1-(2-Meth­oxy-2-oxoeth­yl)pyridinium bis­(2-thioxo-1,3-dithiole-4,5-dithiol­ato)nickelate(III)

The title complex, (C₈H₁₀NO₂)[Ni(C₃H₂S₅)₂], crystallizes with the cation sandwiched by two [Ni(dmit)₂]⁻ anions (dmit is 2-thioxo-1,3-dithiole-4,5-dithiol­ate). The crystal packing is stabilized by short inter­molecular S...S contacts between neighbouring anions and C—H...O hydrogen bonds, which link the cations into ribbons extending along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.043
• wR factor = 0.088
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.92
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002), ORTEPIII and Mercury.

1-(2-Methoxy-2-oxoethyl)pyridinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III)

Crystal data

(C8H10NO2)[Ni(C3H2S5)2]	Z = 2
Mr = 603.54	F(000) = 610
Triclinic, P1	Dx = 1.801 Mg m^−3
a = 8.1870 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2783 (12) Å	Cell parameters from 2126 reflections
c = 13.0752 (14) Å	θ = 2.8–27.3°
α = 69.190 (2)°	µ = 1.82 mm^−1
β = 80.777 (2)°	T = 273 K
γ = 89.274 (2)°	Plate, dark green
V = 1112.7 (2) Å^3	0.20 × 0.09 × 0.04 mm

Data collection

Bruker SMART APEX CCD-detector diffractometer	4674 independent reflections
Radiation source: fine-focus sealed tube	3072 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 8.366 pixels mm^-1	θmax = 27.4°, θmin = 1.7°
ω scans	h = −10→9
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001)	k = −14→14
Tmin = 0.756, Tmax = 0.934	l = −14→16
6648 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0263P)^2] where P = (Fo^2 + 2Fc^2)/3
4674 reflections	(Δ/σ)max = 0.001
254 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

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.

Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

5.3372 (0.0095) x - 8.0458 (0.0119) y + 0.8369 (0.0180) z = 0.5442 (0.0092)

* -0.0048 (0.0022) N1 * 0.0041 (0.0025) C7 * 0.0000 (0.0027) C8 * -0.0033 (0.0027) C9 * 0.0025 (0.0029) C10 * 0.0015 (0.0026) C11

Rms deviation of fitted atoms = 0.0031

- 6.1786 (0.0016) x + 7.0107 (0.0020) y - 0.8224 (0.0022) z = 4.7755 (0.0019)

Angle to previous plane (with approximate e.s.d.) = 8.44 (0.15)

* -0.0290 (0.0006) Ni1 * 0.0470 (0.0010) S1 * -0.0071 (0.0011) S2 * 0.0443 (0.0012) S3 * 0.0087 (0.0012) S4 * -0.0518 (0.0014) S5 * -0.0829 (0.0010) S6 * -0.0918 (0.0010) S7 * -0.0277 (0.0011) S8 * 0.0888 (0.0012) S9 * 0.0159 (0.0014) S10 * 0.0610 (0.0027) C1 * 0.0338 (0.0028) C2 * -0.0019 (0.0031) C3 * -0.0276 (0.0027) C4 * -0.0151 (0.0028) C5 * 0.0353 (0.0029) C6

Rms deviation of fitted atoms = 0.0480

- 6.2593 (0.0021) x + 6.8993 (0.0030) y - 0.7928 (0.0036) z = 4.7141 (0.0028)

Angle to previous plane (with approximate e.s.d.) = 0.91 (0.04)

* -0.0539 (0.0008) Ni1 * 0.0037 (0.0009) S1 * -0.0019 (0.0010) S2 * 0.0148 (0.0012) S3 * 0.0237 (0.0012) S4 * -0.0490 (0.0014) S5 * 0.0373 (0.0026) C1 * 0.0308 (0.0027) C2 * -0.0054 (0.0029) C3

Rms deviation of fitted atoms = 0.0307

- 6.1537 (0.0022) x + 6.9749 (0.0028) y - 1.1038 (0.0034) z = 4.5368 (0.0035)

Angle to previous plane (with approximate e.s.d.) = 1.94 (0.05)

* 0.0416 (0.0008) Ni1 * -0.0116 (0.0010) S6 * -0.0712 (0.0010) S7 * -0.0078 (0.0011) S8 * 0.0616 (0.0011) S9 * -0.0298 (0.0014) S10 * 0.0053 (0.0026) C4 * -0.0042 (0.0027) C5 * 0.0162 (0.0027) C6

Rms deviation of fitted atoms = 0.0365

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
C1	0.0732 (4)	0.7882 (3)	0.2878 (3)	0.0451 (8)
C2	−0.0334 (4)	0.6995 (3)	0.3658 (3)	0.0496 (9)
C3	−0.0445 (4)	0.6630 (3)	0.1815 (3)	0.0580 (10)
C4	0.2486 (4)	0.9702 (3)	0.6296 (3)	0.0471 (8)
C5	0.1387 (4)	0.8844 (3)	0.7091 (3)	0.0470 (8)
C6	0.2652 (4)	1.0150 (3)	0.8103 (3)	0.0566 (9)
C7	0.6205 (4)	0.3564 (3)	0.1239 (3)	0.0554 (9)
H7	0.7014	0.4095	0.1301	0.066*
C8	0.6178 (5)	0.3448 (3)	0.0248 (3)	0.0616 (10)
H8	0.6955	0.3900	−0.0368	0.074*
C9	0.5004 (5)	0.2664 (4)	0.0160 (3)	0.0684 (11)
H9	0.4967	0.2576	−0.0517	0.082*
C10	0.3886 (5)	0.2010 (4)	0.1072 (4)	0.0711 (12)
H10	0.3082	0.1466	0.1023	0.085*
C11	0.3942 (4)	0.2151 (3)	0.2055 (3)	0.0594 (10)
H11	0.3176	0.1702	0.2678	0.071*
C12	0.5086 (5)	0.3189 (3)	0.3151 (3)	0.0557 (9)
H12A	0.6208	0.3202	0.3298	0.067*
H12B	0.4437	0.2525	0.3771	0.067*
C13	0.4348 (4)	0.4456 (3)	0.3023 (3)	0.0496 (9)
C14	0.3960 (5)	0.6029 (3)	0.3809 (3)	0.0725 (11)
H14A	0.4444	0.6678	0.3125	0.109*
H14B	0.4235	0.6221	0.4421	0.109*
H14C	0.2778	0.5993	0.3857	0.109*
N1	0.5095 (3)	0.2931 (2)	0.2132 (2)	0.0457 (7)
Ni1	0.10762 (5)	0.83067 (4)	0.50107 (4)	0.04505 (13)
O1	0.3633 (4)	0.5035 (2)	0.2295 (2)	0.0810 (9)
O2	0.4595 (3)	0.4817 (2)	0.38431 (19)	0.0562 (6)
S1	0.18678 (11)	0.89045 (8)	0.32369 (7)	0.0518 (2)
S2	−0.06285 (12)	0.68384 (9)	0.50360 (8)	0.0609 (3)
S3	0.09452 (12)	0.78882 (8)	0.15363 (8)	0.0592 (3)
S4	−0.13627 (13)	0.59968 (9)	0.31855 (9)	0.0691 (3)
S5	−0.08405 (16)	0.60968 (11)	0.08495 (10)	0.0863 (4)
S6	0.28159 (11)	0.97566 (8)	0.49566 (7)	0.0532 (2)
S7	0.03038 (11)	0.77453 (8)	0.67925 (8)	0.0565 (3)
S8	0.35712 (12)	1.07090 (9)	0.67296 (8)	0.0589 (3)
S9	0.11482 (13)	0.89371 (9)	0.84125 (8)	0.0621 (3)
S10	0.31551 (16)	1.06743 (12)	0.90292 (10)	0.0870 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0408 (19)	0.0389 (17)	0.058 (2)	0.0031 (15)	−0.0157 (17)	−0.0174 (16)
C2	0.0370 (19)	0.0444 (19)	0.069 (2)	−0.0005 (16)	−0.0171 (18)	−0.0191 (18)
C3	0.055 (2)	0.053 (2)	0.072 (3)	−0.0090 (18)	−0.022 (2)	−0.0235 (19)
C4	0.044 (2)	0.0443 (19)	0.056 (2)	0.0060 (16)	−0.0163 (17)	−0.0189 (17)
C5	0.045 (2)	0.0453 (19)	0.048 (2)	0.0050 (16)	−0.0067 (17)	−0.0145 (16)
C6	0.060 (2)	0.055 (2)	0.060 (2)	0.0118 (18)	−0.0169 (19)	−0.0252 (19)
C7	0.055 (2)	0.051 (2)	0.059 (2)	−0.0092 (18)	−0.0069 (19)	−0.0189 (19)
C8	0.063 (3)	0.061 (2)	0.052 (2)	−0.005 (2)	0.004 (2)	−0.016 (2)
C9	0.079 (3)	0.076 (3)	0.057 (3)	0.005 (2)	−0.015 (2)	−0.030 (2)
C10	0.072 (3)	0.075 (3)	0.074 (3)	−0.018 (2)	−0.014 (2)	−0.033 (2)
C11	0.056 (2)	0.053 (2)	0.060 (3)	−0.0122 (18)	−0.0009 (19)	−0.0128 (19)
C12	0.075 (3)	0.049 (2)	0.046 (2)	0.0114 (18)	−0.0169 (19)	−0.0176 (17)
C13	0.051 (2)	0.049 (2)	0.044 (2)	0.0042 (17)	−0.0047 (17)	−0.0122 (17)
C14	0.085 (3)	0.061 (2)	0.083 (3)	0.021 (2)	−0.021 (2)	−0.037 (2)
N1	0.0523 (18)	0.0361 (15)	0.0464 (17)	0.0021 (13)	−0.0080 (14)	−0.0120 (13)
Ni1	0.0413 (3)	0.0412 (2)	0.0524 (3)	−0.00141 (18)	−0.0103 (2)	−0.0151 (2)
O1	0.121 (2)	0.0750 (18)	0.0567 (17)	0.0407 (17)	−0.0418 (17)	−0.0248 (14)
O2	0.0591 (16)	0.0567 (14)	0.0627 (16)	0.0129 (12)	−0.0221 (13)	−0.0286 (13)
S1	0.0570 (6)	0.0431 (5)	0.0550 (6)	−0.0127 (4)	−0.0090 (4)	−0.0170 (4)
S2	0.0540 (6)	0.0623 (6)	0.0608 (6)	−0.0200 (5)	−0.0040 (5)	−0.0170 (5)
S3	0.0654 (6)	0.0551 (5)	0.0596 (6)	−0.0146 (5)	−0.0128 (5)	−0.0221 (5)
S4	0.0632 (7)	0.0650 (6)	0.0785 (7)	−0.0257 (5)	−0.0161 (5)	−0.0221 (5)
S5	0.1031 (9)	0.0820 (7)	0.0854 (8)	−0.0308 (7)	−0.0277 (7)	−0.0376 (7)
S6	0.0578 (6)	0.0512 (5)	0.0488 (5)	−0.0138 (4)	−0.0056 (4)	−0.0164 (4)
S7	0.0546 (6)	0.0536 (5)	0.0568 (6)	−0.0097 (4)	−0.0035 (5)	−0.0165 (5)
S8	0.0646 (6)	0.0569 (5)	0.0608 (6)	−0.0063 (5)	−0.0127 (5)	−0.0266 (5)
S9	0.0734 (7)	0.0619 (6)	0.0489 (6)	0.0018 (5)	−0.0083 (5)	−0.0180 (5)
S10	0.1115 (10)	0.0930 (8)	0.0760 (8)	0.0000 (7)	−0.0271 (7)	−0.0487 (7)

Geometric parameters (Å, º)

C1—C2	1.347 (4)	C9—C10	1.359 (5)
C1—S1	1.723 (3)	C9—H9	0.9300
C1—S3	1.732 (3)	C10—C11	1.358 (5)
C2—S2	1.724 (4)	C10—H10	0.9300
C2—S4	1.745 (3)	C11—N1	1.338 (4)
C3—S5	1.654 (4)	C11—H11	0.9300
C3—S4	1.720 (4)	C12—N1	1.459 (4)
C3—S3	1.727 (3)	C12—C13	1.509 (4)
C4—C5	1.355 (4)	C12—H12A	0.9700
C4—S6	1.707 (3)	C12—H12B	0.9700
C4—S8	1.746 (3)	C13—O1	1.183 (4)
C5—S7	1.720 (3)	C13—O2	1.319 (4)
C5—S9	1.747 (3)	C14—O2	1.444 (4)
C6—S10	1.631 (4)	C14—H14A	0.9600
C6—S8	1.721 (4)	C14—H14B	0.9600
C6—S9	1.744 (4)	C14—H14C	0.9600
C7—N1	1.335 (4)	Ni1—S6	2.1569 (9)
C7—C8	1.352 (5)	Ni1—S1	2.1615 (10)
C7—H7	0.9300	Ni1—S2	2.1671 (9)
C8—C9	1.359 (5)	Ni1—S7	2.1721 (11)
C8—H8	0.9300
S6···S8^i	3.5466 (15)	S6···S6^i	3.6508 (18)
C2—C1—S1	120.4 (3)	N1—C12—C13	109.2 (3)
C2—C1—S3	116.8 (2)	N1—C12—H12A	109.8
S1—C1—S3	122.8 (2)	C13—C12—H12A	109.8
C1—C2—S2	122.1 (2)	N1—C12—H12B	109.8
C1—C2—S4	115.6 (3)	C13—C12—H12B	109.8
S2—C2—S4	122.3 (2)	H12A—C12—H12B	108.3
S5—C3—S4	123.87 (19)	O1—C13—O2	125.0 (3)
S5—C3—S3	122.8 (2)	O1—C13—C12	124.7 (3)
S4—C3—S3	113.4 (2)	O2—C13—C12	110.3 (3)
C5—C4—S6	121.5 (2)	O2—C14—H14A	109.5
C5—C4—S8	116.1 (3)	O2—C14—H14B	109.5
S6—C4—S8	122.4 (2)	H14A—C14—H14B	109.5
C4—C5—S7	121.0 (3)	O2—C14—H14C	109.5
C4—C5—S9	116.0 (3)	H14A—C14—H14C	109.5
S7—C5—S9	123.0 (2)	H14B—C14—H14C	109.5
S10—C6—S8	123.8 (2)	C7—N1—C11	119.7 (3)
S10—C6—S9	123.2 (2)	C7—N1—C12	118.8 (3)
S8—C6—S9	113.0 (2)	C11—N1—C12	121.3 (3)
N1—C7—C8	121.3 (3)	S6—Ni1—S1	86.13 (3)
N1—C7—H7	119.3	S6—Ni1—S2	178.61 (4)
C8—C7—H7	119.3	S1—Ni1—S2	92.80 (4)
C7—C8—C9	119.4 (4)	S6—Ni1—S7	92.66 (4)
C7—C8—H8	120.3	S1—Ni1—S7	178.73 (4)
C9—C8—H8	120.3	S2—Ni1—S7	88.42 (4)
C8—C9—C10	119.3 (4)	C13—O2—C14	115.7 (3)
C8—C9—H9	120.4	C1—S1—Ni1	102.81 (12)
C10—C9—H9	120.4	C2—S2—Ni1	101.89 (11)
C11—C10—C9	120.0 (4)	C3—S3—C1	97.00 (16)
C11—C10—H10	120.0	C3—S4—C2	97.28 (16)
C9—C10—H10	120.0	C4—S6—Ni1	102.62 (11)
N1—C11—C10	120.4 (3)	C5—S7—Ni1	102.01 (12)
N1—C11—H11	119.8	C6—S8—C4	97.67 (17)
C10—C11—H11	119.8	C6—S9—C5	97.17 (16)
S1—C1—C2—S2	0.3 (4)	S4—C2—S2—Ni1	177.86 (17)
S3—C1—C2—S2	177.92 (18)	S1—Ni1—S2—C2	0.78 (12)
S1—C1—C2—S4	−178.42 (17)	S7—Ni1—S2—C2	−179.59 (12)
S3—C1—C2—S4	−0.8 (3)	S5—C3—S3—C1	−179.3 (2)
S6—C4—C5—S7	1.4 (4)	S4—C3—S3—C1	0.7 (2)
S8—C4—C5—S7	−176.96 (17)	C2—C1—S3—C3	0.1 (3)
S6—C4—C5—S9	−178.32 (18)	S1—C1—S3—C3	177.6 (2)
S8—C4—C5—S9	3.3 (3)	S5—C3—S4—C2	178.9 (2)
N1—C7—C8—C9	−0.5 (6)	S3—C3—S4—C2	−1.0 (2)
C7—C8—C9—C10	−0.2 (6)	C1—C2—S4—C3	1.1 (3)
C8—C9—C10—C11	0.5 (6)	S2—C2—S4—C3	−177.6 (2)
C9—C10—C11—N1	0.0 (6)	C5—C4—S6—Ni1	2.4 (3)
N1—C12—C13—O1	12.1 (5)	S8—C4—S6—Ni1	−179.30 (16)
N1—C12—C13—O2	−168.7 (3)	S1—Ni1—S6—C4	175.66 (12)
C8—C7—N1—C11	1.0 (5)	S7—Ni1—S6—C4	−3.95 (12)
C8—C7—N1—C12	−174.1 (3)	C4—C5—S7—Ni1	−4.4 (3)
C10—C11—N1—C7	−0.7 (5)	S9—C5—S7—Ni1	175.36 (17)
C10—C11—N1—C12	174.2 (3)	S6—Ni1—S7—C5	4.48 (12)
C13—C12—N1—C7	74.3 (4)	S2—Ni1—S7—C5	−176.41 (12)
C13—C12—N1—C11	−100.6 (3)	S10—C6—S8—C4	178.1 (2)
O1—C13—O2—C14	−1.5 (5)	S9—C6—S8—C4	−0.7 (2)
C12—C13—O2—C14	179.3 (3)	C5—C4—S8—C6	−1.5 (3)
C2—C1—S1—Ni1	0.3 (3)	S6—C4—S8—C6	−179.9 (2)
S3—C1—S1—Ni1	−177.08 (17)	S10—C6—S9—C5	−176.7 (2)
S6—Ni1—S1—C1	178.45 (11)	S8—C6—S9—C5	2.1 (2)
S2—Ni1—S1—C1	−0.65 (11)	C4—C5—S9—C6	−3.3 (3)
C1—C2—S2—Ni1	−0.8 (3)	S7—C5—S9—C6	177.0 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1^ii	0.93	2.50	3.132 (4)	125
C14—H14B···O2^iii	0.96	2.49	3.285 (5)	140

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1.