[5,15-Bis(2-methyl­prop­yl)porphyrinato]nickel(II)

Senge, M.O.

doi:10.1107/S1600536812035726

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1191-m1192

doi:10.1107/S1600536812035726

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[5,15-Bis(2-methylpropyl)porphyrinato]nickel(II)

Mathias O. Senge ^a ^*

^aSchool of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, 152-160 Pearse Street, Trinity College Dublin, Dublin 2, Ireland
^*Correspondence e-mail: sengem@tcd.ie

(Received 1 August 2012; accepted 14 August 2012; online 23 August 2012)

The title compound, [Ni(C₂₈H₂₈N₄)], crystallizes with two independent molecules in the unit cell, one of which is located on an inversion center. Both macrocycles exhibit a planar conformation with average deviation from the least-squares-plane of the 24 macrocycle atoms of Δ24 = 0.043 Å for the first molecule and 0.026 Å for the molecule located on an inversion center. The average Ni—N bond lengths are 1.955 (2) and 1.956 (2) Å in the two molecules. The molecules form π–π dimers of intermediary strength with a mean plane separation of 3.36 (2) Å.

Related literature

For the conformation of porphyrins, see: Senge (2006 ). For the structural analysis of π-aggregates, see: Scheidt & Lee (1987 ). For Ni(II) porphyrin structures, see: Song et al. (1996 , 1998 ); Davis et al. (2010 ); Jentzen et al. (1996 ); Senge & Davis (2010 ); Senge et al. (2000 , 2010 );. For the preparation, see: Wiehe et al. (2005 ).

Experimental

Crystal data

[Ni(C₂₈H₂₈N₄)]
M_r = 479.25
Triclinic, $[P \overline 1]$
a = 9.951 (2) Å
b = 13.197 (3) Å
c = 13.700 (3) Å
α = 73.03 (3)°
β = 75.27 (3)°
γ = 73.39 (3)°
V = 1620.1 (7) Å³
Z = 3
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 90 K
0.20 × 0.15 × 0.01 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.837, T_max = 0.995
21454 measured reflections
7431 independent reflections
5881 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.096
S = 1.04
7431 reflections
454 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N24	1.9497 (16)
Ni1—N22	1.9508 (16)
Ni1—N23	1.9595 (15)
Ni1—N21	1.9623 (15)
Ni2—N28	1.9537 (16)
Ni2—N25	1.9580 (15)

Table 2
Comparison of Ni^II 5,15-dialkylporphyrins (Å, °)

Δ is the deviation from the least-squares-plane of the 24 macrocycle atoms and N—Ni—Nadj is the angle between neighboring pyrrole units.

Alkyl residue	tert-Butyl	Isopropyl	iso-Butyl	none
Ni—N	1.897 (2)	1.930 (2)	1.955 (2)	1.951 (2)
Δ	0.4	0.26	0.04	0.02
N—Ni—Nadj	92.3, 87.7	91.8, 88.2	91.6, 88.4	90, 90
Reference	Song et al. (1996)	Song et al. (1998)	This work	Jentzen et al. (1996)

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812035726/rn2107sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035726/rn2107Isup2.hkl

checkCIF report

Comment top

meso-Alkylporphyrins are increasingly used in porphyrin chemistry, but their structural chemistry is less well established (Senge et al., 2010). The compound is another example for the expanding body of Ni(II) porphyrins with a planar macrocycle (Davis et al., 2010; Jentzen et al., 1996; Senge & Davis (2010). In the crystal this allows the formation of π-aggregates which are characterized by a mean plane separation of 3.36 (2) Å, a center-to-center distance of 4.88 (2) Å, a slip angle of 133.5 (1) ° which, according to the classification given by Scheidt & Lee (1987), results in a lateral shift of the metal centers of 3.54 (2) Å. Thus, the π-π-stacks are of intermediary strength. The compound forms part of a series of Ni(II) 5,15-dialkylporphyrins with different steric demand of the meso residue. The respective tert-butyl derivative (Song et al., 1996) is clearly the most nonplanar one with the shortest Ni—N bond length and largest deviation from planarity (Table 2). The iso-propyl derivative (Song et al., 1998) shows still significant out-of-plane deformations, while Ni(II)porphyrin without any non-hydrogen residues is planar (Jentzen et al., 1996). The title compound has the sterically least demanding alkyl residue and exhibits an almost planar macrocycle. However, as indicated by the different N—Ni—N adj bond angles, the compound still exhibits some degree of in-plane distortion, which becomes more pronounced with larger meso alkyl residues.

Related literature top

For the conformation of porphyrins, see: Senge (2006). For the structural analysis of π-aggregates, see: Scheidt & Lee (1987). For Ni(II) porphyrin structures, see: Song et al. (1996, 1998); Davis et al. (2010); Jentzen et al. (1996); Senge & Davis (2010); Senge et al. (2000, 2010);. For the preparation, see: Wiehe et al. (2005).

Experimental top

The compound was prepared as described by Wiehe et al. (2005) and crystallized from CH₂Cl₂/CH₃OH.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : Molecular structure of molecule 1 of the title compound. Thermal ellipsoids are drawn at 50% probability level; hydrogen atoms have been omitted for clarity.
	Fig. 2. : View of the π-aggregates formed by the title compound in the crystal.

[5,15-Bis(2-methylpropylporphyrinato]nickel(II) top

Crystal data top

[Ni(C₂₈H₂₈N₄)]	Z = 3
M_r = 479.25	F(000) = 756
Triclinic, P1	D_x = 1.474 Mg m⁻³ D_m = n/d Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Melting point: n/d K
a = 9.951 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.197 (3) Å	Cell parameters from 7215 reflections
c = 13.700 (3) Å	θ = 4.8–62.9°
α = 73.03 (3)°	µ = 0.92 mm⁻¹
β = 75.27 (3)°	T = 90 K
γ = 73.39 (3)°	Plate, red
V = 1620.1 (7) Å³	0.20 × 0.15 × 0.01 mm

Data collection top

Bruker SMART APEXII diffractometer	7431 independent reflections
Radiation source: fine-focus sealed tube	5881 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 8.3 pixels mm^-1	θ_max = 27.6°, θ_min = 2.0°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→17
T_min = 0.837, T_max = 0.995	l = −17→17
21454 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0528P)² + 0.238P] where P = (F_o² + 2F_c²)/3
7431 reflections	(Δ/σ)_max = 0.001
454 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Ni(C₂₈H₂₈N₄)]	γ = 73.39 (3)°
M_r = 479.25	V = 1620.1 (7) Å³
Triclinic, P1	Z = 3
a = 9.951 (2) Å	Mo Kα radiation
b = 13.197 (3) Å	µ = 0.92 mm⁻¹
c = 13.700 (3) Å	T = 90 K
α = 73.03 (3)°	0.20 × 0.15 × 0.01 mm
β = 75.27 (3)°

Data collection top

Bruker SMART APEXII diffractometer	7431 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5881 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.995	R_int = 0.033
21454 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	Δρ_max = 0.73 e Å⁻³
7431 reflections	Δρ_min = −0.38 e Å⁻³
454 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
Ni1	0.01600 (2)	0.178583 (17)	0.287430 (16)	0.01052 (7)
N21	0.09964 (15)	0.13788 (11)	0.41252 (11)	0.0120 (3)
N22	−0.17178 (15)	0.18586 (11)	0.37693 (11)	0.0119 (3)
N23	−0.06732 (15)	0.21932 (11)	0.16241 (11)	0.0123 (3)
N24	0.20411 (15)	0.16763 (11)	0.19834 (11)	0.0117 (3)
C1	0.24215 (19)	0.11741 (14)	0.41507 (13)	0.0133 (3)
C2	0.26587 (19)	0.08745 (14)	0.51990 (13)	0.0151 (4)
H2A	0.3549	0.0709	0.5412	0.018*
C3	0.13722 (19)	0.08738 (14)	0.58197 (14)	0.0152 (4)
H3A	0.1186	0.0696	0.6558	0.018*
C4	0.03290 (19)	0.11912 (13)	0.51629 (13)	0.0132 (3)
C5	−0.11240 (19)	0.12848 (13)	0.55287 (13)	0.0135 (3)
C6	−0.20684 (18)	0.16178 (13)	0.48477 (13)	0.0134 (3)
C7	−0.35888 (19)	0.17765 (14)	0.51781 (14)	0.0156 (4)
H7A	−0.4091	0.1656	0.5876	0.019*
C8	−0.41722 (19)	0.21270 (14)	0.43196 (14)	0.0152 (4)
H8A	−0.5160	0.2313	0.4294	0.018*
C9	−0.30068 (19)	0.21646 (14)	0.34503 (14)	0.0137 (3)
C10	−0.32030 (19)	0.24546 (14)	0.24399 (13)	0.0143 (3)
H10A	−0.4154	0.2667	0.2318	0.017*
C11	−0.21063 (19)	0.24565 (13)	0.15931 (13)	0.0133 (3)
C12	−0.23387 (19)	0.27354 (14)	0.05493 (13)	0.0152 (4)
H12A	−0.3234	0.2946	0.0334	0.018*
C13	−0.10439 (19)	0.26420 (14)	−0.00671 (14)	0.0154 (4)
H13A	−0.0853	0.2775	−0.0803	0.019*
C14	−0.00007 (19)	0.23047 (13)	0.05900 (13)	0.0126 (3)
C15	0.14609 (19)	0.21209 (13)	0.02340 (13)	0.0128 (3)
C16	0.24007 (18)	0.18209 (13)	0.09133 (13)	0.0134 (3)
C17	0.39244 (19)	0.16363 (14)	0.05829 (14)	0.0153 (4)
H17A	0.4433	0.1683	−0.0111	0.018*
C18	0.44959 (19)	0.13858 (14)	0.14356 (13)	0.0150 (4)
H18A	0.5482	0.1223	0.1462	0.018*
C19	0.33268 (18)	0.14126 (13)	0.22971 (13)	0.0132 (3)
C20	0.35183 (19)	0.11896 (14)	0.33050 (14)	0.0144 (3)
H20A	0.4464	0.1038	0.3423	0.017*
C51	−0.17085 (19)	0.10162 (14)	0.66844 (13)	0.0144 (3)
H51A	−0.0921	0.0545	0.7042	0.017*
H51B	−0.2432	0.0588	0.6813	0.017*
C52	−0.23936 (19)	0.19972 (14)	0.71841 (13)	0.0163 (4)
H52A	−0.3204	0.2464	0.6834	0.020*
C53	−0.2991 (2)	0.15754 (17)	0.83269 (14)	0.0247 (4)
H53A	−0.3481	0.2192	0.8644	0.037*
H53B	−0.2208	0.1125	0.8685	0.037*
H53C	−0.3668	0.1138	0.8387	0.037*
C54	−0.1336 (2)	0.26873 (14)	0.70584 (14)	0.0192 (4)
H54A	−0.1823	0.3318	0.7356	0.029*
H54B	−0.0956	0.2938	0.6319	0.029*
H54C	−0.0551	0.2249	0.7419	0.029*
C151	0.20745 (19)	0.22250 (14)	−0.09139 (13)	0.0144 (4)
H15A	0.2840	0.2628	−0.1108	0.017*
H15B	0.1315	0.2664	−0.1313	0.017*
C152	0.26898 (19)	0.11315 (14)	−0.12369 (13)	0.0156 (4)
H15C	0.3450	0.0692	−0.0826	0.019*
C153	0.1561 (2)	0.04767 (15)	−0.10150 (15)	0.0211 (4)
H15D	0.1999	−0.0209	−0.1229	0.032*
H15E	0.0798	0.0897	−0.1403	0.032*
H15F	0.1162	0.0322	−0.0270	0.032*
C154	0.3382 (2)	0.13526 (15)	−0.23833 (14)	0.0215 (4)
H15G	0.3870	0.0661	−0.2575	0.032*
H15H	0.4074	0.1797	−0.2508	0.032*
H15I	0.2645	0.1742	−0.2804	0.032*
Ni2	0.0000	0.5000	0.0000	0.01010 (8)
N25	0.07725 (16)	0.46002 (11)	0.12751 (11)	0.0121 (3)
N28	0.19117 (15)	0.48543 (11)	−0.08547 (11)	0.0119 (3)
C21	0.21889 (19)	0.43651 (13)	0.13368 (13)	0.0132 (3)
C22	0.2379 (2)	0.41090 (14)	0.23900 (14)	0.0160 (4)
H22A	0.3258	0.3936	0.2622	0.019*
C23	0.10709 (19)	0.41616 (14)	0.29854 (14)	0.0158 (4)
H23A	0.0852	0.4020	0.3722	0.019*
C24	0.00630 (19)	0.44711 (13)	0.23025 (13)	0.0130 (3)
C25	−0.14021 (19)	0.46298 (13)	0.26333 (13)	0.0127 (3)
C36	0.23108 (18)	0.50284 (13)	−0.19230 (13)	0.0126 (3)
C37	0.38420 (19)	0.48051 (14)	−0.22192 (14)	0.0155 (4)
H37A	0.4376	0.4863	−0.2907	0.019*
C38	0.43770 (19)	0.44991 (14)	−0.13422 (14)	0.0155 (4)
H38A	0.5357	0.4293	−0.1290	0.019*
C39	0.31770 (18)	0.45454 (13)	−0.05027 (13)	0.0132 (3)
C40	0.33182 (19)	0.43296 (14)	0.05146 (14)	0.0144 (3)
H40A	0.4255	0.4144	0.0659	0.017*
C251	−0.20483 (19)	0.44345 (14)	0.37852 (13)	0.0143 (4)
H25B	−0.1304	0.3949	0.4178	0.017*
H25C	−0.2818	0.4047	0.3918	0.017*
C252	−0.26687 (19)	0.54652 (14)	0.42135 (13)	0.0147 (4)
H25D	−0.3437	0.5947	0.3827	0.018*
C253	−0.3340 (2)	0.51309 (15)	0.53581 (14)	0.0217 (4)
H25E	−0.3883	0.5782	0.5608	0.033*
H25F	−0.2587	0.4737	0.5763	0.033*
H25G	−0.3982	0.4659	0.5437	0.033*
C254	−0.1548 (2)	0.61033 (15)	0.40823 (15)	0.0197 (4)
H25H	−0.1994	0.6750	0.4362	0.029*
H25I	−0.1145	0.6327	0.3343	0.029*
H25J	−0.0787	0.5643	0.4457	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01265 (12)	0.01100 (12)	0.00933 (12)	−0.00463 (9)	−0.00089 (8)	−0.00364 (8)
N21	0.0146 (7)	0.0121 (7)	0.0108 (7)	−0.0055 (6)	−0.0006 (6)	−0.0039 (6)
N22	0.0159 (7)	0.0116 (7)	0.0100 (7)	−0.0059 (6)	−0.0018 (6)	−0.0032 (5)
N23	0.0152 (7)	0.0104 (7)	0.0124 (7)	−0.0041 (6)	−0.0014 (6)	−0.0042 (6)
N24	0.0146 (7)	0.0104 (7)	0.0116 (7)	−0.0049 (6)	−0.0025 (6)	−0.0031 (5)
C1	0.0176 (9)	0.0119 (8)	0.0127 (8)	−0.0053 (7)	−0.0038 (7)	−0.0035 (7)
C2	0.0181 (9)	0.0150 (8)	0.0144 (9)	−0.0036 (7)	−0.0061 (7)	−0.0045 (7)
C3	0.0202 (9)	0.0156 (8)	0.0126 (8)	−0.0060 (7)	−0.0034 (7)	−0.0053 (7)
C4	0.0193 (9)	0.0106 (8)	0.0113 (8)	−0.0051 (7)	−0.0022 (7)	−0.0036 (6)
C5	0.0214 (9)	0.0102 (8)	0.0111 (8)	−0.0062 (7)	−0.0008 (7)	−0.0050 (6)
C6	0.0162 (9)	0.0109 (8)	0.0144 (8)	−0.0068 (7)	0.0017 (7)	−0.0054 (7)
C7	0.0168 (9)	0.0170 (9)	0.0151 (9)	−0.0081 (7)	0.0030 (7)	−0.0080 (7)
C8	0.0151 (9)	0.0149 (8)	0.0178 (9)	−0.0061 (7)	−0.0002 (7)	−0.0069 (7)
C9	0.0153 (9)	0.0118 (8)	0.0165 (9)	−0.0066 (7)	0.0002 (7)	−0.0065 (7)
C10	0.0126 (8)	0.0147 (8)	0.0180 (9)	−0.0036 (7)	−0.0044 (7)	−0.0058 (7)
C11	0.0167 (9)	0.0100 (8)	0.0148 (9)	−0.0039 (7)	−0.0034 (7)	−0.0040 (7)
C12	0.0185 (9)	0.0140 (8)	0.0151 (9)	−0.0035 (7)	−0.0058 (7)	−0.0041 (7)
C13	0.0207 (9)	0.0143 (8)	0.0125 (8)	−0.0040 (7)	−0.0040 (7)	−0.0042 (7)
C14	0.0197 (9)	0.0087 (8)	0.0111 (8)	−0.0038 (7)	−0.0043 (7)	−0.0033 (6)
C15	0.0197 (9)	0.0095 (8)	0.0098 (8)	−0.0056 (7)	−0.0003 (7)	−0.0029 (6)
C16	0.0164 (9)	0.0114 (8)	0.0132 (8)	−0.0058 (7)	0.0012 (7)	−0.0049 (7)
C17	0.0164 (9)	0.0157 (8)	0.0142 (9)	−0.0058 (7)	0.0012 (7)	−0.0056 (7)
C18	0.0147 (9)	0.0149 (8)	0.0163 (9)	−0.0058 (7)	−0.0002 (7)	−0.0048 (7)
C19	0.0153 (9)	0.0107 (8)	0.0153 (9)	−0.0056 (7)	−0.0010 (7)	−0.0047 (7)
C20	0.0147 (9)	0.0135 (8)	0.0175 (9)	−0.0045 (7)	−0.0047 (7)	−0.0048 (7)
C51	0.0168 (9)	0.0146 (8)	0.0126 (8)	−0.0073 (7)	−0.0005 (7)	−0.0029 (7)
C52	0.0180 (9)	0.0174 (9)	0.0140 (9)	−0.0051 (7)	−0.0007 (7)	−0.0057 (7)
C53	0.0296 (11)	0.0291 (11)	0.0170 (10)	−0.0108 (9)	0.0026 (8)	−0.0098 (8)
C54	0.0256 (10)	0.0170 (9)	0.0193 (9)	−0.0083 (8)	−0.0046 (8)	−0.0069 (7)
C151	0.0166 (9)	0.0166 (9)	0.0101 (8)	−0.0046 (7)	−0.0009 (7)	−0.0040 (7)
C152	0.0194 (9)	0.0153 (8)	0.0123 (8)	−0.0030 (7)	−0.0044 (7)	−0.0036 (7)
C153	0.0242 (10)	0.0162 (9)	0.0254 (10)	−0.0048 (8)	−0.0051 (8)	−0.0080 (8)
C154	0.0283 (10)	0.0212 (10)	0.0138 (9)	−0.0027 (8)	−0.0012 (8)	−0.0074 (7)
Ni2	0.01232 (16)	0.01096 (15)	0.00837 (15)	−0.00425 (12)	−0.00116 (11)	−0.00341 (11)
N25	0.0144 (7)	0.0115 (7)	0.0115 (7)	−0.0048 (6)	−0.0012 (6)	−0.0038 (6)
N28	0.0149 (7)	0.0113 (7)	0.0115 (7)	−0.0049 (6)	−0.0021 (6)	−0.0041 (6)
C21	0.0177 (9)	0.0100 (8)	0.0138 (8)	−0.0040 (7)	−0.0048 (7)	−0.0032 (7)
C22	0.0183 (9)	0.0166 (9)	0.0151 (9)	−0.0029 (7)	−0.0053 (7)	−0.0062 (7)
C23	0.0198 (9)	0.0159 (9)	0.0126 (8)	−0.0035 (7)	−0.0036 (7)	−0.0047 (7)
C24	0.0199 (9)	0.0090 (8)	0.0116 (8)	−0.0048 (7)	−0.0027 (7)	−0.0035 (6)
C25	0.0204 (9)	0.0095 (8)	0.0102 (8)	−0.0062 (7)	−0.0007 (7)	−0.0042 (6)
C36	0.0160 (9)	0.0111 (8)	0.0120 (8)	−0.0063 (7)	0.0015 (7)	−0.0048 (6)
C37	0.0175 (9)	0.0174 (9)	0.0135 (8)	−0.0078 (7)	0.0013 (7)	−0.0066 (7)
C38	0.0141 (9)	0.0161 (9)	0.0173 (9)	−0.0054 (7)	0.0005 (7)	−0.0065 (7)
C39	0.0148 (8)	0.0110 (8)	0.0148 (9)	−0.0052 (7)	−0.0004 (7)	−0.0045 (7)
C40	0.0129 (8)	0.0140 (8)	0.0182 (9)	−0.0033 (7)	−0.0048 (7)	−0.0047 (7)
C251	0.0198 (9)	0.0132 (8)	0.0108 (8)	−0.0067 (7)	−0.0005 (7)	−0.0035 (7)
C252	0.0188 (9)	0.0133 (8)	0.0120 (8)	−0.0029 (7)	−0.0024 (7)	−0.0041 (7)
C253	0.0278 (10)	0.0216 (10)	0.0141 (9)	−0.0044 (8)	0.0004 (8)	−0.0068 (7)
C254	0.0254 (10)	0.0163 (9)	0.0207 (9)	−0.0064 (8)	−0.0054 (8)	−0.0070 (7)

Geometric parameters (Å, º) top

Ni1—N24	1.9497 (16)	C54—H54A	0.9800
Ni1—N22	1.9508 (16)	C54—H54B	0.9800
Ni1—N23	1.9595 (15)	C54—H54C	0.9800
Ni1—N21	1.9623 (15)	C151—C152	1.544 (2)
N21—C1	1.373 (2)	C151—H15A	0.9900
N21—C4	1.390 (2)	C151—H15B	0.9900
N22—C9	1.373 (2)	C152—C154	1.524 (2)
N22—C6	1.390 (2)	C152—C153	1.526 (3)
N23—C11	1.377 (2)	C152—H15C	1.0000
N23—C14	1.389 (2)	C153—H15D	0.9800
N24—C19	1.371 (2)	C153—H15E	0.9800
N24—C16	1.387 (2)	C153—H15F	0.9800
C1—C20	1.375 (2)	C154—H15G	0.9800
C1—C2	1.436 (2)	C154—H15H	0.9800
C2—C3	1.345 (3)	C154—H15I	0.9800
C2—H2A	0.9500	Ni2—N28ⁱ	1.9537 (16)
C3—C4	1.438 (2)	Ni2—N28	1.9537 (16)
C3—H3A	0.9500	Ni2—N25ⁱ	1.9580 (15)
C4—C5	1.387 (3)	Ni2—N25	1.9580 (15)
C5—C6	1.385 (2)	N25—C21	1.373 (2)
C5—C51	1.514 (2)	N25—C24	1.390 (2)
C6—C7	1.437 (2)	N28—C39	1.373 (2)
C7—C8	1.346 (3)	N28—C36	1.383 (2)
C7—H7A	0.9500	C21—C40	1.375 (3)
C8—C9	1.436 (2)	C21—C22	1.432 (2)
C8—H8A	0.9500	C22—C23	1.344 (3)
C9—C10	1.373 (2)	C22—H22A	0.9500
C10—C11	1.376 (2)	C23—C24	1.438 (2)
C10—H10A	0.9500	C23—H23A	0.9500
C11—C12	1.430 (2)	C24—C25	1.385 (3)
C12—C13	1.344 (3)	C25—C36ⁱ	1.388 (2)
C12—H12A	0.9500	C25—C251	1.521 (2)
C13—C14	1.436 (2)	C36—C25ⁱ	1.388 (2)
C13—H13A	0.9500	C36—C37	1.439 (2)
C14—C15	1.385 (2)	C37—C38	1.345 (3)
C15—C16	1.383 (3)	C37—H37A	0.9500
C15—C151	1.516 (2)	C38—C39	1.433 (2)
C16—C17	1.438 (2)	C38—H38A	0.9500
C17—C18	1.343 (3)	C39—C40	1.374 (2)
C17—H17A	0.9500	C40—H40A	0.9500
C18—C19	1.432 (2)	C251—C252	1.542 (2)
C18—H18A	0.9500	C251—H25B	0.9900
C19—C20	1.376 (2)	C251—H25C	0.9900
C20—H20A	0.9500	C252—C253	1.527 (2)
C51—C52	1.544 (2)	C252—C254	1.527 (2)
C51—H51A	0.9900	C252—H25D	1.0000
C51—H51B	0.9900	C253—H25E	0.9800
C52—C53	1.524 (3)	C253—H25F	0.9800
C52—C54	1.526 (2)	C253—H25G	0.9800
C52—H52A	1.0000	C254—H25H	0.9800
C53—H53A	0.9800	C254—H25I	0.9800
C53—H53B	0.9800	C254—H25J	0.9800
C53—H53C	0.9800

N24—Ni1—N22	178.64 (6)	C52—C54—H54A	109.5
N24—Ni1—N23	88.41 (6)	C52—C54—H54B	109.5
N22—Ni1—N23	91.64 (6)	H54A—C54—H54B	109.5
N24—Ni1—N21	91.53 (6)	C52—C54—H54C	109.5
N22—Ni1—N21	88.42 (6)	H54A—C54—H54C	109.5
N23—Ni1—N21	179.93 (7)	H54B—C54—H54C	109.5
C1—N21—C4	104.64 (14)	C15—C151—C152	114.61 (14)
C1—N21—Ni1	126.10 (12)	C15—C151—H15A	108.6
C4—N21—Ni1	129.22 (12)	C152—C151—H15A	108.6
C9—N22—C6	104.52 (14)	C15—C151—H15B	108.6
C9—N22—Ni1	126.38 (12)	C152—C151—H15B	108.6
C6—N22—Ni1	129.09 (12)	H15A—C151—H15B	107.6
C11—N23—C14	104.41 (14)	C154—C152—C153	111.25 (15)
C11—N23—Ni1	126.11 (12)	C154—C152—C151	108.95 (14)
C14—N23—Ni1	129.47 (12)	C153—C152—C151	112.31 (15)
C19—N24—C16	104.29 (14)	C154—C152—H15C	108.1
C19—N24—Ni1	126.62 (12)	C153—C152—H15C	108.1
C16—N24—Ni1	129.08 (12)	C151—C152—H15C	108.1
N21—C1—C20	125.99 (16)	C152—C153—H15D	109.5
N21—C1—C2	111.28 (16)	C152—C153—H15E	109.5
C20—C1—C2	122.66 (16)	H15D—C153—H15E	109.5
C3—C2—C1	106.52 (16)	C152—C153—H15F	109.5
C3—C2—H2A	126.7	H15D—C153—H15F	109.5
C1—C2—H2A	126.7	H15E—C153—H15F	109.5
C2—C3—C4	107.54 (15)	C152—C154—H15G	109.5
C2—C3—H3A	126.2	C152—C154—H15H	109.5
C4—C3—H3A	126.2	H15G—C154—H15H	109.5
C5—C4—N21	125.86 (16)	C152—C154—H15I	109.5
C5—C4—C3	124.13 (16)	H15G—C154—H15I	109.5
N21—C4—C3	110.01 (15)	H15H—C154—H15I	109.5
C6—C5—C4	120.85 (16)	N28ⁱ—Ni2—N28	180.0
C6—C5—C51	118.64 (16)	N28ⁱ—Ni2—N25ⁱ	91.69 (6)
C4—C5—C51	120.51 (16)	N28—Ni2—N25ⁱ	88.31 (6)
C5—C6—N22	126.42 (16)	N28ⁱ—Ni2—N25	88.31 (6)
C5—C6—C7	123.47 (16)	N28—Ni2—N25	91.69 (6)
N22—C6—C7	110.11 (15)	N25ⁱ—Ni2—N25	180.0
C8—C7—C6	107.54 (16)	C21—N25—C24	104.31 (15)
C8—C7—H7A	126.2	C21—N25—Ni2	126.14 (12)
C6—C7—H7A	126.2	C24—N25—Ni2	129.55 (12)
C7—C8—C9	106.44 (16)	C39—N28—C36	104.53 (14)
C7—C8—H8A	126.8	C39—N28—Ni2	126.32 (12)
C9—C8—H8A	126.8	C36—N28—Ni2	129.15 (12)
N22—C9—C10	125.99 (16)	N25—C21—C40	125.86 (16)
N22—C9—C8	111.37 (15)	N25—C21—C22	111.58 (16)
C10—C9—C8	122.63 (17)	C40—C21—C22	122.52 (17)
C9—C10—C11	123.98 (17)	C23—C22—C21	106.51 (16)
C9—C10—H10A	118.0	C23—C22—H22A	126.7
C11—C10—H10A	118.0	C21—C22—H22A	126.7
C10—C11—N23	125.79 (16)	C22—C23—C24	107.43 (16)
C10—C11—C12	122.87 (16)	C22—C23—H23A	126.3
N23—C11—C12	111.34 (15)	C24—C23—H23A	126.3
C13—C12—C11	106.63 (16)	C25—C24—N25	125.59 (16)
C13—C12—H12A	126.7	C25—C24—C23	124.25 (16)
C11—C12—H12A	126.7	N25—C24—C23	110.15 (15)
C12—C13—C14	107.52 (15)	C24—C25—C36ⁱ	120.86 (16)
C12—C13—H13A	126.2	C24—C25—C251	120.56 (16)
C14—C13—H13A	126.2	C36ⁱ—C25—C251	118.58 (16)
C15—C14—N23	125.46 (16)	N28—C36—C25ⁱ	126.47 (16)
C15—C14—C13	124.44 (16)	N28—C36—C37	110.24 (16)
N23—C14—C13	110.10 (15)	C25ⁱ—C36—C37	123.29 (16)
C16—C15—C14	121.16 (16)	C38—C37—C36	107.33 (16)
C16—C15—C151	118.16 (16)	C38—C37—H37A	126.3
C14—C15—C151	120.67 (16)	C36—C37—H37A	126.3
C15—C16—N24	126.37 (16)	C37—C38—C39	106.44 (16)
C15—C16—C17	123.36 (16)	C37—C38—H38A	126.8
N24—C16—C17	110.26 (15)	C39—C38—H38A	126.8
C18—C17—C16	107.38 (16)	N28—C39—C40	125.81 (16)
C18—C17—H17A	126.3	N28—C39—C38	111.44 (15)
C16—C17—H17A	126.3	C40—C39—C38	122.73 (17)
C17—C18—C19	106.45 (16)	C39—C40—C21	124.11 (17)
C17—C18—H18A	126.8	C39—C40—H40A	117.9
C19—C18—H18A	126.8	C21—C40—H40A	117.9
N24—C19—C20	125.87 (16)	C25—C251—C252	115.43 (14)
N24—C19—C18	111.62 (15)	C25—C251—H25B	108.4
C20—C19—C18	122.51 (17)	C252—C251—H25B	108.4
C1—C20—C19	123.85 (17)	C25—C251—H25C	108.4
C1—C20—H20A	118.1	C252—C251—H25C	108.4
C19—C20—H20A	118.1	H25B—C251—H25C	107.5
C5—C51—C52	116.05 (14)	C253—C252—C254	110.50 (15)
C5—C51—H51A	108.3	C253—C252—C251	108.62 (14)
C52—C51—H51A	108.3	C254—C252—C251	112.58 (15)
C5—C51—H51B	108.3	C253—C252—H25D	108.3
C52—C51—H51B	108.3	C254—C252—H25D	108.3
H51A—C51—H51B	107.4	C251—C252—H25D	108.3
C53—C52—C54	111.04 (15)	C252—C253—H25E	109.5
C53—C52—C51	108.59 (15)	C252—C253—H25F	109.5
C54—C52—C51	112.07 (15)	H25E—C253—H25F	109.5
C53—C52—H52A	108.3	C252—C253—H25G	109.5
C54—C52—H52A	108.3	H25E—C253—H25G	109.5
C51—C52—H52A	108.3	H25F—C253—H25G	109.5
C52—C53—H53A	109.5	C252—C254—H25H	109.5
C52—C53—H53B	109.5	C252—C254—H25I	109.5
H53A—C53—H53B	109.5	H25H—C254—H25I	109.5
C52—C53—H53C	109.5	C252—C254—H25J	109.5
H53A—C53—H53C	109.5	H25H—C254—H25J	109.5
H53B—C53—H53C	109.5	H25I—C254—H25J	109.5

N24—Ni1—N21—C1	2.07 (14)	C14—C15—C16—C17	−179.05 (15)
N22—Ni1—N21—C1	−179.29 (14)	C151—C15—C16—C17	2.0 (2)
N24—Ni1—N21—C4	−175.14 (14)	C19—N24—C16—C15	−178.49 (16)
N22—Ni1—N21—C4	3.50 (14)	Ni1—N24—C16—C15	2.6 (3)
N23—Ni1—N22—C9	−2.96 (14)	C19—N24—C16—C17	0.25 (18)
N21—Ni1—N22—C9	177.00 (14)	Ni1—N24—C16—C17	−178.67 (11)
N23—Ni1—N22—C6	176.73 (14)	C15—C16—C17—C18	178.55 (16)
N21—Ni1—N22—C6	−3.31 (14)	N24—C16—C17—C18	−0.2 (2)
N24—Ni1—N23—C11	−178.31 (14)	C16—C17—C18—C19	0.11 (19)
N22—Ni1—N23—C11	3.05 (14)	C16—N24—C19—C20	−179.83 (16)
N24—Ni1—N23—C14	0.39 (14)	Ni1—N24—C19—C20	−0.9 (2)
N22—Ni1—N23—C14	−178.25 (14)	C16—N24—C19—C18	−0.18 (18)
N23—Ni1—N24—C19	179.15 (14)	Ni1—N24—C19—C18	178.77 (11)
N21—Ni1—N24—C19	−0.81 (14)	C17—C18—C19—N24	0.0 (2)
N23—Ni1—N24—C16	−2.16 (14)	C17—C18—C19—C20	179.71 (16)
N21—Ni1—N24—C16	177.88 (14)	N21—C1—C20—C19	−0.4 (3)
C4—N21—C1—C20	175.90 (16)	C2—C1—C20—C19	176.13 (16)
Ni1—N21—C1—C20	−1.9 (2)	N24—C19—C20—C1	1.8 (3)
C4—N21—C1—C2	−0.93 (18)	C18—C19—C20—C1	−177.79 (16)
Ni1—N21—C1—C2	−178.70 (11)	C6—C5—C51—C52	−79.0 (2)
N21—C1—C2—C3	1.3 (2)	C4—C5—C51—C52	101.41 (19)
C20—C1—C2—C3	−175.68 (16)	C5—C51—C52—C53	176.87 (15)
C1—C2—C3—C4	−1.03 (19)	C5—C51—C52—C54	−60.1 (2)
C1—N21—C4—C5	−179.38 (16)	C16—C15—C151—C152	76.6 (2)
Ni1—N21—C4—C5	−1.7 (2)	C14—C15—C151—C152	−102.33 (19)
C1—N21—C4—C3	0.27 (18)	C15—C151—C152—C154	−175.11 (15)
Ni1—N21—C4—C3	177.95 (11)	C15—C151—C152—C153	61.2 (2)
C2—C3—C4—C5	−179.83 (16)	N28ⁱ—Ni2—N25—C21	−178.71 (14)
C2—C3—C4—N21	0.51 (19)	N28—Ni2—N25—C21	1.29 (14)
N21—C4—C5—C6	−1.8 (3)	N28ⁱ—Ni2—N25—C24	2.36 (14)
C3—C4—C5—C6	178.60 (16)	N28—Ni2—N25—C24	−177.64 (14)
N21—C4—C5—C51	177.76 (15)	N25ⁱ—Ni2—N28—C39	−178.68 (14)
C3—C4—C5—C51	−1.8 (3)	N25—Ni2—N28—C39	1.32 (14)
C4—C5—C6—N22	2.0 (3)	N25ⁱ—Ni2—N28—C36	1.21 (14)
C51—C5—C6—N22	−177.56 (15)	N25—Ni2—N28—C36	−178.79 (14)
C4—C5—C6—C7	−177.16 (16)	C24—N25—C21—C40	176.54 (16)
C51—C5—C6—C7	3.3 (2)	Ni2—N25—C21—C40	−2.6 (3)
C9—N22—C6—C5	−178.95 (16)	C24—N25—C21—C22	−1.09 (19)
Ni1—N22—C6—C5	1.3 (2)	Ni2—N25—C21—C22	179.76 (11)
C9—N22—C6—C7	0.32 (18)	N25—C21—C22—C23	1.4 (2)
Ni1—N22—C6—C7	−179.43 (11)	C40—C21—C22—C23	−176.30 (16)
C5—C6—C7—C8	178.30 (16)	C21—C22—C23—C24	−1.10 (19)
N22—C6—C7—C8	−0.99 (19)	C21—N25—C24—C25	179.50 (16)
C6—C7—C8—C9	1.20 (19)	Ni2—N25—C24—C25	−1.4 (2)
C6—N22—C9—C10	−178.37 (16)	C21—N25—C24—C23	0.38 (18)
Ni1—N22—C9—C10	1.4 (2)	Ni2—N25—C24—C23	179.49 (11)
C6—N22—C9—C8	0.44 (18)	C22—C23—C24—C25	−178.65 (16)
Ni1—N22—C9—C8	−179.81 (11)	C22—C23—C24—N25	0.5 (2)
C7—C8—C9—N22	−1.1 (2)	N25—C24—C25—C36ⁱ	−1.6 (3)
C7—C8—C9—C10	177.79 (16)	C23—C24—C25—C36ⁱ	177.35 (16)
N22—C9—C10—C11	1.4 (3)	N25—C24—C25—C251	178.48 (15)
C8—C9—C10—C11	−177.30 (16)	C23—C24—C25—C251	−2.5 (3)
C9—C10—C11—N23	−1.3 (3)	C39—N28—C36—C25ⁱ	−179.01 (16)
C9—C10—C11—C12	178.34 (16)	Ni2—N28—C36—C25ⁱ	1.1 (3)
C14—N23—C11—C10	179.45 (16)	C39—N28—C36—C37	0.88 (18)
Ni1—N23—C11—C10	−1.6 (2)	Ni2—N28—C36—C37	−179.03 (11)
C14—N23—C11—C12	−0.20 (18)	N28—C36—C37—C38	−0.1 (2)
Ni1—N23—C11—C12	178.77 (11)	C25ⁱ—C36—C37—C38	179.78 (16)
C10—C11—C12—C13	−179.53 (16)	C36—C37—C38—C39	−0.68 (19)
N23—C11—C12—C13	0.1 (2)	C36—N28—C39—C40	177.03 (16)
C11—C12—C13—C14	0.00 (19)	Ni2—N28—C39—C40	−3.1 (2)
C11—N23—C14—C15	−179.85 (16)	C36—N28—C39—C38	−1.32 (19)
Ni1—N23—C14—C15	1.2 (2)	Ni2—N28—C39—C38	178.59 (11)
C11—N23—C14—C13	0.20 (18)	C37—C38—C39—N28	1.3 (2)
Ni1—N23—C14—C13	−178.72 (11)	C37—C38—C39—C40	−177.12 (16)
C12—C13—C14—C15	179.92 (16)	N28—C39—C40—C21	2.0 (3)
C12—C13—C14—N23	−0.13 (19)	C38—C39—C40—C21	−179.87 (16)
N23—C14—C15—C16	−1.5 (3)	N25—C21—C40—C39	1.0 (3)
C13—C14—C15—C16	178.50 (16)	C22—C21—C40—C39	178.43 (16)
N23—C14—C15—C151	177.48 (15)	C24—C25—C251—C252	100.67 (19)
C13—C14—C15—C151	−2.6 (3)	C36ⁱ—C25—C251—C252	−79.2 (2)
C14—C15—C16—N24	−0.5 (3)	C25—C251—C252—C253	177.00 (15)
C151—C15—C16—N24	−179.42 (15)	C25—C251—C252—C254	−60.3 (2)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₂₈H₂₈N₄)]
M_r	479.25
Crystal system, space group	Triclinic, P1
Temperature (K)	90
a, b, c (Å)	9.951 (2), 13.197 (3), 13.700 (3)
α, β, γ (°)	73.03 (3), 75.27 (3), 73.39 (3)
V (Å³)	1620.1 (7)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.20 × 0.15 × 0.01

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.837, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	21454, 7431, 5881
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.096, 1.04
No. of reflections	7431
No. of parameters	454
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.38

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N24	1.9497 (16)	Ni1—N21	1.9623 (15)
Ni1—N22	1.9508 (16)	Ni2—N28	1.9537 (16)
Ni1—N23	1.9595 (15)	Ni2—N25	1.9580 (15)

Comparison of Ni^II 5,15-dialkylporphyrins (Å, °). top

Δ is the deviation from the least-squares-plane of the 24 macrocycle atoms and N—Ni—Nadj is the angle between neighboring pyrrole units.

Alkyl residue	tert-Butyl	Isopropyl	iso-Butyl	none
Ni—N	1.897 (2)	1.930 (2)	1.955 (2)	1.951 (2)
Δ	0.4	0.26	0.04	0.02
N—Ni—N adj	92.3, 87.7	91.8, 88.2	91.6, 88.4	90, 90
Reference	Song et al. (1996)	Song et al. (1998)	This work	Jentzen et al. (1996)

Acknowledgements

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

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