[meso-5,10,15,20-Tetra­kis(3-methyl­thio­phen-2-yl)porphyrinato-κ4N,N′,N′′,N′′′]nickel(II) benzene hemisolvate

Prasath, R.; Bhavana, P.; Gupta, S.K.; Butcher, R.J.

doi:10.1107/S1600536813030468

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages m652-m653

doi:10.1107/S1600536813030468

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[meso-5,10,15,20-Tetrakis(3-methylthiophen-2-yl)porphyrinato-κ⁴N,N′,N′′,N′′′]nickel(II) benzene hemisolvate

R. Prasath,^a P. Bhavana,^a Sushil K. Gupta ^b and Ray J. Butcher ^c ^*

^aDepartment of Chemistry, BITS, Pilani – K. K. Birla Goa Campus, Goa 403 726, India, ^bSchool of Studies in Chemistry, Jiwaji University, Gwalior 474 011, India, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 29 October 2013; accepted 6 November 2013; online 13 November 2013)

In the title compound, [Ni(C₄₀H₂₈N₄S₄)]·0.5C₆H₆, the Ni^II atom is in a square-planar geometry defined by four pyrrole N atoms. There is considerable buckling in the porphyrin ring with the dihedral angles between the N₄ donor set and the pyrrole rings being in the range 16.24 (5)–22.47 (5)°. Each of the six-membered chelate rings is twisted about an Ni—N bond and the dihedral angles between diagonally opposite chelate rings are 21.36 (4) and 23.87 (4)°; each pair of rings is oriented in opposite directions. The methylthienyl rings are twisted out of the plane of the central N₄ core with dihedral angles in the range 75.98 (2)–88.70 (5)°. All four methylthienyl groups are disordered over two sets of sites, as is commonly found with such groups, with occupancies of 0.553 (8):0.447 (8), 0.579 (7):0.421 (7), 0.796 (6):0.204 (6) and 0.956 (7):0.044 (7). The benzene solvent molecule was found to be present in half-occupancy.

CCDC reference: 970588

Related literature

For related structures, see: Prasath et al. (2012a ,b ); Purushothaman et al. (2001 ); Song et al. (2005 ). For the synthesis, see: Sun et al. (2005 ); Prasath et al. (2012a). For general background and potential applications of thienylporphyrins, see: Boyle et al. (2010 ); Rochford et al. (2008 ); Chen et al. (2010 ); Friedlein et al. (2005 ); Wallin et al. (2006 ).

Experimental

Crystal data

[Ni(C₄₀H₂₈N₄S₄)]·0.5C₆H₆
M_r = 790.67
Orthorhombic, P n a 2₁
a = 12.4854 (6) Å
b = 11.3906 (5) Å
c = 28.365 (2) Å
V = 4034.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 295 K
0.39 × 0.22 × 0.05 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ), using a multi-faceted crystal model (Clark & Reid (1995 )] T_min = 0.830, T_max = 0.965
12922 measured reflections
5674 independent reflections
2720 reflections with I > 2σ(I)
R_int = 0.091

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.240
S = 0.99
5674 reflections
562 parameters
709 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 55% of Friedels measured
Absolute structure parameter: 0.35 (4)

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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

CCDC reference: 970588

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813030468/zs2280sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030468/zs2280Isup2.hkl

checkCIF report

Comment top

Thienylporphyrins are of growing interest owing to physiochemical (Boyle et al., 2010), energy transfer (Wallin et al., 2006), thin films (Friedlein et al.,2005), electrochemical (Chen et al., 2010) and photophysical (Rochford et al., 2008) properties. In continuation of our work on thienylpophyrins (Prasath et al., 2012a, 2012b; Purushothaman et al., 2001), we report herein the crystal structure of 5,10,15,20-tetrakis(3-methylthien-2-yl)porphyrinatonickel(II) hemi(benzene) solvate (Fig.1). The 24-membered porphyrin moiety of the title compound is planar with a mean deviation of 0.0389 (3) Å. The Ni^II atom (Fig.1) is in a square planar geometry defined by four pyrrole-N atoms, Table 1. These bond lengths are in agreement with those found in other nickel porphyrin compounds (Prasath et al., 2012a,b; Purushothaman et al., 2001; Song et al., 2005). There is considerable buckling in the porphyrin ring with the dihedral angles between the N₄ donor set and the N1—N4 pyrrole rings of 16.24 (5), 20.87 (5), 20.52 (4) and 22.47 (5)°, respectively. Each of the six–membered chelate rings is twisted about an Ni–N bond and the dihedral angles between diagonally opposite chelate rings are 21.36 (4) and 23.87 (4)°; each pair of rings is oriented in opposite directions. The usual ruffling in the structure is further indicated by the deviations of C5, C15, C25 and C35 from the NiN₄ plane [C5 (-0.4076 Å), C15 (0.4171 Å), C25 (-0.3973 Å), C35 (0.3878 Å)]. The methylthienyl rings are twisted out of the plne of the central N₄ core with dihedral angles being 75.98 (2), 88.70 (5), 84.60 (5) and 85.44 (4)°, respectively. All four methylthienyl groups are disordered over two sets of sites, as is commonly found with such groups, with occupancies of 0.553 (8), 0.447 (8); 0.579 (7), 0.421 (7); 0.796 (6), 0.204 (6); and 0.956 (7), 0.044 (7), respectively. The benzene solvent molecule was found to be present in half occupancy.

Related literature top

For related structures, see: Prasath et al. (2012a,b); Purushothaman et al. (2001); Song et al. (2005). For the synthesis, see: Sun et al. (2005); Prasath et al. (2012a). For general background and potential applications of thienylporphyrins, see: Boyle et al. (2010); Rochford et al. (2008); Chen et al. (2010); Friedlein et al. (2005); Wallin et al. (2006).

Experimental top

[meso-5,10,15,20-Tetrakis(3-methylthien-2-yl)porphyrinato- κ⁴N,N',N'',N''']nickel(II) hemi(benzene) solvate was synthesized as reported in the literature (Sun et al., 2005; Prasath et al., 2012a). Recrystallization by slow evaporation of a chloroform/benzene solution yielded purple crystals. Yield: 80%.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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. Diagram of the title compound showing the atom labeling scheme and 30% probability displacement ellipsoids showing the major component only, and including the benzene solvate molecule.
	Fig. 2. Molecular packing of Ni(C₄₀H₂₈N₄S₄)·0.5(C₆H₆) viewed along the c axis.

[meso-5,10,15,20-Tetrakis(3-methylthiophen-2-yl)porphyrinato-κ⁴N,N',N'',N''']nickel(II) benzene hemisolvate top

Crystal data top

[Ni(C₄₀H₂₈N₄S₄)]·0.5C₆H₆	F(000) = 1636
M_r = 790.67	D_x = 1.302 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2n	Cell parameters from 1901 reflections
a = 12.4854 (6) Å	θ = 3.2–28.5°
b = 11.3906 (5) Å	µ = 0.72 mm⁻¹
c = 28.365 (2) Å	T = 295 K
V = 4034.0 (4) Å³	Prism, dark purple
Z = 4	0.39 × 0.22 × 0.05 mm

Data collection top

Agilent Xcalibur (Ruby, Gemini) diffractometer	5674 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2720 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
Detector resolution: 10.5081 pixels mm^-1	θ_max = 25.3°, θ_min = 3.2°
ω scans	h = −14→14
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model (Clark & Reid (1995)]	k = −13→12
T_min = 0.830, T_max = 0.965	l = −20→34
12922 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.077	H-atom parameters constrained
wR(F²) = 0.240	w = 1/[σ²(F_o²) + (0.1154P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.005
5674 reflections	Δρ_max = 0.32 e Å⁻³
562 parameters	Δρ_min = −0.24 e Å⁻³
709 restraints	Absolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.35 (4)

Crystal data top

[Ni(C₄₀H₂₈N₄S₄)]·0.5C₆H₆	V = 4034.0 (4) Å³
M_r = 790.67	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 12.4854 (6) Å	µ = 0.72 mm⁻¹
b = 11.3906 (5) Å	T = 295 K
c = 28.365 (2) Å	0.39 × 0.22 × 0.05 mm

Data collection top

Agilent Xcalibur (Ruby, Gemini) diffractometer	5674 independent reflections
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model (Clark & Reid (1995)]	2720 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.965	R_int = 0.091
12922 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	H-atom parameters constrained
wR(F²) = 0.240	Δρ_max = 0.32 e Å⁻³
S = 0.99	Δρ_min = −0.24 e Å⁻³
5674 reflections	Absolute structure: Flack (1983), ???? Friedel pairs
562 parameters	Absolute structure parameter: 0.35 (4)
709 restraints

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)
Ni	0.14310 (8)	0.51145 (8)	0.50592 (10)	0.0744 (4)
N1	0.0343 (6)	0.4084 (7)	0.4852 (3)	0.081 (2)
N2	0.0723 (6)	0.5254 (6)	0.5661 (3)	0.071 (2)
N3	0.2520 (6)	0.6232 (6)	0.5259 (3)	0.083 (3)
N4	0.2174 (6)	0.4911 (6)	0.4466 (3)	0.079 (2)
C1	0.0111 (8)	0.3714 (9)	0.4404 (5)	0.090 (3)
C2	−0.0831 (10)	0.3000 (11)	0.4370 (6)	0.127 (5)
H2A	−0.1124	0.2670	0.4099	0.152*
C3	−0.1200 (9)	0.2909 (11)	0.4815 (5)	0.112 (4)
H3A	−0.1801	0.2494	0.4914	0.135*
C4	−0.0495 (8)	0.3568 (8)	0.5105 (5)	0.092 (3)
C5	−0.0628 (7)	0.3698 (8)	0.5590 (4)	0.089 (3)
C6	−0.0068 (8)	0.4544 (9)	0.5839 (4)	0.079 (3)
C7	−0.0271 (9)	0.4850 (9)	0.6326 (4)	0.086 (3)
H7A	−0.0735	0.4470	0.6532	0.104*
C8	0.0330 (8)	0.5775 (8)	0.6420 (5)	0.084 (3)
H8A	0.0326	0.6196	0.6701	0.101*
C9	0.0978 (8)	0.6019 (8)	0.6027 (4)	0.078 (3)
C10	0.1738 (8)	0.6880 (7)	0.6011 (3)	0.087 (3)
C11	0.2458 (9)	0.6990 (9)	0.5649 (5)	0.095 (4)
C12	0.3381 (11)	0.7722 (10)	0.5651 (5)	0.122 (5)
H12A	0.3523	0.8327	0.5862	0.146*
C13	0.4007 (10)	0.7378 (10)	0.5293 (5)	0.116 (5)
H13A	0.4681	0.7678	0.5223	0.139*
C14	0.3462 (8)	0.6468 (8)	0.5035 (6)	0.091 (3)
C15	0.3855 (6)	0.5940 (9)	0.4632 (4)	0.088 (3)
C16	0.3189 (9)	0.5242 (9)	0.4349 (5)	0.088 (3)
C17	0.3435 (9)	0.4928 (9)	0.3878 (5)	0.094 (3)
H17A	0.4081	0.5049	0.3722	0.112*
C18	0.2570 (9)	0.4431 (10)	0.3705 (5)	0.094 (3)
H18A	0.2487	0.4158	0.3398	0.113*
C19	0.1805 (9)	0.4385 (9)	0.4056 (4)	0.088 (3)
C20	0.0775 (9)	0.3858 (8)	0.4025 (3)	0.095 (4)
S1A	−0.2681 (4)	0.3838 (5)	0.6016 (2)	0.146 (2)	0.796 (6)
C21A	−0.1537 (7)	0.3093 (9)	0.5828 (4)	0.094 (4)	0.796 (6)
C22A	−0.1604 (11)	0.1952 (12)	0.5935 (5)	0.138 (6)	0.796 (6)
C23A	−0.2587 (11)	0.1713 (12)	0.6198 (6)	0.118 (5)	0.796 (6)
H23A	−0.2741	0.0983	0.6328	0.142*	0.796 (6)
C24A	−0.3192 (13)	0.2555 (12)	0.6231 (7)	0.141 (6)	0.796 (6)
H24A	−0.3873	0.2501	0.6363	0.170*	0.796 (6)
C25A	−0.0842 (11)	0.1202 (10)	0.5797 (6)	0.104 (4)	0.796 (6)
H25A	−0.0163	0.1452	0.5919	0.156*	0.796 (6)
H25B	−0.0813	0.1185	0.5459	0.156*	0.796 (6)
H25C	−0.1005	0.0431	0.5913	0.156*	0.796 (6)
S1B	−0.0775 (13)	0.1502 (16)	0.6113 (8)	0.146 (2)	0.204 (6)
C21B	−0.1258 (15)	0.2723 (17)	0.5803 (10)	0.094 (4)	0.204 (6)
C22B	−0.2334 (17)	0.270 (2)	0.5802 (11)	0.138 (6)	0.204 (6)
C23B	−0.2729 (18)	0.168 (3)	0.6064 (17)	0.118 (5)	0.204 (6)
H23B	−0.3454	0.1533	0.6111	0.142*	0.204 (6)
C24B	−0.2020 (19)	0.103 (3)	0.6217 (17)	0.141 (6)	0.204 (6)
H24B	−0.2166	0.0339	0.6377	0.170*	0.204 (6)
C25B	−0.293 (3)	0.351 (3)	0.5566 (16)	0.104 (4)	0.204 (6)
H25D	−0.2679	0.3564	0.5247	0.156*	0.204 (6)
H25E	−0.2855	0.4259	0.5717	0.156*	0.204 (6)
H25F	−0.3666	0.3277	0.5568	0.156*	0.204 (6)
S2A	0.2984 (7)	0.7338 (6)	0.6854 (3)	0.142 (2)	0.579 (7)
C26A	0.1993 (12)	0.7618 (11)	0.6429 (4)	0.085 (4)	0.579 (7)
C27A	0.1426 (12)	0.8552 (14)	0.6570 (6)	0.115 (6)	0.579 (7)
C28A	0.1804 (16)	0.8939 (17)	0.7031 (7)	0.121 (6)	0.579 (7)
H28A	0.1452	0.9517	0.7202	0.145*	0.579 (7)
C29A	0.2619 (14)	0.8453 (14)	0.7179 (6)	0.104 (5)	0.579 (7)
H29A	0.2987	0.8695	0.7447	0.124*	0.579 (7)
C30A	0.0552 (14)	0.8893 (17)	0.6305 (7)	0.089 (5)	0.579 (7)
H30A	0.0728	0.9587	0.6129	0.133*	0.579 (7)
H30B	−0.0042	0.9053	0.6510	0.133*	0.579 (7)
H30C	0.0362	0.8274	0.6090	0.133*	0.579 (7)
S2B	0.0856 (10)	0.8896 (10)	0.6463 (5)	0.142 (2)	0.421 (7)
C26B	0.1713 (15)	0.7704 (13)	0.6416 (5)	0.085 (4)	0.421 (7)
C27B	0.2416 (14)	0.7757 (15)	0.6770 (7)	0.115 (6)	0.421 (7)
C28B	0.226 (2)	0.879 (2)	0.7063 (9)	0.121 (6)	0.421 (7)
H28B	0.2692	0.8978	0.7318	0.145*	0.421 (7)
C29B	0.1483 (17)	0.9389 (18)	0.6937 (8)	0.104 (5)	0.421 (7)
H29B	0.1270	1.0064	0.7096	0.124*	0.421 (7)
C30B	0.3154 (19)	0.6871 (19)	0.6832 (11)	0.089 (5)	0.421 (7)
H30D	0.3127	0.6345	0.6568	0.133*	0.421 (7)
H30E	0.2991	0.6448	0.7115	0.133*	0.421 (7)
H30F	0.3859	0.7203	0.6855	0.133*	0.421 (7)
S3A	0.5088 (8)	0.7604 (12)	0.4087 (6)	0.181 (4)	0.447 (8)
C31A	0.4899 (8)	0.6423 (15)	0.4470 (7)	0.101 (4)	0.447 (8)
C32A	0.5847 (14)	0.5906 (15)	0.4552 (7)	0.119 (7)	0.447 (8)
C33A	0.6712 (14)	0.652 (2)	0.4307 (11)	0.124 (6)	0.447 (8)
H33A	0.7432	0.6355	0.4355	0.149*	0.447 (8)
C34A	0.6397 (13)	0.729 (2)	0.4033 (9)	0.122 (6)	0.447 (8)
H34A	0.6843	0.7657	0.3816	0.147*	0.447 (8)
C35A	0.588 (2)	0.4925 (18)	0.4840 (9)	0.089 (5)	0.447 (8)
H35A	0.6399	0.4382	0.4723	0.133*	0.447 (8)
H35B	0.5184	0.4557	0.4842	0.133*	0.447 (8)
H35C	0.6063	0.5156	0.5155	0.133*	0.447 (8)
S3B	0.6010 (8)	0.5209 (9)	0.4721 (5)	0.181 (4)	0.553 (8)
C31B	0.4997 (7)	0.6126 (14)	0.4503 (7)	0.101 (4)	0.553 (8)
C32B	0.5424 (12)	0.7030 (14)	0.4258 (6)	0.119 (7)	0.553 (8)
C33B	0.6590 (12)	0.6905 (19)	0.4249 (10)	0.124 (6)	0.553 (8)
H33B	0.7033	0.7430	0.4090	0.149*	0.553 (8)
C34B	0.6949 (13)	0.6042 (16)	0.4469 (8)	0.122 (6)	0.553 (8)
H34B	0.7676	0.5878	0.4492	0.147*	0.553 (8)
C35B	0.4711 (15)	0.7776 (17)	0.4026 (8)	0.089 (5)	0.553 (8)
H35D	0.4266	0.7325	0.3817	0.133*	0.553 (8)
H35E	0.5105	0.8346	0.3847	0.133*	0.553 (8)
H35F	0.4269	0.8169	0.4254	0.133*	0.553 (8)
S4A	−0.0458 (4)	0.4210 (5)	0.3214 (2)	0.168 (2)	0.956 (7)
C36A	0.0449 (8)	0.3410 (9)	0.3554 (3)	0.108 (4)	0.956 (7)
C37A	0.0649 (9)	0.2366 (10)	0.3346 (4)	0.122 (4)	0.956 (7)
C38A	0.0050 (11)	0.2233 (13)	0.2904 (5)	0.141 (5)	0.956 (7)
H38A	0.0103	0.1578	0.2710	0.169*	0.956 (7)
C39A	−0.0527 (11)	0.3077 (12)	0.2819 (5)	0.143 (5)	0.956 (7)
H39A	−0.0974	0.3100	0.2556	0.172*	0.956 (7)
C40A	0.1352 (11)	0.1616 (11)	0.3512 (6)	0.135 (5)	0.956 (7)
H40A	0.1512	0.1806	0.3834	0.203*	0.956 (7)
H40B	0.1996	0.1657	0.3328	0.203*	0.956 (7)
H40C	0.1063	0.0836	0.3496	0.203*	0.956 (7)
S4B	0.119 (5)	0.139 (3)	0.3825 (12)	0.168 (2)	0.044 (7)
C36B	0.090 (5)	0.286 (2)	0.3691 (9)	0.108 (4)	0.044 (7)
C37B	0.061 (5)	0.294 (2)	0.3237 (11)	0.122 (4)	0.044 (7)
C38B	0.063 (8)	0.178 (3)	0.3009 (14)	0.141 (5)	0.044 (7)
H38B	0.0439	0.1669	0.2695	0.169*	0.044 (7)
C39B	0.091 (8)	0.098 (3)	0.3271 (16)	0.143 (5)	0.044 (7)
H39B	0.0971	0.0210	0.3170	0.172*	0.044 (7)
C40B	0.035 (8)	0.400 (4)	0.305 (2)	0.135 (5)	0.044 (7)
H40D	−0.0190	0.4370	0.3239	0.203*	0.044 (7)
H40E	0.0071	0.3888	0.2734	0.203*	0.044 (7)
H40F	0.0972	0.4486	0.3035	0.203*	0.044 (7)
C1S	0.136 (3)	0.662 (2)	0.2600 (11)	0.167 (11)	0.50
H1SA	0.1119	0.5848	0.2596	0.200*	0.50
C2S	0.0717 (19)	0.751 (3)	0.2425 (12)	0.264 (18)	0.50
H2SA	0.0043	0.7341	0.2304	0.316*	0.50
C3S	0.108 (2)	0.867 (3)	0.2431 (13)	0.31 (2)	0.50
H3SA	0.0649	0.9266	0.2314	0.371*	0.50
C4S	0.209 (3)	0.893 (2)	0.2612 (11)	0.169 (12)	0.50
H4SA	0.2330	0.9699	0.2616	0.203*	0.50
C5S	0.273 (2)	0.803 (3)	0.2786 (12)	0.251 (18)	0.50
H5SA	0.3406	0.8205	0.2907	0.301*	0.50
C6S	0.237 (2)	0.688 (3)	0.2780 (12)	0.276 (19)	0.50
H6SA	0.2801	0.6280	0.2897	0.332*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0721 (6)	0.0712 (6)	0.0800 (8)	−0.0072 (5)	−0.0074 (8)	−0.0046 (9)
N1	0.079 (5)	0.090 (5)	0.074 (6)	−0.014 (4)	−0.011 (4)	−0.026 (4)
N2	0.066 (4)	0.065 (4)	0.082 (6)	−0.010 (4)	−0.006 (4)	0.000 (4)
N3	0.079 (5)	0.078 (5)	0.091 (7)	−0.022 (4)	−0.004 (5)	0.006 (4)
N4	0.070 (5)	0.083 (5)	0.082 (7)	−0.005 (4)	−0.004 (5)	−0.008 (5)
C1	0.068 (6)	0.096 (7)	0.108 (10)	−0.020 (6)	0.013 (7)	−0.015 (7)
C2	0.125 (10)	0.130 (10)	0.125 (13)	−0.056 (9)	−0.016 (9)	−0.028 (9)
C3	0.090 (7)	0.143 (10)	0.103 (11)	−0.054 (7)	0.014 (7)	−0.017 (8)
C4	0.082 (6)	0.098 (6)	0.096 (9)	−0.027 (5)	0.000 (8)	−0.018 (8)
C5	0.083 (7)	0.081 (6)	0.102 (10)	−0.019 (6)	0.012 (7)	−0.011 (7)
C6	0.071 (6)	0.084 (6)	0.083 (9)	−0.004 (5)	0.000 (6)	0.001 (6)
C7	0.098 (7)	0.085 (6)	0.076 (8)	0.012 (6)	0.012 (6)	0.012 (6)
C8	0.091 (7)	0.060 (5)	0.101 (9)	−0.009 (5)	0.007 (7)	−0.009 (6)
C9	0.083 (6)	0.070 (6)	0.080 (8)	−0.004 (5)	−0.003 (6)	0.000 (6)
C10	0.086 (7)	0.078 (6)	0.098 (9)	−0.019 (6)	0.014 (6)	−0.008 (6)
C11	0.105 (8)	0.074 (6)	0.107 (11)	−0.021 (6)	−0.004 (7)	−0.017 (7)
C12	0.150 (11)	0.107 (8)	0.107 (11)	−0.069 (8)	0.033 (9)	−0.027 (8)
C13	0.111 (9)	0.124 (9)	0.113 (12)	−0.044 (8)	−0.001 (8)	−0.029 (8)
C14	0.081 (6)	0.089 (5)	0.103 (9)	−0.024 (5)	−0.009 (8)	−0.020 (9)
C15	0.076 (6)	0.100 (7)	0.087 (9)	−0.018 (6)	0.002 (6)	0.001 (7)
C16	0.084 (7)	0.081 (6)	0.100 (10)	0.006 (6)	0.004 (7)	0.001 (6)
C17	0.077 (7)	0.112 (8)	0.092 (10)	−0.003 (6)	0.001 (6)	0.002 (7)
C18	0.079 (7)	0.126 (8)	0.078 (9)	−0.012 (7)	0.010 (6)	−0.008 (7)
C19	0.101 (8)	0.093 (6)	0.069 (8)	−0.020 (6)	−0.009 (7)	−0.008 (6)
C20	0.089 (7)	0.095 (7)	0.102 (10)	−0.001 (6)	−0.008 (8)	−0.022 (7)
S1A	0.123 (3)	0.157 (3)	0.159 (4)	−0.008 (3)	0.028 (3)	−0.013 (3)
C21A	0.099 (6)	0.086 (6)	0.095 (7)	−0.008 (5)	−0.002 (5)	−0.004 (5)
C22A	0.131 (8)	0.142 (8)	0.141 (9)	−0.005 (6)	0.000 (6)	0.004 (6)
C23A	0.116 (7)	0.118 (6)	0.121 (8)	−0.030 (5)	−0.001 (6)	0.001 (6)
C24A	0.139 (8)	0.140 (8)	0.145 (8)	−0.011 (6)	0.006 (6)	−0.003 (6)
C25A	0.121 (7)	0.083 (6)	0.108 (7)	−0.016 (5)	−0.002 (6)	−0.014 (5)
S1B	0.123 (3)	0.157 (3)	0.159 (4)	−0.008 (3)	0.028 (3)	−0.013 (3)
C21B	0.099 (6)	0.086 (6)	0.095 (7)	−0.008 (5)	−0.002 (5)	−0.004 (5)
C22B	0.131 (8)	0.142 (8)	0.141 (9)	−0.005 (6)	0.000 (6)	0.004 (6)
C23B	0.116 (7)	0.118 (6)	0.121 (8)	−0.030 (5)	−0.001 (6)	0.001 (6)
C24B	0.139 (8)	0.140 (8)	0.145 (8)	−0.011 (6)	0.006 (6)	−0.003 (6)
C25B	0.121 (7)	0.083 (6)	0.108 (7)	−0.016 (5)	−0.002 (6)	−0.014 (5)
S2A	0.160 (4)	0.128 (4)	0.136 (5)	−0.004 (4)	−0.006 (4)	−0.021 (4)
C26A	0.075 (6)	0.086 (5)	0.093 (6)	−0.003 (5)	0.010 (5)	−0.012 (5)
C27A	0.120 (8)	0.114 (8)	0.112 (9)	−0.002 (6)	−0.007 (6)	−0.005 (6)
C28A	0.122 (9)	0.119 (7)	0.121 (8)	0.003 (6)	−0.005 (6)	−0.005 (6)
C29A	0.110 (7)	0.103 (7)	0.098 (8)	−0.004 (6)	0.005 (6)	−0.005 (6)
C30A	0.099 (7)	0.083 (6)	0.085 (8)	0.002 (6)	−0.015 (6)	−0.010 (6)
S2B	0.160 (4)	0.128 (4)	0.136 (5)	−0.004 (4)	−0.006 (4)	−0.021 (4)
C26B	0.075 (6)	0.086 (5)	0.093 (6)	−0.003 (5)	0.010 (5)	−0.012 (5)
C27B	0.120 (8)	0.114 (8)	0.112 (9)	−0.002 (6)	−0.007 (6)	−0.005 (6)
C28B	0.122 (9)	0.119 (7)	0.121 (8)	0.003 (6)	−0.005 (6)	−0.005 (6)
C29B	0.110 (7)	0.103 (7)	0.098 (8)	−0.004 (6)	0.005 (6)	−0.005 (6)
C30B	0.099 (7)	0.083 (6)	0.085 (8)	0.002 (6)	−0.015 (6)	−0.010 (6)
S3A	0.104 (4)	0.212 (7)	0.226 (9)	−0.015 (5)	0.032 (5)	0.073 (7)
C31A	0.098 (6)	0.099 (7)	0.107 (7)	0.001 (5)	0.003 (5)	−0.001 (6)
C32A	0.114 (8)	0.123 (8)	0.120 (9)	−0.006 (6)	0.009 (6)	−0.004 (6)
C33A	0.122 (7)	0.122 (8)	0.130 (8)	−0.003 (6)	−0.001 (6)	0.002 (6)
C34A	0.114 (8)	0.129 (8)	0.124 (9)	−0.010 (6)	0.003 (6)	0.003 (6)
C35A	0.079 (7)	0.094 (7)	0.094 (8)	−0.010 (6)	0.006 (6)	0.013 (6)
S3B	0.104 (4)	0.212 (7)	0.226 (9)	−0.015 (5)	0.032 (5)	0.073 (7)
C31B	0.098 (6)	0.099 (7)	0.107 (7)	0.001 (5)	0.003 (5)	−0.001 (6)
C32B	0.114 (8)	0.123 (8)	0.120 (9)	−0.006 (6)	0.009 (6)	−0.004 (6)
C33B	0.122 (7)	0.122 (8)	0.130 (8)	−0.003 (6)	−0.001 (6)	0.002 (6)
C34B	0.114 (8)	0.129 (8)	0.124 (9)	−0.010 (6)	0.003 (6)	0.003 (6)
C35B	0.079 (7)	0.094 (7)	0.094 (8)	−0.010 (6)	0.006 (6)	0.013 (6)
S4A	0.163 (4)	0.200 (4)	0.141 (4)	−0.030 (3)	−0.040 (3)	0.007 (3)
C36A	0.099 (6)	0.120 (6)	0.105 (7)	−0.015 (5)	−0.008 (5)	−0.002 (5)
C37A	0.130 (6)	0.128 (7)	0.109 (7)	−0.019 (6)	−0.010 (6)	−0.012 (6)
C38A	0.140 (7)	0.153 (7)	0.131 (8)	−0.011 (6)	−0.004 (6)	−0.017 (6)
C39A	0.147 (7)	0.150 (7)	0.133 (8)	−0.016 (6)	−0.008 (6)	−0.007 (6)
C40A	0.141 (7)	0.129 (6)	0.135 (8)	−0.002 (6)	0.016 (6)	−0.033 (6)
S4B	0.163 (4)	0.200 (4)	0.141 (4)	−0.030 (3)	−0.040 (3)	0.007 (3)
C36B	0.099 (6)	0.120 (6)	0.105 (7)	−0.015 (5)	−0.008 (5)	−0.002 (5)
C37B	0.130 (6)	0.128 (7)	0.109 (7)	−0.019 (6)	−0.010 (6)	−0.012 (6)
C38B	0.140 (7)	0.153 (7)	0.131 (8)	−0.011 (6)	−0.004 (6)	−0.017 (6)
C39B	0.147 (7)	0.150 (7)	0.133 (8)	−0.016 (6)	−0.008 (6)	−0.007 (6)
C40B	0.141 (7)	0.129 (6)	0.135 (8)	−0.002 (6)	0.016 (6)	−0.033 (6)
C1S	0.176 (14)	0.156 (13)	0.167 (14)	−0.006 (9)	−0.001 (9)	−0.003 (9)
C2S	0.263 (19)	0.26 (2)	0.26 (2)	0.000 (10)	−0.001 (10)	−0.002 (10)
C3S	0.31 (2)	0.31 (2)	0.31 (2)	0.007 (10)	−0.002 (10)	0.002 (10)
C4S	0.176 (14)	0.156 (13)	0.174 (15)	0.000 (9)	−0.007 (9)	−0.007 (9)
C5S	0.248 (19)	0.254 (19)	0.25 (2)	−0.002 (10)	0.000 (10)	−0.004 (10)
C6S	0.28 (2)	0.27 (2)	0.28 (2)	0.005 (10)	0.006 (10)	−0.001 (10)

Geometric parameters (Å, º) top

Ni—N1	1.888 (8)	C27A—C28A	1.458 (15)
Ni—N2	1.930 (9)	C28A—C29A	1.232 (17)
Ni—N4	1.936 (9)	C28A—H28A	0.9300
Ni—N3	1.948 (8)	C29A—H29A	0.9300
N1—C1	1.371 (15)	C30A—H30A	0.9600
N1—C4	1.397 (14)	C30A—H30B	0.9600
N2—C6	1.372 (12)	C30A—H30C	0.9600
N2—C9	1.391 (13)	S2B—C29B	1.654 (16)
N3—C14	1.364 (13)	S2B—C26B	1.734 (14)
N3—C11	1.404 (14)	C26B—C27B	1.334 (16)
N4—C16	1.363 (13)	C27B—C30B	1.378 (16)
N4—C19	1.386 (14)	C27B—C28B	1.454 (16)
C1—C20	1.367 (15)	C28B—C29B	1.237 (18)
C1—C2	1.433 (15)	C28B—H28B	0.9300
C2—C3	1.350 (18)	C29B—H29B	0.9300
C2—H2A	0.9300	C30B—H30D	0.9600
C3—C4	1.419 (16)	C30B—H30E	0.9600
C3—H3A	0.9300	C30B—H30F	0.9600
C4—C5	1.396 (16)	S3A—C34A	1.680 (15)
C5—C6	1.383 (14)	S3A—C31A	1.746 (14)
C5—C21B	1.488 (7)	C31A—C32A	1.342 (16)
C5—C21A	1.489 (6)	C32A—C35A	1.384 (16)
C6—C7	1.448 (16)	C32A—C33A	1.464 (16)
C7—C8	1.321 (13)	C33A—C34A	1.234 (18)
C7—H7A	0.9300	C33A—H33A	0.9300
C8—C9	1.405 (15)	C34A—H34A	0.9300
C8—H8A	0.9300	C35A—H35A	0.9600
C9—C10	1.366 (13)	C35A—H35B	0.9600
C10—C11	1.370 (15)	C35A—H35C	0.9600
C10—C26B	1.486 (7)	S3B—C34B	1.669 (15)
C10—C26A	1.488 (7)	S3B—C31B	1.755 (14)
C11—C12	1.422 (14)	C31B—C32B	1.351 (15)
C12—C13	1.339 (16)	C32B—C35B	1.396 (16)
C12—H12A	0.9300	C32B—C33B	1.463 (15)
C13—C14	1.440 (15)	C33B—C34B	1.248 (18)
C13—H13A	0.9300	C33B—H33B	0.9300
C14—C15	1.380 (16)	C34B—H34B	0.9300
C15—C16	1.404 (15)	C35B—H35D	0.9600
C15—C31B	1.488 (7)	C35B—H35E	0.9600
C15—C31A	1.488 (7)	C35B—H35F	0.9600
C16—C17	1.417 (17)	S4A—C39A	1.713 (12)
C17—C18	1.314 (14)	S4A—C36A	1.743 (10)
C17—H17A	0.9300	C36A—C37A	1.350 (12)
C18—C19	1.382 (15)	C37A—C40A	1.311 (13)
C18—H18A	0.9300	C37A—C38A	1.469 (14)
C19—C20	1.422 (14)	C38A—C39A	1.226 (14)
C20—C36A	1.487 (6)	C38A—H38A	0.9300
C20—C36B	1.488 (7)	C39A—H39A	0.9300
S1A—C24A	1.708 (13)	C40A—H40A	0.9600
S1A—C21A	1.744 (10)	C40A—H40B	0.9600
C21A—C22A	1.337 (14)	C40A—H40C	0.9600
C22A—C25A	1.337 (14)	S4B—C39B	1.674 (17)
C22A—C23A	1.461 (14)	S4B—C36B	1.751 (16)
C23A—C24A	1.225 (15)	C36B—C37B	1.343 (17)
C23A—H23A	0.9300	C37B—C40B	1.363 (18)
C24A—H24A	0.9300	C37B—C38B	1.462 (17)
C25A—H25A	0.9600	C38B—C39B	1.231 (19)
C25A—H25B	0.9600	C38B—H38B	0.9300
C25A—H25C	0.9600	C39B—H39B	0.9300
S1B—C24B	1.670 (17)	C40B—H40D	0.9600
S1B—C21B	1.752 (15)	C40B—H40E	0.9600
C21B—C22B	1.344 (17)	C40B—H40F	0.9600
C22B—C25B	1.362 (17)	C1S—C2S	1.3900
C22B—C23B	1.461 (17)	C1S—C6S	1.3900
C23B—C24B	1.230 (19)	C1S—H1SA	0.9300
C23B—H23B	0.9300	C2S—C3S	1.3900
C24B—H24B	0.9300	C2S—H2SA	0.9300
C25B—H25D	0.9600	C3S—C4S	1.3900
C25B—H25E	0.9600	C3S—H3SA	0.9300
C25B—H25F	0.9600	C4S—C5S	1.3900
S2A—C29A	1.632 (14)	C4S—H4SA	0.9300
S2A—C26A	1.758 (13)	C5S—C6S	1.3900
C26A—C27A	1.339 (15)	C5S—H5SA	0.9300
C27A—C30A	1.381 (16)	C6S—H6SA	0.9300

N1—Ni—N2	89.8 (3)	C26A—C27A—C30A	118.5 (14)
N1—Ni—N4	90.0 (4)	C26A—C27A—C28A	109.7 (12)
N2—Ni—N4	177.4 (3)	C30A—C27A—C28A	131.2 (15)
N1—Ni—N3	177.5 (4)	C29A—C28A—C27A	115.9 (15)
N2—Ni—N3	90.5 (3)	C29A—C28A—H28A	122.0
N4—Ni—N3	89.8 (4)	C27A—C28A—H28A	122.0
C1—N1—C4	100.8 (9)	C28A—C29A—S2A	112.8 (13)
C1—N1—Ni	129.2 (7)	C28A—C29A—H29A	123.6
C4—N1—Ni	129.9 (8)	S2A—C29A—H29A	123.6
C6—N2—C9	105.1 (9)	C27A—C30A—H30A	109.5
C6—N2—Ni	127.3 (7)	C27A—C30A—H30B	109.5
C9—N2—Ni	127.3 (6)	H30A—C30A—H30B	109.5
C14—N3—C11	107.1 (8)	C27A—C30A—H30C	109.5
C14—N3—Ni	126.5 (8)	H30A—C30A—H30C	109.5
C11—N3—Ni	126.3 (7)	H30B—C30A—H30C	109.5
C16—N4—C19	103.0 (10)	C29B—S2B—C26B	92.1 (9)
C16—N4—Ni	128.6 (8)	C27B—C26B—C10	126.7 (14)
C19—N4—Ni	128.4 (7)	C27B—C26B—S2B	108.3 (10)
C20—C1—N1	124.3 (9)	C10—C26B—S2B	124.5 (12)
C20—C1—C2	120.8 (12)	C26B—C27B—C30B	120.2 (17)
N1—C1—C2	114.3 (11)	C26B—C27B—C28B	112.1 (13)
C3—C2—C1	105.1 (12)	C30B—C27B—C28B	127.6 (18)
C3—C2—H2A	127.5	C29B—C28B—C27B	112.8 (16)
C1—C2—H2A	127.5	C29B—C28B—H28B	123.6
C2—C3—C4	106.8 (11)	C27B—C28B—H28B	123.6
C2—C3—H3A	126.6	C28B—C29B—S2B	114.7 (15)
C4—C3—H3A	126.6	C28B—C29B—H29B	122.7
C5—C4—N1	123.4 (9)	S2B—C29B—H29B	122.7
C5—C4—C3	123.6 (11)	C27B—C30B—H30D	109.5
N1—C4—C3	113.0 (12)	C27B—C30B—H30E	109.5
C6—C5—C4	121.0 (8)	H30D—C30B—H30E	109.5
C6—C5—C21B	125.5 (16)	C27B—C30B—H30F	109.5
C4—C5—C21B	112.7 (15)	H30D—C30B—H30F	109.5
C6—C5—C21A	118.5 (11)	H30E—C30B—H30F	109.5
C4—C5—C21A	119.3 (10)	C34A—S3A—C31A	91.4 (9)
N2—C6—C5	126.0 (10)	C32A—C31A—C15	123.8 (13)
N2—C6—C7	109.5 (9)	C32A—C31A—S3A	109.1 (9)
C5—C6—C7	124.4 (10)	C15—C31A—S3A	126.6 (11)
C8—C7—C6	106.6 (10)	C31A—C32A—C35A	118.7 (17)
C8—C7—H7A	126.7	C31A—C32A—C33A	110.9 (13)
C6—C7—H7A	126.7	C35A—C32A—C33A	130.5 (17)
C7—C8—C9	108.9 (11)	C34A—C33A—C32A	113.9 (16)
C7—C8—H8A	125.6	C34A—C33A—H33A	123.1
C9—C8—H8A	125.6	C32A—C33A—H33A	123.1
C10—C9—N2	125.7 (10)	C33A—C34A—S3A	113.7 (15)
C10—C9—C8	124.6 (10)	C33A—C34A—H34A	123.1
N2—C9—C8	109.7 (9)	S3A—C34A—H34A	123.1
C9—C10—C11	123.2 (9)	C32A—C35A—H35A	109.5
C9—C10—C26B	114.4 (11)	C32A—C35A—H35B	109.5
C11—C10—C26B	122.4 (11)	H35A—C35A—H35B	109.5
C9—C10—C26A	121.8 (10)	C32A—C35A—H35C	109.5
C11—C10—C26A	113.9 (10)	H35A—C35A—H35C	109.5
C10—C11—N3	124.7 (9)	H35B—C35A—H35C	109.5
C10—C11—C12	125.6 (11)	C34B—S3B—C31B	90.9 (8)
N3—C11—C12	108.6 (11)	C32B—C31B—C15	127.9 (12)
C13—C12—C11	107.4 (11)	C32B—C31B—S3B	110.5 (8)
C13—C12—H12A	126.3	C15—C31B—S3B	121.3 (10)
C11—C12—H12A	126.3	C31B—C32B—C35B	117.0 (14)
C12—C13—C14	108.7 (11)	C31B—C32B—C33B	109.1 (12)
C12—C13—H13A	125.7	C35B—C32B—C33B	133.4 (16)
C14—C13—H13A	125.7	C34B—C33B—C32B	115.1 (15)
N3—C14—C15	127.3 (8)	C34B—C33B—H33B	122.4
N3—C14—C13	108.2 (12)	C32B—C33B—H33B	122.4
C15—C14—C13	124.5 (11)	C33B—C34B—S3B	114.3 (13)
C14—C15—C16	120.7 (8)	C33B—C34B—H34B	122.9
C14—C15—C31B	118.9 (11)	S3B—C34B—H34B	122.9
C16—C15—C31B	120.5 (12)	C32B—C35B—H35D	109.5
C14—C15—C31A	114.0 (12)	C32B—C35B—H35E	109.5
C16—C15—C31A	123.5 (13)	H35D—C35B—H35E	109.5
N4—C16—C15	124.6 (11)	C32B—C35B—H35F	109.5
N4—C16—C17	111.2 (10)	H35D—C35B—H35F	109.5
C15—C16—C17	123.7 (11)	H35E—C35B—H35F	109.5
C18—C17—C16	106.4 (11)	C39A—S4A—C36A	90.1 (6)
C18—C17—H17A	126.8	C37A—C36A—C20	130.0 (10)
C16—C17—H17A	126.8	C37A—C36A—S4A	109.9 (8)
C17—C18—C19	108.4 (12)	C20—C36A—S4A	119.6 (8)
C17—C18—H18A	125.8	C40A—C37A—C36A	122.8 (11)
C19—C18—H18A	125.8	C40A—C37A—C38A	125.5 (12)
C18—C19—N4	111.0 (9)	C36A—C37A—C38A	111.6 (11)
C18—C19—C20	126.6 (11)	C39A—C38A—C37A	112.8 (13)
N4—C19—C20	122.4 (10)	C39A—C38A—H38A	123.6
C1—C20—C19	123.4 (9)	C37A—C38A—H38A	123.6
C1—C20—C36A	119.9 (10)	C38A—C39A—S4A	115.5 (11)
C19—C20—C36A	116.6 (10)	C38A—C39A—H39A	122.2
C1—C20—C36B	118 (2)	S4A—C39A—H39A	122.2
C19—C20—C36B	106 (3)	C37A—C40A—H40A	109.5
C24A—S1A—C21A	90.0 (6)	C37A—C40A—H40B	109.5
C22A—C21A—C5	126.9 (10)	H40A—C40A—H40B	109.5
C22A—C21A—S1A	110.6 (8)	C37A—C40A—H40C	109.5
C5—C21A—S1A	122.5 (8)	H40A—C40A—H40C	109.5
C25A—C22A—C21A	120.7 (12)	H40B—C40A—H40C	109.5
C25A—C22A—C23A	128.9 (13)	C39B—S4B—C36B	91.1 (11)
C21A—C22A—C23A	110.4 (11)	C37B—C36B—C20	122 (3)
C24A—C23A—C22A	114.4 (13)	C37B—C36B—S4B	109.1 (13)
C24A—C23A—H23A	122.8	C20—C36B—S4B	128 (2)
C22A—C23A—H23A	122.8	C36B—C37B—C40B	120 (2)
C23A—C24A—S1A	114.3 (12)	C36B—C37B—C38B	111.1 (15)
C23A—C24A—H24A	122.9	C40B—C37B—C38B	129 (2)
S1A—C24A—H24A	122.9	C39B—C38B—C37B	113.8 (18)
C22A—C25A—H25A	109.5	C39B—C38B—H38B	123.1
C22A—C25A—H25B	109.5	C37B—C38B—H38B	123.1
H25A—C25A—H25B	109.5	C38B—C39B—S4B	114.8 (17)
C22A—C25A—H25C	109.5	C38B—C39B—H39B	122.6
H25A—C25A—H25C	109.5	S4B—C39B—H39B	122.6
H25B—C25A—H25C	109.5	C37B—C40B—H40D	109.5
C24B—S1B—C21B	91.3 (10)	C37B—C40B—H40E	109.5
C22B—C21B—C5	123.0 (16)	H40D—C40B—H40E	109.5
C22B—C21B—S1B	109.1 (11)	C37B—C40B—H40F	109.5
C5—C21B—S1B	127.9 (14)	H40D—C40B—H40F	109.5
C21B—C22B—C25B	122 (2)	H40E—C40B—H40F	109.5
C21B—C22B—C23B	110.7 (14)	C2S—C1S—C6S	120.0
C25B—C22B—C23B	127 (2)	C2S—C1S—H1SA	120.0
C24B—C23B—C22B	114.2 (17)	C6S—C1S—H1SA	120.0
C24B—C23B—H23B	122.9	C3S—C2S—C1S	120.0
C22B—C23B—H23B	122.9	C3S—C2S—H2SA	120.0
C23B—C24B—S1B	114.6 (16)	C1S—C2S—H2SA	120.0
C23B—C24B—H24B	122.7	C2S—C3S—C4S	120.0
S1B—C24B—H24B	122.7	C2S—C3S—H3SA	120.0
C22B—C25B—H25D	109.5	C4S—C3S—H3SA	120.0
C22B—C25B—H25E	109.5	C5S—C4S—C3S	120.0
H25D—C25B—H25E	109.5	C5S—C4S—H4SA	120.0
C22B—C25B—H25F	109.5	C3S—C4S—H4SA	120.0
H25D—C25B—H25F	109.5	C4S—C5S—C6S	120.0
H25E—C25B—H25F	109.5	C4S—C5S—H5SA	120.0
C29A—S2A—C26A	92.9 (7)	C6S—C5S—H5SA	120.0
C27A—C26A—C10	125.0 (12)	C5S—C6S—C1S	120.0
C27A—C26A—S2A	108.1 (8)	C5S—C6S—H6SA	120.0
C10—C26A—S2A	126.6 (10)	C1S—C6S—H6SA	120.0

N2—Ni—N1—C1	165.7 (9)	S1A—C21A—C22A—C25A	175.7 (12)
N4—Ni—N1—C1	−16.8 (9)	C5—C21A—C22A—C23A	175.9 (14)
N2—Ni—N1—C4	−8.3 (8)	S1A—C21A—C22A—C23A	−3.1 (13)
N4—Ni—N1—C4	169.1 (8)	C25A—C22A—C23A—C24A	−172.6 (17)
N1—Ni—N2—C6	15.1 (8)	C21A—C22A—C23A—C24A	6 (2)
N3—Ni—N2—C6	−167.3 (8)	C22A—C23A—C24A—S1A	−6 (2)
N1—Ni—N2—C9	−171.9 (8)	C21A—S1A—C24A—C23A	3.7 (16)
N3—Ni—N2—C9	5.6 (8)	C6—C5—C21B—C22B	108 (2)
N2—Ni—N3—C14	168.2 (9)	C4—C5—C21B—C22B	−83 (3)
N4—Ni—N3—C14	−9.2 (9)	C21A—C5—C21B—C22B	30 (3)
N2—Ni—N3—C11	−15.2 (9)	C6—C5—C21B—S1B	−69 (3)
N4—Ni—N3—C11	167.4 (9)	C4—C5—C21B—S1B	101 (2)
N1—Ni—N4—C16	−168.1 (8)	C21A—C5—C21B—S1B	−147 (6)
N3—Ni—N4—C16	14.3 (8)	C24B—S1B—C21B—C22B	0.3 (14)
N1—Ni—N4—C19	11.3 (8)	C24B—S1B—C21B—C5	177 (4)
N3—Ni—N4—C19	−166.2 (8)	C5—C21B—C22B—C25B	6 (4)
C4—N1—C1—C20	−171.2 (10)	S1B—C21B—C22B—C25B	−177 (2)
Ni—N1—C1—C20	13.5 (16)	C5—C21B—C22B—C23B	−176 (3)
C4—N1—C1—C2	0.2 (12)	S1B—C21B—C22B—C23B	1.0 (18)
Ni—N1—C1—C2	−175.2 (8)	C21B—C22B—C23B—C24B	−3 (4)
C20—C1—C2—C3	171.2 (12)	C25B—C22B—C23B—C24B	175 (3)
N1—C1—C2—C3	−0.5 (15)	C22B—C23B—C24B—S1B	3 (5)
C1—C2—C3—C4	0.6 (15)	C21B—S1B—C24B—C23B	−2 (3)
C1—N1—C4—C5	−179.2 (10)	C9—C10—C26A—C27A	−80.9 (16)
Ni—N1—C4—C5	−3.9 (15)	C11—C10—C26A—C27A	110.9 (15)
C1—N1—C4—C3	0.2 (12)	C26B—C10—C26A—C27A	−19 (4)
Ni—N1—C4—C3	175.5 (8)	C9—C10—C26A—S2A	91.8 (15)
C2—C3—C4—C5	178.9 (12)	C11—C10—C26A—S2A	−76.4 (15)
C2—C3—C4—N1	−0.6 (15)	C26B—C10—C26A—S2A	153 (6)
N1—C4—C5—C6	13.7 (16)	C29A—S2A—C26A—C27A	−1.1 (10)
C3—C4—C5—C6	−165.7 (11)	C29A—S2A—C26A—C10	−174.8 (15)
N1—C4—C5—C21B	−156.2 (12)	C10—C26A—C27A—C30A	−2 (2)
C3—C4—C5—C21B	24.3 (17)	S2A—C26A—C27A—C30A	−175.9 (13)
N1—C4—C5—C21A	−178.8 (9)	C10—C26A—C27A—C28A	170.8 (17)
C3—C4—C5—C21A	1.7 (16)	S2A—C26A—C27A—C28A	−3.0 (13)
C9—N2—C6—C5	175.1 (10)	C26A—C27A—C28A—C29A	8 (2)
Ni—N2—C6—C5	−10.7 (14)	C30A—C27A—C28A—C29A	179.4 (19)
C9—N2—C6—C7	−2.2 (10)	C27A—C28A—C29A—S2A	−9 (2)
Ni—N2—C6—C7	172.0 (6)	C26A—S2A—C29A—C28A	5.7 (17)
C4—C5—C6—N2	−6.3 (16)	C9—C10—C26B—C27B	107.3 (18)
C21B—C5—C6—N2	162.3 (13)	C11—C10—C26B—C27B	−73 (2)
C21A—C5—C6—N2	−173.9 (9)	C26A—C10—C26B—C27B	−18 (4)
C4—C5—C6—C7	170.6 (10)	C9—C10—C26B—S2B	−82.1 (16)
C21B—C5—C6—C7	−20.8 (18)	C11—C10—C26B—S2B	97.2 (17)
C21A—C5—C6—C7	3.0 (15)	C26A—C10—C26B—S2B	153 (6)
N2—C6—C7—C8	4.5 (11)	C29B—S2B—C26B—C27B	0.6 (12)
C5—C6—C7—C8	−172.9 (10)	C29B—S2B—C26B—C10	−171.5 (19)
C6—C7—C8—C9	−4.8 (11)	C10—C26B—C27B—C30B	−12 (3)
C6—N2—C9—C10	179.4 (10)	S2B—C26B—C27B—C30B	176.2 (16)
Ni—N2—C9—C10	5.2 (14)	C10—C26B—C27B—C28B	170 (2)
C6—N2—C9—C8	−0.7 (10)	S2B—C26B—C27B—C28B	−1.7 (16)
Ni—N2—C9—C8	−174.9 (6)	C26B—C27B—C28B—C29B	2 (3)
C7—C8—C9—C10	−176.5 (10)	C30B—C27B—C28B—C29B	−175 (2)
C7—C8—C9—N2	3.6 (12)	C27B—C28B—C29B—S2B	−2 (3)
N2—C9—C10—C11	−9.7 (16)	C26B—S2B—C29B—C28B	1 (2)
C8—C9—C10—C11	170.4 (11)	C14—C15—C31A—C32A	100.1 (19)
N2—C9—C10—C26B	169.6 (11)	C16—C15—C31A—C32A	−95.5 (19)
C8—C9—C10—C26B	−10.3 (16)	C31B—C15—C31A—C32A	−13 (5)
N2—C9—C10—C26A	−176.8 (10)	C14—C15—C31A—S3A	−88.9 (18)
C8—C9—C10—C26A	3.3 (17)	C16—C15—C31A—S3A	75.5 (19)
C9—C10—C11—N3	−1.2 (18)	C31B—C15—C31A—S3A	158 (7)
C26B—C10—C11—N3	179.6 (12)	C34A—S3A—C31A—C32A	3.3 (12)
C26A—C10—C11—N3	166.9 (11)	C34A—S3A—C31A—C15	−169 (2)
C9—C10—C11—C12	−167.9 (11)	C15—C31A—C32A—C35A	−6 (3)
C26B—C10—C11—C12	12.9 (19)	S3A—C31A—C32A—C35A	−178.4 (16)
C26A—C10—C11—C12	0.2 (17)	C15—C31A—C32A—C33A	174 (2)
C14—N3—C11—C10	−167.2 (11)	S3A—C31A—C32A—C33A	1.8 (15)
Ni—N3—C11—C10	15.7 (16)	C31A—C32A—C33A—C34A	−8 (3)
C14—N3—C11—C12	1.5 (13)	C35A—C32A—C33A—C34A	172 (2)
Ni—N3—C11—C12	−175.6 (8)	C32A—C33A—C34A—S3A	11 (3)
C10—C11—C12—C13	165.2 (12)	C31A—S3A—C34A—C33A	−9 (2)
N3—C11—C12—C13	−3.3 (15)	C14—C15—C31B—C32B	−84.9 (19)
C11—C12—C13—C14	3.8 (16)	C16—C15—C31B—C32B	95.0 (19)
C11—N3—C14—C15	−179.5 (11)	C31A—C15—C31B—C32B	−11 (5)
Ni—N3—C14—C15	−2.4 (17)	C14—C15—C31B—S3B	87.9 (16)
C11—N3—C14—C13	0.8 (13)	C16—C15—C31B—S3B	−92.2 (16)
Ni—N3—C14—C13	177.9 (8)	C31A—C15—C31B—S3B	161 (7)
C12—C13—C14—N3	−3.0 (15)	C34B—S3B—C31B—C32B	−1.2 (11)
C12—C13—C14—C15	177.4 (12)	C34B—S3B—C31B—C15	−175.1 (18)
N3—C14—C15—C16	13.6 (18)	C15—C31B—C32B—C35B	−12 (2)
C13—C14—C15—C16	−166.8 (11)	S3B—C31B—C32B—C35B	174.3 (14)
N3—C14—C15—C31B	−166.5 (11)	C15—C31B—C32B—C33B	175 (2)
C13—C14—C15—C31B	13.1 (18)	S3B—C31B—C32B—C33B	1.7 (14)
N3—C14—C15—C31A	178.5 (12)	C31B—C32B—C33B—C34B	−2 (3)
C13—C14—C15—C31A	−1.9 (18)	C35B—C32B—C33B—C34B	−173 (2)
C19—N4—C16—C15	172.1 (10)	C32B—C33B—C34B—S3B	1 (3)
Ni—N4—C16—C15	−8.3 (15)	C31B—S3B—C34B—C33B	0 (2)
C19—N4—C16—C17	0.2 (11)	C1—C20—C36A—C37A	−92.4 (14)
Ni—N4—C16—C17	179.7 (7)	C19—C20—C36A—C37A	85.2 (14)
C14—C15—C16—N4	−8.0 (17)	C36B—C20—C36A—C37A	5 (4)
C31B—C15—C16—N4	172.1 (11)	C1—C20—C36A—S4A	79.0 (12)
C31A—C15—C16—N4	−171.4 (11)	C19—C20—C36A—S4A	−103.4 (10)
C14—C15—C16—C17	162.9 (11)	C36B—C20—C36A—S4A	177 (4)
C31B—C15—C16—C17	−17.0 (17)	C39A—S4A—C36A—C37A	0.9 (9)
C31A—C15—C16—C17	−0.4 (18)	C39A—S4A—C36A—C20	−172.1 (10)
N4—C16—C17—C18	1.3 (13)	C20—C36A—C37A—C40A	−12.0 (19)
C15—C16—C17—C18	−170.8 (10)	S4A—C36A—C37A—C40A	175.9 (11)
C16—C17—C18—C19	−2.2 (13)	C20—C36A—C37A—C38A	172.2 (12)
C17—C18—C19—N4	2.4 (14)	S4A—C36A—C37A—C38A	0.1 (11)
C17—C18—C19—C20	−176.3 (10)	C40A—C37A—C38A—C39A	−177.3 (15)
C16—N4—C19—C18	−1.5 (12)	C36A—C37A—C38A—C39A	−1.7 (17)
Ni—N4—C19—C18	178.9 (7)	C37A—C38A—C39A—S4A	2.5 (18)
C16—N4—C19—C20	177.3 (9)	C36A—S4A—C39A—C38A	−2.1 (14)
Ni—N4—C19—C20	−2.3 (14)	C1—C20—C36B—C37B	118 (4)
N1—C1—C20—C19	1.8 (17)	C19—C20—C36B—C37B	−100 (4)
C2—C1—C20—C19	−169.0 (11)	C36A—C20—C36B—C37B	14 (3)
N1—C1—C20—C36A	179.2 (10)	C1—C20—C36B—S4B	−50 (6)
C2—C1—C20—C36A	8.4 (16)	C19—C20—C36B—S4B	92 (5)
N1—C1—C20—C36B	138 (2)	C36A—C20—C36B—S4B	−154 (7)
C2—C1—C20—C36B	−33 (3)	C39B—S4B—C36B—C37B	0.1 (16)
C18—C19—C20—C1	171.4 (12)	C39B—S4B—C36B—C20	169 (7)
N4—C19—C20—C1	−7.2 (16)	C20—C36B—C37B—C40B	11 (7)
C18—C19—C20—C36A	−6.1 (16)	S4B—C36B—C37B—C40B	−179 (2)
N4—C19—C20—C36A	175.3 (9)	C20—C36B—C37B—C38B	−170 (6)
C18—C19—C20—C36B	31 (2)	S4B—C36B—C37B—C38B	0.3 (19)
N4—C19—C20—C36B	−147.4 (16)	C36B—C37B—C38B—C39B	−1 (4)
C6—C5—C21A—C22A	−115.9 (13)	C40B—C37B—C38B—C39B	179 (4)
C4—C5—C21A—C22A	76.3 (16)	C37B—C38B—C39B—S4B	1 (5)
C21B—C5—C21A—C22A	−1 (4)	C36B—S4B—C39B—C38B	−1 (4)
C6—C5—C21A—S1A	63.0 (14)	C6S—C1S—C2S—C3S	0.0
C4—C5—C21A—S1A	−104.8 (11)	C1S—C2S—C3S—C4S	0.0
C21B—C5—C21A—S1A	178 (4)	C2S—C3S—C4S—C5S	0.0
C24A—S1A—C21A—C22A	0.1 (10)	C3S—C4S—C5S—C6S	0.0
C24A—S1A—C21A—C5	−179.0 (12)	C4S—C5S—C6S—C1S	0.0
C5—C21A—C22A—C25A	−5 (2)	C2S—C1S—C6S—C5S	0.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C30A—H30A···S1Aⁱ	0.96	2.70	3.50 (2)	141

Symmetry code: (i) x+1/2, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[Ni(C₄₀H₂₈N₄S₄)]·0.5C₆H₆
M_r	790.67
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	295
a, b, c (Å)	12.4854 (6), 11.3906 (5), 28.365 (2)
V (Å³)	4034.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.39 × 0.22 × 0.05

Data collection
Diffractometer	Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction	Analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model (Clark & Reid (1995)]
T_min, T_max	0.830, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	12922, 5674, 2720
R_int	0.091
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.240, 0.99
No. of reflections	5674
No. of parameters	562
No. of restraints	709
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.24
Absolute structure	Flack (1983), ???? Friedel pairs
Absolute structure parameter	0.35 (4)

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

PB and RP gratefully acknowledge the Council of Scientific and Industrial Research (CSIR), India, for financial assistance [grant No. 02 (0076)/12/EMR-II and SRF (09/919/(0014)/2012 EMR-I), respectively]. RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer as well as the Howard University Nanoscience Facility for access to liquid nitrogen. SKG wishes to acknowledge the USIEF for the award of a Fulbright–Nehru Senior Research Fellowship.

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