2)	C8—C9	1.389 (2)
N1—N2	1.365 (2)	C8—C13	1.390 (2)
N2—C1	1.334 (2)	C9—C10	1.386 (2)
N3—C7	1.333 (2)	C9—H9	0.9300
N3—C3	1.348 (2)	C10—C11	1.376 (2)
N4—C2	1.348 (2)	C10—H10	0.9300
N4—C1	1.363 (2)	C11—C12	1.393 (3)
O1—H1WA	0.78 (2)	C11—C14	1.512 (2)
O2—H2WA	0.80 (2)	C12—C13	1.382 (3)
C1—C8	1.475 (2)	C12—H12	0.9300
C2—C3^i	1.469 (2)	C13—H13	0.9300
C3—C4	1.385 (2)	C14—H14A	0.9600
C3—C2^i	1.469 (2)	C14—H14B	0.9600
C4—C5	1.378 (3)	C14—H14C	0.9600
N1^i—Ni1—N1	172.98 (7)	C5—C4—H4	120.7
N1^i—Ni1—N3	78.90 (5)	C3—C4—H4	120.7
N1—Ni1—N3	101.45 (5)	C6—C5—C4	119.87 (16)
N1^i—Ni1—N3^i	101.46 (5)	C6—C5—H5	120.1
N1—Ni1—N3^i	78.91 (5)	C4—C5—H5	120.1
N3—Ni1—N3^i	174.22 (7)	C5—C6—C7	118.62 (16)
N1^i—Ni1—O1	93.51 (4)	C5—C6—H6	120.7
N1—Ni1—O1	93.51 (4)	C7—C6—H6	120.7
N3—Ni1—O1	87.11 (3)	N3—C7—C6	122.26 (15)
N3^i—Ni1—O1	87.11 (3)	N3—C7—H7	118.9
N1^i—Ni1—O2	86.49 (4)	C6—C7—H7	118.9
N1—Ni1—O2	86.49 (4)	C9—C8—C13	117.60 (15)
N3—Ni1—O2	92.89 (3)	C9—C8—C1	122.20 (15)
N3^i—Ni1—O2	92.89 (3)	C13—C8—C1	120.09 (14)
O1—Ni1—O2	180.0	C10—C9—C8	120.74 (16)
C2—N1—N2	107.05 (13)	C10—C9—H9	119.6
C2—N1—Ni1	114.50 (11)	C8—C9—H9	119.6
N2—N1—Ni1	137.47 (10)	C11—C10—C9	121.96 (15)
C1—N2—N1	104.93 (13)	C11—C10—H10	119.0
C7—N3—C3	119.12 (13)	C9—C10—H10	119.0
C7—N3—Ni1	125.76 (11)	C10—C11—C12	117.27 (15)
C3—N3—Ni1	115.03 (11)	C10—C11—C14	121.60 (16)
C2—N4—C1	101.42 (13)	C12—C11—C14	121.13 (17)
Ni1—O1—H1WA	123.2 (17)	C13—C12—C11	121.29 (16)
Ni1—O2—H2WA	121.7 (16)	C13—C12—H12	119.4
N2—C1—N4	113.65 (14)	C11—C12—H12	119.4
N2—C1—C8	120.99 (14)	C12—C13—C8	121.14 (16)
N4—C1—C8	125.33 (14)	C12—C13—H13	119.4
N1—C2—N4	112.96 (14)	C8—C13—H13	119.4
N1—C2—C3^i	117.50 (14)	C11—C14—H14A	109.5
N4—C2—C3^i	129.54 (14)	C11—C14—H14B	109.5
N3—C3—C4	121.46 (15)	H14A—C14—H14B	109.5
N3—C3—C2^i	113.59 (13)	C11—C14—H14C	109.5
C4—C3—C2^i	124.94 (15)	H14A—C14—H14C	109.5
C5—C4—C3	118.65 (16)	H14B—C14—H14C	109.5
C2—N1—N2—C1	−0.27 (16)	C4—C5—C6—C7	0.8 (3)
Ni1—N1—N2—C1	−167.63 (12)	C3—N3—C7—C6	−0.8 (2)
N1—N2—C1—N4	−0.07 (17)	Ni1—N3—C7—C6	−177.00 (13)
N1—N2—C1—C8	177.85 (13)	C5—C6—C7—N3	−0.3 (3)
C2—N4—C1—N2	0.37 (17)	N2—C1—C8—C9	−167.16 (16)
C2—N4—C1—C8	−177.44 (15)	N4—C1—C8—C9	10.5 (2)
N2—N1—C2—N4	0.54 (17)	N2—C1—C8—C13	9.0 (2)
Ni1—N1—C2—N4	171.18 (10)	N4—C1—C8—C13	−173.35 (16)
N2—N1—C2—C3^i	−178.69 (13)	C13—C8—C9—C10	−0.5 (3)
Ni1—N1—C2—C3^i	−8.05 (17)	C1—C8—C9—C10	175.77 (15)
C1—N4—C2—N1	−0.55 (16)	C8—C9—C10—C11	−0.5 (3)
C1—N4—C2—C3^i	178.56 (15)	C9—C10—C11—C12	1.0 (3)
C7—N3—C3—C4	1.4 (2)	C9—C10—C11—C14	−179.97 (18)
Ni1—N3—C3—C4	178.00 (13)	C10—C11—C12—C13	−0.5 (3)
C7—N3—C3—C2^i	−177.52 (14)	C14—C11—C12—C13	−179.52 (19)
Ni1—N3—C3—C2^i	−0.88 (16)	C11—C12—C13—C8	−0.5 (3)
N3—C3—C4—C5	−0.9 (3)	C9—C8—C13—C12	1.0 (3)
C2^i—C3—C4—C5	177.87 (17)	C1—C8—C13—C12	−175.34 (17)
C3—C4—C5—C6	−0.2 (3)

Symmetry code: (i) −x+1/2, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1WA···N4^ii	0.78 (2)	2.16 (2)	2.9351 (17)	174 (3)
O2—H2WA···N4^iii	0.80 (2)	2.17 (2)	2.9575 (17)	169 (2)
C7—H7···N2	0.93	2.62	3.378 (2)	139

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