Bis(piperidinium) bis­(1,2-dicyano­ethene-1,2-dithiol­ato-κ²S,S′)nickel(II)

The title compound, (C₅H₁₂N)₂[Ni(C₄N₂S₂)₂], is a new [Ni(mnt)₂]²⁻ salt (mnt²⁻ is 1,2-dicyano­ethene-1,2-dithiol­ate) with piperidinium [(PIH)⁺] cations. The Ni^II ion lies on an inversion centre and the asymmetric unit contains a (PIH)⁺ cation and one half of the [Ni(mnt)₂]²⁻ anion. The Ni^II ion exhibits a square-planar coordination geometry. In the crystal structure, weak C—H...N, C—H...S and C—H...Ni hydrogen bonds are observed between the anions and the cations.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.108
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         N3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         C7
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.42 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.42 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT432_ALERT_2_C Short Inter X...Y Contact  N2     ..  C7      ..       2.97 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       2.76

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Salts containing M(mnt)₂^n- anion have aroused great interest in recent years and the topology and the size of the counterions used with Ni(mnt)₂^2- anions play an important role in tuning the stacks of anions and cations (Robertson & Cronin, 2002).

The structure of (I) consists of one (PIH)⁺ cation and one-half of a Ni(mnt)₂ anion in the asymmetric unit as the Ni^II ion lies on an inversion centre. The NiS₄ core exhibits a square planar coordination geometry with Ni—S distances 2.182 (1) and 2.174 (1) Å respectively. The two N atoms of the CN groups deviate from the Ni1/S1/S2 plane by 0.392 (2) Å for N1 and 0.451 (2) Å for N2. The (PIH)⁺ cation adopts a classical chair conformation. Five types of hydrogen bonds were observed in the crystal structure of the title complex: C6—H6B···N2, C7—H7B···N2, C7—H7A···S1, C7—H7B···N1 and C6—H6A···Ni1 (Table 1 and Fig. 2). C—H···Ni interactions are unusual but not unprecedented (Yang & Ni, 2006; Yang et al., 2004; Braga et al., 1997).

Related literature

For background, see: Robertson & Cronin (2002). For a related [Ni(mnt)₂]^2- complex of square-planar geometry and displaying C—H···S and C—H···Ni hydrogen bonds, see: Yang & Ni (2006). For other instances of C—H···Ni hydrogen bonds, see: Yang et al. (2004); Braga et al. (1997).

S2. Experimental

The title compound was prepared by the direct reaction of NiCl₂.6H₂O, Na₂mnt and (PIH)⁺Cl^- in H₂O. Red block-like single crystals were obtained by slow evaporation of a CH₃CN solution at room temperature about two weeks.

S3. Refinement

H atoms bonded to the piperidine N atom were located in a difference map and refined with distance restraints of N—H = 0.90 (2) Å, and with U_iso(H) = 1.2U_eq(N). Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.97 Å, and with U_iso(H) = 1.2 times U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The hydrogen bonds between anions and cations.

Bis(piperidinium) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickel(II)

Crystal data

(C5H12N)2[Ni(C4N2S2)2]	Z = 1
Mr = 511.38	F(000) = 266
Triclinic, P1	Dx = 1.476 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5959 (9) Å	Cell parameters from 2647 reflections
b = 9.4351 (13) Å	θ = 3.0–29.8°
c = 9.5669 (13) Å	µ = 1.22 mm^−1
α = 91.477 (2)°	T = 293 K
β = 100.083 (2)°	Block, red
γ = 100.425 (2)°	0.41 × 0.36 × 0.24 mm
V = 575.49 (14) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2213 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −8→7
Tmin = 0.622, Tmax = 0.736	k = −11→10
3282 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0671P)^2 + 0.3691P] where P = (Fo^2 + 2Fc^2)/3
2213 reflections	(Δ/σ)max = 0.001
133 parameters	Δρmax = 0.63 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.0000	0.02917 (16)
S1	0.67713 (10)	0.37773 (7)	0.15080 (7)	0.03905 (19)
S2	0.24609 (10)	0.48199 (7)	0.11978 (7)	0.03761 (19)
N1	0.6624 (5)	0.2290 (3)	0.5088 (3)	0.0610 (7)
N2	0.1297 (5)	0.3650 (4)	0.4721 (3)	0.0616 (7)
N3	0.0823 (6)	−0.0310 (4)	0.7782 (5)	0.0899 (12)
H3A	0.1473	−0.0330	0.8688	0.108*
H3B	0.0572	−0.1212	0.7379	0.108*
C1	0.6037 (4)	0.2850 (3)	0.4081 (3)	0.0421 (6)
C2	0.5287 (4)	0.3541 (3)	0.2844 (3)	0.0351 (5)
C3	0.3420 (4)	0.4004 (3)	0.2707 (3)	0.0337 (5)
C4	0.2229 (4)	0.3819 (3)	0.3816 (3)	0.0406 (6)
C5	0.2229 (6)	0.0684 (4)	0.6987 (4)	0.0632 (9)
H5A	0.3568	0.0376	0.7062	0.076*
H5B	0.1593	0.0629	0.5988	0.076*
C6	0.2571 (5)	0.2211 (3)	0.7584 (3)	0.0522 (7)
H6A	0.3318	0.2282	0.8558	0.063*
H6B	0.3422	0.2840	0.7035	0.063*
C7	0.0525 (4)	0.2688 (2)	0.7541 (3)	0.0342 (5)
H7A	0.0782	0.3669	0.7951	0.041*
H7B	−0.0164	0.2688	0.6558	0.041*
C8	−0.0891 (6)	0.1742 (3)	0.8328 (4)	0.0529 (7)
H8A	−0.2225	0.2059	0.8229	0.063*
H8B	−0.0274	0.1813	0.9331	0.063*
C9	−0.1238 (6)	0.0194 (3)	0.7759 (4)	0.0585 (8)
H9A	−0.2014	0.0105	0.6791	0.070*
H9B	−0.2073	−0.0418	0.8330	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0303 (3)	0.0321 (3)	0.0261 (2)	0.00943 (17)	0.00428 (17)	0.00203 (16)
S1	0.0389 (4)	0.0475 (4)	0.0374 (4)	0.0201 (3)	0.0110 (3)	0.0122 (3)
S2	0.0332 (3)	0.0502 (4)	0.0334 (3)	0.0160 (3)	0.0073 (2)	0.0092 (3)
N1	0.0587 (16)	0.0760 (19)	0.0519 (16)	0.0217 (14)	0.0072 (13)	0.0293 (14)
N2	0.0522 (15)	0.092 (2)	0.0470 (15)	0.0183 (15)	0.0201 (13)	0.0165 (14)
N3	0.100 (3)	0.0516 (18)	0.115 (3)	0.0232 (18)	0.002 (2)	−0.0007 (18)
C1	0.0385 (14)	0.0478 (15)	0.0418 (15)	0.0110 (11)	0.0078 (11)	0.0114 (12)
C2	0.0370 (13)	0.0361 (12)	0.0326 (12)	0.0084 (10)	0.0057 (10)	0.0062 (9)
C3	0.0336 (12)	0.0365 (12)	0.0302 (12)	0.0060 (10)	0.0042 (9)	0.0032 (9)
C4	0.0367 (13)	0.0500 (15)	0.0355 (14)	0.0100 (11)	0.0055 (11)	0.0064 (11)
C5	0.059 (2)	0.0600 (19)	0.071 (2)	0.0180 (16)	0.0084 (17)	−0.0130 (16)
C6	0.0488 (17)	0.0530 (17)	0.0501 (17)	0.0038 (13)	0.0030 (13)	−0.0016 (13)
C7	0.0465 (14)	0.0247 (11)	0.0308 (12)	0.0076 (10)	0.0049 (10)	0.0020 (8)
C8	0.064 (2)	0.0479 (16)	0.0532 (17)	0.0147 (14)	0.0234 (15)	0.0085 (13)
C9	0.063 (2)	0.0414 (15)	0.068 (2)	0.0025 (14)	0.0093 (16)	0.0082 (14)

Geometric parameters (Å, º)

Ni1—S2^i	2.1739 (7)	C5—C6	1.500 (4)
Ni1—S2	2.1739 (7)	C5—H5A	0.9700
Ni1—S1^i	2.1819 (6)	C5—H5B	0.9700
Ni1—S1	2.1819 (6)	C6—C7	1.492 (4)
S1—C2	1.737 (3)	C6—H6A	0.9700
S2—C3	1.730 (3)	C6—H6B	0.9700
N1—C1	1.151 (4)	C7—C8	1.489 (4)
N2—C4	1.145 (4)	C7—H7A	0.9700
N3—C5	1.512 (5)	C7—H7B	0.9700
N3—C9	1.517 (5)	C8—C9	1.508 (4)
N3—H3A	0.9000	C8—H8A	0.9700
N3—H3B	0.9000	C8—H8B	0.9700
C1—C2	1.422 (4)	C9—H9A	0.9700
C2—C3	1.366 (4)	C9—H9B	0.9700
C3—C4	1.422 (4)
S2^i—Ni1—S2	180.00 (4)	N3—C5—H5B	109.5
S2^i—Ni1—S1^i	92.32 (2)	H5A—C5—H5B	108.1
S2—Ni1—S1^i	87.68 (2)	C7—C6—C5	110.6 (3)
S2^i—Ni1—S1	87.68 (2)	C7—C6—H6A	109.5
S2—Ni1—S1	92.32 (2)	C5—C6—H6A	109.5
S1^i—Ni1—S1	180.00 (3)	C7—C6—H6B	109.5
C2—S1—Ni1	102.68 (9)	C5—C6—H6B	109.5
C3—S2—Ni1	102.88 (9)	H6A—C6—H6B	108.1
C5—N3—C9	110.8 (3)	C8—C7—C6	112.4 (2)
C5—N3—H3A	109.5	C8—C7—H7A	109.1
C9—N3—H3A	109.5	C6—C7—H7A	109.1
C5—N3—H3B	109.5	C8—C7—H7B	109.1
C9—N3—H3B	109.5	C6—C7—H7B	109.1
H3A—N3—H3B	108.1	H7A—C7—H7B	107.9
N1—C1—C2	179.3 (3)	C7—C8—C9	110.3 (3)
C3—C2—C1	120.4 (2)	C7—C8—H8A	109.6
C3—C2—S1	120.59 (19)	C9—C8—H8A	109.6
C1—C2—S1	119.0 (2)	C7—C8—H8B	109.6
C2—C3—C4	120.1 (2)	C9—C8—H8B	109.6
C2—C3—S2	121.05 (19)	H8A—C8—H8B	108.1
C4—C3—S2	118.9 (2)	C8—C9—N3	111.4 (3)
N2—C4—C3	178.5 (3)	C8—C9—H9A	109.3
C6—C5—N3	110.6 (3)	N3—C9—H9A	109.3
C6—C5—H5A	109.5	C8—C9—H9B	109.3
N3—C5—H5A	109.5	N3—C9—H9B	109.3
C6—C5—H5B	109.5	H9A—C9—H9B	108.0

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···N2	0.97	2.61	3.139 (4)	114
C7—H7B···N2	0.97	2.28	2.967 (4)	127
C7—H7A···S1^ii	0.97	2.63	3.501 (3)	150
C7—H7B···N1^iii	0.97	2.29	3.124 (4)	143
C6—H6A···Ni1	0.97	Missing	Missing	Missing

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