1-Methyl-N-(4-nitro­benzyl)­pyridinium bis(2-thio­xo-1,3-di­thiole-4,5-di­thiol­ato)­nickelate(III)

The title compound, (C₁₃H₁₃N₂O₂)[Ni(C₃S₅)₂], is composed of layers of cations and anions. The Ni^III ion is in a planar environment, coordinated by the four S atoms of two dmit²⁻ ligands. There are some weak S...S and Ni...S interactions, and some non-classical hydrogen bonds (C—H...S) are also observed. These interactions generate a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.056
• wR factor = 0.102
• Data-to-parameter ratio = 14.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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.

(I)

Crystal data

(C13H13N2O2)[Ni(C3S5)2]	Z = 2
Mr = 680.70	F(000) = 690
Triclinic, P1	Dx = 1.808 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.982 (1) Å	Cell parameters from 885 reflections
b = 12.364 (2) Å	θ = 2.2–23.4°
c = 13.978 (2) Å	µ = 1.64 mm^−1
α = 105.43 (1)°	T = 293 K
β = 92.45 (1)°	Block, black
γ = 108.34 (1)°	0.3 × 0.25 × 0.2 mm
V = 1250.1 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4322 independent reflections
Radiation source: sealed tube	2588 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: ψ scan (SADABS; Bruker, 2000)	h = −7→9
Tmin = 0.611, Tmax = 0.714	k = −14→14
6270 measured reflections	l = −12→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.02P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4322 reflections	Δρmax = 0.47 e Å^−3
302 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.60 (10)

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	0.52897 (9)	0.25431 (6)	0.33683 (5)	0.0427 (2)
C1	0.3490 (7)	0.0211 (5)	0.3805 (4)	0.0436 (14)
C2	0.1901 (7)	−0.0984 (5)	0.4992 (4)	0.0501 (15)
C3	0.3338 (6)	0.1043 (5)	0.4629 (4)	0.0441 (14)
C4	0.7222 (7)	0.4007 (5)	0.2079 (4)	0.0437 (14)
C5	0.8959 (7)	0.6045 (5)	0.1781 (4)	0.0486 (15)
C6	0.7169 (7)	0.4849 (5)	0.2914 (4)	0.0426 (14)
S1	0.4539 (2)	0.06132 (13)	0.28558 (10)	0.0503 (4)
S2	0.2602 (2)	−0.12605 (13)	0.38170 (11)	0.0546 (4)
S3	0.0891 (2)	−0.20400 (15)	0.54650 (12)	0.0694 (5)
S4	0.2337 (2)	0.05109 (14)	0.55649 (11)	0.0565 (4)
S5	0.4099 (2)	0.25278 (13)	0.47240 (11)	0.0536 (4)
S6	0.62811 (19)	0.25232 (13)	0.19579 (10)	0.0519 (4)
S7	0.83319 (19)	0.45336 (14)	0.11630 (10)	0.0504 (4)
S8	1.0164 (2)	0.70748 (15)	0.13238 (12)	0.0682 (5)
S9	0.8223 (2)	0.63313 (13)	0.29412 (11)	0.0528 (4)
S10	0.6176 (2)	0.44666 (13)	0.39030 (10)	0.0503 (4)
C7	0.9103 (7)	0.6524 (5)	0.7213 (4)	0.0480 (15)
H7	0.9824	0.7263	0.7178	0.058*
C8	0.8917 (7)	0.5533 (5)	0.6443 (4)	0.0525 (15)
H8	0.9484	0.5594	0.5882	0.063*
C9	0.7882 (7)	0.4448 (5)	0.6508 (4)	0.0537 (16)
H9	0.7753	0.3757	0.5998	0.064*
C10	0.7038 (7)	0.4391 (5)	0.7335 (4)	0.0525 (16)
H10	0.6326	0.3653	0.7377	0.063*
C11	0.7216 (7)	0.5386 (5)	0.8095 (4)	0.0459 (15)
C12	0.8457 (7)	0.7557 (5)	0.8845 (4)	0.0515 (15)
H12A	0.8660	0.7407	0.9479	0.062*
H12B	0.7336	0.7708	0.8821	0.062*
C13	0.9930 (7)	0.8669 (5)	0.8824 (4)	0.0460 (14)
C14	0.9762 (7)	0.9268 (5)	0.8149 (4)	0.0521 (16)
H14	0.8722	0.8987	0.7698	0.062*
C15	1.1106 (8)	1.0277 (5)	0.8129 (4)	0.0540 (16)
H15	1.1003	1.0670	0.7659	0.065*
C16	1.2592 (8)	1.0685 (5)	0.8816 (4)	0.0525 (16)
C17	1.2808 (7)	1.0157 (5)	0.9533 (4)	0.0517 (16)
H17	1.3821	1.0473	1.0008	0.062*
C18	1.1437 (7)	0.9119 (5)	0.9516 (4)	0.0479 (15)
H18	1.1545	0.8722	0.9982	0.058*
C19	0.6364 (7)	0.5339 (5)	0.9013 (4)	0.0580 (16)
H19A	0.7268	0.5649	0.9586	0.087*
H19B	0.5677	0.4527	0.8957	0.087*
H19C	0.5596	0.5809	0.9090	0.087*
N1	0.8275 (5)	0.6464 (4)	0.8022 (3)	0.0434 (11)
N2	1.4052 (9)	1.1774 (6)	0.8802 (5)	0.087
O1	1.3955 (6)	1.2170 (4)	0.8104 (4)	0.1025 (17)
O2	1.5303 (7)	1.2182 (5)	0.9458 (4)	0.135 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0477 (5)	0.0372 (4)	0.0429 (4)	0.0124 (3)	0.0079 (3)	0.0134 (3)
C1	0.048 (4)	0.037 (3)	0.045 (3)	0.011 (3)	0.003 (3)	0.014 (3)
C2	0.056 (4)	0.044 (4)	0.048 (4)	0.009 (3)	0.006 (3)	0.018 (3)
C3	0.045 (4)	0.040 (4)	0.043 (3)	0.007 (3)	0.004 (3)	0.013 (3)
C4	0.046 (4)	0.046 (4)	0.041 (3)	0.014 (3)	0.006 (3)	0.018 (3)
C5	0.049 (4)	0.052 (4)	0.052 (4)	0.019 (3)	0.007 (3)	0.024 (3)
C6	0.049 (4)	0.041 (4)	0.040 (3)	0.015 (3)	0.006 (3)	0.017 (3)
S1	0.0663 (11)	0.0398 (9)	0.0456 (9)	0.0174 (8)	0.0150 (8)	0.0134 (7)
S2	0.0746 (12)	0.0387 (9)	0.0499 (9)	0.0159 (8)	0.0147 (8)	0.0149 (8)
S3	0.0906 (13)	0.0540 (11)	0.0622 (11)	0.0127 (9)	0.0225 (10)	0.0273 (9)
S4	0.0675 (11)	0.0458 (10)	0.0510 (10)	0.0105 (8)	0.0196 (8)	0.0141 (8)
S5	0.0657 (11)	0.0383 (9)	0.0534 (10)	0.0122 (8)	0.0214 (8)	0.0124 (8)
S6	0.0658 (11)	0.0410 (9)	0.0434 (9)	0.0132 (8)	0.0140 (8)	0.0084 (8)
S7	0.0594 (10)	0.0507 (10)	0.0408 (9)	0.0154 (8)	0.0132 (8)	0.0157 (8)
S8	0.0802 (13)	0.0603 (12)	0.0583 (11)	0.0062 (9)	0.0152 (9)	0.0284 (9)
S9	0.0720 (11)	0.0411 (10)	0.0466 (9)	0.0166 (8)	0.0139 (8)	0.0171 (8)
S10	0.0700 (11)	0.0392 (9)	0.0450 (9)	0.0188 (8)	0.0189 (8)	0.0156 (7)
C7	0.052 (4)	0.041 (4)	0.050 (4)	0.011 (3)	0.010 (3)	0.017 (3)
C8	0.057 (4)	0.044 (4)	0.052 (4)	0.012 (3)	0.009 (3)	0.013 (3)
C9	0.057 (4)	0.041 (4)	0.057 (4)	0.010 (3)	0.004 (3)	0.015 (3)
C10	0.051 (4)	0.039 (4)	0.062 (4)	0.004 (3)	0.003 (3)	0.019 (3)
C11	0.044 (4)	0.040 (4)	0.054 (4)	0.010 (3)	0.003 (3)	0.021 (3)
C12	0.056 (4)	0.039 (4)	0.054 (4)	0.010 (3)	0.015 (3)	0.010 (3)
C13	0.050 (4)	0.038 (4)	0.050 (4)	0.016 (3)	0.017 (3)	0.010 (3)
C14	0.053 (4)	0.044 (4)	0.058 (4)	0.016 (3)	0.009 (3)	0.015 (3)
C15	0.065 (4)	0.042 (4)	0.057 (4)	0.018 (3)	0.014 (4)	0.017 (3)
C16	0.059 (4)	0.041 (4)	0.051 (4)	0.013 (3)	0.020 (3)	0.009 (3)
C17	0.054 (4)	0.050 (4)	0.044 (4)	0.015 (3)	0.011 (3)	0.003 (3)
C18	0.057 (4)	0.043 (4)	0.044 (3)	0.018 (3)	0.014 (3)	0.011 (3)
C19	0.059 (4)	0.049 (4)	0.061 (4)	0.005 (3)	0.010 (3)	0.025 (3)
N1	0.048 (3)	0.036 (3)	0.047 (3)	0.011 (2)	0.009 (2)	0.016 (2)
N2	0.110	0.060	0.067	−0.002	0.023	0.013
O1	0.109 (4)	0.070 (3)	0.118 (4)	−0.001 (3)	0.024 (3)	0.049 (3)
O2	0.124 (5)	0.124 (5)	0.077 (4)	−0.059 (4)	−0.007 (3)	0.022 (3)

Geometric parameters (Å, º)

Ni1—S6	2.1526 (16)	C9—H9	0.9300
Ni1—S5	2.1577 (16)	C10—C11	1.358 (7)
Ni1—S10	2.1599 (16)	C10—H10	0.9300
Ni1—S1	2.1725 (16)	C11—N1	1.368 (6)
C1—C3	1.363 (6)	C11—C19	1.484 (7)
C1—S1	1.701 (5)	C12—N1	1.485 (6)
C1—S2	1.737 (5)	C12—C13	1.510 (7)
C2—S3	1.623 (6)	C12—H12A	0.9700
C2—S4	1.721 (6)	C12—H12B	0.9700
C2—S2	1.740 (5)	C13—C14	1.370 (8)
C3—S5	1.709 (5)	C13—C18	1.373 (7)
C3—S4	1.732 (5)	C14—C15	1.374 (7)
C4—C6	1.354 (6)	C14—H14	0.9300
C4—S6	1.708 (6)	C15—C16	1.361 (7)
C4—S7	1.739 (5)	C15—H15	0.9300
C5—S8	1.634 (6)	C16—C17	1.366 (8)
C5—S7	1.733 (6)	C16—N2	1.483 (8)
C5—S9	1.735 (5)	C17—C18	1.394 (7)
C6—S10	1.722 (5)	C17—H17	0.9300
C6—S9	1.749 (5)	C18—H18	0.9300
C7—N1	1.341 (6)	C19—H19A	0.9600
C7—C8	1.361 (6)	C19—H19B	0.9600
C7—H7	0.9300	C19—H19C	0.9600
C8—C9	1.366 (7)	N2—O2	1.204 (7)
C8—H8	0.9300	N2—O1	1.213 (7)
C9—C10	1.369 (7)
S6—Ni1—S5	175.72 (7)	C11—C10—H10	119.2
S6—Ni1—S10	93.35 (6)	C9—C10—H10	119.2
S5—Ni1—S10	87.64 (6)	C10—C11—N1	118.4 (5)
S6—Ni1—S1	86.27 (6)	C10—C11—C19	122.4 (5)
S5—Ni1—S1	92.95 (6)	N1—C11—C19	119.1 (5)
S10—Ni1—S1	176.97 (7)	N1—C12—C13	115.5 (4)
C3—C1—S1	121.4 (4)	N1—C12—H12A	108.4
C3—C1—S2	115.5 (4)	C13—C12—H12A	108.4
S1—C1—S2	123.2 (3)	N1—C12—H12B	108.4
S3—C2—S4	124.5 (3)	C13—C12—H12B	108.4
S3—C2—S2	122.8 (3)	H12A—C12—H12B	107.5
S4—C2—S2	112.7 (3)	C14—C13—C18	119.1 (5)
C1—C3—S5	121.4 (4)	C14—C13—C12	121.1 (6)
C1—C3—S4	116.4 (4)	C18—C13—C12	119.7 (6)
S5—C3—S4	122.2 (3)	C13—C14—C15	121.1 (6)
C6—C4—S6	121.3 (4)	C13—C14—H14	119.5
C6—C4—S7	116.0 (4)	C15—C14—H14	119.5
S6—C4—S7	122.8 (3)	C16—C15—C14	118.1 (6)
S8—C5—S7	123.1 (3)	C16—C15—H15	120.9
S8—C5—S9	124.2 (3)	C14—C15—H15	120.9
S7—C5—S9	112.6 (3)	C15—C16—C17	123.6 (6)
C4—C6—S10	121.4 (4)	C15—C16—N2	118.7 (6)
C4—C6—S9	116.1 (4)	C17—C16—N2	117.8 (6)
S10—C6—S9	122.5 (3)	C16—C17—C18	116.7 (6)
C1—S1—Ni1	102.06 (19)	C16—C17—H17	121.6
C1—S2—C2	97.6 (3)	C18—C17—H17	121.6
C2—S4—C3	97.8 (3)	C13—C18—C17	121.3 (6)
C3—S5—Ni1	102.15 (19)	C13—C18—H18	119.3
C4—S6—Ni1	102.34 (19)	C17—C18—H18	119.3
C5—S7—C4	97.9 (3)	C11—C19—H19A	109.5
C5—S9—C6	97.4 (3)	C11—C19—H19B	109.5
C6—S10—Ni1	101.65 (19)	H19A—C19—H19B	109.5
N1—C7—C8	121.8 (5)	C11—C19—H19C	109.5
N1—C7—H7	119.1	H19A—C19—H19C	109.5
C8—C7—H7	119.1	H19B—C19—H19C	109.5
C7—C8—C9	118.8 (6)	C7—N1—C11	120.2 (5)
C7—C8—H8	120.6	C7—N1—C12	121.1 (5)
C9—C8—H8	120.6	C11—N1—C12	118.7 (5)
C8—C9—C10	119.2 (6)	O2—N2—O1	123.7 (7)
C8—C9—H9	120.4	O2—N2—C16	118.3 (7)
C10—C9—H9	120.4	O1—N2—C16	117.9 (7)
C11—C10—C9	121.6 (6)