Crystal structure of bis­[1-(4-bromo­benz­yl)pyridinium] bis­(1,2-di­cyano­ethene-1,2-di­thiol­ato-κ2S,S′)nickelate(II)

Zeng, D.; Yang, S.-B.; Tian, Z.-F.

doi:10.1107/S1600536814024222

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages m395-m396

doi:10.1107/S1600536814024222

Open

access

Crystal structure of bis[1-(4-bromobenzyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickelate(II)

Dong Zeng,^a Shui-Bin Yang ^a and Zheng-Fang Tian ^a ^*

^aHubei Key Laboratory for Processing and Application of, Catalytic Materials, College of Chemical Engineering, Huanggang Normal University, Huanggang 438000, People's Republic of China
^*Correspondence e-mail: tzf7801@163.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 14 October 2014; accepted 3 November 2014; online 12 November 2014)

The asymmetric unit of the title salt, (C₁₂H₁₁BrN)₂[Ni(C₄N₂S₂)₂], consists of one 1-(4-bromobenzyl)pyridinium cation and one half of a complex [Ni(mnt)₂]²⁻ (mnt²⁻ is the maleonitriledithiolate dianion). The Ni²⁺ ion is located on an inversion centre and is coordinated by four S atoms from two mnt²⁻ ligands, exhibiting a square-planar coordination environment. In the cation, the planes of the pyridinium and benzene rings make a dihedral angle of 69.86 (19)°. The cations and anions are alternately arranged in layers parallel to (001) and are held together by non-classical C—H⋯N hydrogen bonds.

Keywords: crystal structure; 1-(4-bromobenzyl)pyridinium cation; maleonitriledithiolate dianion; square-planar bis-1,2-dithiolate complex; Ni²⁺ ion; hydrogen bonding.

CCDC reference: 1032163

1. Related literature

For general background to square-planar bis-1,2-dithiolate complexes of transition metals showing potential application as magnetic materials and conductors besides others, see: Duan et al. (2010 ); Pei et al. (2011 ); Ren et al. (2002 ). For the structure of a closely related compound, see: Zhang et al. (2011 ). For synthetic aspects, see: Davison & Holm (1967 ).

2. Experimental

2.1. Crystal data

(C₁₂H₁₁BrN)₂[Ni(C₄N₂S₂)₂]
M_r = 837.29
Monoclinic, P 2₁ /n
a = 9.783 (2) Å
b = 11.962 (3) Å
c = 14.858 (3) Å
β = 97.385 (7)°
V = 1724.3 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.16 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.15 mm

2.2. Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.571, T_max = 0.649
14683 measured reflections
3040 independent reflections
2204 reflections with I > 2σ(I)
R_int = 0.061

2.3. Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.102
S = 1.03
3040 reflections
205 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯N2	0.93	2.49	3.384 (6)	162

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: SHELXL97.

Supporting information

CCDC reference: 1032163

Crystal structure: contains datablocks I, 111. DOI: 10.1107/S1600536814024222/wm5078sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024222/wm5078Isup2.hkl

checkCIF report

Related literature top

For general background to square-planar bis-1,2-dithiolate complexes of transition metals showing potential application as magnetic materials and conductors besides others, see: Duan et al. (2010); Pei et al. (2011); Ren et al. (2002). For the structure of a closely related compound, see: Zhang et al. (2011). For synthetic aspects, see: Davison & Holm (1967).

Experimental top

Disodium maleonitriledithiolate (456 mg, 2.5 mmol) and nickel chloride hexahydrate (297 mg, 1.25 mmol) were mixed under stirring in water (20 ml) and heated to boiling for about 20 min. The resuting red solution was filtered and to the filtrate was added dropwise to an aqueous solution of 1-(4'-bromobenzyl)pyridinium chloride (711.5 mg, 2.5 mmol). The dark red precipitate was filtered off, washed with water three times and dried in vacuum. The crude product was recrystallized from acetone to give red crystals (yield: 76%) with a block-like form.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXL97 (Sheldrick, 2008).

Figures top

The molecular components of the title structure. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) = 1 - x, 1 - y, -z).]

Packing diagram of the title structure viewed along [100]. The origin is at the upper right corner of the unit cell.

Bis[1-(4-bromobenzyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickelate(II) top

Crystal data top

(C₁₂H₁₁BrN)₂[Ni(C₄N₂S₂)₂]	F(000) = 836
M_r = 837.29	D_x = 1.613 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 473 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.783 (2) Å	Cell parameters from 14683 reflections
b = 11.962 (3) Å	θ = 2.2–25.0°
c = 14.858 (3) Å	µ = 3.16 mm⁻¹
β = 97.385 (7)°	T = 296 K
V = 1724.3 (6) Å³	Block, red
Z = 2	0.20 × 0.15 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	3040 independent reflections
Radiation source: fine-focus sealed tube	2204 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
phi and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.571, T_max = 0.649	k = −14→14
14683 measured reflections	l = −17→17

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0517P)² + 0.2393P] where P = (F_o² + 2F_c²)/3
3040 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.91 e Å⁻³

Crystal data top

(C₁₂H₁₁BrN)₂[Ni(C₄N₂S₂)₂]	V = 1724.3 (6) Å³
M_r = 837.29	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.783 (2) Å	µ = 3.16 mm⁻¹
b = 11.962 (3) Å	T = 296 K
c = 14.858 (3) Å	0.20 × 0.15 × 0.15 mm
β = 97.385 (7)°

Data collection top

Bruker SMART CCD diffractometer	3040 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2204 reflections with I > 2σ(I)
T_min = 0.571, T_max = 0.649	R_int = 0.061
14683 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.03	Δρ_max = 0.44 e Å⁻³
3040 reflections	Δρ_min = −0.91 e Å⁻³
205 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
Ni1	0.5000	0.5000	0.0000	0.03497 (19)
Br1	−0.05497 (5)	0.44064 (4)	0.19128 (4)	0.0857 (2)
S1	0.68740 (9)	0.59888 (8)	0.02861 (6)	0.0445 (3)
S2	0.37034 (9)	0.64490 (8)	0.01000 (7)	0.0479 (3)
C3	0.4306 (4)	0.8595 (3)	0.0544 (3)	0.0472 (9)
N2	0.3771 (4)	0.9425 (3)	0.0661 (3)	0.0651 (10)
C8	0.1115 (3)	0.8032 (3)	0.2369 (3)	0.0438 (9)
C1	0.6257 (3)	0.7321 (3)	0.0478 (2)	0.0398 (8)
N3	0.0716 (3)	1.0079 (2)	0.2122 (2)	0.0426 (7)
C11	0.1688 (4)	0.9204 (3)	0.2526 (3)	0.0532 (10)
H11A	0.1894	0.9335	0.3173	0.064*
H11B	0.2544	0.9263	0.2264	0.064*
C9	0.0500 (4)	0.7490 (3)	0.3036 (3)	0.0563 (11)
H9	0.0417	0.7855	0.3579	0.068*
C5	0.0120 (4)	0.5898 (3)	0.2097 (3)	0.0537 (11)
C10	0.0009 (4)	0.6417 (4)	0.2903 (3)	0.0620 (11)
H10	−0.0392	0.6051	0.3355	0.074*
C2	0.4878 (3)	0.7516 (3)	0.0400 (2)	0.0401 (8)
C14	−0.1102 (5)	1.1646 (3)	0.1387 (3)	0.0698 (13)
H14	−0.1726	1.2181	0.1132	0.084*
C4	0.7257 (4)	0.8173 (3)	0.0722 (3)	0.0501 (9)
C15	0.0006 (5)	1.1360 (4)	0.0964 (3)	0.0710 (13)
H15	0.0142	1.1702	0.0420	0.085*
C16	0.0911 (4)	1.0574 (3)	0.1337 (3)	0.0586 (11)
H16	0.1666	1.0380	0.1049	0.070*
C12	−0.0375 (4)	1.0353 (3)	0.2544 (3)	0.0546 (10)
H12	−0.0503	0.9998	0.3084	0.066*
C6	0.0723 (4)	0.6405 (3)	0.1425 (3)	0.0622 (11)
H6	0.0794	0.6036	0.0881	0.075*
N1	0.8110 (4)	0.8818 (3)	0.0910 (3)	0.0770 (11)
C13	−0.1290 (4)	1.1141 (4)	0.2192 (3)	0.0632 (12)
H13	−0.2034	1.1335	0.2491	0.076*
C7	0.1227 (4)	0.7476 (3)	0.1569 (3)	0.0566 (11)
H7	0.1649	0.7828	0.1120	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0332 (3)	0.0344 (4)	0.0365 (4)	0.0045 (3)	0.0013 (3)	−0.0016 (3)
Br1	0.0699 (4)	0.0431 (3)	0.1335 (5)	−0.0074 (2)	−0.0270 (3)	−0.0002 (3)
S1	0.0350 (5)	0.0405 (5)	0.0563 (6)	0.0044 (4)	−0.0003 (4)	−0.0029 (5)
S2	0.0349 (5)	0.0382 (5)	0.0699 (7)	0.0047 (4)	0.0047 (5)	−0.0076 (5)
C3	0.040 (2)	0.044 (2)	0.057 (2)	−0.0019 (18)	0.0059 (18)	−0.004 (2)
N2	0.063 (2)	0.048 (2)	0.086 (3)	0.0080 (18)	0.013 (2)	−0.010 (2)
C8	0.037 (2)	0.040 (2)	0.052 (2)	0.0020 (16)	−0.0039 (17)	0.000 (2)
C1	0.041 (2)	0.038 (2)	0.039 (2)	−0.0011 (16)	0.0011 (16)	−0.0029 (16)
N3	0.0439 (18)	0.0342 (17)	0.0487 (18)	−0.0015 (14)	0.0017 (14)	−0.0087 (16)
C11	0.048 (2)	0.047 (2)	0.061 (3)	−0.0023 (18)	−0.0080 (19)	−0.002 (2)
C9	0.069 (3)	0.049 (3)	0.048 (2)	−0.002 (2)	−0.001 (2)	−0.002 (2)
C5	0.038 (2)	0.039 (2)	0.079 (3)	0.0039 (17)	−0.014 (2)	0.005 (2)
C10	0.069 (3)	0.053 (3)	0.063 (3)	−0.004 (2)	0.005 (2)	0.014 (2)
C2	0.043 (2)	0.038 (2)	0.0396 (19)	0.0048 (16)	0.0044 (15)	−0.0023 (17)
C14	0.071 (3)	0.039 (2)	0.092 (4)	0.010 (2)	−0.020 (3)	−0.003 (3)
C4	0.047 (2)	0.045 (2)	0.056 (2)	0.004 (2)	0.0011 (19)	−0.005 (2)
C15	0.086 (3)	0.053 (3)	0.075 (3)	0.009 (3)	0.010 (3)	0.013 (2)
C16	0.066 (3)	0.049 (3)	0.065 (3)	−0.003 (2)	0.025 (2)	0.005 (2)
C12	0.054 (3)	0.061 (3)	0.048 (2)	−0.003 (2)	0.005 (2)	−0.009 (2)
C6	0.063 (3)	0.055 (3)	0.069 (3)	−0.003 (2)	0.012 (2)	−0.017 (2)
N1	0.059 (2)	0.064 (3)	0.103 (3)	−0.011 (2)	−0.011 (2)	−0.016 (2)
C13	0.052 (3)	0.062 (3)	0.074 (3)	0.009 (2)	0.002 (2)	−0.020 (3)
C7	0.056 (2)	0.050 (3)	0.065 (3)	−0.005 (2)	0.016 (2)	−0.004 (2)

Geometric parameters (Å, º) top

Ni1—S2ⁱ	2.1642 (9)	C9—C10	1.376 (5)
Ni1—S2	2.1642 (9)	C9—H9	0.9300
Ni1—S1	2.1773 (9)	C5—C10	1.366 (6)
Ni1—S1ⁱ	2.1773 (9)	C5—C6	1.366 (6)
Br1—C5	1.908 (4)	C10—H10	0.9300
S1—C1	1.740 (3)	C14—C15	1.366 (6)
S2—C2	1.737 (3)	C14—C13	1.373 (6)
C3—N2	1.146 (4)	C14—H14	0.9300
C3—C2	1.433 (5)	C4—N1	1.144 (5)
C8—C7	1.379 (5)	C15—C16	1.360 (6)
C8—C9	1.385 (5)	C15—H15	0.9300
C8—C11	1.517 (5)	C16—H16	0.9300
C1—C2	1.360 (5)	C12—C13	1.358 (6)
C1—C4	1.427 (5)	C12—H12	0.9300
N3—C16	1.343 (5)	C6—C7	1.379 (5)
N3—C12	1.346 (5)	C6—H6	0.9300
N3—C11	1.487 (4)	C13—H13	0.9300
C11—H11A	0.9700	C7—H7	0.9300
C11—H11B	0.9700

S2ⁱ—Ni1—S2	180.00 (5)	C6—C5—Br1	118.9 (3)
S2ⁱ—Ni1—S1	87.84 (4)	C5—C10—C9	119.0 (4)
S2—Ni1—S1	92.16 (4)	C5—C10—H10	120.5
S2ⁱ—Ni1—S1ⁱ	92.16 (4)	C9—C10—H10	120.5
S2—Ni1—S1ⁱ	87.84 (4)	C1—C2—C3	123.0 (3)
S1—Ni1—S1ⁱ	180.0	C1—C2—S2	120.8 (3)
C1—S1—Ni1	103.21 (11)	C3—C2—S2	116.2 (3)
C2—S2—Ni1	103.42 (12)	C15—C14—C13	119.6 (4)
N2—C3—C2	175.7 (4)	C15—C14—H14	120.2
C7—C8—C9	118.7 (4)	C13—C14—H14	120.2
C7—C8—C11	120.7 (3)	N1—C4—C1	176.5 (4)
C9—C8—C11	120.6 (3)	C16—C15—C14	119.9 (4)
C2—C1—C4	122.6 (3)	C16—C15—H15	120.0
C2—C1—S1	120.3 (3)	C14—C15—H15	120.0
C4—C1—S1	117.1 (2)	N3—C16—C15	120.2 (4)
C16—N3—C12	120.4 (3)	N3—C16—H16	119.9
C16—N3—C11	120.4 (3)	C15—C16—H16	119.9
C12—N3—C11	119.2 (3)	N3—C12—C13	120.9 (4)
N3—C11—C8	112.6 (3)	N3—C12—H12	119.6
N3—C11—H11A	109.1	C13—C12—H12	119.6
C8—C11—H11A	109.1	C5—C6—C7	118.5 (4)
N3—C11—H11B	109.1	C5—C6—H6	120.7
C8—C11—H11B	109.1	C7—C6—H6	120.7
H11A—C11—H11B	107.8	C12—C13—C14	119.0 (4)
C10—C9—C8	120.7 (4)	C12—C13—H13	120.5
C10—C9—H9	119.7	C14—C13—H13	120.5
C8—C9—H9	119.7	C8—C7—C6	121.1 (4)
C10—C5—C6	122.0 (4)	C8—C7—H7	119.4
C10—C5—Br1	119.1 (3)	C6—C7—H7	119.4

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N2	0.93	2.49	3.384 (6)	162

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N2	0.93	2.49	3.384 (6)	162

Acknowledgements

This work was supported by the Educational Commission of Hubei Province of China (grant No. Q20082702).

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Davison, A. & Holm, H. R. (1967). Inorg. Synth. 10, 8–26. CrossRef CAS Google Scholar
Duan, H. B., Ren, X. M. & Meng, Q. J. (2010). Coord. Chem. Rev. 254, 1509–1522. Web of Science CrossRef CAS Google Scholar
Pei, W. B., Wu, J. S., Tian, Z. F., Ren, X. M. & Song, Y. (2011). Inorg. Chem. 50, 3970–3980. Web of Science CSD CrossRef CAS PubMed Google Scholar
Ren, X. M., Meng, Q. J., Song, Y., Hu, C. J., Lu, C. S., Chen, X. Y. & Xue, Z. L. (2002). Inorg. Chem. 41, 5931–5933. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, H., Pei, W.-B., Yu, S.-S. & Ren, X.-M. (2011). Acta Cryst. E67, m943. Web of Science CSD CrossRef IUCr Journals 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.