Bis{2-[(2-amino­ethyl­imino)(phenyl)­methyl]­pyridine-κ³N}nickel(II) diperchlorate

In the title compound, [Ni(C₁₅H₁₇N₃)₂](ClO₄)₂, the Ni atom is hexacoordinated by six N atoms from two independent N,N′,N′′-tridentate 2-[(2-amino­ethyl­imino)(phenyl)­methyl]­pyridine ligands, with the NiN₆ group forming a distorted octahedral geometry. In the asymmetric unit, the ligand-coordinated nickel cation and two perchlorate anions are linked by one N—H...O and two C—H...O hydrogen bonds. In the crystal structure, the complexes are linked by four N—H...O bonds and three C—H...O bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.068
• wR factor = 0.199
• Data-to-parameter ratio = 14.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.36
         From the CIF: _reflns_number_total               5925
         Count of symmetry unique reflns         4317
         Completeness (_total/calc)            137.25%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1608
         Fraction of Friedel pairs measured     0.372
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure

---

S1. Comment

Polydentate Schiff base ligands have been widely studied because of their simple syntheses, inherent stability associated with such systems, and different coordination to various metal ions leading to numerous species of complexes (Brudenell et al., 1996; Chandra et al., 1990; Garnovskii et al., 1993; Lee et al., 1996; Vigato et al., 1990). The coordination chemistry of nickel Schiff bases have also attracted much attentions due to their versatile stereochemistry and bio-inorganic relevances (Cotton et al., 1999; Lancaster et al., 1988). Tridentate Schiff base ligands have been poorly studied compared with those of tetradentate systems (Holm et al., 1966). We report here the crystal structure analysis of the title Ni^II complex, (I), with tridentate ligand which was derived from the condensation between 1,3-diaminopropane and 2-benzoylpyridine in 1:1 molar ratio.

The asymmetric unit consists of a Ni^II complex cation and two perchlorate counter-anions with mutual electrostatic interactions (Fig. 1). The Ni1 atom is hexacoordinated by two 2-[(2-aminoethylimino)(phenyl)methyl]pyridine ligands, which act as N,N',N''-tridentate ligands. The NiN₆ group forms a distorted octahedral geometry. The almost linear N1—Ni1—N3 group is nearly perpendicular to the basal N2/N4/N5/N6 group. This supproted by the subtended angles at Ni1 (Table 1). The coordinated Ni—N bond distances [2.086 (5)–2.124 (5) Å] are normal (Allen et al., 1987), and agree with those in bis(diethylenetriamine)nickel(II) [Ni—N = 2.094 (5)–2.129 (5) Å; Liu-Gonzalez et al., 2001].

The three coordinated N atoms of one ligand and Ni atom form a NiN₃ plane, and the two NiN₃ planes are orthogonal to each other with the dihedral angle of 89.3 (2)°. The Ni—N—C—C—C—N six-membered rings are out of planarity towards half chair conformations. The atoms C1 and C2 deviate from the Ni1/N1/N2/C3 plane by −0.321 (8) and 0.506 (7) Å, respectively, and the deviations of the atoms C16 and C17 are −0.328 (9) and 0.404 (9) Å out of the Ni1/N4/N6/C18 plane. The dihedral angle between the rings C5–C10 and N3,C11–C15 is 65.2 (4)°, and that between the rings C20–C25 and N5,C26–C30 is 84.8 (4)°. This remarkable difference is due to the free rotation of the phenyl ring about the C_phenyl—C_methylene bond.

In the asymmetric unit, the ligand-coordinated Ni^II cation and two perchlorate counter anions are linked by N6—H6B···O5, C3—H3C···O4, and C30—H30A···O2 hydrogen bonds (Table 2). In the crystal packing, the perchlorate anions also play an important role in the intermolecular hydrogen-bonding scheme. The complex are linked by four types of intermolecular N—H···O bonds and three types of intermolecular C—H···O bonds involving the perchlorate anions. The C23—H23A···O6ⁱⁱⁱ and C28—H28A···O7^iv hydrogen bonds (see Table 2 for geometries and symmetry codes), together with the hydrogen bond in the asymmetric units, link the complexes into layers (Fig. 2). Each layer consists of hydrogen-bonded rings [R⁶₆(39) (Bernstein, 1995)] invloving three symmetrically related Ni^II complex cations and three symmetrically related perchlorate anions. The layers are further interconnected into a three-dimensional network throughout the crystal by N1—H1A···O1ⁱ, N6—H6A···O3ⁱ, N1—H1B···O7ⁱⁱ, N1—H1B···O8ⁱⁱ and C25—H25A···O5ⁱⁱ hydrogen bonds.

S2. Experimental

2-Benzoylpyridine (366.4 mg, 2 mmol) and 1,3-diaminopropane (148 mg, 2 mmol) was refluxed for 4–5 h. To the resulting solution was added Ni(ClO₄)₂·6H₂O (365.7 mg, 1 mmol) and stirred for 30 min. The solution was filtered and was left for slow evaporation and after 5–6 d yellow crystals of the title compound (I) were obtained -(yield 60%).

S3. Refinement

Phenyl ring C20—C25 had to be contrained. This, together with the rather large U_eq value of C25 and the R_int value of 0.078, may be a result of the poor quality of the crystal. All H atoms were fixed geometrically with C—H = 0.93–0.97 Å and N—H = 0.90 Å, and were treated as riding atoms. The maximum and minimum electron-density peaks are located 0.03 and 0.99 Å, respectively, from atom Ni1.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of title complex, showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms attached to C atoms and not involved in hydrogen bonding have been omitted for clarity.
	Fig. 2. Packing diagram of the title complex, showing the formation of layers comprising the R^66(39) ring pattern.

Bis{2-[(2-aminoethylimino)(phenyl)methyl]pyridine-κ³N}nickel(II) diperchlorate

Crystal data

[Ni(C15H17N3)2](ClO4)2	F(000) = 764
Mr = 736.24	Dx = 1.464 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.0632 (2) Å	Cell parameters from 8192 reflections
b = 16.5301 (3) Å	θ = 2.5–28.3°
c = 10.2627 (1) Å	µ = 0.80 mm^−1
β = 101.991 (1)°	T = 293 K
V = 1669.91 (5) Å^3	Prism, yellow
Z = 2	0.50 × 0.44 × 0.20 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5925 independent reflections
Radiation source: fine-focus sealed tube	4981 reflections with I > 2σ(I)'
Graphite monochromator	Rint = 0.078
Detector resolution: 8.33 pixels mm^-1	θmax = 28.4°, θmin = 2.5°
ω scans	h = −12→13
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −9→21
Tmin = 0.691, Tmax = 0.857	l = −13→13
10219 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.068	w = 1/[σ^2(Fo^2) + (0.1096P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.199	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.89 e Å^−3
5925 reflections	Δρmin = −0.60 e Å^−3
407 parameters	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.032 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1608 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (2)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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	0.52556 (5)	0.34807 (4)	0.37743 (6)	0.0326 (2)
Cl1	0.59324 (17)	0.09923 (12)	−0.0621 (2)	0.0634 (5)
Cl2	0.01677 (15)	0.42567 (12)	0.36050 (15)	0.0525 (4)
O1	0.4613 (5)	0.0770 (4)	−0.1319 (6)	0.0733 (16)
O2	0.6050 (9)	0.0814 (7)	0.0763 (7)	0.126 (4)
O3	0.6909 (6)	0.0561 (5)	−0.1128 (7)	0.0831 (19)
O4	0.6083 (8)	0.1829 (5)	−0.0695 (11)	0.121 (3)
O5	0.1271 (6)	0.4246 (7)	0.4708 (6)	0.110 (3)
O6	0.0715 (9)	0.4470 (9)	0.2536 (7)	0.154 (5)
O7	−0.0776 (8)	0.4827 (6)	0.3934 (12)	0.123 (3)
O8	−0.0583 (8)	0.3539 (6)	0.3373 (13)	0.140 (4)
N1	0.6299 (5)	0.4061 (3)	0.2484 (5)	0.0412 (10)
H1A	0.6052	0.4586	0.2438	0.049*
H1B	0.7191	0.4043	0.2853	0.049*
N2	0.3956 (4)	0.2840 (3)	0.2262 (4)	0.0364 (9)
N3	0.4078 (5)	0.2794 (3)	0.4870 (5)	0.0413 (10)
N4	0.6567 (5)	0.3899 (3)	0.5489 (5)	0.0406 (11)
N5	0.6743 (5)	0.2567 (3)	0.4146 (5)	0.0403 (10)
N6	0.3918 (5)	0.4453 (3)	0.3682 (5)	0.0441 (11)
H6A	0.3613	0.4577	0.2817	0.053*
H6B	0.3197	0.4283	0.4000	0.053*
C1	0.6115 (7)	0.3753 (5)	0.1124 (7)	0.0552 (17)
H1C	0.6554	0.3230	0.1138	0.066*
H1D	0.6549	0.4118	0.0601	0.066*
C2	0.4636 (7)	0.3669 (4)	0.0475 (6)	0.0523 (16)
H2B	0.4553	0.3682	−0.0484	0.063*
H2C	0.4153	0.4135	0.0716	0.063*
C3	0.3934 (7)	0.2902 (4)	0.0834 (6)	0.0470 (13)
H3B	0.2999	0.2899	0.0347	0.056*
H3C	0.4383	0.2432	0.0557	0.056*
C4	0.3109 (5)	0.2368 (4)	0.2655 (6)	0.0376 (11)
C5	0.2095 (6)	0.1856 (4)	0.1728 (6)	0.0433 (13)
C6	0.2542 (7)	0.1257 (5)	0.0954 (9)	0.0599 (18)
H6C	0.3465	0.1149	0.1053	0.072*
C7	0.1594 (10)	0.0828 (5)	0.0040 (9)	0.076 (2)
H7B	0.1888	0.0443	−0.0500	0.091*
C8	0.0218 (10)	0.0964 (7)	−0.0080 (12)	0.085 (3)
H8B	−0.0412	0.0664	−0.0680	0.102*
C9	−0.0220 (8)	0.1560 (6)	0.0713 (10)	0.076 (3)
H9A	−0.1143	0.1664	0.0623	0.091*
C10	0.0716 (7)	0.1991 (5)	0.1626 (9)	0.064 (2)
H10A	0.0422	0.2371	0.2172	0.077*
C11	0.3145 (5)	0.2315 (4)	0.4090 (6)	0.0385 (11)
C12	0.2328 (7)	0.1793 (5)	0.4652 (8)	0.0563 (16)
H12A	0.1704	0.1461	0.4104	0.068*
C13	0.2438 (8)	0.1767 (5)	0.5985 (8)	0.065 (2)
H13A	0.1902	0.1415	0.6360	0.078*
C14	0.3369 (7)	0.2277 (6)	0.6791 (7)	0.0612 (18)
H14A	0.3458	0.2276	0.7712	0.073*
C15	0.4160 (7)	0.2787 (5)	0.6183 (6)	0.0554 (17)
H15A	0.4768	0.3135	0.6713	0.066*
C16	0.4422 (8)	0.5219 (5)	0.4397 (8)	0.0616 (18)
H16A	0.5065	0.5479	0.3947	0.074*
H16B	0.3666	0.5586	0.4377	0.074*
C17	0.5095 (10)	0.5050 (5)	0.5811 (8)	0.070 (2)
H17A	0.4515	0.4683	0.6177	0.084*
H17B	0.5128	0.5553	0.6303	0.084*
C18	0.6507 (8)	0.4697 (5)	0.6087 (9)	0.065 (2)
H18A	0.7108	0.5061	0.5743	0.079*
H18B	0.6834	0.4655	0.7042	0.079*
C19	0.7533 (5)	0.3424 (4)	0.6001 (5)	0.0393 (11)
C20	0.8566 (4)	0.3599 (4)	0.7234 (3)	0.0436 (14)
C21	0.8313 (4)	0.3387 (4)	0.8470 (4)	0.0617 (19)
H21A	0.7504	0.3129	0.8525	0.074*
C22	0.9267 (5)	0.3559 (5)	0.9624 (3)	0.077 (3)
H22A	0.9097	0.3417	1.0451	0.093*
C23	1.0474 (5)	0.3944 (5)	0.9541 (4)	0.087 (3)
H23A	1.1113	0.4059	1.0313	0.105*
C24	1.0728 (5)	0.4156 (6)	0.8305 (5)	0.119 (4)
H24A	1.1537	0.4414	0.8250	0.143*
C25	0.9774 (5)	0.3984 (5)	0.7152 (4)	0.119 (4)
H25A	0.9944	0.4126	0.6325	0.143*
C26	0.7646 (5)	0.2652 (4)	0.5290 (6)	0.0398 (12)
C27	0.8641 (7)	0.2085 (5)	0.5727 (8)	0.0562 (17)
H27A	0.9243	0.2151	0.6540	0.067*
C28	0.8733 (8)	0.1422 (5)	0.4948 (10)	0.071 (2)
H28A	0.9396	0.1031	0.5230	0.085*
C29	0.7833 (8)	0.1339 (4)	0.3737 (9)	0.0600 (18)
H29A	0.7896	0.0903	0.3181	0.072*
C30	0.6845 (6)	0.1915 (4)	0.3376 (7)	0.0478 (14)
H30A	0.6224	0.1856	0.2574	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0258 (3)	0.0361 (3)	0.0337 (3)	−0.0013 (3)	0.0009 (2)	−0.0022 (3)
Cl1	0.0462 (8)	0.0632 (11)	0.0747 (11)	0.0022 (8)	−0.0010 (7)	−0.0324 (9)
Cl2	0.0432 (8)	0.0700 (11)	0.0447 (7)	−0.0130 (7)	0.0103 (6)	−0.0038 (7)
O1	0.045 (3)	0.079 (4)	0.089 (4)	−0.008 (3)	−0.001 (3)	−0.023 (3)
O2	0.115 (6)	0.184 (11)	0.067 (4)	0.036 (6)	−0.008 (4)	−0.041 (5)
O3	0.054 (3)	0.095 (5)	0.103 (5)	−0.004 (3)	0.024 (3)	−0.041 (4)
O4	0.090 (5)	0.067 (5)	0.208 (10)	−0.025 (4)	0.039 (6)	−0.050 (6)
O5	0.048 (3)	0.224 (11)	0.055 (3)	−0.004 (4)	0.007 (2)	0.020 (4)
O6	0.104 (6)	0.308 (16)	0.052 (4)	−0.074 (8)	0.018 (4)	0.029 (6)
O7	0.069 (4)	0.085 (6)	0.203 (10)	−0.001 (4)	0.005 (5)	−0.036 (6)
O8	0.080 (5)	0.060 (4)	0.292 (13)	−0.018 (4)	0.064 (7)	−0.048 (7)
N1	0.029 (2)	0.047 (3)	0.046 (3)	−0.007 (2)	0.0050 (18)	0.000 (2)
N2	0.035 (2)	0.039 (2)	0.033 (2)	−0.0012 (19)	0.0004 (17)	−0.0031 (17)
N3	0.036 (2)	0.045 (3)	0.043 (2)	−0.003 (2)	0.0103 (19)	0.002 (2)
N4	0.032 (2)	0.042 (3)	0.043 (2)	−0.0047 (19)	−0.0035 (18)	−0.006 (2)
N5	0.033 (2)	0.038 (3)	0.049 (3)	−0.0001 (19)	0.0063 (19)	0.003 (2)
N6	0.035 (2)	0.055 (3)	0.042 (2)	0.006 (2)	0.0061 (19)	0.004 (2)
C1	0.057 (4)	0.065 (4)	0.050 (3)	−0.013 (3)	0.026 (3)	−0.002 (3)
C2	0.064 (4)	0.052 (4)	0.036 (3)	−0.009 (3)	0.001 (3)	0.005 (2)
C3	0.053 (3)	0.053 (4)	0.033 (3)	−0.009 (3)	0.004 (2)	−0.004 (2)
C4	0.029 (2)	0.036 (3)	0.045 (3)	0.001 (2)	−0.001 (2)	−0.005 (2)
C5	0.036 (3)	0.037 (3)	0.052 (3)	−0.007 (2)	−0.001 (2)	−0.007 (2)
C6	0.044 (3)	0.050 (4)	0.083 (5)	−0.015 (3)	0.006 (3)	−0.014 (3)
C7	0.076 (5)	0.055 (5)	0.094 (6)	−0.018 (4)	0.012 (5)	−0.039 (4)
C8	0.069 (6)	0.065 (5)	0.106 (6)	−0.010 (5)	−0.017 (5)	−0.038 (5)
C9	0.043 (4)	0.082 (6)	0.094 (6)	−0.015 (4)	−0.005 (4)	−0.032 (5)
C10	0.035 (3)	0.057 (4)	0.093 (6)	−0.004 (3)	−0.005 (3)	−0.026 (4)
C11	0.030 (2)	0.035 (3)	0.050 (3)	−0.003 (2)	0.009 (2)	0.003 (2)
C12	0.043 (3)	0.054 (4)	0.071 (4)	−0.012 (3)	0.011 (3)	0.006 (3)
C13	0.060 (4)	0.065 (5)	0.077 (5)	0.002 (4)	0.030 (4)	0.024 (4)
C14	0.056 (4)	0.079 (5)	0.050 (4)	0.005 (4)	0.014 (3)	0.011 (3)
C15	0.051 (4)	0.073 (5)	0.041 (3)	−0.003 (3)	0.007 (3)	0.008 (3)
C16	0.067 (4)	0.052 (4)	0.064 (4)	0.019 (4)	0.010 (3)	−0.005 (3)
C17	0.089 (6)	0.065 (5)	0.052 (4)	0.019 (4)	0.004 (4)	−0.004 (3)
C18	0.062 (4)	0.048 (4)	0.073 (5)	0.006 (3)	−0.015 (4)	−0.017 (3)
C19	0.032 (2)	0.045 (3)	0.039 (2)	−0.006 (3)	0.0026 (18)	0.005 (3)
C20	0.033 (2)	0.056 (4)	0.038 (2)	0.004 (3)	−0.0019 (19)	−0.001 (3)
C21	0.055 (3)	0.083 (6)	0.045 (3)	−0.001 (4)	0.006 (3)	0.013 (4)
C22	0.066 (4)	0.122 (8)	0.039 (3)	0.018 (6)	0.003 (3)	0.017 (5)
C23	0.061 (5)	0.144 (10)	0.044 (4)	0.019 (5)	−0.016 (3)	−0.022 (5)
C24	0.061 (4)	0.239 (13)	0.051 (3)	−0.060 (6)	0.000 (3)	−0.007 (5)
C25	0.061 (4)	0.239 (13)	0.051 (3)	−0.060 (6)	0.000 (3)	−0.007 (5)
C26	0.031 (2)	0.042 (3)	0.046 (3)	0.002 (2)	0.006 (2)	0.004 (2)
C27	0.038 (3)	0.055 (4)	0.069 (4)	0.011 (3)	−0.003 (3)	0.007 (3)
C28	0.045 (4)	0.051 (4)	0.114 (7)	0.018 (3)	0.012 (4)	0.008 (4)
C29	0.053 (4)	0.039 (3)	0.088 (5)	−0.002 (3)	0.017 (4)	−0.012 (3)
C30	0.043 (3)	0.037 (3)	0.060 (4)	0.002 (2)	0.005 (3)	−0.013 (3)

Geometric parameters (Å, º)

Ni1—N1	2.086 (5)	C7—H7B	0.9300
Ni1—N2	2.097 (4)	C8—C9	1.406 (13)
Ni1—N3	2.124 (5)	C8—H8B	0.9300
Ni1—N4	2.086 (5)	C9—C10	1.380 (10)
Ni1—N5	2.104 (5)	C9—H9A	0.9300
Ni1—N6	2.087 (5)	C10—H10A	0.9300
Cl1—O4	1.395 (9)	C11—C12	1.397 (9)
Cl1—O3	1.399 (6)	C12—C13	1.350 (11)
Cl1—O1	1.420 (5)	C12—H12A	0.9300
Cl1—O2	1.431 (9)	C13—C14	1.397 (12)
Cl2—O6	1.372 (7)	C13—H13A	0.9300
Cl2—O8	1.401 (8)	C14—C15	1.393 (11)
Cl2—O5	1.411 (6)	C14—H14A	0.9300
Cl2—O7	1.427 (9)	C15—H15A	0.9300
N1—C1	1.461 (8)	C16—C17	1.495 (11)
N1—H1A	0.9000	C16—H16A	0.9700
N1—H1B	0.9000	C16—H16B	0.9700
N2—C4	1.281 (8)	C17—C18	1.508 (12)
N2—C3	1.465 (7)	C17—H17A	0.9700
N3—C15	1.333 (8)	C17—H17B	0.9700
N3—C11	1.355 (8)	C18—H18A	0.9700
N4—C19	1.273 (8)	C18—H18B	0.9700
N4—C18	1.461 (9)	C19—C26	1.486 (9)
N5—C26	1.334 (8)	C19—C20	1.490 (6)
N5—C30	1.353 (8)	C20—C21	1.3900
N6—C16	1.497 (10)	C20—C25	1.3900
N6—H6A	0.9000	C21—C22	1.3900
N6—H6B	0.9000	C21—H21A	0.9300
C1—C2	1.506 (10)	C22—C23	1.3900
C1—H1C	0.9700	C22—H22A	0.9300
C1—H1D	0.9700	C23—C24	1.3900
C2—C3	1.533 (9)	C23—H23A	0.9300
C2—H2B	0.9700	C24—C25	1.3900
C2—H2C	0.9700	C24—H24A	0.9300
C3—H3B	0.9700	C25—H25A	0.9300
C3—H3C	0.9700	C26—C27	1.378 (8)
C4—C11	1.469 (8)	C27—C28	1.371 (12)
C4—C5	1.504 (7)	C27—H27A	0.9300
C5—C10	1.388 (9)	C28—C29	1.384 (12)
C5—C6	1.400 (10)	C28—H28A	0.9300
C6—C7	1.387 (10)	C29—C30	1.371 (10)
C6—H6C	0.9300	C29—H29A	0.9300
C7—C8	1.383 (14)	C30—H30A	0.9300
N1—Ni1—N4	94.0 (2)	C6—C7—H7B	119.6
N4—Ni1—N6	94.2 (2)	C7—C8—C9	119.4 (8)
N1—Ni1—N6	91.2 (2)	C7—C8—H8B	120.3
N4—Ni1—N2	168.4 (2)	C9—C8—H8B	120.3
N1—Ni1—N2	94.7 (2)	C10—C9—C8	120.2 (8)
N6—Ni1—N2	93.3 (2)	C10—C9—H9A	119.9
N4—Ni1—N5	77.5 (2)	C8—C9—H9A	119.9
N1—Ni1—N5	90.7 (2)	C9—C10—C5	119.9 (7)
N6—Ni1—N5	171.5 (2)	C9—C10—H10A	120.1
N2—Ni1—N5	94.74 (19)	C5—C10—H10A	120.1
N4—Ni1—N3	93.2 (2)	N3—C11—C12	120.8 (6)
N1—Ni1—N3	172.5 (2)	N3—C11—C4	115.3 (5)
N6—Ni1—N3	90.6 (2)	C12—C11—C4	123.9 (6)
N2—Ni1—N3	78.0 (2)	C13—C12—C11	120.5 (7)
N5—Ni1—N3	88.5 (2)	C13—C12—H12A	119.8
O4—Cl1—O3	113.1 (5)	C11—C12—H12A	119.8
O4—Cl1—O1	109.3 (5)	C12—C13—C14	119.0 (7)
O3—Cl1—O1	109.6 (4)	C12—C13—H13A	120.5
O4—Cl1—O2	105.7 (6)	C14—C13—H13A	120.5
O3—Cl1—O2	110.2 (5)	C15—C14—C13	118.3 (7)
O1—Cl1—O2	108.9 (5)	C15—C14—H14A	120.8
O6—Cl2—O8	111.9 (7)	C13—C14—H14A	120.8
O6—Cl2—O5	105.4 (5)	N3—C15—C14	122.5 (7)
O8—Cl2—O5	115.6 (6)	N3—C15—H15A	118.7
O6—Cl2—O7	114.6 (8)	C14—C15—H15A	118.7
O8—Cl2—O7	103.8 (5)	C17—C16—N6	110.9 (7)
O5—Cl2—O7	105.7 (6)	C17—C16—H16A	109.5
C1—N1—Ni1	117.7 (4)	N6—C16—H16A	109.5
C1—N1—H1A	107.9	C17—C16—H16B	109.5
Ni1—N1—H1A	107.9	N6—C16—H16B	109.5
C1—N1—H1B	107.9	H16A—C16—H16B	108.0
Ni1—N1—H1B	107.9	C16—C17—C18	118.2 (7)
H1A—N1—H1B	107.2	C16—C17—H17A	107.8
C4—N2—C3	119.0 (5)	C18—C17—H17A	107.8
C4—N2—Ni1	115.4 (4)	C16—C17—H17B	107.8
C3—N2—Ni1	125.7 (4)	C18—C17—H17B	107.8
C15—N3—C11	118.7 (5)	H17A—C17—H17B	107.1
C15—N3—Ni1	128.0 (5)	N4—C18—C17	113.0 (6)
C11—N3—Ni1	113.2 (4)	N4—C18—H18A	109.0
C19—N4—C18	118.5 (5)	C17—C18—H18A	109.0
C19—N4—Ni1	116.0 (4)	N4—C18—H18B	109.0
C18—N4—Ni1	125.4 (4)	C17—C18—H18B	109.0
C26—N5—C30	118.5 (5)	H18A—C18—H18B	107.8
C26—N5—Ni1	114.4 (4)	N4—C19—C26	117.1 (5)
C30—N5—Ni1	127.1 (4)	N4—C19—C20	124.7 (6)
C16—N6—Ni1	118.6 (4)	C26—C19—C20	118.2 (5)
C16—N6—H6A	107.7	C21—C20—C25	120.0
Ni1—N6—H6A	107.7	C21—C20—C19	119.9 (3)
C16—N6—H6B	107.7	C25—C20—C19	120.1 (3)
Ni1—N6—H6B	107.7	C20—C21—C22	120.0
H6A—N6—H6B	107.1	C20—C21—H21A	120.0
N1—C1—C2	111.8 (5)	C22—C21—H21A	120.0
N1—C1—H1C	109.2	C21—C22—C23	120.0
C2—C1—H1C	109.2	C21—C22—H22A	120.0
N1—C1—H1D	109.2	C23—C22—H22A	120.0
C2—C1—H1D	109.2	C22—C23—C24	120.0
H1C—C1—H1D	107.9	C22—C23—H23A	120.0
C1—C2—C3	115.6 (6)	C24—C23—H23A	120.0
C1—C2—H2B	108.4	C25—C24—C23	120.0
C3—C2—H2B	108.4	C25—C24—H24A	120.0
C1—C2—H2C	108.4	C23—C24—H24A	120.0
C3—C2—H2C	108.4	C24—C25—C20	120.0
H2B—C2—H2C	107.4	C24—C25—H25A	120.0
N2—C3—C2	112.7 (5)	C20—C25—H25A	120.0
N2—C3—H3B	109.1	N5—C26—C27	122.1 (6)
C2—C3—H3B	109.1	N5—C26—C19	114.5 (5)
N2—C3—H3C	109.1	C27—C26—C19	123.3 (6)
C2—C3—H3C	109.1	C28—C27—C26	119.1 (7)
H3B—C3—H3C	107.8	C28—C27—H27A	120.4
N2—C4—C11	118.2 (5)	C26—C27—H27A	120.4
N2—C4—C5	123.6 (5)	C27—C28—C29	119.4 (7)
C11—C4—C5	118.2 (5)	C27—C28—H28A	120.3
C10—C5—C6	120.4 (6)	C29—C28—H28A	120.3
C10—C5—C4	119.6 (6)	C30—C29—C28	118.5 (7)
C6—C5—C4	120.0 (5)	C30—C29—H29A	120.8
C7—C6—C5	119.2 (7)	C28—C29—H29A	120.8
C7—C6—H6C	120.4	N5—C30—C29	122.3 (6)
C5—C6—H6C	120.4	N5—C30—H30A	118.8
C8—C7—C6	120.8 (8)	C29—C30—H30A	118.8
C8—C7—H7B	119.6
N4—Ni1—N1—C1	158.5 (5)	C4—C5—C6—C7	−175.7 (8)
N6—Ni1—N1—C1	−107.3 (5)	C5—C6—C7—C8	−2.3 (15)
N2—Ni1—N1—C1	−13.9 (5)	C6—C7—C8—C9	1.6 (18)
N5—Ni1—N1—C1	81.0 (5)	C7—C8—C9—C10	−1.6 (19)
N4—Ni1—N2—C4	40.7 (11)	C8—C9—C10—C5	2.3 (16)
N1—Ni1—N2—C4	178.9 (4)	C6—C5—C10—C9	−3.1 (14)
N6—Ni1—N2—C4	−89.6 (4)	C4—C5—C10—C9	175.7 (8)
N5—Ni1—N2—C4	87.8 (4)	C15—N3—C11—C12	−3.1 (9)
N3—Ni1—N2—C4	0.3 (4)	Ni1—N3—C11—C12	176.9 (5)
N4—Ni1—N2—C3	−140.3 (9)	C15—N3—C11—C4	179.1 (6)
N1—Ni1—N2—C3	−2.1 (5)	Ni1—N3—C11—C4	−0.9 (6)
N6—Ni1—N2—C3	89.4 (5)	N2—C4—C11—N3	1.2 (8)
N5—Ni1—N2—C3	−93.2 (5)	C5—C4—C11—N3	−179.7 (5)
N3—Ni1—N2—C3	179.3 (5)	N2—C4—C11—C12	−176.5 (6)
N4—Ni1—N3—C15	7.8 (6)	C5—C4—C11—C12	2.6 (9)
N6—Ni1—N3—C15	−86.4 (6)	N3—C11—C12—C13	1.1 (11)
N2—Ni1—N3—C15	−179.6 (6)	C4—C11—C12—C13	178.7 (6)
N5—Ni1—N3—C15	85.2 (6)	C11—C12—C13—C14	0.8 (12)
N4—Ni1—N3—C11	−172.2 (4)	C12—C13—C14—C15	−0.7 (12)
N6—Ni1—N3—C11	93.6 (4)	C11—N3—C15—C14	3.2 (11)
N2—Ni1—N3—C11	0.4 (4)	Ni1—N3—C15—C14	−176.8 (6)
N5—Ni1—N3—C11	−94.8 (4)	C13—C14—C15—N3	−1.3 (12)
N1—Ni1—N4—C19	−94.7 (4)	Ni1—N6—C16—C17	−50.9 (8)
N6—Ni1—N4—C19	173.8 (4)	N6—C16—C17—C18	76.4 (10)
N2—Ni1—N4—C19	43.5 (12)	C19—N4—C18—C17	−155.7 (7)
N5—Ni1—N4—C19	−4.8 (4)	Ni1—N4—C18—C17	28.1 (10)
N3—Ni1—N4—C19	82.9 (4)	C16—C17—C18—N4	−62.6 (11)
N1—Ni1—N4—C18	81.6 (6)	C18—N4—C19—C26	−174.0 (6)
N6—Ni1—N4—C18	−9.9 (6)	Ni1—N4—C19—C26	2.6 (6)
N2—Ni1—N4—C18	−140.2 (9)	C18—N4—C19—C20	4.4 (9)
N5—Ni1—N4—C18	171.4 (6)	Ni1—N4—C19—C20	−179.0 (4)
N3—Ni1—N4—C18	−100.8 (6)	N4—C19—C20—C21	88.4 (7)
N4—Ni1—N5—C26	6.5 (4)	N4—C19—C20—C25	−90.7 (6)
N1—Ni1—N5—C26	100.4 (4)	C26—C19—C20—C21	−93.2 (6)
N2—Ni1—N5—C26	−164.9 (4)	C26—C19—C20—C25	87.7 (6)
N3—Ni1—N5—C26	−87.1 (4)	C25—C20—C21—C22	0.0
N4—Ni1—N5—C30	−175.2 (5)	C19—C20—C21—C22	−179.1 (6)
N1—Ni1—N5—C30	−81.3 (5)	C20—C21—C22—C23	0.0
N2—Ni1—N5—C30	13.5 (5)	C21—C22—C23—C24	0.0
N3—Ni1—N5—C30	91.2 (5)	C22—C23—C24—C25	0.0
N4—Ni1—N6—C16	20.8 (5)	C23—C24—C25—C20	0.0
N1—Ni1—N6—C16	−73.3 (5)	C21—C20—C25—C24	0.0
N2—Ni1—N6—C16	−168.1 (5)	C19—C20—C25—C24	179.1 (6)
N3—Ni1—N6—C16	114.0 (5)	C30—N5—C26—C27	−2.3 (9)
Ni1—N1—C1—C2	51.1 (7)	Ni1—N5—C26—C27	176.2 (5)
N1—C1—C2—C3	−81.2 (8)	C30—N5—C26—C19	174.4 (5)
C4—N2—C3—C2	160.8 (6)	Ni1—N5—C26—C19	−7.1 (6)
Ni1—N2—C3—C2	−18.1 (8)	N4—C19—C26—N5	3.1 (7)
C1—C2—C3—N2	60.4 (8)	C20—C19—C26—N5	−175.4 (4)
C3—N2—C4—C11	−180.0 (5)	N4—C19—C26—C27	179.8 (6)
Ni1—N2—C4—C11	−0.9 (6)	C20—C19—C26—C27	1.2 (8)
C3—N2—C4—C5	1.0 (9)	N5—C26—C27—C28	1.8 (10)
Ni1—N2—C4—C5	−179.9 (4)	C19—C26—C27—C28	−174.6 (7)
N2—C4—C5—C6	62.1 (9)	C26—C27—C28—C29	0.4 (12)
N2—C4—C5—C10	−116.7 (8)	C27—C28—C29—C30	−2.0 (12)
C11—C4—C5—C6	−116.9 (7)	C26—N5—C30—C29	0.6 (10)
C11—C4—C5—C10	64.3 (9)	Ni1—N5—C30—C29	−177.7 (5)
C10—C5—C6—C7	3.1 (13)	C28—C29—C30—N5	1.5 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.90	2.30	3.130 (8)	154
N1—H1B···O7^ii	0.90	2.48	3.265 (11)	146
N1—H1B···O8^ii	0.90	2.35	3.199 (10)	158
N6—H6A···O3^i	0.90	2.36	3.164 (9)	149
N6—H6B···O5	0.90	2.21	3.080 (8)	163
C3—H3C···O4	0.97	2.55	3.420 (11)	150
C23—H23A···O6^iii	0.93	2.49	3.155 (9)	128
C25—H25A···O5^ii	0.93	2.34	3.212 (8)	155
C28—H28A···O7^iv	0.93	2.48	3.393 (13)	169
C30—H30A···O2	0.93	2.51	3.202 (11)	131

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