Zinc(II) and nickel(II) com­plexes of 3,5-dimethyl-1-(pyri­din-2-yl)-1H-pyrazole: relationship between fluorescence and crystal packing

Two novel coordination com­plexes, namely, di­chlorido­[3,5-dimethyl-1-(pyri­din-2-yl-κN)-1H-pyrazole-κN²]zinc(II), [ZnCl₂(C₁₀H₁₁N₃)], 1, and aqua­chlorido­bis­[3,5-dimethyl-1-(pyri­din-2-yl-κN)-1H-pyrazole-κN²]nickel(II) chloride mono­hydrate, [NiCl(C₁₀H₁₁N₃)(H₂O)]Cl·H₂O, 2, have been synthesized. The crystal structure analyses revealed that com­plexes 1 and 2 are mononuclear and have ZnN₂Cl₂ distorted tetra­hedral and NiN₄OCl distorted octa­hedral structures, respectively. Complex 1 displays a dimer in the crystal structure, while com­plex 2 forms a chain along the [010] direction. The fluorescence properties of both com­plexes were also investigated. A search of the Cambridge Structural Data­base for other com­plexes of the ligand 3,5-dimethyl-1-(pyri­din-2-yl)-1H-pyrazole (L) shows that there exist different coordination polyhedra with different arrangements as monomers, dimers and polycyclic structures. Here it has also been demonstrated that there is a relationship between the crystal packing and the fluorescence properties of Zn^II and Cd^II com­plexes of L.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015) for compound1; CrysAlis PRO (Agilent, 2014) for compound2. Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for compound1; CrysAlis PRO (Agilent, 2014) for compound2. Data reduction: CrysAlis PRO (Rigaku OD, 2015) for compound1; CrysAlis PRO (Agilent, 2014) for compound2. Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for compound1; SIR97 (Altomare et al., 1999) for compound2. Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) for compound1; SHELXTL (Sheldrick, 2008). for compound2. Molecular graphics: DIAMOND (Brandenburg & Putz, 1999) for compound1. Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010) for compound1.

Dichlorido[3,5-dimethyl-1-(pyridin-2-yl-κN)-1H-pyrazole-κN²]zinc(II) (compound1)

Crystal data

[ZnCl2(C10H11N3)]	Z = 2
Mr = 309.49	F(000) = 312
Triclinic, P1	Dx = 1.680 Mg m^−3
a = 7.4115 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5345 (4) Å	Cell parameters from 2568 reflections
c = 10.7790 (5) Å	θ = 3.4–35.3°
α = 89.682 (4)°	µ = 2.42 mm^−1
β = 72.145 (5)°	T = 100 K
γ = 71.405 (5)°	Block, colorless
V = 611.87 (6) Å^3	0.32 × 0.26 × 0.2 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	2459 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2245 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.012
Detector resolution: 10.4498 pixels mm^-1	θmax = 26.5°, θmin = 3.1°
ω–scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −10→9
Tmin = 0.559, Tmax = 1.000	l = −12→13
4062 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0381P)^2 + 0.182P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.016
2459 reflections	Δρmax = 0.53 e Å^−3
147 parameters	Δρmin = −0.27 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.

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

	x	y	z	Uiso*/Ueq
Zn1	0.70552 (4)	0.82724 (3)	0.28173 (2)	0.04414 (10)
Cl1	0.79199 (9)	0.90792 (7)	0.44293 (6)	0.05502 (15)
Cl2	0.60875 (10)	1.00140 (7)	0.14694 (6)	0.06016 (16)
N1	0.9263 (2)	0.60899 (18)	0.19004 (16)	0.0404 (4)
N2	0.8725 (2)	0.47124 (18)	0.22315 (16)	0.0387 (3)
N3	0.5532 (2)	0.65702 (19)	0.32436 (16)	0.0400 (3)
C2	1.1206 (3)	0.5550 (2)	0.1243 (2)	0.0423 (4)
C5	0.6658 (3)	0.4978 (2)	0.28763 (18)	0.0374 (4)
C4	1.0366 (3)	0.3306 (2)	0.1781 (2)	0.0442 (4)
C3	1.1936 (3)	0.3809 (3)	0.1147 (2)	0.0481 (5)
H3	1.3280	0.3113	0.0717	0.058*
C9	0.3540 (3)	0.6942 (3)	0.3823 (2)	0.0486 (5)
H9	0.2729	0.8075	0.4077	0.058*
C6	0.5860 (3)	0.3708 (3)	0.3080 (2)	0.0484 (5)
H6	0.6693	0.2584	0.2808	0.058*
C7	0.3819 (3)	0.4116 (3)	0.3691 (2)	0.0514 (5)
H7	0.3229	0.3265	0.3856	0.062*
C8	0.2638 (3)	0.5750 (3)	0.4060 (2)	0.0520 (5)
H8	0.1227	0.6047	0.4471	0.062*
C21	1.2277 (4)	0.6748 (3)	0.0753 (3)	0.0580 (6)
H21A	1.1297	0.7869	0.0872	0.087*
H21B	1.3042	0.6437	−0.0180	0.087*
H21C	1.3199	0.6729	0.1244	0.087*
C41	1.0408 (4)	0.1560 (3)	0.1999 (3)	0.0638 (7)
H41A	0.9638	0.1242	0.1511	0.096*
H41B	0.9812	0.1491	0.2935	0.096*
H41C	1.1803	0.0805	0.1692	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.05413 (16)	0.02706 (13)	0.05909 (16)	−0.01673 (11)	−0.02577 (12)	0.00539 (10)
Cl1	0.0641 (3)	0.0473 (3)	0.0621 (3)	−0.0241 (3)	−0.0260 (3)	−0.0031 (2)
Cl2	0.0768 (4)	0.0389 (3)	0.0728 (4)	−0.0151 (3)	−0.0396 (3)	0.0139 (2)
N1	0.0478 (9)	0.0276 (8)	0.0510 (9)	−0.0168 (7)	−0.0187 (8)	0.0066 (7)
N2	0.0449 (9)	0.0256 (7)	0.0495 (9)	−0.0148 (7)	−0.0173 (7)	0.0051 (6)
N3	0.0457 (9)	0.0318 (8)	0.0460 (8)	−0.0139 (7)	−0.0186 (7)	0.0004 (6)
C2	0.0482 (11)	0.0376 (10)	0.0466 (10)	−0.0183 (9)	−0.0187 (9)	0.0059 (8)
C5	0.0460 (10)	0.0321 (9)	0.0401 (9)	−0.0163 (8)	−0.0187 (8)	0.0043 (7)
C4	0.0485 (11)	0.0297 (9)	0.0583 (12)	−0.0131 (9)	−0.0226 (9)	0.0045 (8)
C3	0.0446 (11)	0.0386 (11)	0.0603 (12)	−0.0134 (9)	−0.0160 (10)	0.0032 (9)
C9	0.0492 (12)	0.0414 (11)	0.0529 (11)	−0.0121 (9)	−0.0163 (10)	−0.0039 (9)
C6	0.0550 (12)	0.0345 (10)	0.0612 (12)	−0.0211 (9)	−0.0198 (10)	0.0057 (9)
C7	0.0573 (13)	0.0497 (12)	0.0573 (12)	−0.0305 (11)	−0.0193 (10)	0.0100 (10)
C8	0.0480 (11)	0.0578 (13)	0.0527 (12)	−0.0224 (10)	−0.0146 (10)	0.0028 (10)
C21	0.0568 (13)	0.0501 (13)	0.0708 (15)	−0.0284 (11)	−0.0145 (11)	0.0117 (11)
C41	0.0566 (14)	0.0294 (11)	0.101 (2)	−0.0116 (10)	−0.0216 (13)	0.0116 (11)

Geometric parameters (Å, º)

Zn1—N1	2.0514 (16)	C3—H3	0.9500
Zn1—N3	2.0773 (16)	C9—C8	1.369 (3)
Zn1—Cl2	2.1840 (6)	C9—H9	0.9500
Zn1—Cl1	2.2094 (6)	C6—C7	1.378 (3)
N1—C2	1.320 (3)	C6—H6	0.9500
N1—N2	1.370 (2)	C7—C8	1.373 (3)
N2—C4	1.368 (3)	C7—H7	0.9500
N2—C5	1.417 (2)	C8—H8	0.9500
N3—C5	1.334 (2)	C21—H21A	0.9800
N3—C9	1.345 (3)	C21—H21B	0.9800
C2—C3	1.402 (3)	C21—H21C	0.9800
C2—C21	1.486 (3)	C41—H41A	0.9800
C5—C6	1.378 (3)	C41—H41B	0.9800
C4—C3	1.354 (3)	C41—H41C	0.9800
C4—C41	1.499 (3)
N1—Zn1—N3	77.90 (6)	C2—C3—H3	126.4
N1—Zn1—Cl2	113.82 (5)	N3—C9—C8	122.5 (2)
N3—Zn1—Cl2	113.42 (5)	N3—C9—H9	118.8
N1—Zn1—Cl1	106.89 (5)	C8—C9—H9	118.8
N3—Zn1—Cl1	115.74 (5)	C7—C6—C5	118.1 (2)
Cl2—Zn1—Cl1	120.83 (2)	C7—C6—H6	120.9
C2—N1—N2	106.69 (15)	C5—C6—H6	120.9
C2—N1—Zn1	138.76 (13)	C8—C7—C6	119.99 (19)
N2—N1—Zn1	113.28 (12)	C8—C7—H7	120.0
C4—N2—N1	110.06 (15)	C6—C7—H7	120.0
C4—N2—C5	132.82 (15)	C9—C8—C7	118.5 (2)
N1—N2—C5	117.00 (15)	C9—C8—H8	120.8
C5—N3—C9	118.37 (17)	C7—C8—H8	120.8
C5—N3—Zn1	115.84 (13)	C2—C21—H21A	109.5
C9—N3—Zn1	125.77 (13)	C2—C21—H21B	109.5
N1—C2—C3	109.49 (17)	H21A—C21—H21B	109.5
N1—C2—C21	120.34 (18)	C2—C21—H21C	109.5
C3—C2—C21	130.2 (2)	H21A—C21—H21C	109.5
N3—C5—C6	122.55 (19)	H21B—C21—H21C	109.5
N3—C5—N2	114.33 (15)	C4—C41—H41A	109.5
C6—C5—N2	123.10 (18)	C4—C41—H41B	109.5
C3—C4—N2	106.58 (17)	H41A—C41—H41B	109.5
C3—C4—C41	127.3 (2)	C4—C41—H41C	109.5
N2—C4—C41	126.10 (19)	H41A—C41—H41C	109.5
C4—C3—C2	107.17 (19)	H41B—C41—H41C	109.5
C4—C3—H3	126.4
C2—N1—N2—C4	0.5 (2)	N1—N2—C4—C3	−0.9 (2)
Zn1—N1—N2—C4	−169.07 (12)	C5—N2—C4—C3	174.92 (19)
C2—N1—N2—C5	−176.00 (15)	N1—N2—C4—C41	177.1 (2)
Zn1—N1—N2—C5	14.38 (19)	C5—N2—C4—C41	−7.1 (4)
N2—N1—C2—C3	0.0 (2)	N2—C4—C3—C2	0.9 (2)
Zn1—N1—C2—C3	165.46 (16)	C41—C4—C3—C2	−177.1 (2)
N2—N1—C2—C21	−179.17 (18)	N1—C2—C3—C4	−0.6 (2)
Zn1—N1—C2—C21	−13.7 (3)	C21—C2—C3—C4	178.5 (2)
C9—N3—C5—C6	−0.7 (3)	C5—N3—C9—C8	0.8 (3)
Zn1—N3—C5—C6	−179.35 (15)	Zn1—N3—C9—C8	179.27 (16)
C9—N3—C5—N2	177.77 (16)	N3—C5—C6—C7	−0.1 (3)
Zn1—N3—C5—N2	−0.9 (2)	N2—C5—C6—C7	−178.45 (18)
C4—N2—C5—N3	175.43 (19)	C5—C6—C7—C8	0.9 (3)
N1—N2—C5—N3	−9.0 (2)	N3—C9—C8—C7	0.0 (3)
C4—N2—C5—C6	−6.1 (3)	C6—C7—C8—C9	−0.8 (3)
N1—N2—C5—C6	169.45 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cl1^i	0.95	2.75	3.568 (2)	145

Symmetry code: (i) −x+1, −y+2, −z+1.

Aquachloridobis[3,5-dimethyl-1-(pyridin-2-yl-κN)-1H-pyrazole-κN²]nickel(II) chloride monohydrate (compound2)

Crystal data

[NiCl(C10H11N3)2(H2O)]Cl·H2O	F(000) = 1064
Mr = 512.08	Dx = 1.519 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.2306 (11) Å	Cell parameters from 1291 reflections
b = 13.2638 (10) Å	θ = 4.4–24.6°
c = 14.0560 (14) Å	µ = 1.14 mm^−1
β = 100.981 (8)°	T = 173 K
V = 2238.5 (3) Å^3	Rod, blue
Z = 4	0.24 × 0.08 × 0.04 mm

Data collection

Oxford XCalibur diffractometer	4070 independent reflections
Radiation source: fine-focus sealed tube, Spellman generator	2776 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 15.9809 pixels mm^-1	θmax = 25.4°, θmin = 4.2°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −8→15
Tmin = 0.994, Tmax = 1.000	l = −16→16
7459 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 0.0834P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
4070 reflections	Δρmax = 0.50 e Å^−3
351 parameters	Δρmin = −0.38 e Å^−3
160 restraints

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. The coordinates of the O-bound hydrogen atoms have been refined freely while the isotropic displacement parameters have been calculated: U(H) = 1.5 U(O). The O-H distances have been restrained to be equal within a standard deviation of 0.01 Angstroem. The disorder of one of the ligands has been described by a split model with the non-disordered ligand acting as geometrical model (SAME restraint). The ratio of site occupation factors refined to 0.88/0.12. All atoms of the minor part have been refined isotropically involving the SIMU restraint for similar refinement of the displacement parameters of atoms with a maximum distance of 0.8 Angstroem.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.2969 (3)	0.9197 (2)	0.4126 (2)	0.0304 (8)
N2	0.2467 (3)	0.7632 (2)	0.3021 (2)	0.0261 (8)
N3	0.3332 (2)	0.7542 (2)	0.3803 (2)	0.0250 (8)
C1	0.3135 (4)	1.0019 (3)	0.4700 (3)	0.0383 (11)
H1	0.275204	1.062413	0.448228	0.046*
C2	0.3837 (4)	1.0015 (4)	0.5586 (3)	0.0462 (13)
H2	0.395910	1.061356	0.596227	0.055*
C3	0.4360 (4)	0.9137 (4)	0.5922 (3)	0.0444 (12)
H3	0.483258	0.911524	0.654232	0.053*
C4	0.4198 (3)	0.8301 (3)	0.5364 (3)	0.0382 (11)
H4	0.454059	0.768193	0.559174	0.046*
C5	0.3521 (3)	0.8361 (3)	0.4450 (3)	0.0294 (10)
C6	0.1575 (4)	0.6514 (3)	0.1698 (3)	0.0427 (12)
H6A	0.083361	0.667835	0.182176	0.064*
H6B	0.160686	0.579501	0.154348	0.064*
H6C	0.172350	0.691515	0.115162	0.064*
C7	0.2422 (3)	0.6743 (3)	0.2571 (3)	0.0297 (10)
C8	0.3254 (3)	0.6098 (3)	0.3054 (3)	0.0326 (10)
H8	0.338829	0.542441	0.287785	0.039*
C9	0.3828 (3)	0.6612 (3)	0.3815 (3)	0.0311 (10)
C10	0.4829 (4)	0.6274 (3)	0.4522 (3)	0.0522 (14)
H10A	0.539775	0.680340	0.459825	0.078*
H10B	0.512561	0.565734	0.428358	0.078*
H10C	0.461998	0.613992	0.514970	0.078*
N4	0.0443 (3)	0.8814 (3)	0.3283 (3)	0.0248 (10)	0.879 (4)
N5	0.0766 (3)	0.8851 (3)	0.1514 (3)	0.0268 (9)	0.879 (4)
N6	−0.0304 (3)	0.8704 (8)	0.1658 (3)	0.0251 (10)	0.879 (4)
C11	0.0354 (4)	0.8851 (4)	0.4226 (4)	0.0295 (13)	0.879 (4)
H11A	0.100498	0.897129	0.470081	0.035*	0.879 (4)
C12	−0.0638 (4)	0.8722 (4)	0.4523 (4)	0.0330 (13)	0.879 (4)
H12A	−0.068114	0.874616	0.519072	0.040*	0.879 (4)
C13	−0.1578 (4)	0.8555 (3)	0.3818 (4)	0.0319 (12)	0.879 (4)
H13	−0.227585	0.844275	0.400253	0.038*	0.879 (4)
C14	−0.1509 (6)	0.8552 (18)	0.2876 (4)	0.0295 (13)	0.879 (4)
H14	−0.215894	0.846080	0.239212	0.035*	0.879 (4)
C15	−0.0478 (4)	0.8682 (3)	0.2615 (3)	0.0245 (11)	0.879 (4)
C16	0.1700 (5)	0.8942 (5)	0.0124 (4)	0.0432 (15)	0.879 (4)
H16A	0.211318	0.954765	0.037988	0.065*	0.879 (4)
H16B	0.147458	0.899971	−0.058116	0.065*	0.879 (4)
H16C	0.217545	0.834780	0.028295	0.065*	0.879 (4)
C17	0.0701 (4)	0.8839 (3)	0.0562 (3)	0.0300 (12)	0.879 (4)
C18	−0.0403 (5)	0.8691 (9)	0.0094 (4)	0.0316 (17)	0.879 (4)
H18	−0.066756	0.866262	−0.058617	0.038*	0.879 (4)
C19	−0.1024 (4)	0.8595 (3)	0.0785 (3)	0.0324 (13)	0.879 (4)
C20	−0.2251 (4)	0.8403 (4)	0.0636 (4)	0.0458 (15)	0.879 (4)
H20A	−0.261022	0.894984	0.093035	0.069*	0.879 (4)
H20B	−0.238388	0.776117	0.094104	0.069*	0.879 (4)
H20C	−0.256052	0.837055	−0.005924	0.069*	0.879 (4)
N4B	0.1222 (18)	0.898 (2)	0.1254 (16)	0.027 (3)*	0.121 (4)
N5B	0.0308 (18)	0.880 (2)	0.2751 (14)	0.024 (3)*	0.121 (4)
N6B	−0.036 (2)	0.865 (6)	0.1851 (15)	0.024 (3)*	0.121 (4)
C11B	0.182 (2)	0.898 (5)	0.0538 (19)	0.047 (6)*	0.121 (4)
H11B	0.259704	0.909507	0.069110	0.056*	0.121 (4)
C12B	0.131 (2)	0.883 (3)	−0.0404 (19)	0.033 (11)*	0.121 (4)
H12B	0.173949	0.883514	−0.090125	0.040*	0.121 (4)
C13B	0.017 (2)	0.866 (2)	−0.0631 (17)	0.032 (9)*	0.121 (4)
H13B	−0.019604	0.860282	−0.128805	0.038*	0.121 (4)
C14B	−0.040 (3)	0.857 (8)	0.0091 (18)	0.030 (3)*	0.121 (4)
H14B	−0.117691	0.841595	−0.004607	0.036*	0.121 (4)
C15B	0.0154 (19)	0.871 (3)	0.1041 (15)	0.027 (9)*	0.121 (4)
C16B	−0.002 (3)	0.884 (4)	0.4410 (16)	0.026 (5)*	0.121 (4)
H16D	−0.066232	0.886369	0.472907	0.038*	0.121 (4)
H16E	0.041360	0.946678	0.454998	0.038*	0.121 (4)
H16F	0.045371	0.826508	0.465257	0.038*	0.121 (4)
C17B	−0.0400 (19)	0.874 (2)	0.3354 (14)	0.024 (8)*	0.121 (4)
C18B	−0.148 (4)	0.852 (13)	0.2874 (17)	0.029 (3)*	0.121 (4)
H18B	−0.210534	0.836092	0.316193	0.035*	0.121 (4)
C19B	−0.1467 (16)	0.857 (2)	0.1931 (15)	0.018 (7)*	0.121 (4)
C20B	−0.245 (2)	0.839 (3)	0.114 (2)	0.034 (5)*	0.121 (4)
H20D	−0.313861	0.850560	0.138884	0.051*	0.121 (4)
H20E	−0.243855	0.769358	0.091196	0.051*	0.121 (4)
H20F	−0.242822	0.885368	0.060096	0.051*	0.121 (4)
Cl1	0.13307 (9)	1.08796 (7)	0.27704 (8)	0.0388 (3)
Cl2	0.45368 (9)	0.34181 (9)	0.27094 (9)	0.0478 (3)
Ni1	0.18951 (4)	0.91142 (4)	0.27749 (4)	0.02430 (16)
O1	0.3217 (3)	0.9446 (2)	0.2126 (2)	0.0432 (9)
H11	0.339 (4)	1.0041 (19)	0.202 (3)	0.065*
H12	0.387 (2)	0.923 (3)	0.230 (3)	0.065*
O2	0.3326 (3)	0.3528 (2)	0.6845 (3)	0.0566 (10)
H21	0.275 (3)	0.350 (3)	0.708 (4)	0.085*
H22	0.370 (4)	0.304 (3)	0.712 (4)	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.025 (2)	0.033 (2)	0.033 (2)	−0.0029 (17)	0.0035 (15)	−0.0038 (18)
N2	0.023 (2)	0.0287 (19)	0.025 (2)	0.0013 (16)	0.0024 (14)	0.0011 (16)
N3	0.0159 (18)	0.0306 (19)	0.028 (2)	0.0039 (15)	0.0018 (14)	0.0047 (17)
C1	0.037 (3)	0.035 (3)	0.042 (3)	0.001 (2)	0.003 (2)	−0.011 (2)
C2	0.041 (3)	0.057 (3)	0.040 (3)	−0.012 (3)	0.005 (2)	−0.022 (3)
C3	0.034 (3)	0.069 (3)	0.029 (3)	−0.010 (3)	0.003 (2)	−0.008 (3)
C4	0.032 (3)	0.052 (3)	0.029 (3)	−0.001 (2)	0.000 (2)	0.000 (2)
C5	0.021 (2)	0.039 (3)	0.028 (3)	−0.005 (2)	0.0051 (18)	−0.003 (2)
C6	0.047 (3)	0.038 (3)	0.040 (3)	0.001 (2)	0.001 (2)	−0.007 (2)
C7	0.031 (3)	0.028 (2)	0.032 (3)	−0.001 (2)	0.0078 (19)	−0.001 (2)
C8	0.034 (3)	0.026 (2)	0.040 (3)	0.005 (2)	0.013 (2)	0.006 (2)
C9	0.028 (2)	0.034 (2)	0.034 (3)	0.013 (2)	0.011 (2)	0.014 (2)
C10	0.051 (3)	0.064 (3)	0.040 (3)	0.028 (3)	0.005 (2)	0.007 (3)
N4	0.025 (2)	0.0242 (19)	0.025 (2)	0.0018 (16)	0.0035 (17)	0.0008 (19)
N5	0.027 (2)	0.028 (2)	0.026 (2)	0.0016 (18)	0.0076 (17)	−0.0009 (18)
N6	0.020 (2)	0.029 (2)	0.026 (2)	0.0020 (17)	0.0030 (17)	0.000 (3)
C11	0.026 (3)	0.032 (3)	0.029 (3)	0.003 (3)	0.003 (2)	0.003 (2)
C12	0.032 (3)	0.039 (3)	0.030 (3)	−0.002 (3)	0.011 (2)	−0.002 (2)
C13	0.027 (3)	0.029 (3)	0.043 (3)	−0.003 (2)	0.016 (2)	−0.005 (2)
C14	0.023 (2)	0.030 (3)	0.034 (3)	0.004 (2)	0.002 (2)	0.001 (2)
C15	0.028 (3)	0.020 (2)	0.024 (3)	0.001 (2)	0.000 (2)	−0.004 (2)
C16	0.045 (3)	0.048 (3)	0.042 (4)	0.013 (3)	0.021 (3)	0.009 (4)
C17	0.040 (3)	0.025 (3)	0.025 (3)	0.009 (2)	0.008 (2)	0.003 (2)
C18	0.035 (3)	0.032 (4)	0.025 (2)	0.007 (2)	−0.002 (2)	−0.003 (2)
C19	0.033 (3)	0.030 (3)	0.030 (3)	0.001 (2)	−0.004 (2)	−0.004 (2)
C20	0.034 (3)	0.064 (4)	0.035 (3)	−0.003 (3)	−0.007 (2)	−0.007 (3)
Cl1	0.0342 (7)	0.0273 (6)	0.0575 (8)	0.0051 (5)	0.0154 (5)	0.0030 (5)
Cl2	0.0307 (7)	0.0489 (7)	0.0592 (9)	−0.0070 (6)	−0.0031 (5)	0.0159 (6)
Ni1	0.0196 (3)	0.0246 (3)	0.0283 (3)	0.0016 (2)	0.0036 (2)	−0.0006 (2)
O1	0.0304 (19)	0.0392 (18)	0.065 (2)	0.0070 (16)	0.0214 (17)	0.0130 (18)
O2	0.060 (3)	0.038 (2)	0.080 (3)	0.0051 (18)	0.033 (2)	0.0027 (19)

Geometric parameters (Å, º)

N1—C5	1.333 (5)	C16—H16A	0.9800
N1—C1	1.348 (5)	C16—H16B	0.9800
N1—Ni1	2.096 (3)	C16—H16C	0.9800
N2—C7	1.334 (4)	C17—C18	1.399 (7)
N2—N3	1.378 (4)	C18—C19	1.347 (7)
N2—Ni1	2.093 (3)	C18—H18	0.9500
N3—C9	1.374 (4)	C19—C20	1.497 (6)
N3—C5	1.407 (5)	C20—H20A	0.9800
C1—C2	1.372 (6)	C20—H20B	0.9800
C1—H1	0.9500	C20—H20C	0.9800
C2—C3	1.368 (6)	N4B—C15B	1.335 (16)
C2—H2	0.9500	N4B—C11B	1.349 (16)
C3—C4	1.350 (5)	N4B—Ni1	2.15 (2)
C3—H3	0.9500	N5B—C17B	1.326 (16)
C4—C5	1.391 (5)	N5B—N6B	1.386 (16)
C4—H4	0.9500	N5B—Ni1	1.98 (2)
C6—C7	1.478 (5)	N6B—C19B	1.377 (15)
C6—H6A	0.9800	N6B—C15B	1.408 (15)
C6—H6B	0.9800	C11B—C12B	1.365 (17)
C6—H6C	0.9800	C11B—H11B	0.9500
C7—C8	1.402 (5)	C12B—C13B	1.387 (16)
C8—C9	1.347 (5)	C12B—H12B	0.9500
C8—H8	0.9500	C13B—C14B	1.347 (17)
C9—C10	1.491 (5)	C13B—H13B	0.9500
C10—H10A	0.9800	C14B—C15B	1.390 (16)
C10—H10B	0.9800	C14B—H14B	0.9500
C10—H10C	0.9800	C16B—C17B	1.474 (16)
N4—C15	1.334 (5)	C16B—H16D	0.9800
N4—C11	1.352 (6)	C16B—H16E	0.9800
N4—Ni1	2.075 (4)	C16B—H16F	0.9800
N5—C17	1.326 (5)	C17B—C18B	1.400 (17)
N5—N6	1.376 (5)	C18B—C19B	1.332 (17)
N5—Ni1	2.059 (4)	C18B—H18B	0.9500
N6—C19	1.375 (6)	C19B—C20B	1.496 (15)
N6—C15	1.402 (5)	C20B—H20D	0.9800
C11—C12	1.366 (6)	C20B—H20E	0.9800
C11—H11A	0.9500	C20B—H20F	0.9800
C12—C13	1.385 (6)	Cl1—Ni1	2.4408 (11)
C12—H12A	0.9500	Ni1—O1	2.050 (3)
C13—C14	1.344 (6)	O1—H11	0.84 (2)
C13—H13	0.9500	O1—H12	0.84 (2)
C14—C15	1.389 (6)	O2—H21	0.84 (2)
C14—H14	0.9500	O2—H22	0.84 (2)
C16—C17	1.475 (6)
C5—N1—C1	117.3 (4)	C18—C19—C20	127.1 (5)
C5—N1—Ni1	117.1 (3)	N6—C19—C20	126.6 (4)
C1—N1—Ni1	125.6 (3)	C19—C20—H20A	109.5
C7—N2—N3	105.0 (3)	C19—C20—H20B	109.5
C7—N2—Ni1	140.3 (3)	H20A—C20—H20B	109.5
N3—N2—Ni1	113.2 (2)	C19—C20—H20C	109.5
C9—N3—N2	110.9 (3)	H20A—C20—H20C	109.5
C9—N3—C5	131.9 (3)	H20B—C20—H20C	109.5
N2—N3—C5	117.1 (3)	C15B—N4B—C11B	118.4 (18)
N1—C1—C2	122.5 (4)	C15B—N4B—Ni1	114.8 (14)
N1—C1—H1	118.8	C11B—N4B—Ni1	125.7 (17)
C2—C1—H1	118.8	C17B—N5B—N6B	103.2 (15)
C3—C2—C1	119.2 (4)	C17B—N5B—Ni1	139.5 (15)
C3—C2—H2	120.4	N6B—N5B—Ni1	117.2 (12)
C1—C2—H2	120.4	C19B—N6B—N5B	110.9 (15)
C4—C3—C2	119.4 (4)	C19B—N6B—C15B	131.9 (18)
C4—C3—H3	120.3	N5B—N6B—C15B	116.7 (15)
C2—C3—H3	120.3	N4B—C11B—C12B	121 (2)
C3—C4—C5	119.1 (4)	N4B—C11B—H11B	119.5
C3—C4—H4	120.5	C12B—C11B—H11B	119.5
C5—C4—H4	120.5	C11B—C12B—C13B	120 (2)
N1—C5—C4	122.4 (4)	C11B—C12B—H12B	120.1
N1—C5—N3	114.3 (3)	C13B—C12B—H12B	120.1
C4—C5—N3	123.3 (4)	C14B—C13B—C12B	119.2 (19)
C7—C6—H6A	109.5	C14B—C13B—H13B	120.4
C7—C6—H6B	109.5	C12B—C13B—H13B	120.4
H6A—C6—H6B	109.5	C13B—C14B—C15B	119 (2)
C7—C6—H6C	109.5	C13B—C14B—H14B	120.6
H6A—C6—H6C	109.5	C15B—C14B—H14B	120.6
H6B—C6—H6C	109.5	N4B—C15B—C14B	122.1 (17)
N2—C7—C8	110.4 (4)	N4B—C15B—N6B	113.9 (17)
N2—C7—C6	122.3 (4)	C14B—C15B—N6B	123.8 (18)
C8—C7—C6	127.3 (4)	C17B—C16B—H16D	109.5
C9—C8—C7	107.2 (3)	C17B—C16B—H16E	109.5
C9—C8—H8	126.4	H16D—C16B—H16E	109.5
C7—C8—H8	126.4	C17B—C16B—H16F	109.5
C8—C9—N3	106.4 (3)	H16D—C16B—H16F	109.5
C8—C9—C10	127.9 (4)	H16E—C16B—H16F	109.5
N3—C9—C10	125.6 (4)	N5B—C17B—C18B	112.2 (16)
C9—C10—H10A	109.5	N5B—C17B—C16B	121 (2)
C9—C10—H10B	109.5	C18B—C17B—C16B	126.5 (19)
H10A—C10—H10B	109.5	C19B—C18B—C17B	106.0 (18)
C9—C10—H10C	109.5	C19B—C18B—H18B	127.0
H10A—C10—H10C	109.5	C17B—C18B—H18B	127.0
H10B—C10—H10C	109.5	C18B—C19B—N6B	106.6 (17)
C15—N4—C11	118.6 (4)	C18B—C19B—C20B	124.5 (19)
C15—N4—Ni1	116.6 (3)	N6B—C19B—C20B	127.9 (19)
C11—N4—Ni1	124.4 (3)	C19B—C20B—H20D	109.5
C17—N5—N6	105.7 (4)	C19B—C20B—H20E	109.5
C17—N5—Ni1	140.6 (3)	H20D—C20B—H20E	109.5
N6—N5—Ni1	113.5 (3)	C19B—C20B—H20F	109.5
C19—N6—N5	110.4 (4)	H20D—C20B—H20F	109.5
C19—N6—C15	131.8 (4)	H20E—C20B—H20F	109.5
N5—N6—C15	117.8 (4)	N5B—Ni1—O1	153.1 (6)
N4—C11—C12	122.5 (4)	O1—Ni1—N5	96.31 (14)
N4—C11—H11A	118.7	O1—Ni1—N4	173.55 (14)
C12—C11—H11A	118.7	N5—Ni1—N4	77.64 (15)
C11—C12—C13	117.7 (4)	N5B—Ni1—N2	95.9 (9)
C11—C12—H12A	121.1	O1—Ni1—N2	90.48 (12)
C13—C12—H12A	121.1	N5—Ni1—N2	97.53 (14)
C14—C13—C12	120.5 (4)	N4—Ni1—N2	92.51 (13)
C14—C13—H13	119.8	N5B—Ni1—N1	118.0 (6)
C12—C13—H13	119.8	O1—Ni1—N1	88.88 (13)
C13—C14—C15	119.4 (5)	N5—Ni1—N1	172.23 (14)
C13—C14—H14	120.3	N4—Ni1—N1	97.37 (14)
C15—C14—H14	120.3	N2—Ni1—N1	76.59 (12)
N4—C15—C14	121.2 (4)	N5B—Ni1—N4B	77.1 (8)
N4—C15—N6	114.2 (4)	O1—Ni1—N4B	76.1 (6)
C14—C15—N6	124.6 (4)	N2—Ni1—N4B	98.1 (8)
C17—C16—H16A	109.5	N1—Ni1—N4B	164.1 (6)
C17—C16—H16B	109.5	N5B—Ni1—Cl1	85.6 (9)
H16A—C16—H16B	109.5	O1—Ni1—Cl1	92.26 (9)
C17—C16—H16C	109.5	N5—Ni1—Cl1	90.99 (11)
H16A—C16—H16C	109.5	N4—Ni1—Cl1	85.68 (10)
H16B—C16—H16C	109.5	N2—Ni1—Cl1	170.71 (9)
N5—C17—C18	110.1 (4)	N1—Ni1—Cl1	94.59 (9)
N5—C17—C16	121.6 (4)	N4B—Ni1—Cl1	91.2 (8)
C18—C17—C16	128.3 (5)	Ni1—O1—H11	122 (3)
C19—C18—C17	107.5 (5)	Ni1—O1—H12	125 (3)
C19—C18—H18	126.3	H11—O1—H12	97 (4)
C17—C18—H18	126.3	H21—O2—H22	102 (5)
C18—C19—N6	106.3 (5)
C7—N2—N3—C9	1.5 (4)	N5—N6—C15—N4	0.2 (10)
Ni1—N2—N3—C9	−167.4 (2)	C19—N6—C15—C14	−1.2 (18)
C7—N2—N3—C5	−175.9 (3)	N5—N6—C15—C14	179.2 (13)
Ni1—N2—N3—C5	15.2 (4)	N6—N5—C17—C18	0.3 (8)
C5—N1—C1—C2	−0.1 (6)	Ni1—N5—C17—C18	−173.7 (6)
Ni1—N1—C1—C2	178.7 (3)	N6—N5—C17—C16	−178.0 (6)
N1—C1—C2—C3	−2.5 (7)	Ni1—N5—C17—C16	7.9 (8)
C1—C2—C3—C4	1.8 (7)	N5—C17—C18—C19	−0.9 (10)
C2—C3—C4—C5	1.4 (7)	C16—C17—C18—C19	177.3 (6)
C1—N1—C5—C4	3.5 (6)	C17—C18—C19—N6	1.1 (10)
Ni1—N1—C5—C4	−175.5 (3)	C17—C18—C19—C20	−178.5 (5)
C1—N1—C5—N3	−178.3 (3)	N5—N6—C19—C18	−0.9 (10)
Ni1—N1—C5—N3	2.7 (4)	C15—N6—C19—C18	179.5 (10)
C3—C4—C5—N1	−4.2 (6)	N5—N6—C19—C20	178.7 (5)
C3—C4—C5—N3	177.8 (4)	C15—N6—C19—C20	−0.9 (14)
C9—N3—C5—N1	171.3 (4)	C17B—N5B—N6B—C19B	5 (7)
N2—N3—C5—N1	−12.0 (5)	Ni1—N5B—N6B—C19B	−172 (4)
C9—N3—C5—C4	−10.6 (7)	C17B—N5B—N6B—C15B	177 (6)
N2—N3—C5—C4	166.2 (4)	Ni1—N5B—N6B—C15B	1 (8)
N3—N2—C7—C8	−0.5 (4)	C15B—N4B—C11B—C12B	8 (7)
Ni1—N2—C7—C8	163.3 (3)	Ni1—N4B—C11B—C12B	176 (4)
N3—N2—C7—C6	178.2 (4)	N4B—C11B—C12B—C13B	0 (8)
Ni1—N2—C7—C6	−17.9 (7)	C11B—C12B—C13B—C14B	−5 (8)
N2—C7—C8—C9	−0.6 (5)	C12B—C13B—C14B—C15B	3 (10)
C6—C7—C8—C9	−179.3 (4)	C11B—N4B—C15B—C14B	−10 (7)
C7—C8—C9—N3	1.4 (5)	Ni1—N4B—C15B—C14B	−179 (6)
C7—C8—C9—C10	−176.6 (4)	C11B—N4B—C15B—N6B	175 (5)
N2—N3—C9—C8	−1.8 (4)	Ni1—N4B—C15B—N6B	6 (5)
C5—N3—C9—C8	175.1 (4)	C13B—C14B—C15B—N4B	4 (11)
N2—N3—C9—C10	176.3 (4)	C13B—C14B—C15B—N6B	179 (7)
C5—N3—C9—C10	−6.8 (7)	C19B—N6B—C15B—N4B	167 (7)
C17—N5—N6—C19	0.3 (8)	N5B—N6B—C15B—N4B	−5 (8)
Ni1—N5—N6—C19	176.2 (5)	C19B—N6B—C15B—C14B	−9 (12)
C17—N5—N6—C15	180.0 (6)	N5B—N6B—C15B—C14B	−180 (7)
Ni1—N5—N6—C15	−4.1 (9)	N6B—N5B—C17B—C18B	2 (9)
C15—N4—C11—C12	2.4 (7)	Ni1—N5B—C17B—C18B	177 (8)
Ni1—N4—C11—C12	175.0 (3)	N6B—N5B—C17B—C16B	178 (5)
N4—C11—C12—C13	−0.5 (7)	Ni1—N5B—C17B—C16B	−7 (6)
C11—C12—C13—C14	−1.9 (13)	N5B—C17B—C18B—C19B	−8 (14)
C12—C13—C14—C15	2 (2)	C16B—C17B—C18B—C19B	176 (6)
C11—N4—C15—C14	−2.0 (13)	C17B—C18B—C19B—N6B	10 (13)
Ni1—N4—C15—C14	−175.2 (12)	C17B—C18B—C19B—C20B	−180 (6)
C11—N4—C15—N6	177.1 (6)	N5B—N6B—C19B—C18B	−10 (10)
Ni1—N4—C15—N6	3.9 (6)	C15B—N6B—C19B—C18B	179 (11)
C13—C14—C15—N4	0 (2)	N5B—N6B—C19B—C20B	−179 (4)
C13—C14—C15—N6	−179.2 (12)	C15B—N6B—C19B—C20B	10 (12)
C19—N6—C15—N4	179.7 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O2^i	0.84 (2)	1.91 (2)	2.722 (4)	162 (4)
O1—H12···Cl2^ii	0.84 (2)	2.23 (3)	3.036 (3)	161 (4)
O2—H21···Cl1^iii	0.84 (2)	2.29 (2)	3.078 (4)	157 (3)
O2—H22···Cl2^iv	0.84 (2)	2.27 (2)	3.106 (4)	171 (5)

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