Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021530/ww6054sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021530/ww6054Isup2.hkl |
CCDC reference: 202309
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.008 Å
- R factor = 0.040
- wR factor = 0.136
- Data-to-parameter ratio = 16.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_734 Alert C Contact Calc 4.2067(9), Rep 4.206(2) .... 2.22 su-Ratio NI1 -NI1 1.555 3.657
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Dmit(COPh)2 (0.412 g, 1 mmol) was treated with an excess of sodium methylate (9.0 mmol) in 20 ml MeOH under nitrogen at room temperature with stirring. To the resulting dark-red solution, NiCl2·6H2O (0.118 g, 0.5 mmol) in 20 ml MeOH, and benzyltrimethylammonium bromide (0.232 g, 1 mmol) in 20 ml MeOH were added. Precipatates were washed with MeOH and dried in a vacuum desiccator. This product was recrystallized from acetone in air to produce the title complex, instead of bis(benzyltrimethylammonium) bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(II), as could be deduced from its IR spectrum; 1348 [s, ν(C═C)], 1045 cm−1 [s, ν(C═S)].
After checking their presence in the difference map, all H atoms were fixed geometrically and allowed to ride on their attached atoms, which C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.
(C10H16N)[Ni(C3S5)2] | F(000) = 1228 |
Mr = 601.66 | Dx = 1.671 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 38 reflections |
a = 10.3539 (13) Å | θ = 5.1–12.4° |
b = 17.0677 (12) Å | µ = 1.69 mm−1 |
c = 13.5370 (13) Å | T = 293 K |
β = 90.729 (8)° | Plate, black |
V = 2392.0 (4) Å3 | 0.34 × 0.30 × 0.08 mm |
Z = 4 |
Bruker P4 diffractometer | 2783 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
θ/2θ scans | h = −1→12 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −1→20 |
Tmin = 0.572, Tmax = 0.874 | l = −16→16 |
5307 measured reflections | 3 standard reflections every 97 reflections |
4204 independent reflections | intensity decay: 2% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 0.80 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
4204 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
(C10H16N)[Ni(C3S5)2] | V = 2392.0 (4) Å3 |
Mr = 601.66 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.3539 (13) Å | µ = 1.69 mm−1 |
b = 17.0677 (12) Å | T = 293 K |
c = 13.5370 (13) Å | 0.34 × 0.30 × 0.08 mm |
β = 90.729 (8)° |
Bruker P4 diffractometer | 2783 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.030 |
Tmin = 0.572, Tmax = 0.874 | 3 standard reflections every 97 reflections |
5307 measured reflections | intensity decay: 2% |
4204 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 0.80 | Δρmax = 0.28 e Å−3 |
4204 reflections | Δρmin = −0.24 e Å−3 |
253 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 | 0.34135 (5) | 0.07578 (3) | 0.98139 (4) | 0.04461 (19) | |
S1 | −0.10616 (16) | 0.11574 (11) | 1.37259 (11) | 0.0861 (5) | |
S2 | −0.01033 (13) | 0.03450 (9) | 1.19538 (10) | 0.0641 (4) | |
S3 | 0.12188 (14) | 0.17363 (8) | 1.26150 (10) | 0.0662 (4) | |
S4 | 0.17757 (12) | 0.00850 (7) | 1.02899 (9) | 0.0572 (3) | |
S5 | 0.32268 (12) | 0.15998 (8) | 1.10021 (9) | 0.0562 (3) | |
S6 | 0.36313 (12) | −0.01305 (7) | 0.86956 (9) | 0.0548 (3) | |
S7 | 0.49665 (13) | 0.14639 (8) | 0.92350 (9) | 0.0581 (4) | |
S8 | 0.55400 (14) | −0.02906 (7) | 0.70382 (10) | 0.0605 (4) | |
S9 | 0.68108 (13) | 0.11557 (8) | 0.75420 (10) | 0.0609 (4) | |
S10 | 0.78103 (15) | 0.02248 (8) | 0.58728 (11) | 0.0697 (4) | |
N1 | 0.1729 (4) | 0.1884 (2) | 0.6373 (3) | 0.0577 (11) | |
C1 | −0.0040 (5) | 0.1078 (3) | 1.2810 (3) | 0.0588 (13) | |
C2 | 0.1256 (4) | 0.0615 (3) | 1.1286 (3) | 0.0485 (11) | |
C3 | 0.1877 (4) | 0.1271 (3) | 1.1596 (3) | 0.0499 (11) | |
C4 | 0.4922 (4) | 0.0209 (3) | 0.8044 (3) | 0.0479 (11) | |
C5 | 0.5509 (4) | 0.0900 (3) | 0.8284 (3) | 0.0471 (11) | |
C6 | 0.6788 (5) | 0.0351 (3) | 0.6768 (3) | 0.0533 (12) | |
C7 | 0.3628 (5) | 0.2848 (3) | 0.4749 (4) | 0.0650 (14) | |
H7A | 0.2957 | 0.3211 | 0.4745 | 0.078* | |
C8 | 0.4838 (6) | 0.3081 (4) | 0.4480 (5) | 0.0819 (18) | |
H8A | 0.4987 | 0.3598 | 0.4297 | 0.098* | |
C9 | 0.5831 (6) | 0.2549 (4) | 0.4479 (4) | 0.0782 (17) | |
H9A | 0.6653 | 0.2707 | 0.4294 | 0.094* | |
C10 | 0.5622 (6) | 0.1798 (4) | 0.4746 (5) | 0.0807 (18) | |
H10A | 0.6302 | 0.1442 | 0.4746 | 0.097* | |
C11 | 0.4400 (6) | 0.1553 (3) | 0.5020 (4) | 0.0720 (15) | |
H11A | 0.4262 | 0.1033 | 0.5198 | 0.086* | |
C12 | 0.3386 (5) | 0.2081 (3) | 0.5028 (3) | 0.0499 (11) | |
C13 | 0.2046 (5) | 0.1829 (3) | 0.5284 (4) | 0.0569 (13) | |
H13A | 0.1927 | 0.1291 | 0.5072 | 0.068* | |
H13B | 0.1435 | 0.2149 | 0.4915 | 0.068* | |
C14 | 0.1803 (6) | 0.2713 (4) | 0.6707 (5) | 0.0852 (19) | |
H14A | 0.1610 | 0.2741 | 0.7398 | 0.128* | |
H14B | 0.1189 | 0.3022 | 0.6339 | 0.128* | |
H14C | 0.2657 | 0.2911 | 0.6600 | 0.128* | |
C15 | 0.2588 (7) | 0.1379 (4) | 0.6977 (5) | 0.111 (3) | |
H15A | 0.2370 | 0.1430 | 0.7661 | 0.167* | |
H15B | 0.3469 | 0.1535 | 0.6886 | 0.167* | |
H15C | 0.2482 | 0.0843 | 0.6776 | 0.167* | |
C16 | 0.0372 (6) | 0.1606 (4) | 0.6491 (5) | 0.091 (2) | |
H16A | 0.0142 | 0.1634 | 0.7175 | 0.136* | |
H16B | 0.0303 | 0.1073 | 0.6267 | 0.136* | |
H16C | −0.0200 | 0.1931 | 0.6107 | 0.136* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0409 (3) | 0.0477 (4) | 0.0453 (3) | −0.0026 (3) | 0.0029 (2) | 0.0022 (3) |
S1 | 0.0737 (10) | 0.1218 (14) | 0.0634 (9) | −0.0042 (10) | 0.0275 (8) | −0.0020 (9) |
S2 | 0.0565 (8) | 0.0811 (9) | 0.0550 (8) | −0.0211 (7) | 0.0126 (6) | −0.0008 (7) |
S3 | 0.0736 (9) | 0.0710 (9) | 0.0545 (8) | −0.0134 (7) | 0.0201 (7) | −0.0109 (7) |
S4 | 0.0569 (8) | 0.0554 (7) | 0.0597 (8) | −0.0136 (6) | 0.0132 (6) | −0.0067 (6) |
S5 | 0.0537 (7) | 0.0638 (8) | 0.0514 (7) | −0.0178 (6) | 0.0088 (6) | −0.0064 (6) |
S6 | 0.0570 (8) | 0.0440 (6) | 0.0639 (8) | −0.0072 (6) | 0.0142 (6) | −0.0030 (6) |
S7 | 0.0551 (8) | 0.0623 (8) | 0.0573 (8) | −0.0165 (6) | 0.0133 (6) | −0.0141 (6) |
S8 | 0.0711 (9) | 0.0489 (7) | 0.0621 (8) | −0.0046 (6) | 0.0177 (7) | −0.0084 (6) |
S9 | 0.0592 (8) | 0.0631 (8) | 0.0609 (8) | −0.0143 (6) | 0.0184 (6) | −0.0097 (6) |
S10 | 0.0764 (10) | 0.0673 (9) | 0.0661 (9) | −0.0035 (8) | 0.0288 (7) | −0.0054 (7) |
N1 | 0.049 (2) | 0.062 (3) | 0.063 (3) | −0.003 (2) | −0.002 (2) | 0.016 (2) |
C1 | 0.056 (3) | 0.073 (3) | 0.047 (3) | −0.004 (3) | 0.002 (2) | 0.007 (2) |
C2 | 0.043 (3) | 0.058 (3) | 0.044 (2) | −0.007 (2) | 0.007 (2) | 0.007 (2) |
C3 | 0.050 (3) | 0.060 (3) | 0.040 (2) | −0.006 (2) | 0.005 (2) | 0.000 (2) |
C4 | 0.048 (3) | 0.046 (3) | 0.050 (3) | 0.002 (2) | 0.002 (2) | 0.003 (2) |
C5 | 0.045 (3) | 0.051 (3) | 0.045 (2) | −0.002 (2) | 0.006 (2) | −0.001 (2) |
C6 | 0.054 (3) | 0.058 (3) | 0.048 (3) | 0.002 (2) | 0.003 (2) | 0.003 (2) |
C7 | 0.073 (4) | 0.060 (3) | 0.063 (3) | −0.002 (3) | 0.000 (3) | 0.006 (3) |
C8 | 0.087 (5) | 0.076 (4) | 0.084 (4) | −0.019 (4) | 0.018 (4) | 0.001 (3) |
C9 | 0.058 (4) | 0.112 (5) | 0.064 (4) | −0.011 (4) | 0.005 (3) | −0.014 (4) |
C10 | 0.057 (4) | 0.106 (5) | 0.080 (4) | 0.016 (4) | 0.006 (3) | −0.009 (4) |
C11 | 0.073 (4) | 0.061 (3) | 0.083 (4) | 0.008 (3) | 0.005 (3) | 0.002 (3) |
C12 | 0.051 (3) | 0.051 (3) | 0.047 (3) | 0.004 (2) | −0.006 (2) | −0.007 (2) |
C13 | 0.057 (3) | 0.054 (3) | 0.060 (3) | 0.008 (2) | −0.006 (2) | 0.000 (2) |
C14 | 0.102 (5) | 0.081 (4) | 0.072 (4) | −0.014 (4) | 0.017 (3) | −0.022 (3) |
C15 | 0.095 (5) | 0.143 (7) | 0.097 (5) | 0.042 (5) | 0.001 (4) | 0.055 (5) |
C16 | 0.070 (4) | 0.088 (4) | 0.114 (5) | −0.006 (4) | 0.013 (4) | 0.023 (4) |
Ni1—S4 | 2.1534 (13) | C7—C8 | 1.368 (8) |
Ni1—S6 | 2.1564 (13) | C7—C12 | 1.386 (7) |
Ni1—S7 | 2.1643 (13) | C7—H7A | 0.9300 |
Ni1—S5 | 2.1675 (14) | C8—C9 | 1.371 (8) |
S1—C1 | 1.645 (5) | C8—H8A | 0.9300 |
S2—C1 | 1.707 (5) | C9—C10 | 1.351 (8) |
S2—C2 | 1.744 (4) | C9—H9A | 0.9300 |
S3—C3 | 1.739 (5) | C10—C11 | 1.387 (8) |
S3—C1 | 1.743 (5) | C10—H10A | 0.9300 |
S4—C2 | 1.716 (5) | C11—C12 | 1.385 (7) |
S5—C3 | 1.715 (5) | C11—H11A | 0.9300 |
S6—C4 | 1.712 (5) | C12—C13 | 1.498 (7) |
S7—C5 | 1.707 (4) | C13—H13A | 0.9700 |
S8—C6 | 1.736 (5) | C13—H13B | 0.9700 |
S8—C4 | 1.736 (5) | C14—H14A | 0.9600 |
S9—C6 | 1.728 (5) | C14—H14B | 0.9600 |
S9—C5 | 1.747 (4) | C14—H14C | 0.9600 |
S10—C6 | 1.633 (5) | C15—H15A | 0.9600 |
N1—C15 | 1.478 (7) | C15—H15B | 0.9600 |
N1—C14 | 1.488 (7) | C15—H15C | 0.9600 |
N1—C16 | 1.494 (7) | C16—H16A | 0.9600 |
N1—C13 | 1.516 (6) | C16—H16B | 0.9600 |
C2—C3 | 1.356 (6) | C16—H16C | 0.9600 |
C4—C5 | 1.364 (6) | ||
S1···S10i | 3.526 (2) | S5···S8iv | 3.685 (2) |
S2···S4ii | 3.555 (2) | Ni1···S6iv | 3.797 (2) |
S3···S9iii | 3.651 (2) | Ni1···Ni1iv | 4.206 (2) |
S4—Ni1—S6 | 85.70 (5) | C12—C7—H7A | 119.5 |
S4—Ni1—S7 | 175.41 (6) | C7—C8—C9 | 119.8 (6) |
S6—Ni1—S7 | 93.01 (5) | C7—C8—H8A | 120.1 |
S4—Ni1—S5 | 93.06 (5) | C9—C8—H8A | 120.1 |
S6—Ni1—S5 | 176.65 (6) | C10—C9—C8 | 120.4 (6) |
S7—Ni1—S5 | 88.46 (5) | C10—C9—H9A | 119.8 |
C1—S2—C2 | 97.7 (2) | C8—C9—H9A | 119.8 |
C3—S3—C1 | 97.3 (2) | C9—C10—C11 | 120.5 (6) |
C2—S4—Ni1 | 102.13 (16) | C9—C10—H10A | 119.7 |
C3—S5—Ni1 | 102.23 (16) | C11—C10—H10A | 119.7 |
C4—S6—Ni1 | 102.30 (16) | C12—C11—C10 | 120.0 (6) |
C5—S7—Ni1 | 102.25 (16) | C12—C11—H11A | 120.0 |
C6—S8—C4 | 97.9 (2) | C10—C11—H11A | 120.0 |
C6—S9—C5 | 98.4 (2) | C11—C12—C7 | 118.3 (5) |
C15—N1—C14 | 111.0 (5) | C11—C12—C13 | 121.3 (5) |
C15—N1—C16 | 108.4 (5) | C7—C12—C13 | 120.4 (5) |
C14—N1—C16 | 108.3 (5) | C12—C13—N1 | 114.8 (4) |
C15—N1—C13 | 111.5 (5) | C12—C13—H13A | 108.6 |
C14—N1—C13 | 110.1 (4) | N1—C13—H13A | 108.6 |
C16—N1—C13 | 107.4 (4) | C12—C13—H13B | 108.6 |
S1—C1—S2 | 123.5 (3) | N1—C13—H13B | 108.6 |
S1—C1—S3 | 123.4 (3) | H13A—C13—H13B | 107.5 |
S2—C1—S3 | 113.1 (3) | N1—C14—H14A | 109.5 |
C3—C2—S4 | 121.8 (3) | N1—C14—H14B | 109.5 |
C3—C2—S2 | 116.1 (4) | H14A—C14—H14B | 109.5 |
S4—C2—S2 | 122.1 (3) | N1—C14—H14C | 109.5 |
C2—C3—S5 | 120.8 (4) | H14A—C14—H14C | 109.5 |
C2—C3—S3 | 115.7 (3) | H14B—C14—H14C | 109.5 |
S5—C3—S3 | 123.5 (3) | N1—C15—H15A | 109.5 |
C5—C4—S6 | 121.2 (3) | N1—C15—H15B | 109.5 |
C5—C4—S8 | 116.4 (3) | H15A—C15—H15B | 109.5 |
S6—C4—S8 | 122.4 (3) | N1—C15—H15C | 109.5 |
C4—C5—S7 | 121.1 (3) | H15A—C15—H15C | 109.5 |
C4—C5—S9 | 115.0 (3) | H15B—C15—H15C | 109.5 |
S7—C5—S9 | 123.8 (3) | N1—C16—H16A | 109.5 |
S10—C6—S9 | 123.4 (3) | N1—C16—H16B | 109.5 |
S10—C6—S8 | 124.4 (3) | H16A—C16—H16B | 109.5 |
S9—C6—S8 | 112.2 (3) | N1—C16—H16C | 109.5 |
C8—C7—C12 | 121.1 (5) | H16A—C16—H16C | 109.5 |
C8—C7—H7A | 119.5 | H16B—C16—H16C | 109.5 |
Symmetry codes: (i) x−1, y, z+1; (ii) −x, −y, −z+2; (iii) x−1/2, −y+1/2, z+1/2; (iv) −x+1, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C10H16N)[Ni(C3S5)2] |
Mr | 601.66 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.3539 (13), 17.0677 (12), 13.5370 (13) |
β (°) | 90.729 (8) |
V (Å3) | 2392.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.69 |
Crystal size (mm) | 0.34 × 0.30 × 0.08 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.572, 0.874 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5307, 4204, 2783 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.136, 0.80 |
No. of reflections | 4204 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.24 |
Computer programs: XSCANS (Bruker, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.
Ni1—S4 | 2.1534 (13) | S5—C3 | 1.715 (5) |
Ni1—S6 | 2.1564 (13) | S6—C4 | 1.712 (5) |
Ni1—S7 | 2.1643 (13) | S7—C5 | 1.707 (4) |
Ni1—S5 | 2.1675 (14) | S8—C6 | 1.736 (5) |
S1—C1 | 1.645 (5) | S8—C4 | 1.736 (5) |
S2—C1 | 1.707 (5) | S9—C6 | 1.728 (5) |
S2—C2 | 1.744 (4) | S9—C5 | 1.747 (4) |
S3—C3 | 1.739 (5) | S10—C6 | 1.633 (5) |
S3—C1 | 1.743 (5) | C2—C3 | 1.356 (6) |
S4—C2 | 1.716 (5) | C4—C5 | 1.364 (6) |
S1···S10i | 3.526 (2) | S5···S8iv | 3.685 (2) |
S2···S4ii | 3.555 (2) | Ni1···S6iv | 3.797 (2) |
S3···S9iii | 3.651 (2) | Ni1···Ni1iv | 4.206 (2) |
S4—Ni1—S6 | 85.70 (5) | S2—C1—S3 | 113.1 (3) |
S4—Ni1—S7 | 175.41 (6) | C3—C2—S4 | 121.8 (3) |
S6—Ni1—S7 | 93.01 (5) | C3—C2—S2 | 116.1 (4) |
S4—Ni1—S5 | 93.06 (5) | S4—C2—S2 | 122.1 (3) |
S6—Ni1—S5 | 176.65 (6) | C2—C3—S5 | 120.8 (4) |
S7—Ni1—S5 | 88.46 (5) | C2—C3—S3 | 115.7 (3) |
C1—S2—C2 | 97.7 (2) | S5—C3—S3 | 123.5 (3) |
C3—S3—C1 | 97.3 (2) | C5—C4—S6 | 121.2 (3) |
C2—S4—Ni1 | 102.13 (16) | C5—C4—S8 | 116.4 (3) |
C3—S5—Ni1 | 102.23 (16) | S6—C4—S8 | 122.4 (3) |
C4—S6—Ni1 | 102.30 (16) | C4—C5—S7 | 121.1 (3) |
C5—S7—Ni1 | 102.25 (16) | C4—C5—S9 | 115.0 (3) |
C6—S8—C4 | 97.9 (2) | S7—C5—S9 | 123.8 (3) |
C6—S9—C5 | 98.4 (2) | S10—C6—S9 | 123.4 (3) |
S1—C1—S2 | 123.5 (3) | S10—C6—S8 | 124.4 (3) |
S1—C1—S3 | 123.4 (3) | S9—C6—S8 | 112.2 (3) |
Symmetry codes: (i) x−1, y, z+1; (ii) −x, −y, −z+2; (iii) x−1/2, −y+1/2, z+1/2; (iv) −x+1, −y, −z+2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Dmit (4,5-dimercapto-1,3-dithiole-2-thione) coordinated transition metal complexes have received significant attention since the first open-shell molecular superconductor TTF[Ni(dmit)2]2 (Bousseau et al., 1986) and then the first closed-shell molecular superconductor [N(CH3)4][Ni(dmit)2]2 (Kobayashi et al., 1987) were synthesized. Although the closed-shell cations have no contribution to the conductivity, their sizes and shapes play a predominant role in influencing the crystal structures and consequently influencing the electronic properties. So far, most of the closed-shell cations are tetraalkylammonium, in addition, four planar aromatic cations were reported (Miyazaki et al., 1992; Veldhuizen et al., 1997; Xu et al., 2001). In order to explore new members of the dmit complexes and get more insight into the structure–conductivity correlations, the title complex, (I), substituting an aromatic ring for an H atom in the Me4N cation, has been synthesized and its structure reported here.
The unit cell of (I) contains one crystallographically independent [Ni(dmit)2]− anion and one cation, as depicted in Fig. 1. The Ni—S bond distances range from 2.1534 (13) to 2.1675 (14) Å, with an average of 2.1604 (13) Å, and the S—Ni—S angles range from 85.70 (5) to 93.06 (5)°; the NiS4 coordinative polyhedron thus adopts a slightly distorted square-planar configuration. Both of the coordinated (C3S5)2− anions are perfectly planar, but the whole [Ni(dmit)2]− anion is quasi-planar with Ni as a twist centre, as could be concluded by the dihedral angle of 4.7° between the planes of the two coordinated (C3S5)2− ligands and the relatively large deviations from the least-squares plane (17 atoms) of S7 and S5, viz.0.118 and −0.103 Å, respectively.
In Fig. 2, S···S contacts shorter than 3.70 Å, the sum of van der Waals radii, are shown by dotted lines and Ni···S contacts are shown by thin solid lines. The anions form weak face-to-face dimmers, with Ni···Ni, Ni···S6 and S5···S8 contacts in between (shown in Table 2), dimers loosely stack to form columns with side-by-side contacts (S2···S4). Terminal-to-terminal S···S contacts link neighboring columns resulting in anion sheets along the (010) plane. Along the b direction between neighboring sheets, the only short contact is S3···S9. Although the cations are located in the anionic network, three-dimensional interanionic contacts still remain. Nevertheless, this kind of three-dimensional contacts is not strong, It is no surprise that its single-crystal conductivity is not very high, with a measure value of 3 × 10−7 S cm−1 at room temperature.