Bis(3,5,7-triaza-1-azoniatricyclo-[3.3.1.1]deca-ne) bis-(1,2-dicyano-ethene-1,2-dithiol-ato)nickelate(II).

The asymmetric unit of the title complex, (C(6)H(13)N(4))(2)[Ni(C(4)N(2)S(2))(2)], comprises one 1-azonia-3,5,7-triaza-tricyclo-[3.3.1.1(3,7)]decane cation and one half of an [Ni(mnt)(2)](2-) (mnt(2-) is maleonitrile-dithiol-ate or 1,2-dicyano-ethene-1,2-dithiol-ate) dianion. The Ni(2+) ion is located on a center of inversion and is coordinated by four S atoms from two mnt(2-) ligands in a square-planar coordination mode. Inter-molecular N-H⋯N hydrogen-bond inter-actions link one anion and two cations in the crystal structure.

Related literature

For general background to square-planar M[dithiol­ene]2 complexes acting as magnetic materials or showing non-linear optical properties, see: Duan et al. (2010 ▶). For the synthesis, see: Pei et al. (2010 ▶). For related structures, see: Ren et al. (2002 ▶). For related literature on spectroscopic properties, see: Bigoli et al. (2002 ▶).

Experimental

Crystal data

(C6H13N4)2[Ni(C4N2S2)2]

M = 621.50

Monoclinic,

a = 10.2274 (9) Å

b = 10.7676 (10) Å

c = 12.7030 (11) Å

β = 112.212 (2)°

V = 1295.1 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.11 mm−1

T = 296 K

0.20 × 0.15 × 0.15 mm

Data collection

Siemens SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick 2002 ▶) T min = 0.819, T max = 0.847

7528 measured reflections

2530 independent reflections

1784 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.075

S = 1.00

2530 reflections

173 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.33 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101645X/im2281sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101645X/im2281Isup2.hkl

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

(C6H13N4)2[Ni(C4N2S2)2]	F(000) = 644
Mr = 621.50	Dx = 1.594 Mg m−3
Monoclinic, P21/n	Melting point: 448 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.2274 (9) Å	Cell parameters from 8518 reflections
b = 10.7676 (10) Å	θ = 2.2–26.0°
c = 12.7030 (11) Å	µ = 1.11 mm−1
β = 112.212 (2)°	T = 296 K
V = 1295.1 (2) Å3	Block-shaped, red
Z = 2	0.2 × 0.15 × 0.15 mm

Siemens SMART CCD area-detector diffractometer	2530 independent reflections
Radiation source: fine-focus sealed tube	1784 reflections with I > 2σ(I)
graphite	Rint = 0.049
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick 2002)	h = −12→12
Tmin = 0.819, Tmax = 0.847	k = −13→9
7528 measured reflections	l = −15→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0279P)2] where P = (Fo2 + 2Fc2)/3
2530 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Experimental. Anal. Calcd. for C20H26N12NiS4: C, 38.65; H, 4.22; N, 27.05%.Found: C, 38.69; H, 4.19; N, 27.04%. FT—IR data (KBr pellets, cm-1): 3461 (m), 3118 (s), 2202 (s), 1650 (m), 1479 (s), 1257 (s), 1008 (s).

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
C1	0.1231 (3)	1.2643 (3)	0.0413 (2)	0.0280 (7)
C2	0.1719 (3)	1.3813 (3)	0.0941 (2)	0.0340 (7)
C3	−0.0743 (3)	0.7460 (3)	0.0733 (2)	0.0293 (7)
C4	−0.0880 (3)	0.6437 (3)	0.1406 (2)	0.0365 (8)
C5	0.1017 (3)	0.1801 (3)	0.5935 (2)	0.0482 (9)
H5A	0.0671	0.2124	0.6494	0.058*
H5B	0.1362	0.0965	0.6162	0.058*
C6	0.1637 (3)	0.3842 (3)	0.5569 (2)	0.0416 (8)
H6A	0.1299	0.4190	0.6124	0.050*
H6B	0.2399	0.4365	0.5547	0.050*
C7	0.0982 (3)	0.3365 (3)	0.3613 (2)	0.0408 (8)
H7A	0.1731	0.3893	0.3573	0.049*
H7B	0.0222	0.3356	0.2869	0.049*
C8	−0.0650 (3)	0.3039 (3)	0.4492 (3)	0.0505 (9)
H8A	−0.1421	0.3029	0.3755	0.061*
H8B	−0.1007	0.3376	0.5039	0.061*
C9	0.2719 (3)	0.2090 (3)	0.5110 (2)	0.0380 (8)
H9A	0.3093	0.1261	0.5334	0.046*
H9B	0.3478	0.2615	0.5086	0.046*
C10	0.0343 (3)	0.1257 (3)	0.3993 (3)	0.0461 (9)
H10A	−0.0421	0.1245	0.3251	0.055*
H10B	0.0667	0.0412	0.4194	0.055*
N1	0.2058 (3)	1.4760 (3)	0.1335 (2)	0.0540 (8)
N2	−0.1037 (3)	0.5627 (3)	0.1924 (2)	0.0576 (9)
N3	−0.0157 (3)	0.1754 (3)	0.4820 (2)	0.0454 (7)
N4	0.2179 (3)	0.2575 (2)	0.59227 (18)	0.0382 (6)
N5	0.0478 (3)	0.3842 (2)	0.44391 (19)	0.0377 (6)
N6	0.1541 (3)	0.2049 (2)	0.3949 (2)	0.0347 (6)
Ni1	0.0000	1.0000	0.0000	0.02636 (15)
S1	0.11966 (8)	1.13766 (7)	0.12444 (5)	0.0364 (2)
S2	0.00440 (9)	0.88177 (8)	0.14071 (5)	0.0384 (2)
H1	0.189 (3)	0.175 (3)	0.348 (2)	0.031 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0344 (16)	0.0198 (16)	0.0287 (14)	−0.0032 (14)	0.0108 (12)	0.0003 (12)
C2	0.0470 (19)	0.030 (2)	0.0262 (14)	−0.0073 (16)	0.0150 (14)	0.0020 (14)
C3	0.0359 (17)	0.0241 (17)	0.0312 (14)	−0.0033 (14)	0.0166 (13)	0.0006 (13)
C4	0.0475 (19)	0.033 (2)	0.0295 (15)	−0.0052 (17)	0.0157 (14)	−0.0044 (15)
C5	0.065 (2)	0.043 (2)	0.0456 (18)	−0.0046 (19)	0.0315 (18)	0.0071 (16)
C6	0.056 (2)	0.030 (2)	0.0441 (17)	0.0013 (17)	0.0251 (16)	−0.0042 (15)
C7	0.057 (2)	0.030 (2)	0.0391 (16)	0.0067 (17)	0.0233 (15)	0.0081 (15)
C8	0.042 (2)	0.055 (3)	0.061 (2)	0.0079 (19)	0.0267 (17)	−0.0028 (19)
C9	0.0333 (17)	0.034 (2)	0.0450 (17)	0.0032 (15)	0.0125 (14)	0.0010 (15)
C10	0.049 (2)	0.032 (2)	0.0549 (19)	−0.0128 (17)	0.0175 (16)	−0.0037 (16)
N1	0.084 (2)	0.036 (2)	0.0383 (14)	−0.0203 (17)	0.0189 (14)	−0.0041 (13)
N2	0.094 (2)	0.042 (2)	0.0406 (15)	−0.0115 (18)	0.0292 (16)	0.0059 (15)
N3	0.0440 (16)	0.0391 (17)	0.0607 (17)	−0.0061 (15)	0.0286 (14)	−0.0016 (15)
N4	0.0474 (16)	0.0313 (16)	0.0359 (13)	0.0021 (14)	0.0158 (12)	−0.0007 (12)
N5	0.0460 (15)	0.0306 (17)	0.0420 (14)	0.0071 (13)	0.0228 (12)	0.0028 (12)
N6	0.0437 (16)	0.0305 (17)	0.0354 (13)	0.0040 (13)	0.0212 (12)	−0.0046 (12)
Ni1	0.0352 (3)	0.0193 (3)	0.0253 (2)	−0.0012 (3)	0.0122 (2)	−0.0014 (2)
S1	0.0552 (5)	0.0234 (4)	0.0241 (3)	−0.0058 (4)	0.0076 (3)	0.0014 (3)
S2	0.0607 (5)	0.0292 (5)	0.0253 (4)	−0.0124 (4)	0.0162 (4)	−0.0043 (3)

C1—C3i	1.354 (3)	C7—H7B	0.9700
C1—C2	1.425 (4)	C8—N5	1.463 (4)
C1—S1	1.733 (3)	C8—N3	1.477 (4)
C2—N1	1.132 (4)	C8—H8A	0.9700
C3—C1i	1.354 (3)	C8—H8B	0.9700
C3—C4	1.433 (4)	C9—N4	1.440 (3)
C3—S2	1.731 (3)	C9—N6	1.512 (3)
C4—N2	1.139 (4)	C9—H9A	0.9700
C5—N4	1.457 (4)	C9—H9B	0.9700
C5—N3	1.471 (4)	C10—N3	1.434 (4)
C5—H5A	0.9700	C10—N6	1.511 (4)
C5—H5B	0.9700	C10—H10A	0.9700
C6—N5	1.477 (3)	C10—H10B	0.9700
C6—N4	1.478 (4)	N6—H1	0.86 (3)
C6—H6A	0.9700	Ni1—S1i	2.1751 (7)
C6—H6B	0.9700	Ni1—S1	2.1751 (7)
C7—N5	1.429 (3)	Ni1—S2	2.1810 (7)
C7—N6	1.528 (4)	Ni1—S2i	2.1810 (7)
C7—H7A	0.9700
C3i—C1—C2	119.9 (3)	N6—C9—H9A	109.8
C3i—C1—S1	120.4 (2)	N4—C9—H9B	109.8
C2—C1—S1	119.57 (19)	N6—C9—H9B	109.8
N1—C2—C1	177.4 (4)	H9A—C9—H9B	108.3
C1i—C3—C4	120.0 (3)	N3—C10—N6	109.6 (3)
C1i—C3—S2	121.0 (2)	N3—C10—H10A	109.7
C4—C3—S2	119.06 (19)	N6—C10—H10A	109.7
N2—C4—C3	177.7 (3)	N3—C10—H10B	109.7
N4—C5—N3	112.5 (2)	N6—C10—H10B	109.7
N4—C5—H5A	109.1	H10A—C10—H10B	108.2
N3—C5—H5A	109.1	C10—N3—C5	109.3 (3)
N4—C5—H5B	109.1	C10—N3—C8	108.7 (3)
N3—C5—H5B	109.1	C5—N3—C8	107.8 (3)
H5A—C5—H5B	107.8	C9—N4—C5	109.6 (2)
N5—C6—N4	111.5 (2)	C9—N4—C6	108.6 (2)
N5—C6—H6A	109.3	C5—N4—C6	108.5 (2)
N4—C6—H6A	109.3	C7—N5—C8	109.4 (3)
N5—C6—H6B	109.3	C7—N5—C6	109.5 (2)
N4—C6—H6B	109.3	C8—N5—C6	108.2 (2)
H6A—C6—H6B	108.0	C10—N6—C9	109.8 (2)
N5—C7—N6	109.2 (2)	C10—N6—C7	108.1 (2)
N5—C7—H7A	109.8	C9—N6—C7	108.7 (2)
N6—C7—H7A	109.8	C10—N6—H1	111.8 (19)
N5—C7—H7B	109.8	C9—N6—H1	107.4 (17)
N6—C7—H7B	109.8	C7—N6—H1	111 (2)
H7A—C7—H7B	108.3	S1i—Ni1—S1	180.0
N5—C8—N3	112.1 (2)	S1i—Ni1—S2	91.69 (3)
N5—C8—H8A	109.2	S1—Ni1—S2	88.31 (3)
N3—C8—H8A	109.2	S1i—Ni1—S2i	88.31 (3)
N5—C8—H8B	109.2	S1—Ni1—S2i	91.69 (3)
N3—C8—H8B	109.2	S2—Ni1—S2i	180.00 (4)
H8A—C8—H8B	107.9	C1—S1—Ni1	103.24 (9)
N4—C9—N6	109.3 (2)	C3—S2—Ni1	103.06 (9)
N4—C9—H9A	109.8

D—H···A	D—H	H···A	D···A	D—H···A
N6—H1···N1ii	0.87 (4)	2.37 (4)	2.941 (5)	124 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H1⋯N1i	0.87 (4)	2.37 (4)	2.941 (5)	124 (3)

Symmetry code: (i) .