metal-organic compounds
In the new ion-pair title complex, (C12H11N2O2)2[Ni(C4N2S2)2] or 2(NO2BzPy)+·[Ni(i-mnt)2]2−, where NO2BzPy+ is 1-(4-nitrobenzyl)pyridinium and i-mnt is 2,2-dicyanoethylene-1,1-dithiolate, the [Ni(i-mnt)2]2− complex anion lies on an inversion centre and exhibits an almost structure. Weak C—HN and C—HNi contacts are observed between anions and cations in the crystal structure.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806041973/bh2049sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806041973/bh2049Isup2.hkl |
CCDC reference: 627315
Computing details top
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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.
Crystal data top
(C12H11N2O2)2[Ni(C4N2S2)2] | F(000) = 788 |
Mr = 769.53 | Dx = 1.491 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 607 reflections |
a = 9.825 (1) Å | θ = 2.7–26.5° |
b = 12.092 (1) Å | µ = 0.86 mm−1 |
c = 14.660 (2) Å | T = 293 K |
β = 100.11 (1)° | Block, brown |
V = 1714.6 (3) Å3 | 0.46 × 0.32 × 0.24 mm |
Z = 2 |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3017 independent reflections |
Radiation source: fine-focus sealed tube | 1649 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→11 |
Tmin = 0.716, Tmax = 0.804 | k = −14→12 |
16784 measured reflections | l = −17→15 |
Refinement top
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.03P)2] where P = (Fo2 + 2Fc2)/3 |
3017 reflections | (Δ/σ)max < 0.001 |
223 parameters | Δρmax = 0.35 e Å−3 |
2 restraints | Δρmin = −0.27 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.0459 (2) | |
S1 | −0.10543 (12) | 0.15741 (9) | 0.01222 (9) | 0.0564 (4) | |
S2 | 0.17713 (11) | 0.11399 (9) | 0.02447 (8) | 0.0534 (3) | |
N1 | −0.1117 (4) | 0.4509 (3) | 0.0844 (3) | 0.0822 (14) | |
N2 | 0.3353 (4) | 0.3941 (3) | 0.0902 (3) | 0.0806 (14) | |
N3 | 0.9123 (4) | 1.0135 (3) | 0.2841 (3) | 0.0523 (10) | |
N4 | 1.0560 (5) | 0.4937 (4) | 0.3312 (3) | 0.0674 (12) | |
O1 | 1.0226 (4) | 0.4438 (3) | 0.3963 (3) | 0.0976 (13) | |
O2 | 1.1361 (4) | 0.4583 (3) | 0.2845 (3) | 0.0926 (13) | |
C1 | 0.0577 (4) | 0.2150 (3) | 0.0357 (3) | 0.0471 (11) | |
C2 | 0.0870 (5) | 0.3222 (3) | 0.0622 (3) | 0.0481 (11) | |
C3 | −0.0223 (5) | 0.3942 (4) | 0.0748 (3) | 0.0569 (13) | |
C4 | 0.2247 (5) | 0.3633 (4) | 0.0781 (3) | 0.0556 (13) | |
C5 | 0.8601 (4) | 0.7541 (4) | 0.3465 (3) | 0.0605 (13) | |
H5 | 0.8054 | 0.7860 | 0.3851 | 0.073* | |
C6 | 0.9183 (5) | 0.6513 (4) | 0.3678 (3) | 0.0627 (13) | |
H6 | 0.9049 | 0.6144 | 0.4212 | 0.075* | |
C7 | 0.9958 (5) | 0.6050 (4) | 0.3094 (3) | 0.0496 (12) | |
C8 | 1.0183 (5) | 0.6561 (4) | 0.2313 (3) | 0.0625 (13) | |
H8 | 1.0713 | 0.6227 | 0.1924 | 0.075* | |
C9 | 0.9600 (5) | 0.7601 (4) | 0.2106 (3) | 0.0672 (14) | |
H9 | 0.9738 | 0.7966 | 0.1571 | 0.081* | |
C10 | 0.8822 (4) | 0.8093 (3) | 0.2690 (3) | 0.0496 (12) | |
C11 | 0.8193 (4) | 0.9214 (3) | 0.2448 (3) | 0.0612 (14) | |
H11A | 0.7985 | 0.9289 | 0.1779 | 0.073* | |
H11B | 0.7329 | 0.9269 | 0.2680 | 0.073* | |
C12 | 0.8938 (5) | 1.0647 (4) | 0.3610 (4) | 0.0692 (15) | |
H12 | 0.8239 | 1.0414 | 0.3919 | 0.083* | |
C13 | 0.9763 (6) | 1.1508 (4) | 0.3951 (4) | 0.0848 (17) | |
H13 | 0.9618 | 1.1875 | 0.4483 | 0.102* | |
C14 | 1.0806 (6) | 1.1828 (4) | 0.3505 (4) | 0.0796 (17) | |
H14 | 1.1378 | 1.2415 | 0.3734 | 0.095* | |
C15 | 1.1007 (5) | 1.1287 (4) | 0.2726 (4) | 0.0751 (16) | |
H15 | 1.1717 | 1.1494 | 0.2417 | 0.090* | |
C16 | 1.0150 (6) | 1.0440 (4) | 0.2410 (3) | 0.0674 (14) | |
H16 | 1.0282 | 1.0061 | 0.1880 | 0.081* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0456 (5) | 0.0457 (5) | 0.0459 (5) | 0.0053 (4) | 0.0069 (4) | −0.0042 (4) |
S1 | 0.0427 (7) | 0.0497 (7) | 0.0768 (9) | 0.0037 (6) | 0.0103 (6) | −0.0070 (6) |
S2 | 0.0445 (7) | 0.0520 (7) | 0.0625 (8) | 0.0076 (6) | 0.0061 (6) | −0.0049 (6) |
N1 | 0.072 (3) | 0.056 (3) | 0.124 (4) | 0.007 (2) | 0.033 (3) | −0.001 (3) |
N2 | 0.058 (3) | 0.083 (3) | 0.098 (4) | −0.007 (3) | 0.005 (3) | −0.008 (2) |
N3 | 0.055 (3) | 0.052 (2) | 0.049 (2) | 0.006 (2) | 0.007 (2) | 0.006 (2) |
N4 | 0.069 (3) | 0.053 (3) | 0.076 (3) | −0.004 (3) | 0.002 (3) | −0.006 (3) |
O1 | 0.119 (3) | 0.066 (2) | 0.116 (4) | 0.006 (2) | 0.043 (3) | 0.027 (2) |
O2 | 0.100 (3) | 0.081 (3) | 0.096 (3) | 0.030 (2) | 0.016 (3) | −0.009 (2) |
C1 | 0.045 (3) | 0.049 (3) | 0.046 (3) | 0.006 (2) | 0.004 (2) | 0.000 (2) |
C2 | 0.048 (2) | 0.043 (3) | 0.052 (3) | 0.006 (2) | 0.006 (2) | −0.001 (2) |
C3 | 0.060 (4) | 0.042 (3) | 0.069 (4) | −0.007 (3) | 0.014 (3) | 0.004 (3) |
C4 | 0.051 (3) | 0.052 (3) | 0.062 (3) | 0.005 (3) | 0.005 (3) | −0.008 (2) |
C5 | 0.056 (3) | 0.055 (3) | 0.077 (4) | 0.010 (3) | 0.029 (3) | 0.001 (3) |
C6 | 0.061 (3) | 0.064 (3) | 0.066 (4) | −0.007 (3) | 0.019 (3) | 0.010 (3) |
C7 | 0.047 (3) | 0.048 (3) | 0.054 (3) | −0.005 (2) | 0.009 (3) | −0.004 (2) |
C8 | 0.070 (4) | 0.064 (3) | 0.056 (3) | 0.007 (3) | 0.015 (3) | −0.014 (3) |
C9 | 0.088 (4) | 0.065 (3) | 0.047 (3) | 0.004 (3) | 0.008 (3) | 0.003 (3) |
C10 | 0.043 (3) | 0.048 (3) | 0.054 (3) | 0.002 (2) | −0.002 (3) | −0.008 (2) |
C11 | 0.052 (3) | 0.059 (3) | 0.066 (3) | 0.001 (3) | −0.006 (3) | −0.002 (3) |
C12 | 0.067 (4) | 0.068 (3) | 0.079 (4) | −0.012 (3) | 0.031 (3) | −0.015 (3) |
C13 | 0.089 (5) | 0.071 (4) | 0.102 (5) | −0.016 (3) | 0.037 (4) | −0.034 (3) |
C14 | 0.071 (4) | 0.049 (3) | 0.117 (5) | −0.010 (3) | 0.013 (4) | 0.004 (3) |
C15 | 0.072 (4) | 0.070 (4) | 0.088 (5) | −0.007 (3) | 0.026 (3) | 0.013 (3) |
C16 | 0.077 (4) | 0.070 (4) | 0.059 (4) | 0.009 (3) | 0.021 (3) | 0.011 (3) |
Geometric parameters (Å, º) top
Ni1—S1 | 2.1894 (11) | C6—C7 | 1.363 (6) |
Ni1—S1i | 2.1894 (11) | C6—H6 | 0.9300 |
Ni1—S2 | 2.1996 (11) | C7—C8 | 1.352 (6) |
Ni1—S2i | 2.1996 (11) | C8—C9 | 1.393 (5) |
S1—C1 | 1.725 (4) | C8—H8 | 0.9300 |
S2—C1 | 1.721 (4) | C9—C10 | 1.378 (6) |
N1—C3 | 1.142 (5) | C9—H9 | 0.9300 |
N2—C4 | 1.133 (5) | C10—C11 | 1.507 (5) |
N3—C12 | 1.325 (5) | C11—H11A | 0.9700 |
N3—C16 | 1.334 (6) | C11—H11B | 0.9700 |
N3—C11 | 1.491 (5) | C12—C13 | 1.360 (6) |
N4—O2 | 1.210 (5) | C12—H12 | 0.9300 |
N4—O1 | 1.221 (5) | C13—C14 | 1.365 (7) |
N4—C7 | 1.482 (5) | C13—H13 | 0.9300 |
C1—C2 | 1.370 (5) | C14—C15 | 1.361 (7) |
C2—C3 | 1.419 (6) | C14—H14 | 0.9300 |
C2—C4 | 1.421 (6) | C15—C16 | 1.355 (6) |
C5—C10 | 1.367 (6) | C15—H15 | 0.9300 |
C5—C6 | 1.381 (5) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | ||
S1—Ni1—S1i | 180.00 (8) | C7—C8—C9 | 118.4 (5) |
S1—Ni1—S2 | 79.28 (4) | C7—C8—H8 | 120.8 |
S1i—Ni1—S2 | 100.72 (4) | C9—C8—H8 | 120.8 |
S1—Ni1—S2i | 100.72 (4) | C10—C9—C8 | 120.4 (5) |
S1i—Ni1—S2i | 79.28 (4) | C10—C9—H9 | 119.8 |
S2—Ni1—S2i | 180.00 (8) | C8—C9—H9 | 119.8 |
C1—S1—Ni1 | 86.03 (14) | C5—C10—C9 | 119.5 (4) |
C1—S2—Ni1 | 85.80 (15) | C5—C10—C11 | 121.1 (4) |
C12—N3—C16 | 120.1 (4) | C9—C10—C11 | 119.4 (5) |
C12—N3—C11 | 120.8 (4) | N3—C11—C10 | 112.5 (3) |
C16—N3—C11 | 119.1 (4) | N3—C11—H11A | 109.1 |
O2—N4—O1 | 124.0 (5) | C10—C11—H11A | 109.1 |
O2—N4—C7 | 118.2 (5) | N3—C11—H11B | 109.1 |
O1—N4—C7 | 117.8 (5) | C10—C11—H11B | 109.1 |
C2—C1—S2 | 125.8 (3) | H11A—C11—H11B | 107.8 |
C2—C1—S1 | 125.5 (3) | N3—C12—C13 | 120.6 (5) |
S2—C1—S1 | 108.7 (2) | N3—C12—H12 | 119.7 |
C1—C2—C3 | 119.4 (4) | C13—C12—H12 | 119.7 |
C1—C2—C4 | 121.6 (4) | C12—C13—C14 | 119.4 (5) |
C3—C2—C4 | 119.0 (4) | C12—C13—H13 | 120.3 |
N1—C3—C2 | 178.9 (5) | C14—C13—H13 | 120.3 |
N2—C4—C2 | 178.7 (5) | C15—C14—C13 | 119.8 (5) |
C10—C5—C6 | 120.5 (4) | C15—C14—H14 | 120.1 |
C10—C5—H5 | 119.8 | C13—C14—H14 | 120.1 |
C6—C5—H5 | 119.8 | C16—C15—C14 | 118.5 (5) |
C7—C6—C5 | 118.9 (5) | C16—C15—H15 | 120.7 |
C7—C6—H6 | 120.6 | C14—C15—H15 | 120.7 |
C5—C6—H6 | 120.6 | N3—C16—C15 | 121.5 (5) |
C8—C7—C6 | 122.4 (5) | N3—C16—H16 | 119.2 |
C8—C7—N4 | 118.7 (5) | C15—C16—H16 | 119.2 |
C6—C7—N4 | 118.9 (5) |
Symmetry code: (i) −x, −y, −z. |