{5,10,15,20-Tetra­kis[4-(hex­yloxy)phen­yl]porphyrinato}nickel(II)

Wang, Y.-F.; Zhao, H.-B.; Chen, L.; Yang, D.-L.; Wang, B.-Y.

doi:10.1107/S160053681202226X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m814

doi:10.1107/S160053681202226X

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{5,10,15,20-Tetrakis[4-(hexyloxy)phenyl]porphyrinato}nickel(II)

Yu-Fang Wang,^a Hong-Bin Zhao,^a,^b ^* Liang Chen,^a De-Liang Yang ^a and Bang-Ying Wang ^a

^aDepartment of Organic Chemistry, the College of Chemistry, Xiangtan University, Hunan 411105, People's Republic of China, and ^bCollege of Chemistry and Environmental Engineering, Dongguan University of Technology, Guangdong 523808, People's Republic of China
^*Correspondence e-mail: zhaohbhanlf@163.com

(Received 28 April 2012; accepted 16 May 2012; online 26 May 2012)

The molecule of the title compound, [Ni(C₆₈H₇₆N₄O₄)], is located on a crystallographic inversion center. The Ni—N distances within the square-shaped coordination environment are 1.951 (2) and 1.954 (2) Å. Three terminal C atoms in one of the hexyl groups are disordered over two sets of sites, with site-occupancy factors of 0.615 (13) and 0.385 (13).

Related literature

For related structures, see: Scheidt (1977 ); Maclean et al. (1996 ); Jentzen et al. (1996 ); Chen et al. (2010 ). For potential applications of porphyrins and metalloporphyrins in liquid crystals, prototypical multistate counters and artificial light-harvesting antennas, see: Castella et al. (2002 ); Schweikart et al. (2002 ); Imahori (2004 ). For their applications in dye-sensitised solar cells, see: Barea et al. (2011 ); Yella et al. (2011 ) and for their applications in enzyme mimics, see: Anderson & Sanders (1995 ).

Experimental

Crystal data

[Ni(C₆₈H₇₆N₄O₄)]
M_r = 1072.04
Orthorhombic, P b c n
a = 18.7735 (10) Å
b = 10.8439 (6) Å
c = 28.7173 (16) Å
V = 5846.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 185 K
0.27 × 0.19 × 0.10 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.904, T_max = 0.963
30888 measured reflections
5173 independent reflections
3950 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.156
S = 1.03
5173 reflections
380 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681202226X/bt5904sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202226X/bt5904Isup2.hkl

checkCIF report

Comment top

Porphyrins and metalloporphyrins are researched in many aspects, e.g. as liquid crystals (Castella et al., 2002), prototypical multistate counters (Schweikart et al., 2002), artificial light-harvesting antennas (Imahori,2004), dye-sensitized solar cells (Barea et al.,2011; Yella et al., 2011) or enzyme mimics (Anderson et al., 1995).

The porphyrin moiety is essentially planar, the macrocyclic core is planar with a mean deviation of 0.0244 Å. The four-coordinate Ni ion is located on the inversion center with Ni–N distances of 1.950 (3) and 1.954 (2) Å. These bond lengths are in agreement with those found in other nickel porphyrin compounds (Scheidt, 1977; Maclean et al., 1996; Jentzen et al., 1996; Chen et al., 2010.).

Three terminal C atoms (C32, C33 & C34) in one of the hexyl group are disordered over two positions with site occupancy factors of 0.615 (13) and 0.385 (13).

Related literature top

For related structures, see: Scheidt (1977); Maclean et al. (1996); Jentzen et al.(1996); Chen et al. (2010). For potential applications of porphyrins and metalloporphyrins in liquid crystals, prototypical multistate counters and artificial light-harvesting antennas, see: Castella et al. (2002); Schweikart et al. (2002); Imahori (2004). For their applications in dye-sensitised solar cells, see: Barea et al. (2011); Yella et al. (2011) and for their applications in enzyme mimics, see: Anderson & Sanders (1995).

Experimental top

0.04 mmol meso-tetrakis[p-(hexyloxy)phenyl] porphyrin and 0.40 mmol Ni(CH₃COO₎₂.4H₂O were dissolved in 20 ml chloroform, refluxed for 8 h, and the solvent was removed by a rotary evaporator, the residue was purified by column chromatography with chloroform, then crystallized by methanol and chloroform, and a purple solid was obtained (yield = 68%). Single crystals were recrystallization from a dichloromethane solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The minor occupied atoms of the disordered group are not shown. Symmetry code: (i) -x, 1 - y, -z.

{5,10,15,20-Tetrakis[4-(hexyloxy)phenyl]porphyrinato}nickel(II) top

Crystal data top

[Ni(C₆₈H₇₆N₄O₄)]	D_x = 1.218 Mg m⁻³
M_r = 1072.04	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 7739 reflections
a = 18.7735 (10) Å	θ = 2.3–25.0°
b = 10.8439 (6) Å	µ = 0.38 mm⁻¹
c = 28.7173 (16) Å	T = 185 K
V = 5846.2 (6) Å³	Block, purple
Z = 4	0.27 × 0.19 × 0.10 mm
F(000) = 2288

Data collection top

Bruker APEX CCD diffractometer	5173 independent reflections
Radiation source: fine-focus sealed tube	3950 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −22→11
T_min = 0.904, T_max = 0.963	k = −12→12
30888 measured reflections	l = −34→34

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0695P)² + 7.6994P] where P = (F_o² + 2F_c²)/3
5173 reflections	(Δ/σ)_max = 0.005
380 parameters	Δρ_max = 0.92 e Å⁻³
10 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Ni(C₆₈H₇₆N₄O₄)]	V = 5846.2 (6) Å³
M_r = 1072.04	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 18.7735 (10) Å	µ = 0.38 mm⁻¹
b = 10.8439 (6) Å	T = 185 K
c = 28.7173 (16) Å	0.27 × 0.19 × 0.10 mm

Data collection top

Bruker APEX CCD diffractometer	5173 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3950 reflections with I > 2σ(I)
T_min = 0.904, T_max = 0.963	R_int = 0.031
30888 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	10 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.03	Δρ_max = 0.92 e Å⁻³
5173 reflections	Δρ_min = −0.32 e Å⁻³
380 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.0000	0.5000	0.0000	0.03368 (17)
N1	0.05923 (12)	0.4241 (2)	0.04806 (8)	0.0365 (6)
N2	−0.08523 (12)	0.4574 (2)	0.03539 (8)	0.0360 (5)
O1	0.47501 (10)	0.4148 (2)	0.05027 (8)	0.0470 (6)
O2	−0.1075 (2)	0.0150 (3)	0.24746 (10)	0.0912 (11)
C1	0.17914 (15)	0.4636 (3)	0.01680 (11)	0.0383 (7)
C2	0.13284 (15)	0.4180 (3)	0.04994 (10)	0.0389 (7)
C3	0.15575 (16)	0.3543 (3)	0.09105 (10)	0.0433 (7)
H3	0.2036	0.3402	0.1004	0.052*
C4	0.09688 (16)	0.3184 (3)	0.11395 (11)	0.0449 (8)
H4	0.0952	0.2728	0.1422	0.054*
C5	0.03718 (15)	0.3619 (3)	0.08767 (10)	0.0389 (7)
C6	−0.03289 (16)	0.3440 (3)	0.10139 (10)	0.0402 (7)
C7	−0.08952 (15)	0.3932 (3)	0.07679 (10)	0.0400 (7)
C8	−0.16234 (16)	0.3787 (3)	0.09132 (11)	0.0466 (8)
H8	−0.1787	0.3383	0.1186	0.056*
C9	−0.20280 (16)	0.4336 (3)	0.05864 (11)	0.0458 (8)
H9	−0.2533	0.4401	0.0588	0.055*
C10	−0.15578 (15)	0.4803 (3)	0.02365 (11)	0.0375 (7)
C11	0.25789 (15)	0.4496 (3)	0.02455 (10)	0.0395 (7)
C12	0.29479 (16)	0.5322 (3)	0.05231 (11)	0.0442 (8)
H12	0.2700	0.5987	0.0665	0.053*
C13	0.36741 (16)	0.5192 (3)	0.05977 (11)	0.0442 (8)
H13	0.3920	0.5768	0.0788	0.053*
C14	0.40400 (15)	0.4222 (3)	0.03951 (10)	0.0397 (7)
C15	0.36835 (16)	0.3412 (3)	0.01064 (12)	0.0498 (8)
H15	0.3934	0.2763	−0.0044	0.060*
C16	0.29529 (17)	0.3554 (3)	0.00380 (12)	0.0502 (8)
H16	0.2708	0.2987	−0.0157	0.060*
C17	0.51606 (16)	0.3211 (3)	0.02732 (12)	0.0483 (8)
H17A	0.5212	0.3410	−0.0062	0.058*
H17B	0.4919	0.2402	0.0301	0.058*
C18	0.58842 (15)	0.3160 (3)	0.05030 (11)	0.0478 (8)
H18A	0.6074	0.4008	0.0532	0.057*
H18B	0.6214	0.2685	0.0303	0.057*
C19	0.58589 (16)	0.2569 (3)	0.09827 (12)	0.0506 (8)
H19A	0.5524	0.3041	0.1180	0.061*
H19B	0.5669	0.1721	0.0952	0.061*
C20	0.65764 (17)	0.2511 (4)	0.12263 (12)	0.0565 (9)
H20A	0.6921	0.2087	0.1020	0.068*
H20B	0.6751	0.3362	0.1277	0.068*
C21	0.6552 (2)	0.1846 (5)	0.16901 (15)	0.0810 (13)
H21A	0.6363	0.1004	0.1641	0.097*
H21B	0.6220	0.2286	0.1900	0.097*
C22	0.7278 (3)	0.1760 (7)	0.1922 (2)	0.143 (3)
H22A	0.7617	0.1372	0.1708	0.215*
H22B	0.7240	0.1263	0.2206	0.215*
H22C	0.7445	0.2590	0.2002	0.215*
C23	−0.04850 (16)	0.2638 (3)	0.14258 (11)	0.0470 (8)
C24	−0.06468 (19)	0.3105 (4)	0.18589 (12)	0.0599 (10)
H24	−0.0634	0.3970	0.1911	0.072*
C25	−0.08340 (19)	0.2286 (5)	0.22295 (12)	0.0676 (12)
H25	−0.0939	0.2595	0.2531	0.081*
C26	−0.0859 (2)	0.1039 (4)	0.21393 (15)	0.0678 (11)
C27	−0.0687 (2)	0.0577 (4)	0.17204 (15)	0.0728 (11)
H27	−0.0694	−0.0289	0.1670	0.087*
C28	−0.05038 (19)	0.1361 (4)	0.13678 (14)	0.0616 (10)
H28	−0.0385	0.1024	0.1072	0.074*
C29	−0.1321 (3)	0.0598 (5)	0.28906 (16)	0.1011 (17)
H29A	−0.1692	0.1231	0.2838	0.121*
H29B	−0.0928	0.0972	0.3071	0.121*
C30	−0.1638 (3)	−0.0529 (6)	0.31558 (17)	0.1079 (19)
H30A	−0.1854	−0.0229	0.3449	0.129*
H30B	−0.2026	−0.0884	0.2964	0.129*
C31	−0.1156 (4)	−0.1477 (5)	0.3265 (2)	0.143 (3)
H31A	−0.0793	−0.1165	0.3486	0.172*	0.615 (13)
H31B	−0.0909	−0.1752	0.2979	0.172*	0.615 (13)
H31C	−0.0758	−0.1019	0.3411	0.172*	0.385 (13)
H31D	−0.0975	−0.1720	0.2954	0.172*	0.385 (13)
C32A	−0.1552 (5)	−0.2553 (7)	0.3481 (3)	0.090 (3)	0.615 (13)
H32C	−0.1738	−0.2315	0.3791	0.109*	0.615 (13)
H32D	−0.1960	−0.2788	0.3282	0.109*	0.615 (13)
C33A	−0.1051 (5)	−0.3617 (8)	0.3529 (4)	0.105 (4)	0.615 (13)
H33A	−0.0625	−0.3350	0.3705	0.126*	0.615 (13)
H33B	−0.1286	−0.4283	0.3708	0.126*	0.615 (13)
C34A	−0.0823 (12)	−0.4111 (15)	0.3060 (6)	0.189 (12)	0.615 (13)
H34A	−0.1233	−0.4489	0.2904	0.284*	0.615 (13)
H34B	−0.0449	−0.4731	0.3103	0.284*	0.615 (13)
H34C	−0.0640	−0.3434	0.2869	0.284*	0.615 (13)
C32B	−0.1148 (13)	−0.2696 (12)	0.3530 (7)	0.201 (16)	0.385 (13)
H32E	−0.0653	−0.3000	0.3557	0.241*	0.385 (13)
H32F	−0.1337	−0.2567	0.3848	0.241*	0.385 (13)
C33B	−0.1599 (8)	−0.3646 (10)	0.3279 (6)	0.111 (7)	0.385 (13)
H33C	−0.1948	−0.3227	0.3075	0.133*	0.385 (13)
H33D	−0.1864	−0.4150	0.3508	0.133*	0.385 (13)
C34B	−0.1117 (18)	−0.447 (2)	0.2988 (8)	0.156 (14)	0.385 (13)
H34D	−0.0900	−0.3987	0.2737	0.233*	0.385 (13)
H34E	−0.1398	−0.5144	0.2853	0.233*	0.385 (13)
H34F	−0.0741	−0.4818	0.3186	0.233*	0.385 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0224 (3)	0.0412 (3)	0.0374 (3)	0.0014 (2)	−0.0036 (2)	−0.0020 (2)
N1	0.0252 (12)	0.0438 (14)	0.0405 (13)	0.0027 (10)	−0.0047 (10)	−0.0028 (11)
N2	0.0257 (12)	0.0418 (13)	0.0406 (13)	0.0017 (10)	−0.0042 (10)	−0.0026 (11)
O1	0.0249 (10)	0.0562 (14)	0.0599 (13)	0.0074 (10)	−0.0073 (10)	−0.0135 (11)
O2	0.114 (3)	0.089 (2)	0.0700 (19)	−0.023 (2)	0.0205 (17)	−0.0054 (17)
C1	0.0277 (15)	0.0418 (16)	0.0455 (16)	0.0025 (12)	−0.0053 (13)	−0.0065 (14)
C2	0.0281 (15)	0.0448 (17)	0.0439 (16)	0.0041 (13)	−0.0045 (13)	−0.0051 (14)
C3	0.0299 (16)	0.0527 (19)	0.0473 (17)	0.0071 (14)	−0.0075 (13)	−0.0021 (15)
C4	0.0359 (17)	0.0529 (19)	0.0459 (17)	0.0058 (14)	−0.0061 (14)	0.0045 (15)
C5	0.0333 (16)	0.0427 (17)	0.0408 (16)	0.0022 (13)	−0.0051 (13)	−0.0021 (13)
C6	0.0340 (16)	0.0445 (17)	0.0422 (16)	0.0006 (13)	−0.0028 (13)	−0.0018 (14)
C7	0.0309 (15)	0.0451 (17)	0.0439 (16)	−0.0003 (13)	−0.0004 (13)	−0.0009 (14)
C8	0.0309 (16)	0.062 (2)	0.0471 (18)	−0.0005 (15)	0.0022 (14)	0.0050 (16)
C9	0.0257 (15)	0.060 (2)	0.0517 (18)	−0.0008 (14)	−0.0001 (14)	0.0008 (16)
C10	0.0280 (14)	0.0392 (16)	0.0453 (17)	0.0004 (12)	−0.0016 (13)	−0.0038 (13)
C11	0.0274 (15)	0.0486 (17)	0.0424 (16)	0.0019 (13)	−0.0026 (13)	0.0016 (14)
C12	0.0286 (15)	0.0517 (19)	0.0524 (18)	0.0080 (13)	−0.0030 (14)	−0.0082 (15)
C13	0.0321 (16)	0.0498 (19)	0.0508 (18)	0.0014 (13)	−0.0082 (14)	−0.0121 (15)
C14	0.0243 (14)	0.0501 (18)	0.0447 (16)	0.0041 (13)	−0.0037 (12)	−0.0008 (14)
C15	0.0319 (17)	0.057 (2)	0.061 (2)	0.0085 (15)	−0.0066 (14)	−0.0185 (17)
C16	0.0334 (17)	0.056 (2)	0.061 (2)	0.0039 (15)	−0.0116 (15)	−0.0188 (17)
C17	0.0322 (17)	0.059 (2)	0.0535 (19)	0.0081 (15)	−0.0008 (14)	−0.0086 (16)
C18	0.0274 (15)	0.061 (2)	0.0554 (19)	0.0092 (14)	−0.0006 (14)	−0.0037 (16)
C19	0.0324 (17)	0.060 (2)	0.059 (2)	0.0016 (15)	0.0011 (15)	−0.0034 (17)
C20	0.0341 (18)	0.078 (3)	0.058 (2)	0.0042 (17)	−0.0023 (15)	0.0047 (18)
C21	0.053 (2)	0.120 (4)	0.070 (3)	−0.001 (2)	−0.007 (2)	0.027 (3)
C22	0.078 (4)	0.257 (9)	0.094 (4)	0.002 (5)	−0.025 (3)	0.072 (5)
C23	0.0287 (16)	0.068 (2)	0.0445 (17)	0.0011 (15)	−0.0028 (13)	0.0063 (16)
C24	0.050 (2)	0.081 (3)	0.048 (2)	0.0041 (19)	−0.0055 (16)	0.0026 (19)
C25	0.046 (2)	0.119 (4)	0.0381 (18)	0.004 (2)	−0.0017 (16)	−0.006 (2)
C26	0.063 (3)	0.068 (3)	0.073 (3)	−0.008 (2)	−0.003 (2)	0.013 (2)
C27	0.077 (3)	0.073 (3)	0.068 (3)	−0.010 (2)	0.017 (2)	0.006 (2)
C28	0.052 (2)	0.069 (3)	0.065 (2)	−0.0036 (19)	0.0091 (18)	0.011 (2)
C29	0.114 (4)	0.127 (5)	0.062 (3)	0.010 (4)	−0.013 (3)	−0.023 (3)
C30	0.136 (5)	0.125 (5)	0.062 (3)	−0.029 (4)	0.026 (3)	0.007 (3)
C31	0.220 (8)	0.111 (5)	0.098 (4)	0.031 (6)	0.063 (5)	0.008 (4)
C32A	0.107 (8)	0.085 (6)	0.079 (6)	−0.030 (6)	0.038 (5)	−0.005 (5)
C33A	0.090 (7)	0.099 (7)	0.125 (8)	0.003 (6)	−0.001 (6)	0.052 (7)
C34A	0.22 (2)	0.085 (10)	0.27 (2)	0.070 (14)	0.137 (18)	0.050 (11)
C32B	0.19 (3)	0.14 (2)	0.27 (3)	−0.03 (2)	−0.17 (2)	0.04 (2)
C33B	0.113 (13)	0.107 (14)	0.112 (12)	−0.014 (10)	−0.041 (10)	0.044 (11)
C34B	0.27 (4)	0.108 (18)	0.094 (13)	−0.04 (2)	0.039 (18)	0.011 (11)

Geometric parameters (Å, º) top

Ni1—N2ⁱ	1.951 (2)	C20—H20A	0.9900
Ni1—N2	1.951 (2)	C20—H20B	0.9900
Ni1—N1ⁱ	1.954 (2)	C21—C22	1.520 (6)
Ni1—N1	1.954 (2)	C21—H21A	0.9900
N1—C2	1.385 (4)	C21—H21B	0.9900
N1—C5	1.386 (4)	C22—H22A	0.9800
N2—C7	1.380 (4)	C22—H22B	0.9800
N2—C10	1.389 (4)	C22—H22C	0.9800
O1—C14	1.371 (3)	C23—C24	1.377 (5)
O1—C17	1.436 (4)	C23—C28	1.396 (5)
O2—C29	1.370 (5)	C24—C25	1.431 (5)
O2—C26	1.421 (5)	C24—H24	0.9500
C1—C2	1.381 (4)	C25—C26	1.378 (6)
C1—C10ⁱ	1.383 (4)	C25—H25	0.9500
C1—C11	1.503 (4)	C26—C27	1.342 (6)
C2—C3	1.434 (4)	C27—C28	1.367 (5)
C3—C4	1.344 (4)	C27—H27	0.9500
C3—H3	0.9500	C28—H28	0.9500
C4—C5	1.431 (4)	C29—C30	1.558 (7)
C4—H4	0.9500	C29—H29A	0.9900
C5—C6	1.387 (4)	C29—H29B	0.9900
C6—C7	1.383 (4)	C30—C31	1.405 (8)
C6—C23	1.497 (4)	C30—H30A	0.9900
C7—C8	1.438 (4)	C30—H30B	0.9900
C8—C9	1.346 (4)	C31—C32A	1.517 (7)
C8—H8	0.9500	C31—C32B	1.526 (10)
C9—C10	1.430 (4)	C31—H31A	0.9900
C9—H9	0.9500	C31—H31B	0.9900
C10—C1ⁱ	1.383 (4)	C31—H31C	0.9900
C11—C16	1.375 (4)	C31—H31D	0.9900
C11—C12	1.385 (4)	C32A—C33A	1.496 (8)
C12—C13	1.387 (4)	C32A—H32C	0.9900
C12—H12	0.9500	C32A—H32D	0.9900
C13—C14	1.384 (4)	C33A—C34A	1.510 (9)
C13—H13	0.9500	C33A—H33A	0.9900
C14—C15	1.381 (4)	C33A—H33B	0.9900
C15—C16	1.394 (4)	C34A—H34A	0.9800
C15—H15	0.9500	C34A—H34B	0.9800
C16—H16	0.9500	C34A—H34C	0.9800
C17—C18	1.511 (4)	C32B—C33B	1.516 (9)
C17—H17A	0.9900	C32B—H32E	0.9900
C17—H17B	0.9900	C32B—H32F	0.9900
C18—C19	1.520 (5)	C33B—C34B	1.524 (10)
C18—H18A	0.9900	C33B—H33C	0.9900
C18—H18B	0.9900	C33B—H33D	0.9900
C19—C20	1.519 (4)	C34B—H34D	0.9800
C19—H19A	0.9900	C34B—H34E	0.9800
C19—H19B	0.9900	C34B—H34F	0.9800
C20—C21	1.515 (5)

N2ⁱ—Ni1—N2	180.0	C20—C21—C22	112.8 (4)
N2ⁱ—Ni1—N1ⁱ	89.94 (10)	C20—C21—H21A	109.0
N2—Ni1—N1ⁱ	90.06 (10)	C22—C21—H21A	109.0
N2ⁱ—Ni1—N1	90.06 (10)	C20—C21—H21B	109.0
N2—Ni1—N1	89.94 (10)	C22—C21—H21B	109.0
N1ⁱ—Ni1—N1	180.0	H21A—C21—H21B	107.8
C2—N1—C5	104.0 (2)	C21—C22—H22A	109.5
C2—N1—Ni1	128.0 (2)	C21—C22—H22B	109.5
C5—N1—Ni1	127.94 (19)	H22A—C22—H22B	109.5
C7—N2—C10	104.1 (2)	C21—C22—H22C	109.5
C7—N2—Ni1	128.03 (19)	H22A—C22—H22C	109.5
C10—N2—Ni1	127.8 (2)	H22B—C22—H22C	109.5
C14—O1—C17	117.4 (2)	C24—C23—C28	117.9 (3)
C29—O2—C26	116.5 (4)	C24—C23—C6	122.9 (3)
C2—C1—C10ⁱ	122.5 (3)	C28—C23—C6	119.1 (3)
C2—C1—C11	118.8 (3)	C23—C24—C25	119.9 (4)
C10ⁱ—C1—C11	118.7 (3)	C23—C24—H24	120.1
C1—C2—N1	125.7 (3)	C25—C24—H24	120.1
C1—C2—C3	123.5 (3)	C26—C25—C24	118.6 (4)
N1—C2—C3	110.8 (3)	C26—C25—H25	120.7
C4—C3—C2	107.2 (3)	C24—C25—H25	120.7
C4—C3—H3	126.4	C27—C26—C25	121.8 (4)
C2—C3—H3	126.4	C27—C26—O2	115.0 (4)
C3—C4—C5	106.9 (3)	C25—C26—O2	123.2 (4)
C3—C4—H4	126.6	C26—C27—C28	119.5 (4)
C5—C4—H4	126.6	C26—C27—H27	120.3
N1—C5—C6	125.8 (3)	C28—C27—H27	120.3
N1—C5—C4	111.1 (3)	C27—C28—C23	122.4 (4)
C6—C5—C4	123.2 (3)	C27—C28—H28	118.8
C7—C6—C5	122.0 (3)	C23—C28—H28	118.8
C7—C6—C23	118.5 (3)	O2—C29—C30	106.1 (4)
C5—C6—C23	119.4 (3)	O2—C29—H29A	110.5
N2—C7—C6	126.1 (3)	C30—C29—H29A	110.5
N2—C7—C8	111.1 (3)	O2—C29—H29B	110.5
C6—C7—C8	122.7 (3)	C30—C29—H29B	110.5
C9—C8—C7	106.6 (3)	H29A—C29—H29B	108.7
C9—C8—H8	126.7	C31—C30—C29	115.8 (5)
C7—C8—H8	126.7	C31—C30—H30A	108.3
C8—C9—C10	107.3 (3)	C29—C30—H30A	108.3
C8—C9—H9	126.3	C31—C30—H30B	108.3
C10—C9—H9	126.3	C29—C30—H30B	108.3
C1ⁱ—C10—N2	125.8 (3)	H30A—C30—H30B	107.4
C1ⁱ—C10—C9	123.4 (3)	C30—C31—C32A	109.7 (7)
N2—C10—C9	110.8 (3)	C30—C31—C32B	138.6 (12)
C16—C11—C12	118.3 (3)	C30—C31—H31A	109.7
C16—C11—C1	120.9 (3)	C32A—C31—H31A	109.7
C12—C11—C1	120.8 (3)	C30—C31—H31B	109.7
C11—C12—C13	121.0 (3)	C32A—C31—H31B	109.7
C11—C12—H12	119.5	H31A—C31—H31B	108.2
C13—C12—H12	119.5	C30—C31—H31C	102.4
C14—C13—C12	120.0 (3)	C32B—C31—H31C	102.4
C14—C13—H13	120.0	C30—C31—H31D	102.4
C12—C13—H13	120.0	C32A—C31—H31D	109.4
O1—C14—C15	124.7 (3)	C32B—C31—H31D	102.4
O1—C14—C13	115.6 (3)	H31C—C31—H31D	104.9
C15—C14—C13	119.7 (3)	C33A—C32A—C31	108.8 (6)
C14—C15—C16	119.4 (3)	C33A—C32A—H32C	109.9
C14—C15—H15	120.3	C31—C32A—H32C	109.9
C16—C15—H15	120.3	C33A—C32A—H32D	109.9
C11—C16—C15	121.6 (3)	C31—C32A—H32D	109.9
C11—C16—H16	119.2	H32C—C32A—H32D	108.3
C15—C16—H16	119.2	C34A—C33A—C32A	111.8 (7)
O1—C17—C18	107.9 (3)	C34A—C33A—H33A	109.3
O1—C17—H17A	110.1	C32A—C33A—H33A	109.3
C18—C17—H17A	110.1	C34A—C33A—H33B	109.3
O1—C17—H17B	110.1	C32A—C33A—H33B	109.3
C18—C17—H17B	110.1	H33A—C33A—H33B	107.9
H17A—C17—H17B	108.4	C33B—C32B—C31	110.3 (8)
C17—C18—C19	112.5 (3)	C33B—C32B—H32E	109.6
C17—C18—H18A	109.1	C31—C32B—H32E	109.6
C19—C18—H18A	109.1	C33B—C32B—H32F	109.6
C17—C18—H18B	109.1	C31—C32B—H32F	109.6
C19—C18—H18B	109.1	H32E—C32B—H32F	108.1
H18A—C18—H18B	107.8	C32B—C33B—C34B	109.2 (9)
C20—C19—C18	114.0 (3)	C32B—C33B—H33C	109.8
C20—C19—H19A	108.7	C34B—C33B—H33C	109.8
C18—C19—H19A	108.7	C32B—C33B—H33D	109.8
C20—C19—H19B	108.7	C34B—C33B—H33D	109.8
C18—C19—H19B	108.7	H33C—C33B—H33D	108.3
H19A—C19—H19B	107.6	C33B—C34B—H34D	109.5
C21—C20—C19	113.4 (3)	C33B—C34B—H34E	109.5
C21—C20—H20A	108.9	H34D—C34B—H34E	109.5
C19—C20—H20A	108.9	C33B—C34B—H34F	109.5
C21—C20—H20B	108.9	H34D—C34B—H34F	109.5
C19—C20—H20B	108.9	H34E—C34B—H34F	109.5
H20A—C20—H20B	107.7

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₆₈H₇₆N₄O₄)]
M_r	1072.04
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	185
a, b, c (Å)	18.7735 (10), 10.8439 (6), 28.7173 (16)
V (Å³)	5846.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.27 × 0.19 × 0.10

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.904, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	30888, 5173, 3950
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.156, 1.03
No. of reflections	5173
No. of parameters	380
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.32

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Changchun, China.

References

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