Crystal structure of bis-[1-(4-bromo-benz-yl)pyridinium] bis-(1,2-di-cyano-ethene-1,2-di-thiol-ato-κ(2) S,S')nickelate(II).

The asymmetric unit of the title salt, (C12H11BrN)2[Ni(C4N2S2)2], consists of one 1-(4-bromo-benz-yl)pyridinium cation and one half of a complex [Ni(mnt)2](2-) (mnt(2-) is the maleo-nitrile-dithiol-ate dianion). The Ni(2+) ion is located on an inversion centre and is coordinated by four S atoms from two mnt(2-) 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.

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 ▶).

Experimental

Crystal data

(C12H11BrN)2[Ni(C4N2S2)2]

M = 837.29

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.102

S = 1.03

3040 reflections

205 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.91 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: SHELXL97.

Crystal structure: contains datablock(s) I, 111. DOI: 10.1107/S1600536814024222/wm5078sup1.cif

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

Click here for additional data file.

x y z . DOI: 10.1107/S1600536814024222/wm5078fig1.tif

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

Click here for additional data file.

. DOI: 10.1107/S1600536814024222/wm5078fig2.tif

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

CCDC reference: 1032163

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C12H11BrN)2[Ni(C4N2S2)2]	F(000) = 836
Mr = 837.29	Dx = 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

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

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(Fo2) + (0.0517P)2 + 0.2393P] where P = (Fo2 + 2Fc2)/3
3040 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.91 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	Uiso*/Ueq
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*

	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)

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

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

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C16H16N2	0.93	2.49	3.384(6)	162