[5,10,15,20-Tetra­kis(2,6-dimethoxy­phenyl)­porphyrinato]nickel(II)-toluene-dichloro­methane (3/2/4):a mixed solvate

The crystal structure, electronic spectroscopy, and ¹H NMR data for the title compound, [Ni(C₅₂H₄₄N₄O₈)]·0.67C₇H₈·1.33CH₂Cl₂, are reported. The compound was prepared by the reaction of nickel(II) acetate with the ligand in refluxing glacial acetic acid. The asymmetric unit consists of 1.5 nickel porphyrins, two dichloro­methane molecules and one toluene mol­ecule. One of the nickel-porphyrinate mol­ecules is located on an inversion center and is planar in the solid state, while the other assumes a saddle-shaped geometry. In both cases, the nickel ion is four-coordinate.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.048
• wR factor = 0.117
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.583     0.818
            Tmin(prime) and Tmax expected:      0.814     0.818
            RR(prime) =      0.717
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.71
PLAT231_ALERT_4_B Hirshfeld Test (Solvent)   C93    -   C94     ..       9.47 su
PLAT231_ALERT_4_B Hirshfeld Test (Solvent)   C94    -   C95     ..      11.79 su

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.33 Ratio
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...         30
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.23 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.02 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.38 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C94
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O11     ..       3.25 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C19    ..  C37     ..       3.16 Ang.

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C58 H52 Cl2.67 N4 Ni1 O8
            Atom count from _chemical_formula_moiety:C58.02 H52.02 Cl2.66 N4 Ni1
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.03
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2         (2)       2.16

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

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Diane Conrad, Christopher Yeisley, and Jennifer DeCoskey are undergraduates who worked on synthesizing, purifying, and crystallizing the samples of the porphyrin. Edward Zovinka is the research advisor and Allen Hunter and Matthias Zeller are the crystallographers on the project.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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S1. Comment

The chemistry of the enzyme hydroxylamine oxidoreductase (HAO) from nitrosomonas europaea has been of interest for a number of years (Arciero & Hooper, 1997). The X-ray crystal structure of HAO shows a complex trimer with each subunit containing seven c-type heme units in addition to a novel heme at the active site, heme P460 (Igarashi et al., 1997). The 5-coordinate heme P460 active site appears to have originated from a five-coordinate c-type heme from one subunit that has been modified with a covalent crosslink to a tyrosine residue from the adjacent subunit (Arciero & Hooper, 1997; Igarashi et al., 1997; Arciero et al., 1993). The C3 ring carbon of the tyrosine is linked to the 5 meso position of the heme, so that the oxygen of the tyrosine is "ortho" to the porphyrin meso carbon (Igarashi et al., 1997; Arciero et al., 1993). In order to explore the chemistry of synthetic models of heme P460, we have begun a systematic examination of ortho substituted porphyrins, beginning with tetra(2',6'-dimethoxyphenyl)porphyrin, (H₂T-2',6'-DMP)P. The molecule has oxygen substituents in the ortho position and serves as the non reactive control to compare with the more redox active ligand, tetra(2',6'-dihydroxyphenyl)porphyrin. Future work will focus on synthesizing and studying the more reactive metal ligand complexes with the biologically important iron ion.

The characterized metalloporphyrin is stable to both air and moisture in both the solid and solution environments. Following purification, different solvent systems including toluene, were examined in order to determine the best system. X-ray quality crystals were obtained by layering a dichloromethane solution of the metalloporphyrin with pentane. The asymmetric unit consists of 1.5 nickel porphyrins, 2 dichloromethanes, and one toluene molecule. The toluene molecule was carried over from the test solutions. One of the Ni[T(2',6'-DMP)P] molecules is located on an inversion center and is planar in the solid state (Figure 1) while the other assumes a saddle-shaped geometry (Figure 2). In both cases the nickel ion are 1.9474 (19) Å and 1.9554 (19) Å while they range between 1.9198 (19) Å and 1.9319 (19) Å for the ruffled complex. Non-planar nickel porphyrins are commonly known to exist because the small nickel ion favors a short metal-nitrogen bond distance leading to porphyrin conformational flexibility (Kadish et al., 2002). The coordination geometry is unexceptional and similar to other nickel porphyrin systems, average Ni—N bond distance of 1.920 Å listed in the Cambridge Crystallographic Database (Allen, 2002).

Related literature

For details of the synthesis, see: Tsuchida, et al.(1990). For related examples of ortho-substituted porphyrins, see: Bhyrappa, et al. (1997). For related literature, see: Allen (2002); Arciero & Hooper (1997); Arciero et al. (1993); Igarashi et al. (1997); Kadish et al. (2002); Rothemund & Menotti (1948).

S2. Experimental

All of the starting materials were purchased from Aldrich and used without further purification. The ligand, 5,10,15,20-tetra-(2',6'-dimethoxyphenyl)porphyrin, [(H₂T-2',6'-DMP)P] was synthesized following literature methods (Tsuchida et al., 1990). The porphyrin ligand, (H₂T-2',6'-DMP)P, (17.0 mg, 2.0×10 ^-5 mol) was dissolved in glacial acetic acid (20 ml). Nickel acetate (0.50 mg, 2.0×10 ^-4 mol) was added after all of the ligand dissolved and then heated to reflux at 391 K (118 °C) for half an hour (Rothemund, 1948). Upon cooling, the solvent was removed through rotary evaporation. The resulting red crystals were dissolved in dichloromethane and the solution was chromatographed on a dry alumina column with dichloromethane as the eluent. (60% Yield); Rf (Alumina, DCM) 0.95; I·R·(KBr): 1587, 1471, 1431, 1348, 1250 [µ_as (C—O—C)], 1110, and 1002 [µ (C—H)] cm^-1; λ_max(DCM): 413, 526, and 557 nm; ε: 1.2×105, 7.8×103, and 2.2×103 cm^-1M^{-1. 1}HNMR (CDCl₃): 3.5(–OMe), 6.9–7.5(aromatic), and 8.6(pyrrole) p.p.m..

S3. Refinement

Methyl and methylene chloride H atoms were placed in calculated positions with C—H = 0.98 and 0.99 Å, respectively. All other H atoms were located in difference density Fourier maps. H atoms were refined with U_iso(H) = 1.2 U_eq or 1.5 U_eq (C_Me only) of the respective carrier atoms.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. Ellipsoid (50% probability) plot of planar Ni[T(2',6'-DMP)P]
	Fig. 2. : Ellispoid (50% probability) plot of saddle-shaped Ni[T(2',6'-DMP)P]

[5,10,15,20-Tetrakis(2,6-dimethoxyphenyl)porphyrinato]nickel(II)–toluene– dichloromethane (3/2/4)

Crystal data

[Ni(C52H44N4O8)]·0.67C7H8·1.33CH2Cl2	F(000) = 3392
Mr = 1086.26	Dx = 1.395 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9043 reflections
a = 16.8286 (10) Å	θ = 2.3–32.0°
b = 26.1041 (15) Å	µ = 0.57 mm^−1
c = 17.6845 (10) Å	T = 100 K
β = 92.813 (1)°	Octagonal column, red
V = 7759.4 (8) Å^3	0.35 × 0.35 × 0.35 mm
Z = 6

Data collection

Bruker SMART APEX CCD diffractometer	15859 independent reflections
Radiation source: fine-focus sealed tube	13340 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 26.4°, θmin = 1.4°
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	h = −21→21
Tmin = 0.583, Tmax = 0.818	k = 0→32
72528 measured reflections	l = 0→22

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 10.5281P] where P = (Fo^2 + 2Fc^2)/3
15859 reflections	(Δ/σ)max = 0.001
1100 parameters	Δρmax = 1.07 e Å^−3
0 restraints	Δρmin = −0.59 e Å^−3

Special details

Experimental. Hydrogen atoms of the solvent molecules and methyl hydrogen atoms were placed in calculated positions and were refined with an isotropic displacement parameter 1.2 (methylene, aromatic) or 1.5 (methyl) times that of the adjacent carbon atom. Methyl hydrogen atoms were allowed to rotate to best fit the experimental electron density. All other hydrogen atoms were located in the difference Fourier map and were refined with an isotropic displacement parameter 1.2 times that of the adjacent carbon atom.

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 > 2σ(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
Ni2	0.596867 (17)	0.241274 (11)	0.612644 (16)	0.01220 (8)
N4	0.68062 (11)	0.28069 (8)	0.57001 (11)	0.0142 (4)
N3	0.53415 (11)	0.24643 (7)	0.51849 (11)	0.0141 (4)
O7	0.89977 (10)	0.18742 (7)	0.63691 (10)	0.0237 (4)
N6	0.50932 (11)	0.20910 (7)	0.65961 (11)	0.0141 (4)
N5	0.66332 (11)	0.22972 (7)	0.70310 (11)	0.0137 (4)
O8	0.84678 (11)	0.35033 (7)	0.72834 (11)	0.0262 (4)
O11	0.40439 (10)	0.09919 (7)	0.48806 (11)	0.0236 (4)
O6	0.69411 (11)	0.25715 (7)	0.33494 (10)	0.0251 (4)
O10	0.49128 (11)	0.27889 (7)	0.86637 (10)	0.0265 (4)
C19	0.75781 (14)	0.28722 (9)	0.59886 (13)	0.0151 (5)
O12	0.27877 (11)	0.25079 (7)	0.55419 (12)	0.0273 (4)
C61	0.87726 (14)	0.26963 (10)	0.68284 (13)	0.0171 (5)
O9	0.60155 (12)	0.11457 (7)	0.87314 (10)	0.0267 (4)
C21	0.74458 (14)	0.23685 (9)	0.71209 (13)	0.0149 (5)
C16	0.67716 (14)	0.30818 (9)	0.50290 (13)	0.0158 (5)
C20	0.79052 (13)	0.26313 (9)	0.66264 (13)	0.0148 (5)
C11	0.46349 (14)	0.22146 (9)	0.49961 (13)	0.0159 (5)
C81	0.33861 (14)	0.17382 (10)	0.52166 (13)	0.0179 (5)
C76	0.50707 (15)	0.23676 (10)	0.90949 (14)	0.0206 (5)
O5	0.56918 (13)	0.40381 (7)	0.42029 (12)	0.0332 (5)
C51	0.62966 (14)	0.33097 (10)	0.37358 (14)	0.0196 (5)
C63	1.01218 (15)	0.23661 (11)	0.69016 (14)	0.0227 (5)
H63	1.0486 (18)	0.2099 (12)	0.6846 (17)	0.027*
C14	0.55155 (14)	0.27339 (9)	0.45416 (13)	0.0161 (5)
C25	0.56294 (14)	0.20379 (9)	0.79141 (13)	0.0170 (5)
C71	0.54430 (14)	0.19650 (10)	0.87226 (13)	0.0183 (5)
C26	0.50200 (14)	0.20021 (9)	0.73618 (13)	0.0163 (5)
C24	0.64059 (14)	0.21387 (9)	0.77339 (13)	0.0161 (5)
C66	0.90475 (15)	0.31501 (10)	0.71644 (14)	0.0204 (5)
C27	0.42455 (15)	0.18019 (10)	0.74965 (15)	0.0199 (5)
H27	0.4072 (17)	0.1712 (11)	0.7960 (17)	0.024*
C29	0.43799 (14)	0.19333 (9)	0.62593 (14)	0.0159 (5)
C18	0.80039 (15)	0.32123 (10)	0.55187 (14)	0.0180 (5)
H18	0.8524 (18)	0.3318 (11)	0.5610 (16)	0.022*
C13	0.49232 (15)	0.26431 (10)	0.39483 (14)	0.0198 (5)
H13	0.4931 (17)	0.2790 (11)	0.3487 (17)	0.024*
C82	0.26848 (15)	0.20226 (10)	0.52574 (15)	0.0218 (5)
C12	0.43876 (15)	0.23178 (10)	0.42224 (14)	0.0199 (5)
H12	0.3946 (18)	0.2196 (11)	0.3989 (17)	0.024*
C15	0.61727 (14)	0.30463 (9)	0.44733 (13)	0.0163 (5)
C86	0.33303 (15)	0.12423 (10)	0.49208 (14)	0.0206 (5)
C30	0.41679 (14)	0.19564 (9)	0.54936 (13)	0.0153 (5)
C28	0.38597 (15)	0.17516 (9)	0.68174 (14)	0.0186 (5)
H28	0.3333 (18)	0.1630 (11)	0.6689 (16)	0.022*
C23	0.70803 (15)	0.20973 (10)	0.82528 (14)	0.0193 (5)
H23	0.7059 (17)	0.2007 (11)	0.8756 (17)	0.023*
C64	1.03728 (16)	0.28227 (12)	0.72230 (15)	0.0255 (6)
H64	1.0896 (19)	0.2870 (12)	0.7353 (17)	0.031*
C17	0.75053 (15)	0.33476 (10)	0.49350 (14)	0.0192 (5)
H17	0.7602 (17)	0.3581 (11)	0.4515 (17)	0.023*
C88	0.40178 (17)	0.04627 (10)	0.46742 (16)	0.0260 (6)
H88A	0.3704	0.0273	0.5034	0.039*
H88B	0.4560	0.0325	0.4684	0.039*
H88C	0.3772	0.0427	0.4163	0.039*
C62	0.93145 (14)	0.23035 (10)	0.66991 (13)	0.0178 (5)
C74	0.51001 (15)	0.18744 (11)	1.02360 (15)	0.0241 (6)
H74	0.4990 (18)	0.1845 (12)	1.0741 (18)	0.029*
C73	0.54676 (16)	0.14733 (11)	0.98899 (15)	0.0242 (6)
H73	0.5597 (18)	0.1172 (12)	1.0135 (18)	0.029*
C22	0.77252 (15)	0.22230 (10)	0.78716 (14)	0.0179 (5)
H22	0.8257 (18)	0.2238 (11)	0.8041 (16)	0.022*
C72	0.56433 (15)	0.15206 (10)	0.91275 (14)	0.0210 (5)
C52	0.67073 (15)	0.30599 (11)	0.31744 (14)	0.0221 (5)
C56	0.60523 (16)	0.38164 (11)	0.36116 (16)	0.0259 (6)
C75	0.48903 (15)	0.23228 (11)	0.98583 (15)	0.0238 (6)
H75	0.4628 (18)	0.2612 (12)	1.0097 (17)	0.029*
C85	0.26012 (16)	0.10302 (11)	0.46886 (17)	0.0272 (6)
H85	0.2583 (18)	0.0686 (13)	0.4495 (18)	0.033*
C65	0.98518 (16)	0.32191 (11)	0.73549 (14)	0.0241 (6)
H65	1.0034 (18)	0.3505 (12)	0.7589 (17)	0.029*
C67	0.95131 (17)	0.14461 (11)	0.62543 (17)	0.0291 (6)
H67A	0.9947	0.1552	0.5938	0.044*
H67B	0.9209	0.1169	0.6001	0.044*
H67C	0.9735	0.1325	0.6745	0.044*
C78	0.4623 (2)	0.32409 (12)	0.90185 (17)	0.0370 (7)
H78A	0.4090	0.3176	0.9195	0.055*
H78B	0.4600	0.3523	0.8653	0.055*
H78C	0.4982	0.3333	0.9450	0.055*
C54	0.65872 (17)	0.38009 (13)	0.23798 (17)	0.0339 (7)
H54	0.6695 (19)	0.3962 (13)	0.190 (2)	0.041*
C87	0.20951 (17)	0.28180 (11)	0.55885 (17)	0.0297 (6)
H87A	0.1831	0.2851	0.5084	0.045*
H87B	0.2248	0.3158	0.5780	0.045*
H87C	0.1730	0.2658	0.5933	0.045*
C53	0.68507 (16)	0.33037 (13)	0.24927 (15)	0.0293 (6)
H53	0.7141 (19)	0.3126 (12)	0.2121 (19)	0.035*
C83	0.19512 (16)	0.18168 (12)	0.50232 (17)	0.0283 (6)
H83	0.1481 (19)	0.2020 (12)	0.5056 (18)	0.034*
C84	0.19222 (17)	0.13226 (12)	0.47404 (18)	0.0315 (7)
H84	0.142 (2)	0.1179 (13)	0.4588 (18)	0.038*
C57	0.75223 (17)	0.23331 (12)	0.28985 (17)	0.0331 (7)
H57A	0.7305	0.2296	0.2377	0.050*
H57B	0.7657	0.1994	0.3107	0.050*
H57C	0.8002	0.2546	0.2903	0.050*
C55	0.61919 (18)	0.40616 (13)	0.29261 (18)	0.0340 (7)
H55	0.601 (2)	0.4378 (14)	0.2860 (19)	0.041*
C77	0.6456 (2)	0.07702 (13)	0.91679 (19)	0.0421 (8)
H77A	0.6825	0.0942	0.9531	0.063*
H77B	0.6757	0.0555	0.8830	0.063*
H77C	0.6087	0.0556	0.9442	0.063*
C58	0.5607 (2)	0.45806 (12)	0.4196 (2)	0.0420 (8)
H58A	0.6127	0.4740	0.4131	0.063*
H58B	0.5399	0.4694	0.4676	0.063*
H58C	0.5238	0.4682	0.3777	0.063*
C68	0.8687 (2)	0.39563 (13)	0.7681 (2)	0.0446 (9)
H68A	0.8940	0.3866	0.8174	0.067*
H68B	0.8212	0.4164	0.7756	0.067*
H68C	0.9062	0.4153	0.7388	0.067*
Ni1	1.0000	0.0000	0.5000	0.01166 (9)
O1	0.77710 (10)	0.14246 (7)	0.45736 (10)	0.0232 (4)
N2	0.95487 (11)	0.02206 (7)	0.40132 (11)	0.0135 (4)
N1	0.89857 (11)	0.01353 (7)	0.54459 (11)	0.0133 (4)
O3	1.11481 (11)	0.10768 (7)	0.28228 (10)	0.0251 (4)
O4	1.09479 (11)	−0.06494 (7)	0.22073 (10)	0.0247 (4)
O2	0.70622 (11)	−0.01526 (7)	0.35264 (12)	0.0299 (4)
C4	0.82942 (14)	0.03238 (9)	0.50919 (13)	0.0146 (5)
C31	0.73783 (14)	0.06384 (9)	0.40707 (13)	0.0155 (5)
C5	0.81837 (14)	0.04401 (9)	0.43304 (13)	0.0147 (5)
C6	0.87830 (14)	0.03886 (9)	0.38304 (13)	0.0155 (5)
C2	0.79852 (14)	0.02140 (9)	0.62966 (14)	0.0175 (5)
H2	0.7739 (16)	0.0204 (11)	0.6768 (16)	0.021*
C9	0.99282 (14)	0.02552 (9)	0.33387 (13)	0.0152 (5)
C41	1.10539 (14)	0.02204 (9)	0.24785 (13)	0.0162 (5)
C10	1.07108 (14)	0.01279 (9)	0.32309 (13)	0.0146 (5)
C1	0.87928 (14)	0.00641 (9)	0.61884 (13)	0.0153 (5)
C3	0.76809 (15)	0.03784 (9)	0.56207 (14)	0.0173 (5)
H3	0.7178 (17)	0.0510 (11)	0.5498 (16)	0.021*
C7	0.86906 (15)	0.05238 (10)	0.30469 (14)	0.0185 (5)
H7	0.8211 (18)	0.0655 (11)	0.2842 (16)	0.022*
C32	0.71661 (15)	0.11368 (10)	0.42606 (14)	0.0196 (5)
C8	0.93984 (15)	0.04450 (9)	0.27425 (14)	0.0179 (5)
H8	0.9556 (16)	0.0515 (11)	0.2239 (17)	0.022*
C46	1.11854 (15)	−0.01760 (10)	0.19747 (14)	0.0197 (5)
C36	0.68011 (15)	0.03202 (10)	0.37257 (15)	0.0214 (5)
C34	0.58228 (16)	0.09765 (11)	0.38401 (15)	0.0256 (6)
H34	0.5295 (19)	0.1092 (12)	0.3801 (17)	0.031*
C33	0.63846 (16)	0.13127 (11)	0.41439 (15)	0.0232 (6)
H33	0.6255 (18)	0.1634 (12)	0.4278 (17)	0.028*
C42	1.12752 (15)	0.07169 (10)	0.22874 (14)	0.0202 (5)
C35	0.60150 (16)	0.04870 (11)	0.36158 (16)	0.0253 (6)
H35	0.5617 (19)	0.0263 (12)	0.3412 (17)	0.030*
C37	0.75520 (18)	0.18772 (11)	0.49739 (16)	0.0293 (6)
H37A	0.7317	0.2127	0.4615	0.044*
H37B	0.8026	0.2025	0.5233	0.044*
H37C	0.7163	0.1788	0.5347	0.044*
C44	1.17342 (18)	0.04142 (12)	0.11123 (16)	0.0307 (7)
H44	1.1991 (19)	0.0461 (12)	0.0677 (19)	0.037*
C43	1.16141 (17)	0.08176 (12)	0.15954 (16)	0.0279 (6)
H43	1.1753 (19)	0.1135 (13)	0.1495 (18)	0.034*
C47	1.13464 (18)	0.15975 (10)	0.26538 (18)	0.0309 (6)
H47A	1.1915	0.1621	0.2562	0.046*
H47B	1.1225	0.1817	0.3083	0.046*
H47C	1.1035	0.1710	0.2201	0.046*
C45	1.15278 (17)	−0.00822 (12)	0.12861 (15)	0.0269 (6)
H45	1.1582 (18)	−0.0353 (12)	0.0956 (18)	0.032*
C48	1.1157 (2)	−0.10829 (11)	0.17662 (18)	0.0379 (7)
H48A	1.0897	−0.1057	0.1260	0.057*
H48B	1.0983	−0.1397	0.2012	0.057*
H48C	1.1736	−0.1092	0.1724	0.057*
C38	0.6501 (2)	−0.04850 (12)	0.3142 (2)	0.0472 (9)
H38A	0.6095	−0.0588	0.3489	0.071*
H38B	0.6777	−0.0790	0.2964	0.071*
H38C	0.6248	−0.0305	0.2708	0.071*
Cl1	0.56586 (5)	0.08927 (3)	0.59577 (5)	0.03955 (19)
Cl2	0.60288 (5)	0.02551 (3)	0.72804 (5)	0.0425 (2)
C98	0.6032 (3)	0.08763 (13)	0.6895 (2)	0.0544 (10)
H98A	0.5708	0.1104	0.7204	0.065*
H98B	0.6584	0.1009	0.6920	0.065*
Cl3	0.91634 (7)	0.16930 (4)	0.17449 (6)	0.0580 (3)
Cl4	0.87511 (8)	0.10083 (4)	0.04958 (6)	0.0727 (4)
C99	0.9249 (2)	0.15800 (14)	0.0773 (2)	0.0499 (9)
H99A	0.9818	0.1553	0.0661	0.060*
H99B	0.9017	0.1871	0.0480	0.060*
C94	0.4412 (4)	1.0101 (3)	0.8930 (3)	0.106 (2)
H94	0.4951	1.0199	0.9028	0.127*
C91	0.3222 (2)	0.89776 (14)	0.8166 (2)	0.0481 (9)
H91A	0.2679	0.8882	0.8287	0.072*
H91B	0.3595	0.8717	0.8366	0.072*
H91C	0.3256	0.9001	0.7616	0.072*
C95	0.3817 (4)	1.0449 (3)	0.9115 (4)	0.0999 (19)
H95	0.3947	1.0779	0.9312	0.120*
C92	0.3420 (2)	0.94673 (17)	0.8504 (2)	0.0513 (9)
C97	0.2852 (3)	0.98259 (17)	0.8662 (3)	0.0628 (11)
H97	0.2308	0.9753	0.8538	0.075*
C93	0.4256 (3)	0.96124 (19)	0.8604 (2)	0.0669 (13)
H93	0.4672	0.9392	0.8459	0.080*
C96	0.3056 (3)	1.0300 (2)	0.9004 (3)	0.0848 (17)
H96	0.2644	1.0519	0.9159	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni2	0.01087 (14)	0.01424 (15)	0.01158 (14)	−0.00010 (11)	0.00142 (11)	−0.00092 (11)
N4	0.0120 (9)	0.0166 (10)	0.0141 (9)	0.0004 (8)	0.0022 (7)	−0.0026 (8)
N3	0.0135 (10)	0.0170 (10)	0.0118 (9)	0.0001 (8)	0.0018 (7)	−0.0009 (8)
O7	0.0203 (9)	0.0212 (9)	0.0297 (10)	0.0046 (7)	0.0021 (8)	−0.0025 (8)
N6	0.0130 (10)	0.0151 (10)	0.0143 (9)	0.0000 (8)	0.0024 (7)	−0.0007 (8)
N5	0.0136 (10)	0.0153 (10)	0.0124 (9)	0.0014 (8)	0.0014 (7)	−0.0021 (8)
O8	0.0208 (9)	0.0256 (10)	0.0322 (10)	−0.0015 (8)	−0.0008 (8)	−0.0126 (8)
O11	0.0191 (9)	0.0173 (9)	0.0343 (10)	0.0004 (7)	−0.0004 (8)	−0.0054 (8)
O6	0.0246 (10)	0.0296 (10)	0.0218 (9)	−0.0030 (8)	0.0085 (8)	−0.0020 (8)
O10	0.0332 (11)	0.0270 (10)	0.0200 (9)	0.0077 (8)	0.0081 (8)	−0.0013 (8)
C19	0.0133 (11)	0.0165 (12)	0.0157 (11)	0.0008 (9)	0.0025 (9)	−0.0046 (9)
O12	0.0174 (9)	0.0235 (10)	0.0407 (11)	0.0047 (7)	−0.0021 (8)	−0.0096 (8)
C61	0.0148 (12)	0.0239 (13)	0.0126 (11)	−0.0034 (10)	0.0006 (9)	0.0011 (9)
O9	0.0343 (11)	0.0226 (10)	0.0235 (10)	0.0024 (8)	0.0045 (8)	−0.0002 (8)
C21	0.0146 (11)	0.0131 (11)	0.0172 (11)	0.0024 (9)	0.0008 (9)	−0.0024 (9)
C16	0.0175 (12)	0.0148 (11)	0.0152 (11)	0.0020 (9)	0.0025 (9)	−0.0016 (9)
C20	0.0124 (11)	0.0168 (12)	0.0153 (11)	0.0003 (9)	0.0018 (9)	−0.0071 (9)
C11	0.0152 (12)	0.0162 (11)	0.0162 (11)	0.0021 (9)	0.0008 (9)	−0.0022 (9)
C81	0.0180 (12)	0.0202 (12)	0.0156 (11)	−0.0020 (10)	0.0002 (9)	0.0015 (9)
C76	0.0166 (12)	0.0269 (14)	0.0183 (12)	−0.0017 (10)	0.0020 (9)	−0.0008 (10)
O5	0.0423 (12)	0.0232 (10)	0.0338 (11)	0.0084 (9)	0.0006 (9)	0.0043 (9)
C51	0.0150 (12)	0.0253 (13)	0.0181 (12)	−0.0054 (10)	−0.0030 (9)	0.0042 (10)
C63	0.0172 (13)	0.0335 (15)	0.0176 (12)	0.0049 (11)	0.0025 (10)	0.0067 (11)
C14	0.0164 (12)	0.0162 (12)	0.0156 (11)	0.0047 (9)	0.0021 (9)	−0.0010 (9)
C25	0.0192 (12)	0.0161 (12)	0.0162 (12)	−0.0006 (9)	0.0043 (9)	−0.0011 (9)
C71	0.0146 (12)	0.0262 (13)	0.0143 (11)	−0.0030 (10)	0.0019 (9)	−0.0011 (10)
C26	0.0170 (12)	0.0171 (12)	0.0153 (11)	0.0021 (9)	0.0059 (9)	−0.0027 (9)
C24	0.0182 (12)	0.0143 (11)	0.0162 (11)	0.0006 (9)	0.0028 (9)	−0.0024 (9)
C66	0.0181 (12)	0.0269 (14)	0.0162 (12)	−0.0009 (10)	0.0020 (9)	−0.0004 (10)
C27	0.0181 (12)	0.0228 (13)	0.0194 (12)	−0.0008 (10)	0.0067 (10)	0.0004 (10)
C29	0.0135 (11)	0.0134 (11)	0.0209 (12)	0.0017 (9)	0.0017 (9)	−0.0020 (9)
C18	0.0146 (12)	0.0199 (12)	0.0195 (12)	−0.0034 (10)	0.0023 (9)	−0.0008 (10)
C13	0.0187 (13)	0.0261 (14)	0.0147 (12)	0.0003 (10)	0.0002 (9)	0.0011 (10)
C82	0.0182 (13)	0.0249 (13)	0.0222 (13)	0.0000 (10)	−0.0011 (10)	−0.0018 (11)
C12	0.0168 (12)	0.0239 (13)	0.0188 (12)	−0.0017 (10)	−0.0017 (10)	−0.0029 (10)
C15	0.0168 (12)	0.0151 (12)	0.0173 (11)	0.0022 (9)	0.0036 (9)	0.0007 (9)
C86	0.0173 (12)	0.0220 (13)	0.0225 (13)	0.0003 (10)	0.0013 (10)	−0.0002 (10)
C30	0.0127 (11)	0.0144 (11)	0.0190 (12)	0.0028 (9)	0.0016 (9)	−0.0023 (9)
C28	0.0139 (12)	0.0183 (12)	0.0239 (13)	−0.0020 (10)	0.0034 (10)	−0.0013 (10)
C23	0.0219 (13)	0.0215 (13)	0.0147 (12)	−0.0003 (10)	0.0011 (10)	0.0002 (10)
C64	0.0132 (12)	0.0460 (17)	0.0170 (12)	−0.0039 (12)	−0.0016 (10)	0.0052 (12)
C17	0.0200 (13)	0.0186 (12)	0.0191 (12)	−0.0016 (10)	0.0032 (10)	0.0012 (10)
C88	0.0296 (15)	0.0183 (13)	0.0302 (15)	0.0010 (11)	0.0010 (11)	−0.0022 (11)
C62	0.0177 (12)	0.0238 (13)	0.0120 (11)	0.0002 (10)	0.0015 (9)	0.0036 (9)
C74	0.0193 (13)	0.0395 (16)	0.0138 (12)	−0.0079 (11)	0.0044 (10)	−0.0003 (11)
C73	0.0219 (13)	0.0306 (15)	0.0200 (13)	−0.0075 (11)	−0.0004 (10)	0.0043 (11)
C22	0.0158 (12)	0.0213 (13)	0.0164 (12)	−0.0002 (10)	−0.0020 (9)	−0.0018 (10)
C72	0.0188 (12)	0.0257 (13)	0.0188 (12)	−0.0037 (10)	0.0026 (10)	−0.0017 (10)
C52	0.0152 (12)	0.0321 (15)	0.0189 (12)	−0.0079 (11)	−0.0009 (10)	0.0012 (11)
C56	0.0214 (13)	0.0276 (14)	0.0283 (14)	−0.0041 (11)	−0.0038 (11)	0.0060 (11)
C75	0.0186 (13)	0.0345 (15)	0.0186 (13)	−0.0022 (11)	0.0052 (10)	−0.0039 (11)
C85	0.0243 (14)	0.0227 (14)	0.0340 (15)	−0.0044 (11)	−0.0037 (11)	−0.0059 (12)
C65	0.0213 (13)	0.0351 (16)	0.0157 (12)	−0.0094 (12)	0.0004 (10)	−0.0030 (11)
C67	0.0319 (15)	0.0229 (14)	0.0332 (15)	0.0069 (12)	0.0094 (12)	0.0014 (12)
C78	0.0453 (19)	0.0361 (17)	0.0300 (16)	0.0179 (14)	0.0072 (13)	−0.0049 (13)
C54	0.0255 (15)	0.052 (2)	0.0240 (14)	−0.0140 (14)	−0.0038 (12)	0.0179 (14)
C87	0.0256 (15)	0.0316 (15)	0.0322 (15)	0.0098 (12)	0.0027 (12)	−0.0062 (12)
C53	0.0199 (13)	0.0488 (18)	0.0192 (13)	−0.0125 (13)	0.0020 (11)	0.0027 (13)
C83	0.0143 (13)	0.0337 (16)	0.0366 (16)	0.0020 (11)	−0.0010 (11)	−0.0028 (13)
C84	0.0183 (14)	0.0358 (16)	0.0396 (17)	−0.0065 (12)	−0.0060 (12)	−0.0048 (13)
C57	0.0249 (15)	0.0431 (18)	0.0323 (16)	−0.0026 (13)	0.0115 (12)	−0.0084 (13)
C55	0.0299 (16)	0.0340 (17)	0.0369 (17)	−0.0071 (13)	−0.0091 (13)	0.0173 (14)
C77	0.054 (2)	0.0326 (17)	0.0401 (18)	0.0138 (15)	0.0014 (15)	0.0043 (14)
C58	0.0438 (19)	0.0247 (16)	0.057 (2)	0.0080 (14)	−0.0073 (16)	0.0017 (15)
C68	0.0324 (17)	0.0385 (19)	0.063 (2)	−0.0021 (14)	0.0007 (15)	−0.0281 (17)
Ni1	0.0108 (2)	0.0125 (2)	0.0118 (2)	0.00122 (15)	0.00184 (15)	0.00077 (16)
O1	0.0208 (9)	0.0195 (9)	0.0291 (10)	0.0050 (7)	−0.0023 (7)	−0.0079 (8)
N2	0.0127 (9)	0.0137 (10)	0.0141 (9)	0.0009 (7)	0.0017 (7)	0.0006 (8)
N1	0.0124 (9)	0.0140 (9)	0.0136 (9)	0.0000 (7)	0.0013 (7)	0.0001 (8)
O3	0.0336 (11)	0.0161 (9)	0.0264 (10)	−0.0035 (8)	0.0112 (8)	0.0021 (7)
O4	0.0330 (11)	0.0187 (9)	0.0231 (9)	0.0005 (8)	0.0099 (8)	−0.0028 (7)
O2	0.0236 (10)	0.0205 (10)	0.0448 (12)	−0.0026 (8)	−0.0075 (9)	−0.0047 (9)
C4	0.0132 (11)	0.0110 (11)	0.0195 (12)	−0.0014 (9)	0.0009 (9)	−0.0002 (9)
C31	0.0123 (11)	0.0197 (12)	0.0146 (11)	0.0027 (9)	0.0022 (9)	0.0041 (9)
C5	0.0131 (11)	0.0132 (11)	0.0177 (11)	−0.0006 (9)	−0.0017 (9)	−0.0023 (9)
C6	0.0142 (11)	0.0143 (11)	0.0182 (12)	0.0003 (9)	0.0011 (9)	−0.0005 (9)
C2	0.0156 (12)	0.0188 (12)	0.0184 (12)	0.0006 (9)	0.0043 (9)	−0.0001 (10)
C9	0.0182 (12)	0.0105 (11)	0.0170 (11)	−0.0002 (9)	0.0011 (9)	0.0000 (9)
C41	0.0130 (11)	0.0212 (12)	0.0145 (11)	0.0010 (9)	0.0019 (9)	0.0034 (9)
C10	0.0178 (12)	0.0114 (11)	0.0151 (11)	−0.0014 (9)	0.0051 (9)	−0.0001 (9)
C1	0.0150 (11)	0.0127 (11)	0.0184 (12)	−0.0011 (9)	0.0026 (9)	−0.0001 (9)
C3	0.0137 (12)	0.0178 (12)	0.0206 (12)	0.0007 (9)	0.0010 (9)	−0.0017 (10)
C7	0.0192 (13)	0.0204 (12)	0.0158 (12)	0.0032 (10)	−0.0001 (10)	0.0014 (10)
C32	0.0194 (13)	0.0243 (13)	0.0153 (12)	0.0026 (10)	0.0024 (9)	0.0017 (10)
C8	0.0201 (12)	0.0193 (12)	0.0145 (12)	0.0016 (10)	0.0016 (9)	0.0018 (10)
C46	0.0181 (12)	0.0232 (13)	0.0181 (12)	0.0015 (10)	0.0020 (10)	0.0014 (10)
C36	0.0185 (13)	0.0224 (13)	0.0233 (13)	−0.0005 (10)	0.0015 (10)	0.0048 (10)
C34	0.0144 (13)	0.0388 (16)	0.0237 (13)	0.0073 (11)	0.0030 (10)	0.0109 (12)
C33	0.0202 (13)	0.0274 (14)	0.0221 (13)	0.0092 (11)	0.0037 (10)	0.0026 (11)
C42	0.0173 (12)	0.0224 (13)	0.0214 (13)	0.0015 (10)	0.0047 (10)	0.0018 (10)
C35	0.0164 (13)	0.0325 (15)	0.0265 (14)	−0.0054 (11)	−0.0038 (10)	0.0063 (12)
C37	0.0347 (16)	0.0242 (14)	0.0287 (15)	0.0070 (12)	−0.0010 (12)	−0.0091 (12)
C44	0.0314 (16)	0.0424 (18)	0.0194 (13)	−0.0033 (13)	0.0125 (12)	0.0044 (12)
C43	0.0325 (15)	0.0277 (15)	0.0241 (14)	−0.0049 (12)	0.0070 (11)	0.0082 (12)
C47	0.0353 (16)	0.0157 (13)	0.0425 (17)	−0.0041 (11)	0.0096 (13)	0.0025 (12)
C45	0.0284 (15)	0.0330 (16)	0.0200 (13)	−0.0007 (12)	0.0079 (11)	−0.0046 (12)
C48	0.056 (2)	0.0216 (15)	0.0380 (17)	0.0058 (14)	0.0166 (15)	−0.0060 (13)
C38	0.0360 (18)	0.0269 (16)	0.077 (3)	−0.0056 (14)	−0.0147 (17)	−0.0142 (17)
Cl1	0.0371 (4)	0.0414 (4)	0.0392 (4)	0.0162 (3)	−0.0074 (3)	−0.0107 (3)
Cl2	0.0602 (5)	0.0289 (4)	0.0393 (4)	0.0004 (4)	0.0128 (4)	−0.0051 (3)
C98	0.097 (3)	0.0266 (17)	0.0376 (19)	0.0003 (18)	−0.0127 (19)	−0.0066 (14)
Cl3	0.0790 (7)	0.0395 (5)	0.0535 (5)	−0.0142 (5)	−0.0165 (5)	0.0081 (4)
Cl4	0.1128 (10)	0.0517 (6)	0.0563 (6)	−0.0378 (6)	0.0321 (6)	−0.0142 (5)
C99	0.053 (2)	0.0367 (19)	0.061 (2)	−0.0149 (16)	0.0108 (18)	0.0124 (17)
C94	0.075 (4)	0.157 (6)	0.082 (4)	−0.053 (4)	−0.017 (3)	0.012 (4)
C91	0.046 (2)	0.057 (2)	0.0427 (19)	0.0159 (17)	0.0148 (16)	0.0271 (17)
C95	0.082 (4)	0.103 (5)	0.114 (5)	−0.009 (4)	−0.002 (4)	−0.028 (4)
C92	0.048 (2)	0.067 (3)	0.0395 (19)	0.0072 (19)	0.0044 (16)	0.0194 (18)
C97	0.050 (2)	0.066 (3)	0.073 (3)	−0.002 (2)	0.008 (2)	−0.013 (2)
C93	0.063 (3)	0.084 (3)	0.051 (2)	−0.023 (2)	−0.018 (2)	0.018 (2)
C96	0.058 (3)	0.089 (4)	0.107 (4)	0.002 (3)	−0.006 (3)	−0.061 (3)

Geometric parameters (Å, º)

Ni2—N6	1.9198 (19)	C53—H53	0.96 (3)
Ni2—N4	1.928 (2)	C83—C84	1.383 (4)
Ni2—N5	1.9300 (19)	C83—H83	0.96 (3)
Ni2—N3	1.9319 (19)	C84—H84	0.95 (3)
N4—C19	1.383 (3)	C57—H57A	0.9800
N4—C16	1.386 (3)	C57—H57B	0.9800
N3—C14	1.381 (3)	C57—H57C	0.9800
N3—C11	1.383 (3)	C55—H55	0.89 (4)
O7—C62	1.360 (3)	C77—H77A	0.9800
O7—C67	1.435 (3)	C77—H77B	0.9800
N6—C29	1.377 (3)	C77—H77C	0.9800
N6—C26	1.385 (3)	C58—H58A	0.9800
N5—C21	1.381 (3)	C58—H58B	0.9800
N5—C24	1.382 (3)	C58—H58C	0.9800
O8—C66	1.366 (3)	C68—H68A	0.9800
O8—C68	1.415 (3)	C68—H68B	0.9800
O11—C86	1.372 (3)	C68—H68C	0.9800
O11—C88	1.429 (3)	Ni1—N1	1.9474 (19)
O6—C52	1.365 (3)	Ni1—N1^i	1.9474 (19)
O6—C57	1.434 (3)	Ni1—N2	1.9554 (19)
O10—C76	1.357 (3)	Ni1—N2^i	1.9554 (19)
O10—C78	1.433 (3)	O1—C32	1.361 (3)
C19—C20	1.382 (3)	O1—C37	1.435 (3)
C19—C18	1.432 (3)	N2—C9	1.383 (3)
O12—C82	1.371 (3)	N2—C6	1.384 (3)
O12—C87	1.425 (3)	N1—C1	1.381 (3)
C61—C66	1.394 (4)	N1—C4	1.384 (3)
C61—C62	1.399 (3)	O3—C42	1.358 (3)
C61—C20	1.495 (3)	O3—C47	1.435 (3)
O9—C72	1.373 (3)	O4—C46	1.368 (3)
O9—C77	1.432 (4)	O4—C48	1.428 (3)
C21—C20	1.378 (3)	O2—C36	1.362 (3)
C21—C22	1.437 (3)	O2—C38	1.430 (3)
C16—C15	1.376 (3)	C4—C5	1.384 (3)
C16—C17	1.433 (3)	C4—C3	1.433 (3)
C11—C30	1.383 (3)	C31—C32	1.395 (3)
C11—C12	1.436 (3)	C31—C36	1.396 (4)
C81—C86	1.398 (4)	C31—C5	1.502 (3)
C81—C82	1.399 (4)	C5—C6	1.380 (3)
C81—C30	1.494 (3)	C6—C7	1.431 (3)
C76—C75	1.403 (3)	C2—C3	1.347 (3)
C76—C71	1.404 (4)	C2—C1	1.436 (3)
O5—C56	1.363 (3)	C2—H2	0.95 (3)
O5—C58	1.423 (4)	C9—C10	1.381 (3)
C51—C52	1.399 (4)	C9—C8	1.435 (3)
C51—C56	1.399 (4)	C41—C46	1.390 (4)
C51—C15	1.498 (3)	C41—C42	1.395 (3)
C63—C64	1.378 (4)	C41—C10	1.496 (3)
C63—C62	1.398 (4)	C10—C1^i	1.385 (3)
C63—H63	0.94 (3)	C1—C10^i	1.385 (3)
C14—C15	1.384 (3)	C3—H3	0.93 (3)
C14—C13	1.431 (3)	C7—C8	1.347 (3)
C25—C26	1.384 (3)	C7—H7	0.93 (3)
C25—C24	1.385 (3)	C32—C33	1.399 (4)
C25—C71	1.491 (3)	C8—H8	0.96 (3)
C71—C72	1.396 (4)	C46—C45	1.394 (4)
C26—C27	1.435 (3)	C36—C35	1.397 (4)
C24—C23	1.428 (3)	C34—C33	1.379 (4)
C66—C65	1.390 (4)	C34—C35	1.381 (4)
C27—C28	1.343 (4)	C34—H34	0.94 (3)
C27—H27	0.91 (3)	C33—H33	0.90 (3)
C29—C30	1.385 (3)	C42—C43	1.400 (4)
C29—C28	1.432 (3)	C35—H35	0.95 (3)
C18—C17	1.345 (4)	C37—H37A	0.9800
C18—H18	0.92 (3)	C37—H37B	0.9800
C13—C12	1.346 (4)	C37—H37C	0.9800
C13—H13	0.90 (3)	C44—C43	1.377 (4)
C82—C83	1.391 (4)	C44—C45	1.380 (4)
C12—H12	0.89 (3)	C44—H44	0.91 (3)
C86—C85	1.390 (4)	C43—H43	0.88 (3)
C28—H28	0.96 (3)	C47—H47A	0.9800
C23—C22	1.346 (4)	C47—H47B	0.9800
C23—H23	0.92 (3)	C47—H47C	0.9800
C64—C65	1.384 (4)	C45—H45	0.92 (3)
C64—H64	0.91 (3)	C48—H48A	0.9800
C17—H17	0.98 (3)	C48—H48B	0.9800
C88—H88A	0.9800	C48—H48C	0.9800
C88—H88B	0.9800	C38—H38A	0.9800
C88—H88C	0.9800	C38—H38B	0.9800
C74—C73	1.375 (4)	C38—H38C	0.9800
C74—C75	1.385 (4)	Cl1—C98	1.745 (4)
C74—H74	0.92 (3)	Cl2—C98	1.759 (4)
C73—C72	1.400 (4)	C98—H98A	0.9900
C73—H73	0.92 (3)	C98—H98B	0.9900
C22—H22	0.93 (3)	Cl3—C99	1.757 (4)
C52—C53	1.395 (4)	Cl4—C99	1.769 (4)
C56—C55	1.401 (4)	C99—H99A	0.9900
C75—H75	0.98 (3)	C99—H99B	0.9900
C85—C84	1.381 (4)	C94—C95	1.403 (9)
C85—H85	0.96 (3)	C94—C93	1.420 (8)
C65—H65	0.90 (3)	C94—H94	0.9500
C67—H67A	0.9800	C91—C92	1.444 (6)
C67—H67B	0.9800	C91—H91A	0.9800
C67—H67C	0.9800	C91—H91B	0.9800
C78—H78A	0.9800	C91—H91C	0.9800
C78—H78B	0.9800	C95—C96	1.343 (7)
C78—H78C	0.9800	C95—H95	0.9500
C54—C55	1.379 (5)	C92—C97	1.377 (6)
C54—C53	1.383 (5)	C92—C93	1.458 (6)
C54—H54	0.97 (3)	C97—C96	1.412 (6)
C87—H87A	0.9800	C97—H97	0.9500
C87—H87B	0.9800	C93—H93	0.9500
C87—H87C	0.9800	C96—H96	0.9500
N6—Ni2—N4	173.60 (8)	C84—C83—H83	121.6 (19)
N6—Ni2—N5	89.93 (8)	C82—C83—H83	119.5 (19)
N4—Ni2—N5	90.14 (8)	C85—C84—C83	121.7 (3)
N6—Ni2—N3	90.28 (8)	C85—C84—H84	119 (2)
N4—Ni2—N3	90.27 (8)	C83—C84—H84	119 (2)
N5—Ni2—N3	174.32 (8)	O6—C57—H57A	109.5
C19—N4—C16	104.56 (19)	O6—C57—H57B	109.5
C19—N4—Ni2	127.81 (16)	H57A—C57—H57B	109.5
C16—N4—Ni2	127.62 (16)	O6—C57—H57C	109.5
C14—N3—C11	104.83 (19)	H57A—C57—H57C	109.5
C14—N3—Ni2	128.06 (16)	H57B—C57—H57C	109.5
C11—N3—Ni2	127.04 (16)	C54—C55—C56	119.2 (3)
C62—O7—C67	118.4 (2)	C54—C55—H55	123 (2)
C29—N6—C26	104.79 (19)	C56—C55—H55	118 (2)
C29—N6—Ni2	127.95 (16)	O9—C77—H77A	109.5
C26—N6—Ni2	127.10 (16)	O9—C77—H77B	109.5
C21—N5—C24	104.65 (19)	H77A—C77—H77B	109.5
C21—N5—Ni2	127.19 (16)	O9—C77—H77C	109.5
C24—N5—Ni2	128.14 (16)	H77A—C77—H77C	109.5
C66—O8—C68	118.0 (2)	H77B—C77—H77C	109.5
C86—O11—C88	117.2 (2)	O5—C58—H58A	109.5
C52—O6—C57	118.4 (2)	O5—C58—H58B	109.5
C76—O10—C78	118.9 (2)	H58A—C58—H58B	109.5
C20—C19—N4	125.1 (2)	O5—C58—H58C	109.5
C20—C19—C18	124.4 (2)	H58A—C58—H58C	109.5
N4—C19—C18	110.5 (2)	H58B—C58—H58C	109.5
C82—O12—C87	117.2 (2)	O8—C68—H68A	109.5
C66—C61—C62	119.2 (2)	O8—C68—H68B	109.5
C66—C61—C20	119.9 (2)	H68A—C68—H68B	109.5
C62—C61—C20	121.0 (2)	O8—C68—H68C	109.5
C72—O9—C77	116.8 (2)	H68A—C68—H68C	109.5
C20—C21—N5	125.2 (2)	H68B—C68—H68C	109.5
C20—C21—C22	123.3 (2)	N1—Ni1—N1^i	180.0
N5—C21—C22	110.4 (2)	N1—Ni1—N2	89.90 (8)
C15—C16—N4	125.1 (2)	N1^i—Ni1—N2	90.10 (8)
C15—C16—C17	123.7 (2)	N1—Ni1—N2^i	90.10 (8)
N4—C16—C17	110.5 (2)	N1^i—Ni1—N2^i	89.90 (8)
C21—C20—C19	122.1 (2)	N2—Ni1—N2^i	180.00 (12)
C21—C20—C61	118.4 (2)	C32—O1—C37	116.8 (2)
C19—C20—C61	119.2 (2)	C9—N2—C6	104.00 (19)
N3—C11—C30	125.8 (2)	C9—N2—Ni1	127.83 (16)
N3—C11—C12	110.3 (2)	C6—N2—Ni1	128.16 (16)
C30—C11—C12	123.4 (2)	C1—N1—C4	104.26 (19)
C86—C81—C82	118.0 (2)	C1—N1—Ni1	127.76 (16)
C86—C81—C30	121.2 (2)	C4—N1—Ni1	127.98 (16)
C82—C81—C30	120.8 (2)	C42—O3—C47	117.6 (2)
O10—C76—C75	124.2 (2)	C46—O4—C48	117.9 (2)
O10—C76—C71	115.0 (2)	C36—O2—C38	117.3 (2)
C75—C76—C71	120.8 (2)	C5—C4—N1	126.0 (2)
C56—O5—C58	117.6 (2)	C5—C4—C3	123.1 (2)
C52—C51—C56	118.7 (2)	N1—C4—C3	110.9 (2)
C52—C51—C15	119.9 (2)	C32—C31—C36	118.7 (2)
C56—C51—C15	121.2 (2)	C32—C31—C5	119.1 (2)
C64—C63—C62	118.8 (3)	C36—C31—C5	121.8 (2)
C64—C63—H63	119.8 (19)	C6—C5—C4	122.3 (2)
C62—C63—H63	121.3 (19)	C6—C5—C31	121.0 (2)
N3—C14—C15	125.1 (2)	C4—C5—C31	116.7 (2)
N3—C14—C13	110.6 (2)	C5—C6—N2	125.6 (2)
C15—C14—C13	124.4 (2)	C5—C6—C7	123.2 (2)
C26—C25—C24	121.7 (2)	N2—C6—C7	111.1 (2)
C26—C25—C71	119.0 (2)	C3—C2—C1	106.8 (2)
C24—C25—C71	119.3 (2)	C3—C2—H2	128.7 (17)
C72—C71—C76	118.9 (2)	C1—C2—H2	124.4 (17)
C72—C71—C25	122.8 (2)	C10—C9—N2	126.0 (2)
C76—C71—C25	118.3 (2)	C10—C9—C8	123.0 (2)
C25—C26—N6	125.5 (2)	N2—C9—C8	111.1 (2)
C25—C26—C27	123.7 (2)	C46—C41—C42	118.9 (2)
N6—C26—C27	110.4 (2)	C46—C41—C10	122.0 (2)
N5—C24—C25	124.7 (2)	C42—C41—C10	119.0 (2)
N5—C24—C23	110.8 (2)	C9—C10—C1^i	122.0 (2)
C25—C24—C23	124.5 (2)	C9—C10—C41	119.8 (2)
O8—C66—C65	124.7 (2)	C1^i—C10—C41	118.2 (2)
O8—C66—C61	114.5 (2)	N1—C1—C10^i	126.3 (2)
C65—C66—C61	120.8 (2)	N1—C1—C2	111.0 (2)
C28—C27—C26	106.9 (2)	C10^i—C1—C2	122.7 (2)
C28—C27—H27	127.9 (18)	C2—C3—C4	107.0 (2)
C26—C27—H27	125.2 (18)	C2—C3—H3	128.8 (17)
N6—C29—C30	126.0 (2)	C4—C3—H3	124.1 (17)
N6—C29—C28	110.5 (2)	C8—C7—C6	107.0 (2)
C30—C29—C28	123.5 (2)	C8—C7—H7	131.7 (18)
C17—C18—C19	107.3 (2)	C6—C7—H7	121.1 (18)
C17—C18—H18	127.3 (18)	O1—C32—C31	114.7 (2)
C19—C18—H18	125.4 (18)	O1—C32—C33	123.9 (2)
C12—C13—C14	107.2 (2)	C31—C32—C33	121.4 (2)
C12—C13—H13	129.3 (19)	C7—C8—C9	106.8 (2)
C14—C13—H13	123.5 (19)	C7—C8—H8	129.3 (17)
O12—C82—C83	124.1 (2)	C9—C8—H8	123.9 (17)
O12—C82—C81	114.7 (2)	O4—C46—C41	114.9 (2)
C83—C82—C81	121.2 (2)	O4—C46—C45	124.1 (2)
C13—C12—C11	107.1 (2)	C41—C46—C45	121.0 (2)
C13—C12—H12	128.1 (19)	O2—C36—C31	115.2 (2)
C11—C12—H12	124.8 (19)	O2—C36—C35	124.2 (2)
C16—C15—C14	122.5 (2)	C31—C36—C35	120.6 (2)
C16—C15—C51	117.6 (2)	C33—C34—C35	122.3 (2)
C14—C15—C51	119.5 (2)	C33—C34—H34	117.0 (19)
O11—C86—C85	123.9 (2)	C35—C34—H34	120.6 (19)
O11—C86—C81	114.7 (2)	C34—C33—C32	118.0 (3)
C85—C86—C81	121.5 (2)	C34—C33—H33	121.6 (19)
C11—C30—C29	121.1 (2)	C32—C33—H33	120 (2)
C11—C30—C81	119.7 (2)	O3—C42—C41	114.9 (2)
C29—C30—C81	119.0 (2)	O3—C42—C43	124.3 (2)
C27—C28—C29	107.4 (2)	C41—C42—C43	120.8 (2)
C27—C28—H28	130.2 (17)	C34—C35—C36	118.8 (3)
C29—C28—H28	122.4 (17)	C34—C35—H35	120.6 (19)
C22—C23—C24	107.1 (2)	C36—C35—H35	120.5 (19)
C22—C23—H23	128.0 (18)	O1—C37—H37A	109.5
C24—C23—H23	124.8 (18)	O1—C37—H37B	109.5
C63—C64—C65	122.2 (2)	H37A—C37—H37B	109.5
C63—C64—H64	120 (2)	O1—C37—H37C	109.5
C65—C64—H64	118 (2)	H37A—C37—H37C	109.5
C18—C17—C16	107.0 (2)	H37B—C37—H37C	109.5
C18—C17—H17	128.6 (17)	C43—C44—C45	122.2 (3)
C16—C17—H17	124.4 (17)	C43—C44—H44	121 (2)
O11—C88—H88A	109.5	C45—C44—H44	117 (2)
O11—C88—H88B	109.5	C44—C43—C42	118.5 (3)
H88A—C88—H88B	109.5	C44—C43—H43	123 (2)
O11—C88—H88C	109.5	C42—C43—H43	118 (2)
H88A—C88—H88C	109.5	O3—C47—H47A	109.5
H88B—C88—H88C	109.5	O3—C47—H47B	109.5
O7—C62—C63	124.2 (2)	H47A—C47—H47B	109.5
O7—C62—C61	115.4 (2)	O3—C47—H47C	109.5
C63—C62—C61	120.4 (2)	H47A—C47—H47C	109.5
C73—C74—C75	122.6 (2)	H47B—C47—H47C	109.5
C73—C74—H74	118.9 (19)	C44—C45—C46	118.6 (3)
C75—C74—H74	118.5 (19)	C44—C45—H45	123 (2)
C74—C73—C72	118.8 (3)	C46—C45—H45	118 (2)
C74—C73—H73	122.9 (19)	O4—C48—H48A	109.5
C72—C73—H73	118 (2)	O4—C48—H48B	109.5
C23—C22—C21	107.0 (2)	H48A—C48—H48B	109.5
C23—C22—H22	129.5 (18)	O4—C48—H48C	109.5
C21—C22—H22	123.5 (18)	H48A—C48—H48C	109.5
O9—C72—C71	115.8 (2)	H48B—C48—H48C	109.5
O9—C72—C73	123.5 (2)	O2—C38—H38A	109.5
C71—C72—C73	120.7 (2)	O2—C38—H38B	109.5
O6—C52—C53	124.2 (3)	H38A—C38—H38B	109.5
O6—C52—C51	114.9 (2)	O2—C38—H38C	109.5
C53—C52—C51	120.9 (3)	H38A—C38—H38C	109.5
O5—C56—C51	114.8 (2)	H38B—C38—H38C	109.5
O5—C56—C55	124.7 (3)	Cl1—C98—Cl2	112.50 (19)
C51—C56—C55	120.5 (3)	Cl1—C98—H98A	109.1
C74—C75—C76	118.2 (3)	Cl2—C98—H98A	109.1
C74—C75—H75	123.5 (18)	Cl1—C98—H98B	109.1
C76—C75—H75	118.3 (18)	Cl2—C98—H98B	109.1
C84—C85—C86	118.8 (3)	H98A—C98—H98B	107.8
C84—C85—H85	121.9 (19)	Cl3—C99—Cl4	110.61 (18)
C86—C85—H85	119.3 (19)	Cl3—C99—H99A	109.5
C64—C65—C66	118.7 (3)	Cl4—C99—H99A	109.5
C64—C65—H65	120 (2)	Cl3—C99—H99B	109.5
C66—C65—H65	122 (2)	Cl4—C99—H99B	109.5
O7—C67—H67A	109.5	H99A—C99—H99B	108.1
O7—C67—H67B	109.5	C95—C94—C93	123.8 (5)
H67A—C67—H67B	109.5	C95—C94—H94	118.1
O7—C67—H67C	109.5	C93—C94—H94	118.1
H67A—C67—H67C	109.5	C92—C91—H91A	109.5
H67B—C67—H67C	109.5	C92—C91—H91B	109.5
O10—C78—H78A	109.5	H91A—C91—H91B	109.5
O10—C78—H78B	109.5	C92—C91—H91C	109.5
H78A—C78—H78B	109.5	H91A—C91—H91C	109.5
O10—C78—H78C	109.5	H91B—C91—H91C	109.5
H78A—C78—H78C	109.5	C96—C95—C94	117.7 (6)
H78B—C78—H78C	109.5	C96—C95—H95	121.2
C55—C54—C53	121.6 (3)	C94—C95—H95	121.2
C55—C54—H54	121 (2)	C97—C92—C91	122.4 (4)
C53—C54—H54	117 (2)	C97—C92—C93	118.3 (4)
O12—C87—H87A	109.5	C91—C92—C93	118.8 (4)
O12—C87—H87B	109.5	C92—C97—C96	121.7 (4)
H87A—C87—H87B	109.5	C92—C97—H97	119.2
O12—C87—H87C	109.5	C96—C97—H97	119.2
H87A—C87—H87C	109.5	C94—C93—C92	116.1 (5)
H87B—C87—H87C	109.5	C94—C93—H93	121.9
C54—C53—C52	119.0 (3)	C92—C93—H93	121.9
C54—C53—H53	122 (2)	C95—C96—C97	121.8 (5)
C52—C53—H53	119 (2)	C95—C96—H96	119.1
C84—C83—C82	118.9 (3)	C97—C96—H96	119.1

Symmetry code: (i) −x+2, −y, −z+1.