Bis[1-benzyl-4-(dimethyl­amino)­pyridinium] bis­(2,2-dicyano­ethylene-1,1-dithiol­ato-κ²S,S′)nickelate(II)

A new ion-pair complex, (C₁₄H₁₇N₂)₂[Ni(C₄N₂S₂)₂] or (BzDMAP)₂[Ni(i-mnt)₂], where BzDMAP is 1-benzyl-4-(dimethyl­amino)pyridinium and i-mnt is 2,2-dicyano­ethyl­ene-1,1-dithiol­ate, has been prepared. The [Ni(i-mnt)₂]²⁻ anion, which is located on an inversion center, exhibits a planar structure. The crystal packing is governed by short C—H...N and C—H...S contacts between anions and cations and by π–π stacking inter­actions between the phenyl groups of the cations (the centroid–centroid distance is 3.802 Å; symmetry code: −x + 2, −y + 2, −z).

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.037
• wR factor = 0.128
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   S1      ..       6.88 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   S2      ..       7.26 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C11
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C3     ...       1.42 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C4     ...       1.43 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  N2     ..  C12     ..       3.03 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.19

   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

   1 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
   0 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

---

S1. Comment

As shown in Fig.1 the asymmetric unit of the title compound consists of one [BzDMAP]⁺ cation and one-half of Ni(i-mnt)₂ anion located on an inversion center. The nickel(II) ion is coordinated by four S atoms from two i-mnt ligands and the complex anion Ni(i-mnt)₂ is in square planar configuration. The [BzDMAP]⁺ cation adopts a conformation where both the phenyl ring and the pyridine rings are twisted with respect to the C10\C11\N3 reference plane with the dihedral angles of 86.4 (3) and 89.7 (3)°, respectively.

Molecules are linked by C—H···N and C—H···S hydrogen bonds between anions and cations and π···π stacking interaction between cations (Fig. 2).

Related literature

For the i-mnt complex of square-planar geometry with substituted pyridinium as counter-ion, see: Liu et al. (2006).

S2. Experimental

The title compound was prepared by the direct reaction of NiCl₂.6H₂O, K₂(i-mnt)and (BzDMAP)Br in methanol. The brown block single crystals were obtained by slow evaporation of a CH₃CN solution at room temperature for about two weeks.

S3. Refinement

All H atoms were placed in geometrically calculated positions (C—H = 0.93–0.97 Å) and refined as riding on their parent atoms with U_iso = 1.2 U_eq(C)

Computing details

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

Figures

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound viewed down the c axis. Hydrogen atoms have been omitted for clarity.

Bis[1-benzyl-4-(dimethylamino)pyridinium] bis(2,2-dicyanoethylene-1,1-dithiolato-κ²S,S')nickelate(II)

Crystal data

(C14H17N2)2[Ni(C4N2S2)2]	Z = 1
Mr = 765.66	F(000) = 398
Triclinic, P1	Dx = 1.377 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0456 (12) Å	Cell parameters from 2430 reflections
b = 9.6829 (15) Å	θ = 2.3–26.9°
c = 13.202 (2) Å	µ = 0.79 mm^−1
α = 76.134 (2)°	T = 291 K
β = 78.312 (2)°	Block, brown
γ = 68.834 (2)°	0.38 × 0.22 × 0.20 mm
V = 923.5 (2) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	3180 independent reflections
Radiation source: fine-focus sealed tube	2431 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −5→9
Tmin = 0.798, Tmax = 0.858	k = −11→11
4642 measured reflections	l = −14→15

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.08P)^2] where P = (Fo^2 + 2Fc^2)/3
3180 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.0000	0.5000	0.0519 (2)
S1	0.37050 (10)	0.05129 (8)	0.35743 (6)	0.0583 (2)
S2	0.63405 (10)	0.15279 (9)	0.39411 (6)	0.0613 (2)
N1	0.2591 (4)	0.2793 (3)	0.0912 (2)	0.0764 (8)
N2	0.6676 (5)	0.4409 (4)	0.1454 (2)	0.0951 (10)
N3	0.8270 (3)	0.6225 (3)	0.25242 (19)	0.0604 (6)
N4	0.8293 (3)	0.3522 (3)	0.5458 (2)	0.0673 (7)
C1	0.4950 (3)	0.1708 (3)	0.3041 (2)	0.0499 (6)
C2	0.4823 (4)	0.2637 (3)	0.2104 (2)	0.0525 (7)
C3	0.3600 (4)	0.2714 (3)	0.1435 (2)	0.0566 (7)
C4	0.5878 (4)	0.3613 (3)	0.1738 (2)	0.0634 (8)
C5	1.1483 (5)	0.7158 (4)	0.0913 (2)	0.0750 (9)
H5	1.1762	0.6217	0.0739	0.090*
C6	1.2810 (5)	0.7788 (5)	0.0786 (3)	0.0907 (11)
H6	1.3980	0.7271	0.0527	0.109*
C7	1.2422 (6)	0.9167 (5)	0.1037 (3)	0.0901 (11)
H7	1.3328	0.9582	0.0958	0.108*
C8	1.0716 (6)	0.9932 (4)	0.1402 (3)	0.0893 (11)
H8	1.0448	1.0881	0.1560	0.107*
C9	0.9375 (5)	0.9307 (4)	0.1541 (3)	0.0746 (9)
H9	0.8210	0.9831	0.1802	0.089*
C10	0.9749 (4)	0.7903 (3)	0.1295 (2)	0.0611 (7)
C11	0.8306 (5)	0.7209 (4)	0.1471 (2)	0.0785 (10)
H11A	0.7151	0.7998	0.1416	0.094*
H11B	0.8514	0.6619	0.0931	0.094*
C12	0.9269 (4)	0.4776 (4)	0.2663 (2)	0.0625 (8)
H12	0.9952	0.4379	0.2077	0.075*
C13	0.9340 (4)	0.3853 (3)	0.3610 (2)	0.0616 (7)
H13	1.0074	0.2851	0.3666	0.074*
C14	0.8300 (4)	0.4407 (3)	0.4516 (2)	0.0564 (7)
C15	0.7280 (4)	0.5943 (4)	0.4341 (2)	0.0678 (8)
H15	0.6574	0.6383	0.4905	0.081*
C16	0.7305 (4)	0.6790 (4)	0.3371 (3)	0.0709 (8)
H16	0.6625	0.7807	0.3286	0.085*
C17	0.7161 (5)	0.4124 (5)	0.6370 (3)	0.0962 (12)
H17A	0.7433	0.4977	0.6448	0.144*
H17B	0.7385	0.3362	0.6991	0.144*
H17C	0.5920	0.4428	0.6273	0.144*
C18	0.9379 (5)	0.1947 (4)	0.5619 (3)	0.0876 (10)
H18A	0.9062	0.1439	0.5184	0.131*
H18B	0.9170	0.1500	0.6344	0.131*
H18C	1.0626	0.1857	0.5435	0.131*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0539 (3)	0.0459 (3)	0.0456 (3)	−0.0108 (2)	−0.0076 (2)	0.0030 (2)
S1	0.0626 (5)	0.0545 (4)	0.0535 (5)	−0.0221 (4)	−0.0120 (3)	0.0065 (3)
S2	0.0632 (5)	0.0658 (5)	0.0522 (5)	−0.0248 (4)	−0.0151 (3)	0.0064 (3)
N1	0.089 (2)	0.090 (2)	0.0581 (17)	−0.0432 (17)	−0.0213 (15)	0.0035 (14)
N2	0.132 (3)	0.105 (2)	0.072 (2)	−0.080 (2)	−0.0298 (18)	0.0162 (17)
N3	0.0685 (15)	0.0629 (16)	0.0529 (15)	−0.0263 (13)	−0.0175 (11)	−0.0009 (12)
N4	0.0744 (17)	0.0784 (18)	0.0507 (15)	−0.0310 (15)	−0.0118 (12)	−0.0019 (13)
C1	0.0479 (15)	0.0435 (14)	0.0522 (16)	−0.0072 (12)	−0.0036 (11)	−0.0120 (13)
C2	0.0577 (16)	0.0528 (16)	0.0461 (16)	−0.0195 (13)	−0.0048 (12)	−0.0065 (13)
C3	0.0696 (19)	0.0539 (17)	0.0424 (16)	−0.0255 (15)	−0.0019 (14)	0.0022 (13)
C4	0.081 (2)	0.0644 (19)	0.0468 (17)	−0.0340 (18)	−0.0112 (14)	0.0042 (14)
C5	0.102 (3)	0.0560 (18)	0.0533 (19)	−0.0225 (19)	0.0051 (17)	−0.0027 (15)
C6	0.086 (3)	0.093 (3)	0.061 (2)	−0.018 (2)	0.0101 (18)	0.010 (2)
C7	0.101 (3)	0.096 (3)	0.074 (3)	−0.051 (3)	−0.011 (2)	0.011 (2)
C8	0.123 (3)	0.072 (2)	0.079 (3)	−0.044 (2)	−0.015 (2)	−0.007 (2)
C9	0.079 (2)	0.061 (2)	0.067 (2)	−0.0103 (17)	−0.0073 (16)	−0.0047 (16)
C10	0.079 (2)	0.0591 (18)	0.0398 (15)	−0.0207 (16)	−0.0159 (13)	0.0036 (13)
C11	0.099 (3)	0.085 (2)	0.058 (2)	−0.037 (2)	−0.0327 (17)	0.0049 (17)
C12	0.0691 (19)	0.0636 (19)	0.0571 (19)	−0.0233 (16)	−0.0019 (14)	−0.0182 (15)
C13	0.0631 (18)	0.0534 (17)	0.0622 (19)	−0.0143 (14)	−0.0066 (14)	−0.0082 (15)
C14	0.0563 (16)	0.0635 (18)	0.0546 (18)	−0.0243 (14)	−0.0109 (13)	−0.0099 (14)
C15	0.071 (2)	0.066 (2)	0.059 (2)	−0.0138 (16)	−0.0022 (15)	−0.0158 (16)
C16	0.071 (2)	0.0573 (19)	0.075 (2)	−0.0087 (16)	−0.0132 (16)	−0.0118 (17)
C17	0.108 (3)	0.132 (4)	0.051 (2)	−0.050 (3)	−0.0025 (19)	−0.012 (2)
C18	0.106 (3)	0.075 (2)	0.078 (2)	−0.033 (2)	−0.030 (2)	0.0153 (19)

Geometric parameters (Å, º)

Ni1—S1^i	2.2019 (8)	C7—H7	0.9300
Ni1—S1	2.2019 (8)	C8—C9	1.379 (5)
Ni1—S2^i	2.2037 (8)	C8—H8	0.9300
Ni1—S2	2.2037 (8)	C9—C10	1.385 (4)
S1—C1	1.732 (3)	C9—H9	0.9300
S2—C1	1.730 (3)	C10—C11	1.495 (4)
N1—C3	1.140 (4)	C11—H11A	0.9700
N2—C4	1.126 (4)	C11—H11B	0.9700
N3—C12	1.330 (4)	C12—C13	1.350 (4)
N3—C16	1.337 (4)	C12—H12	0.9300
N3—C11	1.487 (4)	C13—C14	1.413 (4)
N4—C14	1.331 (4)	C13—H13	0.9300
N4—C18	1.446 (4)	C14—C15	1.404 (4)
N4—C17	1.459 (4)	C15—C16	1.346 (4)
C1—C2	1.342 (4)	C15—H15	0.9300
C2—C3	1.421 (4)	C16—H16	0.9300
C2—C4	1.429 (4)	C17—H17A	0.9600
C5—C10	1.372 (4)	C17—H17B	0.9600
C5—C6	1.375 (5)	C17—H17C	0.9600
C5—H5	0.9300	C18—H18A	0.9600
C6—C7	1.364 (5)	C18—H18B	0.9600
C6—H6	0.9300	C18—H18C	0.9600
C7—C8	1.354 (5)
S1^i—Ni1—S1	180.0	C5—C10—C9	118.3 (3)
S1^i—Ni1—S2^i	78.96 (3)	C5—C10—C11	121.2 (3)
S1—Ni1—S2^i	101.04 (3)	C9—C10—C11	120.5 (3)
S1^i—Ni1—S2	101.04 (3)	N3—C11—C10	111.0 (2)
S1—Ni1—S2	78.96 (3)	N3—C11—H11A	109.4
S2^i—Ni1—S2	180.00 (3)	C10—C11—H11A	109.4
C1—S1—Ni1	86.41 (10)	N3—C11—H11B	109.4
C1—S2—Ni1	86.40 (10)	C10—C11—H11B	109.4
C12—N3—C16	118.0 (3)	H11A—C11—H11B	108.0
C12—N3—C11	121.1 (3)	N3—C12—C13	123.3 (3)
C16—N3—C11	120.8 (3)	N3—C12—H12	118.3
C14—N4—C18	122.0 (3)	C13—C12—H12	118.3
C14—N4—C17	120.3 (3)	C12—C13—C14	120.1 (3)
C18—N4—C17	117.7 (3)	C12—C13—H13	120.0
C2—C1—S2	126.1 (2)	C14—C13—H13	120.0
C2—C1—S1	125.8 (2)	N4—C14—C15	123.2 (3)
S2—C1—S1	108.02 (16)	N4—C14—C13	121.9 (3)
C1—C2—C3	121.3 (3)	C15—C14—C13	115.0 (3)
C1—C2—C4	121.9 (3)	C16—C15—C14	121.1 (3)
C3—C2—C4	116.8 (3)	C16—C15—H15	119.4
N1—C3—C2	178.6 (3)	C14—C15—H15	119.4
N2—C4—C2	178.4 (4)	N3—C16—C15	122.5 (3)
C10—C5—C6	120.6 (3)	N3—C16—H16	118.7
C10—C5—H5	119.7	C15—C16—H16	118.7
C6—C5—H5	119.7	N4—C17—H17A	109.5
C7—C6—C5	120.4 (4)	N4—C17—H17B	109.5
C7—C6—H6	119.8	H17A—C17—H17B	109.5
C5—C6—H6	119.8	N4—C17—H17C	109.5
C8—C7—C6	120.0 (4)	H17A—C17—H17C	109.5
C8—C7—H7	120.0	H17B—C17—H17C	109.5
C6—C7—H7	120.0	N4—C18—H18A	109.5
C7—C8—C9	120.2 (4)	N4—C18—H18B	109.5
C7—C8—H8	119.9	H18A—C18—H18B	109.5
C9—C8—H8	119.9	N4—C18—H18C	109.5
C8—C9—C10	120.5 (3)	H18A—C18—H18C	109.5
C8—C9—H9	119.7	H18B—C18—H18C	109.5
C10—C9—H9	119.7

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···N1^ii	0.97	2.62	3.368 (4)	134
C12—H12···N1^iii	0.93	2.59	3.477 (4)	161
C16—H16···S1^iv	0.93	2.86	3.750 (4)	160

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