Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]nickel(II) tetra­hydrate

In the title complex, [Ni(C₁₁H₉ClN₃O₂)₂]·4H₂O, the Ni atom is coordinated by four N atoms and two O atoms derived from two tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The cis-N₄O₂ donor set defines a distorted octa­hedral geometry. In the crystal structure, the complex and water mol­ecules are linked by O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.040
• wR factor = 0.107
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact  Cl2    ..  Cl2     ..       3.13 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.53 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C12    -   C13    ...       1.54 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently we reported the crystal structures of bis[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]zinc(II) trihydrate (Yin et al., 2007) and bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]cobalt(II) 2.5- hydrate (Zhao et al., 2007). As a continuation of these investigations, the crystal structure of the title complex, (I), is described.

In (I), Fig. 1, the Ni atom is six-coordinated by four N atoms and two O atoms derived from two uninegative tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The resultant cis-N₄O₂ donor set defines an approximate octahedral geometry with the range of the angles around Ni(II) center being 76.82 (9) to 178.42 (10)°. A complex network of O—H···O hydrogen bonds involving the ligand-O and water molecules of crystallization consolidate the crystal structure (Table 1).

Related literature

For related literature, see: Yin et al. (2007); Zhao et al. (2007).

S2. Experimental

6-(3,5-Dimethyl-1H-pyrazol-1-yl)picolinic acid (1 mmol, 250 mg) was dissolved in anhydrous alcohol (15 ml) and stirred until a clear solution resulted. A solution of NiCl₂.6H₂O (0.5 mmol, 113 mg) in anhydrous alcohol (10 ml) was then added. After keeping the resulting solution in air to evaporate about half of the volume, blue prisms of (I) formed. The crystals were isolated, washed with ethanol three times and dried in a vacuum desiccator using silica gel as the dessicant; yield 75%. Elemental analysis: Found: C 41.70, H 4.25, N 13.20, O 20.35%. C₂₂H₂₆NiN₆O₈ requires: C 41.80, H 4.15, N 13.30, O 20.25%.

S3. Refinement

C-bound H atoms were included in the riding model approximation with C—H = 0.93 to 0.96 Å, and with U_iso(H) = 1.2–1.5U_eq(C). The water H atoms were located in a difference Fourier map and the O—H distances were constrained to 0.85 Å, and with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.

Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]nickel(II) tetrahydrate

Crystal data

[Ni(C11H9ClN3O2)2]·4H2O	Z = 2
Mr = 632.10	F(000) = 652
Triclinic, P1	Dx = 1.564 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5907 (10) Å	Cell parameters from 3154 reflections
b = 11.2776 (17) Å	θ = 2.4–27.3°
c = 14.2659 (19) Å	µ = 0.98 mm^−1
α = 92.593 (2)°	T = 298 K
β = 105.206 (3)°	Prism, blue
γ = 113.820 (3)°	0.52 × 0.49 × 0.37 mm
V = 1342.0 (3) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	4644 independent reflections
Radiation source: fine-focus sealed tube	3549 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
Tmin = 0.630, Tmax = 0.713	k = −13→13
6957 measured reflections	l = −13→16

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) = 0.107	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0567P)^2 + 0.1899P] where P = (Fo^2 + 2Fc^2)/3
4644 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ni1	0.77264 (5)	0.52387 (4)	0.75140 (3)	0.03203 (14)
Cl1	0.55546 (12)	0.91209 (9)	0.67524 (7)	0.0551 (3)
Cl2	0.57607 (13)	0.07074 (9)	0.92174 (8)	0.0640 (3)
N1	0.7176 (3)	0.6405 (2)	0.66193 (16)	0.0292 (5)
N2	0.7517 (3)	0.5219 (2)	0.54309 (17)	0.0337 (6)
N3	0.7717 (3)	0.4465 (2)	0.61479 (18)	0.0363 (6)
N4	0.8219 (3)	0.4031 (2)	0.83869 (17)	0.0313 (6)
N5	1.0849 (3)	0.5382 (2)	0.86026 (17)	0.0326 (6)
N6	1.0248 (3)	0.6181 (2)	0.80948 (18)	0.0337 (6)
O1	0.7411 (3)	0.6477 (2)	0.84674 (15)	0.0448 (6)
O2	0.6899 (3)	0.8231 (3)	0.85594 (17)	0.0582 (7)
O3	0.5445 (3)	0.3791 (2)	0.73513 (17)	0.0479 (6)
O4	0.4125 (3)	0.2055 (3)	0.7966 (2)	0.0870 (10)
O5	0.1053 (4)	0.1080 (3)	0.6606 (2)	0.0812 (9)
H5A	0.2027	0.1390	0.6960	0.097*
H5B	0.0472	0.0878	0.6985	0.097*
O6	0.9476 (4)	0.0534 (4)	0.8033 (2)	0.0994 (11)
H6A	0.8799	−0.0101	0.8208	0.119*
H6B	1.0368	0.0837	0.8488	0.119*
O7	0.7637 (4)	0.8418 (4)	0.0580 (2)	0.1187 (15)
H7D	0.6933	0.8234	0.0877	0.142*
H7E	0.7179	0.8303	−0.0036	0.142*
O8	0.0584 (6)	0.8775 (5)	0.5293 (3)	0.159 (2)
H8A	0.0092	0.8812	0.4713	0.191*
H8B	0.0733	0.9439	0.5682	0.191*
C1	0.7039 (4)	0.7344 (3)	0.8106 (2)	0.0371 (7)
C2	0.6770 (3)	0.7295 (3)	0.6994 (2)	0.0302 (7)
C3	0.6215 (4)	0.8021 (3)	0.6372 (2)	0.0359 (7)
C4	0.6125 (4)	0.7840 (3)	0.5382 (2)	0.0439 (8)
H4	0.5775	0.8340	0.4964	0.053*
C5	0.6548 (4)	0.6931 (3)	0.5015 (2)	0.0426 (8)
H5	0.6478	0.6797	0.4353	0.051*
C6	0.7084 (3)	0.6222 (3)	0.5670 (2)	0.0296 (6)
C7	0.7597 (5)	0.5369 (4)	0.3668 (2)	0.0557 (10)
H7A	0.7964	0.4988	0.3225	0.083*
H7B	0.8259	0.6300	0.3843	0.083*
H7C	0.6508	0.5212	0.3351	0.083*
C8	0.7691 (4)	0.4755 (3)	0.4583 (2)	0.0394 (8)
C9	0.7988 (4)	0.3697 (3)	0.4775 (2)	0.0455 (8)
H9	0.8166	0.3174	0.4341	0.055*
C10	0.7979 (4)	0.3533 (3)	0.5734 (2)	0.0396 (8)
C11	0.8165 (5)	0.2478 (4)	0.6281 (3)	0.0616 (11)
H11A	0.9201	0.2833	0.6768	0.092*
H11B	0.8063	0.1771	0.5827	0.092*
H11C	0.7350	0.2153	0.6600	0.092*
C12	0.5349 (4)	0.2929 (4)	0.7887 (2)	0.0465 (9)
C13	0.6969 (4)	0.2984 (3)	0.8487 (2)	0.0364 (7)
C14	0.7263 (4)	0.2110 (3)	0.9064 (2)	0.0399 (8)
C15	0.8827 (4)	0.2345 (3)	0.9545 (2)	0.0451 (9)
H15	0.9027	0.1769	0.9947	0.054*
C16	1.0094 (4)	0.3425 (3)	0.9436 (2)	0.0412 (8)
H16	1.1150	0.3592	0.9755	0.049*
C17	0.9719 (4)	0.4250 (3)	0.8826 (2)	0.0309 (7)
C18	1.3525 (4)	0.5291 (4)	0.9329 (3)	0.0599 (11)
H18A	1.4596	0.5778	0.9307	0.090*
H18B	1.3108	0.4403	0.8998	0.090*
H18C	1.3534	0.5288	1.0004	0.090*
C19	1.2490 (4)	0.5920 (3)	0.8830 (2)	0.0378 (7)
C20	1.2925 (4)	0.7063 (3)	0.8466 (2)	0.0428 (8)
H20	1.3962	0.7644	0.8502	0.051*
C21	1.1525 (4)	0.7206 (3)	0.8024 (2)	0.0362 (7)
C22	1.1358 (4)	0.8304 (3)	0.7544 (3)	0.0535 (9)
H22A	1.0583	0.7956	0.6901	0.080*
H22B	1.2373	0.8890	0.7483	0.080*
H22C	1.1010	0.8774	0.7937	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0331 (2)	0.0372 (2)	0.0302 (2)	0.01843 (18)	0.00948 (17)	0.01627 (17)
Cl1	0.0667 (6)	0.0481 (6)	0.0634 (6)	0.0382 (5)	0.0177 (5)	0.0138 (4)
Cl2	0.0823 (8)	0.0401 (5)	0.0683 (6)	0.0134 (5)	0.0392 (6)	0.0272 (5)
N1	0.0298 (14)	0.0313 (14)	0.0260 (13)	0.0131 (12)	0.0074 (11)	0.0094 (11)
N2	0.0381 (15)	0.0348 (15)	0.0293 (13)	0.0165 (12)	0.0100 (11)	0.0091 (11)
N3	0.0433 (16)	0.0348 (15)	0.0369 (14)	0.0211 (13)	0.0131 (12)	0.0159 (12)
N4	0.0318 (14)	0.0329 (14)	0.0292 (13)	0.0131 (12)	0.0094 (11)	0.0128 (11)
N5	0.0324 (15)	0.0336 (15)	0.0329 (13)	0.0172 (12)	0.0059 (11)	0.0118 (11)
N6	0.0357 (15)	0.0307 (14)	0.0368 (14)	0.0161 (12)	0.0098 (12)	0.0149 (11)
O1	0.0596 (15)	0.0607 (16)	0.0280 (11)	0.0382 (13)	0.0141 (11)	0.0165 (11)
O2	0.084 (2)	0.0719 (18)	0.0388 (13)	0.0514 (16)	0.0211 (13)	0.0079 (13)
O3	0.0323 (13)	0.0596 (16)	0.0479 (14)	0.0162 (11)	0.0093 (11)	0.0251 (12)
O4	0.0405 (17)	0.102 (2)	0.096 (2)	0.0064 (16)	0.0172 (16)	0.059 (2)
O5	0.071 (2)	0.100 (2)	0.0615 (18)	0.0352 (18)	0.0067 (15)	0.0182 (17)
O6	0.066 (2)	0.123 (3)	0.076 (2)	0.017 (2)	0.0131 (17)	−0.008 (2)
O7	0.072 (2)	0.231 (5)	0.0458 (17)	0.063 (3)	0.0129 (16)	0.011 (2)
O8	0.271 (6)	0.195 (5)	0.079 (3)	0.178 (5)	0.034 (3)	0.025 (3)
C1	0.0340 (18)	0.048 (2)	0.0336 (17)	0.0217 (16)	0.0099 (14)	0.0101 (15)
C2	0.0284 (16)	0.0295 (17)	0.0323 (16)	0.0123 (13)	0.0084 (13)	0.0090 (13)
C3	0.0350 (18)	0.0303 (17)	0.0409 (18)	0.0146 (14)	0.0078 (14)	0.0112 (14)
C4	0.056 (2)	0.044 (2)	0.0390 (19)	0.0291 (18)	0.0120 (16)	0.0215 (16)
C5	0.054 (2)	0.048 (2)	0.0292 (17)	0.0240 (18)	0.0123 (15)	0.0163 (15)
C6	0.0300 (16)	0.0290 (16)	0.0281 (15)	0.0112 (13)	0.0083 (13)	0.0079 (13)
C7	0.076 (3)	0.064 (3)	0.0370 (19)	0.034 (2)	0.0263 (19)	0.0120 (18)
C8	0.0387 (19)	0.043 (2)	0.0336 (17)	0.0129 (16)	0.0137 (14)	0.0040 (15)
C9	0.050 (2)	0.042 (2)	0.046 (2)	0.0204 (17)	0.0167 (17)	−0.0007 (16)
C10	0.0408 (19)	0.0324 (18)	0.049 (2)	0.0167 (15)	0.0165 (16)	0.0089 (15)
C11	0.082 (3)	0.049 (2)	0.076 (3)	0.042 (2)	0.035 (2)	0.024 (2)
C12	0.036 (2)	0.052 (2)	0.0426 (19)	0.0090 (17)	0.0119 (16)	0.0176 (17)
C13	0.0414 (19)	0.0356 (18)	0.0294 (16)	0.0116 (15)	0.0136 (14)	0.0103 (14)
C14	0.059 (2)	0.0297 (18)	0.0356 (17)	0.0173 (16)	0.0230 (16)	0.0147 (14)
C15	0.070 (3)	0.042 (2)	0.0381 (18)	0.0340 (19)	0.0213 (18)	0.0220 (16)
C16	0.048 (2)	0.046 (2)	0.0369 (18)	0.0271 (17)	0.0100 (16)	0.0183 (16)
C17	0.0360 (18)	0.0318 (17)	0.0272 (15)	0.0164 (14)	0.0097 (13)	0.0090 (13)
C18	0.043 (2)	0.070 (3)	0.074 (3)	0.035 (2)	0.010 (2)	0.027 (2)
C19	0.0325 (18)	0.044 (2)	0.0378 (17)	0.0200 (15)	0.0061 (14)	0.0047 (15)
C20	0.0312 (18)	0.043 (2)	0.049 (2)	0.0114 (16)	0.0111 (15)	0.0026 (16)
C21	0.0370 (18)	0.0296 (17)	0.0387 (17)	0.0104 (14)	0.0126 (14)	0.0068 (14)
C22	0.052 (2)	0.042 (2)	0.069 (3)	0.0179 (18)	0.022 (2)	0.0237 (19)

Geometric parameters (Å, º)

Ni1—N4	1.998 (2)	C3—C4	1.393 (4)
Ni1—N1	2.000 (2)	C4—C5	1.374 (4)
Ni1—O1	2.069 (2)	C4—H4	0.9300
Ni1—O3	2.079 (2)	C5—C6	1.387 (4)
Ni1—N3	2.096 (3)	C5—H5	0.9300
Ni1—N6	2.112 (3)	C7—C8	1.505 (5)
Cl1—C3	1.729 (3)	C7—H7A	0.9600
Cl2—C14	1.726 (3)	C7—H7B	0.9600
N1—C6	1.335 (4)	C7—H7C	0.9600
N1—C2	1.349 (4)	C8—C9	1.358 (5)
N2—C8	1.372 (4)	C9—C10	1.390 (5)
N2—N3	1.384 (3)	C9—H9	0.9300
N2—C6	1.409 (4)	C10—C11	1.497 (4)
N3—C10	1.323 (4)	C11—H11A	0.9600
N4—C17	1.323 (4)	C11—H11B	0.9600
N4—C13	1.347 (4)	C11—H11C	0.9600
N5—C19	1.377 (4)	C12—C13	1.539 (4)
N5—N6	1.389 (3)	C13—C14	1.381 (4)
N5—C17	1.416 (4)	C14—C15	1.383 (5)
N6—C21	1.333 (4)	C15—C16	1.380 (5)
O1—C1	1.256 (4)	C15—H15	0.9300
O2—C1	1.238 (4)	C16—C17	1.389 (4)
O3—C12	1.253 (4)	C16—H16	0.9300
O4—C12	1.228 (4)	C18—C19	1.496 (4)
O5—H5A	0.8500	C18—H18A	0.9600
O5—H5B	0.8500	C18—H18B	0.9600
O6—H6A	0.8499	C18—H18C	0.9600
O6—H6B	0.8500	C19—C20	1.359 (5)
O7—H7D	0.8500	C20—C21	1.402 (4)
O7—H7E	0.8499	C20—H20	0.9300
O8—H8A	0.8500	C21—C22	1.486 (4)
O8—H8B	0.8500	C22—H22A	0.9600
C1—C2	1.535 (4)	C22—H22B	0.9600
C2—C3	1.382 (4)	C22—H22C	0.9600
N4—Ni1—N1	178.42 (10)	H7A—C7—H7B	109.5
N4—Ni1—O1	101.86 (9)	C8—C7—H7C	109.5
N1—Ni1—O1	78.75 (9)	H7A—C7—H7C	109.5
N4—Ni1—O3	78.49 (9)	H7B—C7—H7C	109.5
N1—Ni1—O3	100.08 (9)	C9—C8—N2	105.6 (3)
O1—Ni1—O3	90.29 (10)	C9—C8—C7	129.8 (3)
N4—Ni1—N3	102.51 (10)	N2—C8—C7	124.6 (3)
N1—Ni1—N3	76.82 (9)	C8—C9—C10	108.0 (3)
O1—Ni1—N3	155.49 (9)	C8—C9—H9	126.0
O3—Ni1—N3	92.01 (10)	C10—C9—H9	126.0
N4—Ni1—N6	76.94 (10)	N3—C10—C9	110.1 (3)
N1—Ni1—N6	104.50 (10)	N3—C10—C11	120.7 (3)
O1—Ni1—N6	93.55 (10)	C9—C10—C11	129.2 (3)
O3—Ni1—N6	155.40 (9)	C10—C11—H11A	109.5
N3—Ni1—N6	94.43 (10)	C10—C11—H11B	109.5
C6—N1—C2	121.9 (2)	H11A—C11—H11B	109.5
C6—N1—Ni1	120.58 (19)	C10—C11—H11C	109.5
C2—N1—Ni1	117.24 (18)	H11A—C11—H11C	109.5
C8—N2—N3	110.6 (2)	H11B—C11—H11C	109.5
C8—N2—C6	132.8 (3)	O4—C12—O3	127.2 (3)
N3—N2—C6	116.5 (2)	O4—C12—C13	118.0 (3)
C10—N3—N2	105.6 (2)	O3—C12—C13	114.8 (3)
C10—N3—Ni1	141.3 (2)	N4—C13—C14	118.9 (3)
N2—N3—Ni1	112.77 (17)	N4—C13—C12	112.3 (3)
C17—N4—C13	122.1 (3)	C14—C13—C12	128.7 (3)
C17—N4—Ni1	120.6 (2)	C13—C14—C15	119.4 (3)
C13—N4—Ni1	117.3 (2)	C13—C14—Cl2	123.2 (3)
C19—N5—N6	110.6 (2)	C15—C14—Cl2	117.4 (2)
C19—N5—C17	133.0 (2)	C16—C15—C14	120.8 (3)
N6—N5—C17	116.4 (2)	C16—C15—H15	119.6
C21—N6—N5	105.4 (2)	C14—C15—H15	119.6
C21—N6—Ni1	141.8 (2)	C15—C16—C17	116.9 (3)
N5—N6—Ni1	111.64 (18)	C15—C16—H16	121.5
C1—O1—Ni1	116.31 (19)	C17—C16—H16	121.5
C12—O3—Ni1	116.7 (2)	N4—C17—C16	121.8 (3)
H5A—O5—H5B	108.1	N4—C17—N5	113.0 (2)
H6A—O6—H6B	108.5	C16—C17—N5	125.2 (3)
H7D—O7—H7E	108.8	C19—C18—H18A	109.5
H8A—O8—H8B	108.4	C19—C18—H18B	109.5
O2—C1—O1	126.6 (3)	H18A—C18—H18B	109.5
O2—C1—C2	117.7 (3)	C19—C18—H18C	109.5
O1—C1—C2	115.7 (3)	H18A—C18—H18C	109.5
N1—C2—C3	119.0 (3)	H18B—C18—H18C	109.5
N1—C2—C1	111.5 (2)	C20—C19—N5	106.2 (3)
C3—C2—C1	129.4 (3)	C20—C19—C18	128.6 (3)
C2—C3—C4	119.3 (3)	N5—C19—C18	125.1 (3)
C2—C3—Cl1	123.1 (2)	C19—C20—C21	107.5 (3)
C4—C3—Cl1	117.5 (2)	C19—C20—H20	126.2
C5—C4—C3	120.8 (3)	C21—C20—H20	126.2
C5—C4—H4	119.6	N6—C21—C20	110.3 (3)
C3—C4—H4	119.6	N6—C21—C22	121.1 (3)
C4—C5—C6	117.4 (3)	C20—C21—C22	128.6 (3)
C4—C5—H5	121.3	C21—C22—H22A	109.5
C6—C5—H5	121.3	C21—C22—H22B	109.5
N1—C6—C5	121.5 (3)	H22A—C22—H22B	109.5
N1—C6—N2	112.5 (2)	C21—C22—H22C	109.5
C5—C6—N2	126.0 (3)	H22A—C22—H22C	109.5
C8—C7—H7A	109.5	H22B—C22—H22C	109.5
C8—C7—H7B	109.5
O1—Ni1—N1—C6	−179.1 (2)	N1—C2—C3—Cl1	176.3 (2)
O3—Ni1—N1—C6	−90.8 (2)	C1—C2—C3—Cl1	−4.7 (5)
N3—Ni1—N1—C6	−1.1 (2)	C2—C3—C4—C5	1.4 (5)
N6—Ni1—N1—C6	90.1 (2)	Cl1—C3—C4—C5	−176.5 (3)
O1—Ni1—N1—C2	−4.8 (2)	C3—C4—C5—C6	−0.8 (5)
O3—Ni1—N1—C2	83.5 (2)	C2—N1—C6—C5	−0.7 (4)
N3—Ni1—N1—C2	173.2 (2)	Ni1—N1—C6—C5	173.4 (2)
N6—Ni1—N1—C2	−95.6 (2)	C2—N1—C6—N2	−178.1 (3)
C8—N2—N3—C10	−1.2 (3)	Ni1—N1—C6—N2	−4.1 (3)
C6—N2—N3—C10	174.8 (3)	C4—C5—C6—N1	0.5 (5)
C8—N2—N3—Ni1	173.52 (19)	C4—C5—C6—N2	177.6 (3)
C6—N2—N3—Ni1	−10.5 (3)	C8—N2—C6—N1	−175.5 (3)
N4—Ni1—N3—C10	−3.4 (4)	N3—N2—C6—N1	9.6 (4)
N1—Ni1—N3—C10	178.0 (4)	C8—N2—C6—C5	7.2 (5)
O1—Ni1—N3—C10	−177.2 (3)	N3—N2—C6—C5	−167.7 (3)
O3—Ni1—N3—C10	−82.1 (4)	N3—N2—C8—C9	0.5 (3)
N6—Ni1—N3—C10	74.1 (4)	C6—N2—C8—C9	−174.6 (3)
N4—Ni1—N3—N2	−175.31 (19)	N3—N2—C8—C7	−178.1 (3)
N1—Ni1—N3—N2	6.15 (19)	C6—N2—C8—C7	6.8 (5)
O1—Ni1—N3—N2	10.9 (4)	N2—C8—C9—C10	0.4 (4)
O3—Ni1—N3—N2	106.0 (2)	C7—C8—C9—C10	178.9 (3)
N6—Ni1—N3—N2	−97.7 (2)	N2—N3—C10—C9	1.4 (4)
O1—Ni1—N4—C17	−96.3 (2)	Ni1—N3—C10—C9	−170.8 (3)
O3—Ni1—N4—C17	175.9 (2)	N2—N3—C10—C11	−176.7 (3)
N3—Ni1—N4—C17	86.3 (2)	Ni1—N3—C10—C11	11.1 (6)
N6—Ni1—N4—C17	−5.4 (2)	C8—C9—C10—N3	−1.2 (4)
O1—Ni1—N4—C13	85.2 (2)	C8—C9—C10—C11	176.7 (4)
O3—Ni1—N4—C13	−2.7 (2)	Ni1—O3—C12—O4	173.8 (3)
N3—Ni1—N4—C13	−92.2 (2)	Ni1—O3—C12—C13	−7.6 (4)
N6—Ni1—N4—C13	176.1 (2)	C17—N4—C13—C14	−0.1 (4)
C19—N5—N6—C21	−0.6 (3)	Ni1—N4—C13—C14	178.4 (2)
C17—N5—N6—C21	176.3 (2)	C17—N4—C13—C12	−178.7 (3)
C19—N5—N6—Ni1	169.89 (19)	Ni1—N4—C13—C12	−0.2 (3)
C17—N5—N6—Ni1	−13.2 (3)	O4—C12—C13—N4	−176.0 (3)
N4—Ni1—N6—C21	174.8 (4)	O3—C12—C13—N4	5.2 (4)
N1—Ni1—N6—C21	−4.6 (4)	O4—C12—C13—C14	5.6 (6)
O1—Ni1—N6—C21	−83.9 (3)	O3—C12—C13—C14	−173.2 (3)
O3—Ni1—N6—C21	177.6 (3)	N4—C13—C14—C15	1.6 (4)
N3—Ni1—N6—C21	72.9 (3)	C12—C13—C14—C15	179.9 (3)
N4—Ni1—N6—N5	9.66 (17)	N4—C13—C14—Cl2	−178.0 (2)
N1—Ni1—N6—N5	−169.68 (17)	C12—C13—C14—Cl2	0.3 (5)
O1—Ni1—N6—N5	111.03 (18)	C13—C14—C15—C16	−1.6 (5)
O3—Ni1—N6—N5	12.5 (3)	Cl2—C14—C15—C16	178.1 (2)
N3—Ni1—N6—N5	−92.17 (18)	C14—C15—C16—C17	0.0 (5)
N4—Ni1—O1—C1	−178.3 (2)	C13—N4—C17—C16	−1.5 (4)
N1—Ni1—O1—C1	0.2 (2)	Ni1—N4—C17—C16	−179.9 (2)
O3—Ni1—O1—C1	−100.0 (2)	C13—N4—C17—N5	178.3 (2)
N3—Ni1—O1—C1	−4.5 (4)	Ni1—N4—C17—N5	−0.2 (3)
N6—Ni1—O1—C1	104.3 (2)	C15—C16—C17—N4	1.5 (5)
N4—Ni1—O3—C12	5.9 (2)	C15—C16—C17—N5	−178.3 (3)
N1—Ni1—O3—C12	−174.7 (2)	C19—N5—C17—N4	−174.7 (3)
O1—Ni1—O3—C12	−96.1 (3)	N6—N5—C17—N4	9.2 (4)
N3—Ni1—O3—C12	108.3 (3)	C19—N5—C17—C16	5.0 (5)
N6—Ni1—O3—C12	3.1 (4)	N6—N5—C17—C16	−171.0 (3)
Ni1—O1—C1—O2	−174.9 (3)	N6—N5—C19—C20	0.1 (3)
Ni1—O1—C1—C2	3.8 (4)	C17—N5—C19—C20	−176.1 (3)
C6—N1—C2—C3	1.2 (4)	N6—N5—C19—C18	−176.8 (3)
Ni1—N1—C2—C3	−173.1 (2)	C17—N5—C19—C18	7.0 (5)
C6—N1—C2—C1	−178.0 (3)	N5—C19—C20—C21	0.4 (4)
Ni1—N1—C2—C1	7.7 (3)	C18—C19—C20—C21	177.1 (3)
O2—C1—C2—N1	171.3 (3)	N5—N6—C21—C20	0.9 (3)
O1—C1—C2—N1	−7.5 (4)	Ni1—N6—C21—C20	−164.8 (3)
O2—C1—C2—C3	−7.8 (5)	N5—N6—C21—C22	−178.3 (3)
O1—C1—C2—C3	173.4 (3)	Ni1—N6—C21—C22	16.1 (5)
N1—C2—C3—C4	−1.5 (5)	C19—C20—C21—N6	−0.8 (4)
C1—C2—C3—C4	177.6 (3)	C19—C20—C21—C22	178.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4	0.85	1.96	2.800 (4)	170
O5—H5B···O6^i	0.85	1.95	2.790 (4)	170
O6—H6A···O2^ii	0.85	2.21	3.063 (5)	176
O6—H6B···O7^iii	0.85	1.84	2.693 (4)	176
O7—H7D···O4^iv	0.85	2.13	2.942 (4)	161
O7—H7E···O2^v	0.85	1.94	2.758 (4)	160
O8—H8A···O5^vi	0.85	1.95	2.802 (5)	179
O8—H8B···O5^vii	0.85	2.09	2.939 (5)	178

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