Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031157/rz2152sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031157/rz2152Isup2.hkl |
CCDC reference: 657513
The title compound was prepared by the direct reaction of NiCl2.6H2O (1 mmol, 0.24 g), Na2mnt (2 mmol, 0.37 g) and 4-dimethylaminopyridinium chloride (2 mmol, 0.32 g) in water (60 ml). Red block-shaped single crystals were obtained by slow evaporation of a CH3CN solution at room temperature for about two weeks.
The pyridinium H atom was located in a difference Fourier map and refined freely. All other H atoms were placed in geometrically calculated positions with C—H = 0.93–0.96 Å, and refined using the riding atom approximation, with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for the methyl groups.
The syntheses, crystal structures and properties of maleonitriledithiolate (mnt2-) transition metal complexes have received much attention in many areas such as non-linear optics and magnetic and conducting materials [Robertson & Cronin, 2002]. The introduction of some organic cations was recognized to be a powerful strategy to tune the stacking pattern of the Ni(mnt)2 dianion in order to obtain molecular materials with unusual magnetic properties.
The asymmetric unit of the title compound consists of one DMAPH+ cation (DMAPH is 4-dimethylaminopyridinium) and one half-anion of formula Ni(mnt)22- (mnt is 1,2-dicyanoethylene-1,2-dithiolate or maleonitriledithiolate). The nickel(II) metal, which lies on a crystallographic centre of symmetry, is coordinated by four S atoms from two mnt ligands in a square planar geometry (Fig. 1). The five-membered chelating ring is essentially planar (maximum displacement 0.019 (2) Å for atom C2). The conformations of anion and cation are similar to those observed in the corresponding copper(II) complex (Zhou & Ren, 2006). The Ni(mnt)2 anions (A) and DMAPH+ cations (C) are stacked in a ACCA arrangement to form one-dimensional columns along the a axis, with a centroid···centroid separation between the pyridine rings of 4.032 (4) Å. The columns are linked by intermolecular N—H···N hydrogen bonds (Table 1) resulting in a two-dimensional network (Fig. 2).
For general background, see: Robertson & Cronin (2002). For a related structure, see: (Zhou & Ren, 2006).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(C7H11N2)2[Ni(C4N2S2)2] | F(000) = 604 |
Mr = 585.43 | Dx = 1.523 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4341 reflections |
a = 14.1631 (12) Å | θ = 2.7–29.3° |
b = 6.5833 (6) Å | µ = 1.12 mm−1 |
c = 15.0751 (13) Å | T = 291 K |
β = 114.771 (1)° | Block, red |
V = 1276.27 (19) Å3 | 0.46 × 0.40 × 0.15 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 3075 independent reflections |
Radiation source: fine-focus sealed tube | 2744 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
φ and ω scans | θmax = 28.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −10→18 |
Tmin = 0.628, Tmax = 0.851 | k = −8→8 |
8238 measured reflections | l = −19→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.1627P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3075 reflections | Δρmax = 0.37 e Å−3 |
167 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0060 (8) |
(C7H11N2)2[Ni(C4N2S2)2] | V = 1276.27 (19) Å3 |
Mr = 585.43 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.1631 (12) Å | µ = 1.12 mm−1 |
b = 6.5833 (6) Å | T = 291 K |
c = 15.0751 (13) Å | 0.46 × 0.40 × 0.15 mm |
β = 114.771 (1)° |
Bruker SMART APEX CCD diffractometer | 3075 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2744 reflections with I > 2σ(I) |
Tmin = 0.628, Tmax = 0.851 | Rint = 0.015 |
8238 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.37 e Å−3 |
3075 reflections | Δρmin = −0.24 e Å−3 |
167 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.03144 (10) | |
S1 | 0.09496 (3) | 0.27334 (6) | 0.03137 (3) | 0.04174 (12) | |
S2 | 0.11660 (3) | −0.16103 (6) | 0.12276 (3) | 0.04267 (12) | |
C1 | 0.20511 (11) | 0.2056 (2) | 0.13333 (11) | 0.0355 (3) | |
C2 | 0.21416 (12) | 0.0182 (2) | 0.17392 (11) | 0.0360 (3) | |
C3 | 0.30409 (13) | −0.0369 (2) | 0.25921 (12) | 0.0423 (4) | |
C4 | 0.28715 (12) | 0.3503 (2) | 0.17446 (12) | 0.0418 (3) | |
N1 | 0.35347 (13) | 0.4638 (2) | 0.20822 (13) | 0.0602 (4) | |
N2 | 0.37520 (13) | −0.0796 (3) | 0.32811 (12) | 0.0621 (4) | |
C5 | 0.57111 (14) | 0.1127 (3) | −0.10347 (14) | 0.0569 (5) | |
H5 | 0.5327 | 0.1986 | −0.1550 | 0.068* | |
C6 | 0.66305 (13) | 0.1782 (3) | −0.03421 (13) | 0.0484 (4) | |
H6 | 0.6866 | 0.3081 | −0.0385 | 0.058* | |
C7 | 0.72351 (12) | 0.0507 (2) | 0.04465 (11) | 0.0382 (3) | |
C8 | 0.68034 (14) | −0.1433 (3) | 0.04575 (14) | 0.0486 (4) | |
H8 | 0.7159 | −0.2338 | 0.0961 | 0.058* | |
C9 | 0.58738 (15) | −0.1975 (3) | −0.02630 (16) | 0.0572 (5) | |
H9 | 0.5602 | −0.3252 | −0.0244 | 0.069* | |
C10 | 0.88001 (16) | −0.0288 (3) | 0.18988 (14) | 0.0552 (5) | |
H10A | 0.8451 | −0.0643 | 0.2302 | 0.083* | |
H10B | 0.9447 | 0.0368 | 0.2290 | 0.083* | |
H10C | 0.8932 | −0.1495 | 0.1612 | 0.083* | |
C11 | 0.85807 (15) | 0.3081 (3) | 0.11201 (15) | 0.0578 (5) | |
H11A | 0.8942 | 0.3057 | 0.0705 | 0.087* | |
H11B | 0.9056 | 0.3447 | 0.1771 | 0.087* | |
H11C | 0.8028 | 0.4060 | 0.0876 | 0.087* | |
H4 | 0.472 (2) | −0.107 (4) | −0.1457 (19) | 0.094 (9)* | |
N3 | 0.81502 (10) | 0.1083 (2) | 0.11314 (10) | 0.0425 (3) | |
N4 | 0.53422 (12) | −0.0721 (3) | −0.09962 (13) | 0.0596 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02752 (15) | 0.03259 (15) | 0.03065 (15) | −0.00072 (9) | 0.00868 (11) | 0.00233 (9) |
S1 | 0.0343 (2) | 0.0353 (2) | 0.0432 (2) | −0.00337 (14) | 0.00413 (16) | 0.00727 (15) |
S2 | 0.0382 (2) | 0.0373 (2) | 0.0404 (2) | −0.00338 (15) | 0.00455 (16) | 0.00841 (15) |
C1 | 0.0302 (7) | 0.0374 (7) | 0.0356 (7) | 0.0001 (6) | 0.0104 (6) | −0.0025 (6) |
C2 | 0.0303 (7) | 0.0400 (8) | 0.0336 (7) | 0.0018 (5) | 0.0093 (6) | −0.0005 (5) |
C3 | 0.0384 (8) | 0.0399 (7) | 0.0416 (9) | 0.0033 (6) | 0.0099 (7) | −0.0001 (6) |
C4 | 0.0357 (8) | 0.0403 (8) | 0.0417 (8) | 0.0008 (6) | 0.0085 (6) | 0.0020 (6) |
N1 | 0.0455 (9) | 0.0502 (8) | 0.0626 (10) | −0.0107 (7) | 0.0007 (7) | 0.0012 (7) |
N2 | 0.0491 (9) | 0.0626 (10) | 0.0536 (9) | 0.0113 (8) | 0.0008 (7) | 0.0056 (8) |
C5 | 0.0447 (9) | 0.0711 (13) | 0.0450 (9) | 0.0119 (9) | 0.0092 (8) | 0.0012 (8) |
C6 | 0.0460 (9) | 0.0480 (9) | 0.0476 (9) | 0.0029 (7) | 0.0162 (7) | 0.0034 (7) |
C7 | 0.0358 (8) | 0.0428 (7) | 0.0380 (8) | −0.0001 (6) | 0.0174 (6) | −0.0031 (6) |
C8 | 0.0459 (9) | 0.0437 (8) | 0.0549 (10) | −0.0032 (7) | 0.0198 (8) | −0.0002 (7) |
C9 | 0.0496 (10) | 0.0505 (10) | 0.0726 (13) | −0.0114 (8) | 0.0267 (10) | −0.0149 (9) |
C10 | 0.0484 (10) | 0.0668 (12) | 0.0411 (9) | 0.0072 (8) | 0.0095 (8) | 0.0001 (8) |
C11 | 0.0544 (11) | 0.0585 (11) | 0.0591 (11) | −0.0190 (9) | 0.0224 (9) | −0.0131 (9) |
N3 | 0.0368 (7) | 0.0470 (7) | 0.0401 (7) | −0.0027 (6) | 0.0126 (5) | −0.0033 (6) |
N4 | 0.0366 (8) | 0.0743 (11) | 0.0589 (10) | −0.0031 (8) | 0.0113 (7) | −0.0196 (9) |
Ni1—S2 | 2.1714 (4) | C7—N3 | 1.330 (2) |
Ni1—S2i | 2.1714 (4) | C7—C8 | 1.419 (2) |
Ni1—S1 | 2.1766 (4) | C8—C9 | 1.357 (3) |
Ni1—S1i | 2.1766 (4) | C8—H8 | 0.9300 |
S1—C1 | 1.7278 (15) | C9—N4 | 1.332 (3) |
S2—C2 | 1.7330 (15) | C9—H9 | 0.9300 |
C1—C2 | 1.359 (2) | C10—N3 | 1.452 (2) |
C1—C4 | 1.428 (2) | C10—H10A | 0.9600 |
C2—C3 | 1.426 (2) | C10—H10B | 0.9600 |
C3—N2 | 1.138 (2) | C10—H10C | 0.9600 |
C4—N1 | 1.140 (2) | C11—N3 | 1.453 (2) |
C5—N4 | 1.335 (3) | C11—H11A | 0.9600 |
C5—C6 | 1.354 (3) | C11—H11B | 0.9600 |
C5—H5 | 0.9300 | C11—H11C | 0.9600 |
C6—C7 | 1.414 (2) | N4—H4 | 0.89 (3) |
C6—H6 | 0.9300 | ||
S2—Ni1—S2i | 180.00 (4) | C9—C8—C7 | 120.37 (17) |
S2—Ni1—S1 | 92.200 (14) | C9—C8—H8 | 119.8 |
S2i—Ni1—S1 | 87.800 (14) | C7—C8—H8 | 119.8 |
S2—Ni1—S1i | 87.800 (14) | N4—C9—C8 | 121.51 (18) |
S2i—Ni1—S1i | 92.200 (14) | N4—C9—H9 | 119.2 |
S1—Ni1—S1i | 180.00 (2) | C8—C9—H9 | 119.2 |
C1—S1—Ni1 | 103.03 (5) | N3—C10—H10A | 109.5 |
C2—S2—Ni1 | 103.11 (5) | N3—C10—H10B | 109.5 |
C2—C1—C4 | 120.26 (13) | H10A—C10—H10B | 109.5 |
C2—C1—S1 | 120.95 (12) | N3—C10—H10C | 109.5 |
C4—C1—S1 | 118.78 (11) | H10A—C10—H10C | 109.5 |
C1—C2—C3 | 121.12 (14) | H10B—C10—H10C | 109.5 |
C1—C2—S2 | 120.69 (12) | N3—C11—H11A | 109.5 |
C3—C2—S2 | 118.19 (11) | N3—C11—H11B | 109.5 |
N2—C3—C2 | 179.0 (2) | H11A—C11—H11B | 109.5 |
N1—C4—C1 | 179.03 (19) | N3—C11—H11C | 109.5 |
N4—C5—C6 | 121.62 (18) | H11A—C11—H11C | 109.5 |
N4—C5—H5 | 119.2 | H11B—C11—H11C | 109.5 |
C6—C5—H5 | 119.2 | C7—N3—C10 | 121.84 (15) |
C5—C6—C7 | 120.49 (18) | C7—N3—C11 | 121.77 (15) |
C5—C6—H6 | 119.8 | C10—N3—C11 | 116.30 (15) |
C7—C6—H6 | 119.8 | C9—N4—C5 | 120.39 (16) |
N3—C7—C6 | 122.23 (15) | C9—N4—H4 | 120.9 (18) |
N3—C7—C8 | 122.16 (16) | C5—N4—H4 | 118.6 (18) |
C6—C7—C8 | 115.61 (15) | ||
S2—Ni1—S1—C1 | −0.14 (5) | N4—C5—C6—C7 | 0.4 (3) |
S2i—Ni1—S1—C1 | 179.86 (5) | C5—C6—C7—N3 | 178.82 (16) |
S1—Ni1—S2—C2 | 0.74 (6) | C5—C6—C7—C8 | −0.9 (3) |
S1i—Ni1—S2—C2 | −179.26 (6) | N3—C7—C8—C9 | −179.04 (17) |
Ni1—S1—C1—C2 | −0.76 (14) | C6—C7—C8—C9 | 0.7 (3) |
Ni1—S1—C1—C4 | 179.09 (11) | C7—C8—C9—N4 | 0.1 (3) |
C4—C1—C2—C3 | 1.4 (2) | C6—C7—N3—C10 | −175.46 (16) |
S1—C1—C2—C3 | −178.76 (13) | C8—C7—N3—C10 | 4.3 (3) |
C4—C1—C2—S2 | −178.27 (12) | C6—C7—N3—C11 | 1.0 (2) |
S1—C1—C2—S2 | 1.57 (19) | C8—C7—N3—C11 | −179.29 (16) |
Ni1—S2—C2—C1 | −1.46 (14) | C8—C9—N4—C5 | −0.7 (3) |
Ni1—S2—C2—C3 | 178.86 (12) | C6—C5—N4—C9 | 0.4 (3) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1ii | 0.89 (3) | 2.34 (3) | 3.040 (2) | 135 (2) |
Symmetry code: (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C7H11N2)2[Ni(C4N2S2)2] |
Mr | 585.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 14.1631 (12), 6.5833 (6), 15.0751 (13) |
β (°) | 114.771 (1) |
V (Å3) | 1276.27 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.46 × 0.40 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.628, 0.851 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8238, 3075, 2744 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.079, 1.08 |
No. of reflections | 3075 |
No. of parameters | 167 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.24 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.89 (3) | 2.34 (3) | 3.040 (2) | 135 (2) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
The syntheses, crystal structures and properties of maleonitriledithiolate (mnt2-) transition metal complexes have received much attention in many areas such as non-linear optics and magnetic and conducting materials [Robertson & Cronin, 2002]. The introduction of some organic cations was recognized to be a powerful strategy to tune the stacking pattern of the Ni(mnt)2 dianion in order to obtain molecular materials with unusual magnetic properties.
The asymmetric unit of the title compound consists of one DMAPH+ cation (DMAPH is 4-dimethylaminopyridinium) and one half-anion of formula Ni(mnt)22- (mnt is 1,2-dicyanoethylene-1,2-dithiolate or maleonitriledithiolate). The nickel(II) metal, which lies on a crystallographic centre of symmetry, is coordinated by four S atoms from two mnt ligands in a square planar geometry (Fig. 1). The five-membered chelating ring is essentially planar (maximum displacement 0.019 (2) Å for atom C2). The conformations of anion and cation are similar to those observed in the corresponding copper(II) complex (Zhou & Ren, 2006). The Ni(mnt)2 anions (A) and DMAPH+ cations (C) are stacked in a ACCA arrangement to form one-dimensional columns along the a axis, with a centroid···centroid separation between the pyridine rings of 4.032 (4) Å. The columns are linked by intermolecular N—H···N hydrogen bonds (Table 1) resulting in a two-dimensional network (Fig. 2).