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The title compound, (C13H10BrN2)[Ni(C3S5)2]·C3H6O, is a new ionic complex in which the NiIII atom exhibits a square-planar coordination involving four S atoms from two 2-thioxo-1,3-dithiole-4,5-dithiol­ate (dmit) ligands. In the crystal structure, weak S...S and hydrogen-bonding inter­actions form a three-dimensional supra­molecular network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806012207/sj2035sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806012207/sj2035Isup2.hkl
Contains datablock I

CCDC reference: 608494

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.055
  • wR factor = 0.105
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

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Alert level C PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C21 PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 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

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 and PLATON (Spek, 2003).

N-(4-Bromobenzyl)-4-cyanopyridinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III) acetone solvate top
Crystal data top
(C13H10BrN2)[Ni(C3S5)2]·C3H6OZ = 2
Mr = 783.66F(000) = 786.0
Triclinic, P1Dx = 1.729 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.197 (2) ÅCell parameters from 804 reflections
b = 10.601 (3) Åθ = 2.5–22.4°
c = 15.714 (4) ŵ = 2.69 mm1
α = 98.265 (5)°T = 293 K
β = 92.767 (4)°Needle, black
γ = 95.821 (5)°0.3 × 0.1 × 0.1 mm
V = 1505.3 (7) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5213 independent reflections
Radiation source: fine-focus sealed tube2680 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.739, Tmax = 0.760k = 712
7546 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.02P)2 + 0.04P]
where P = (Fo2 + 2Fc2)/3
5213 reflections(Δ/σ)max = 0.001
330 parametersΔρmax = 0.55 e Å3
14 restraintsΔρmin = 0.49 e Å3
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. Two DFIX restraints on two bonds (C16–C19 and C21–C22). Twelve DELU restraints on the pyridine ring (N1 C14 > C18).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.69767 (8)1.01287 (6)0.39871 (4)0.0618 (2)
C10.8245 (7)1.3721 (5)0.1881 (3)0.0785 (18)
C20.7028 (6)1.1851 (5)0.2615 (3)0.0658 (16)
C30.8296 (7)1.2275 (5)0.3080 (3)0.0657 (16)
C40.5717 (6)0.7980 (5)0.4908 (3)0.0594 (15)
C50.6955 (5)0.8467 (5)0.5394 (3)0.0556 (14)
C60.5817 (6)0.6592 (5)0.6133 (3)0.0716 (17)
C70.1092 (7)0.0243 (6)0.8882 (4)0.0754 (18)
H70.12060.04750.84860.091*
C80.1850 (7)0.0406 (6)0.9673 (4)0.088 (2)
H80.24630.01920.98090.105*
C90.1687 (8)0.1457 (8)1.0250 (4)0.096
C100.0809 (7)0.2305 (6)1.0055 (4)0.086 (2)
H100.07110.30251.04540.104*
C110.0035 (7)0.2123 (5)0.9258 (4)0.0740 (17)
H110.05940.27130.91320.089*
C120.0188 (6)0.1087 (5)0.8659 (3)0.0607 (15)
C130.0633 (7)0.0870 (5)0.7803 (3)0.0744 (18)
H13A0.05140.00170.75140.089*
H13B0.16670.09050.78860.089*
C140.1106 (7)0.2299 (5)0.6763 (3)0.0714 (17)
H140.21000.20760.68080.086*
C150.0674 (7)0.3116 (5)0.6198 (3)0.0700 (16)
H150.13690.34370.58630.084*
C160.0804 (7)0.3460 (5)0.6130 (3)0.0594 (14)
C170.1756 (7)0.2979 (5)0.6660 (3)0.0700 (16)
H170.27560.32170.66510.084*
C180.1259 (7)0.2144 (5)0.7209 (3)0.0694 (16)
H180.19270.18110.75560.083*
C190.1278 (6)0.4236 (5)0.5553 (3)0.0660 (16)
O10.6721 (7)0.2594 (6)0.8238 (4)0.169 (3)
C200.6395 (11)0.4577 (10)0.8934 (5)0.200 (5)
H20A0.72280.48570.86370.300*
H20B0.66240.47630.95450.300*
H20C0.55800.50180.87850.300*
C210.6025 (10)0.3226 (9)0.8689 (5)0.123 (3)
C220.4850 (11)0.2644 (11)0.9124 (7)0.302 (9)
H22A0.39410.26260.87920.453*
H22B0.47970.31330.96830.453*
H22C0.50270.17840.91860.453*
N10.0145 (5)0.1818 (4)0.7244 (3)0.0591 (12)
S10.8584 (2)1.48341 (17)0.12731 (12)0.1117 (7)
S20.6668 (2)1.26554 (16)0.17419 (10)0.0865 (5)
S30.93637 (19)1.35129 (14)0.27390 (10)0.0794 (5)
S40.58654 (17)1.05888 (15)0.28470 (9)0.0774 (5)
S50.88065 (16)1.15543 (13)0.39461 (9)0.0686 (4)
S60.52012 (16)0.86344 (14)0.40212 (9)0.0690 (4)
S70.80795 (16)0.97166 (14)0.51400 (9)0.0680 (4)
S80.47060 (17)0.66924 (15)0.52389 (9)0.0760 (5)
S90.73328 (17)0.77180 (15)0.62845 (9)0.0714 (5)
S100.5507 (2)0.55030 (18)0.67645 (10)0.1042 (7)
Br10.27186 (10)0.17125 (9)1.13312 (5)0.1400 (4)
N20.1693 (5)0.4865 (5)0.5061 (3)0.0831 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0574 (5)0.0547 (5)0.0727 (5)0.0113 (4)0.0023 (4)0.0065 (4)
C10.101 (5)0.060 (4)0.078 (4)0.032 (4)0.019 (4)0.004 (3)
C20.075 (4)0.057 (4)0.069 (4)0.025 (3)0.012 (3)0.007 (3)
C30.074 (4)0.057 (4)0.064 (4)0.016 (3)0.008 (3)0.005 (3)
C40.051 (4)0.059 (4)0.065 (3)0.007 (3)0.013 (3)0.003 (3)
C50.047 (3)0.059 (4)0.059 (3)0.006 (3)0.008 (3)0.002 (3)
C60.082 (4)0.072 (4)0.057 (3)0.002 (3)0.020 (3)0.003 (3)
C70.095 (5)0.069 (5)0.065 (4)0.011 (4)0.021 (4)0.012 (3)
C80.090 (5)0.085 (5)0.096 (5)0.009 (4)0.004 (4)0.046 (4)
C90.1110.0940.0810.0110.0130.019
C100.122 (6)0.070 (5)0.060 (4)0.016 (4)0.025 (4)0.006 (3)
C110.097 (5)0.057 (4)0.071 (4)0.012 (4)0.016 (4)0.012 (3)
C120.080 (4)0.051 (4)0.052 (4)0.006 (3)0.013 (3)0.009 (3)
C130.113 (5)0.047 (4)0.063 (4)0.002 (3)0.015 (4)0.013 (3)
C140.070 (4)0.080 (4)0.062 (4)0.006 (3)0.002 (3)0.016 (3)
C150.079 (4)0.075 (4)0.058 (4)0.003 (3)0.004 (3)0.023 (3)
C160.075 (4)0.054 (4)0.053 (3)0.008 (3)0.020 (3)0.015 (3)
C170.076 (4)0.073 (4)0.067 (4)0.017 (3)0.024 (3)0.016 (3)
C180.079 (4)0.073 (4)0.063 (4)0.022 (4)0.009 (3)0.021 (3)
C190.070 (4)0.059 (4)0.075 (4)0.007 (3)0.020 (3)0.022 (3)
O10.200 (7)0.160 (6)0.145 (5)0.038 (5)0.055 (5)0.010 (4)
C200.318 (15)0.143 (9)0.146 (8)0.032 (9)0.020 (9)0.040 (7)
C210.171 (10)0.102 (8)0.090 (6)0.017 (7)0.018 (6)0.012 (5)
C220.216 (13)0.279 (15)0.350 (16)0.127 (11)0.149 (12)0.096 (12)
N10.069 (3)0.058 (3)0.048 (3)0.006 (3)0.006 (3)0.012 (2)
S10.160 (2)0.0857 (14)0.1027 (13)0.0311 (13)0.0248 (14)0.0397 (11)
S20.1004 (14)0.0845 (12)0.0808 (11)0.0303 (11)0.0023 (10)0.0217 (9)
S30.0958 (13)0.0594 (10)0.0850 (11)0.0099 (9)0.0074 (10)0.0156 (9)
S40.0698 (11)0.0772 (11)0.0848 (11)0.0089 (9)0.0098 (9)0.0150 (9)
S50.0662 (10)0.0615 (10)0.0782 (10)0.0047 (8)0.0075 (8)0.0162 (8)
S60.0540 (10)0.0744 (11)0.0763 (10)0.0048 (8)0.0068 (8)0.0088 (8)
S70.0607 (10)0.0616 (10)0.0784 (10)0.0011 (8)0.0099 (8)0.0098 (8)
S80.0700 (11)0.0807 (12)0.0712 (10)0.0129 (9)0.0093 (9)0.0045 (9)
S90.0760 (11)0.0745 (11)0.0607 (9)0.0018 (9)0.0017 (8)0.0076 (8)
S100.1355 (17)0.1062 (15)0.0676 (11)0.0177 (13)0.0177 (11)0.0199 (10)
Br10.1362 (8)0.1885 (9)0.0855 (5)0.0509 (7)0.0260 (5)0.0461 (5)
N20.075 (4)0.083 (4)0.103 (4)0.011 (3)0.026 (3)0.043 (3)
Geometric parameters (Å, º) top
Ni1—S72.1545 (16)C10—H100.9300
Ni1—S52.1547 (16)C11—C121.363 (6)
Ni1—S42.1605 (16)C11—H110.9300
Ni1—S62.1649 (16)C12—C131.487 (6)
C1—S11.638 (6)C13—N11.477 (6)
C1—S31.709 (6)C13—H13A0.9700
C1—S21.730 (6)C13—H13B0.9700
C2—C31.347 (7)C14—N11.323 (6)
C2—S41.719 (6)C14—C151.371 (7)
C2—S21.751 (5)C14—H140.9300
C3—S51.722 (6)C15—C161.384 (7)
C3—S31.722 (6)C15—H150.9300
C4—C51.353 (6)C16—C171.365 (7)
C4—S61.711 (5)C16—C191.367 (7)
C4—S81.730 (5)C17—C181.384 (7)
C5—S71.702 (5)C17—H170.9300
C5—S91.742 (5)C18—N11.308 (6)
C6—S101.640 (6)C18—H180.9300
C6—S81.719 (5)C19—N21.146 (6)
C6—S91.724 (5)O1—C211.165 (8)
C7—C121.352 (7)C20—C211.430 (10)
C7—C81.374 (7)C20—H20A0.9600
C7—H70.9300C20—H20B0.9600
C8—C91.358 (8)C20—H20C0.9600
C8—H80.9300C21—C221.440 (14)
C9—C101.325 (8)C22—H22A0.9600
C9—Br11.876 (7)C22—H22B0.9600
C10—C111.389 (7)C22—H22C0.9600
S7—Ni1—S586.20 (6)N1—C13—H13B109.0
S7—Ni1—S4178.59 (6)C12—C13—H13B109.0
S5—Ni1—S493.18 (6)H13A—C13—H13B107.8
S7—Ni1—S692.71 (6)N1—C14—C15121.7 (6)
S5—Ni1—S6177.58 (7)N1—C14—H14119.1
S4—Ni1—S687.96 (6)C15—C14—H14119.1
S1—C1—S3124.3 (4)C16—C15—C14119.6 (6)
S1—C1—S2123.1 (4)C16—C15—H15120.2
S3—C1—S2112.6 (3)C14—C15—H15120.2
C3—C2—S4122.4 (5)C17—C16—C15116.8 (5)
C3—C2—S2115.2 (5)C17—C16—C19121.9 (6)
S4—C2—S2122.4 (4)C15—C16—C19121.3 (6)
C2—C3—S5120.2 (5)C16—C17—C18121.1 (6)
C2—C3—S3116.5 (5)C16—C17—H17119.5
S5—C3—S3123.2 (4)C18—C17—H17119.5
C5—C4—S6120.7 (4)N1—C18—C17120.4 (6)
C5—C4—S8116.5 (4)N1—C18—H18119.8
S6—C4—S8122.9 (3)C17—C18—H18119.8
C4—C5—S7121.9 (4)N2—C19—C16178.5 (7)
C4—C5—S9115.7 (4)C21—C20—H20A109.5
S7—C5—S9122.4 (3)C21—C20—H20B109.5
S10—C6—S8123.6 (3)H20A—C20—H20B109.5
S10—C6—S9122.9 (3)C21—C20—H20C109.5
S8—C6—S9113.5 (3)H20A—C20—H20C109.5
C12—C7—C8122.5 (6)H20B—C20—H20C109.5
C12—C7—H7118.7O1—C21—C22120.5 (10)
C8—C7—H7118.7O1—C21—C20122.8 (9)
C9—C8—C7118.6 (7)C22—C21—C20116.2 (9)
C9—C8—H8120.7C21—C22—H22A109.5
C7—C8—H8120.7C21—C22—H22B109.5
C10—C9—C8120.6 (7)H22A—C22—H22B109.5
C10—C9—Br1119.8 (7)C21—C22—H22C109.5
C8—C9—Br1119.6 (6)H22A—C22—H22C109.5
C9—C10—C11120.2 (6)H22B—C22—H22C109.5
C9—C10—H10119.9C18—N1—C14120.3 (5)
C11—C10—H10119.9C18—N1—C13118.9 (5)
C12—C11—C10120.7 (6)C14—N1—C13120.7 (5)
C12—C11—H11119.6C1—S2—C297.4 (3)
C10—C11—H11119.6C1—S3—C398.3 (3)
C7—C12—C11117.3 (6)C2—S4—Ni1101.6 (2)
C7—C12—C13121.1 (6)C3—S5—Ni1102.5 (2)
C11—C12—C13121.7 (6)C4—S6—Ni1102.33 (18)
N1—C13—C12113.1 (4)C5—S7—Ni1102.37 (18)
N1—C13—H13A109.0C6—S8—C497.3 (3)
C12—C13—H13A109.0C6—S9—C597.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C15—H15···N2i0.932.503.290 (8)143
C14—H14···O1ii0.932.553.135 (8)121
C13—H13B···O1ii0.972.463.230 (9)136
Symmetry codes: (i) x, y+1, z+1; (ii) x1, y, z.
 

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