3-Butyl-1-methyl-1H-imidazol-3-ium bis­(1,2-dicyano­ethene-1,2-dithiol­ato-κ2S,S′)nickel(III)

Yu, S.-S.

doi:10.1107/S1600536811046824

3-Butyl-1-methyl-1H-imidazol-3-ium bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickel(III)

In the title compound, (C₈H₁₅N₂)[Ni(C₄N₂S₂)₂], the Ni^III atom is coordinated by four S atoms of two maleonitriledithiolate ligands and exhibits a distorted square-planar geometry. In the crystal, the cations and anions are connected alternately by weak intermolecular C—H

N hydrogen bonds, forming a zigzag chain along [201].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811046824/is2799sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811046824/is2799Isup2.hkl Contains datablock I

CCDC reference: 858154

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.006 Å
R factor = 0.050
wR factor = 0.099
Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...        3.2 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1    --  S4      ..        5.7 su
PLAT371_ALERT_2_G Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.43 Ang.
PLAT371_ALERT_2_G Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.44 Ang.
PLAT371_ALERT_2_G Long   C(sp2)-C(sp1) Bond  C5     -   C6     ...       1.43 Ang.
PLAT371_ALERT_2_G Long   C(sp2)-C(sp1) Bond  C7     -   C8     ...       1.43 Ang.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Bis(1,2-dithiolene) complexes of transition metals have been widely studied due to their novel properties and applications in the areas of near-infrared (near-IR) dyes, conducting, magnetic and nonlinear optical materials (Nishijo et al., 2000; Ni et al., 2005). The behavior of the packing structure for bis(1,2-dithiolene) complexes monoanions was strongly affected by the type of counterions. Herein we introduce a flexible organic cation into dithiolene monoanions system and report the crystal structure of the title compound (I).

The molecular structure of (I) is illustrated in Fig. 1. The asymmmetric unit comprises one [Ni(mnt)₂]^- monoanion and one 1-methyl-3-butyl-imidazolinium cation. The Ni ion in the [Ni(mnt)₂]^- anion is coordinated by four S atoms of two mnt^2- ligands, and exhibits square-planar coordination geometry, and their molecular planes defined by four coordination S atom are approximately parallel to each other. The bond lengths and angles of anions are in good agreement with the various [Ni(mnt)₂]^- compounds (Ni et al., 2004; Ren et al., 2004, 2008; Duan et al., 2010). The cation adopts a bent conformation, its hydrocarbon chain slightly disrupted close to the imidazole ring with an almost completely trans-planar conformation.

Related literature top

For applications of bis(1,2-dithiolene) complexes of transition metals, see: Nishijo et al. (2000); Ni et al. (2005). For related structures, see: Ni et al. (2004); Ren et al. (2004, 2008); Duan et al. (2010).

Experimental top

Disodium maleonitriledithiolate (1.5 mmol) and nickel chloride hexahydrate (0.8 mmol) were mixed under stirring in water (20 mL) at room temperature. Subsequently, a solution of 1-methyl-3-butyl-imidazolinium bromide (1.5 mmol) in water (10 mL) was added to the mixture, and the red precipitate that was immediately formed was filtered off, and washed with water. Then, a methanol solution of I₂ (0.8 mmol) was slowly added to a red precipitate, after stirred for 20 min, the mixture was allowed standing overnight. The microcryatalline formed and the crude product was recrystallized in acetone to give black block crystals.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.

3-Butyl-1-methyl-1H-imidazol-3-ium bis(1,2-dicyanoethene-1,2-dithiolato- κ²S,S')nickel(III) top

Crystal data top

(C₈H₁₅N₂)[Ni(C₄N₂S₂)₂]	F(000) = 980.0
M_r = 478.31	D_x = 1.515 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -p 2Ybc	Cell parameters from 778 reflections
a = 10.650 (2) Å	θ = 2.6–21.2°
b = 7.3924 (13) Å	µ = 1.34 mm⁻¹
c = 26.691 (5) Å	T = 298 K
β = 93.463 (5)°	Block, black
V = 2097.5 (7) Å³	0.40 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3824 independent reflections
Radiation source: fine-focus sealed tube	3246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
φ and ω scans	θ_max = 25.4°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
T_min = 0.733, T_max = 0.818	k = −8→7
19183 measured reflections	l = −32→30

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0319P)² + 1.4061P] where P = (F_o² + 2F_c²)/3
3824 reflections	(Δ/σ)_max = 0.001
247 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

(C₈H₁₅N₂)[Ni(C₄N₂S₂)₂]	V = 2097.5 (7) Å³
M_r = 478.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.650 (2) Å	µ = 1.34 mm⁻¹
b = 7.3924 (13) Å	T = 298 K
c = 26.691 (5) Å	0.40 × 0.20 × 0.15 mm
β = 93.463 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3824 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3246 reflections with I > 2σ(I)
T_min = 0.733, T_max = 0.818	R_int = 0.044
19183 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.16	Δρ_max = 0.35 e Å⁻³
3824 reflections	Δρ_min = −0.34 e Å⁻³
247 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.09847 (4)	0.70716 (6)	0.503296 (15)	0.04030 (15)
S1	0.13066 (8)	0.76184 (13)	0.42646 (3)	0.0483 (2)
S2	−0.09351 (8)	0.79241 (12)	0.49400 (3)	0.0456 (2)
S3	0.28875 (9)	0.61212 (14)	0.51160 (3)	0.0507 (3)
S4	0.06746 (9)	0.65718 (13)	0.58064 (3)	0.0486 (2)
N1	−0.0210 (4)	0.9489 (6)	0.31048 (14)	0.0832 (12)
N2	−0.3277 (3)	0.9738 (5)	0.40060 (15)	0.0789 (11)
N3	0.5208 (4)	0.4175 (6)	0.60350 (16)	0.0882 (13)
N4	0.2194 (4)	0.4677 (6)	0.69608 (14)	0.0956 (14)
N5	0.6606 (3)	0.8606 (4)	0.59871 (10)	0.0476 (7)
N6	0.7729 (3)	0.7519 (4)	0.66100 (11)	0.0510 (8)
C1	−0.2310 (4)	0.9224 (5)	0.41389 (15)	0.0532 (10)
C2	−0.1106 (3)	0.8554 (4)	0.43214 (13)	0.0425 (8)
C3	−0.0107 (3)	0.8444 (4)	0.40249 (13)	0.0432 (8)
C4	−0.0187 (3)	0.9029 (6)	0.35110 (15)	0.0550 (10)
C5	0.4244 (4)	0.4750 (6)	0.59122 (15)	0.0596 (11)
C6	0.3061 (3)	0.5491 (5)	0.57365 (13)	0.0477 (9)
C7	0.2078 (3)	0.5671 (5)	0.60397 (13)	0.0478 (9)
C8	0.2156 (4)	0.5117 (6)	0.65538 (16)	0.0612 (11)
C9	0.5952 (6)	0.3532 (9)	0.7533 (3)	0.157 (3)
H9A	0.5596	0.2909	0.7243	0.236*
H9B	0.5289	0.3953	0.7732	0.236*
H9C	0.6487	0.2722	0.7729	0.236*
C10	0.6682 (5)	0.5058 (7)	0.7376 (2)	0.0941 (17)
H10A	0.7005	0.5701	0.7673	0.113*
H10B	0.6124	0.5875	0.7185	0.113*
C11	0.7771 (4)	0.4598 (6)	0.70632 (16)	0.0681 (12)
H11A	0.8329	0.3767	0.7249	0.082*
H11B	0.7455	0.3992	0.6759	0.082*
C12	0.8509 (4)	0.6250 (6)	0.69236 (15)	0.0665 (12)
H12A	0.8823	0.6863	0.7227	0.080*
H12B	0.9226	0.5876	0.6742	0.080*
C13	0.7196 (4)	0.9081 (6)	0.67674 (14)	0.0592 (10)
H13	0.7301	0.9583	0.7087	0.071*
C14	0.6497 (4)	0.9761 (5)	0.63792 (14)	0.0573 (10)
H14	0.6027	1.0821	0.6377	0.069*
C15	0.6000 (4)	0.8833 (6)	0.54840 (13)	0.0624 (11)
H15A	0.6348	0.9871	0.5326	0.094*
H15B	0.5112	0.9002	0.5509	0.094*
H15C	0.6144	0.7774	0.5287	0.094*
C16	0.7359 (3)	0.7259 (5)	0.61352 (13)	0.0493 (9)
H16	0.7588	0.6291	0.5937	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0425 (3)	0.0390 (3)	0.0395 (3)	−0.0044 (2)	0.0042 (2)	−0.00279 (19)
S1	0.0432 (5)	0.0599 (6)	0.0422 (5)	0.0011 (4)	0.0067 (4)	0.0003 (4)
S2	0.0430 (5)	0.0454 (5)	0.0490 (5)	−0.0041 (4)	0.0084 (4)	−0.0038 (4)
S3	0.0461 (5)	0.0585 (6)	0.0476 (5)	−0.0001 (5)	0.0036 (4)	0.0011 (5)
S4	0.0529 (6)	0.0490 (6)	0.0446 (5)	−0.0023 (4)	0.0076 (4)	0.0001 (4)
N1	0.076 (3)	0.118 (3)	0.054 (2)	−0.009 (2)	−0.005 (2)	0.012 (2)
N2	0.052 (2)	0.081 (3)	0.102 (3)	0.006 (2)	−0.004 (2)	−0.003 (2)
N3	0.056 (2)	0.100 (3)	0.107 (3)	−0.001 (2)	−0.013 (2)	0.027 (3)
N4	0.121 (4)	0.112 (4)	0.053 (2)	−0.006 (3)	−0.001 (2)	0.019 (2)
N5	0.0408 (17)	0.058 (2)	0.0440 (17)	−0.0021 (15)	0.0029 (14)	0.0024 (15)
N6	0.0439 (18)	0.064 (2)	0.0444 (18)	−0.0002 (16)	−0.0010 (14)	0.0042 (16)
C1	0.051 (2)	0.047 (2)	0.061 (2)	−0.0069 (19)	0.002 (2)	−0.0057 (19)
C2	0.042 (2)	0.0330 (18)	0.052 (2)	−0.0043 (15)	−0.0030 (17)	−0.0037 (16)
C3	0.044 (2)	0.040 (2)	0.045 (2)	−0.0047 (16)	−0.0017 (16)	−0.0040 (16)
C4	0.048 (2)	0.065 (3)	0.051 (2)	−0.0016 (19)	−0.0032 (19)	−0.003 (2)
C5	0.054 (3)	0.060 (3)	0.064 (3)	−0.007 (2)	−0.002 (2)	0.011 (2)
C6	0.051 (2)	0.044 (2)	0.048 (2)	−0.0071 (17)	−0.0043 (18)	0.0020 (17)
C7	0.056 (2)	0.045 (2)	0.041 (2)	−0.0131 (17)	−0.0027 (18)	0.0002 (17)
C8	0.069 (3)	0.061 (3)	0.052 (3)	−0.007 (2)	−0.003 (2)	0.004 (2)
C9	0.149 (6)	0.121 (6)	0.211 (8)	0.013 (5)	0.089 (6)	0.062 (5)
C10	0.081 (3)	0.093 (4)	0.112 (4)	0.006 (3)	0.033 (3)	0.029 (3)
C11	0.070 (3)	0.072 (3)	0.062 (3)	0.016 (2)	0.003 (2)	0.012 (2)
C12	0.048 (2)	0.091 (3)	0.060 (2)	0.009 (2)	−0.001 (2)	0.019 (2)
C13	0.066 (3)	0.065 (3)	0.047 (2)	−0.003 (2)	0.004 (2)	−0.009 (2)
C14	0.060 (3)	0.055 (2)	0.057 (2)	0.007 (2)	0.007 (2)	0.001 (2)
C15	0.050 (2)	0.086 (3)	0.050 (2)	0.000 (2)	−0.0053 (19)	0.005 (2)
C16	0.044 (2)	0.057 (2)	0.047 (2)	0.0003 (18)	0.0053 (17)	−0.0027 (18)

Geometric parameters (Å, º) top

Ni1—S1	2.1382 (10)	C6—C7	1.368 (5)
Ni1—S2	2.1395 (10)	C7—C8	1.429 (5)
Ni1—S4	2.1424 (10)	C9—C10	1.446 (7)
Ni1—S3	2.1436 (11)	C9—H9A	0.9600
S1—C3	1.712 (4)	C9—H9B	0.9600
S2—C2	1.715 (4)	C9—H9C	0.9600
S3—C6	1.719 (4)	C10—C11	1.509 (6)
S4—C7	1.718 (4)	C10—H10A	0.9700
N1—C4	1.135 (5)	C10—H10B	0.9700
N2—C1	1.134 (5)	C11—C12	1.510 (6)
N3—C5	1.140 (5)	C11—H11A	0.9700
N4—C8	1.133 (5)	C11—H11B	0.9700
N5—C16	1.324 (4)	C12—H12A	0.9700
N5—C14	1.361 (5)	C12—H12B	0.9700
N5—C15	1.464 (4)	C13—C14	1.337 (5)
N6—C16	1.318 (4)	C13—H13	0.9300
N6—C13	1.364 (5)	C14—H14	0.9300
N6—C12	1.479 (5)	C15—H15A	0.9600
C1—C2	1.433 (5)	C15—H15B	0.9600
C2—C3	1.366 (5)	C15—H15C	0.9600
C3—C4	1.436 (5)	C16—H16	0.9300
C5—C6	1.428 (5)

S1—Ni1—S2	92.32 (4)	H9A—C9—H9C	109.5
S1—Ni1—S4	178.96 (4)	H9B—C9—H9C	109.5
S2—Ni1—S4	87.75 (4)	C9—C10—C11	115.5 (5)
S1—Ni1—S3	87.47 (4)	C9—C10—H10A	108.4
S2—Ni1—S3	177.89 (4)	C11—C10—H10A	108.4
S4—Ni1—S3	92.50 (4)	C9—C10—H10B	108.4
C3—S1—Ni1	103.73 (12)	C11—C10—H10B	108.4
C2—S2—Ni1	103.70 (12)	H10A—C10—H10B	107.5
C6—S3—Ni1	103.54 (13)	C12—C11—C10	112.5 (4)
C7—S4—Ni1	103.58 (12)	C12—C11—H11A	109.1
C16—N5—C14	108.7 (3)	C10—C11—H11A	109.1
C16—N5—C15	125.8 (3)	C12—C11—H11B	109.1
C14—N5—C15	125.5 (3)	C10—C11—H11B	109.1
C16—N6—C13	108.3 (3)	H11A—C11—H11B	107.8
C16—N6—C12	125.2 (3)	N6—C12—C11	111.7 (3)
C13—N6—C12	126.3 (3)	N6—C12—H12A	109.3
N2—C1—C2	178.1 (5)	C11—C12—H12A	109.3
C3—C2—C1	122.4 (3)	N6—C12—H12B	109.3
C3—C2—S2	120.0 (3)	C11—C12—H12B	109.3
C1—C2—S2	117.5 (3)	H12A—C12—H12B	107.9
C2—C3—C4	122.1 (3)	C14—C13—N6	107.6 (3)
C2—C3—S1	120.2 (3)	C14—C13—H13	126.2
C4—C3—S1	117.7 (3)	N6—C13—H13	126.2
N1—C4—C3	177.8 (4)	C13—C14—N5	106.9 (4)
N3—C5—C6	177.3 (5)	C13—C14—H14	126.5
C7—C6—C5	122.3 (3)	N5—C14—H14	126.5
C7—C6—S3	120.1 (3)	N5—C15—H15A	109.5
C5—C6—S3	117.5 (3)	N5—C15—H15B	109.5
C6—C7—C8	122.5 (4)	H15A—C15—H15B	109.5
C6—C7—S4	120.2 (3)	N5—C15—H15C	109.5
C8—C7—S4	117.3 (3)	H15A—C15—H15C	109.5
N4—C8—C7	178.7 (5)	H15B—C15—H15C	109.5
C10—C9—H9A	109.5	N6—C16—N5	108.5 (3)
C10—C9—H9B	109.5	N6—C16—H16	125.7
H9A—C9—H9B	109.5	N5—C16—H16	125.7
C10—C9—H9C	109.5

S3—Ni1—S1—C3	179.03 (12)	C5—C6—C7—S4	−179.9 (3)
S1—Ni1—S2—C2	−0.41 (12)	S3—C6—C7—S4	−1.4 (4)
S4—Ni1—S2—C2	178.55 (12)	Ni1—S4—C7—C6	1.9 (3)
S1—Ni1—S3—C6	179.74 (13)	Ni1—S4—C7—C8	−177.6 (3)
S4—Ni1—S3—C6	0.78 (13)	C9—C10—C11—C12	−178.6 (5)
S2—Ni1—S4—C7	176.57 (13)	C16—N6—C12—C11	−72.9 (5)
Ni1—S2—C2—C3	−0.7 (3)	C13—N6—C12—C11	102.1 (5)
Ni1—S2—C2—C1	−179.3 (2)	C10—C11—C12—N6	−62.5 (5)
C1—C2—C3—C4	1.3 (5)	C16—N6—C13—C14	0.0 (4)
S2—C2—C3—C4	−177.2 (3)	C12—N6—C13—C14	−175.7 (3)
C1—C2—C3—S1	−179.6 (3)	N6—C13—C14—N5	0.1 (4)
S2—C2—C3—S1	1.8 (4)	C16—N5—C14—C13	−0.2 (4)
Ni1—S1—C3—C2	−1.9 (3)	C15—N5—C14—C13	−179.5 (3)
Ni1—S1—C3—C4	177.2 (3)	C13—N6—C16—N5	−0.1 (4)
Ni1—S3—C6—C7	0.2 (3)	C12—N6—C16—N5	175.6 (3)
Ni1—S3—C6—C5	178.7 (3)	C14—N5—C16—N6	0.2 (4)
C5—C6—C7—C8	−0.5 (6)	C15—N5—C16—N6	179.6 (3)
S3—C6—C7—C8	178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N4ⁱ	0.93	2.57	3.446 (5)	158
C15—H15B···N2ⁱⁱ	0.96	2.58	3.443 (5)	149

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

Experimental details

Crystal data
Chemical formula	(C₈H₁₅N₂)[Ni(C₄N₂S₂)₂]
M_r	478.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.650 (2), 7.3924 (13), 26.691 (5)
β (°)	93.463 (5)
V (Å³)	2097.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.40 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.733, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	19183, 3824, 3246
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.099, 1.16
No. of reflections	3824
No. of parameters	247
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.34

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).