Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023847/hk2244sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023847/hk2244Isup2.hkl |
CCDC reference: 650700
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.010 Å
- R factor = 0.060
- wR factor = 0.078
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.113 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11 PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 40 Perc. PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT220_ALERT_2_C Large Non-Solvent N Ueq(max)/Ueq(min) ... 3.07 Ratio PLAT220_ALERT_2_C Large Non-Solvent N Ueq(max)/Ueq(min) ... 2.89 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C47 - C48 .. 5.05 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C47 - C50_b .. 5.05 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C50 - C47_b .. 5.05 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C22 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C19 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C25 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 10 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.45 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C15 - C16 ... 1.42 Ang.
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 8530 From the CIF: _diffrn_reflns_limit_ max hkl 47. 7. 36. From the CIF: _diffrn_reflns_limit_ min hkl -50. -8. -36. TEST1: Expected hkl limits for theta max Calculated maximum hkl 50. 8. 38. Calculated minimum hkl -50. -8. -38. PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (3) 3.05 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2 (3) 3.05 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni3 (3) 3.01
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 16 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
For general backgroud, see: de Caro et al. (2004); Ray et al. (2005); Liu (2007); Liu et al. (2005); Wang et al. (2006). For related literature, see: Sellmann et al. (1991); Xie et al. (2002).
Benzene-1,2-dithiol (142 mg, 1.0 mmol) was added to a solution of sodium metal (46 mg, 2.0 mmol) in absolute ethanol (25 ml), under nitrogen atmosphere at room temperature, and then a solution of NiCl2.6H2O (120 mg, 0.5 mmol) in ethanol (25 ml) was added, resulting in a mixture turning a muddy red–brown color. Following this, [NCBzPyCH3]Br (289 mg, 1.0 mmol) was added and the mixture allowed to stand with stirring for 1 h, and then stirred for an additional 24 h in air. The color of the mixture gradually turned green, indicating oxidation from a dianionic species to the more stable monoanionic form. The precipitate was washed with absolute ethanol and diethyl ether and then dried. The crude product was recrystallized twice from dichloromethane to give the title compound (yield; 241 mg, 69%, m.p. 483–485 K).
H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Since their discovery in 1963, square planar bis(benzene-1,2-dithiolato)metal complexes have received considerable attention due to their interesting and often unusual electronic structures. It has been established that the square planar complexes [M(L)2]2-, [M(L)2]-, and [M(L)2]0 (where M = Ni, Pt) form a three membered electron-transfer series, where the neutral species and the dianionic forms are diamagnetic (S = 0), whereas the monoanions are paramagnetic (S = 1/2) (de Caro et al., 2004; Ray et al., 2005). In our previous research using benzylpyridinium derivatives ([RBzPy]+) as the counter-cation of TCNQ- (where TCNQ = 7,7,8,8-tetracyanoquinodimethanide), a series of ion-pair compounds with segregated columnar stacks of cations and anions has been prepared (Liu, 2007; Liu et al., 2005; Wang et al., 2006). The quasi one-dimensional magnetic nature of these compounds was attributed to intermolecular-orbital interactions within the anionic columns. As an extension of our work on this series of complexes, we herein report the crystal structure of the title compound, (I).
The asymmetric unit of (I), contains two (C14H13N2)+ cations, one and two halves centrosymmetric [Ni(C6H4S2)2] anions. In the anions, the Ni ions are surrounded by four S atoms in a distorted square-planar geometry. The dihedral angle between (Ni1/S5/S6/C41/C46) and (Ni1/S5A/S6A/C41A/C46A) planes is 18.98 (2)° [symmetry code (A): -x, y, 1/2 - z]. It is peculiar and interesting. The Ni—S bond lengths and S—Ni—S bond angles (Table 1) are in agreement with the corresponding values in analogous complexes (Sellmann et al., 1991; Xie et al., 2002). The cations have Λ-shaped conformations with the dihedral angles of A/B = 65.03 (3), A/C = 46.37 (4), B/C = 86.96 (4) ° and D/E = 60.62 (3), D/F = 59.72 (3), E/F = 83.56 (4) ° between A (C5/C8/N1), B (C2—C7), C (N1/C9—C13) and D (C19/C22/N2), E (C16—C21), F (N2/C23—C28) planes.
In the crystal structure, the packing of the two anions is different (Fig. 2). The Ni1, Ni3-containing anions stack in a face-to-face fashion with an alternating arrangement of anions and cations, such that the pyridine ring of the cation lies above the benzene ring of the anion. The shortest distance between the adjacent NiIII ions is 7.245 (2) Å. The Ni2-containing anions stack in a side by side fashion with C—H···S interactions (Table 2).
For general backgroud, see: de Caro et al. (2004); Ray et al. (2005); Liu (2007); Liu et al. (2005); Wang et al. (2006). For related literature, see: Sellmann et al. (1991); Xie et al. (2002).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(C14H13N2)[Ni(C6H4S2)2] | F(000) = 4528 |
Mr = 548.40 | Dx = 1.459 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1320 reflections |
a = 42.344 (3) Å | θ = 2.9–16.5° |
b = 7.2455 (6) Å | µ = 1.13 mm−1 |
c = 32.768 (2) Å | T = 294 K |
β = 96.480 (5)° | Prism, dark green |
V = 9988.9 (13) Å3 | 0.20 × 0.12 × 0.10 mm |
Z = 16 |
Bruker SMART APEX CCD area-detector diffractometer | 8530 independent reflections |
Radiation source: sealed tube | 3392 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.113 |
φ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −50→47 |
Tmin = 0.806, Tmax = 0.896 | k = −8→7 |
27982 measured reflections | l = −36→36 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
8530 reflections | (Δ/σ)max = 0.001 |
599 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
(C14H13N2)[Ni(C6H4S2)2] | V = 9988.9 (13) Å3 |
Mr = 548.40 | Z = 16 |
Monoclinic, C2/c | Mo Kα radiation |
a = 42.344 (3) Å | µ = 1.13 mm−1 |
b = 7.2455 (6) Å | T = 294 K |
c = 32.768 (2) Å | 0.20 × 0.12 × 0.10 mm |
β = 96.480 (5)° |
Bruker SMART APEX CCD area-detector diffractometer | 8530 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 3392 reflections with I > 2σ(I) |
Tmin = 0.806, Tmax = 0.896 | Rint = 0.113 |
27982 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.34 e Å−3 |
8530 reflections | Δρmin = −0.27 e Å−3 |
599 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.56508 (13) | 0.2500 | 0.0602 (3) | |
Ni2 | 0.125597 (16) | 0.62664 (10) | 0.12628 (2) | 0.0551 (2) | |
Ni3 | 0.2500 | 0.2500 | 0.5000 | 0.0615 (3) | |
S1 | 0.11139 (3) | 0.88755 (19) | 0.09943 (4) | 0.0620 (4) | |
S2 | 0.09055 (4) | 0.48396 (19) | 0.08584 (5) | 0.0667 (5) | |
S3 | 0.16124 (4) | 0.7690 (2) | 0.16585 (5) | 0.0700 (5) | |
S4 | 0.13900 (3) | 0.3664 (2) | 0.15386 (4) | 0.0641 (4) | |
S5 | 0.04314 (4) | 0.5815 (2) | 0.22143 (4) | 0.0647 (5) | |
S6 | 0.02601 (4) | 0.5293 (2) | 0.30913 (4) | 0.0737 (5) | |
S7 | 0.22258 (4) | 0.1943 (2) | 0.44230 (4) | 0.0718 (5) | |
S8 | 0.29206 (4) | 0.19526 (19) | 0.47107 (5) | 0.0646 (5) | |
N1 | 0.31857 (14) | 0.6691 (6) | 0.45220 (15) | 0.0574 (13) | |
N2 | 0.06481 (13) | 1.1024 (6) | 0.20015 (15) | 0.0563 (13) | |
N3 | 0.17638 (18) | 0.9953 (13) | 0.3108 (2) | 0.177 (4) | |
N4 | −0.06790 (18) | 0.6563 (12) | 0.0635 (2) | 0.162 (3) | |
C1 | 0.1980 (2) | 0.9276 (13) | 0.3264 (2) | 0.118 (3) | |
C2 | 0.2261 (2) | 0.8448 (13) | 0.3481 (2) | 0.082 (2) | |
C3 | 0.22698 (19) | 0.6628 (13) | 0.3573 (2) | 0.098 (3) | |
H3 | 0.2091 | 0.5914 | 0.3494 | 0.118* | |
C4 | 0.2529 (2) | 0.5804 (10) | 0.3775 (2) | 0.087 (2) | |
H4 | 0.2526 | 0.4552 | 0.3837 | 0.105* | |
C5 | 0.27987 (16) | 0.6851 (10) | 0.38877 (17) | 0.0586 (17) | |
C6 | 0.27969 (15) | 0.8707 (9) | 0.37946 (17) | 0.0627 (17) | |
H6 | 0.2976 | 0.9424 | 0.3871 | 0.075* | |
C7 | 0.25306 (19) | 0.9490 (9) | 0.35900 (19) | 0.072 (2) | |
H7 | 0.2531 | 1.0738 | 0.3524 | 0.087* | |
C8 | 0.30959 (14) | 0.5990 (7) | 0.40965 (16) | 0.0659 (17) | |
H8A | 0.3066 | 0.4664 | 0.4107 | 0.079* | |
H8B | 0.3269 | 0.6229 | 0.3934 | 0.079* | |
C9 | 0.29658 (14) | 0.6769 (7) | 0.4786 (2) | 0.0640 (18) | |
H9 | 0.2755 | 0.6482 | 0.4698 | 0.077* | |
C10 | 0.30535 (18) | 0.7270 (7) | 0.5183 (2) | 0.071 (2) | |
H10 | 0.2899 | 0.7319 | 0.5363 | 0.085* | |
C11 | 0.3359 (2) | 0.7703 (8) | 0.5326 (3) | 0.074 (2) | |
C12 | 0.35750 (19) | 0.7611 (8) | 0.5045 (3) | 0.084 (2) | |
H12 | 0.3787 | 0.7897 | 0.5127 | 0.101* | |
C13 | 0.34874 (17) | 0.7113 (8) | 0.4649 (2) | 0.073 (2) | |
H13 | 0.3639 | 0.7065 | 0.4465 | 0.088* | |
C14 | 0.34560 (16) | 0.8237 (8) | 0.57622 (19) | 0.102 (2) | |
H14A | 0.3680 | 0.8039 | 0.5828 | 0.152* | |
H14B | 0.3342 | 0.7499 | 0.5940 | 0.152* | |
H14C | 0.3408 | 0.9517 | 0.5800 | 0.152* | |
C15 | −0.0476 (2) | 0.7422 (13) | 0.0787 (3) | 0.124 (3) | |
C16 | −0.0223 (2) | 0.8514 (12) | 0.09821 (19) | 0.076 (2) | |
C17 | 0.00624 (19) | 0.7662 (8) | 0.11170 (19) | 0.0665 (19) | |
H17 | 0.0088 | 0.6403 | 0.1077 | 0.080* | |
C18 | 0.03053 (14) | 0.8689 (9) | 0.13096 (16) | 0.0612 (17) | |
H18 | 0.0498 | 0.8122 | 0.1400 | 0.073* | |
C19 | 0.02699 (17) | 1.0549 (9) | 0.13723 (16) | 0.0556 (17) | |
C20 | −0.0010 (2) | 1.1392 (9) | 0.1235 (2) | 0.081 (2) | |
H20 | −0.0036 | 1.2654 | 0.1272 | 0.097* | |
C21 | −0.02549 (17) | 1.0359 (12) | 0.1041 (2) | 0.088 (2) | |
H21 | −0.0446 | 1.0933 | 0.0948 | 0.106* | |
C22 | 0.05457 (14) | 1.1652 (8) | 0.15794 (17) | 0.0750 (19) | |
H22A | 0.0723 | 1.1558 | 0.1418 | 0.090* | |
H22B | 0.0485 | 1.2941 | 0.1586 | 0.090* | |
C23 | 0.04440 (14) | 1.1099 (7) | 0.2284 (2) | 0.0643 (17) | |
H23 | 0.0237 | 1.1489 | 0.2208 | 0.077* | |
C24 | 0.05327 (16) | 1.0622 (7) | 0.2678 (2) | 0.0666 (19) | |
H24 | 0.0386 | 1.0658 | 0.2869 | 0.080* | |
C25 | 0.08412 (19) | 1.0082 (7) | 0.2799 (2) | 0.0576 (18) | |
C26 | 0.09546 (15) | 0.9591 (7) | 0.32383 (18) | 0.092 (2) | |
H26A | 0.1087 | 0.8512 | 0.3244 | 0.137* | |
H26B | 0.0775 | 0.9347 | 0.3384 | 0.137* | |
H26C | 0.1075 | 1.0600 | 0.3366 | 0.137* | |
C27 | 0.10478 (18) | 0.9985 (7) | 0.2500 (3) | 0.076 (2) | |
H27 | 0.1256 | 0.9598 | 0.2568 | 0.091* | |
C28 | 0.09443 (17) | 1.0457 (8) | 0.2108 (2) | 0.0685 (19) | |
H28 | 0.1084 | 1.0383 | 0.1908 | 0.082* | |
C29 | 0.08084 (13) | 0.8376 (9) | 0.06148 (16) | 0.0535 (15) | |
C30 | 0.06495 (15) | 0.9756 (8) | 0.0381 (2) | 0.0685 (19) | |
H30 | 0.0707 | 1.0985 | 0.0426 | 0.082* | |
C31 | 0.04077 (15) | 0.9301 (10) | 0.00835 (19) | 0.074 (2) | |
H31 | 0.0302 | 1.0234 | −0.0072 | 0.089* | |
C32 | 0.03178 (15) | 0.7498 (10) | 0.0011 (2) | 0.082 (2) | |
H32 | 0.0154 | 0.7214 | −0.0193 | 0.099* | |
C33 | 0.04738 (15) | 0.6106 (9) | 0.02449 (19) | 0.0724 (18) | |
H33 | 0.0415 | 0.4881 | 0.0197 | 0.087* | |
C34 | 0.07160 (13) | 0.6535 (8) | 0.05490 (16) | 0.0526 (15) | |
C35 | 0.18004 (13) | 0.5986 (9) | 0.19720 (17) | 0.0573 (16) | |
C36 | 0.16966 (13) | 0.4172 (9) | 0.19115 (16) | 0.0563 (16) | |
C37 | 0.18521 (16) | 0.2797 (8) | 0.2164 (2) | 0.074 (2) | |
H37 | 0.1786 | 0.1577 | 0.2130 | 0.089* | |
C38 | 0.20967 (17) | 0.3218 (10) | 0.2457 (2) | 0.085 (2) | |
H38 | 0.2196 | 0.2293 | 0.2621 | 0.102* | |
C39 | 0.21959 (16) | 0.5034 (11) | 0.2507 (2) | 0.086 (2) | |
H39 | 0.2363 | 0.5324 | 0.2705 | 0.103* | |
C40 | 0.20502 (15) | 0.6400 (9) | 0.2270 (2) | 0.0742 (18) | |
H40 | 0.2119 | 0.7614 | 0.2307 | 0.089* | |
C41 | 0.07300 (17) | 0.5359 (6) | 0.2607 (2) | 0.0542 (17) | |
C42 | 0.1047 (2) | 0.5224 (7) | 0.2529 (2) | 0.070 (2) | |
H42 | 0.1099 | 0.5408 | 0.2263 | 0.084* | |
C43 | 0.12827 (17) | 0.4822 (8) | 0.2840 (3) | 0.085 (2) | |
H43 | 0.1493 | 0.4726 | 0.2786 | 0.102* | |
C44 | 0.12051 (17) | 0.4560 (7) | 0.3236 (2) | 0.079 (2) | |
H44 | 0.1363 | 0.4280 | 0.3448 | 0.095* | |
C45 | 0.0897 (2) | 0.4715 (7) | 0.3313 (2) | 0.073 (2) | |
H45 | 0.0847 | 0.4551 | 0.3580 | 0.088* | |
C46 | 0.06564 (16) | 0.5109 (7) | 0.3005 (2) | 0.0590 (18) | |
C47 | 0.18323 (15) | 0.2118 (7) | 0.4527 (2) | 0.0563 (17) | |
C48 | 0.15871 (19) | 0.1752 (7) | 0.42208 (19) | 0.0690 (19) | |
H48 | 0.1633 | 0.1424 | 0.3959 | 0.083* | |
C49 | 0.12791 (17) | 0.1871 (8) | 0.4301 (2) | 0.0752 (19) | |
H49 | 0.1115 | 0.1633 | 0.4094 | 0.090* | |
C50 | 0.32329 (17) | 0.2401 (6) | 0.50796 (18) | 0.0539 (18) | |
C51 | 0.35497 (18) | 0.2307 (7) | 0.5006 (2) | 0.064 (2) | |
H51 | 0.3598 | 0.2000 | 0.4745 | 0.077* | |
C52 | 0.37907 (16) | 0.2653 (7) | 0.5308 (2) | 0.078 (2) | |
H52 | 0.4001 | 0.2571 | 0.5253 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0747 (9) | 0.0539 (7) | 0.0541 (7) | 0.000 | 0.0170 (6) | 0.000 |
Ni2 | 0.0557 (5) | 0.0523 (5) | 0.0574 (5) | −0.0065 (4) | 0.0069 (4) | −0.0029 (4) |
Ni3 | 0.0682 (9) | 0.0607 (7) | 0.0576 (8) | −0.0042 (6) | 0.0156 (6) | 0.0002 (5) |
S1 | 0.0613 (11) | 0.0554 (10) | 0.0674 (11) | −0.0082 (9) | −0.0007 (9) | −0.0025 (8) |
S2 | 0.0686 (13) | 0.0552 (10) | 0.0733 (12) | −0.0089 (8) | −0.0053 (10) | −0.0027 (8) |
S3 | 0.0744 (13) | 0.0597 (11) | 0.0725 (12) | −0.0112 (9) | −0.0062 (10) | −0.0029 (9) |
S4 | 0.0635 (12) | 0.0553 (10) | 0.0717 (11) | −0.0046 (8) | 0.0000 (9) | −0.0001 (8) |
S5 | 0.0771 (13) | 0.0637 (11) | 0.0550 (10) | −0.0004 (9) | 0.0154 (9) | 0.0043 (8) |
S6 | 0.0834 (14) | 0.0861 (13) | 0.0541 (11) | 0.0030 (9) | 0.0185 (10) | 0.0024 (8) |
S7 | 0.0742 (13) | 0.0874 (13) | 0.0560 (11) | −0.0049 (9) | 0.0170 (10) | −0.0041 (8) |
S8 | 0.0729 (13) | 0.0640 (11) | 0.0586 (11) | 0.0006 (9) | 0.0149 (9) | −0.0025 (8) |
N1 | 0.065 (4) | 0.049 (3) | 0.062 (4) | 0.009 (3) | 0.023 (4) | 0.008 (2) |
N2 | 0.064 (4) | 0.049 (3) | 0.056 (4) | −0.007 (3) | 0.009 (3) | −0.004 (3) |
N3 | 0.097 (7) | 0.267 (10) | 0.159 (7) | 0.039 (6) | −0.030 (5) | 0.070 (6) |
N4 | 0.128 (7) | 0.229 (9) | 0.125 (6) | −0.074 (6) | −0.003 (5) | −0.019 (6) |
C1 | 0.090 (8) | 0.183 (9) | 0.079 (6) | 0.028 (7) | −0.001 (6) | 0.031 (6) |
C2 | 0.072 (7) | 0.118 (7) | 0.057 (5) | 0.003 (6) | 0.016 (5) | 0.013 (5) |
C3 | 0.082 (7) | 0.134 (8) | 0.075 (6) | −0.035 (6) | −0.013 (5) | 0.002 (5) |
C4 | 0.097 (7) | 0.085 (6) | 0.080 (6) | −0.027 (6) | 0.008 (5) | 0.004 (4) |
C5 | 0.061 (5) | 0.068 (5) | 0.050 (4) | 0.006 (4) | 0.017 (4) | 0.003 (4) |
C6 | 0.067 (5) | 0.057 (5) | 0.065 (4) | 0.004 (4) | 0.007 (4) | −0.006 (4) |
C7 | 0.072 (6) | 0.080 (5) | 0.066 (5) | 0.024 (5) | 0.012 (4) | 0.006 (4) |
C8 | 0.092 (5) | 0.061 (4) | 0.046 (4) | 0.012 (4) | 0.013 (4) | −0.003 (3) |
C9 | 0.058 (5) | 0.084 (5) | 0.052 (5) | 0.004 (3) | 0.012 (4) | 0.010 (4) |
C10 | 0.087 (6) | 0.075 (5) | 0.053 (5) | 0.002 (4) | 0.019 (5) | 0.008 (4) |
C11 | 0.082 (7) | 0.049 (4) | 0.087 (7) | 0.009 (4) | −0.001 (6) | 0.005 (4) |
C12 | 0.075 (7) | 0.078 (5) | 0.093 (7) | 0.002 (4) | −0.011 (6) | −0.012 (4) |
C13 | 0.053 (5) | 0.069 (5) | 0.100 (7) | 0.005 (4) | 0.021 (5) | 0.003 (4) |
C14 | 0.156 (8) | 0.077 (5) | 0.065 (5) | −0.002 (5) | −0.016 (5) | −0.011 (4) |
C15 | 0.120 (10) | 0.169 (10) | 0.082 (7) | −0.052 (7) | 0.011 (6) | −0.018 (6) |
C16 | 0.082 (7) | 0.100 (7) | 0.046 (4) | −0.014 (6) | 0.002 (4) | −0.005 (4) |
C17 | 0.078 (6) | 0.066 (5) | 0.058 (5) | −0.005 (5) | 0.018 (4) | 0.009 (4) |
C18 | 0.055 (5) | 0.071 (5) | 0.056 (4) | −0.010 (4) | 0.003 (3) | 0.009 (4) |
C19 | 0.070 (6) | 0.057 (5) | 0.039 (4) | −0.007 (4) | 0.004 (4) | 0.001 (3) |
C20 | 0.089 (6) | 0.070 (5) | 0.080 (5) | 0.025 (5) | −0.004 (5) | −0.006 (4) |
C21 | 0.052 (6) | 0.126 (8) | 0.083 (6) | 0.025 (5) | −0.006 (4) | −0.002 (5) |
C22 | 0.104 (6) | 0.072 (5) | 0.049 (4) | −0.014 (4) | 0.009 (4) | 0.008 (3) |
C23 | 0.069 (5) | 0.065 (4) | 0.060 (5) | 0.005 (4) | 0.012 (4) | 0.001 (4) |
C24 | 0.071 (6) | 0.062 (4) | 0.068 (5) | 0.007 (4) | 0.012 (4) | −0.009 (4) |
C25 | 0.081 (6) | 0.043 (4) | 0.045 (5) | −0.009 (4) | −0.011 (5) | −0.004 (3) |
C26 | 0.127 (7) | 0.069 (5) | 0.073 (5) | −0.006 (4) | −0.017 (5) | 0.011 (4) |
C27 | 0.067 (6) | 0.081 (5) | 0.076 (6) | −0.005 (4) | −0.005 (5) | 0.004 (4) |
C28 | 0.065 (6) | 0.067 (5) | 0.075 (6) | −0.002 (4) | 0.015 (5) | −0.006 (4) |
C29 | 0.042 (4) | 0.070 (5) | 0.049 (4) | −0.004 (4) | 0.005 (3) | 0.000 (3) |
C30 | 0.061 (5) | 0.076 (5) | 0.068 (5) | 0.007 (4) | 0.007 (4) | 0.008 (4) |
C31 | 0.057 (5) | 0.098 (6) | 0.065 (5) | 0.011 (4) | −0.005 (4) | 0.003 (4) |
C32 | 0.058 (5) | 0.098 (6) | 0.088 (6) | −0.006 (5) | −0.004 (4) | −0.020 (5) |
C33 | 0.059 (5) | 0.076 (5) | 0.081 (5) | −0.002 (4) | 0.002 (4) | −0.007 (4) |
C34 | 0.042 (4) | 0.064 (4) | 0.050 (4) | −0.010 (3) | −0.003 (3) | −0.009 (3) |
C35 | 0.037 (4) | 0.075 (5) | 0.061 (4) | −0.001 (4) | 0.009 (3) | −0.003 (4) |
C36 | 0.049 (4) | 0.062 (4) | 0.058 (4) | 0.003 (4) | 0.009 (3) | 0.004 (4) |
C37 | 0.074 (6) | 0.075 (5) | 0.071 (5) | 0.012 (4) | 0.003 (4) | 0.005 (4) |
C38 | 0.074 (6) | 0.099 (6) | 0.080 (6) | 0.014 (5) | −0.005 (4) | 0.016 (5) |
C39 | 0.057 (5) | 0.117 (7) | 0.080 (6) | 0.005 (5) | −0.007 (4) | 0.004 (5) |
C40 | 0.058 (5) | 0.085 (5) | 0.077 (5) | −0.004 (4) | −0.005 (4) | −0.009 (4) |
C41 | 0.065 (6) | 0.040 (4) | 0.058 (5) | 0.001 (3) | 0.008 (4) | −0.004 (3) |
C42 | 0.085 (7) | 0.062 (5) | 0.066 (6) | 0.008 (4) | 0.019 (5) | 0.002 (3) |
C43 | 0.084 (7) | 0.083 (5) | 0.091 (6) | −0.001 (4) | 0.021 (6) | −0.005 (4) |
C44 | 0.076 (6) | 0.074 (5) | 0.085 (6) | 0.013 (4) | −0.001 (5) | −0.004 (4) |
C45 | 0.099 (7) | 0.059 (4) | 0.062 (5) | 0.009 (4) | 0.011 (5) | 0.004 (3) |
C46 | 0.068 (6) | 0.049 (4) | 0.062 (5) | 0.001 (3) | 0.014 (4) | −0.001 (3) |
C47 | 0.051 (5) | 0.049 (4) | 0.068 (5) | −0.004 (3) | 0.001 (4) | 0.011 (3) |
C48 | 0.083 (6) | 0.065 (5) | 0.063 (5) | 0.000 (4) | 0.026 (5) | 0.012 (3) |
C49 | 0.081 (6) | 0.081 (5) | 0.061 (5) | −0.005 (4) | −0.004 (4) | 0.010 (4) |
C50 | 0.078 (6) | 0.046 (4) | 0.039 (5) | 0.002 (3) | 0.013 (4) | 0.006 (3) |
C51 | 0.069 (6) | 0.075 (5) | 0.054 (5) | 0.005 (4) | 0.024 (5) | 0.003 (3) |
C52 | 0.065 (6) | 0.082 (5) | 0.086 (6) | −0.010 (4) | 0.000 (5) | 0.012 (4) |
Ni1—S6 | 2.1337 (16) | C19—C20 | 1.365 (7) |
Ni1—S6i | 2.1338 (16) | C19—C22 | 1.511 (7) |
Ni1—S5 | 2.1477 (14) | C20—C21 | 1.374 (8) |
Ni1—S5i | 2.1478 (14) | C20—H20 | 0.9300 |
Ni2—S4 | 2.1400 (16) | C21—H21 | 0.9300 |
Ni2—S3 | 2.1405 (17) | C22—H22A | 0.9700 |
Ni2—S2 | 2.1408 (17) | C22—H22B | 0.9700 |
Ni2—S1 | 2.1424 (16) | C23—C24 | 1.348 (7) |
Ni3—S7 | 2.1424 (15) | C23—H23 | 0.9300 |
Ni3—S7ii | 2.1424 (15) | C24—C25 | 1.378 (7) |
Ni3—S8ii | 2.1470 (14) | C24—H24 | 0.9300 |
Ni3—S8 | 2.1470 (14) | C25—C27 | 1.387 (8) |
S1—C29 | 1.728 (6) | C25—C26 | 1.508 (7) |
S2—C34 | 1.731 (6) | C26—H26A | 0.9600 |
S3—C35 | 1.741 (6) | C26—H26B | 0.9600 |
S4—C36 | 1.719 (6) | C26—H26C | 0.9600 |
S5—C41 | 1.732 (6) | C27—C28 | 1.354 (8) |
S6—C46 | 1.738 (6) | C27—H27 | 0.9300 |
S7—C47 | 1.742 (6) | C28—H28 | 0.9300 |
S8—C50 | 1.719 (6) | C29—C30 | 1.387 (7) |
N1—C13 | 1.333 (6) | C29—C34 | 1.400 (6) |
N1—C9 | 1.342 (6) | C30—C31 | 1.371 (7) |
N1—C8 | 1.492 (6) | C30—H30 | 0.9300 |
N2—C28 | 1.328 (6) | C31—C32 | 1.374 (7) |
N2—C23 | 1.338 (6) | C31—H31 | 0.9300 |
N2—C22 | 1.474 (6) | C32—C33 | 1.388 (7) |
N3—C1 | 1.109 (8) | C32—H32 | 0.9300 |
N4—C15 | 1.129 (8) | C33—C34 | 1.383 (7) |
C1—C2 | 1.449 (9) | C33—H33 | 0.9300 |
C2—C3 | 1.352 (9) | C35—C40 | 1.388 (7) |
C2—C7 | 1.381 (8) | C35—C36 | 1.393 (7) |
C3—C4 | 1.356 (8) | C36—C37 | 1.410 (7) |
C3—H3 | 0.9300 | C37—C38 | 1.364 (7) |
C4—C5 | 1.385 (8) | C37—H37 | 0.9300 |
C4—H4 | 0.9300 | C38—C39 | 1.386 (7) |
C5—C6 | 1.379 (7) | C38—H38 | 0.9300 |
C5—C8 | 1.499 (7) | C39—C40 | 1.363 (7) |
C6—C7 | 1.369 (7) | C39—H39 | 0.9300 |
C6—H6 | 0.9300 | C40—H40 | 0.9300 |
C7—H7 | 0.9300 | C41—C46 | 1.386 (7) |
C8—H8A | 0.9700 | C41—C42 | 1.400 (8) |
C8—H8B | 0.9700 | C42—C43 | 1.375 (8) |
C9—C10 | 1.361 (7) | C42—H42 | 0.9300 |
C9—H9 | 0.9300 | C43—C44 | 1.387 (7) |
C10—C11 | 1.363 (8) | C43—H43 | 0.9300 |
C10—H10 | 0.9300 | C44—C45 | 1.360 (7) |
C11—C12 | 1.370 (9) | C44—H44 | 0.9300 |
C11—C14 | 1.494 (8) | C45—C46 | 1.381 (8) |
C12—C13 | 1.357 (8) | C45—H45 | 0.9300 |
C12—H12 | 0.9300 | C47—C48 | 1.385 (7) |
C13—H13 | 0.9300 | C47—C50ii | 1.394 (7) |
C14—H14A | 0.9600 | C48—C49 | 1.362 (7) |
C14—H14B | 0.9600 | C48—H48 | 0.9300 |
C14—H14C | 0.9600 | C49—C52ii | 1.389 (7) |
C15—C16 | 1.426 (9) | C49—H49 | 0.9300 |
C16—C21 | 1.359 (8) | C50—C51 | 1.391 (7) |
C16—C17 | 1.384 (8) | C50—C47ii | 1.394 (7) |
C17—C18 | 1.365 (7) | C51—C52 | 1.362 (8) |
C17—H17 | 0.9300 | C51—H51 | 0.9300 |
C18—C19 | 1.374 (7) | C52—C49ii | 1.389 (7) |
C18—H18 | 0.9300 | C52—H52 | 0.9300 |
S6—Ni1—S6i | 166.03 (9) | N2—C22—H22A | 109.0 |
S6—Ni1—S5 | 91.45 (6) | C19—C22—H22A | 109.0 |
S6i—Ni1—S5 | 89.32 (6) | N2—C22—H22B | 109.0 |
S6—Ni1—S5i | 89.33 (6) | C19—C22—H22B | 109.0 |
S6i—Ni1—S5i | 91.45 (6) | H22A—C22—H22B | 107.8 |
S5—Ni1—S5i | 173.64 (10) | N2—C23—C24 | 121.4 (6) |
S4—Ni2—S3 | 91.93 (7) | N2—C23—H23 | 119.3 |
S4—Ni2—S2 | 88.17 (6) | C24—C23—H23 | 119.3 |
S3—Ni2—S2 | 178.93 (8) | C23—C24—C25 | 120.0 (6) |
S4—Ni2—S1 | 178.82 (6) | C23—C24—H24 | 120.0 |
S3—Ni2—S1 | 88.26 (6) | C25—C24—H24 | 120.0 |
S2—Ni2—S1 | 91.66 (6) | C24—C25—C27 | 117.7 (7) |
S7—Ni3—S7ii | 179.998 (1) | C24—C25—C26 | 122.0 (7) |
S7—Ni3—S8ii | 91.76 (6) | C27—C25—C26 | 120.3 (7) |
S7ii—Ni3—S8ii | 88.25 (6) | C25—C26—H26A | 109.5 |
S7—Ni3—S8 | 88.25 (6) | C25—C26—H26B | 109.5 |
S7ii—Ni3—S8 | 91.75 (6) | H26A—C26—H26B | 109.5 |
S8ii—Ni3—S8 | 179.998 (1) | C25—C26—H26C | 109.5 |
C29—S1—Ni2 | 105.3 (2) | H26A—C26—H26C | 109.5 |
C34—S2—Ni2 | 105.2 (2) | H26B—C26—H26C | 109.5 |
C35—S3—Ni2 | 105.1 (2) | C28—C27—C25 | 119.7 (7) |
C36—S4—Ni2 | 104.7 (2) | C28—C27—H27 | 120.2 |
C41—S5—Ni1 | 104.5 (2) | C25—C27—H27 | 120.2 |
C46—S6—Ni1 | 105.7 (3) | N2—C28—C27 | 121.4 (6) |
C47—S7—Ni3 | 104.4 (3) | N2—C28—H28 | 119.3 |
C50—S8—Ni3 | 105.4 (2) | C27—C28—H28 | 119.3 |
C13—N1—C9 | 120.0 (6) | C30—C29—C34 | 119.5 (6) |
C13—N1—C8 | 120.2 (5) | C30—C29—S1 | 121.6 (5) |
C9—N1—C8 | 119.6 (6) | C34—C29—S1 | 118.9 (5) |
C28—N2—C23 | 119.7 (6) | C31—C30—C29 | 119.8 (6) |
C28—N2—C22 | 120.7 (6) | C31—C30—H30 | 120.1 |
C23—N2—C22 | 119.5 (6) | C29—C30—H30 | 120.1 |
N3—C1—C2 | 177.6 (12) | C30—C31—C32 | 121.4 (6) |
C3—C2—C7 | 118.4 (8) | C30—C31—H31 | 119.3 |
C3—C2—C1 | 120.9 (9) | C32—C31—H31 | 119.3 |
C7—C2—C1 | 120.7 (9) | C31—C32—C33 | 119.4 (7) |
C2—C3—C4 | 122.5 (8) | C31—C32—H32 | 120.3 |
C2—C3—H3 | 118.7 | C33—C32—H32 | 120.3 |
C4—C3—H3 | 118.7 | C34—C33—C32 | 120.1 (7) |
C3—C4—C5 | 119.1 (7) | C34—C33—H33 | 119.9 |
C3—C4—H4 | 120.4 | C32—C33—H33 | 119.9 |
C5—C4—H4 | 120.4 | C33—C34—C29 | 119.8 (6) |
C6—C5—C4 | 119.4 (6) | C33—C34—S2 | 121.3 (5) |
C6—C5—C8 | 119.3 (6) | C29—C34—S2 | 118.9 (5) |
C4—C5—C8 | 121.2 (7) | C40—C35—C36 | 120.5 (6) |
C7—C6—C5 | 119.8 (6) | C40—C35—S3 | 121.5 (5) |
C7—C6—H6 | 120.1 | C36—C35—S3 | 118.0 (5) |
C5—C6—H6 | 120.1 | C35—C36—C37 | 117.6 (6) |
C6—C7—C2 | 120.7 (7) | C35—C36—S4 | 120.3 (5) |
C6—C7—H7 | 119.6 | C37—C36—S4 | 122.1 (5) |
C2—C7—H7 | 119.6 | C38—C37—C36 | 121.5 (6) |
N1—C8—C5 | 113.4 (5) | C38—C37—H37 | 119.3 |
N1—C8—H8A | 108.9 | C36—C37—H37 | 119.3 |
C5—C8—H8A | 108.9 | C37—C38—C39 | 119.5 (7) |
N1—C8—H8B | 108.9 | C37—C38—H38 | 120.3 |
C5—C8—H8B | 108.9 | C39—C38—H38 | 120.3 |
H8A—C8—H8B | 107.7 | C40—C39—C38 | 120.6 (7) |
N1—C9—C10 | 119.5 (6) | C40—C39—H39 | 119.7 |
N1—C9—H9 | 120.2 | C38—C39—H39 | 119.7 |
C10—C9—H9 | 120.2 | C39—C40—C35 | 120.3 (7) |
C9—C10—C11 | 122.4 (7) | C39—C40—H40 | 119.8 |
C9—C10—H10 | 118.8 | C35—C40—H40 | 119.8 |
C11—C10—H10 | 118.8 | C46—C41—C42 | 119.1 (7) |
C10—C11—C12 | 116.0 (8) | C46—C41—S5 | 120.1 (6) |
C10—C11—C14 | 122.4 (8) | C42—C41—S5 | 120.8 (6) |
C12—C11—C14 | 121.6 (8) | C43—C42—C41 | 120.6 (7) |
C13—C12—C11 | 121.6 (8) | C43—C42—H42 | 119.7 |
C13—C12—H12 | 119.2 | C41—C42—H42 | 119.7 |
C11—C12—H12 | 119.2 | C42—C43—C44 | 119.7 (7) |
N1—C13—C12 | 120.5 (7) | C42—C43—H43 | 120.2 |
N1—C13—H13 | 119.7 | C44—C43—H43 | 120.2 |
C12—C13—H13 | 119.7 | C45—C44—C43 | 119.7 (7) |
C11—C14—H14A | 109.5 | C45—C44—H44 | 120.2 |
C11—C14—H14B | 109.5 | C43—C44—H44 | 120.2 |
H14A—C14—H14B | 109.5 | C44—C45—C46 | 121.7 (7) |
C11—C14—H14C | 109.5 | C44—C45—H45 | 119.2 |
H14A—C14—H14C | 109.5 | C46—C45—H45 | 119.2 |
H14B—C14—H14C | 109.5 | C45—C46—C41 | 119.3 (7) |
N4—C15—C16 | 179.3 (11) | C45—C46—S6 | 122.9 (6) |
C21—C16—C17 | 119.4 (7) | C41—C46—S6 | 117.8 (6) |
C21—C16—C15 | 121.8 (9) | C48—C47—C50ii | 120.4 (6) |
C17—C16—C15 | 118.8 (9) | C48—C47—S7 | 120.0 (6) |
C18—C17—C16 | 119.3 (7) | C50ii—C47—S7 | 119.5 (6) |
C18—C17—H17 | 120.3 | C49—C48—C47 | 120.3 (6) |
C16—C17—H17 | 120.3 | C49—C48—H48 | 119.9 |
C17—C18—C19 | 121.0 (6) | C47—C48—H48 | 119.9 |
C17—C18—H18 | 119.5 | C48—C49—C52ii | 120.1 (6) |
C19—C18—H18 | 119.5 | C48—C49—H49 | 119.9 |
C20—C19—C18 | 119.7 (6) | C52ii—C49—H49 | 119.9 |
C20—C19—C22 | 120.7 (7) | C51—C50—C47ii | 117.9 (6) |
C18—C19—C22 | 119.6 (6) | C51—C50—S8 | 123.3 (5) |
C19—C20—C21 | 119.4 (7) | C47ii—C50—S8 | 118.8 (6) |
C19—C20—H20 | 120.3 | C52—C51—C50 | 121.5 (7) |
C21—C20—H20 | 120.3 | C52—C51—H51 | 119.2 |
C16—C21—C20 | 121.3 (7) | C50—C51—H51 | 119.2 |
C16—C21—H21 | 119.4 | C51—C52—C49ii | 119.7 (7) |
C20—C21—H21 | 119.4 | C51—C52—H52 | 120.2 |
N2—C22—C19 | 112.9 (5) | C49ii—C52—H52 | 120.2 |
S3—Ni2—S1—C29 | 178.71 (17) | C24—C25—C27—C28 | 1.5 (8) |
S2—Ni2—S1—C29 | −0.22 (17) | C26—C25—C27—C28 | −179.0 (5) |
S4—Ni2—S2—C34 | 179.64 (18) | C23—N2—C28—C27 | −1.4 (8) |
S1—Ni2—S2—C34 | 0.82 (19) | C22—N2—C28—C27 | 175.8 (5) |
S4—Ni2—S3—C35 | −0.44 (18) | C25—C27—C28—N2 | 0.4 (9) |
S1—Ni2—S3—C35 | 178.39 (18) | Ni2—S1—C29—C30 | 178.1 (4) |
S3—Ni2—S4—C36 | 0.29 (18) | Ni2—S1—C29—C34 | −0.6 (4) |
S2—Ni2—S4—C36 | 179.22 (18) | C34—C29—C30—C31 | −1.1 (8) |
S6—Ni1—S5—C41 | 5.32 (18) | S1—C29—C30—C31 | −179.8 (4) |
S6i—Ni1—S5—C41 | −160.73 (17) | C29—C30—C31—C32 | 0.1 (9) |
S6i—Ni1—S6—C46 | 87.36 (18) | C30—C31—C32—C33 | 0.3 (10) |
S5—Ni1—S6—C46 | −5.65 (19) | C31—C32—C33—C34 | 0.4 (9) |
S5i—Ni1—S6—C46 | −179.34 (19) | C32—C33—C34—C29 | −1.4 (8) |
S8ii—Ni3—S7—C47 | −3.25 (18) | C32—C33—C34—S2 | 177.6 (4) |
S8—Ni3—S7—C47 | 176.75 (18) | C30—C29—C34—C33 | 1.8 (8) |
S7—Ni3—S8—C50 | 176.17 (17) | S1—C29—C34—C33 | −179.5 (4) |
S7ii—Ni3—S8—C50 | −3.83 (17) | C30—C29—C34—S2 | −177.3 (4) |
C7—C2—C3—C4 | 1.5 (10) | S1—C29—C34—S2 | 1.4 (6) |
C1—C2—C3—C4 | 179.9 (6) | Ni2—S2—C34—C33 | 179.5 (4) |
C2—C3—C4—C5 | −1.0 (11) | Ni2—S2—C34—C29 | −1.5 (4) |
C3—C4—C5—C6 | 0.4 (9) | Ni2—S3—C35—C40 | 179.4 (4) |
C3—C4—C5—C8 | −177.5 (6) | Ni2—S3—C35—C36 | 0.6 (4) |
C4—C5—C6—C7 | −0.4 (8) | C40—C35—C36—C37 | 0.5 (8) |
C8—C5—C6—C7 | 177.5 (5) | S3—C35—C36—C37 | 179.4 (4) |
C5—C6—C7—C2 | 1.0 (9) | C40—C35—C36—S4 | −179.3 (4) |
C3—C2—C7—C6 | −1.5 (9) | S3—C35—C36—S4 | −0.4 (6) |
C1—C2—C7—C6 | −179.9 (6) | Ni2—S4—C36—C35 | 0.0 (4) |
C13—N1—C8—C5 | −136.2 (6) | Ni2—S4—C36—C37 | −179.8 (4) |
C9—N1—C8—C5 | 48.6 (7) | C35—C36—C37—C38 | −0.3 (8) |
C6—C5—C8—N1 | 66.0 (6) | S4—C36—C37—C38 | 179.5 (5) |
C4—C5—C8—N1 | −116.1 (6) | C36—C37—C38—C39 | −0.2 (10) |
C13—N1—C9—C10 | −0.4 (8) | C37—C38—C39—C40 | 0.4 (11) |
C8—N1—C9—C10 | 174.9 (5) | C38—C39—C40—C35 | −0.2 (10) |
N1—C9—C10—C11 | 0.0 (9) | C36—C35—C40—C39 | −0.3 (9) |
C9—C10—C11—C12 | 0.2 (9) | S3—C35—C40—C39 | −179.2 (5) |
C9—C10—C11—C14 | −179.4 (5) | Ni1—S5—C41—C46 | −3.9 (4) |
C10—C11—C12—C13 | −0.2 (9) | Ni1—S5—C41—C42 | 175.7 (4) |
C14—C11—C12—C13 | 179.5 (6) | C46—C41—C42—C43 | 1.0 (8) |
C9—N1—C13—C12 | 0.4 (8) | S5—C41—C42—C43 | −178.6 (4) |
C8—N1—C13—C12 | −174.8 (5) | C41—C42—C43—C44 | −0.4 (9) |
C11—C12—C13—N1 | −0.2 (10) | C42—C43—C44—C45 | −0.4 (9) |
C21—C16—C17—C18 | 0.6 (9) | C43—C44—C45—C46 | 0.7 (9) |
C15—C16—C17—C18 | −179.1 (6) | C44—C45—C46—C41 | −0.2 (8) |
C16—C17—C18—C19 | 0.2 (8) | C44—C45—C46—S6 | 179.3 (4) |
C17—C18—C19—C20 | −1.0 (8) | C42—C41—C46—C45 | −0.7 (8) |
C17—C18—C19—C22 | −178.8 (5) | S5—C41—C46—C45 | 178.9 (4) |
C18—C19—C20—C21 | 0.9 (9) | C42—C41—C46—S6 | 179.8 (4) |
C22—C19—C20—C21 | 178.8 (5) | S5—C41—C46—S6 | −0.6 (6) |
C17—C16—C21—C20 | −0.7 (10) | Ni1—S6—C46—C45 | −174.7 (4) |
C15—C16—C21—C20 | 179.1 (6) | Ni1—S6—C46—C41 | 4.8 (4) |
C19—C20—C21—C16 | −0.1 (10) | Ni3—S7—C47—C48 | −177.0 (4) |
C28—N2—C22—C19 | 121.6 (6) | Ni3—S7—C47—C50ii | 1.9 (4) |
C23—N2—C22—C19 | −61.2 (7) | C50ii—C47—C48—C49 | 0.5 (8) |
C20—C19—C22—N2 | 120.5 (6) | S7—C47—C48—C49 | 179.4 (4) |
C18—C19—C22—N2 | −61.7 (7) | C47—C48—C49—C52ii | −0.5 (9) |
C28—N2—C23—C24 | 0.4 (8) | Ni3—S8—C50—C51 | −176.4 (4) |
C22—N2—C23—C24 | −176.8 (5) | Ni3—S8—C50—C47ii | 3.7 (4) |
N2—C23—C24—C25 | 1.5 (9) | C47ii—C50—C51—C52 | 0.6 (8) |
C23—C24—C25—C27 | −2.4 (8) | S8—C50—C51—C52 | −179.3 (4) |
C23—C24—C25—C26 | 178.1 (5) | C50—C51—C52—C49ii | −0.6 (9) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C14H13N2)[Ni(C6H4S2)2] |
Mr | 548.40 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 294 |
a, b, c (Å) | 42.344 (3), 7.2455 (6), 32.768 (2) |
β (°) | 96.480 (5) |
V (Å3) | 9988.9 (13) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.20 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.806, 0.896 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27982, 8530, 3392 |
Rint | 0.113 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.078, 0.89 |
No. of reflections | 8530 |
No. of parameters | 599 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.27 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
Ni1—S6 | 2.1337 (16) | Ni2—S2 | 2.1408 (17) |
Ni1—S6i | 2.1338 (16) | Ni2—S1 | 2.1424 (16) |
Ni1—S5 | 2.1477 (14) | Ni3—S7 | 2.1424 (15) |
Ni1—S5i | 2.1478 (14) | Ni3—S7ii | 2.1424 (15) |
Ni2—S4 | 2.1400 (16) | Ni3—S8ii | 2.1470 (14) |
Ni2—S3 | 2.1405 (17) | Ni3—S8 | 2.1470 (14) |
S6—Ni1—S6i | 166.03 (9) | S4—Ni2—S1 | 178.82 (6) |
S6—Ni1—S5 | 91.45 (6) | S3—Ni2—S1 | 88.26 (6) |
S6i—Ni1—S5 | 89.32 (6) | S2—Ni2—S1 | 91.66 (6) |
S6—Ni1—S5i | 89.33 (6) | S7—Ni3—S7ii | 179.998 (1) |
S6i—Ni1—S5i | 91.45 (6) | S7—Ni3—S8ii | 91.76 (6) |
S5—Ni1—S5i | 173.64 (10) | S7ii—Ni3—S8ii | 88.25 (6) |
S4—Ni2—S3 | 91.93 (7) | S7—Ni3—S8 | 88.25 (6) |
S4—Ni2—S2 | 88.17 (6) | S7ii—Ni3—S8 | 91.75 (6) |
S3—Ni2—S2 | 178.93 (8) | S8ii—Ni3—S8 | 179.998 (1) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···S4i | 0.97 | 2.846 | 3.721 (3) | 150.63 |
Symmetry code: (i) 1/2 - x, y + 1/2, 1/2 - z. |
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Since their discovery in 1963, square planar bis(benzene-1,2-dithiolato)metal complexes have received considerable attention due to their interesting and often unusual electronic structures. It has been established that the square planar complexes [M(L)2]2-, [M(L)2]-, and [M(L)2]0 (where M = Ni, Pt) form a three membered electron-transfer series, where the neutral species and the dianionic forms are diamagnetic (S = 0), whereas the monoanions are paramagnetic (S = 1/2) (de Caro et al., 2004; Ray et al., 2005). In our previous research using benzylpyridinium derivatives ([RBzPy]+) as the counter-cation of TCNQ- (where TCNQ = 7,7,8,8-tetracyanoquinodimethanide), a series of ion-pair compounds with segregated columnar stacks of cations and anions has been prepared (Liu, 2007; Liu et al., 2005; Wang et al., 2006). The quasi one-dimensional magnetic nature of these compounds was attributed to intermolecular-orbital interactions within the anionic columns. As an extension of our work on this series of complexes, we herein report the crystal structure of the title compound, (I).
The asymmetric unit of (I), contains two (C14H13N2)+ cations, one and two halves centrosymmetric [Ni(C6H4S2)2] anions. In the anions, the Ni ions are surrounded by four S atoms in a distorted square-planar geometry. The dihedral angle between (Ni1/S5/S6/C41/C46) and (Ni1/S5A/S6A/C41A/C46A) planes is 18.98 (2)° [symmetry code (A): -x, y, 1/2 - z]. It is peculiar and interesting. The Ni—S bond lengths and S—Ni—S bond angles (Table 1) are in agreement with the corresponding values in analogous complexes (Sellmann et al., 1991; Xie et al., 2002). The cations have Λ-shaped conformations with the dihedral angles of A/B = 65.03 (3), A/C = 46.37 (4), B/C = 86.96 (4) ° and D/E = 60.62 (3), D/F = 59.72 (3), E/F = 83.56 (4) ° between A (C5/C8/N1), B (C2—C7), C (N1/C9—C13) and D (C19/C22/N2), E (C16—C21), F (N2/C23—C28) planes.
In the crystal structure, the packing of the two anions is different (Fig. 2). The Ni1, Ni3-containing anions stack in a face-to-face fashion with an alternating arrangement of anions and cations, such that the pyridine ring of the cation lies above the benzene ring of the anion. The shortest distance between the adjacent NiIII ions is 7.245 (2) Å. The Ni2-containing anions stack in a side by side fashion with C—H···S interactions (Table 2).