Literature DB >> 22346841

Bis(4-cyano-1-methyl-pyridinium) bis-(1,2-dicyano-ethene-1,2-dithiol-ato-κS,S')cuprate(II).

Na Wang, Jin-Guo Wang, An-Jie Min, Yao-Wen Fu.

Abstract

The title ion-pair compound, (C(7)H(7)N(2))(2)[Cu(C(4)N(2)S(2))(2)], was obtained by the direct reaction of CuCl(2)·2H(2)O, disodium maleonitrile-dithiol-ate (Na(2)mnt) and 4-cyano-1-methyl-pyridinium iodide. The anion and one pyridinium cation lie entirely on a mirror plane, whereas for the other cation, a crystallographic mirror plane runs through the N and para-C atoms of the pyridine ring, the methyl C atom, and the cyano group. In the crystal, ions are linked into a three-dimensional network by C-H⋯N hydrogen bonds.

Entities: CellLine Chemical Disease Species

Year: 2012 PMID： 22346841 PMCID： PMC3274894 DOI： 10.1107/S1600536812001377

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For details of other square-planar M(dithiolene)2 complexes, see: Robin & Fromm (2006 ▶); Nishijo et al. (2003 ▶); Robertson & Cronin (2002 ▶); Coomber et al. (1996 ▶); Duan et al. (2010 ▶). For a study on CN⋯π interactions, see: Tian et al. (2007 ▶).

Experimental

Crystal data

(C7H7N2)2[Cu(C4N2S2)2] M = 582.19 Monoclinic, a = 12.063 (2) Å b = 6.9282 (14) Å c = 15.118 (3) Å β = 91.530 (3)° V = 1263.0 (4) Å3 Z = 2 Mo Kα radiation μ = 1.22 mm−1 T = 291 K 0.20 × 0.18 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.784, T max = 0.863 6296 measured reflections 2418 independent reflections 1717 reflections with I > 2σ(I) R int = 0.090

Refinement

R[F 2 > 2σ(F 2)] = 0.041 wR(F 2) = 0.101 S = 1.00 2418 reflections 205 parameters H-atom parameters constrained Δρmax = 0.32 e Å−3 Δρmin = −0.50 e Å−3 Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812001377/rz2689sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001377/rz2689Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C₇H₇N₂)₂[Cu(C₄N₂S₂)₂]	F(000) = 590
M_r = 582.19	D_x = 1.531 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2205 reflections
a = 12.063 (2) Å	θ = 2.7–26.5°
b = 6.9282 (14) Å	µ = 1.22 mm⁻¹
c = 15.118 (3) Å	T = 291 K
β = 91.530 (3)°	Block, brown-red
V = 1263.0 (4) Å³	0.20 × 0.18 × 0.12 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	2418 independent reflections
Radiation source: sealed tube	1717 reflections with I > 2σ(I)
graphite	R_int = 0.090
φ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→13
T_min = 0.784, T_max = 0.863	k = −8→7
6296 measured reflections	l = −17→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0386P)²] where P = (F_o² + 2F_c²)/3
2418 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

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.

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6179 (4)	0.7500	0.2599 (3)	0.0729 (13)
H1A	0.5519	0.7500	0.2903	0.087*
C2	0.7158 (4)	0.7500	0.3051 (3)	0.0713 (12)
H2A	0.7173	0.7500	0.3667	0.086*
C3	0.8129 (3)	0.7500	0.2605 (2)	0.0607 (11)
C4	0.8091 (3)	0.7500	0.1692 (2)	0.0617 (11)
H4A	0.8741	0.7500	0.1374	0.074*
C5	0.7088 (4)	0.7500	0.1267 (2)	0.0664 (12)
H5A	0.7051	0.7500	0.0652	0.080*
C6	0.9162 (4)	0.7500	0.3084 (3)	0.0741 (13)
C7	0.5079 (4)	0.7500	0.1235 (3)	0.1021 (17)
H7A	0.4495	0.7500	0.1653	0.153*
H7B	0.5019	0.8631	0.0870	0.153*
C8	0.1754 (3)	0.0879 (5)	0.3350 (2)	0.0932 (11)
H8A	0.1563	−0.0273	0.3623	0.112*
C9	0.2320 (3)	0.0829 (5)	0.2571 (2)	0.0982 (12)
H9A	0.2510	−0.0344	0.2317	0.118*
C10	0.2595 (3)	0.2500	0.2183 (2)	0.0680 (12)
C11	0.3235 (4)	0.2500	0.1392 (3)	0.1017 (19)
C12	0.0896 (4)	0.2500	0.4554 (3)	0.0953 (17)
H12A	0.0752	0.3806	0.4730	0.143*	0.50
H12B	0.1349	0.1877	0.5001	0.143*	0.50
H12C	0.0208	0.1817	0.4482	0.143*	0.50
C13	0.8020 (3)	0.2500	0.0685 (2)	0.0554 (10)
C14	0.7986 (3)	0.2500	−0.0259 (3)	0.0646 (11)
C15	0.8992 (3)	0.2500	0.1138 (2)	0.0552 (10)
C16	1.0025 (4)	0.2500	0.0683 (2)	0.0690 (12)
C17	0.5487 (3)	0.2500	0.4089 (2)	0.0583 (10)
C18	0.4441 (3)	0.2500	0.4523 (2)	0.0638 (11)
C19	0.6436 (3)	0.2500	0.4574 (2)	0.0612 (11)
C20	0.6390 (3)	0.2500	0.5519 (3)	0.0728 (13)
Cu1	0.72603 (3)	0.2500	0.26339 (3)	0.0546 (2)
N1	0.6152 (3)	0.7500	0.1718 (2)	0.0664 (9)
N2	0.9963 (4)	0.7500	0.3493 (3)	0.0960 (13)
N3	0.1483 (2)	0.2500	0.3706 (2)	0.0610 (9)
N4	0.3757 (4)	0.2500	0.0790 (3)	0.139 (2)
N5	0.7914 (4)	0.2500	−0.1020 (2)	0.0927 (13)
N6	1.0837 (3)	0.2500	0.0328 (2)	0.0997 (14)
N7	0.3600 (3)	0.2500	0.4858 (2)	0.0807 (12)
N8	0.6352 (3)	0.2500	0.6273 (2)	0.0951 (13)
S1	0.67434 (8)	0.2500	0.11804 (6)	0.0613 (3)
S2	0.90748 (8)	0.2500	0.22849 (6)	0.0623 (3)
S3	0.54354 (8)	0.2500	0.29465 (6)	0.0699 (4)
S4	0.77358 (8)	0.2500	0.41093 (6)	0.0713 (4)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.060 (3)	0.102 (4)	0.057 (3)	0.000	0.017 (2)	0.000
C2	0.067 (3)	0.105 (4)	0.042 (2)	0.000	0.011 (2)	0.000
C3	0.054 (2)	0.083 (3)	0.046 (2)	0.000	0.0019 (18)	0.000
C4	0.053 (2)	0.085 (3)	0.048 (2)	0.000	0.0102 (18)	0.000
C5	0.065 (3)	0.092 (3)	0.042 (2)	0.000	0.004 (2)	0.000
C6	0.067 (3)	0.105 (4)	0.051 (3)	0.000	0.006 (2)	0.000
C7	0.059 (3)	0.144 (5)	0.102 (4)	0.000	−0.019 (3)	0.000
C8	0.098 (3)	0.080 (3)	0.102 (3)	−0.019 (2)	0.028 (2)	0.003 (2)
C9	0.118 (3)	0.089 (3)	0.089 (3)	−0.011 (2)	0.028 (2)	−0.029 (2)
C10	0.044 (2)	0.116 (4)	0.044 (2)	0.000	−0.0071 (18)	0.000
C11	0.058 (3)	0.191 (6)	0.056 (3)	0.000	−0.015 (2)	0.000
C12	0.057 (3)	0.163 (5)	0.066 (3)	0.000	0.015 (2)	0.000
C13	0.051 (2)	0.076 (3)	0.039 (2)	0.000	0.0050 (17)	0.000
C14	0.059 (3)	0.088 (3)	0.046 (2)	0.000	0.001 (2)	0.000
C15	0.045 (2)	0.081 (3)	0.040 (2)	0.000	0.0070 (17)	0.000
C16	0.048 (2)	0.116 (4)	0.043 (2)	0.000	0.0027 (19)	0.000
C17	0.041 (2)	0.091 (3)	0.043 (2)	0.000	0.0052 (17)	0.000
C18	0.049 (2)	0.104 (3)	0.038 (2)	0.000	0.0008 (18)	0.000
C19	0.047 (2)	0.098 (3)	0.039 (2)	0.000	0.0052 (17)	0.000
C20	0.044 (2)	0.122 (4)	0.052 (3)	0.000	−0.0014 (19)	0.000
Cu1	0.0387 (3)	0.0830 (4)	0.0423 (3)	0.000	0.0045 (2)	0.000
N1	0.055 (2)	0.085 (3)	0.059 (2)	0.000	0.0019 (17)	0.000
N2	0.075 (3)	0.139 (4)	0.074 (3)	0.000	−0.010 (2)	0.000
N3	0.0400 (18)	0.087 (3)	0.056 (2)	0.000	−0.0011 (15)	0.000
N4	0.064 (3)	0.299 (7)	0.053 (2)	0.000	−0.006 (2)	0.000
N5	0.112 (3)	0.119 (3)	0.047 (2)	0.000	0.004 (2)	0.000
N6	0.061 (3)	0.177 (4)	0.062 (2)	0.000	0.022 (2)	0.000
N7	0.052 (2)	0.139 (4)	0.052 (2)	0.000	0.0095 (17)	0.000
N8	0.076 (3)	0.165 (4)	0.044 (2)	0.000	0.0012 (19)	0.000
S1	0.0427 (6)	0.0950 (8)	0.0461 (5)	0.000	0.0003 (4)	0.000
S2	0.0401 (5)	0.1060 (8)	0.0409 (5)	0.000	0.0018 (4)	0.000
S3	0.0391 (5)	0.1299 (10)	0.0408 (5)	0.000	0.0024 (4)	0.000
S4	0.0391 (6)	0.1282 (10)	0.0465 (6)	0.000	0.0005 (4)	0.000

C1—N1	1.331 (5)	C12—N3	1.481 (5)
C1—C2	1.350 (6)	C12—H12A	0.9600
C1—H1A	0.9300	C12—H12B	0.9600
C2—C3	1.367 (6)	C12—H12C	0.9600
C2—H2A	0.9300	C13—C15	1.342 (5)
C3—C4	1.380 (5)	C13—C14	1.428 (5)
C3—C6	1.424 (6)	C13—S1	1.729 (4)
C4—C5	1.354 (6)	C14—N5	1.151 (5)
C4—H4A	0.9300	C15—C16	1.440 (5)
C5—N1	1.334 (5)	C15—S2	1.734 (3)
C5—H5A	0.9300	C16—N6	1.129 (5)
C6—N2	1.134 (6)	C17—C19	1.343 (5)
C7—N1	1.470 (5)	C17—C18	1.437 (5)
C7—H7A	0.9589	C17—S3	1.727 (4)
C7—H7B	0.9600	C18—N7	1.146 (5)
C8—N3	1.292 (4)	C19—C20	1.431 (5)
C8—C9	1.378 (4)	C19—S4	1.735 (4)
C8—H8A	0.9300	C20—N8	1.142 (4)
C9—C10	1.343 (4)	Cu1—S3	2.2638 (11)
C9—H9A	0.9300	Cu1—S2	2.2652 (11)
C10—C9ⁱ	1.343 (4)	Cu1—S1	2.2679 (11)
C10—C11	1.441 (6)	Cu1—S4	2.2883 (11)
C11—N4	1.120 (6)	N3—C8ⁱ	1.292 (4)

N1—C1—C2	120.3 (4)	H12B—C12—H12C	109.5
N1—C1—H1A	119.9	C15—C13—C14	120.7 (3)
C2—C1—H1A	119.9	C15—C13—S1	123.7 (3)
C1—C2—C3	120.0 (4)	C14—C13—S1	115.5 (3)
C1—C2—H2A	120.0	N5—C14—C13	177.3 (5)
C3—C2—H2A	120.0	C13—C15—C16	120.8 (3)
C2—C3—C4	119.2 (4)	C13—C15—S2	122.4 (3)
C2—C3—C6	119.9 (4)	C16—C15—S2	116.8 (3)
C4—C3—C6	120.9 (3)	N6—C16—C15	179.8 (5)
C5—C4—C3	118.6 (3)	C19—C17—C18	119.8 (3)
C5—C4—H4A	120.7	C19—C17—S3	123.6 (3)
C3—C4—H4A	120.7	C18—C17—S3	116.6 (3)
N1—C5—C4	121.0 (3)	N7—C18—C17	179.1 (4)
N1—C5—H5A	119.5	C17—C19—C20	119.3 (3)
C4—C5—H5A	119.5	C17—C19—S4	123.1 (3)
N2—C6—C3	177.4 (5)	C20—C19—S4	117.6 (3)
N1—C7—H7A	109.0	N8—C20—C19	179.9 (4)
N1—C7—H7B	109.7	S3—Cu1—S2	178.59 (4)
H7A—C7—H7B	109.5	S3—Cu1—S1	87.63 (4)
N3—C8—C9	121.0 (3)	S2—Cu1—S1	90.96 (4)
N3—C8—H8A	119.5	S3—Cu1—S4	90.93 (4)
C9—C8—H8A	119.5	S2—Cu1—S4	90.48 (4)
C10—C9—C8	119.0 (3)	S1—Cu1—S4	178.56 (4)
C10—C9—H9A	120.5	C1—N1—C5	120.9 (4)
C8—C9—H9A	120.5	C1—N1—C7	119.6 (4)
C9—C10—C9ⁱ	119.1 (4)	C5—N1—C7	119.5 (4)
C9—C10—C11	120.4 (2)	C8ⁱ—N3—C8	120.9 (4)
C9ⁱ—C10—C11	120.4 (2)	C8ⁱ—N3—C12	119.5 (2)
N4—C11—C10	178.2 (5)	C8—N3—C12	119.5 (2)
N3—C12—H12A	109.5	C13—S1—Cu1	101.21 (13)
N3—C12—H12B	109.5	C15—S2—Cu1	101.68 (13)
H12A—C12—H12B	109.5	C17—S3—Cu1	101.52 (13)
N3—C12—H12C	109.5	C19—S4—Cu1	100.90 (13)
H12A—C12—H12C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N8ⁱⁱ	0.93	2.60	3.533 (6)	179
C2—H2A···N7ⁱⁱ	0.93	2.44	3.309 (6)	156
C5—H5A···N4ⁱⁱⁱ	0.93	2.36	3.247 (6)	159
C8—H8A···N2^iv	0.93	2.48	3.196 (5)	134
C9—H9A···N5^v	0.93	2.51	3.297 (4)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N8ⁱ	0.93	2.60	3.533 (6)	179
C2—H2A⋯N7ⁱ	0.93	2.44	3.309 (6)	156
C5—H5A⋯N4ⁱⁱ	0.93	2.36	3.247 (6)	159
C8—H8A⋯N2ⁱⁱⁱ	0.93	2.48	3.196 (5)	134
C9—H9A⋯N5^iv	0.93	2.51	3.297 (4)	143

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

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Authors: Zhengfang Tian; Xiaoming Ren; Yizhi Li; You Song; Qingjin Meng
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Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

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