1-(4-Cyano-benz-yl)-3,5-dimethyl-pyridinium bis-(benzene-1,2-dithiol-ato)nickelate(III).

The asymmetric unit of the title compound, (C(15)H(15)N(2))[Ni(C(6)H(4)S(2))(2)], contains half each of two independent centrosymmetric anions and a single cation in a general position. The Ni(III) ions are coordinated by four S atoms in a square-planar geometry. The anions exhibit two packing modes, viz. stacked along the a axis in a face-to-face fashion with an alternate arrangement of anions and cations, and stacked in a side-by-side fashion, forming ribbons parallel to (011).

Related literature

For general background to mol­ecular-based magnetic materials, see: Jones (1997 ▶); Akutagawa et al. (2009 ▶). For the role played by the size and shape of the counter-cations in determining the ground-state properties of the resulting materials, see: Ren et al. (2003 ▶). For related structures, see: Sellmann et al. (1991 ▶); Xie et al. (2002 ▶, 2003 ▶); Ren et al. (2002 ▶).

Experimental

Crystal data

(C15H15N2)[Ni(C6H4S2)2]

M = 562.42

Triclinic,

a = 7.1517 (7) Å

b = 12.8190 (13) Å

c = 15.3294 (16) Å

α = 69.774 (1)°

β = 77.740 (1)°

γ = 87.721 (1)°

V = 1287.8 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.10 mm−1

T = 296 K

0.36 × 0.30 × 0.28 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.694, T max = 0.749

6530 measured reflections

4530 independent reflections

3728 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.098

S = 1.02

4530 reflections

312 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.39 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 datablocks I, global. DOI: 10.1107/S1600536811004971/rz2554sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004971/rz2554Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C15H15N2)[Ni(C6H4S2)2]	Z = 2
Mr = 562.42	F(000) = 582
Triclinic, P1	Dx = 1.450 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1517 (7) Å	Cell parameters from 3577 reflections
b = 12.8190 (13) Å	θ = 2.6–27.0°
c = 15.3294 (16) Å	µ = 1.10 mm−1
α = 69.774 (1)°	T = 296 K
β = 77.740 (1)°	Block, dark green
γ = 87.721 (1)°	0.36 × 0.30 × 0.28 mm
V = 1287.8 (2) Å3

Bruker SMART APEX CCD area-detector diffractometer	4530 independent reflections
Radiation source: sealed tube	3728 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
Tmin = 0.694, Tmax = 0.749	k = −12→15
6530 measured reflections	l = −18→15

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0581P)2] where P = (Fo2 + 2Fc2)/3
4530 reflections	(Δ/σ)max = 0.001
312 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.39 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	0.5000	0.05051 (14)
Ni2	0.5000	1.0000	0.0000	0.06279 (16)
S1	0.38833 (9)	0.43210 (6)	0.41084 (5)	0.06354 (19)
S2	0.78410 (8)	0.44650 (5)	0.45826 (4)	0.05774 (17)
S3	0.52163 (10)	0.85288 (5)	0.11833 (6)	0.0751 (2)
S4	0.44027 (9)	1.09946 (6)	0.09034 (6)	0.0758 (2)
C1	0.5817 (3)	0.3696 (2)	0.36074 (16)	0.0563 (6)
C2	0.5622 (4)	0.3134 (2)	0.29922 (18)	0.0710 (7)
H2	0.4429	0.3068	0.2862	0.085*
C3	0.7171 (4)	0.2681 (3)	0.2582 (2)	0.0800 (8)
H3	0.7024	0.2306	0.2177	0.096*
C4	0.8974 (4)	0.2777 (2)	0.2765 (2)	0.0779 (8)
H4	1.0026	0.2472	0.2480	0.093*
C5	0.9189 (4)	0.3322 (2)	0.33656 (18)	0.0674 (7)
H5	1.0394	0.3392	0.3482	0.081*
C6	0.7616 (3)	0.37727 (19)	0.38061 (15)	0.0544 (5)
C7	0.4721 (4)	0.8937 (2)	0.2174 (2)	0.0750 (8)
C8	0.4671 (4)	0.8185 (3)	0.3089 (3)	0.0933 (10)
H8	0.4884	0.7438	0.3178	0.112*
C9	0.4315 (5)	0.8526 (4)	0.3851 (3)	0.1155 (14)
H9	0.4298	0.8014	0.4456	0.139*
C10	0.3978 (5)	0.9626 (5)	0.3733 (3)	0.1139 (14)
H10	0.3753	0.9851	0.4261	0.137*
C11	0.3969 (4)	1.0402 (3)	0.2847 (3)	0.0971 (10)
H11	0.3712	1.1140	0.2779	0.116*
C12	0.4356 (3)	1.0061 (2)	0.2045 (2)	0.0734 (7)
C13	0.7251 (6)	0.5985 (3)	−0.0472 (2)	0.0964 (10)
C14	0.8167 (5)	0.6096 (2)	0.0246 (2)	0.0708 (7)
C15	1.0079 (5)	0.6423 (2)	0.0003 (2)	0.0809 (8)
H15	1.0773	0.6544	−0.0612	0.097*
C16	1.0958 (4)	0.6572 (2)	0.06717 (19)	0.0723 (7)
H16	1.2245	0.6796	0.0505	0.087*
C17	0.9938 (4)	0.63901 (18)	0.15919 (17)	0.0571 (6)
C18	0.8028 (4)	0.60457 (19)	0.18304 (18)	0.0614 (6)
H18	0.7338	0.5916	0.2447	0.074*
C19	0.7138 (4)	0.5892 (2)	0.1172 (2)	0.0713 (7)
H19	0.5858	0.5654	0.1343	0.086*
C20	1.0872 (4)	0.65782 (19)	0.23205 (18)	0.0632 (6)
H20A	1.0577	0.5944	0.2906	0.076*
H20B	1.2250	0.6635	0.2093	0.076*
C21	0.9853 (4)	0.7593 (2)	0.34242 (17)	0.0622 (6)
H21	0.9952	0.6936	0.3918	0.075*
C22	0.9338 (4)	0.8545 (2)	0.36168 (17)	0.0648 (7)
C23	0.9208 (3)	0.9501 (2)	0.28705 (17)	0.0597 (6)
H23	0.8853	1.0150	0.2995	0.072*
C24	0.9592 (3)	0.95288 (18)	0.19364 (15)	0.0512 (5)
C25	1.0102 (3)	0.85467 (18)	0.17933 (15)	0.0509 (5)
H25	1.0374	0.8532	0.1177	0.061*
C26	0.8910 (5)	0.8506 (3)	0.46412 (19)	0.0950 (10)
H26A	0.8574	0.9231	0.4661	0.142*
H26B	1.0023	0.8277	0.4907	0.142*
H26C	0.7864	0.7985	0.5004	0.142*
C27	0.9439 (3)	1.0558 (2)	0.11151 (17)	0.0617 (6)
H27A	1.0669	1.0761	0.0692	0.093*
H27B	0.9012	1.1153	0.1346	0.093*
H27C	0.8536	1.0422	0.0781	0.093*
N1	0.6563 (6)	0.5905 (3)	−0.1048 (2)	0.1353 (14)
N2	1.0217 (3)	0.76078 (14)	0.25195 (12)	0.0528 (5)

	U11	U22	U33	U12	U13	U23
Ni1	0.0451 (2)	0.0580 (3)	0.0509 (2)	−0.00616 (18)	−0.01511 (17)	−0.01801 (19)
Ni2	0.0386 (2)	0.0489 (3)	0.0962 (4)	0.00137 (17)	−0.0198 (2)	−0.0160 (2)
S1	0.0478 (3)	0.0842 (4)	0.0722 (4)	−0.0036 (3)	−0.0202 (3)	−0.0387 (3)
S2	0.0473 (3)	0.0721 (4)	0.0593 (3)	−0.0029 (3)	−0.0192 (3)	−0.0244 (3)
S3	0.0622 (4)	0.0528 (4)	0.1011 (5)	0.0018 (3)	−0.0223 (4)	−0.0121 (3)
S4	0.0527 (4)	0.0594 (4)	0.1193 (6)	0.0036 (3)	−0.0267 (4)	−0.0308 (4)
C1	0.0559 (14)	0.0622 (14)	0.0501 (12)	−0.0090 (11)	−0.0119 (10)	−0.0171 (11)
C2	0.0641 (16)	0.0864 (18)	0.0730 (16)	−0.0116 (14)	−0.0170 (13)	−0.0376 (15)
C3	0.083 (2)	0.090 (2)	0.0773 (18)	−0.0109 (16)	−0.0060 (15)	−0.0465 (16)
C4	0.0702 (18)	0.088 (2)	0.0779 (18)	0.0033 (15)	−0.0050 (14)	−0.0381 (16)
C5	0.0548 (15)	0.0792 (18)	0.0669 (15)	0.0004 (12)	−0.0127 (12)	−0.0235 (14)
C6	0.0538 (13)	0.0553 (13)	0.0505 (12)	−0.0052 (10)	−0.0133 (10)	−0.0118 (10)
C7	0.0439 (14)	0.0775 (19)	0.095 (2)	−0.0151 (12)	−0.0167 (13)	−0.0157 (16)
C8	0.0681 (19)	0.099 (2)	0.095 (2)	−0.0250 (17)	−0.0201 (17)	−0.006 (2)
C9	0.082 (2)	0.150 (4)	0.098 (3)	−0.045 (3)	−0.019 (2)	−0.018 (3)
C10	0.077 (2)	0.165 (4)	0.102 (3)	−0.036 (3)	−0.007 (2)	−0.052 (3)
C11	0.0607 (18)	0.113 (3)	0.129 (3)	−0.0204 (17)	−0.0139 (19)	−0.057 (3)
C12	0.0415 (13)	0.0823 (19)	0.096 (2)	−0.0117 (12)	−0.0158 (13)	−0.0276 (16)
C13	0.131 (3)	0.077 (2)	0.090 (2)	0.0043 (19)	−0.047 (2)	−0.0267 (18)
C14	0.095 (2)	0.0486 (14)	0.0756 (17)	0.0042 (13)	−0.0351 (16)	−0.0201 (13)
C15	0.113 (3)	0.0626 (17)	0.0636 (16)	−0.0043 (16)	−0.0130 (16)	−0.0199 (13)
C16	0.0724 (18)	0.0616 (16)	0.0770 (18)	−0.0079 (13)	−0.0066 (14)	−0.0209 (14)
C17	0.0669 (15)	0.0398 (12)	0.0625 (14)	0.0040 (10)	−0.0202 (12)	−0.0113 (10)
C18	0.0655 (15)	0.0529 (14)	0.0629 (14)	0.0007 (11)	−0.0178 (12)	−0.0137 (11)
C19	0.0727 (17)	0.0596 (15)	0.0846 (19)	−0.0003 (13)	−0.0283 (15)	−0.0213 (14)
C20	0.0626 (15)	0.0515 (14)	0.0749 (16)	0.0057 (11)	−0.0262 (13)	−0.0145 (12)
C21	0.0633 (15)	0.0659 (16)	0.0537 (14)	−0.0124 (12)	−0.0227 (11)	−0.0084 (12)
C22	0.0615 (15)	0.0786 (18)	0.0563 (14)	−0.0147 (13)	−0.0149 (12)	−0.0226 (14)
C23	0.0522 (14)	0.0626 (15)	0.0682 (15)	−0.0056 (11)	−0.0131 (11)	−0.0265 (13)
C24	0.0393 (11)	0.0540 (13)	0.0609 (13)	−0.0056 (9)	−0.0159 (10)	−0.0168 (11)
C25	0.0479 (12)	0.0544 (13)	0.0508 (12)	−0.0033 (10)	−0.0187 (10)	−0.0132 (10)
C26	0.114 (3)	0.114 (3)	0.0588 (16)	−0.019 (2)	−0.0142 (16)	−0.0323 (17)
C27	0.0556 (14)	0.0527 (13)	0.0729 (15)	0.0009 (10)	−0.0198 (12)	−0.0130 (12)
N1	0.186 (4)	0.134 (3)	0.112 (2)	−0.004 (3)	−0.083 (3)	−0.044 (2)
N2	0.0505 (11)	0.0507 (11)	0.0562 (11)	−0.0044 (8)	−0.0207 (9)	−0.0109 (9)

Ni1—S1	2.1459 (6)	C13—C14	1.443 (4)
Ni1—S1i	2.1459 (6)	C14—C15	1.380 (4)
Ni1—S2	2.1560 (6)	C14—C19	1.392 (4)
Ni1—S2i	2.1560 (6)	C15—C16	1.379 (4)
Ni2—S3ii	2.1451 (7)	C15—H15	0.9300
Ni2—S3	2.1451 (7)	C16—C17	1.388 (4)
Ni2—S4ii	2.1569 (8)	C16—H16	0.9300
Ni2—S4	2.1569 (8)	C17—C18	1.385 (3)
S1—C1	1.741 (3)	C17—C20	1.506 (3)
S2—C6	1.747 (2)	C18—C19	1.372 (3)
S3—C7	1.735 (3)	C18—H18	0.9300
S4—C12	1.739 (3)	C19—H19	0.9300
C1—C6	1.399 (3)	C20—N2	1.491 (3)
C1—C2	1.400 (3)	C20—H20A	0.9700
C2—C3	1.366 (4)	C20—H20B	0.9700
C2—H2	0.9300	C21—N2	1.349 (3)
C3—C4	1.395 (4)	C21—C22	1.370 (4)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.368 (4)	C22—C23	1.373 (4)
C4—H4	0.9300	C22—C26	1.518 (4)
C5—C6	1.397 (4)	C23—C24	1.388 (3)
C5—H5	0.9300	C23—H23	0.9300
C7—C8	1.395 (4)	C24—C25	1.374 (3)
C7—C12	1.407 (4)	C24—C27	1.496 (3)
C8—C9	1.356 (5)	C25—N2	1.341 (3)
C8—H8	0.9300	C25—H25	0.9300
C9—C10	1.377 (6)	C26—H26A	0.9600
C9—H9	0.9300	C26—H26B	0.9600
C10—C11	1.379 (5)	C26—H26C	0.9600
C10—H10	0.9300	C27—H27A	0.9600
C11—C12	1.414 (4)	C27—H27B	0.9600
C11—H11	0.9300	C27—H27C	0.9600
C13—N1	1.133 (4)
S1—Ni1—S1i	180.00 (3)	C15—C14—C13	119.2 (3)
S1—Ni1—S2	92.04 (2)	C19—C14—C13	120.8 (3)
S1i—Ni1—S2	87.97 (2)	C16—C15—C14	119.9 (3)
S1—Ni1—S2i	87.97 (2)	C16—C15—H15	120.0
S1i—Ni1—S2i	92.03 (2)	C14—C15—H15	120.0
S2—Ni1—S2i	180.0	C15—C16—C17	120.5 (3)
S3ii—Ni2—S3	180.00 (4)	C15—C16—H16	119.8
S3ii—Ni2—S4ii	91.75 (3)	C17—C16—H16	119.8
S3—Ni2—S4ii	88.25 (3)	C18—C17—C16	119.0 (2)
S3ii—Ni2—S4	88.25 (3)	C18—C17—C20	120.1 (2)
S3—Ni2—S4	91.75 (3)	C16—C17—C20	120.9 (2)
S4ii—Ni2—S4	180.00 (2)	C19—C18—C17	121.1 (2)
C1—S1—Ni1	104.89 (8)	C19—C18—H18	119.5
C6—S2—Ni1	104.81 (8)	C17—C18—H18	119.5
C7—S3—Ni2	105.49 (11)	C18—C19—C14	119.5 (3)
C12—S4—Ni2	104.82 (11)	C18—C19—H19	120.3
C6—C1—C2	119.0 (2)	C14—C19—H19	120.3
C6—C1—S1	119.51 (18)	N2—C20—C17	112.08 (18)
C2—C1—S1	121.47 (19)	N2—C20—H20A	109.2
C3—C2—C1	120.5 (3)	C17—C20—H20A	109.2
C3—C2—H2	119.7	N2—C20—H20B	109.2
C1—C2—H2	119.7	C17—C20—H20B	109.2
C2—C3—C4	120.5 (3)	H20A—C20—H20B	107.9
C2—C3—H3	119.8	N2—C21—C22	120.2 (2)
C4—C3—H3	119.8	N2—C21—H21	119.9
C5—C4—C3	119.7 (3)	C22—C21—H21	119.9
C5—C4—H4	120.1	C21—C22—C23	118.4 (2)
C3—C4—H4	120.1	C21—C22—C26	119.2 (3)
C4—C5—C6	120.7 (2)	C23—C22—C26	122.3 (3)
C4—C5—H5	119.7	C22—C23—C24	122.0 (2)
C6—C5—H5	119.7	C22—C23—H23	119.0
C5—C6—C1	119.5 (2)	C24—C23—H23	119.0
C5—C6—S2	121.75 (19)	C25—C24—C23	116.6 (2)
C1—C6—S2	118.69 (19)	C25—C24—C27	120.6 (2)
C8—C7—C12	119.3 (3)	C23—C24—C27	122.8 (2)
C8—C7—S3	122.0 (3)	N2—C25—C24	121.7 (2)
C12—C7—S3	118.7 (2)	N2—C25—H25	119.1
C9—C8—C7	121.0 (4)	C24—C25—H25	119.1
C9—C8—H8	119.5	C22—C26—H26A	109.5
C7—C8—H8	119.5	C22—C26—H26B	109.5
C8—C9—C10	120.2 (4)	H26A—C26—H26B	109.5
C8—C9—H9	119.9	C22—C26—H26C	109.5
C10—C9—H9	119.9	H26A—C26—H26C	109.5
C9—C10—C11	121.3 (4)	H26B—C26—H26C	109.5
C9—C10—H10	119.4	C24—C27—H27A	109.5
C11—C10—H10	119.4	C24—C27—H27B	109.5
C10—C11—C12	119.1 (4)	H27A—C27—H27B	109.5
C10—C11—H11	120.4	C24—C27—H27C	109.5
C12—C11—H11	120.4	H27A—C27—H27C	109.5
C7—C12—C11	119.0 (3)	H27B—C27—H27C	109.5
C7—C12—S4	119.2 (2)	C25—N2—C21	121.1 (2)
C11—C12—S4	121.8 (3)	C25—N2—C20	119.51 (19)
N1—C13—C14	178.7 (4)	C21—N2—C20	119.3 (2)
C15—C14—C19	120.0 (2)
S2—Ni1—S1—C1	2.24 (8)	C8—C7—C12—S4	−179.55 (19)
S2i—Ni1—S1—C1	−177.76 (8)	S3—C7—C12—S4	0.3 (3)
S1—Ni1—S2—C6	−1.49 (8)	C10—C11—C12—C7	0.6 (4)
S1i—Ni1—S2—C6	178.51 (8)	C10—C11—C12—S4	−179.1 (2)
S4ii—Ni2—S3—C7	−177.93 (9)	Ni2—S4—C12—C7	1.4 (2)
S4—Ni2—S3—C7	2.07 (9)	Ni2—S4—C12—C11	−179.0 (2)
S3ii—Ni2—S4—C12	178.07 (8)	C19—C14—C15—C16	−1.4 (4)
S3—Ni2—S4—C12	−1.93 (8)	C13—C14—C15—C16	177.7 (3)
Ni1—S1—C1—C6	−2.8 (2)	C14—C15—C16—C17	0.3 (4)
Ni1—S1—C1—C2	178.49 (18)	C15—C16—C17—C18	0.7 (4)
C6—C1—C2—C3	−0.9 (4)	C15—C16—C17—C20	−178.4 (2)
S1—C1—C2—C3	177.8 (2)	C16—C17—C18—C19	−0.5 (4)
C1—C2—C3—C4	−0.4 (4)	C20—C17—C18—C19	178.6 (2)
C2—C3—C4—C5	0.5 (5)	C17—C18—C19—C14	−0.6 (4)
C3—C4—C5—C6	0.7 (4)	C15—C14—C19—C18	1.5 (4)
C4—C5—C6—C1	−2.0 (4)	C13—C14—C19—C18	−177.5 (3)
C4—C5—C6—S2	179.6 (2)	C18—C17—C20—N2	−72.8 (3)
C2—C1—C6—C5	2.1 (3)	C16—C17—C20—N2	106.3 (3)
S1—C1—C6—C5	−176.67 (18)	N2—C21—C22—C23	−0.1 (3)
C2—C1—C6—S2	−179.45 (18)	N2—C21—C22—C26	179.2 (2)
S1—C1—C6—S2	1.8 (3)	C21—C22—C23—C24	−0.3 (3)
Ni1—S2—C6—C5	178.62 (18)	C26—C22—C23—C24	−179.7 (2)
Ni1—S2—C6—C1	0.16 (19)	C22—C23—C24—C25	0.3 (3)
Ni2—S3—C7—C8	178.04 (19)	C22—C23—C24—C27	179.3 (2)
Ni2—S3—C7—C12	−1.8 (2)	C23—C24—C25—N2	0.2 (3)
C12—C7—C8—C9	−1.4 (4)	C27—C24—C25—N2	−178.85 (19)
S3—C7—C8—C9	178.8 (2)	C24—C25—N2—C21	−0.7 (3)
C7—C8—C9—C10	0.6 (5)	C24—C25—N2—C20	−177.0 (2)
C8—C9—C10—C11	0.8 (6)	C22—C21—N2—C25	0.6 (3)
C9—C10—C11—C12	−1.4 (5)	C22—C21—N2—C20	176.9 (2)
C8—C7—C12—C11	0.8 (4)	C17—C20—N2—C25	−44.8 (3)
S3—C7—C12—C11	−179.4 (2)	C17—C20—N2—C21	138.9 (2)