Bis(4-amino-1-hexylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato)cuprate(II)

Liu, Q.; Liu, J.

doi:10.1107/S1600536811021611

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m916

doi:10.1107/S1600536811021611

Open

access

Bis(4-amino-1-hexylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato)cuprate(II)

Qi Liu ^a ^* and Jianlan Liu ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No.5 Xinmofan Road, Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: liuqi198721@163.com

(Received 28 May 2011; accepted 4 June 2011; online 11 June 2011)

The complete complex anion in the title salt, (C₁₁H₁₉N₂)₂[Cu(C₄N₂S₂)₂], has 2/m symmetry while the complete cation is generated by mirror symmetry with the non-H atoms of the alkyl chain lying on the plane. A square-planar geometry based on an S₄ donor set is found in the anion; the Cu—S distance is 2.2663 (5) Å. In the crystal, intermolecular N—H⋯N hydrogen bonds link the ions into layers in the bc plane comprising alternating rows of cations and anions.

Related literature

For square-planar M[dithiolene]₂ complexes acting as magnetic materials or showing nonlinear optical properties, see: Cassoux et al. (1991 ); Robertson & Cronin (2002 ).

Experimental

Crystal data

(C₁₁H₁₉N₂)₂[Cu(C₄N₂S₂)₂]
M_r = 702.51
Monoclinic, C 2/m
a = 13.3648 (9) Å
b = 10.0768 (4) Å
c = 13.8550 (8) Å
β = 111.902 (8)°
V = 1731.24 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.939, T_max = 1.000
4194 measured reflections
1805 independent reflections
1299 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.074
S = 0.92
1805 reflections
117 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.81 (2)	2.39 (2)	3.157 (2)	160 (2)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811021611/tk2752sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021611/tk2752Isup2.hkl

checkCIF report

Comment top

Square-planar M[dithiolene]₂ complexes have attracted extensive interest in the areas of conducting and magnetic materials, dyes, non-linear optics and catalysis (Robertson et al., 2002; Cassoux et al., 1991). Herein, we report the crystal structure of the title compound, Fig.1.

The [Cu(mnt)₂]^2- dianion is located about a site of symmetry 2/m. The 1-hexyl-4-aminopyridinium cation lies on a mirror plane whereby the non-H atoms of the alkyl chain lie on the plane which bisects the 1,4 atoms of the benzene ring.

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the cations and anions to form a layer in the bc plane comprising alternating cations and anions.

Related literature top

For square-planar M[dithiolene]₂ complexes, see: Cassoux et al. (1991); Robertson & Cronin (2002).

Experimental top

Disodium maleonitriledithiolate (468 mg, 2.5 mmol) and cupric nitrate trihydrate (302 mg, 1.25 mmol) were mixed under stirring in water (20 mL) at room temperature. Subsequently, a solution of 1-hexyl-4-aminopyridinium iodide (765 mg, 2.5 mmol) in water (10 mL) was added to the mixture. The brown precipitate that formed immediately was filtered off and washed with water. The crude product was recrystallized from acetone (20 mL) to give brown crystals. The crystals suitable for X-ray diffraction measurements were obtained by diffusing diethyl ether into the solution of the salt in acetone for 6 days.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the ions comprising (I) showing atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The cation has mirror symmetry with i: x, 1-y, z. The Cu atom in the anion is located on a site of symmetry 2/m. Symmetry operations ii: -x, y, -z and iii: -x, 1-y, -z.
	Fig. 2. Partial packing view showing the layer in the bc plane. Dashed lines indicate intermolecular N—H···N hydrogen bonds.

Bis(4-amino-1-hexylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato)cuprate(II) top

Crystal data top

(C₁₁H₁₉N₂)₂[Cu(C₄N₂S₂)₂]	F(000) = 734
M_r = 702.51	D_x = 1.348 Mg m⁻³
Monoclinic, C2/m	Melting point = 430–432 K
Hall symbol: -C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 13.3648 (9) Å	Cell parameters from 2059 reflections
b = 10.0768 (4) Å	θ = 3.1–29.2°
c = 13.8550 (8) Å	µ = 0.91 mm⁻¹
β = 111.902 (8)°	T = 293 K
V = 1731.24 (17) Å³	Block, brown
Z = 2	0.3 × 0.2 × 0.1 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	1805 independent reflections
Radiation source: fine-focus sealed tube	1299 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→16
T_min = 0.939, T_max = 1.000	k = −11→12
4194 measured reflections	l = −17→16

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ²(F_o²) + (0.0411P)²] where P = (F_o² + 2F_c²)/3
1805 reflections	(Δ/σ)_max < 0.001
117 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

(C₁₁H₁₉N₂)₂[Cu(C₄N₂S₂)₂]	V = 1731.24 (17) Å³
M_r = 702.51	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 13.3648 (9) Å	µ = 0.91 mm⁻¹
b = 10.0768 (4) Å	T = 293 K
c = 13.8550 (8) Å	0.3 × 0.2 × 0.1 mm
β = 111.902 (8)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1805 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1299 reflections with I > 2σ(I)
T_min = 0.939, T_max = 1.000	R_int = 0.019
4194 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	Δρ_max = 0.22 e Å⁻³
1805 reflections	Δρ_min = −0.17 e Å⁻³
117 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
Cu1	0.0000	0.5000	0.0000	0.04510 (17)
S1	0.04362 (5)	0.66007 (5)	0.12376 (4)	0.0623 (2)
N1	0.12555 (15)	0.7075 (2)	0.40284 (14)	0.0721 (6)
N2	0.3513 (2)	0.5000	0.5099 (2)	0.0615 (8)
N3	0.39247 (19)	0.5000	0.23171 (18)	0.0536 (6)
C1	0.07750 (14)	0.56692 (18)	0.23653 (14)	0.0445 (4)
C2	0.10516 (16)	0.6424 (2)	0.33068 (15)	0.0507 (5)
C3	0.3637 (2)	0.5000	0.4193 (2)	0.0472 (7)
C4	0.37096 (16)	0.38155 (19)	0.36957 (15)	0.0544 (5)
H4A	0.3666	0.3005	0.3998	0.065*
C5	0.38435 (18)	0.3850 (2)	0.27783 (17)	0.0586 (6)
H5A	0.3881	0.3054	0.2454	0.070*
C6	0.4079 (3)	0.5000	0.1312 (2)	0.0678 (9)
H6A	0.4487	0.4229	0.1280	0.081*
C7	0.3047 (3)	0.5000	0.0398 (3)	0.0810 (10)
H7A	0.2635	0.4226	0.0414	0.097*
C8	0.3282 (3)	0.5000	−0.0612 (3)	0.0819 (11)
H8A	0.3740	0.4117	−0.0657	0.098*
C9	0.2314 (3)	0.5000	−0.1571 (3)	0.0917 (12)
H9A	0.1892	0.4230	−0.1569	0.110*
C10	0.2529 (4)	0.5000	−0.2572 (3)	0.0930 (12)
H10A	0.2950	0.4229	−0.2577	0.112*
C11	0.1534 (3)	0.5000	−0.3517 (3)	0.0931 (12)
H11A	0.1716	0.5000	−0.4125	0.140*
H11B	0.1119	0.4222	−0.3519	0.140*
H2A	0.3461 (18)	0.432 (2)	0.5381 (16)	0.075 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0613 (3)	0.0335 (3)	0.0420 (3)	0.000	0.0211 (2)	0.000
S1	0.1042 (5)	0.0323 (3)	0.0463 (3)	0.0005 (3)	0.0235 (3)	0.0001 (2)
N1	0.0822 (14)	0.0679 (13)	0.0574 (11)	0.0058 (11)	0.0159 (10)	−0.0184 (10)
N2	0.076 (2)	0.0505 (19)	0.0559 (16)	0.000	0.0218 (15)	0.000
N3	0.0594 (15)	0.0435 (14)	0.0669 (15)	0.000	0.0340 (13)	0.000
C1	0.0492 (11)	0.0407 (10)	0.0423 (10)	0.0004 (9)	0.0155 (9)	−0.0020 (8)
C2	0.0538 (13)	0.0454 (11)	0.0486 (11)	0.0054 (10)	0.0143 (10)	0.0004 (10)
C3	0.0386 (16)	0.0423 (17)	0.0544 (17)	0.000	0.0100 (14)	0.000
C4	0.0649 (14)	0.0343 (11)	0.0652 (14)	0.0001 (10)	0.0257 (12)	0.0042 (10)
C5	0.0692 (15)	0.0352 (11)	0.0769 (15)	0.0012 (10)	0.0338 (13)	−0.0054 (11)
C6	0.080 (2)	0.058 (2)	0.083 (2)	0.000	0.051 (2)	0.000
C7	0.090 (3)	0.096 (3)	0.070 (2)	0.000	0.045 (2)	0.000
C8	0.092 (3)	0.087 (3)	0.079 (2)	0.000	0.046 (2)	0.000
C9	0.108 (3)	0.096 (3)	0.084 (3)	0.000	0.051 (3)	0.000
C10	0.114 (3)	0.099 (3)	0.080 (3)	0.000	0.053 (3)	0.000
C11	0.122 (3)	0.073 (3)	0.097 (3)	0.000	0.055 (3)	0.000

Geometric parameters (Å, º) top

Cu1—S1ⁱ	2.2663 (5)	C4—C5	1.349 (3)
Cu1—S1	2.2663 (5)	C4—H4A	0.9300
Cu1—S1ⁱⁱ	2.2663 (5)	C5—H5A	0.9300
Cu1—S1ⁱⁱⁱ	2.2663 (5)	C6—C7	1.483 (4)
S1—C1	1.7319 (19)	C6—H6A	0.9600
N1—C2	1.141 (2)	C7—C8	1.545 (4)
N2—C3	1.327 (4)	C7—H7A	0.9600
N2—H2A	0.80 (2)	C8—C9	1.468 (5)
N3—C5	1.347 (2)	C8—H8A	1.0943
N3—C5ⁱⁱⁱ	1.347 (2)	C9—C10	1.519 (4)
N3—C6	1.482 (3)	C9—H9A	0.9601
C1—C1ⁱⁱⁱ	1.349 (4)	C10—C11	1.478 (5)
C1—C2	1.434 (3)	C10—H10A	0.9600
C3—C4	1.399 (2)	C11—H11A	0.9600
C3—C4ⁱⁱⁱ	1.399 (2)	C11—H11B	0.9600

S1ⁱ—Cu1—S1	180.00 (2)	N3—C5—C4	122.1 (2)
S1ⁱ—Cu1—S1ⁱⁱ	90.75 (3)	N3—C5—H5A	118.9
S1—Cu1—S1ⁱⁱ	89.25 (3)	C4—C5—H5A	118.9
S1ⁱ—Cu1—S1ⁱⁱⁱ	89.25 (3)	N3—C6—C7	113.0 (2)
S1—Cu1—S1ⁱⁱⁱ	90.75 (3)	N3—C6—H6A	108.9
S1ⁱⁱ—Cu1—S1ⁱⁱⁱ	180.00 (3)	C7—C6—H6A	108.9
C1—S1—Cu1	101.76 (6)	C6—C7—C8	109.6 (3)
C3—N2—H2A	121.7 (17)	C6—C7—H7A	109.8
C5—N3—C5ⁱⁱⁱ	118.7 (2)	C8—C7—H7A	109.5
C5—N3—C6	120.65 (12)	C9—C8—C7	114.3 (3)
C5ⁱⁱⁱ—N3—C6	120.65 (12)	C9—C8—H8A	105.7
C1ⁱⁱⁱ—C1—C2	122.02 (11)	C7—C8—H8A	111.0
C1ⁱⁱⁱ—C1—S1	122.82 (6)	C8—C9—C10	115.0 (3)
C2—C1—S1	115.16 (14)	C8—C9—H9A	108.5
N1—C2—C1	176.9 (2)	C10—C9—H9A	108.3
N2—C3—C4	121.46 (13)	C11—C10—C9	113.2 (3)
N2—C3—C4ⁱⁱⁱ	121.46 (13)	C11—C10—H10A	109.3
C4—C3—C4ⁱⁱⁱ	117.1 (3)	C9—C10—H10A	108.5
C5—C4—C3	120.0 (2)	C10—C11—H11A	109.8
C5—C4—H4A	120.0	C10—C11—H11B	109.3
C3—C4—H4A	120.0	H11A—C11—H11B	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1^iv	0.81 (2)	2.39 (2)	3.157 (2)	160 (2)

Symmetry code: (iv) −x+1/2, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₁H₁₉N₂)₂[Cu(C₄N₂S₂)₂]
M_r	702.51
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	293
a, b, c (Å)	13.3648 (9), 10.0768 (4), 13.8550 (8)
β (°)	111.902 (8)
V (Å³)	1731.24 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.939, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4194, 1805, 1299
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.074, 0.92
No. of reflections	1805
No. of parameters	117
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.81 (2)	2.39 (2)	3.157 (2)	160 (2)

Symmetry code: (i) −x+1/2, y−1/2, −z+1.

Acknowledgements

The authors thank the Science and Technology Department of Jiangsu Province, People's Republic of China, for support.

References

Cassoux, P., Valade, L., Kobayashi, H., Kobayashi, A., Clark, R. A. & Underhill, A. E. (1991). Coord. Chem. Rev. 110, 115–160. CrossRef CAS Web of Science Google Scholar
Robertson, N. & Cronin, L. (2002). Coord. Chem. Rev. 227, 93–127. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m916

doi:10.1107/S1600536811021611

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(4-amino-1-hexylpyridinium) bis­(1,2-di­cyanoethene-1,2-di­thiolato)cuprate(II)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(4-amino-1-hexylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato)cuprate(II)