Intra- and intermolecular C-H...[pi] interactions in bis­[benzyl 3-(fluoren-9-yl­idene)­di­thio­carb­aza­to-N³,S]­nickel(II)

The title compound, [Ni(C₂₁H₁₅N₂S₂)₂], has a novel cis configuration with two fluorene moieties on the same side. The Ni atom is in a square-planar configuration. The molecular packing is stabilized by intramolecular stacking between the fluorene moieties and extensive C-H...[pi] interactions.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Intra- and Intermolecular C—H···π interactions in Bis(fluorenedithiocarbazato)Nickel(II)

Crystal data

C42H30N4NiS4	F(000) = 1608
Mr = 777.65	Dx = 1.421 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9463 (1) Å	Cell parameters from 7645 reflections
b = 21.7605 (1) Å	θ = 1.4–28.4°
c = 19.0038 (2) Å	µ = 0.80 mm^−1
β = 100.690 (1)°	T = 293 K
V = 3635.38 (6) Å^3	Needle, black
Z = 4	0.48 × 0.14 × 0.12 mm

Data collection

Siemens SMART CCD area-detector diffractometer	6398 independent reflections
Radiation source: fine-focus sealed tube	3886 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
Detector resolution: 8.33 pixels mm^-1	θmax = 25.0°, θmin = 1.4°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −25→16
Tmin = 0.700, Tmax = 0.910	l = −22→22
20413 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0796P)^2] where P = (Fo^2 + 2Fc^2)/3
6398 reflections	(Δ/σ)max = 0.001
460 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −1.24 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different φ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.61154 (7)	0.25498 (2)	0.26099 (3)	0.0377 (2)
S1	0.76954 (15)	0.33064 (5)	0.27980 (7)	0.0515 (3)
S2	1.07291 (17)	0.32700 (6)	0.36874 (8)	0.0652 (4)
S3	0.42692 (15)	0.31907 (5)	0.23103 (7)	0.0503 (4)
S4	0.12382 (16)	0.28982 (6)	0.14885 (8)	0.0615 (4)
N1	0.7907 (4)	0.20327 (15)	0.27254 (18)	0.0375 (9)
N2	0.9229 (4)	0.22562 (16)	0.3174 (2)	0.0430 (9)
N3	0.4546 (4)	0.19324 (15)	0.25885 (18)	0.0378 (9)
N4	0.3158 (4)	0.20386 (16)	0.2115 (2)	0.0443 (9)
C1	0.8017 (5)	0.14592 (19)	0.2528 (2)	0.0374 (10)
C2	0.9092 (5)	0.09752 (18)	0.2868 (2)	0.0389 (11)
C3	1.0306 (6)	0.0983 (2)	0.3445 (3)	0.0502 (13)
H3A	1.0668	0.1354	0.3655	0.060*
C4	1.0967 (6)	0.0431 (2)	0.3703 (3)	0.0627 (15)
H4A	1.1776	0.0432	0.4089	0.075*
C5	1.0435 (7)	−0.0121 (2)	0.3391 (3)	0.0699 (16)
H5A	1.0889	−0.0487	0.3573	0.084*
C6	0.9252 (6)	−0.0138 (2)	0.2820 (3)	0.0603 (14)
H6A	0.8912	−0.0511	0.2611	0.072*
C7	0.8568 (5)	0.04084 (19)	0.2558 (2)	0.0445 (12)
C8	0.7294 (5)	0.0522 (2)	0.1965 (2)	0.0453 (12)
C9	0.6460 (6)	0.0129 (2)	0.1462 (3)	0.0622 (15)
H9A	0.6648	−0.0292	0.1480	0.075*
C10	0.5347 (7)	0.0376 (3)	0.0935 (3)	0.0713 (17)
H10A	0.4762	0.0115	0.0605	0.086*
C11	0.5085 (6)	0.1002 (3)	0.0887 (3)	0.0661 (15)
H11A	0.4352	0.1156	0.0518	0.079*
C12	0.5903 (6)	0.1405 (2)	0.1383 (2)	0.0527 (13)
H12A	0.5743	0.1827	0.1346	0.063*
C13	0.6968 (5)	0.1154 (2)	0.1937 (2)	0.0412 (11)
C14	0.9202 (5)	0.28486 (19)	0.3210 (2)	0.0433 (11)
C15	1.2187 (6)	0.2699 (2)	0.3921 (3)	0.0601 (14)
H15A	1.2162	0.2435	0.3507	0.072*
H15B	1.3160	0.2909	0.4002	0.072*
C16	1.2146 (6)	0.2288 (2)	0.4563 (2)	0.0469 (12)
C17	1.3210 (6)	0.1829 (3)	0.4707 (3)	0.0677 (15)
H17A	1.3924	0.1783	0.4412	0.081*
C18	1.3249 (8)	0.1428 (3)	0.5283 (4)	0.0806 (18)
H18A	1.3968	0.1115	0.5366	0.097*
C19	1.2216 (9)	0.1503 (3)	0.5720 (3)	0.083 (2)
H19A	1.2226	0.1240	0.6107	0.100*
C20	1.1182 (7)	0.1958 (3)	0.5595 (3)	0.0754 (18)
H20A	1.0497	0.2009	0.5903	0.090*
C21	1.1110 (6)	0.2360 (2)	0.5007 (3)	0.0613 (14)
H21A	1.0375	0.2666	0.4922	0.074*
C22	0.4644 (5)	0.13843 (19)	0.2876 (2)	0.0405 (11)
C23	0.5801 (5)	0.1219 (2)	0.3520 (2)	0.0457 (12)
C24	0.6712 (6)	0.1586 (3)	0.4014 (3)	0.0586 (14)
H24A	0.6710	0.2011	0.3962	0.070*
C25	0.7629 (7)	0.1304 (3)	0.4590 (3)	0.089 (2)
H25A	0.8255	0.1546	0.4926	0.106*
C26	0.7643 (10)	0.0689 (4)	0.4677 (4)	0.116 (3)
H26A	0.8305	0.0515	0.5060	0.140*
C27	0.6683 (9)	0.0310 (3)	0.4203 (4)	0.098 (2)
H27A	0.6674	−0.0112	0.4276	0.118*
C28	0.5728 (7)	0.0579 (2)	0.3613 (3)	0.0630 (15)
C29	0.4559 (6)	0.0327 (2)	0.3045 (3)	0.0589 (15)
C30	0.4138 (9)	−0.0277 (2)	0.2863 (4)	0.091 (2)
H30A	0.4630	−0.0603	0.3126	0.110*
C31	0.2976 (9)	−0.0384 (3)	0.2288 (4)	0.092 (2)
H31A	0.2683	−0.0787	0.2167	0.111*
C32	0.2239 (8)	0.0097 (3)	0.1886 (4)	0.085 (2)
H32A	0.1454	0.0012	0.1504	0.102*
C33	0.2660 (6)	0.0704 (2)	0.2049 (3)	0.0626 (15)
H33A	0.2174	0.1026	0.1777	0.075*
C34	0.3816 (5)	0.08162 (19)	0.2625 (3)	0.0464 (12)
C35	0.2941 (5)	0.2623 (2)	0.1982 (2)	0.0447 (12)
C36	0.0096 (6)	0.2219 (2)	0.1299 (3)	0.0552 (13)
H36A	0.0281	0.1961	0.1723	0.066*
H36B	−0.0964	0.2342	0.1222	0.066*
C37	0.0327 (6)	0.1824 (2)	0.0659 (3)	0.0509 (12)
C38	0.1341 (6)	0.1969 (3)	0.0225 (3)	0.0674 (15)
H38A	0.1950	0.2317	0.0321	0.081*
C39	0.1460 (7)	0.1594 (3)	−0.0365 (3)	0.0773 (17)
H39A	0.2142	0.1697	−0.0660	0.093*
C40	0.0593 (8)	0.1085 (3)	−0.0506 (3)	0.090 (2)
H40A	0.0679	0.0839	−0.0896	0.108*
C41	−0.0410 (9)	0.0933 (3)	−0.0074 (4)	0.107 (2)
H41A	−0.1008	0.0582	−0.0166	0.128*
C42	−0.0529 (7)	0.1305 (3)	0.0500 (3)	0.0820 (19)
H42A	−0.1218	0.1199	0.0791	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0558 (4)	0.0275 (3)	0.0339 (3)	0.0009 (3)	0.0195 (3)	0.0011 (2)
S1	0.0728 (9)	0.0306 (6)	0.0522 (8)	−0.0042 (6)	0.0140 (7)	0.0052 (5)
S2	0.0821 (10)	0.0480 (8)	0.0621 (9)	−0.0234 (7)	0.0043 (8)	0.0056 (7)
S3	0.0659 (9)	0.0298 (6)	0.0585 (8)	0.0073 (5)	0.0203 (7)	0.0006 (5)
S4	0.0689 (9)	0.0537 (8)	0.0603 (9)	0.0145 (7)	0.0076 (7)	0.0027 (7)
N1	0.053 (2)	0.032 (2)	0.032 (2)	−0.0064 (17)	0.0184 (18)	0.0006 (16)
N2	0.052 (2)	0.035 (2)	0.045 (2)	−0.0080 (18)	0.0181 (19)	−0.0020 (17)
N3	0.050 (2)	0.032 (2)	0.035 (2)	0.0102 (17)	0.0190 (18)	0.0029 (16)
N4	0.054 (2)	0.036 (2)	0.046 (2)	0.0021 (18)	0.0155 (19)	−0.0030 (18)
C1	0.049 (3)	0.036 (2)	0.034 (2)	−0.004 (2)	0.025 (2)	0.000 (2)
C2	0.049 (3)	0.035 (2)	0.039 (3)	0.002 (2)	0.026 (2)	−0.002 (2)
C3	0.063 (3)	0.037 (3)	0.053 (3)	0.001 (2)	0.018 (3)	−0.003 (2)
C4	0.078 (4)	0.055 (3)	0.056 (3)	0.010 (3)	0.014 (3)	0.004 (3)
C5	0.097 (5)	0.046 (3)	0.069 (4)	0.018 (3)	0.022 (4)	0.009 (3)
C6	0.083 (4)	0.035 (3)	0.068 (4)	0.005 (3)	0.028 (3)	−0.007 (3)
C7	0.059 (3)	0.039 (3)	0.042 (3)	0.004 (2)	0.025 (2)	−0.006 (2)
C8	0.060 (3)	0.042 (3)	0.042 (3)	−0.005 (2)	0.030 (3)	−0.008 (2)
C9	0.085 (4)	0.055 (3)	0.054 (3)	−0.012 (3)	0.031 (3)	−0.027 (3)
C10	0.094 (5)	0.080 (4)	0.042 (3)	−0.011 (4)	0.020 (3)	−0.027 (3)
C11	0.076 (4)	0.088 (4)	0.037 (3)	−0.002 (3)	0.018 (3)	−0.007 (3)
C12	0.071 (4)	0.057 (3)	0.038 (3)	−0.003 (3)	0.029 (3)	−0.005 (2)
C13	0.052 (3)	0.044 (3)	0.034 (3)	−0.002 (2)	0.026 (2)	−0.003 (2)
C14	0.061 (3)	0.036 (3)	0.037 (3)	−0.010 (2)	0.019 (2)	−0.001 (2)
C15	0.059 (3)	0.075 (4)	0.050 (3)	−0.018 (3)	0.018 (3)	0.000 (3)
C16	0.052 (3)	0.057 (3)	0.034 (3)	−0.010 (2)	0.012 (2)	−0.007 (2)
C17	0.071 (4)	0.076 (4)	0.060 (4)	0.000 (3)	0.022 (3)	−0.006 (3)
C18	0.095 (5)	0.066 (4)	0.076 (5)	0.005 (3)	0.004 (4)	0.000 (4)
C19	0.122 (6)	0.068 (4)	0.053 (4)	−0.017 (4)	−0.001 (4)	0.011 (3)
C20	0.103 (5)	0.093 (5)	0.036 (3)	−0.022 (4)	0.029 (3)	−0.004 (3)
C21	0.068 (4)	0.070 (4)	0.051 (3)	0.004 (3)	0.027 (3)	0.000 (3)
C22	0.053 (3)	0.036 (2)	0.041 (3)	0.006 (2)	0.029 (2)	0.001 (2)
C23	0.061 (3)	0.044 (3)	0.041 (3)	0.007 (2)	0.030 (2)	0.008 (2)
C24	0.065 (3)	0.073 (4)	0.041 (3)	0.010 (3)	0.019 (3)	0.015 (3)
C25	0.096 (5)	0.110 (6)	0.061 (4)	0.000 (4)	0.018 (4)	0.030 (4)
C26	0.134 (7)	0.135 (7)	0.077 (5)	0.023 (6)	0.011 (5)	0.053 (5)
C27	0.132 (6)	0.065 (4)	0.105 (6)	0.030 (4)	0.040 (5)	0.054 (4)
C28	0.084 (4)	0.050 (3)	0.066 (4)	0.015 (3)	0.043 (3)	0.023 (3)
C29	0.084 (4)	0.032 (3)	0.075 (4)	0.000 (3)	0.050 (3)	0.007 (3)
C30	0.125 (6)	0.037 (3)	0.135 (7)	−0.006 (4)	0.085 (5)	0.010 (4)
C31	0.120 (6)	0.048 (4)	0.131 (7)	−0.029 (4)	0.079 (5)	−0.025 (4)
C32	0.111 (5)	0.063 (4)	0.092 (5)	−0.034 (4)	0.052 (4)	−0.027 (4)
C33	0.083 (4)	0.051 (3)	0.063 (4)	−0.014 (3)	0.039 (3)	−0.013 (3)
C34	0.063 (3)	0.030 (2)	0.056 (3)	−0.004 (2)	0.039 (3)	−0.003 (2)
C35	0.060 (3)	0.044 (3)	0.036 (3)	0.010 (2)	0.022 (2)	0.001 (2)
C36	0.058 (3)	0.063 (3)	0.047 (3)	0.012 (3)	0.018 (3)	0.001 (3)
C37	0.056 (3)	0.061 (3)	0.040 (3)	0.006 (3)	0.020 (2)	0.006 (2)
C38	0.079 (4)	0.078 (4)	0.051 (3)	−0.011 (3)	0.027 (3)	0.000 (3)
C39	0.083 (4)	0.111 (5)	0.047 (3)	0.008 (4)	0.034 (3)	0.000 (4)
C40	0.104 (5)	0.098 (5)	0.069 (5)	0.005 (4)	0.022 (4)	−0.032 (4)
C41	0.137 (7)	0.101 (6)	0.094 (6)	−0.033 (5)	0.055 (5)	−0.034 (4)
C42	0.101 (5)	0.080 (4)	0.078 (4)	−0.026 (4)	0.050 (4)	−0.018 (4)

Geometric parameters (Å, º)

Ni1—N1	1.937 (3)	C12—C13	1.394 (6)
Ni1—N3	1.938 (4)	C15—C16	1.519 (7)
Ni1—S3	2.156 (1)	C16—C21	1.372 (7)
Ni1—S1	2.156 (1)	C16—C17	1.373 (7)
S1—C14	1.741 (5)	C17—C18	1.394 (8)
S2—C14	1.752 (4)	C18—C19	1.363 (9)
S2—C15	1.796 (5)	C19—C20	1.346 (8)
S3—C35	1.746 (5)	C20—C21	1.410 (7)
S4—C35	1.740 (5)	C22—C34	1.474 (6)
S4—C36	1.796 (5)	C22—C23	1.493 (6)
N1—C1	1.312 (5)	C23—C24	1.379 (6)
N1—N2	1.410 (5)	C23—C28	1.406 (6)
N2—C14	1.291 (5)	C24—C25	1.382 (7)
N3—C22	1.308 (5)	C25—C26	1.349 (9)
N3—N4	1.410 (5)	C26—C27	1.393 (9)
N4—C35	1.305 (5)	C27—C28	1.405 (8)
C1—C13	1.480 (6)	C28—C29	1.464 (7)
C1—C2	1.490 (6)	C29—C30	1.392 (7)
C2—C3	1.393 (6)	C29—C34	1.420 (6)
C2—C7	1.410 (6)	C30—C31	1.382 (10)
C3—C4	1.388 (6)	C31—C32	1.388 (9)
C4—C5	1.386 (7)	C32—C33	1.394 (7)
C5—C6	1.368 (7)	C33—C34	1.381 (7)
C6—C7	1.387 (6)	C36—C37	1.534 (6)
C7—C8	1.467 (6)	C37—C42	1.366 (7)
C8—C9	1.393 (6)	C37—C38	1.371 (7)
C8—C13	1.405 (6)	C38—C39	1.408 (7)
C9—C10	1.384 (7)	C39—C40	1.350 (8)
C10—C11	1.382 (7)	C40—C41	1.365 (9)
C11—C12	1.392 (6)	C41—C42	1.378 (8)
N1—Ni1—N3	100.4 (1)	C16—C15—S2	118.7 (4)
N1—Ni1—S3	169.4 (1)	C21—C16—C17	118.8 (5)
N3—Ni1—S3	85.8 (1)	C21—C16—C15	123.2 (5)
N1—Ni1—S1	85.5 (1)	C17—C16—C15	118.0 (5)
N3—Ni1—S1	169.4 (1)	C16—C17—C18	121.8 (6)
S3—Ni1—S1	89.79 (5)	C19—C18—C17	118.9 (6)
C14—S1—Ni1	93.8 (1)	C20—C19—C18	120.1 (6)
C14—S2—C15	103.1 (2)	C19—C20—C21	121.7 (6)
C35—S3—Ni1	94.3 (2)	C16—C21—C20	118.7 (5)
C35—S4—C36	103.5 (2)	N3—C22—C34	129.7 (4)
C1—N1—N2	113.7 (3)	N3—C22—C23	123.0 (4)
C1—N1—Ni1	128.6 (3)	C34—C22—C23	107.0 (4)
N2—N1—Ni1	116.8 (3)	C24—C23—C28	121.6 (5)
C14—N2—N1	110.8 (4)	C24—C23—C22	130.6 (4)
C22—N3—N4	113.5 (4)	C28—C23—C22	107.5 (4)
C22—N3—Ni1	129.1 (3)	C23—C24—C25	118.1 (5)
N4—N3—Ni1	116.6 (2)	C26—C25—C24	121.9 (7)
C35—N4—N3	111.4 (4)	C25—C26—C27	121.2 (7)
N1—C1—C13	124.9 (4)	C26—C27—C28	118.7 (6)
N1—C1—C2	128.7 (4)	C27—C28—C23	118.5 (6)
C13—C1—C2	106.2 (4)	C27—C28—C29	132.6 (5)
C3—C2—C7	119.4 (4)	C23—C28—C29	108.8 (5)
C3—C2—C1	132.7 (4)	C30—C29—C34	119.4 (6)
C7—C2—C1	107.4 (4)	C30—C29—C28	131.4 (6)
C4—C3—C2	119.1 (4)	C34—C29—C28	109.2 (4)
C5—C4—C3	120.7 (5)	C31—C30—C29	119.0 (6)
C6—C5—C4	121.1 (5)	C30—C31—C32	121.2 (6)
C5—C6—C7	119.2 (5)	C31—C32—C33	120.8 (6)
C6—C7—C2	120.6 (4)	C34—C33—C32	118.4 (6)
C6—C7—C8	130.5 (4)	C33—C34—C29	121.1 (4)
C2—C7—C8	108.9 (4)	C33—C34—C22	131.4 (4)
C9—C8—C13	119.6 (5)	C29—C34—C22	107.0 (4)
C9—C8—C7	131.6 (4)	N4—C35—S4	121.6 (4)
C13—C8—C7	108.7 (4)	N4—C35—S3	123.6 (4)
C10—C9—C8	118.7 (5)	S4—C35—S3	114.8 (2)
C11—C10—C9	121.4 (5)	C37—C36—S4	117.7 (4)
C10—C11—C12	121.0 (5)	C42—C37—C38	117.6 (5)
C11—C12—C13	117.6 (5)	C42—C37—C36	119.1 (5)
C12—C13—C8	121.4 (4)	C38—C37—C36	123.3 (5)
C12—C13—C1	130.2 (4)	C37—C38—C39	120.1 (5)
C8—C13—C1	108.2 (4)	C40—C39—C38	120.6 (6)
N2—C14—S1	124.6 (3)	C39—C40—C41	119.8 (6)
N2—C14—S2	122.0 (4)	C40—C41—C42	119.3 (7)
S1—C14—S2	113.4 (2)	C37—C42—C41	122.6 (6)
N1—Ni1—S1—C14	−20.24 (18)	C14—S2—C15—C16	−81.0 (4)
N3—Ni1—S1—C14	104.0 (6)	S2—C15—C16—C21	−4.7 (7)
S3—Ni1—S1—C14	169.30 (15)	S2—C15—C16—C17	175.9 (4)
N1—Ni1—S3—C35	106.0 (6)	C21—C16—C17—C18	1.0 (8)
N3—Ni1—S3—C35	−20.07 (18)	C15—C16—C17—C18	−179.6 (5)
S1—Ni1—S3—C35	169.61 (15)	C16—C17—C18—C19	−1.1 (9)
N3—Ni1—N1—C1	26.8 (4)	C17—C18—C19—C20	−0.1 (9)
S3—Ni1—N1—C1	−98.2 (6)	C18—C19—C20—C21	1.3 (9)
S1—Ni1—N1—C1	−162.1 (4)	C17—C16—C21—C20	0.2 (7)
N3—Ni1—N1—N2	−142.2 (3)	C15—C16—C21—C20	−179.2 (4)
S3—Ni1—N1—N2	92.8 (6)	C19—C20—C21—C16	−1.3 (8)
S1—Ni1—N1—N2	28.9 (3)	N4—N3—C22—C34	22.1 (6)
C1—N1—N2—C14	164.5 (4)	Ni1—N3—C22—C34	−147.5 (4)
Ni1—N1—N2—C14	−24.9 (4)	N4—N3—C22—C23	−164.1 (4)
N1—Ni1—N3—C22	26.8 (4)	Ni1—N3—C22—C23	26.3 (6)
S3—Ni1—N3—C22	−161.9 (4)	N3—C22—C23—C24	15.5 (7)
S1—Ni1—N3—C22	−96.3 (6)	C34—C22—C23—C24	−169.5 (5)
N1—Ni1—N3—N4	−142.6 (3)	N3—C22—C23—C28	−171.2 (4)
S3—Ni1—N3—N4	28.7 (3)	C34—C22—C23—C28	3.8 (5)
S1—Ni1—N3—N4	94.3 (6)	C28—C23—C24—C25	3.7 (8)
C22—N3—N4—C35	164.0 (4)	C22—C23—C24—C25	176.2 (5)
Ni1—N3—N4—C35	−25.0 (4)	C23—C24—C25—C26	−0.4 (9)
N2—N1—C1—C13	−165.2 (4)	C24—C25—C26—C27	−2.6 (12)
Ni1—N1—C1—C13	25.5 (6)	C25—C26—C27—C28	2.2 (12)
N2—N1—C1—C2	20.1 (6)	C26—C27—C28—C23	1.0 (10)
Ni1—N1—C1—C2	−149.1 (3)	C26—C27—C28—C29	−176.7 (6)
N1—C1—C2—C3	−3.9 (8)	C24—C23—C28—C27	−4.0 (8)
C13—C1—C2—C3	−179.3 (5)	C22—C23—C28—C27	−178.0 (5)
N1—C1—C2—C7	167.8 (4)	C24—C23—C28—C29	174.3 (4)
C13—C1—C2—C7	−7.6 (5)	C22—C23—C28—C29	0.2 (5)
C7—C2—C3—C4	−0.3 (7)	C27—C28—C29—C30	−8.2 (10)
C1—C2—C3—C4	170.7 (5)	C23—C28—C29—C30	173.9 (5)
C2—C3—C4—C5	0.2 (8)	C27—C28—C29—C34	173.5 (6)
C3—C4—C5—C6	0.3 (9)	C23—C28—C29—C34	−4.4 (6)
C4—C5—C6—C7	−0.8 (8)	C34—C29—C30—C31	−1.6 (8)
C5—C6—C7—C2	0.8 (8)	C28—C29—C30—C31	−179.7 (6)
C5—C6—C7—C8	−179.5 (5)	C29—C30—C31—C32	0.6 (10)
C3—C2—C7—C6	−0.2 (7)	C30—C31—C32—C33	0.6 (10)
C1—C2—C7—C6	−173.3 (4)	C31—C32—C33—C34	−0.8 (8)
C3—C2—C7—C8	180.0 (4)	C32—C33—C34—C29	−0.2 (7)
C1—C2—C7—C8	6.9 (5)	C32—C33—C34—C22	171.1 (5)
C6—C7—C8—C9	−4.9 (9)	C30—C29—C34—C33	1.4 (7)
C2—C7—C8—C9	174.8 (5)	C28—C29—C34—C33	179.9 (4)
C6—C7—C8—C13	176.6 (5)	C30—C29—C34—C22	−171.8 (5)
C2—C7—C8—C13	−3.7 (5)	C28—C29—C34—C22	6.7 (5)
C13—C8—C9—C10	1.4 (7)	N3—C22—C34—C33	−4.1 (8)
C7—C8—C9—C10	−176.9 (5)	C23—C22—C34—C33	−178.7 (5)
C8—C9—C10—C11	2.0 (8)	N3—C22—C34—C29	168.1 (4)
C9—C10—C11—C12	−2.1 (9)	C23—C22—C34—C29	−6.5 (5)
C10—C11—C12—C13	−1.4 (8)	N3—N4—C35—S4	−173.3 (3)
C11—C12—C13—C8	4.8 (7)	N3—N4—C35—S3	3.6 (5)
C11—C12—C13—C1	178.6 (5)	C36—S4—C35—N4	1.8 (4)
C9—C8—C13—C12	−4.9 (7)	C36—S4—C35—S3	−175.4 (2)
C7—C8—C13—C12	173.8 (4)	Ni1—S3—C35—N4	15.1 (4)
C9—C8—C13—C1	−179.9 (4)	Ni1—S3—C35—S4	−167.8 (2)
C7—C8—C13—C1	−1.2 (5)	C35—S4—C36—C37	−82.8 (4)
N1—C1—C13—C12	15.3 (7)	S4—C36—C37—C42	−179.8 (4)
C2—C1—C13—C12	−169.0 (4)	S4—C36—C37—C38	−0.9 (7)
N1—C1—C13—C8	−170.3 (4)	C42—C37—C38—C39	0.7 (8)
C2—C1—C13—C8	5.4 (5)	C36—C37—C38—C39	−178.2 (5)
N1—N2—C14—S1	3.1 (5)	C37—C38—C39—C40	−0.7 (9)
N1—N2—C14—S2	−176.5 (3)	C38—C39—C40—C41	0.1 (10)
Ni1—S1—C14—N2	15.7 (4)	C39—C40—C41—C42	0.3 (11)
Ni1—S1—C14—S2	−164.7 (2)	C38—C37—C42—C41	−0.3 (9)
C15—S2—C14—N2	8.6 (4)	C36—C37—C42—C41	178.7 (6)
C15—S2—C14—S1	−171.0 (3)	C40—C41—C42—C37	−0.3 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N2	0.93	2.43	2.947 (6)	115
C21—H21A···S2	0.93	2.76	3.164 (5)	107
C33—H33A···N4	0.93	2.42	2.937 (6)	115
C36—H36A···N4	0.97	2.55	2.913 (7)	102
C38—H38A···S4	0.93	2.73	3.153 (6)	109
C3—H3A···Cg1	0.93	3.14	3.898	140
C15—H15B···Cg2^i	0.97	2.96	3.798	145
C36—H36B···Cg1^ii	0.97	2.90	3.631	133
C42—H42A···Cg3^iii	0.93	2.97	3.887	168
C42—H42A···Cg4^iii	0.93	3.28	4.113	151

Symmetry codes: (i) x+3/2, −y+1/2, z+1/2; (ii) x−3/2, −y+1/2, z−1/2; (iii) x−1, y, z.