Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020115/gg1142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020115/gg1142Isup2.hkl |
CCDC reference: 204032
Ethyl iodide (15 ml) was mixed with pyridine (24 ml) and then kept at 339–341 K for several hours. The resulting solution was washed with a large excess of petroleum ether until white N-ethylpyridine iodide precipitated. Dmit(COPh)2 (0.816 g, 2 mmol) was treated with an excess of sodium methylate (0.5M) in MeOH (20 ml) under nitrogen at room temperature with stirring. To the resulting red solution, NiCl2·6H2O (0.237 g, 1 mmol) in MeOH (20 ml) and N-ethylpyridine iodide (0.550 g, 2.4 mmol) in MeOH (20 ml) were added. The resulting precipitate was washed with MeOH (yield 0.555 g). This precipitate was then dissolved in acetone and oxidated by I2/NaI. Thick black platelets of (I), one of which was used for the present structure determination, could be obtained from the filtrate by slow evaporation (m.p. 470 K). The crystal could be further purified by recrystallization from acetone in air.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms, with C—H distances in the range 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.
[C7H10N][Ni(C3S5)2] | Z = 4 |
Mr = 559.61 | F(000) = 1132 |
Triclinic, P1 | Dx = 1.792 Mg m−3 |
Hall symbol: -P1 | Melting point: 470 K |
a = 8.7825 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 16.209 (2) Å | Cell parameters from 36 reflections |
c = 16.7077 (16) Å | θ = 5.3–12.4° |
α = 112.555 (9)° | µ = 1.94 mm−1 |
β = 104.477 (7)° | T = 293 K |
γ = 95.876 (10)° | Prism, black |
V = 2073.8 (4) Å3 | 0.24 × 0.22 × 0.20 mm |
Bruker P4 diffractometer | 4722 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
θ/2θ scans | h = −1→10 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −17→17 |
Tmin = 0.566, Tmax = 0.678 | l = −19→19 |
8565 measured reflections | 3 standard reflections every 97 reflections |
7056 independent reflections | intensity decay: 2% |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0509P)2 + 2.0853P] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.001 |
7056 reflections | Δρmax = 0.55 e Å−3 |
449 parameters | Δρmin = −0.40 e Å−3 |
11 restraints | Extinction correction: SHELXTL (Bruker, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00173 (19) |
[C7H10N][Ni(C3S5)2] | γ = 95.876 (10)° |
Mr = 559.61 | V = 2073.8 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.7825 (8) Å | Mo Kα radiation |
b = 16.209 (2) Å | µ = 1.94 mm−1 |
c = 16.7077 (16) Å | T = 293 K |
α = 112.555 (9)° | 0.24 × 0.22 × 0.20 mm |
β = 104.477 (7)° |
Bruker P4 diffractometer | 4722 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.024 |
Tmin = 0.566, Tmax = 0.678 | 3 standard reflections every 97 reflections |
8565 measured reflections | intensity decay: 2% |
7056 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 11 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.55 e Å−3 |
7056 reflections | Δρmin = −0.40 e Å−3 |
449 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.44569 (7) | 0.11278 (4) | 0.07908 (4) | 0.04380 (17) | |
Ni2 | 0.13204 (6) | 0.47959 (4) | 0.41612 (4) | 0.04227 (17) | |
S1 | 0.0926 (2) | −0.29906 (10) | 0.08577 (12) | 0.0791 (5) | |
S2 | 0.07027 (15) | −0.15109 (9) | 0.02304 (10) | 0.0627 (4) | |
S3 | 0.36857 (17) | −0.14206 (9) | 0.15004 (9) | 0.0620 (4) | |
S4 | 0.20784 (14) | 0.02452 (8) | 0.01498 (9) | 0.0557 (3) | |
S5 | 0.53062 (15) | 0.03354 (9) | 0.15274 (9) | 0.0600 (3) | |
S6 | 0.35915 (14) | 0.19539 (9) | 0.00852 (9) | 0.0561 (3) | |
S7 | 0.68467 (14) | 0.19928 (8) | 0.14317 (9) | 0.0527 (3) | |
S8 | 0.52845 (15) | 0.37205 (9) | 0.01430 (9) | 0.0595 (3) | |
S9 | 0.82505 (15) | 0.37524 (8) | 0.13826 (9) | 0.0575 (3) | |
S10 | 0.8120 (2) | 0.52678 (10) | 0.08163 (11) | 0.0790 (5) | |
S11 | −0.24903 (19) | 0.08352 (9) | 0.43960 (11) | 0.0733 (4) | |
S12 | −0.25584 (16) | 0.22509 (9) | 0.36852 (9) | 0.0616 (4) | |
S13 | 0.04297 (16) | 0.22650 (9) | 0.48967 (10) | 0.0617 (4) | |
S14 | −0.10791 (14) | 0.39424 (8) | 0.35476 (9) | 0.0561 (3) | |
S15 | 0.21771 (14) | 0.39629 (9) | 0.48552 (9) | 0.0574 (3) | |
S16 | 0.04955 (14) | 0.55996 (8) | 0.34293 (9) | 0.0554 (3) | |
S17 | 0.37140 (14) | 0.56555 (8) | 0.47898 (9) | 0.0558 (3) | |
S18 | 0.22611 (16) | 0.72704 (9) | 0.33556 (9) | 0.0580 (3) | |
S19 | 0.51998 (15) | 0.73448 (8) | 0.46417 (10) | 0.0599 (4) | |
S20 | 0.51421 (19) | 0.87549 (10) | 0.39244 (12) | 0.0795 (5) | |
N1 | −0.0079 (8) | −0.0472 (4) | 0.2979 (5) | 0.0947 (18) | |
N2 | 0.3953 (8) | 0.4319 (4) | 0.2320 (4) | 0.0866 (16) | |
C1 | 0.1732 (6) | −0.2023 (3) | 0.0862 (3) | 0.0558 (12) | |
C2 | 0.2270 (5) | −0.0579 (3) | 0.0549 (3) | 0.0462 (11) | |
C3 | 0.3659 (6) | −0.0542 (3) | 0.1142 (3) | 0.0459 (11) | |
C4 | 0.5273 (5) | 0.2813 (3) | 0.0461 (3) | 0.0461 (11) | |
C5 | 0.6674 (5) | 0.2830 (3) | 0.1043 (3) | 0.0447 (10) | |
C6 | 0.7257 (6) | 0.4291 (3) | 0.0773 (3) | 0.0548 (12) | |
C7 | −0.1587 (6) | 0.1736 (3) | 0.4329 (3) | 0.0528 (12) | |
C8 | −0.0940 (5) | 0.3126 (3) | 0.3959 (3) | 0.0466 (11) | |
C9 | 0.0480 (6) | 0.3140 (3) | 0.4526 (3) | 0.0495 (11) | |
C10 | 0.2187 (5) | 0.6429 (3) | 0.3755 (3) | 0.0431 (10) | |
C11 | 0.3578 (5) | 0.6454 (3) | 0.4355 (3) | 0.0437 (10) | |
C12 | 0.4229 (6) | 0.7837 (3) | 0.3974 (3) | 0.0535 (12) | |
C13 | −0.1734 (9) | −0.2026 (5) | 0.2393 (5) | 0.125 (3) | |
H13A | −0.2762 | −0.2298 | 0.2388 | 0.188* | |
H13B | −0.1016 | −0.2434 | 0.2399 | 0.188* | |
H13C | −0.1868 | −0.1916 | 0.1857 | 0.188* | |
C14 | −0.1051 (16) | −0.1150 (8) | 0.3215 (9) | 0.103 (5)* | 0.648 (19) |
H14A | −0.0351 | −0.1250 | 0.3703 | 0.123* | 0.648 (19) |
H14B | −0.1912 | −0.0898 | 0.3420 | 0.123* | 0.648 (19) |
C14' | −0.1809 (16) | −0.1029 (7) | 0.2715 (16) | 0.088 (8)* | 0.352 (19) |
H14C | −0.2198 | −0.0838 | 0.3239 | 0.105* | 0.352 (19) |
H14D | −0.2536 | −0.0933 | 0.2233 | 0.105* | 0.352 (19) |
C15 | −0.0526 (10) | −0.0070 (6) | 0.2429 (6) | 0.123 (3) | |
H15A | −0.1607 | −0.0204 | 0.2089 | 0.147* | |
C16 | 0.0503 (15) | 0.0508 (7) | 0.2352 (5) | 0.126 (3) | |
H16A | 0.0149 | 0.0792 | 0.1973 | 0.151* | |
C17 | 0.2059 (12) | 0.0694 (5) | 0.2815 (7) | 0.108 (3) | |
H17A | 0.2804 | 0.1089 | 0.2743 | 0.129* | |
C18 | 0.2539 (9) | 0.0313 (5) | 0.3377 (6) | 0.111 (3) | |
H18A | 0.3620 | 0.0450 | 0.3718 | 0.133* | |
C19 | 0.1461 (12) | −0.0270 (6) | 0.3453 (5) | 0.108 (2) | |
H19A | 0.1801 | −0.0539 | 0.3848 | 0.130* | |
C20 | 0.2410 (12) | 0.2967 (7) | 0.2333 (7) | 0.191 (5) | |
H20A | 0.2451 | 0.2481 | 0.2526 | 0.286* | |
H20B | 0.1984 | 0.2712 | 0.1680 | 0.286* | |
H20C | 0.1727 | 0.3341 | 0.2596 | 0.286* | |
C21 | 0.4016 (11) | 0.3520 (6) | 0.2632 (6) | 0.145 (4) | |
H21A | 0.4711 | 0.3143 | 0.2371 | 0.175* | |
H21B | 0.4456 | 0.3772 | 0.3292 | 0.175* | |
C22 | 0.2846 (18) | 0.4593 (13) | 0.1830 (11) | 0.080 (5)* | 0.45 (2) |
H22B | 0.1797 | 0.4244 | 0.1589 | 0.096* | 0.45 (2) |
C23 | 0.311 (2) | 0.5339 (13) | 0.1650 (11) | 0.071 (5)* | 0.45 (2) |
H23B | 0.2301 | 0.5479 | 0.1277 | 0.085* | 0.45 (2) |
C24 | 0.471 (2) | 0.5890 (10) | 0.2071 (11) | 0.069 (5)* | 0.45 (2) |
H24B | 0.4951 | 0.6417 | 0.1984 | 0.083* | 0.45 (2) |
C25 | 0.580 (3) | 0.5684 (10) | 0.2552 (14) | 0.088 (6)* | 0.45 (2) |
H25B | 0.6856 | 0.6031 | 0.2809 | 0.106* | 0.45 (2) |
C22' | 0.2626 (15) | 0.4234 (14) | 0.1729 (9) | 0.097 (5)* | 0.55 (2) |
H22A | 0.1755 | 0.3738 | 0.1480 | 0.117* | 0.55 (2) |
C23' | 0.2649 (15) | 0.4928 (11) | 0.1520 (8) | 0.079 (4)* | 0.55 (2) |
H23A | 0.1683 | 0.4921 | 0.1127 | 0.094* | 0.55 (2) |
C24' | 0.386 (2) | 0.5662 (8) | 0.1785 (9) | 0.073 (4)* | 0.55 (2) |
H24A | 0.3774 | 0.6132 | 0.1599 | 0.087* | 0.55 (2) |
C25' | 0.524 (2) | 0.5617 (11) | 0.2366 (12) | 0.112 (7)* | 0.55 (2) |
H25A | 0.6148 | 0.6080 | 0.2567 | 0.134* | 0.55 (2) |
C26 | 0.5384 (9) | 0.4946 (5) | 0.2676 (4) | 0.099 (2) | |
H26A | 0.6200 | 0.4836 | 0.3073 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0387 (3) | 0.0409 (3) | 0.0527 (4) | 0.0023 (3) | 0.0127 (3) | 0.0235 (3) |
Ni2 | 0.0398 (3) | 0.0372 (3) | 0.0524 (3) | 0.0023 (2) | 0.0125 (3) | 0.0245 (3) |
S1 | 0.0956 (11) | 0.0564 (9) | 0.1104 (12) | 0.0103 (8) | 0.0477 (10) | 0.0533 (9) |
S2 | 0.0469 (7) | 0.0519 (7) | 0.0944 (10) | −0.0006 (6) | 0.0152 (7) | 0.0435 (7) |
S3 | 0.0696 (9) | 0.0562 (8) | 0.0710 (9) | 0.0145 (7) | 0.0173 (7) | 0.0408 (7) |
S4 | 0.0415 (7) | 0.0531 (7) | 0.0761 (8) | 0.0000 (6) | 0.0061 (6) | 0.0416 (7) |
S5 | 0.0459 (7) | 0.0543 (7) | 0.0750 (9) | 0.0002 (6) | 0.0005 (6) | 0.0368 (7) |
S6 | 0.0416 (6) | 0.0601 (8) | 0.0684 (8) | −0.0018 (6) | 0.0060 (6) | 0.0393 (7) |
S7 | 0.0415 (6) | 0.0478 (7) | 0.0682 (8) | −0.0006 (5) | 0.0061 (6) | 0.0336 (6) |
S8 | 0.0559 (8) | 0.0602 (8) | 0.0740 (9) | 0.0090 (6) | 0.0160 (7) | 0.0440 (7) |
S9 | 0.0492 (7) | 0.0531 (7) | 0.0682 (8) | −0.0063 (6) | 0.0082 (6) | 0.0345 (6) |
S10 | 0.0857 (11) | 0.0584 (9) | 0.1032 (12) | −0.0014 (8) | 0.0260 (9) | 0.0516 (9) |
S11 | 0.0860 (10) | 0.0492 (8) | 0.0923 (10) | −0.0058 (7) | 0.0388 (9) | 0.0365 (7) |
S12 | 0.0565 (8) | 0.0569 (8) | 0.0669 (8) | −0.0121 (6) | 0.0112 (7) | 0.0328 (7) |
S13 | 0.0591 (8) | 0.0549 (8) | 0.0869 (9) | 0.0059 (6) | 0.0226 (7) | 0.0483 (7) |
S14 | 0.0435 (7) | 0.0556 (7) | 0.0697 (8) | −0.0041 (6) | 0.0043 (6) | 0.0392 (7) |
S15 | 0.0421 (7) | 0.0565 (7) | 0.0791 (9) | −0.0034 (6) | 0.0069 (6) | 0.0456 (7) |
S16 | 0.0462 (7) | 0.0486 (7) | 0.0691 (8) | −0.0012 (6) | 0.0037 (6) | 0.0345 (6) |
S17 | 0.0429 (7) | 0.0497 (7) | 0.0784 (9) | −0.0025 (5) | 0.0034 (6) | 0.0437 (7) |
S18 | 0.0630 (8) | 0.0525 (7) | 0.0708 (8) | 0.0100 (6) | 0.0168 (7) | 0.0420 (7) |
S19 | 0.0473 (7) | 0.0511 (7) | 0.0896 (9) | 0.0001 (6) | 0.0136 (7) | 0.0459 (7) |
S20 | 0.0774 (10) | 0.0688 (9) | 0.1244 (13) | 0.0097 (8) | 0.0400 (9) | 0.0704 (10) |
N1 | 0.098 (5) | 0.068 (3) | 0.131 (5) | 0.021 (3) | 0.068 (4) | 0.036 (4) |
N2 | 0.119 (5) | 0.095 (4) | 0.072 (3) | 0.053 (4) | 0.051 (4) | 0.041 (3) |
C1 | 0.065 (3) | 0.046 (3) | 0.068 (3) | 0.015 (2) | 0.030 (3) | 0.029 (2) |
C2 | 0.042 (3) | 0.040 (2) | 0.065 (3) | 0.005 (2) | 0.021 (2) | 0.030 (2) |
C3 | 0.052 (3) | 0.036 (2) | 0.059 (3) | 0.010 (2) | 0.022 (2) | 0.026 (2) |
C4 | 0.047 (3) | 0.049 (3) | 0.050 (3) | 0.009 (2) | 0.019 (2) | 0.028 (2) |
C5 | 0.040 (2) | 0.041 (2) | 0.053 (3) | 0.001 (2) | 0.017 (2) | 0.021 (2) |
C6 | 0.060 (3) | 0.047 (3) | 0.058 (3) | 0.004 (2) | 0.017 (2) | 0.025 (2) |
C7 | 0.059 (3) | 0.042 (3) | 0.058 (3) | 0.000 (2) | 0.028 (2) | 0.019 (2) |
C8 | 0.045 (3) | 0.042 (2) | 0.052 (3) | −0.002 (2) | 0.017 (2) | 0.022 (2) |
C9 | 0.053 (3) | 0.045 (3) | 0.062 (3) | 0.009 (2) | 0.024 (2) | 0.031 (2) |
C10 | 0.049 (3) | 0.035 (2) | 0.051 (3) | 0.007 (2) | 0.017 (2) | 0.025 (2) |
C11 | 0.041 (2) | 0.034 (2) | 0.057 (3) | 0.0004 (19) | 0.014 (2) | 0.024 (2) |
C12 | 0.057 (3) | 0.050 (3) | 0.071 (3) | 0.014 (2) | 0.030 (3) | 0.037 (2) |
C13 | 0.095 (5) | 0.109 (6) | 0.156 (8) | 0.010 (5) | 0.032 (5) | 0.049 (6) |
C15 | 0.079 (5) | 0.108 (7) | 0.138 (8) | 0.018 (5) | −0.012 (5) | 0.037 (6) |
C16 | 0.171 (10) | 0.135 (8) | 0.075 (5) | 0.044 (8) | 0.016 (6) | 0.062 (5) |
C17 | 0.130 (7) | 0.079 (5) | 0.142 (8) | 0.029 (5) | 0.079 (6) | 0.052 (5) |
C18 | 0.069 (5) | 0.080 (5) | 0.139 (7) | 0.016 (4) | −0.007 (4) | 0.026 (5) |
C19 | 0.132 (7) | 0.101 (6) | 0.094 (5) | 0.038 (6) | 0.013 (5) | 0.055 (5) |
C20 | 0.185 (11) | 0.175 (11) | 0.155 (9) | 0.018 (9) | 0.095 (9) | −0.008 (8) |
C21 | 0.143 (9) | 0.176 (10) | 0.097 (6) | 0.075 (8) | 0.041 (6) | 0.025 (6) |
C26 | 0.079 (5) | 0.134 (7) | 0.062 (4) | 0.046 (5) | 0.004 (4) | 0.023 (4) |
Ni1—S7 | 2.1540 (13) | C4—C5 | 1.354 (6) |
Ni1—S4 | 2.1567 (13) | C8—C9 | 1.356 (6) |
Ni1—S5 | 2.1612 (13) | C10—C11 | 1.358 (6) |
Ni1—S6 | 2.1751 (13) | C13—C14 | 1.476 (12) |
Ni2—S17 | 2.1535 (13) | C13—C14' | 1.509 (9) |
Ni2—S14 | 2.1542 (13) | C13—H13A | 0.9600 |
Ni2—S16 | 2.1657 (13) | C13—H13B | 0.9600 |
Ni2—S15 | 2.1693 (13) | C13—H13C | 0.9600 |
S1—C1 | 1.650 (5) | C14—H14A | 0.9700 |
S2—C1 | 1.722 (5) | C14—H14B | 0.9700 |
S2—C2 | 1.746 (4) | C14'—H14C | 0.9700 |
S3—C1 | 1.726 (5) | C14'—H14D | 0.9700 |
S3—C3 | 1.744 (4) | C15—C16 | 1.299 (11) |
S4—C2 | 1.712 (4) | C15—H15A | 0.9300 |
S5—C3 | 1.715 (4) | C16—C17 | 1.329 (11) |
S6—C4 | 1.719 (4) | C16—H16A | 0.9300 |
S7—C5 | 1.719 (4) | C17—C18 | 1.320 (10) |
S8—C6 | 1.726 (5) | C17—H17A | 0.9300 |
S8—C4 | 1.746 (4) | C18—C19 | 1.331 (10) |
S9—C6 | 1.719 (5) | C18—H18A | 0.9300 |
S9—C5 | 1.735 (4) | C19—H19A | 0.9300 |
S10—C6 | 1.651 (5) | C20—C21 | 1.445 (8) |
S11—C7 | 1.646 (4) | C20—H20A | 0.9600 |
S12—C7 | 1.719 (5) | C20—H20B | 0.9600 |
S12—C8 | 1.734 (4) | C20—H20C | 0.9600 |
S13—C7 | 1.731 (5) | C21—H21A | 0.9700 |
S13—C9 | 1.754 (4) | C21—H21B | 0.9700 |
S14—C8 | 1.712 (4) | C22—C23 | 1.365 (10) |
S15—C9 | 1.709 (5) | C22—H22B | 0.9300 |
S16—C10 | 1.713 (4) | C23—C24 | 1.43 (2) |
S17—C11 | 1.711 (4) | C23—H23B | 0.9300 |
S18—C12 | 1.718 (5) | C24—C25 | 1.25 (2) |
S18—C10 | 1.736 (4) | C24—H24B | 0.9300 |
S19—C12 | 1.719 (5) | C25—C26 | 1.322 (9) |
S19—C11 | 1.746 (4) | C25—H25B | 0.9300 |
S20—C12 | 1.658 (4) | C22'—C23' | 1.30 (2) |
N1—C15 | 1.325 (10) | C22'—H22A | 0.9300 |
N1—C19 | 1.319 (9) | C23'—C24' | 1.359 (9) |
N1—C14 | 1.549 (12) | C23'—H23A | 0.9300 |
N1—C14' | 1.548 (9) | C24'—C25' | 1.377 (10) |
N2—C22' | 1.281 (9) | C24'—H24A | 0.9300 |
N2—C22 | 1.336 (9) | C25'—C26 | 1.375 (9) |
N2—C26 | 1.367 (8) | C25'—H25A | 0.9300 |
N2—C21 | 1.571 (7) | C26—H26A | 0.9300 |
C2—C3 | 1.344 (6) | ||
S1···S10i | 3.520 (3) | S15···S17iv | 3.4566 (19) |
S2···S4ii | 3.439 (2) | S15···S19iv | 3.450 (2) |
S4···S4ii | 3.5209 (19) | S17···S17iv | 3.383 (2) |
S7···S12iii | 3.5195 (19) | Ni1···S5v | 3.7586 (15) |
S7···S14iii | 3.582 (2) | Ni2···S14vi | 3.6565 (15) |
S9···S14iii | 3.4014 (19) | Ni1···Ni1v | 3.9778 (10) |
S9···S16iii | 3.4802 (19) | Ni2···Ni2vi | 3.9768 (9) |
S11···S20i | 3.467 (2) | ||
S7—Ni1—S4 | 179.17 (5) | C14'—C13—H13A | 101.7 |
S7—Ni1—S5 | 86.65 (5) | C14—C13—H13B | 109.5 |
S4—Ni1—S5 | 92.63 (5) | H13A—C13—H13B | 109.5 |
S7—Ni1—S6 | 93.09 (5) | C14—C13—H13C | 109.5 |
S4—Ni1—S6 | 87.63 (5) | H13A—C13—H13C | 109.5 |
S5—Ni1—S6 | 178.32 (6) | H13B—C13—H13C | 109.5 |
S17—Ni2—S14 | 179.33 (6) | C13—C14—N1 | 108.9 (8) |
S17—Ni2—S16 | 92.55 (5) | C13—C14—H14A | 109.9 |
S14—Ni2—S16 | 87.66 (5) | N1—C14—H14A | 109.9 |
S17—Ni2—S15 | 87.32 (5) | C13—C14—H14B | 109.9 |
S14—Ni2—S15 | 92.50 (5) | N1—C14—H14B | 109.9 |
S16—Ni2—S15 | 177.97 (6) | H14A—C14—H14B | 108.3 |
C1—S2—C2 | 97.6 (2) | C13—C14'—N1 | 107.2 (8) |
C1—S3—C3 | 97.0 (2) | C13—C14'—H14C | 110.3 |
C2—S4—Ni1 | 102.44 (15) | N1—C14'—H14C | 110.3 |
C3—S5—Ni1 | 102.34 (16) | C13—C14'—H14D | 110.3 |
C4—S6—Ni1 | 101.85 (16) | N1—C14'—H14D | 110.3 |
C5—S7—Ni1 | 102.34 (15) | H14C—C14'—H14D | 108.5 |
C6—S8—C4 | 97.2 (2) | C16—C15—N1 | 121.9 (8) |
C6—S9—C5 | 97.7 (2) | C16—C15—H15A | 119.1 |
C7—S12—C8 | 97.7 (2) | N1—C15—H15A | 119.1 |
C7—S13—C9 | 97.5 (2) | C15—C16—C17 | 120.1 (8) |
C8—S14—Ni2 | 103.14 (16) | C15—C16—H16A | 120.0 |
C9—S15—Ni2 | 102.16 (16) | C17—C16—H16A | 120.0 |
C10—S16—Ni2 | 102.78 (15) | C18—C17—C16 | 119.4 (8) |
C11—S17—Ni2 | 102.68 (15) | C18—C17—H17A | 120.3 |
C12—S18—C10 | 97.6 (2) | C16—C17—H17A | 120.3 |
C12—S19—C11 | 97.3 (2) | C17—C18—C19 | 119.5 (7) |
C15—N1—C19 | 117.8 (7) | C17—C18—H18A | 120.3 |
C15—N1—C14 | 132.1 (9) | C19—C18—H18A | 120.3 |
C19—N1—C14 | 110.1 (9) | N1—C19—C18 | 121.3 (7) |
C15—N1—C14' | 93.4 (10) | N1—C19—H19A | 119.4 |
C19—N1—C14' | 148.7 (11) | C18—C19—H19A | 119.4 |
C22'—N2—C26 | 131.1 (11) | C21—C20—H20A | 109.5 |
C22—N2—C26 | 108.9 (10) | C21—C20—H20B | 109.5 |
C22'—N2—C21 | 115.1 (11) | H20A—C20—H20B | 109.5 |
C22—N2—C21 | 137.4 (11) | C21—C20—H20C | 109.5 |
C26—N2—C21 | 113.6 (7) | H20A—C20—H20C | 109.5 |
S1—C1—S2 | 123.3 (3) | H20B—C20—H20C | 109.5 |
S1—C1—S3 | 123.4 (3) | C20—C21—N2 | 109.6 (8) |
S2—C1—S3 | 113.2 (3) | C20—C21—H21A | 109.7 |
C3—C2—S4 | 121.4 (3) | N2—C21—H21A | 109.7 |
C3—C2—S2 | 115.5 (3) | C20—C21—H21B | 109.7 |
S4—C2—S2 | 123.1 (3) | N2—C21—H21B | 109.7 |
C2—C3—S5 | 121.1 (3) | H21A—C21—H21B | 108.2 |
C2—C3—S3 | 116.7 (3) | N2—C22—C23 | 126.1 (14) |
S5—C3—S3 | 122.2 (3) | N2—C22—H22B | 117.0 |
C5—C4—S6 | 121.3 (3) | C23—C22—H22B | 117.0 |
C5—C4—S8 | 115.8 (3) | C22—C23—C24 | 115.6 (14) |
S6—C4—S8 | 122.9 (3) | C22—C23—H23B | 122.2 |
C4—C5—S7 | 121.4 (3) | C24—C23—H23B | 122.2 |
C4—C5—S9 | 116.0 (3) | C25—C24—C23 | 121.7 (13) |
S7—C5—S9 | 122.5 (3) | C25—C24—H24B | 119.1 |
S10—C6—S9 | 122.5 (3) | C23—C24—H24B | 119.1 |
S10—C6—S8 | 124.3 (3) | C26—C25—C24 | 116.5 (17) |
S9—C6—S8 | 113.2 (3) | C26—C25—H25B | 121.8 |
S11—C7—S12 | 123.2 (3) | C24—C25—H25B | 121.8 |
S11—C7—S13 | 123.8 (3) | N2—C22'—C23' | 111.6 (13) |
S12—C7—S13 | 113.0 (2) | N2—C22'—H22A | 124.2 |
C9—C8—S14 | 120.3 (3) | C23'—C22'—H22A | 124.2 |
C9—C8—S12 | 116.7 (3) | C24'—C23'—C22' | 130.2 (12) |
S14—C8—S12 | 123.0 (3) | C24'—C23'—H23A | 114.9 |
C8—C9—S15 | 121.9 (3) | C22'—C23'—H23A | 114.9 |
C8—C9—S13 | 115.0 (3) | C23'—C24'—C25' | 110.9 (12) |
S15—C9—S13 | 123.1 (3) | C23'—C24'—H24A | 124.6 |
C11—C10—S16 | 120.4 (3) | C25'—C24'—H24A | 124.6 |
C11—C10—S18 | 115.9 (3) | C24'—C25'—C26 | 125.7 (14) |
S16—C10—S18 | 123.7 (3) | C24'—C25'—H25A | 117.1 |
C10—C11—S17 | 121.5 (3) | C26—C25'—H25A | 117.1 |
C10—C11—S19 | 115.7 (3) | C25—C26—N2 | 130.9 (13) |
S17—C11—S19 | 122.8 (3) | C25'—C26—N2 | 110.1 (10) |
S20—C12—S19 | 122.4 (3) | C25—C26—H26A | 114.5 |
S20—C12—S18 | 124.1 (3) | C25'—C26—H26A | 135.3 |
S19—C12—S18 | 113.5 (2) | N2—C26—H26A | 114.5 |
C14—C13—H13A | 109.5 |
Symmetry codes: (i) x−1, y−1, z; (ii) −x, −y, −z; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z; (vi) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [C7H10N][Ni(C3S5)2] |
Mr | 559.61 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.7825 (8), 16.209 (2), 16.7077 (16) |
α, β, γ (°) | 112.555 (9), 104.477 (7), 95.876 (10) |
V (Å3) | 2073.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.94 |
Crystal size (mm) | 0.24 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.566, 0.678 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8565, 7056, 4722 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.118, 0.95 |
No. of reflections | 7056 |
No. of parameters | 449 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.40 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.
Ni1—S7 | 2.1540 (13) | Ni2—S17 | 2.1535 (13) |
Ni1—S4 | 2.1567 (13) | Ni2—S14 | 2.1542 (13) |
Ni1—S5 | 2.1612 (13) | Ni2—S16 | 2.1657 (13) |
Ni1—S6 | 2.1751 (13) | Ni2—S15 | 2.1693 (13) |
S1···S10i | 3.520 (3) | S15···S17iv | 3.4566 (19) |
S2···S4ii | 3.439 (2) | S15···S19iv | 3.450 (2) |
S4···S4ii | 3.5209 (19) | S17···S17iv | 3.383 (2) |
S7···S12iii | 3.5195 (19) | Ni1···S5v | 3.7586 (15) |
S7···S14iii | 3.582 (2) | Ni2···S14vi | 3.6565 (15) |
S9···S14iii | 3.4014 (19) | Ni1···Ni1v | 3.9778 (10) |
S9···S16iii | 3.4802 (19) | Ni2···Ni2vi | 3.9768 (9) |
S11···S20i | 3.467 (2) | ||
S7—Ni1—S4 | 179.17 (5) | S17—Ni2—S14 | 179.33 (6) |
S7—Ni1—S5 | 86.65 (5) | S17—Ni2—S16 | 92.55 (5) |
S4—Ni1—S5 | 92.63 (5) | S14—Ni2—S16 | 87.66 (5) |
S7—Ni1—S6 | 93.09 (5) | S17—Ni2—S15 | 87.32 (5) |
S4—Ni1—S6 | 87.63 (5) | S14—Ni2—S15 | 92.50 (5) |
S5—Ni1—S6 | 178.32 (6) | S16—Ni2—S15 | 177.97 (6) |
Symmetry codes: (i) x−1, y−1, z; (ii) −x, −y, −z; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z; (vi) −x, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Metal-dmit coordination anions, [M(dmit)2]x- (0 ≤ x ≤ 1), as the conducting component in the Z[M(dmit)2]n type of molecular conductors and superconductors, have attracted intense research interest over the past 20 years (Lindqvist et al., 1979; Valade et al., 1985; Bousseau et al., 1986; Kobayashi et al., 1987; Cornelissen et al., 1991; Miyazaki et al., 1992; Tajima et al., 1993; Veldhuizen et al., 1995; Fun et al., 1996; Xu et al., 2001). Various crystals, and consequently various conductivities, can be obtained by using different monocations in the 1:2 salts of Z[Ni(dmit)2]2, which has formed the most dominant group in the Z[M(dmit)2]n family. From the synthesis point of view, conductive 1:2 Z[Ni(dmit)2]2 salts are prepared from the non-conductive precursor of 1:1 Z[Ni(dmit)2] salts. To date, most cations have been tetraalkyl ammonium, and less attention has been paid to planar cations. The synthesis of [guanidinium][Ni(dmit)2]2 (Veldhuizen et al., 1995) has aroused our interest in such small planar cations, such as N-ethylpyridinine, because small planar cations may reduce the spacing between the conductive anions and enhance the overlap between molecular orbitals. Thus, we synthesized the title 1:1 complex, (I), as a precursor of the 1:2 complex [Etpy][Ni(dmit)2]2, which we failed to obtain, and report its structure in this paper. Surprisingly, even the 1:1 title complex shows considerable conductivity. \sch
The unit cell of (I) contains two crystallographically independent [Ni(dmit)2]− anions and two Etpy cations, as depicted in Figs. 1 and 2. Statistically speaking, there are no significant differences in the bond lengths and angles between the two [Ni(dmit)2]− anions, except that the planarity of [Ni2(dmit)2]− is more perfect than that of [Ni1(dmit)2]−. Both of the [Ni(dmit)2]− anions have a D2 h symmetrical conformation and exhibit perfect planarity, with maximum deviations from the least-squares plane of 0.078 (1) Å for atom S10 in [Ni1(dmit)2]− and 0.055 (1) Å for atom S18 in [Ni2(dmit)2]−. The NiS4 core adopts a slightly distorted square-planar conformation. The Ni—S bond lengths range from 2.1535 (13) to 2.1751 (13) Å, with the average length being 2.1604 (13) Å, and S—Ni—S angles range from 86.65 (5) to 93.09 (5)°. The Etpy ring is also planar, as expected. There are two types of disorder in the two Etpy cations. One type affects all four C atoms (C22, C23, C24 and C25) in one Etpy ring, with occupancies of 0.55 (2) and 0.45 (2), and the other affects atom C14 in the ethyl group of another Etpy cation, with occupancies of 0.648 (19) and 0.352 (19).
There are many S···S, Ni···S and Ni···Ni interactions between neighbouring molecules of (I) (Figs. 2 and 3). Table 2 lists all the intermolecular S···S contacts shorter than 3.60 Å (the sum of the van der Waals radii), Ni···S contacts shorter than 4.10 Å and Ni···Ni contacts shorter than 4.60 Å. The shortest intermolecular S···S contact is 3.383 (2) Å, between atoms S17 and S17? [symmetry code?], which is shorter than the shortest value reported in the literature (Cornelissen et al., 1991).
Referring to Figs. 2 and 3 and Table 2, the anions of (I) form weak dimers via Ni···S and Ni···Ni interactions. The angle between the planes of two independent anions is 2.99 (4)°, showing the basic parallel arrangement of the two anions; the two long axes of the two planar anions are also parallel. In fact, all planar [Ni(dmit)2]− anions are parallel to each other. The anions form a kind of zigzag chain via five pairs of strong intermolecular S···S interactions between neighbouring [Ni(dmit)2]− anions. Thus, (I) shows the typical characteristic of one-dimensional structure required for conductivity.
Additionally, the structure of (I) exhibits a slight two- or three-dimensional feature, due to Ni···Ni dimer interactions, terminal S···S interactions and anionic-cationic coulombic interactions. The Etpy cations are located between the anionic zigzag chains. This kind of crystal, with strong intermolecular interactions, may have a high conductivity. In fact, the measured conductivity (by the two-probe contact method) of the crystal of (I) is 5 × 10−7 S cm−1 at room temperature, which is quite high among the Z[M(dmit)2] type of 1:1 complexes.
Table 2 Intermolecular S···S, Ni···S and Ni···Ni contacts (Å) shorter than the van der Waals radii