(5,15-Dianthracen-9-yl-10,20-dihexyl­porphyrinato)nickel(II): a planar nickel(II) porphyrin

Senge, M.O.; Davis, M.

doi:10.1107/S1600536810021434

metal-organic compounds

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Volume 66| Part 7| July 2010| Page m790

doi:10.1107/S1600536810021434

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(5,15-Dianthracen-9-yl-10,20-dihexylporphyrinato)nickel(II): a planar nickel(II) porphyrin

Mathias O. Senge ^a ^* and Mia Davis ^a

^aSFI Tetrapyrrole Laboratory, School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
^*Correspondence e-mail: sengem@tcd.ie

(Received 3 June 2010; accepted 4 June 2010; online 16 June 2010)

The title compound, [Ni(C₆₀H₅₂N₄)], is an example of a meso tetrasubstituted nickel(II) porphyrin with both meso aryl and alkyl residues. The molecule exhibits a planar macrocycle with an average deviation of the 24 macrocycle atoms from their least-squares plane (Δ24) of 0.01 Å and an average Ni—N bond length of 1.960 (2) Å. The Ni^II atom lies on a center of inversion. The structure presents a rare example for a planar nickel(II) porphyrin, as meso-substituted nickel(II) porphyrins with either only meso-aryl or with meso-alkyl residues typically exhibit a ruffled conformation.

Related literature

For the conformation of porphyrins, see: Senge (2006 ). For porphyrins with mixed meso substituents, see: Senge et al. (2010 ). For Ni(II) porphyrin structures, see: Fleischer et al. (1964 ); Gallucci et al. (1982 ); Hoard (1973 ); Lee & Scheidt (1987 ); Senge et al. (1999 , 2000 ) and Runge et al. (1999 ). For anthracenyl porphyrins see: Volz & Schäffer (1985 ); Davis et al. (2008 ); Sooambar et al. (2009 ). For the handling of the crystals, see: Hope (1994 ).

Experimental

Crystal data

[Ni(C₆₀H₅₂N₄)]
M_r = 887.77
Triclinic, $[P \overline 1]$
a = 7.797 (3) Å
b = 9.387 (3) Å
c = 15.285 (5) Å
α = 97.246 (6)°
β = 91.222 (4)°
γ = 91.402 (6)°
V = 1109.1 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 118 K
0.50 × 0.20 × 0.05 mm

Data collection

Rigaku Saturn724 diffractometer
17330 measured reflections
3875 independent reflections
3233 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.087
S = 1.00
3875 reflections
296 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni—N22	1.9570 (17)
Ni—N21	1.9632 (17)

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021434/ng2783sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021434/ng2783Isup2.hkl

checkCIF report

Comment top

In continuation of studies on the conformational flexibility of porphyrins (Senge, 2006) the structure of the title compound was determined as an example for a meso substituted porphyrin with both meso alkyl and meso aryl subsitutents (Senge et al., 2010) and in relation to current synthetic studies on anthracenyl porphyrins (Volz & Schäffer, 1985; Davis et al., 2008; Sooambar et al., 2009).

The structure of (I), is shown in Fig. 1. The molecule exhibits a completely planar macrocycle with an average deviation of the 24 macrocycle atoms from their least-squares-plane (Δ24) of 0.01 Å and an average Ni—N bond length of 1.960 (2) Å. All geometrical parameters are typical for a planar nickel(II) porphyrin (Senge et al., 2000). No individual macrocycle atom was displaced more then 0.015 Å from the mean plane. Likewise, differences in bond angles and lenghts between the meso aryl and meso alkyl quadrants are minimal. The anthracenyl residues are almost orthogonal to the plane of the four nitrogen atoms (96.2°) similarly to the situation found in related zinc(II) systems with meso aryl residues (Sooambar et al., 2009). In the crystal packing there are no close contacts (not shown). The anthracene residues prevent π-stacking of the porphyrins and the hexyl side chains are oriented between neighboring anthracenyl substituents and hinder π-stacking as well.

The structure presents a rare example for a planar nickel(II) porphyrin. Typically, meso substituted nickel(II) porphyrins with only meso aryl residues (Fleischer et al., 1964; Hoard, 1973; Lee & Scheidt, 1987) and those with meso alkyl residues (Senge et al., 1999; Runge et al., 1999) exhibit a ruffled conformation. Only (5,10,15,20-tetramethylporphyrinato)nickel(II) exbihits an almost planar conformation as well (Gallucci et al., 1982).

Related literature top

For the conformation of porphyrins, see: Senge (2006). For porphyrins with mixed meso substituents, see: Senge et al. (2010). For Ni(II) porphyrin structures, see: Fleischer et al. (1964);; Gallucci et al. (1982); Hoard (1973); Lee & Scheidt (1987); Senge et al. (1999, 2000) and Runge et al. (1999). For anthracenyl porphyrins see: Volz & Schäffer (1985); Davis et al. (2008); Sooambar et al. (2009). For the handling of the crystals, see: Hope (1994).

Experimental top

The compound was prepared via metallation of the respective free base porphyrin and crystallized via liquid diffusion of methanol into a solution of the porphyrin in methylene chloride. Crystals were handled as described by Hope (1994).

Computing details top

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

Figures top

Fig. 1. : View of the molecular structure of I in the crystals. Thermal ellipsoids are drawn for 50% occupancy.

(5,15-Dianthracen-9-yl-10,20-dihexylporphyrinato)nickel(II) top

Crystal data top

[Ni(C₆₀H₅₂N₄)]	Z = 1
M_r = 887.77	F(000) = 468
Triclinic, P1	D_x = 1.329 Mg m⁻³
Hall symbol: -P 1	Melting point: n/d K
a = 7.797 (3) Å	Mo Kα radiation, λ = 0.71075 Å
b = 9.387 (3) Å	Cell parameters from 3864 reflections
c = 15.285 (5) Å	θ = 2.4–31.2°
α = 97.246 (6)°	µ = 0.48 mm⁻¹
β = 91.222 (4)°	T = 118 K
γ = 91.402 (6)°	Prism, red
V = 1109.1 (7) Å³	0.50 × 0.20 × 0.05 mm

Data collection top

Rigaku Saturn724 diffractometer	3233 reflections with I > 2σ(I)
Radiation source: Sealed Tube	R_int = 0.070
Graphite Monochromator monochromator	θ_max = 25.0°, θ_min = 3.0°
Detector resolution: 28.5714 pixels mm^-1	h = −9→9
dtprofit.ref scans	k = −11→11
17330 measured reflections	l = −18→18
3875 independent reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0371P)²] where P = (F_o² + 2F_c²)/3
3875 reflections	(Δ/σ)_max < 0.001
296 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³
0 constraints

Crystal data top

[Ni(C₆₀H₅₂N₄)]	γ = 91.402 (6)°
M_r = 887.77	V = 1109.1 (7) Å³
Triclinic, P1	Z = 1
a = 7.797 (3) Å	Mo Kα radiation
b = 9.387 (3) Å	µ = 0.48 mm⁻¹
c = 15.285 (5) Å	T = 118 K
α = 97.246 (6)°	0.50 × 0.20 × 0.05 mm
β = 91.222 (4)°

Data collection top

Rigaku Saturn724 diffractometer	3233 reflections with I > 2σ(I)
17330 measured reflections	R_int = 0.070
3875 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.00	Δρ_max = 0.37 e Å⁻³
3875 reflections	Δρ_min = −0.40 e Å⁻³
296 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
Ni	0.0000	0.5000	0.0000	0.01798 (12)
N21	0.1442 (2)	0.47152 (16)	0.10290 (10)	0.0185 (4)
N22	0.1822 (2)	0.62389 (16)	−0.03788 (10)	0.0192 (4)
C5	−0.0499 (3)	0.31349 (19)	0.17545 (13)	0.0185 (4)
C6	0.1022 (3)	0.3901 (2)	0.16960 (13)	0.0198 (5)
C7	0.2375 (3)	0.3969 (2)	0.23403 (13)	0.0247 (5)
H7A	0.2383	0.3500	0.2856	0.030*
C8	0.3643 (3)	0.4817 (2)	0.20886 (14)	0.0243 (5)
H8A	0.4707	0.5059	0.2391	0.029*
C9	0.3069 (3)	0.5284 (2)	0.12716 (13)	0.0194 (5)
C10	0.4031 (3)	0.6194 (2)	0.08102 (13)	0.0204 (5)
C11	0.3407 (3)	0.6617 (2)	0.00254 (13)	0.0197 (5)
C12	0.4362 (3)	0.7542 (2)	−0.04785 (14)	0.0244 (5)
H12A	0.5476	0.7949	−0.0337	0.029*
C13	0.3384 (3)	0.7725 (2)	−0.11872 (14)	0.0248 (5)
H13A	0.3677	0.8283	−0.1642	0.030*
C14	0.1820 (3)	0.69232 (19)	−0.11298 (13)	0.0190 (5)
C5A	−0.0738 (3)	0.2335 (2)	0.25355 (13)	0.0205 (5)
C5B	−0.0381 (3)	0.0855 (2)	0.24777 (14)	0.0230 (5)
C5C	0.0207 (3)	0.0055 (2)	0.16833 (15)	0.0263 (5)
H5CA	0.0405	0.0534	0.1181	0.032*
C5D	0.0488 (3)	−0.1376 (2)	0.16363 (16)	0.0334 (6)
H5DA	0.0880	−0.1884	0.1104	0.040*
C5E	0.0197 (3)	−0.2119 (2)	0.23800 (17)	0.0360 (6)
H5EA	0.0382	−0.3122	0.2338	0.043*
C5F	−0.0339 (3)	−0.1403 (2)	0.31441 (16)	0.0321 (6)
H5FA	−0.0517	−0.1913	0.3635	0.038*
C5G	−0.0645 (3)	0.0104 (2)	0.32312 (14)	0.0255 (5)
C5H	−0.1190 (3)	0.0864 (2)	0.40177 (14)	0.0276 (5)
H5HA	−0.1338	0.0367	0.4516	0.033*
C5I	−0.1523 (3)	0.2321 (2)	0.40970 (13)	0.0230 (5)
C5J	−0.2098 (3)	0.3101 (2)	0.48906 (14)	0.0318 (6)
H5JA	−0.2196	0.2628	0.5402	0.038*
C5K	−0.2508 (3)	0.4502 (2)	0.49355 (15)	0.0393 (6)
H5KA	−0.2877	0.5003	0.5475	0.047*
C5L	−0.2383 (3)	0.5230 (2)	0.41624 (15)	0.0347 (6)
H5LA	−0.2719	0.6200	0.4186	0.042*
C5M	−0.1797 (3)	0.4549 (2)	0.34139 (15)	0.0298 (5)
H5MA	−0.1677	0.5061	0.2920	0.036*
C5N	−0.1344 (3)	0.3070 (2)	0.33320 (13)	0.0230 (5)
C10A	0.5771 (3)	0.6803 (2)	0.11646 (13)	0.0235 (5)
H10A	0.6577	0.6781	0.0671	0.028*
H10B	0.6232	0.6189	0.1591	0.028*
C10B	0.5667 (3)	0.8359 (2)	0.16236 (13)	0.0265 (5)
H10C	0.6835	0.8805	0.1670	0.032*
H10D	0.4955	0.8913	0.1250	0.032*
C10C	0.4915 (3)	0.8477 (2)	0.25444 (14)	0.0279 (5)
H10E	0.5718	0.8051	0.2943	0.033*
H10F	0.3823	0.7909	0.2514	0.033*
C10D	0.4574 (3)	1.0030 (2)	0.29382 (14)	0.0287 (5)
H10G	0.5637	1.0622	0.2916	0.034*
H10H	0.3681	1.0425	0.2574	0.034*
C10E	0.4000 (3)	1.0138 (2)	0.38747 (15)	0.0356 (6)
H10I	0.4938	0.9824	0.4246	0.043*
H10J	0.3004	0.9473	0.3904	0.043*
C10F	0.3500 (3)	1.1641 (2)	0.42523 (14)	0.0316 (6)
H10K	0.3292	1.1666	0.4884	0.047*
H10L	0.2453	1.1900	0.3950	0.047*
H10M	0.4430	1.2326	0.4166	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0227 (2)	0.0162 (2)	0.0154 (2)	−0.00037 (16)	0.00200 (15)	0.00351 (15)
N21	0.0227 (10)	0.0156 (8)	0.0174 (9)	−0.0013 (7)	0.0034 (7)	0.0021 (7)
N22	0.0240 (10)	0.0184 (9)	0.0155 (9)	0.0016 (8)	0.0008 (7)	0.0030 (7)
C5	0.0243 (12)	0.0137 (10)	0.0171 (10)	−0.0003 (9)	0.0026 (9)	0.0004 (8)
C6	0.0279 (13)	0.0145 (10)	0.0170 (11)	0.0015 (9)	0.0004 (9)	0.0020 (8)
C7	0.0307 (13)	0.0231 (11)	0.0212 (11)	−0.0003 (10)	−0.0011 (10)	0.0069 (9)
C8	0.0244 (12)	0.0235 (11)	0.0252 (12)	−0.0005 (9)	−0.0043 (9)	0.0048 (9)
C9	0.0219 (12)	0.0161 (10)	0.0198 (11)	0.0005 (9)	0.0000 (9)	0.0005 (9)
C10	0.0215 (12)	0.0177 (10)	0.0211 (11)	0.0032 (9)	0.0025 (9)	−0.0015 (9)
C11	0.0208 (12)	0.0171 (10)	0.0204 (11)	−0.0007 (9)	0.0021 (9)	−0.0005 (9)
C12	0.0243 (12)	0.0245 (11)	0.0246 (12)	−0.0043 (9)	0.0021 (9)	0.0047 (9)
C13	0.0282 (13)	0.0248 (11)	0.0221 (11)	−0.0045 (10)	0.0024 (9)	0.0061 (9)
C14	0.0249 (12)	0.0138 (10)	0.0184 (10)	−0.0005 (9)	0.0027 (9)	0.0028 (8)
C5A	0.0206 (12)	0.0199 (11)	0.0209 (11)	−0.0033 (9)	−0.0013 (9)	0.0036 (9)
C5B	0.0215 (12)	0.0224 (11)	0.0254 (12)	−0.0028 (9)	−0.0011 (9)	0.0050 (9)
C5C	0.0235 (12)	0.0243 (12)	0.0312 (13)	−0.0006 (10)	0.0029 (10)	0.0029 (10)
C5D	0.0297 (14)	0.0295 (13)	0.0400 (14)	0.0025 (11)	0.0049 (11)	0.0001 (11)
C5E	0.0338 (15)	0.0204 (12)	0.0548 (17)	0.0030 (10)	0.0046 (12)	0.0073 (11)
C5F	0.0275 (14)	0.0275 (12)	0.0445 (15)	0.0023 (10)	0.0012 (11)	0.0166 (11)
C5G	0.0227 (12)	0.0242 (12)	0.0308 (12)	−0.0018 (9)	−0.0011 (10)	0.0088 (10)
C5H	0.0259 (13)	0.0333 (13)	0.0259 (12)	−0.0043 (10)	−0.0008 (10)	0.0135 (10)
C5I	0.0234 (12)	0.0244 (11)	0.0218 (11)	−0.0032 (9)	0.0020 (9)	0.0056 (9)
C5J	0.0353 (14)	0.0375 (14)	0.0232 (12)	−0.0075 (11)	0.0003 (10)	0.0075 (10)
C5K	0.0509 (17)	0.0376 (14)	0.0268 (13)	−0.0036 (12)	0.0092 (12)	−0.0069 (11)
C5L	0.0490 (17)	0.0188 (11)	0.0359 (14)	0.0024 (11)	0.0132 (12)	−0.0006 (10)
C5M	0.0370 (14)	0.0257 (12)	0.0282 (13)	−0.0016 (10)	0.0020 (10)	0.0090 (10)
C5N	0.0238 (12)	0.0220 (11)	0.0234 (11)	−0.0015 (9)	0.0003 (9)	0.0035 (9)
C10A	0.0212 (12)	0.0290 (12)	0.0209 (11)	−0.0013 (9)	0.0002 (9)	0.0059 (9)
C10B	0.0222 (12)	0.0306 (12)	0.0262 (12)	−0.0058 (10)	−0.0007 (10)	0.0035 (10)
C10C	0.0286 (13)	0.0284 (12)	0.0269 (12)	−0.0013 (10)	−0.0015 (10)	0.0048 (10)
C10D	0.0265 (13)	0.0316 (12)	0.0282 (12)	−0.0031 (10)	−0.0030 (10)	0.0057 (10)
C10E	0.0428 (16)	0.0354 (13)	0.0285 (13)	0.0020 (11)	0.0001 (11)	0.0033 (11)
C10F	0.0368 (15)	0.0288 (12)	0.0289 (13)	0.0039 (11)	0.0004 (11)	0.0019 (10)

Geometric parameters (Å, º) top

Ni—N22	1.9570 (17)	C5E—H5EA	0.9500
Ni—N22ⁱ	1.9570 (17)	C5F—C5G	1.430 (3)
Ni—N21ⁱ	1.9632 (17)	C5F—H5FA	0.9500
Ni—N21	1.9632 (17)	C5G—C5H	1.399 (3)
N21—C6	1.389 (2)	C5H—C5I	1.389 (3)
N21—C9	1.389 (3)	C5H—H5HA	0.9500
N22—C14	1.384 (2)	C5I—C5J	1.423 (3)
N22—C11	1.388 (3)	C5I—C5N	1.446 (3)
C5—C6	1.382 (3)	C5J—C5K	1.354 (3)
C5—C14ⁱ	1.385 (3)	C5J—H5JA	0.9500
C5—C5A	1.501 (3)	C5K—C5L	1.442 (3)
C6—C7	1.423 (3)	C5K—H5KA	0.9500
C7—C8	1.346 (3)	C5L—C5M	1.333 (3)
C7—H7A	0.9500	C5L—H5LA	0.9500
C8—C9	1.441 (3)	C5M—C5N	1.433 (3)
C8—H8A	0.9500	C5M—H5MA	0.9500
C9—C10	1.390 (3)	C10A—C10B	1.544 (3)
C10—C11	1.392 (3)	C10A—H10A	0.9900
C10—C10A	1.521 (3)	C10A—H10B	0.9900
C11—C12	1.436 (3)	C10B—C10C	1.529 (3)
C12—C13	1.343 (3)	C10B—H10C	0.9900
C12—H12A	0.9500	C10B—H10D	0.9900
C13—C14	1.427 (3)	C10C—C10D	1.538 (3)
C13—H13A	0.9500	C10C—H10E	0.9900
C14—C5ⁱ	1.385 (3)	C10C—H10F	0.9900
C5A—C5B	1.416 (3)	C10D—C10E	1.501 (3)
C5A—C5N	1.417 (3)	C10D—H10G	0.9900
C5B—C5C	1.435 (3)	C10D—H10H	0.9900
C5B—C5G	1.440 (3)	C10E—C10F	1.518 (3)
C5C—C5D	1.359 (3)	C10E—H10I	0.9900
C5C—H5CA	0.9500	C10E—H10J	0.9900
C5D—C5E	1.426 (3)	C10F—H10K	0.9800
C5D—H5DA	0.9500	C10F—H10L	0.9800
C5E—C5F	1.352 (3)	C10F—H10M	0.9800

N22—Ni—N22ⁱ	180.00 (8)	C5H—C5G—C5F	122.4 (2)
N22—Ni—N21ⁱ	91.02 (7)	C5H—C5G—C5B	119.23 (19)
N22ⁱ—Ni—N21ⁱ	88.98 (7)	C5F—C5G—C5B	118.4 (2)
N22—Ni—N21	88.98 (7)	C5I—C5H—C5G	122.40 (19)
N22ⁱ—Ni—N21	91.02 (7)	C5I—C5H—H5HA	118.8
N21ⁱ—Ni—N21	180.00 (9)	C5G—C5H—H5HA	118.8
C6—N21—C9	104.27 (16)	C5H—C5I—C5J	122.86 (19)
C6—N21—Ni	126.74 (14)	C5H—C5I—C5N	118.78 (19)
C9—N21—Ni	128.98 (13)	C5J—C5I—C5N	118.31 (19)
C14—N22—C11	104.18 (16)	C5K—C5J—C5I	121.6 (2)
C14—N22—Ni	127.19 (14)	C5K—C5J—H5JA	119.2
C11—N22—Ni	128.63 (13)	C5I—C5J—H5JA	119.2
C6—C5—C14ⁱ	123.17 (18)	C5J—C5K—C5L	119.8 (2)
C6—C5—C5A	118.53 (18)	C5J—C5K—H5KA	120.1
C14ⁱ—C5—C5A	118.30 (18)	C5L—C5K—H5KA	120.1
C5—C6—N21	126.01 (18)	C5M—C5L—C5K	120.3 (2)
C5—C6—C7	123.21 (18)	C5M—C5L—H5LA	119.8
N21—C6—C7	110.77 (18)	C5K—C5L—H5LA	119.8
C8—C7—C6	107.78 (19)	C5L—C5M—C5N	122.0 (2)
C8—C7—H7A	126.1	C5L—C5M—H5MA	119.0
C6—C7—H7A	126.1	C5N—C5M—H5MA	119.0
C7—C8—C9	106.63 (19)	C5A—C5N—C5M	122.31 (19)
C7—C8—H8A	126.7	C5A—C5N—C5I	119.88 (18)
C9—C8—H8A	126.7	C5M—C5N—C5I	117.81 (18)
N21—C9—C10	125.85 (19)	C10—C10A—C10B	112.21 (17)
N21—C9—C8	110.55 (17)	C10—C10A—H10A	109.2
C10—C9—C8	123.6 (2)	C10B—C10A—H10A	109.2
C9—C10—C11	121.1 (2)	C10—C10A—H10B	109.2
C9—C10—C10A	121.00 (19)	C10B—C10A—H10B	109.2
C11—C10—C10A	117.87 (18)	H10A—C10A—H10B	107.9
N22—C11—C10	126.47 (18)	C10C—C10B—C10A	113.98 (17)
N22—C11—C12	110.47 (18)	C10C—C10B—H10C	108.8
C10—C11—C12	123.1 (2)	C10A—C10B—H10C	108.8
C13—C12—C11	107.1 (2)	C10C—C10B—H10D	108.8
C13—C12—H12A	126.4	C10A—C10B—H10D	108.8
C11—C12—H12A	126.4	H10C—C10B—H10D	107.7
C12—C13—C14	107.17 (19)	C10B—C10C—C10D	113.40 (17)
C12—C13—H13A	126.4	C10B—C10C—H10E	108.9
C14—C13—H13A	126.4	C10D—C10C—H10E	108.9
N22—C14—C5ⁱ	125.85 (19)	C10B—C10C—H10F	108.9
N22—C14—C13	111.04 (18)	C10D—C10C—H10F	108.9
C5ⁱ—C14—C13	123.11 (18)	H10E—C10C—H10F	107.7
C5B—C5A—C5N	120.05 (18)	C10E—C10D—C10C	112.63 (18)
C5B—C5A—C5	120.47 (18)	C10E—C10D—H10G	109.1
C5N—C5A—C5	119.47 (17)	C10C—C10D—H10G	109.1
C5A—C5B—C5C	122.32 (19)	C10E—C10D—H10H	109.1
C5A—C5B—C5G	119.53 (19)	C10C—C10D—H10H	109.1
C5C—C5B—C5G	118.13 (18)	H10G—C10D—H10H	107.8
C5D—C5C—C5B	121.2 (2)	C10D—C10E—C10F	113.70 (18)
C5D—C5C—H5CA	119.4	C10D—C10E—H10I	108.8
C5B—C5C—H5CA	119.4	C10F—C10E—H10I	108.8
C5C—C5D—C5E	120.5 (2)	C10D—C10E—H10J	108.8
C5C—C5D—H5DA	119.8	C10F—C10E—H10J	108.8
C5E—C5D—H5DA	119.8	H10I—C10E—H10J	107.7
C5F—C5E—C5D	120.3 (2)	C10E—C10F—H10K	109.5
C5F—C5E—H5EA	119.9	C10E—C10F—H10L	109.5
C5D—C5E—H5EA	119.9	H10K—C10F—H10L	109.5
C5E—C5F—C5G	121.6 (2)	C10E—C10F—H10M	109.5
C5E—C5F—H5FA	119.2	H10K—C10F—H10M	109.5
C5G—C5F—H5FA	119.2	H10L—C10F—H10M	109.5

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₆₀H₅₂N₄)]
M_r	887.77
Crystal system, space group	Triclinic, P1
Temperature (K)	118
a, b, c (Å)	7.797 (3), 9.387 (3), 15.285 (5)
α, β, γ (°)	97.246 (6), 91.222 (4), 91.402 (6)
V (Å³)	1109.1 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.50 × 0.20 × 0.05

Data collection
Diffractometer	Rigaku Saturn724 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	17330, 3875, 3233
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.087, 1.00
No. of reflections	3875
No. of parameters	296
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.40

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni—N22

1.9570 (17)

Ni—N21

1.9632 (17)

Acknowledgements

This work was supported by a grant from Science Foundation Ireland (SFI P.I. 09/IN.1/B2650).

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