supplementary materials


zs2280 scheme

Acta Cryst. (2013). E69, m652-m653    [ doi:10.1107/S1600536813030468 ]

[meso-5,10,15,20-Tetra­kis(3-methyl­thio­phen-2-yl)porphyrinato-[kappa]4N,N',N'',N''']nickel(II) benzene hemisolvate

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

Abstract top

In the title compound, [Ni(C40H28N4S4)]·0.5C6H6, the NiII 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.

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 NiII 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%.

Refinement top

All H atoms were placed in calculated positions and refined using a riding-model approximation with atom—H lengths of 0.93 Å (CH) or 0.96 Å (CH3). Isotropic displacement parameters for these atoms were set to 1.2 (CH) or 1.5 (CH3) times Ueq of the parent atom. 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 has found to be present in half occupancy and was constrained to be hexagonal.

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
[Figure 1] 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.
[Figure 2] 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)]·0.5C6H6F(000) = 1636
Mr = 790.67Dx = 1.302 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2nCell parameters from 1901 reflections
a = 12.4854 (6) Åθ = 3.2–28.5°
b = 11.3906 (5) ŵ = 0.72 mm1
c = 28.365 (2) ÅT = 295 K
V = 4034.0 (4) Å3Prism, dark purple
Z = 40.39 × 0.22 × 0.05 mm
Data collection top
Agilent Xcalibur (Ruby, Gemini)
diffractometer
5674 independent reflections
Radiation source: Enhance (Mo) X-ray Source2720 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.091
Detector resolution: 10.5081 pixels mm-1θmax = 25.3°, θmin = 3.2°
ω scansh = 1414
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model (Clark & Reid (1995)]
k = 1312
Tmin = 0.830, Tmax = 0.965l = 2034
12922 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.077H-atom parameters constrained
wR(F2) = 0.240 w = 1/[σ2(Fo2) + (0.1154P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.005
5674 reflectionsΔρmax = 0.32 e Å3
562 parametersΔρmin = 0.24 e Å3
709 restraintsAbsolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.35 (4)
Crystal data top
[Ni(C40H28N4S4)]·0.5C6H6V = 4034.0 (4) Å3
Mr = 790.67Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 12.4854 (6) ŵ = 0.72 mm1
b = 11.3906 (5) ÅT = 295 K
c = 28.365 (2) Å0.39 × 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)
Tmin = 0.830, Tmax = 0.965Rint = 0.091
12922 measured reflectionsθmax = 25.3°
Refinement top
R[F2 > 2σ(F2)] = 0.077H-atom parameters constrained
wR(F2) = 0.240Δρmax = 0.32 e Å3
S = 0.99Δρmin = 0.24 e Å3
5674 reflectionsAbsolute structure: Flack (1983), ???? Friedel pairs
562 parametersAbsolute 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
xyzUiso*/UeqOcc. (<1)
Ni0.14310 (8)0.51145 (8)0.50592 (10)0.0744 (4)
N10.0343 (6)0.4084 (7)0.4852 (3)0.081 (2)
N20.0723 (6)0.5254 (6)0.5661 (3)0.071 (2)
N30.2520 (6)0.6232 (6)0.5259 (3)0.083 (3)
N40.2174 (6)0.4911 (6)0.4466 (3)0.079 (2)
C10.0111 (8)0.3714 (9)0.4404 (5)0.090 (3)
C20.0831 (10)0.3000 (11)0.4370 (6)0.127 (5)
H2A0.11240.26700.40990.152*
C30.1200 (9)0.2909 (11)0.4815 (5)0.112 (4)
H3A0.18010.24940.49140.135*
C40.0495 (8)0.3568 (8)0.5105 (5)0.092 (3)
C50.0628 (7)0.3698 (8)0.5590 (4)0.089 (3)
C60.0068 (8)0.4544 (9)0.5839 (4)0.079 (3)
C70.0271 (9)0.4850 (9)0.6326 (4)0.086 (3)
H7A0.07350.44700.65320.104*
C80.0330 (8)0.5775 (8)0.6420 (5)0.084 (3)
H8A0.03260.61960.67010.101*
C90.0978 (8)0.6019 (8)0.6027 (4)0.078 (3)
C100.1738 (8)0.6880 (7)0.6011 (3)0.087 (3)
C110.2458 (9)0.6990 (9)0.5649 (5)0.095 (4)
C120.3381 (11)0.7722 (10)0.5651 (5)0.122 (5)
H12A0.35230.83270.58620.146*
C130.4007 (10)0.7378 (10)0.5293 (5)0.116 (5)
H13A0.46810.76780.52230.139*
C140.3462 (8)0.6468 (8)0.5035 (6)0.091 (3)
C150.3855 (6)0.5940 (9)0.4632 (4)0.088 (3)
C160.3189 (9)0.5242 (9)0.4349 (5)0.088 (3)
C170.3435 (9)0.4928 (9)0.3878 (5)0.094 (3)
H17A0.40810.50490.37220.112*
C180.2570 (9)0.4431 (10)0.3705 (5)0.094 (3)
H18A0.24870.41580.33980.113*
C190.1805 (9)0.4385 (9)0.4056 (4)0.088 (3)
C200.0775 (9)0.3858 (8)0.4025 (3)0.095 (4)
S1A0.2681 (4)0.3838 (5)0.6016 (2)0.146 (2)0.796 (6)
C21A0.1537 (7)0.3093 (9)0.5828 (4)0.094 (4)0.796 (6)
C22A0.1604 (11)0.1952 (12)0.5935 (5)0.138 (6)0.796 (6)
C23A0.2587 (11)0.1713 (12)0.6198 (6)0.118 (5)0.796 (6)
H23A0.27410.09830.63280.142*0.796 (6)
C24A0.3192 (13)0.2555 (12)0.6231 (7)0.141 (6)0.796 (6)
H24A0.38730.25010.63630.170*0.796 (6)
C25A0.0842 (11)0.1202 (10)0.5797 (6)0.104 (4)0.796 (6)
H25A0.01630.14520.59190.156*0.796 (6)
H25B0.08130.11850.54590.156*0.796 (6)
H25C0.10050.04310.59130.156*0.796 (6)
S1B0.0775 (13)0.1502 (16)0.6113 (8)0.146 (2)0.204 (6)
C21B0.1258 (15)0.2723 (17)0.5803 (10)0.094 (4)0.204 (6)
C22B0.2334 (17)0.270 (2)0.5802 (11)0.138 (6)0.204 (6)
C23B0.2729 (18)0.168 (3)0.6064 (17)0.118 (5)0.204 (6)
H23B0.34540.15330.61110.142*0.204 (6)
C24B0.2020 (19)0.103 (3)0.6217 (17)0.141 (6)0.204 (6)
H24B0.21660.03390.63770.170*0.204 (6)
C25B0.293 (3)0.351 (3)0.5566 (16)0.104 (4)0.204 (6)
H25D0.26790.35640.52470.156*0.204 (6)
H25E0.28550.42590.57170.156*0.204 (6)
H25F0.36660.32770.55680.156*0.204 (6)
S2A0.2984 (7)0.7338 (6)0.6854 (3)0.142 (2)0.579 (7)
C26A0.1993 (12)0.7618 (11)0.6429 (4)0.085 (4)0.579 (7)
C27A0.1426 (12)0.8552 (14)0.6570 (6)0.115 (6)0.579 (7)
C28A0.1804 (16)0.8939 (17)0.7031 (7)0.121 (6)0.579 (7)
H28A0.14520.95170.72020.145*0.579 (7)
C29A0.2619 (14)0.8453 (14)0.7179 (6)0.104 (5)0.579 (7)
H29A0.29870.86950.74470.124*0.579 (7)
C30A0.0552 (14)0.8893 (17)0.6305 (7)0.089 (5)0.579 (7)
H30A0.07280.95870.61290.133*0.579 (7)
H30B0.00420.90530.65100.133*0.579 (7)
H30C0.03620.82740.60900.133*0.579 (7)
S2B0.0856 (10)0.8896 (10)0.6463 (5)0.142 (2)0.421 (7)
C26B0.1713 (15)0.7704 (13)0.6416 (5)0.085 (4)0.421 (7)
C27B0.2416 (14)0.7757 (15)0.6770 (7)0.115 (6)0.421 (7)
C28B0.226 (2)0.879 (2)0.7063 (9)0.121 (6)0.421 (7)
H28B0.26920.89780.73180.145*0.421 (7)
C29B0.1483 (17)0.9389 (18)0.6937 (8)0.104 (5)0.421 (7)
H29B0.12701.00640.70960.124*0.421 (7)
C30B0.3154 (19)0.6871 (19)0.6832 (11)0.089 (5)0.421 (7)
H30D0.31270.63450.65680.133*0.421 (7)
H30E0.29910.64480.71150.133*0.421 (7)
H30F0.38590.72030.68550.133*0.421 (7)
S3A0.5088 (8)0.7604 (12)0.4087 (6)0.181 (4)0.447 (8)
C31A0.4899 (8)0.6423 (15)0.4470 (7)0.101 (4)0.447 (8)
C32A0.5847 (14)0.5906 (15)0.4552 (7)0.119 (7)0.447 (8)
C33A0.6712 (14)0.652 (2)0.4307 (11)0.124 (6)0.447 (8)
H33A0.74320.63550.43550.149*0.447 (8)
C34A0.6397 (13)0.729 (2)0.4033 (9)0.122 (6)0.447 (8)
H34A0.68430.76570.38160.147*0.447 (8)
C35A0.588 (2)0.4925 (18)0.4840 (9)0.089 (5)0.447 (8)
H35A0.63990.43820.47230.133*0.447 (8)
H35B0.51840.45570.48420.133*0.447 (8)
H35C0.60630.51560.51550.133*0.447 (8)
S3B0.6010 (8)0.5209 (9)0.4721 (5)0.181 (4)0.553 (8)
C31B0.4997 (7)0.6126 (14)0.4503 (7)0.101 (4)0.553 (8)
C32B0.5424 (12)0.7030 (14)0.4258 (6)0.119 (7)0.553 (8)
C33B0.6590 (12)0.6905 (19)0.4249 (10)0.124 (6)0.553 (8)
H33B0.70330.74300.40900.149*0.553 (8)
C34B0.6949 (13)0.6042 (16)0.4469 (8)0.122 (6)0.553 (8)
H34B0.76760.58780.44920.147*0.553 (8)
C35B0.4711 (15)0.7776 (17)0.4026 (8)0.089 (5)0.553 (8)
H35D0.42660.73250.38170.133*0.553 (8)
H35E0.51050.83460.38470.133*0.553 (8)
H35F0.42690.81690.42540.133*0.553 (8)
S4A0.0458 (4)0.4210 (5)0.3214 (2)0.168 (2)0.956 (7)
C36A0.0449 (8)0.3410 (9)0.3554 (3)0.108 (4)0.956 (7)
C37A0.0649 (9)0.2366 (10)0.3346 (4)0.122 (4)0.956 (7)
C38A0.0050 (11)0.2233 (13)0.2904 (5)0.141 (5)0.956 (7)
H38A0.01030.15780.27100.169*0.956 (7)
C39A0.0527 (11)0.3077 (12)0.2819 (5)0.143 (5)0.956 (7)
H39A0.09740.31000.25560.172*0.956 (7)
C40A0.1352 (11)0.1616 (11)0.3512 (6)0.135 (5)0.956 (7)
H40A0.15120.18060.38340.203*0.956 (7)
H40B0.19960.16570.33280.203*0.956 (7)
H40C0.10630.08360.34960.203*0.956 (7)
S4B0.119 (5)0.139 (3)0.3825 (12)0.168 (2)0.044 (7)
C36B0.090 (5)0.286 (2)0.3691 (9)0.108 (4)0.044 (7)
C37B0.061 (5)0.294 (2)0.3237 (11)0.122 (4)0.044 (7)
C38B0.063 (8)0.178 (3)0.3009 (14)0.141 (5)0.044 (7)
H38B0.04390.16690.26950.169*0.044 (7)
C39B0.091 (8)0.098 (3)0.3271 (16)0.143 (5)0.044 (7)
H39B0.09710.02100.31700.172*0.044 (7)
C40B0.035 (8)0.400 (4)0.305 (2)0.135 (5)0.044 (7)
H40D0.01900.43700.32390.203*0.044 (7)
H40E0.00710.38880.27340.203*0.044 (7)
H40F0.09720.44860.30350.203*0.044 (7)
C1S0.136 (3)0.662 (2)0.2600 (11)0.167 (11)0.50
H1SA0.11190.58480.25960.200*0.50
C2S0.0717 (19)0.751 (3)0.2425 (12)0.264 (18)0.50
H2SA0.00430.73410.23040.316*0.50
C3S0.108 (2)0.867 (3)0.2431 (13)0.31 (2)0.50
H3SA0.06490.92660.23140.371*0.50
C4S0.209 (3)0.893 (2)0.2612 (11)0.169 (12)0.50
H4SA0.23300.96990.26160.203*0.50
C5S0.273 (2)0.803 (3)0.2786 (12)0.251 (18)0.50
H5SA0.34060.82050.29070.301*0.50
C6S0.237 (2)0.688 (3)0.2780 (12)0.276 (19)0.50
H6SA0.28010.62800.28970.332*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0721 (6)0.0712 (6)0.0800 (8)0.0072 (5)0.0074 (8)0.0046 (9)
N10.079 (5)0.090 (5)0.074 (6)0.014 (4)0.011 (4)0.026 (4)
N20.066 (4)0.065 (4)0.082 (6)0.010 (4)0.006 (4)0.000 (4)
N30.079 (5)0.078 (5)0.091 (7)0.022 (4)0.004 (5)0.006 (4)
N40.070 (5)0.083 (5)0.082 (7)0.005 (4)0.004 (5)0.008 (5)
C10.068 (6)0.096 (7)0.108 (10)0.020 (6)0.013 (7)0.015 (7)
C20.125 (10)0.130 (10)0.125 (13)0.056 (9)0.016 (9)0.028 (9)
C30.090 (7)0.143 (10)0.103 (11)0.054 (7)0.014 (7)0.017 (8)
C40.082 (6)0.098 (6)0.096 (9)0.027 (5)0.000 (8)0.018 (8)
C50.083 (7)0.081 (6)0.102 (10)0.019 (6)0.012 (7)0.011 (7)
C60.071 (6)0.084 (6)0.083 (9)0.004 (5)0.000 (6)0.001 (6)
C70.098 (7)0.085 (6)0.076 (8)0.012 (6)0.012 (6)0.012 (6)
C80.091 (7)0.060 (5)0.101 (9)0.009 (5)0.007 (7)0.009 (6)
C90.083 (6)0.070 (6)0.080 (8)0.004 (5)0.003 (6)0.000 (6)
C100.086 (7)0.078 (6)0.098 (9)0.019 (6)0.014 (6)0.008 (6)
C110.105 (8)0.074 (6)0.107 (11)0.021 (6)0.004 (7)0.017 (7)
C120.150 (11)0.107 (8)0.107 (11)0.069 (8)0.033 (9)0.027 (8)
C130.111 (9)0.124 (9)0.113 (12)0.044 (8)0.001 (8)0.029 (8)
C140.081 (6)0.089 (5)0.103 (9)0.024 (5)0.009 (8)0.020 (9)
C150.076 (6)0.100 (7)0.087 (9)0.018 (6)0.002 (6)0.001 (7)
C160.084 (7)0.081 (6)0.100 (10)0.006 (6)0.004 (7)0.001 (6)
C170.077 (7)0.112 (8)0.092 (10)0.003 (6)0.001 (6)0.002 (7)
C180.079 (7)0.126 (8)0.078 (9)0.012 (7)0.010 (6)0.008 (7)
C190.101 (8)0.093 (6)0.069 (8)0.020 (6)0.009 (7)0.008 (6)
C200.089 (7)0.095 (7)0.102 (10)0.001 (6)0.008 (8)0.022 (7)
S1A0.123 (3)0.157 (3)0.159 (4)0.008 (3)0.028 (3)0.013 (3)
C21A0.099 (6)0.086 (6)0.095 (7)0.008 (5)0.002 (5)0.004 (5)
C22A0.131 (8)0.142 (8)0.141 (9)0.005 (6)0.000 (6)0.004 (6)
C23A0.116 (7)0.118 (6)0.121 (8)0.030 (5)0.001 (6)0.001 (6)
C24A0.139 (8)0.140 (8)0.145 (8)0.011 (6)0.006 (6)0.003 (6)
C25A0.121 (7)0.083 (6)0.108 (7)0.016 (5)0.002 (6)0.014 (5)
S1B0.123 (3)0.157 (3)0.159 (4)0.008 (3)0.028 (3)0.013 (3)
C21B0.099 (6)0.086 (6)0.095 (7)0.008 (5)0.002 (5)0.004 (5)
C22B0.131 (8)0.142 (8)0.141 (9)0.005 (6)0.000 (6)0.004 (6)
C23B0.116 (7)0.118 (6)0.121 (8)0.030 (5)0.001 (6)0.001 (6)
C24B0.139 (8)0.140 (8)0.145 (8)0.011 (6)0.006 (6)0.003 (6)
C25B0.121 (7)0.083 (6)0.108 (7)0.016 (5)0.002 (6)0.014 (5)
S2A0.160 (4)0.128 (4)0.136 (5)0.004 (4)0.006 (4)0.021 (4)
C26A0.075 (6)0.086 (5)0.093 (6)0.003 (5)0.010 (5)0.012 (5)
C27A0.120 (8)0.114 (8)0.112 (9)0.002 (6)0.007 (6)0.005 (6)
C28A0.122 (9)0.119 (7)0.121 (8)0.003 (6)0.005 (6)0.005 (6)
C29A0.110 (7)0.103 (7)0.098 (8)0.004 (6)0.005 (6)0.005 (6)
C30A0.099 (7)0.083 (6)0.085 (8)0.002 (6)0.015 (6)0.010 (6)
S2B0.160 (4)0.128 (4)0.136 (5)0.004 (4)0.006 (4)0.021 (4)
C26B0.075 (6)0.086 (5)0.093 (6)0.003 (5)0.010 (5)0.012 (5)
C27B0.120 (8)0.114 (8)0.112 (9)0.002 (6)0.007 (6)0.005 (6)
C28B0.122 (9)0.119 (7)0.121 (8)0.003 (6)0.005 (6)0.005 (6)
C29B0.110 (7)0.103 (7)0.098 (8)0.004 (6)0.005 (6)0.005 (6)
C30B0.099 (7)0.083 (6)0.085 (8)0.002 (6)0.015 (6)0.010 (6)
S3A0.104 (4)0.212 (7)0.226 (9)0.015 (5)0.032 (5)0.073 (7)
C31A0.098 (6)0.099 (7)0.107 (7)0.001 (5)0.003 (5)0.001 (6)
C32A0.114 (8)0.123 (8)0.120 (9)0.006 (6)0.009 (6)0.004 (6)
C33A0.122 (7)0.122 (8)0.130 (8)0.003 (6)0.001 (6)0.002 (6)
C34A0.114 (8)0.129 (8)0.124 (9)0.010 (6)0.003 (6)0.003 (6)
C35A0.079 (7)0.094 (7)0.094 (8)0.010 (6)0.006 (6)0.013 (6)
S3B0.104 (4)0.212 (7)0.226 (9)0.015 (5)0.032 (5)0.073 (7)
C31B0.098 (6)0.099 (7)0.107 (7)0.001 (5)0.003 (5)0.001 (6)
C32B0.114 (8)0.123 (8)0.120 (9)0.006 (6)0.009 (6)0.004 (6)
C33B0.122 (7)0.122 (8)0.130 (8)0.003 (6)0.001 (6)0.002 (6)
C34B0.114 (8)0.129 (8)0.124 (9)0.010 (6)0.003 (6)0.003 (6)
C35B0.079 (7)0.094 (7)0.094 (8)0.010 (6)0.006 (6)0.013 (6)
S4A0.163 (4)0.200 (4)0.141 (4)0.030 (3)0.040 (3)0.007 (3)
C36A0.099 (6)0.120 (6)0.105 (7)0.015 (5)0.008 (5)0.002 (5)
C37A0.130 (6)0.128 (7)0.109 (7)0.019 (6)0.010 (6)0.012 (6)
C38A0.140 (7)0.153 (7)0.131 (8)0.011 (6)0.004 (6)0.017 (6)
C39A0.147 (7)0.150 (7)0.133 (8)0.016 (6)0.008 (6)0.007 (6)
C40A0.141 (7)0.129 (6)0.135 (8)0.002 (6)0.016 (6)0.033 (6)
S4B0.163 (4)0.200 (4)0.141 (4)0.030 (3)0.040 (3)0.007 (3)
C36B0.099 (6)0.120 (6)0.105 (7)0.015 (5)0.008 (5)0.002 (5)
C37B0.130 (6)0.128 (7)0.109 (7)0.019 (6)0.010 (6)0.012 (6)
C38B0.140 (7)0.153 (7)0.131 (8)0.011 (6)0.004 (6)0.017 (6)
C39B0.147 (7)0.150 (7)0.133 (8)0.016 (6)0.008 (6)0.007 (6)
C40B0.141 (7)0.129 (6)0.135 (8)0.002 (6)0.016 (6)0.033 (6)
C1S0.176 (14)0.156 (13)0.167 (14)0.006 (9)0.001 (9)0.003 (9)
C2S0.263 (19)0.26 (2)0.26 (2)0.000 (10)0.001 (10)0.002 (10)
C3S0.31 (2)0.31 (2)0.31 (2)0.007 (10)0.002 (10)0.002 (10)
C4S0.176 (14)0.156 (13)0.174 (15)0.000 (9)0.007 (9)0.007 (9)
C5S0.248 (19)0.254 (19)0.25 (2)0.002 (10)0.000 (10)0.004 (10)
C6S0.28 (2)0.27 (2)0.28 (2)0.005 (10)0.006 (10)0.001 (10)
Geometric parameters (Å, º) top
Ni—N11.888 (8)C27A—C28A1.458 (15)
Ni—N21.930 (9)C28A—C29A1.232 (17)
Ni—N41.936 (9)C28A—H28A0.9300
Ni—N31.948 (8)C29A—H29A0.9300
N1—C11.371 (15)C30A—H30A0.9600
N1—C41.397 (14)C30A—H30B0.9600
N2—C61.372 (12)C30A—H30C0.9600
N2—C91.391 (13)S2B—C29B1.654 (16)
N3—C141.364 (13)S2B—C26B1.734 (14)
N3—C111.404 (14)C26B—C27B1.334 (16)
N4—C161.363 (13)C27B—C30B1.378 (16)
N4—C191.386 (14)C27B—C28B1.454 (16)
C1—C201.367 (15)C28B—C29B1.237 (18)
C1—C21.433 (15)C28B—H28B0.9300
C2—C31.350 (18)C29B—H29B0.9300
C2—H2A0.9300C30B—H30D0.9600
C3—C41.419 (16)C30B—H30E0.9600
C3—H3A0.9300C30B—H30F0.9600
C4—C51.396 (16)S3A—C34A1.680 (15)
C5—C61.383 (14)S3A—C31A1.746 (14)
C5—C21B1.488 (7)C31A—C32A1.342 (16)
C5—C21A1.489 (6)C32A—C35A1.384 (16)
C6—C71.448 (16)C32A—C33A1.464 (16)
C7—C81.321 (13)C33A—C34A1.234 (18)
C7—H7A0.9300C33A—H33A0.9300
C8—C91.405 (15)C34A—H34A0.9300
C8—H8A0.9300C35A—H35A0.9600
C9—C101.366 (13)C35A—H35B0.9600
C10—C111.370 (15)C35A—H35C0.9600
C10—C26B1.486 (7)S3B—C34B1.669 (15)
C10—C26A1.488 (7)S3B—C31B1.755 (14)
C11—C121.422 (14)C31B—C32B1.351 (15)
C12—C131.339 (16)C32B—C35B1.396 (16)
C12—H12A0.9300C32B—C33B1.463 (15)
C13—C141.440 (15)C33B—C34B1.248 (18)
C13—H13A0.9300C33B—H33B0.9300
C14—C151.380 (16)C34B—H34B0.9300
C15—C161.404 (15)C35B—H35D0.9600
C15—C31B1.488 (7)C35B—H35E0.9600
C15—C31A1.488 (7)C35B—H35F0.9600
C16—C171.417 (17)S4A—C39A1.713 (12)
C17—C181.314 (14)S4A—C36A1.743 (10)
C17—H17A0.9300C36A—C37A1.350 (12)
C18—C191.382 (15)C37A—C40A1.311 (13)
C18—H18A0.9300C37A—C38A1.469 (14)
C19—C201.422 (14)C38A—C39A1.226 (14)
C20—C36A1.487 (6)C38A—H38A0.9300
C20—C36B1.488 (7)C39A—H39A0.9300
S1A—C24A1.708 (13)C40A—H40A0.9600
S1A—C21A1.744 (10)C40A—H40B0.9600
C21A—C22A1.337 (14)C40A—H40C0.9600
C22A—C25A1.337 (14)S4B—C39B1.674 (17)
C22A—C23A1.461 (14)S4B—C36B1.751 (16)
C23A—C24A1.225 (15)C36B—C37B1.343 (17)
C23A—H23A0.9300C37B—C40B1.363 (18)
C24A—H24A0.9300C37B—C38B1.462 (17)
C25A—H25A0.9600C38B—C39B1.231 (19)
C25A—H25B0.9600C38B—H38B0.9300
C25A—H25C0.9600C39B—H39B0.9300
S1B—C24B1.670 (17)C40B—H40D0.9600
S1B—C21B1.752 (15)C40B—H40E0.9600
C21B—C22B1.344 (17)C40B—H40F0.9600
C22B—C25B1.362 (17)C1S—C2S1.3900
C22B—C23B1.461 (17)C1S—C6S1.3900
C23B—C24B1.230 (19)C1S—H1SA0.9300
C23B—H23B0.9300C2S—C3S1.3900
C24B—H24B0.9300C2S—H2SA0.9300
C25B—H25D0.9600C3S—C4S1.3900
C25B—H25E0.9600C3S—H3SA0.9300
C25B—H25F0.9600C4S—C5S1.3900
S2A—C29A1.632 (14)C4S—H4SA0.9300
S2A—C26A1.758 (13)C5S—C6S1.3900
C26A—C27A1.339 (15)C5S—H5SA0.9300
C27A—C30A1.381 (16)C6S—H6SA0.9300
N1—Ni—N289.8 (3)C26A—C27A—C30A118.5 (14)
N1—Ni—N490.0 (4)C26A—C27A—C28A109.7 (12)
N2—Ni—N4177.4 (3)C30A—C27A—C28A131.2 (15)
N1—Ni—N3177.5 (4)C29A—C28A—C27A115.9 (15)
N2—Ni—N390.5 (3)C29A—C28A—H28A122.0
N4—Ni—N389.8 (4)C27A—C28A—H28A122.0
C1—N1—C4100.8 (9)C28A—C29A—S2A112.8 (13)
C1—N1—Ni129.2 (7)C28A—C29A—H29A123.6
C4—N1—Ni129.9 (8)S2A—C29A—H29A123.6
C6—N2—C9105.1 (9)C27A—C30A—H30A109.5
C6—N2—Ni127.3 (7)C27A—C30A—H30B109.5
C9—N2—Ni127.3 (6)H30A—C30A—H30B109.5
C14—N3—C11107.1 (8)C27A—C30A—H30C109.5
C14—N3—Ni126.5 (8)H30A—C30A—H30C109.5
C11—N3—Ni126.3 (7)H30B—C30A—H30C109.5
C16—N4—C19103.0 (10)C29B—S2B—C26B92.1 (9)
C16—N4—Ni128.6 (8)C27B—C26B—C10126.7 (14)
C19—N4—Ni128.4 (7)C27B—C26B—S2B108.3 (10)
C20—C1—N1124.3 (9)C10—C26B—S2B124.5 (12)
C20—C1—C2120.8 (12)C26B—C27B—C30B120.2 (17)
N1—C1—C2114.3 (11)C26B—C27B—C28B112.1 (13)
C3—C2—C1105.1 (12)C30B—C27B—C28B127.6 (18)
C3—C2—H2A127.5C29B—C28B—C27B112.8 (16)
C1—C2—H2A127.5C29B—C28B—H28B123.6
C2—C3—C4106.8 (11)C27B—C28B—H28B123.6
C2—C3—H3A126.6C28B—C29B—S2B114.7 (15)
C4—C3—H3A126.6C28B—C29B—H29B122.7
C5—C4—N1123.4 (9)S2B—C29B—H29B122.7
C5—C4—C3123.6 (11)C27B—C30B—H30D109.5
N1—C4—C3113.0 (12)C27B—C30B—H30E109.5
C6—C5—C4121.0 (8)H30D—C30B—H30E109.5
C6—C5—C21B125.5 (16)C27B—C30B—H30F109.5
C4—C5—C21B112.7 (15)H30D—C30B—H30F109.5
C6—C5—C21A118.5 (11)H30E—C30B—H30F109.5
C4—C5—C21A119.3 (10)C34A—S3A—C31A91.4 (9)
N2—C6—C5126.0 (10)C32A—C31A—C15123.8 (13)
N2—C6—C7109.5 (9)C32A—C31A—S3A109.1 (9)
C5—C6—C7124.4 (10)C15—C31A—S3A126.6 (11)
C8—C7—C6106.6 (10)C31A—C32A—C35A118.7 (17)
C8—C7—H7A126.7C31A—C32A—C33A110.9 (13)
C6—C7—H7A126.7C35A—C32A—C33A130.5 (17)
C7—C8—C9108.9 (11)C34A—C33A—C32A113.9 (16)
C7—C8—H8A125.6C34A—C33A—H33A123.1
C9—C8—H8A125.6C32A—C33A—H33A123.1
C10—C9—N2125.7 (10)C33A—C34A—S3A113.7 (15)
C10—C9—C8124.6 (10)C33A—C34A—H34A123.1
N2—C9—C8109.7 (9)S3A—C34A—H34A123.1
C9—C10—C11123.2 (9)C32A—C35A—H35A109.5
C9—C10—C26B114.4 (11)C32A—C35A—H35B109.5
C11—C10—C26B122.4 (11)H35A—C35A—H35B109.5
C9—C10—C26A121.8 (10)C32A—C35A—H35C109.5
C11—C10—C26A113.9 (10)H35A—C35A—H35C109.5
C10—C11—N3124.7 (9)H35B—C35A—H35C109.5
C10—C11—C12125.6 (11)C34B—S3B—C31B90.9 (8)
N3—C11—C12108.6 (11)C32B—C31B—C15127.9 (12)
C13—C12—C11107.4 (11)C32B—C31B—S3B110.5 (8)
C13—C12—H12A126.3C15—C31B—S3B121.3 (10)
C11—C12—H12A126.3C31B—C32B—C35B117.0 (14)
C12—C13—C14108.7 (11)C31B—C32B—C33B109.1 (12)
C12—C13—H13A125.7C35B—C32B—C33B133.4 (16)
C14—C13—H13A125.7C34B—C33B—C32B115.1 (15)
N3—C14—C15127.3 (8)C34B—C33B—H33B122.4
N3—C14—C13108.2 (12)C32B—C33B—H33B122.4
C15—C14—C13124.5 (11)C33B—C34B—S3B114.3 (13)
C14—C15—C16120.7 (8)C33B—C34B—H34B122.9
C14—C15—C31B118.9 (11)S3B—C34B—H34B122.9
C16—C15—C31B120.5 (12)C32B—C35B—H35D109.5
C14—C15—C31A114.0 (12)C32B—C35B—H35E109.5
C16—C15—C31A123.5 (13)H35D—C35B—H35E109.5
N4—C16—C15124.6 (11)C32B—C35B—H35F109.5
N4—C16—C17111.2 (10)H35D—C35B—H35F109.5
C15—C16—C17123.7 (11)H35E—C35B—H35F109.5
C18—C17—C16106.4 (11)C39A—S4A—C36A90.1 (6)
C18—C17—H17A126.8C37A—C36A—C20130.0 (10)
C16—C17—H17A126.8C37A—C36A—S4A109.9 (8)
C17—C18—C19108.4 (12)C20—C36A—S4A119.6 (8)
C17—C18—H18A125.8C40A—C37A—C36A122.8 (11)
C19—C18—H18A125.8C40A—C37A—C38A125.5 (12)
C18—C19—N4111.0 (9)C36A—C37A—C38A111.6 (11)
C18—C19—C20126.6 (11)C39A—C38A—C37A112.8 (13)
N4—C19—C20122.4 (10)C39A—C38A—H38A123.6
C1—C20—C19123.4 (9)C37A—C38A—H38A123.6
C1—C20—C36A119.9 (10)C38A—C39A—S4A115.5 (11)
C19—C20—C36A116.6 (10)C38A—C39A—H39A122.2
C1—C20—C36B118 (2)S4A—C39A—H39A122.2
C19—C20—C36B106 (3)C37A—C40A—H40A109.5
C24A—S1A—C21A90.0 (6)C37A—C40A—H40B109.5
C22A—C21A—C5126.9 (10)H40A—C40A—H40B109.5
C22A—C21A—S1A110.6 (8)C37A—C40A—H40C109.5
C5—C21A—S1A122.5 (8)H40A—C40A—H40C109.5
C25A—C22A—C21A120.7 (12)H40B—C40A—H40C109.5
C25A—C22A—C23A128.9 (13)C39B—S4B—C36B91.1 (11)
C21A—C22A—C23A110.4 (11)C37B—C36B—C20122 (3)
C24A—C23A—C22A114.4 (13)C37B—C36B—S4B109.1 (13)
C24A—C23A—H23A122.8C20—C36B—S4B128 (2)
C22A—C23A—H23A122.8C36B—C37B—C40B120 (2)
C23A—C24A—S1A114.3 (12)C36B—C37B—C38B111.1 (15)
C23A—C24A—H24A122.9C40B—C37B—C38B129 (2)
S1A—C24A—H24A122.9C39B—C38B—C37B113.8 (18)
C22A—C25A—H25A109.5C39B—C38B—H38B123.1
C22A—C25A—H25B109.5C37B—C38B—H38B123.1
H25A—C25A—H25B109.5C38B—C39B—S4B114.8 (17)
C22A—C25A—H25C109.5C38B—C39B—H39B122.6
H25A—C25A—H25C109.5S4B—C39B—H39B122.6
H25B—C25A—H25C109.5C37B—C40B—H40D109.5
C24B—S1B—C21B91.3 (10)C37B—C40B—H40E109.5
C22B—C21B—C5123.0 (16)H40D—C40B—H40E109.5
C22B—C21B—S1B109.1 (11)C37B—C40B—H40F109.5
C5—C21B—S1B127.9 (14)H40D—C40B—H40F109.5
C21B—C22B—C25B122 (2)H40E—C40B—H40F109.5
C21B—C22B—C23B110.7 (14)C2S—C1S—C6S120.0
C25B—C22B—C23B127 (2)C2S—C1S—H1SA120.0
C24B—C23B—C22B114.2 (17)C6S—C1S—H1SA120.0
C24B—C23B—H23B122.9C3S—C2S—C1S120.0
C22B—C23B—H23B122.9C3S—C2S—H2SA120.0
C23B—C24B—S1B114.6 (16)C1S—C2S—H2SA120.0
C23B—C24B—H24B122.7C2S—C3S—C4S120.0
S1B—C24B—H24B122.7C2S—C3S—H3SA120.0
C22B—C25B—H25D109.5C4S—C3S—H3SA120.0
C22B—C25B—H25E109.5C5S—C4S—C3S120.0
H25D—C25B—H25E109.5C5S—C4S—H4SA120.0
C22B—C25B—H25F109.5C3S—C4S—H4SA120.0
H25D—C25B—H25F109.5C4S—C5S—C6S120.0
H25E—C25B—H25F109.5C4S—C5S—H5SA120.0
C29A—S2A—C26A92.9 (7)C6S—C5S—H5SA120.0
C27A—C26A—C10125.0 (12)C5S—C6S—C1S120.0
C27A—C26A—S2A108.1 (8)C5S—C6S—H6SA120.0
C10—C26A—S2A126.6 (10)C1S—C6S—H6SA120.0
N2—Ni—N1—C1165.7 (9)S1A—C21A—C22A—C25A175.7 (12)
N4—Ni—N1—C116.8 (9)C5—C21A—C22A—C23A175.9 (14)
N2—Ni—N1—C48.3 (8)S1A—C21A—C22A—C23A3.1 (13)
N4—Ni—N1—C4169.1 (8)C25A—C22A—C23A—C24A172.6 (17)
N1—Ni—N2—C615.1 (8)C21A—C22A—C23A—C24A6 (2)
N3—Ni—N2—C6167.3 (8)C22A—C23A—C24A—S1A6 (2)
N1—Ni—N2—C9171.9 (8)C21A—S1A—C24A—C23A3.7 (16)
N3—Ni—N2—C95.6 (8)C6—C5—C21B—C22B108 (2)
N2—Ni—N3—C14168.2 (9)C4—C5—C21B—C22B83 (3)
N4—Ni—N3—C149.2 (9)C21A—C5—C21B—C22B30 (3)
N2—Ni—N3—C1115.2 (9)C6—C5—C21B—S1B69 (3)
N4—Ni—N3—C11167.4 (9)C4—C5—C21B—S1B101 (2)
N1—Ni—N4—C16168.1 (8)C21A—C5—C21B—S1B147 (6)
N3—Ni—N4—C1614.3 (8)C24B—S1B—C21B—C22B0.3 (14)
N1—Ni—N4—C1911.3 (8)C24B—S1B—C21B—C5177 (4)
N3—Ni—N4—C19166.2 (8)C5—C21B—C22B—C25B6 (4)
C4—N1—C1—C20171.2 (10)S1B—C21B—C22B—C25B177 (2)
Ni—N1—C1—C2013.5 (16)C5—C21B—C22B—C23B176 (3)
C4—N1—C1—C20.2 (12)S1B—C21B—C22B—C23B1.0 (18)
Ni—N1—C1—C2175.2 (8)C21B—C22B—C23B—C24B3 (4)
C20—C1—C2—C3171.2 (12)C25B—C22B—C23B—C24B175 (3)
N1—C1—C2—C30.5 (15)C22B—C23B—C24B—S1B3 (5)
C1—C2—C3—C40.6 (15)C21B—S1B—C24B—C23B2 (3)
C1—N1—C4—C5179.2 (10)C9—C10—C26A—C27A80.9 (16)
Ni—N1—C4—C53.9 (15)C11—C10—C26A—C27A110.9 (15)
C1—N1—C4—C30.2 (12)C26B—C10—C26A—C27A19 (4)
Ni—N1—C4—C3175.5 (8)C9—C10—C26A—S2A91.8 (15)
C2—C3—C4—C5178.9 (12)C11—C10—C26A—S2A76.4 (15)
C2—C3—C4—N10.6 (15)C26B—C10—C26A—S2A153 (6)
N1—C4—C5—C613.7 (16)C29A—S2A—C26A—C27A1.1 (10)
C3—C4—C5—C6165.7 (11)C29A—S2A—C26A—C10174.8 (15)
N1—C4—C5—C21B156.2 (12)C10—C26A—C27A—C30A2 (2)
C3—C4—C5—C21B24.3 (17)S2A—C26A—C27A—C30A175.9 (13)
N1—C4—C5—C21A178.8 (9)C10—C26A—C27A—C28A170.8 (17)
C3—C4—C5—C21A1.7 (16)S2A—C26A—C27A—C28A3.0 (13)
C9—N2—C6—C5175.1 (10)C26A—C27A—C28A—C29A8 (2)
Ni—N2—C6—C510.7 (14)C30A—C27A—C28A—C29A179.4 (19)
C9—N2—C6—C72.2 (10)C27A—C28A—C29A—S2A9 (2)
Ni—N2—C6—C7172.0 (6)C26A—S2A—C29A—C28A5.7 (17)
C4—C5—C6—N26.3 (16)C9—C10—C26B—C27B107.3 (18)
C21B—C5—C6—N2162.3 (13)C11—C10—C26B—C27B73 (2)
C21A—C5—C6—N2173.9 (9)C26A—C10—C26B—C27B18 (4)
C4—C5—C6—C7170.6 (10)C9—C10—C26B—S2B82.1 (16)
C21B—C5—C6—C720.8 (18)C11—C10—C26B—S2B97.2 (17)
C21A—C5—C6—C73.0 (15)C26A—C10—C26B—S2B153 (6)
N2—C6—C7—C84.5 (11)C29B—S2B—C26B—C27B0.6 (12)
C5—C6—C7—C8172.9 (10)C29B—S2B—C26B—C10171.5 (19)
C6—C7—C8—C94.8 (11)C10—C26B—C27B—C30B12 (3)
C6—N2—C9—C10179.4 (10)S2B—C26B—C27B—C30B176.2 (16)
Ni—N2—C9—C105.2 (14)C10—C26B—C27B—C28B170 (2)
C6—N2—C9—C80.7 (10)S2B—C26B—C27B—C28B1.7 (16)
Ni—N2—C9—C8174.9 (6)C26B—C27B—C28B—C29B2 (3)
C7—C8—C9—C10176.5 (10)C30B—C27B—C28B—C29B175 (2)
C7—C8—C9—N23.6 (12)C27B—C28B—C29B—S2B2 (3)
N2—C9—C10—C119.7 (16)C26B—S2B—C29B—C28B1 (2)
C8—C9—C10—C11170.4 (11)C14—C15—C31A—C32A100.1 (19)
N2—C9—C10—C26B169.6 (11)C16—C15—C31A—C32A95.5 (19)
C8—C9—C10—C26B10.3 (16)C31B—C15—C31A—C32A13 (5)
N2—C9—C10—C26A176.8 (10)C14—C15—C31A—S3A88.9 (18)
C8—C9—C10—C26A3.3 (17)C16—C15—C31A—S3A75.5 (19)
C9—C10—C11—N31.2 (18)C31B—C15—C31A—S3A158 (7)
C26B—C10—C11—N3179.6 (12)C34A—S3A—C31A—C32A3.3 (12)
C26A—C10—C11—N3166.9 (11)C34A—S3A—C31A—C15169 (2)
C9—C10—C11—C12167.9 (11)C15—C31A—C32A—C35A6 (3)
C26B—C10—C11—C1212.9 (19)S3A—C31A—C32A—C35A178.4 (16)
C26A—C10—C11—C120.2 (17)C15—C31A—C32A—C33A174 (2)
C14—N3—C11—C10167.2 (11)S3A—C31A—C32A—C33A1.8 (15)
Ni—N3—C11—C1015.7 (16)C31A—C32A—C33A—C34A8 (3)
C14—N3—C11—C121.5 (13)C35A—C32A—C33A—C34A172 (2)
Ni—N3—C11—C12175.6 (8)C32A—C33A—C34A—S3A11 (3)
C10—C11—C12—C13165.2 (12)C31A—S3A—C34A—C33A9 (2)
N3—C11—C12—C133.3 (15)C14—C15—C31B—C32B84.9 (19)
C11—C12—C13—C143.8 (16)C16—C15—C31B—C32B95.0 (19)
C11—N3—C14—C15179.5 (11)C31A—C15—C31B—C32B11 (5)
Ni—N3—C14—C152.4 (17)C14—C15—C31B—S3B87.9 (16)
C11—N3—C14—C130.8 (13)C16—C15—C31B—S3B92.2 (16)
Ni—N3—C14—C13177.9 (8)C31A—C15—C31B—S3B161 (7)
C12—C13—C14—N33.0 (15)C34B—S3B—C31B—C32B1.2 (11)
C12—C13—C14—C15177.4 (12)C34B—S3B—C31B—C15175.1 (18)
N3—C14—C15—C1613.6 (18)C15—C31B—C32B—C35B12 (2)
C13—C14—C15—C16166.8 (11)S3B—C31B—C32B—C35B174.3 (14)
N3—C14—C15—C31B166.5 (11)C15—C31B—C32B—C33B175 (2)
C13—C14—C15—C31B13.1 (18)S3B—C31B—C32B—C33B1.7 (14)
N3—C14—C15—C31A178.5 (12)C31B—C32B—C33B—C34B2 (3)
C13—C14—C15—C31A1.9 (18)C35B—C32B—C33B—C34B173 (2)
C19—N4—C16—C15172.1 (10)C32B—C33B—C34B—S3B1 (3)
Ni—N4—C16—C158.3 (15)C31B—S3B—C34B—C33B0 (2)
C19—N4—C16—C170.2 (11)C1—C20—C36A—C37A92.4 (14)
Ni—N4—C16—C17179.7 (7)C19—C20—C36A—C37A85.2 (14)
C14—C15—C16—N48.0 (17)C36B—C20—C36A—C37A5 (4)
C31B—C15—C16—N4172.1 (11)C1—C20—C36A—S4A79.0 (12)
C31A—C15—C16—N4171.4 (11)C19—C20—C36A—S4A103.4 (10)
C14—C15—C16—C17162.9 (11)C36B—C20—C36A—S4A177 (4)
C31B—C15—C16—C1717.0 (17)C39A—S4A—C36A—C37A0.9 (9)
C31A—C15—C16—C170.4 (18)C39A—S4A—C36A—C20172.1 (10)
N4—C16—C17—C181.3 (13)C20—C36A—C37A—C40A12.0 (19)
C15—C16—C17—C18170.8 (10)S4A—C36A—C37A—C40A175.9 (11)
C16—C17—C18—C192.2 (13)C20—C36A—C37A—C38A172.2 (12)
C17—C18—C19—N42.4 (14)S4A—C36A—C37A—C38A0.1 (11)
C17—C18—C19—C20176.3 (10)C40A—C37A—C38A—C39A177.3 (15)
C16—N4—C19—C181.5 (12)C36A—C37A—C38A—C39A1.7 (17)
Ni—N4—C19—C18178.9 (7)C37A—C38A—C39A—S4A2.5 (18)
C16—N4—C19—C20177.3 (9)C36A—S4A—C39A—C38A2.1 (14)
Ni—N4—C19—C202.3 (14)C1—C20—C36B—C37B118 (4)
N1—C1—C20—C191.8 (17)C19—C20—C36B—C37B100 (4)
C2—C1—C20—C19169.0 (11)C36A—C20—C36B—C37B14 (3)
N1—C1—C20—C36A179.2 (10)C1—C20—C36B—S4B50 (6)
C2—C1—C20—C36A8.4 (16)C19—C20—C36B—S4B92 (5)
N1—C1—C20—C36B138 (2)C36A—C20—C36B—S4B154 (7)
C2—C1—C20—C36B33 (3)C39B—S4B—C36B—C37B0.1 (16)
C18—C19—C20—C1171.4 (12)C39B—S4B—C36B—C20169 (7)
N4—C19—C20—C17.2 (16)C20—C36B—C37B—C40B11 (7)
C18—C19—C20—C36A6.1 (16)S4B—C36B—C37B—C40B179 (2)
N4—C19—C20—C36A175.3 (9)C20—C36B—C37B—C38B170 (6)
C18—C19—C20—C36B31 (2)S4B—C36B—C37B—C38B0.3 (19)
N4—C19—C20—C36B147.4 (16)C36B—C37B—C38B—C39B1 (4)
C6—C5—C21A—C22A115.9 (13)C40B—C37B—C38B—C39B179 (4)
C4—C5—C21A—C22A76.3 (16)C37B—C38B—C39B—S4B1 (5)
C21B—C5—C21A—C22A1 (4)C36B—S4B—C39B—C38B1 (4)
C6—C5—C21A—S1A63.0 (14)C6S—C1S—C2S—C3S0.0
C4—C5—C21A—S1A104.8 (11)C1S—C2S—C3S—C4S0.0
C21B—C5—C21A—S1A178 (4)C2S—C3S—C4S—C5S0.0
C24A—S1A—C21A—C22A0.1 (10)C3S—C4S—C5S—C6S0.0
C24A—S1A—C21A—C5179.0 (12)C4S—C5S—C6S—C1S0.0
C5—C21A—C22A—C25A5 (2)C2S—C1S—C6S—C5S0.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C30A—H30A···S1Ai0.962.703.50 (2)141
Symmetry code: (i) x+1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formula[Ni(C40H28N4S4)]·0.5C6H6
Mr790.67
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)295
a, b, c (Å)12.4854 (6), 11.3906 (5), 28.365 (2)
V3)4034.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.72
Crystal size (mm)0.39 × 0.22 × 0.05
Data collection
DiffractometerAgilent Xcalibur (Ruby, Gemini)
diffractometer
Absorption correctionAnalytical
[CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model (Clark & Reid (1995)]
Tmin, Tmax0.830, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
12922, 5674, 2720
Rint0.091
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.077, 0.240, 0.99
No. of reflections5674
No. of parameters562
No. of restraints709
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.24
Absolute structureFlack (1983), ???? Friedel pairs
Absolute structure parameter0.35 (4)

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

Acknowledgements top

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.

references
References top

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Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

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