Bis(2-amino-1-benzyl­pyridinium) bis­(2,2-dicyano­ethene-1,1-dithiol­ato-κ²S,S′)­nickelate(II)

A new [Ni(imnt)₂]²⁻ salt (imnt²⁻ is 2,2-dicyano­ethene-1,1-dithiol­ate) with a 1-benzyl-2-amino­pyridinium [(Bz2NH₂py)⁺] cation, (C₁₂H₁₃N₂)₂[Ni(C₄N₂S₂)₂], was obtained by the direct reaction of NiCl₂·6H₂O, K₂imnt and (Bz2NH₂py)⁺·Br⁻ in water. The Ni^II ion lies on an inversion centre and the asymmetric unit contains a (Bz2NH₂py)⁺ cation and one-half of the Ni(imnt)₂²⁻ anion. The Ni^II ion adopts a square-planar coordination geometry. In the crystal structure, N—H...N and C—H...N hydrogen bonds are observed between the anions and the cations.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.045
• wR factor = 0.151
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C2      ..       5.17 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   S1      ..       6.06 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.08
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C3     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C4     ...       1.43 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4B    ...          ?

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.13

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

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

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S1. Comment

Transition metal complexes with 2,2-dicyanoethene-1,1-dithiolate have received much attention in molecular materials research (Liu et al., 1998). In these complexes, the topology and the size of the counterions used with Ni(imnt)₂^2- anions play an important role in tuning the stacks of anions and cations (Liu et al., 1996; Liu et al., 2006; Feng et al., 2007).

The structure of (I) consists of one (Bz2NH₂py)⁺ cation and one-half of a Ni(imnt)₂ anion in the asymmetric unit as the Ni^II ion lies on an inversion centre. The [Bz2NH₂py]⁺ cation adopts a conformation in which both the phenyl ring and pyridine ring are twisted with respect to the C10/C11/N3 plane with dihedral angles of 47.3 (2)° for the phenyl ring, 80.0 (3)° for the pyridine ring, respectively. The phenyl ring and the pyridine ring make a dihedral angle of 102.4 (3)° to one another.The N4 atom deviates from pyridine plane by 0.012 (2) Å. The NiS₄ core exhibits a square planar coordination geometry with Ni—S distances 2.2172 (12) and 2.2071 (12) Å respectively, and the S1—Ni1—S2 bond angle within the four-membered ring is 79.16 (4)°. The two N atoms of the CN groups deviate from the Ni1/S1/S2/C1 plane by -0.068 (2) Å for N1 and 0.008 (2) Å for N2.

Four different hydrogen bonds were observed in the crystal structure of (I): C4—H4A···N2, C11—H11B···N2 and C13—H13···N1 (Table 1 and Fig.2).

Related literature

For the use of Ni(imnt)₂^2- complexes in molecular materials research, see: Liu et al. (1998). For related Ni(imnt)₂^2- complexes with square-planar geometry displaying C—H···N hydrogen bonds, see: Liu et al. (1996, 2006); Feng et al. (2007).

S2. Experimental

The title compound was prepared by the direct reaction of NiCl₂.6H₂O, K₂imnt and (Bz2NH₂py)⁺Br^- in H₂O. Red block-like single crystals were obtained by slow evaporation of a CH₃CN solution at room temperature over about two weeks.

S3. Refinement

H atoms bonded to the amine N atom were located in a difference map and refined with distance restraints of N—H = 0.86 (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 = 0.93–0.97 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. Hydrogen atoms have been omitted and labelled atoms are related to unlabelled atoms by the symmetry operation -x, -y,-z + 2.
	Fig. 2. The crystal packing of (I) showing the hydrogen bonds (dashed lines) between the cations and anions.

Bis(2-amino-1-benzylpyridinium) bis(2,2-dicyanoethene-1,1-dithiolato- κ²S,S')nickelate(II)

Crystal data

(C12H13N2)2[Ni(C4N2S2)2]	F(000) = 1464
Mr = 709.56	Dx = 1.405 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3342 reflections
a = 20.247 (5) Å	θ = 2.4–27.2°
b = 10.764 (3) Å	µ = 0.86 mm^−1
c = 15.973 (4) Å	T = 291 K
β = 105.462 (3)°	Block, brown
V = 3355.3 (15) Å^3	0.34 × 0.26 × 0.21 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	2951 independent reflections
Radiation source: fine-focus sealed tube	1915 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −22→24
Tmin = 0.758, Tmax = 0.840	k = −12→12
7805 measured reflections	l = −19→19

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.086P)^2 + 1.2P] where P = (Fo^2 + 2Fc^2)/3
2951 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.0000	1.0000	0.0462 (2)
S1	0.01956 (5)	0.09604 (10)	0.88616 (6)	0.0525 (3)
S2	0.11309 (5)	0.00334 (9)	1.03689 (6)	0.0513 (3)
N1	0.1351 (2)	0.2227 (4)	0.7590 (3)	0.0906 (14)
N2	0.2833 (2)	0.0855 (4)	0.9958 (3)	0.0938 (14)
N3	0.03295 (17)	0.3881 (3)	0.42297 (19)	0.0486 (8)
N4	0.0768 (2)	0.5702 (4)	0.3819 (3)	0.0825 (12)
H4A	0.1177	0.5429	0.4039	0.099*
H4B	0.0706	0.6422	0.3578	0.099*
C1	0.10582 (19)	0.0789 (3)	0.9387 (2)	0.0467 (9)
C2	0.1580 (2)	0.1163 (4)	0.9074 (3)	0.0519 (10)
C3	0.1461 (2)	0.1762 (4)	0.8249 (3)	0.0623 (11)
C4	0.2278 (2)	0.0997 (4)	0.9569 (3)	0.0630 (12)
C5	0.1997 (2)	0.3066 (5)	0.3907 (3)	0.0756 (13)
H5	0.2252	0.3626	0.4309	0.091*
C6	0.2293 (3)	0.2487 (5)	0.3325 (4)	0.0922 (17)
H6	0.2749	0.2646	0.3346	0.111*
C7	0.1924 (3)	0.1688 (5)	0.2723 (3)	0.0878 (16)
H7	0.2124	0.1317	0.2325	0.105*
C8	0.1259 (3)	0.1428 (5)	0.2702 (3)	0.0771 (14)
H8	0.1007	0.0876	0.2292	0.092*
C9	0.0963 (2)	0.1980 (4)	0.3284 (3)	0.0623 (11)
H9	0.0512	0.1790	0.3270	0.075*
C10	0.1327 (2)	0.2820 (4)	0.3895 (2)	0.0543 (10)
C11	0.1030 (2)	0.3355 (4)	0.4583 (2)	0.0593 (11)
H11A	0.1011	0.2709	0.5000	0.071*
H11B	0.1331	0.4004	0.4889	0.071*
C12	0.0231 (2)	0.5009 (4)	0.3852 (2)	0.0547 (10)
C13	−0.0437 (3)	0.5437 (5)	0.3506 (3)	0.0735 (13)
H13	−0.0510	0.6219	0.3250	0.088*
C14	−0.0978 (3)	0.4719 (6)	0.3541 (3)	0.0826 (16)
H14	−0.1423	0.4995	0.3296	0.099*
C15	−0.0864 (3)	0.3576 (6)	0.3943 (4)	0.0835 (16)
H15	−0.1231	0.3080	0.3982	0.100*
C16	−0.0217 (3)	0.3186 (4)	0.4277 (3)	0.0712 (13)
H16	−0.0142	0.2415	0.4549	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0352 (4)	0.0506 (5)	0.0526 (4)	0.0029 (3)	0.0115 (3)	−0.0090 (3)
S1	0.0367 (5)	0.0617 (7)	0.0573 (6)	0.0055 (5)	0.0093 (4)	−0.0032 (5)
S2	0.0376 (5)	0.0602 (7)	0.0537 (6)	0.0044 (5)	0.0080 (4)	−0.0037 (5)
N1	0.073 (3)	0.104 (3)	0.103 (3)	0.020 (2)	0.038 (3)	0.037 (3)
N2	0.043 (2)	0.092 (3)	0.144 (4)	0.008 (2)	0.018 (3)	0.032 (3)
N3	0.053 (2)	0.0446 (19)	0.0499 (17)	0.0025 (15)	0.0167 (15)	0.0033 (14)
N4	0.070 (3)	0.066 (3)	0.102 (3)	−0.018 (2)	0.007 (2)	0.021 (2)
C1	0.041 (2)	0.038 (2)	0.055 (2)	0.0149 (17)	0.0029 (17)	−0.0129 (17)
C2	0.043 (2)	0.049 (2)	0.063 (2)	0.0108 (18)	0.0128 (19)	0.0061 (19)
C3	0.047 (3)	0.056 (3)	0.089 (3)	0.012 (2)	0.029 (2)	0.010 (3)
C4	0.038 (2)	0.059 (3)	0.095 (3)	0.007 (2)	0.022 (2)	0.015 (2)
C5	0.061 (3)	0.086 (4)	0.080 (3)	−0.005 (3)	0.019 (3)	−0.018 (3)
C6	0.065 (3)	0.118 (5)	0.102 (4)	0.009 (3)	0.036 (3)	−0.009 (4)
C7	0.094 (4)	0.102 (4)	0.073 (3)	0.023 (3)	0.034 (3)	−0.017 (3)
C8	0.096 (4)	0.072 (3)	0.065 (3)	−0.001 (3)	0.024 (3)	−0.011 (2)
C9	0.066 (3)	0.058 (3)	0.066 (3)	−0.001 (2)	0.022 (2)	0.003 (2)
C10	0.059 (3)	0.050 (2)	0.053 (2)	0.008 (2)	0.013 (2)	0.0070 (19)
C11	0.066 (3)	0.056 (3)	0.055 (2)	0.014 (2)	0.013 (2)	0.011 (2)
C12	0.061 (3)	0.050 (2)	0.049 (2)	−0.004 (2)	0.0066 (19)	0.002 (2)
C13	0.067 (3)	0.067 (3)	0.073 (3)	0.009 (3)	−0.005 (3)	0.002 (2)
C14	0.053 (3)	0.105 (5)	0.078 (3)	0.012 (3)	−0.002 (3)	−0.031 (3)
C15	0.061 (3)	0.099 (4)	0.100 (4)	−0.023 (3)	0.037 (3)	−0.033 (3)
C16	0.084 (4)	0.056 (3)	0.088 (3)	−0.011 (3)	0.048 (3)	−0.002 (2)

Geometric parameters (Å, º)

Ni1—S2	2.2074 (11)	C6—C7	1.356 (7)
Ni1—S2^i	2.2074 (11)	C6—H6	0.9300
Ni1—S1	2.2173 (11)	C7—C8	1.368 (7)
Ni1—S1^i	2.2173 (11)	C7—H7	0.9300
S1—C1	1.734 (4)	C8—C9	1.368 (6)
S2—C1	1.738 (4)	C8—H8	0.9300
N1—C3	1.133 (5)	C9—C10	1.389 (6)
N2—C4	1.140 (5)	C9—H9	0.9300
N3—C12	1.347 (5)	C10—C11	1.502 (6)
N3—C16	1.356 (5)	C11—H11A	0.9700
N3—C11	1.491 (5)	C11—H11B	0.9700
N4—C12	1.331 (5)	C12—C13	1.396 (6)
N4—H4A	0.8600	C13—C14	1.354 (7)
N4—H4B	0.8600	C13—H13	0.9300
C1—C2	1.345 (6)	C14—C15	1.379 (7)
C2—C3	1.428 (6)	C14—H14	0.9300
C2—C4	1.436 (5)	C15—C16	1.342 (7)
C5—C10	1.377 (6)	C15—H15	0.9300
C5—C6	1.382 (7)	C16—H16	0.9300
C5—H5	0.9300
S2—Ni1—S2^i	180.000 (13)	C9—C8—C7	120.0 (5)
S2—Ni1—S1	79.16 (4)	C9—C8—H8	120.0
S2^i—Ni1—S1	100.84 (4)	C7—C8—H8	120.0
S2—Ni1—S1^i	100.84 (4)	C8—C9—C10	120.9 (4)
S2^i—Ni1—S1^i	79.16 (4)	C8—C9—H9	119.5
S1—Ni1—S1^i	180.0	C10—C9—H9	119.5
C1—S1—Ni1	86.03 (14)	C5—C10—C9	118.1 (4)
C1—S2—Ni1	86.24 (13)	C5—C10—C11	120.1 (4)
C12—N3—C16	119.8 (4)	C9—C10—C11	121.5 (4)
C12—N3—C11	121.6 (4)	N3—C11—C10	113.3 (3)
C16—N3—C11	118.5 (4)	N3—C11—H11A	108.9
C12—N4—H4A	120.0	C10—C11—H11A	108.9
C12—N4—H4B	120.0	N3—C11—H11B	108.9
H4A—N4—H4B	120.0	C10—C11—H11B	108.9
C2—C1—S1	125.3 (3)	H11A—C11—H11B	107.7
C2—C1—S2	126.1 (3)	N4—C12—N3	119.9 (4)
S1—C1—S2	108.6 (2)	N4—C12—C13	121.0 (4)
C1—C2—C3	121.4 (4)	N3—C12—C13	119.2 (4)
C1—C2—C4	120.9 (4)	C14—C13—C12	120.3 (5)
C3—C2—C4	117.7 (4)	C14—C13—H13	119.9
N1—C3—C2	178.4 (5)	C12—C13—H13	119.9
N2—C4—C2	179.3 (6)	C13—C14—C15	119.5 (5)
C10—C5—C6	120.4 (5)	C13—C14—H14	120.3
C10—C5—H5	119.8	C15—C14—H14	120.3
C6—C5—H5	119.8	C16—C15—C14	119.3 (5)
C7—C6—C5	120.5 (5)	C16—C15—H15	120.4
C7—C6—H6	119.8	C14—C15—H15	120.4
C5—C6—H6	119.8	C15—C16—N3	122.0 (5)
C6—C7—C8	120.0 (5)	C15—C16—H16	119.0
C6—C7—H7	120.0	N3—C16—H16	119.0
C8—C7—H7	120.0

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2^ii	0.86	2.25	2.986 (6)	143
C11—H11B···N2^ii	0.97	2.58	3.490 (6)	156
C13—H13···N1^iii	0.93	2.51	3.329 (7)	148

Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x, −y+1, −z+1.