Benzyl­tri­methyl­ammonium bis(2-thio­xo-1,3-di­thiole-4,5-di­thiol­ato)­nickelate(III)

The crystal structure of the title complex, (C₁₀H₁₆N)[Ni(C₃S₅)₂], is characterized by its three-dimensional weak S...S intermolecular interactions and can be described as an arrangement of quasi-planar [Ni(dmit)₂]⁻ anions, separated by closed-shell (benzyl­tri­methyl­ammonium) cations.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

---

S1. Comment

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.

S2. Experimental

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)].

S3. Refinement

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 U_iso(H) = 1.2U_eq(C).

Computing details

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.

Figures

	Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing of the anion, viewed along a axis, showing weak three-dimensional intermolecular interactions.

(I)

Crystal data

(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) Å^3	0.34 × 0.30 × 0.08 mm
Z = 4

Data collection

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

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 0.80	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
4204 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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	0.34135 (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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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···S10^i	3.526 (2)	S5···S8^iv	3.685 (2)
S2···S4^ii	3.555 (2)	Ni1···S6^iv	3.797 (2)
S3···S9^iii	3.651 (2)	Ni1···Ni1^iv	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.