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Acta Cryst. (2007). E63, m1546    [ doi:10.1107/S1600536807020673 ]

[N,N'-Bis(pyrrol-2-ylmethylene)cyclohexane-1,2-diaminato-[kappa]4N]nickel(II)

J.-M. Chen, W.-J. Ruan, F. Gao, Y.-H. Zhang and Z.-A. Zhu

Abstract top

The tetradentate Schiff base ligand derived from the condensation of pyrrole-2-carbaldehyde and cyclohexane-1,2-diamine forms a square-planar four-coordinate Ni complex, [Ni(C16H18N4)]. The compound crystallizes with two crystallographically independent molecules in the asymmetric unit.

Comment top

salen ligands (salen = N,N'-bis(salicyldene)ethylenediamine) and their complexes have received continuous and intensive attention because of their capabilities to serve as catalysts of organic reactions (Baleizao & Garcia, 2006), models of catalytic centers of metalloenzymes (Maruyama et al., 1990; Carey et al., 2004) and nonlinear optical materials (Rigamonti et al., 2006; Tedim et al., 2006). On the contrary, little is known about the ligand behaviour of the analogous compounds derived from pyrrole 2-carboxaldehyde and about the properties of their complexes (Weber, 1967; Downing & Urbach, 1971; Bacchi et al., 2003, Bella et al., 2004). In the present work, we have prepared the title compound (I) and determined its crystal structure.

The complex crystallizes with two crystallographically independent, but quite similar molecules in the asymmetric unit. In both molecules, the ligand is bideprotonated and the Ni(II) ion is tetracoordinated in a square planar environment, with the pyrrole and imine nitrogen atoms as donors. The coordination induces the formation of three five-membered chelate rings, and the N—Ni—N angles are less than 90°. The Ni—N (pyrrole) distances are significantly longer than the Ni—N (imine) distances.

Related literature top

For related literature, see: Bacchi et al. (2003); Baleizao & Garcia (2006); Bella et al. (2004); Carey et al. (2004); Downing & Urbach (1971); Maruyama et al. (1990); Rigamonti et al. (2006); Tedim et al. (2006); Weber (1967).

Experimental top

The title complex was synthesized by dissolving N,N'-bis(pyrrol-2- ylmethylene)cyclohexylenediamine (1 mmol, 268 mg) in ethanol (15 ml), with the addition of nickel(II) acetate (1 mmol, 212 mg) dissolved in distilled water (5 ml). The mixture was stirred at room temperature for 2 h and the resulting red–brown precipitate was filtered, dried and chromatographed on silica gel eluted with CHCl3. Crystals suitable for X-ray diffraction analysis were obtained by recrystallization from a CHCl3 solution. Elemental composition, calculated: C 59.12, H 5.58, N 17.24%; found: C 59.14, H 5.45, N 17.35%. M+ = 324 g mol-1. 1H NMR (300 MHz, CDCl3, 298 K, TMS): 7.23 (s, 2H, H imine), 6.80 (s, 2H, H pyrrole α), 6.59 (t, J = 3.6 Hz, 2H, H pyrrole γ), 6.13 (t, J = 3.0 Hz, 2H, H

pyrrole β), 3.34 (t, J = 3.5 Hz, 2H, CH), 2.24–1.31 (m, 8H, CH2).

Refinement top

The two cyclohexane-1,2-diamine groups are disordered, with site-occupation factors of 0.495 (15) for atoms C6 and C11, 0.505 (15) for atoms C6' and C11', and 0.50 (3) for atoms C22, C27, C22' and C27'. H atoms were positioned geometrically and allowed to ride on their parent C atoms, with C—H ranging from 0.93 to 0.98 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary size, and only one set of disordered C atoms are represented.
[N,N'-Bis(pyrrol-2-ylmethylene)cyclohexane-1,2-diaminato-κ4N]nickel(II) top
Crystal data top
[Ni(C16H18N4)]F(000) = 1360
Mr = 325.05Dx = 1.442 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 21.379 (3) ÅCell parameters from 4354 reflections
b = 8.6247 (10) Åθ = 2.5–25.5°
c = 17.475 (2) ŵ = 1.29 mm−1
β = 111.697 (2)°T = 294 K
V = 2993.9 (6) Å3Block, red
Z = 80.26 × 0.22 × 0.18 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		6100 independent reflections
Radiation source: fine-focus sealed tube4081 reflections with I > 2σ(I)
graphiteRint = 0.040
φ and ω scansθmax = 26.4°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −26→25
Tmin = 0.730, Tmax = 0.800k = −10→7
16412 measured reflectionsl = −20→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.136 w = 1/[σ2(Fo2) + 10.3102P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.001
6100 reflectionsΔρmax = 0.39 e Å−3
418 parametersΔρmin = −0.41 e Å−3
12 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00459 (17)
Crystal data top
[Ni(C16H18N4)]V = 2993.9 (6) Å3
Mr = 325.05Z = 8
Monoclinic, P21/cMo Kα radiation
a = 21.379 (3) ŵ = 1.29 mm−1
b = 8.6247 (10) ÅT = 294 K
c = 17.475 (2) Å0.26 × 0.22 × 0.18 mm
β = 111.697 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		6100 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4081 reflections with I > 2σ(I)
Tmin = 0.730, Tmax = 0.800Rint = 0.040
16412 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.061 w = 1/[σ2(Fo2) + 10.3102P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.136Δρmax = 0.39 e Å−3
S = 1.15Δρmin = −0.41 e Å−3
6100 reflectionsAbsolute structure: ?
418 parametersFlack parameter: ?
12 restraintsRogers parameter: ?
H-atom parameters constrained
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni11.03966 (3)0.31724 (8)0.46424 (4)0.0414 (2)
Ni20.46464 (3)0.30951 (8)0.42360 (4)0.0433 (2)
N11.0592 (2)0.4251 (5)0.3818 (3)0.0465 (11)
N20.9512 (2)0.3281 (5)0.3915 (3)0.0474 (11)
N31.0027 (2)0.2221 (5)0.5330 (3)0.0469 (11)
N41.1217 (2)0.3006 (5)0.5555 (3)0.0459 (11)
N50.4469 (3)0.4146 (5)0.3230 (3)0.0508 (12)
N60.5536 (2)0.3479 (5)0.4403 (3)0.0515 (12)
N70.4986 (2)0.2207 (5)0.5273 (3)0.0449 (11)
N80.3804 (2)0.2682 (5)0.4305 (3)0.0437 (11)
C11.1105 (3)0.4849 (7)0.3641 (4)0.0562 (15)
H11.15580.47150.39620.067*
C21.0866 (4)0.5684 (8)0.2921 (4)0.0667 (18)
H21.11240.62020.26750.080*
C31.0173 (4)0.5614 (7)0.2631 (4)0.0613 (17)
H30.98760.60840.21570.074*
C41.0007 (3)0.4706 (6)0.3183 (3)0.0482 (14)
C50.9415 (3)0.4129 (7)0.3273 (3)0.0542 (15)
H50.89860.43500.28950.065*
C60.9065 (4)0.2229 (14)0.4133 (6)0.047 (4)0.495 (15)
H6A0.91630.11720.40060.056*0.495 (15)
C110.9294 (4)0.2363 (14)0.5065 (7)0.047 (4)0.495 (15)
H11A0.91850.34020.52050.057*0.495 (15)
C6'0.9007 (4)0.2944 (15)0.4278 (6)0.050 (4)0.505 (15)
H6B0.89680.38500.45960.060*0.505 (15)
C11'0.9339 (4)0.1640 (15)0.4875 (6)0.050 (4)0.505 (15)
H11B0.93730.07350.45530.060*0.505 (15)
C220.6002 (8)0.249 (3)0.5056 (13)0.057 (5)0.50 (3)
H22A0.59860.14250.48480.068*0.50 (3)
C270.5722 (7)0.251 (3)0.5742 (11)0.046 (4)0.50 (3)
H27A0.57670.35670.59590.056*0.50 (3)
C22'0.6023 (7)0.322 (3)0.5298 (11)0.050 (5)0.50 (3)
H22B0.59810.40970.56310.060*0.50 (3)
C27'0.5723 (7)0.183 (3)0.5538 (12)0.046 (4)0.50 (3)
H27B0.57730.09470.52140.055*0.50 (3)
C70.8311 (3)0.2486 (8)0.3704 (4)0.0646 (18)
H7A0.82200.35900.36910.078*0.495 (15)
H7B0.81740.21330.31380.078*0.495 (15)
H7C0.80740.34140.34360.078*0.505 (15)
H7D0.83530.18180.32780.078*0.505 (15)
C80.7908 (4)0.1694 (14)0.4093 (5)0.129 (4)
H8A0.76760.08570.37280.155*
H8B0.75650.24210.41040.155*
C90.8204 (4)0.1035 (12)0.4915 (6)0.113 (3)
H9A0.8095−0.00610.48680.136*
H9B0.79730.14940.52440.136*
C100.8935 (3)0.1169 (7)0.5396 (4)0.0586 (16)
H10A0.91430.01650.54060.070*0.495 (15)
H10B0.90010.14400.59590.070*0.495 (15)
H10C0.91020.01810.56560.070*0.505 (15)
H10D0.90070.19300.58290.070*0.505 (15)
C121.0435 (3)0.2008 (6)0.6084 (3)0.0508 (14)
H121.02950.16140.64900.061*
C131.1108 (3)0.2424 (6)0.6237 (3)0.0479 (14)
C141.1706 (3)0.2436 (7)0.6910 (4)0.0601 (16)
H141.17700.21040.74390.072*
C151.2192 (3)0.3041 (8)0.6645 (4)0.0642 (17)
H151.26440.31980.69630.077*
C161.1871 (3)0.3367 (6)0.5807 (4)0.0514 (14)
H161.20820.37760.54720.062*
C170.3959 (4)0.4642 (7)0.2550 (4)0.0617 (17)
H170.35080.43980.24170.074*
C180.4210 (4)0.5572 (8)0.2080 (4)0.072 (2)
H180.39590.60390.15800.086*
C190.4893 (4)0.5680 (7)0.2480 (4)0.071 (2)
H190.51910.62500.23170.085*
C200.5050 (4)0.4761 (7)0.3185 (4)0.0573 (16)
C210.5638 (3)0.4361 (7)0.3859 (4)0.0609 (17)
H210.60640.47020.39090.073*
C230.6741 (3)0.3039 (9)0.5423 (4)0.0725 (19)
H23A0.69600.27800.50420.087*0.50 (3)
H23B0.67470.41580.54770.087*0.50 (3)
H23C0.67790.23790.49920.087*0.50 (3)
H23D0.69290.40440.53800.087*0.50 (3)
C240.7123 (4)0.2366 (13)0.6217 (6)0.127 (4)
H24A0.73940.31960.65530.153*
H24B0.74340.16360.61280.153*
C250.6814 (4)0.1572 (11)0.6722 (5)0.103 (3)
H25A0.69710.20810.72550.124*
H25B0.69930.05250.68120.124*
C260.6071 (3)0.1450 (7)0.6440 (4)0.0592 (16)
H26A0.59320.16950.68960.071*0.50 (3)
H26B0.59370.03910.62730.071*0.50 (3)
H26C0.59110.21480.67640.071*0.50 (3)
H26D0.59510.04020.65350.071*0.50 (3)
C280.4559 (3)0.1853 (6)0.5596 (3)0.0461 (13)
H280.46850.14720.61290.055*
C290.3878 (3)0.2089 (6)0.5076 (3)0.0439 (13)
C300.3251 (3)0.1884 (7)0.5121 (4)0.0581 (15)
H300.31620.15090.55700.070*
C310.2781 (3)0.2348 (7)0.4368 (4)0.0603 (16)
H310.23150.23330.42120.072*
C320.3138 (3)0.2840 (7)0.3890 (4)0.0544 (15)
H320.29430.32250.33570.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0458 (4)0.0390 (4)0.0391 (4)0.0018 (3)0.0154 (3)−0.0003 (3)
Ni20.0506 (4)0.0389 (4)0.0453 (4)−0.0012 (3)0.0233 (3)−0.0032 (3)
N10.053 (3)0.047 (3)0.040 (2)0.003 (2)0.018 (2)0.002 (2)
N20.047 (3)0.051 (3)0.040 (2)0.000 (2)0.011 (2)−0.003 (2)
N30.045 (3)0.051 (3)0.046 (3)0.006 (2)0.019 (2)0.006 (2)
N40.046 (3)0.043 (3)0.047 (3)0.004 (2)0.016 (2)0.001 (2)
N50.071 (3)0.041 (3)0.049 (3)0.000 (2)0.033 (3)−0.006 (2)
N60.060 (3)0.052 (3)0.054 (3)−0.001 (2)0.035 (3)−0.004 (2)
N70.041 (2)0.043 (3)0.050 (3)−0.002 (2)0.016 (2)−0.001 (2)
N80.046 (3)0.040 (3)0.047 (3)−0.002 (2)0.019 (2)−0.002 (2)
C10.062 (4)0.054 (4)0.057 (4)0.003 (3)0.028 (3)0.002 (3)
C20.095 (5)0.060 (4)0.059 (4)−0.008 (4)0.045 (4)0.004 (3)
C30.086 (5)0.055 (4)0.043 (3)0.004 (4)0.024 (3)0.005 (3)
C40.063 (4)0.039 (3)0.043 (3)0.004 (3)0.020 (3)−0.002 (3)
C50.059 (4)0.048 (3)0.045 (3)0.010 (3)0.006 (3)−0.003 (3)
C60.049 (8)0.037 (8)0.052 (8)0.000 (6)0.016 (6)−0.007 (6)
C110.044 (7)0.046 (8)0.061 (9)0.010 (6)0.031 (6)0.000 (7)
C6'0.056 (8)0.054 (9)0.047 (8)−0.004 (7)0.027 (6)−0.006 (7)
C11'0.051 (8)0.050 (9)0.060 (9)0.006 (6)0.033 (7)0.007 (7)
C220.061 (9)0.055 (10)0.064 (10)−0.019 (8)0.035 (8)−0.023 (8)
C270.044 (7)0.047 (10)0.053 (9)−0.002 (7)0.023 (6)−0.021 (7)
C22'0.040 (7)0.062 (12)0.045 (8)−0.010 (7)0.013 (6)−0.017 (8)
C27'0.049 (7)0.036 (10)0.053 (9)0.006 (7)0.019 (6)−0.011 (7)
C70.044 (3)0.071 (4)0.074 (4)0.002 (3)0.017 (3)−0.005 (3)
C80.057 (5)0.217 (12)0.108 (7)−0.036 (7)0.025 (5)0.017 (8)
C90.072 (6)0.139 (9)0.142 (8)−0.019 (5)0.055 (6)0.032 (7)
C100.062 (4)0.054 (4)0.068 (4)−0.006 (3)0.034 (3)−0.008 (3)
C120.063 (4)0.043 (3)0.050 (3)0.010 (3)0.026 (3)0.002 (3)
C130.059 (4)0.043 (3)0.042 (3)0.009 (3)0.019 (3)0.003 (2)
C140.063 (4)0.064 (4)0.044 (3)0.003 (3)0.008 (3)0.006 (3)
C150.054 (4)0.060 (4)0.062 (4)0.005 (3)0.003 (3)0.002 (3)
C160.048 (3)0.046 (3)0.059 (4)0.003 (3)0.018 (3)−0.002 (3)
C170.090 (5)0.048 (4)0.051 (4)0.006 (3)0.030 (4)−0.003 (3)
C180.114 (6)0.056 (4)0.051 (4)0.004 (4)0.036 (4)0.002 (3)
C190.117 (6)0.044 (4)0.078 (5)0.001 (4)0.067 (5)0.001 (3)
C200.088 (5)0.043 (3)0.056 (4)0.003 (3)0.044 (4)−0.004 (3)
C210.071 (4)0.051 (4)0.082 (5)−0.013 (3)0.053 (4)−0.014 (3)
C230.049 (4)0.081 (5)0.091 (5)−0.009 (4)0.030 (4)−0.020 (4)
C240.053 (5)0.170 (10)0.138 (9)−0.011 (6)0.011 (5)0.045 (8)
C250.061 (5)0.136 (8)0.092 (6)0.015 (5)0.004 (4)0.012 (6)
C260.060 (4)0.052 (4)0.058 (4)0.005 (3)0.012 (3)−0.010 (3)
C280.049 (3)0.040 (3)0.049 (3)−0.002 (3)0.017 (3)0.009 (3)
C290.047 (3)0.041 (3)0.046 (3)0.000 (2)0.020 (3)−0.002 (2)
C300.056 (4)0.059 (4)0.068 (4)−0.005 (3)0.033 (3)−0.006 (3)
C310.044 (3)0.062 (4)0.075 (4)−0.001 (3)0.022 (3)−0.003 (3)
C320.046 (3)0.051 (4)0.057 (4)0.000 (3)0.010 (3)−0.006 (3)
Geometric parameters (Å, °) top
Ni1—N21.850 (4)C27'—H27B0.9800
Ni1—N31.855 (4)C7—C81.452 (10)
Ni1—N11.887 (4)C7—H7A0.9700
Ni1—N41.889 (4)C7—H7B0.9700
Ni2—N61.844 (5)C7—H7C0.9700
Ni2—N71.851 (4)C7—H7D0.9700
Ni2—N81.883 (4)C8—C91.454 (8)
Ni2—N51.888 (5)C8—H8A0.9700
N1—C11.347 (7)C8—H8B0.9700
N1—C41.387 (7)C9—C101.481 (9)
N2—C51.290 (7)C9—H9A0.9700
N2—C61.466 (8)C9—H9B0.9700
N2—C6'1.470 (8)C10—H10A0.9700
N3—C121.297 (7)C10—H10B0.9700
N3—C111.466 (8)C10—H10C0.9700
N3—C11'1.477 (9)C10—H10D0.9700
N4—C161.340 (7)C12—C131.410 (8)
N4—C131.390 (7)C12—H120.9300
N5—C171.351 (7)C13—C141.379 (8)
N5—C201.378 (7)C14—C151.388 (9)
N6—C211.297 (7)C14—H140.9300
N6—C221.480 (18)C15—C161.396 (8)
N6—C22'1.543 (16)C15—H150.9300
N7—C281.274 (6)C16—H160.9300
N7—C271.503 (15)C17—C181.391 (9)
N7—C27'1.504 (15)C17—H170.9300
N8—C321.345 (7)C18—C191.368 (10)
N8—C291.394 (6)C18—H180.9300
C1—C21.374 (8)C19—C201.397 (9)
C1—H10.9300C19—H190.9300
C2—C31.378 (9)C20—C211.412 (9)
C2—H20.9300C21—H210.9300
C3—C41.387 (8)C23—C241.446 (10)
C3—H30.9300C23—H23A0.9700
C4—C51.423 (8)C23—H23B0.9700
C5—H50.9300C23—H23C0.9700
C6—C71.521 (9)C23—H23D0.9700
C6—C111.523 (9)C24—C251.454 (8)
C6—H6A0.9800C24—H24A0.9700
C11—C101.520 (9)C24—H24B0.9700
C11—H11A0.9800C25—C261.484 (9)
C6'—C71.507 (9)C25—H25A0.9700
C6'—C11'1.520 (9)C25—H25B0.9700
C6'—H6B0.9800C26—H26A0.9700
C11'—C101.523 (8)C26—H26B0.9700
C11'—H11B0.9800C26—H26C0.9700
C22—C271.53 (3)C26—H26D0.9700
C22—C231.545 (17)C28—C291.417 (7)
C22—H22A0.9800C28—H280.9300
C27—C261.485 (18)C29—C301.383 (7)
C27—H27A0.9800C30—C311.388 (8)
C22'—C231.477 (15)C30—H300.9300
C22'—C27'1.49 (3)C31—C321.389 (8)
C22'—H22B0.9800C31—H310.9300
C27'—C261.511 (18)C32—H320.9300
N2—Ni1—N384.00 (19)C7—C8—C9122.0 (7)
N2—Ni1—N184.78 (19)C7—C8—H8A106.8
N3—Ni1—N1168.47 (19)C9—C8—H8A106.8
N2—Ni1—N4167.79 (19)C7—C8—H8B106.8
N3—Ni1—N484.49 (19)C9—C8—H8B106.8
N1—Ni1—N4106.5 (2)H8A—C8—H8B106.7
N6—Ni2—N784.9 (2)C8—C9—C10120.8 (6)
N6—Ni2—N8168.2 (2)C8—C9—H9A107.1
N7—Ni2—N884.12 (19)C10—C9—H9A107.1
N6—Ni2—N584.3 (2)C8—C9—H9B107.1
N7—Ni2—N5169.0 (2)C10—C9—H9B107.1
N8—Ni2—N5106.4 (2)H9A—C9—H9B106.8
C1—N1—C4106.2 (5)C9—C10—C11114.4 (6)
C1—N1—Ni1142.4 (4)C9—C10—C11'113.2 (6)
C4—N1—Ni1111.2 (4)C11—C10—C11'27.7 (5)
C5—N2—C6131.7 (6)C9—C10—H10A108.7
C5—N2—C6'125.4 (6)C11—C10—H10A108.7
C6—N2—C6'27.4 (5)C11'—C10—H10A83.8
C5—N2—Ni1114.9 (4)C9—C10—H10B108.7
C6—N2—Ni1112.9 (4)C11—C10—H10B108.7
C6'—N2—Ni1114.9 (4)C11'—C10—H10B129.9
C12—N3—C11124.8 (6)H10A—C10—H10B107.6
C12—N3—C11'131.3 (6)C9—C10—H10C108.9
C11—N3—C11'28.7 (5)C11—C10—H10C128.6
C12—N3—Ni1115.7 (4)C11'—C10—H10C108.9
C11—N3—Ni1114.8 (4)H10A—C10—H10C28.4
C11'—N3—Ni1112.3 (4)H10B—C10—H10C81.1
C16—N4—C13106.7 (5)C9—C10—H10D108.9
C16—N4—Ni1142.2 (4)C11—C10—H10D83.3
C13—N4—Ni1110.8 (4)C11'—C10—H10D109.0
C17—N5—C20106.2 (5)H10A—C10—H10D130.6
C17—N5—Ni2142.1 (5)H10B—C10—H10D28.8
C20—N5—Ni2111.3 (4)H10C—C10—H10D107.7
C21—N6—C22131.0 (8)N3—C12—C13114.4 (5)
C21—N6—C22'126.6 (8)N3—C12—H12122.8
C22—N6—C22'28.7 (6)C13—C12—H12122.8
C21—N6—Ni2115.7 (4)C14—C13—N4109.4 (5)
C22—N6—Ni2112.3 (6)C14—C13—C12136.3 (6)
C22'—N6—Ni2113.8 (6)N4—C13—C12114.3 (5)
C28—N7—C27125.3 (8)C13—C14—C15106.9 (5)
C28—N7—C27'130.8 (8)C13—C14—H14126.5
C27—N7—C27'26.2 (5)C15—C14—H14126.5
C28—N7—Ni2116.5 (4)C14—C15—C16106.7 (5)
C27—N7—Ni2114.5 (7)C14—C15—H15126.7
C27'—N7—Ni2112.1 (7)C16—C15—H15126.7
C32—N8—C29106.1 (5)N4—C16—C15110.3 (6)
C32—N8—Ni2142.5 (4)N4—C16—H16124.9
C29—N8—Ni2111.2 (3)C15—C16—H16124.9
N1—C1—C2110.6 (6)N5—C17—C18109.9 (6)
N1—C1—H1124.7N5—C17—H17125.1
C2—C1—H1124.7C18—C17—H17125.1
C1—C2—C3107.4 (6)C19—C18—C17107.9 (6)
C1—C2—H2126.3C19—C18—H18126.0
C3—C2—H2126.3C17—C18—H18126.0
C2—C3—C4106.6 (6)C18—C19—C20106.0 (6)
C2—C3—H3126.7C18—C19—H19127.0
C4—C3—H3126.7C20—C19—H19127.0
N1—C4—C3109.2 (5)N5—C20—C19109.9 (6)
N1—C4—C5112.9 (5)N5—C20—C21113.7 (5)
C3—C4—C5137.9 (6)C19—C20—C21136.4 (7)
N2—C5—C4115.5 (5)N6—C21—C20114.5 (6)
N2—C5—H5122.2N6—C21—H21122.7
C4—C5—H5122.2C20—C21—H21122.7
N2—C6—C7117.1 (7)C24—C23—C22'111.7 (8)
N2—C6—C11104.3 (7)C24—C23—C22113.7 (9)
C7—C6—C11112.4 (8)C22'—C23—C2228.7 (6)
N2—C6—H6A107.5C24—C23—H23A108.8
C7—C6—H6A107.5C22'—C23—H23A131.4
C11—C6—H6A107.5C22—C23—H23A108.8
N3—C11—C10117.0 (7)C24—C23—H23B108.8
N3—C11—C6102.5 (7)C22'—C23—H23B83.5
C10—C11—C6110.3 (8)C22—C23—H23B108.8
N3—C11—H11A108.9H23A—C23—H23B107.7
C10—C11—H11A108.9C24—C23—H23C109.3
C6—C11—H11A108.9C22'—C23—H23C109.1
N2—C6'—C7117.8 (7)C22—C23—H23C82.1
N2—C6'—C11'102.2 (7)H23A—C23—H23C30.0
C7—C6'—C11'111.0 (8)H23B—C23—H23C131.1
N2—C6'—H6B108.5C24—C23—H23D109.3
C7—C6'—H6B108.5C22'—C23—H23D109.4
C11'—C6'—H6B108.5C22—C23—H23D129.2
N3—C11'—C6'103.8 (7)H23A—C23—H23D80.4
N3—C11'—C10116.1 (7)H23B—C23—H23D29.2
C6'—C11'—C10112.5 (8)H23C—C23—H23D107.9
N3—C11'—H11B108.0C23—C24—C25123.4 (7)
C6'—C11'—H11B108.0C23—C24—H24A106.5
C10—C11'—H11B108.0C25—C24—H24A106.5
N6—C22—C27104.5 (15)C23—C24—H24B106.5
N6—C22—C23115.8 (12)C25—C24—H24B106.5
C27—C22—C23108.0 (17)H24A—C24—H24B106.5
N6—C22—H22A109.4C24—C25—C26120.2 (7)
C27—C22—H22A109.4C24—C25—H25A107.3
C23—C22—H22A109.4C26—C25—H25A107.3
C26—C27—N7116.6 (13)C24—C25—H25B107.3
C26—C27—C22114.5 (17)C26—C25—H25B107.3
N7—C27—C22101.9 (14)H25A—C25—H25B106.9
C26—C27—H27A107.8C25—C26—C27112.3 (8)
N7—C27—H27A107.8C25—C26—C27'112.6 (8)
C22—C27—H27A107.8C27—C26—C27'26.3 (5)
C23—C22'—C27'114.1 (17)C25—C26—H26A109.1
C23—C22'—N6116.1 (12)C27—C26—H26A109.1
C27'—C22'—N6101.8 (15)C27'—C26—H26A128.9
C23—C22'—H22B108.2C25—C26—H26B109.1
C27'—C22'—H22B108.2C27—C26—H26B109.1
N6—C22'—H22B108.2C27'—C26—H26B85.1
C22'—C27'—N7104.7 (14)H26A—C26—H26B107.9
C22'—C27'—C26111.9 (17)C25—C26—H26C109.1
N7—C27'—C26115.0 (12)C27—C26—H26C85.4
C22'—C27'—H27B108.3C27'—C26—H26C109.3
N7—C27'—H27B108.3H26A—C26—H26C26.6
C26—C27'—H27B108.3H26B—C26—H26C129.2
C8—C7—C6'114.9 (6)C25—C26—H26D109.1
C8—C7—C6113.9 (7)C27—C26—H26D128.9
C6'—C7—C626.5 (5)C27'—C26—H26D108.9
C8—C7—H7A108.8H26A—C26—H26D83.3
C6'—C7—H7A84.2H26B—C26—H26D26.7
C6—C7—H7A108.8H26C—C26—H26D107.8
C8—C7—H7B108.8N7—C28—C29114.6 (5)
C6'—C7—H7B127.8N7—C28—H28122.7
C6—C7—H7B108.8C29—C28—H28122.7
H7A—C7—H7B107.7C30—C29—N8109.6 (5)
C8—C7—H7C108.5C30—C29—C28137.1 (5)
C6'—C7—H7C108.5N8—C29—C28113.3 (5)
C6—C7—H7C128.9C29—C30—C31106.6 (5)
H7A—C7—H7C27.7C29—C30—H30126.7
H7B—C7—H7C82.1C31—C30—H30126.7
C8—C7—H7D108.5C30—C31—C32107.0 (5)
C6'—C7—H7D108.6C30—C31—H31126.5
C6—C7—H7D84.9C32—C31—H31126.5
H7A—C7—H7D129.8N8—C32—C31110.6 (5)
H7B—C7—H7D27.3N8—C32—H32124.7
H7C—C7—H7D107.5C31—C32—H32124.7
N2—Ni1—N1—C1−179.6 (7)C28—N7—C27—C2642 (2)
N3—Ni1—N1—C1167.3 (8)C27'—N7—C27—C26−70 (3)
N4—Ni1—N1—C15.2 (7)Ni2—N7—C27—C26−161.0 (11)
N2—Ni1—N1—C47.0 (4)C28—N7—C27—C22167.2 (13)
N3—Ni1—N1—C4−6.1 (12)C27'—N7—C27—C2255 (2)
N4—Ni1—N1—C4−168.2 (3)Ni2—N7—C27—C22−36 (2)
N3—Ni1—N2—C5169.7 (4)N6—C22—C27—C26174.1 (9)
N1—Ni1—N2—C5−7.7 (4)C23—C22—C27—C26−62 (3)
N4—Ni1—N2—C5150.1 (8)N6—C22—C27—N747 (2)
N3—Ni1—N2—C6−17.1 (6)C23—C22—C27—N7171.2 (10)
N1—Ni1—N2—C6165.5 (6)C21—N6—C22'—C23−41 (2)
N4—Ni1—N2—C6−36.7 (12)C22—N6—C22'—C2369 (2)
N3—Ni1—N2—C6'12.8 (7)Ni2—N6—C22'—C23162.1 (12)
N1—Ni1—N2—C6'−164.6 (7)C21—N6—C22'—C27'−165.9 (12)
N4—Ni1—N2—C6'−6.8 (13)C22—N6—C22'—C27'−56 (2)
N2—Ni1—N3—C12−170.2 (4)Ni2—N6—C22'—C27'38 (2)
N1—Ni1—N3—C12−157.0 (9)C23—C22'—C27'—N7−173.9 (9)
N4—Ni1—N3—C125.7 (4)N6—C22'—C27'—N7−48 (2)
N2—Ni1—N3—C11−13.1 (6)C23—C22'—C27'—C2661 (3)
N1—Ni1—N3—C110.1 (13)N6—C22'—C27'—C26−173.3 (9)
N4—Ni1—N3—C11162.8 (6)C28—N7—C27'—C22'−145.7 (13)
N2—Ni1—N3—C11'18.2 (6)C27—N7—C27'—C22'−57 (3)
N1—Ni1—N3—C11'31.3 (13)Ni2—N7—C27'—C22'44 (2)
N4—Ni1—N3—C11'−165.9 (6)C28—N7—C27'—C26−22 (2)
N2—Ni1—N4—C16−157.8 (8)C27—N7—C27'—C2666 (3)
N3—Ni1—N4—C16−177.4 (6)Ni2—N7—C27'—C26166.7 (11)
N1—Ni1—N4—C16−1.0 (7)N2—C6'—C7—C8160.8 (9)
N2—Ni1—N4—C1314.6 (11)C11'—C6'—C7—C843.5 (12)
N3—Ni1—N4—C13−5.0 (4)N2—C6'—C7—C666.9 (12)
N1—Ni1—N4—C13171.5 (4)C11'—C6'—C7—C6−50.4 (12)
N6—Ni2—N5—C17−177.9 (7)N2—C6—C7—C8−164.8 (9)
N7—Ni2—N5—C17−166.6 (9)C11—C6—C7—C8−44.0 (12)
N8—Ni2—N5—C17−3.0 (7)N2—C6—C7—C6'−66.4 (12)
N6—Ni2—N5—C20−6.2 (4)C11—C6—C7—C6'54.3 (12)
N7—Ni2—N5—C205.1 (12)C6'—C7—C8—C9−15.5 (15)
N8—Ni2—N5—C20168.7 (4)C6—C7—C8—C913.7 (15)
N7—Ni2—N6—C21−171.0 (4)C7—C8—C9—C100.9 (17)
N8—Ni2—N6—C21−148.9 (9)C8—C9—C10—C1115.0 (14)
N5—Ni2—N6—C216.8 (4)C8—C9—C10—C11'−15.3 (14)
N7—Ni2—N6—C2219.3 (11)N3—C11—C10—C9−160.8 (8)
N8—Ni2—N6—C2241.4 (16)C6—C11—C10—C9−44.3 (11)
N5—Ni2—N6—C22−162.9 (11)N3—C11—C10—C11'−66.9 (11)
N7—Ni2—N6—C22'−11.9 (11)C6—C11—C10—C11'49.7 (11)
N8—Ni2—N6—C22'10.2 (16)N3—C11'—C10—C9163.4 (8)
N5—Ni2—N6—C22'165.9 (11)C6'—C11'—C10—C944.0 (12)
N6—Ni2—N7—C28170.0 (4)N3—C11'—C10—C1164.8 (12)
N8—Ni2—N7—C28−5.5 (4)C6'—C11'—C10—C11−54.5 (12)
N5—Ni2—N7—C28158.7 (9)C11—N3—C12—C13−159.5 (7)
N6—Ni2—N7—C2710.8 (11)C11'—N3—C12—C13164.7 (8)
N8—Ni2—N7—C27−164.8 (11)Ni1—N3—C12—C13−5.0 (6)
N5—Ni2—N7—C27−0.5 (16)C16—N4—C13—C140.1 (6)
N6—Ni2—N7—C27'−17.7 (10)Ni1—N4—C13—C14−175.1 (4)
N8—Ni2—N7—C27'166.7 (10)C16—N4—C13—C12178.9 (5)
N5—Ni2—N7—C27'−29.0 (15)Ni1—N4—C13—C123.7 (6)
N6—Ni2—N8—C32156.7 (9)N3—C12—C13—C14179.0 (6)
N7—Ni2—N8—C32178.9 (6)N3—C12—C13—N40.7 (7)
N5—Ni2—N8—C322.0 (7)N4—C13—C14—C150.3 (7)
N6—Ni2—N8—C29−17.4 (12)C12—C13—C14—C15−178.1 (6)
N7—Ni2—N8—C294.8 (4)C13—C14—C15—C16−0.5 (7)
N5—Ni2—N8—C29−172.1 (3)C13—N4—C16—C15−0.4 (6)
C4—N1—C1—C20.7 (7)Ni1—N4—C16—C15172.2 (5)
Ni1—N1—C1—C2−172.9 (5)C14—C15—C16—N40.6 (7)
N1—C1—C2—C30.1 (7)C20—N5—C17—C18−0.4 (6)
C1—C2—C3—C4−0.9 (7)Ni2—N5—C17—C18171.5 (5)
C1—N1—C4—C3−1.3 (6)N5—C17—C18—C19−0.9 (7)
Ni1—N1—C4—C3174.5 (4)C17—C18—C19—C201.9 (7)
C1—N1—C4—C5178.8 (5)C17—N5—C20—C191.6 (6)
Ni1—N1—C4—C5−5.4 (6)Ni2—N5—C20—C19−173.1 (4)
C2—C3—C4—N11.4 (7)C17—N5—C20—C21179.6 (5)
C2—C3—C4—C5−178.7 (7)Ni2—N5—C20—C214.9 (6)
C6—N2—C5—C4−165.1 (8)C18—C19—C20—N5−2.2 (7)
C6'—N2—C5—C4160.6 (7)C18—C19—C20—C21−179.5 (7)
Ni1—N2—C5—C46.5 (6)C22—N6—C21—C20161.6 (14)
N1—C4—C5—N2−0.5 (7)C22'—N6—C21—C20−161.8 (13)
C3—C4—C5—N2179.6 (7)Ni2—N6—C21—C20−5.7 (7)
C5—N2—C6—C7−22.2 (14)N5—C20—C21—N60.4 (7)
C6'—N2—C6—C765.9 (12)C19—C20—C21—N6177.6 (7)
Ni1—N2—C6—C7166.1 (6)C27'—C22'—C23—C24−46 (3)
C5—N2—C6—C11−147.1 (8)N6—C22'—C23—C24−163.4 (13)
C6'—N2—C6—C11−59.0 (12)C27'—C22'—C23—C2255 (3)
Ni1—N2—C6—C1141.2 (9)N6—C22'—C23—C22−63 (2)
C12—N3—C11—C10−47.1 (12)N6—C22—C23—C24160.6 (13)
C11'—N3—C11—C1066.8 (12)C27—C22—C23—C2444 (2)
Ni1—N3—C11—C10158.2 (6)N6—C22—C23—C22'68 (2)
C12—N3—C11—C6−167.9 (7)C27—C22—C23—C22'−48 (2)
C11'—N3—C11—C6−54.0 (11)C22'—C23—C24—C2516.1 (18)
Ni1—N3—C11—C637.4 (9)C22—C23—C24—C25−15.0 (17)
N2—C6—C11—N3−47.1 (10)C23—C24—C25—C26−1.5 (16)
C7—C6—C11—N3−175.0 (7)C24—C25—C26—C27−13.7 (15)
N2—C6—C11—C10−172.5 (7)C24—C25—C26—C27'14.8 (15)
C7—C6—C11—C1059.7 (12)N7—C27—C26—C25165.2 (11)
C5—N2—C6'—C745.8 (13)C22—C27—C26—C2546 (2)
C6—N2—C6'—C7−67.9 (13)N7—C27—C26—C27'69 (2)
Ni1—N2—C6'—C7−160.1 (7)C22—C27—C26—C27'−50 (2)
C5—N2—C6'—C11'167.7 (7)C22'—C27'—C26—C25−43 (2)
C6—N2—C6'—C11'54.0 (12)N7—C27'—C26—C25−162.2 (11)
Ni1—N2—C6'—C11'−38.1 (10)C22'—C27'—C26—C2752 (3)
C12—N3—C11'—C6'147.2 (8)N7—C27'—C26—C27−67 (2)
C11—N3—C11'—C6'58.5 (12)C27—N7—C28—C29161.5 (12)
Ni1—N3—C11'—C6'−42.8 (10)C27'—N7—C28—C29−165.7 (13)
C12—N3—C11'—C1023.2 (14)Ni2—N7—C28—C294.8 (6)
C11—N3—C11'—C10−65.5 (12)C32—N8—C29—C300.3 (6)
Ni1—N3—C11'—C10−166.8 (7)Ni2—N8—C29—C30176.5 (4)
N2—C6'—C11'—N348.5 (10)C32—N8—C29—C28−179.9 (5)
C7—C6'—C11'—N3174.9 (7)Ni2—N8—C29—C28−3.6 (6)
N2—C6'—C11'—C10174.8 (7)N7—C28—C29—C30179.2 (6)
C7—C6'—C11'—C10−58.8 (12)N7—C28—C29—N8−0.6 (7)
C21—N6—C22—C27148.9 (11)N8—C29—C30—C310.3 (7)
C22'—N6—C22—C2756 (2)C28—C29—C30—C31−179.5 (6)
Ni2—N6—C22—C27−43 (2)C29—C30—C31—C32−0.7 (7)
C21—N6—C22—C2330 (2)C29—N8—C32—C31−0.7 (6)
C22'—N6—C22—C23−63 (2)Ni2—N8—C32—C31−175.0 (5)
Ni2—N6—C22—C23−162.1 (11)C30—C31—C32—N80.9 (7)
Table 1
Selected geometric parameters (Å, °) top
Ni1—N21.850 (4)Ni2—N61.844 (5)
Ni1—N31.855 (4)Ni2—N71.851 (4)
Ni1—N11.887 (4)Ni2—N81.883 (4)
Ni1—N41.889 (4)Ni2—N51.888 (5)
N2—Ni1—N384.00 (19)N6—Ni2—N784.9 (2)
N2—Ni1—N184.78 (19)N7—Ni2—N884.12 (19)
N3—Ni1—N484.49 (19)N6—Ni2—N584.3 (2)
Acknowledgements top

This project was supported by the National Natural Science Foundation of China (grant No. 20671053).

references
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