Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020342/ob6187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020342/ob6187Isup2.hkl |
CCDC reference: 202287
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.048
- wR factor = 0.079
- Data-to-parameter ratio = 16.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
A solution of NaOMe dissolved in methanol was added to a methanol solution of 4,5-bis(benzoylthio)-1,3-dithiol-2-thione, i.e. dmit(COPh)2. After stirring, a solution of NiCl2·6H2O was added. After further stirring, the solution of bromobenzylpyridine chloride was added. After further stirring, the black dedimentations were leached and dissolved in acetone. As the solvent slowly evaporated, well formed crystals of (I) appeared.
The positions of all the H atoms were fixed geometrically and distances to H atoms were set by the refinement program.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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.
Fig. 1. View of (I) (50% probability ellipsoids). | |
Fig. 2. A view of packing form in the crystal for (I). |
(C12H11BrN)[Ni(C3S5)2] | F(000) = 1396 |
Mr = 700.57 | Dx = 1.863 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1002 reflections |
a = 6.275 (1) Å | θ = 2.3–17.8° |
b = 17.438 (3) Å | µ = 3.22 mm−1 |
c = 22.839 (3) Å | T = 293 K |
β = 91.87 (1)° | Block, black |
V = 2497.8 (7) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 4626 independent reflections |
Radiation source: sealed tube | 2953 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.1° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1990) | h = −7→7 |
Tmin = 0.465, Tmax = 0.523 | k = 0→21 |
12855 measured reflections | l = 0→27 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0292P)2 + 0.113P] where P = (Fo2 + 2Fc2)/3 |
4626 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
(C12H11BrN)[Ni(C3S5)2] | V = 2497.8 (7) Å3 |
Mr = 700.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.275 (1) Å | µ = 3.22 mm−1 |
b = 17.438 (3) Å | T = 293 K |
c = 22.839 (3) Å | 0.3 × 0.2 × 0.2 mm |
β = 91.87 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 4626 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1990) | 2953 reflections with I > 2σ(I) |
Tmin = 0.465, Tmax = 0.523 | Rint = 0.043 |
12855 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.45 e Å−3 |
4626 reflections | Δρmin = −0.29 e Å−3 |
280 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. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. 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 | ||
Ni1 | 0.06523 (7) | 0.41992 (3) | 0.04340 (2) | 0.03926 (15) | |
S1 | 0.21937 (15) | 0.37931 (6) | −0.03447 (5) | 0.0456 (3) | |
S2 | 0.05447 (17) | 0.27371 (7) | −0.13195 (5) | 0.0550 (3) | |
S3 | −0.2717 (2) | 0.16967 (8) | −0.18707 (5) | 0.0713 (4) | |
S4 | −0.35241 (16) | 0.25612 (7) | −0.07926 (5) | 0.0505 (3) | |
S5 | −0.22608 (16) | 0.35982 (7) | 0.02180 (5) | 0.0520 (3) | |
S6 | 0.35215 (15) | 0.48273 (6) | 0.06706 (5) | 0.0438 (3) | |
S7 | 0.47233 (17) | 0.57412 (7) | 0.17654 (5) | 0.0552 (3) | |
S8 | 0.3850 (2) | 0.64015 (8) | 0.29276 (6) | 0.0760 (4) | |
S9 | 0.06417 (18) | 0.54654 (7) | 0.22677 (5) | 0.0567 (3) | |
S10 | −0.09431 (16) | 0.45571 (7) | 0.12154 (5) | 0.0497 (3) | |
C1 | 0.0235 (6) | 0.3238 (2) | −0.06698 (16) | 0.0400 (10) | |
C2 | −0.1925 (6) | 0.2303 (2) | −0.13574 (17) | 0.0468 (11) | |
C3 | −0.1699 (6) | 0.3153 (2) | −0.04158 (17) | 0.0418 (10) | |
C4 | 0.2936 (6) | 0.5200 (2) | 0.13376 (16) | 0.0397 (10) | |
C5 | 0.3105 (6) | 0.5889 (2) | 0.23520 (18) | 0.0491 (11) | |
C6 | 0.0998 (6) | 0.5072 (2) | 0.15745 (16) | 0.0410 (10) | |
C7 | 0.9015 (8) | 0.7612 (3) | 0.8442 (2) | 0.0666 (14) | |
H7 | 1.0148 | 0.7945 | 0.8518 | 0.080* | |
C8 | 0.8974 (8) | 0.7178 (3) | 0.7948 (2) | 0.0714 (14) | |
H8 | 1.0073 | 0.7225 | 0.7687 | 0.086* | |
C9 | 0.7367 (9) | 0.6677 (3) | 0.7827 (2) | 0.0719 (14) | |
H9 | 0.7358 | 0.6378 | 0.7490 | 0.086* | |
C10 | 0.5786 (8) | 0.6622 (3) | 0.8209 (2) | 0.0676 (14) | |
H10 | 0.4654 | 0.6289 | 0.8134 | 0.081* | |
C11 | 0.5844 (7) | 0.7059 (3) | 0.8708 (2) | 0.0639 (14) | |
H11 | 0.4767 | 0.7006 | 0.8975 | 0.077* | |
C12 | 0.7426 (8) | 0.8029 (3) | 0.9356 (2) | 0.0698 (14) | |
H12A | 0.7891 | 0.7711 | 0.9685 | 0.084* | |
H12B | 0.5977 | 0.8192 | 0.9425 | 0.084* | |
C13 | 0.8832 (8) | 0.8726 (3) | 0.9338 (2) | 0.0676 (14) | |
C14 | 1.0777 (8) | 0.8759 (3) | 0.9635 (2) | 0.0739 (15) | |
H14 | 1.1219 | 0.8352 | 0.9873 | 0.089* | |
C15 | 1.2048 (8) | 0.9382 (3) | 0.9581 (2) | 0.0760 (15) | |
H15 | 1.3346 | 0.9409 | 0.9788 | 0.091* | |
C16 | 1.1415 (8) | 0.9967 (3) | 0.9222 (2) | 0.0734 (15) | |
C17 | 0.9490 (8) | 0.9963 (3) | 0.8929 (2) | 0.0734 (15) | |
H17 | 0.9070 | 1.0374 | 0.8693 | 0.088* | |
C18 | 0.8177 (8) | 0.9335 (3) | 0.8990 (2) | 0.0711 (14) | |
H18 | 0.6850 | 0.9322 | 0.8797 | 0.085* | |
N1 | 0.7423 (6) | 0.7562 (2) | 0.88191 (17) | 0.0604 (10) | |
Br1 | 1.32793 (10) | 1.08044 (4) | 0.91032 (4) | 0.1280 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0331 (3) | 0.0429 (3) | 0.0418 (3) | −0.0027 (2) | 0.0011 (2) | −0.0031 (3) |
S1 | 0.0362 (6) | 0.0524 (7) | 0.0486 (7) | −0.0095 (5) | 0.0055 (5) | −0.0075 (6) |
S2 | 0.0497 (7) | 0.0665 (8) | 0.0493 (7) | −0.0109 (6) | 0.0072 (6) | −0.0152 (6) |
S3 | 0.0845 (9) | 0.0773 (10) | 0.0517 (8) | −0.0282 (7) | −0.0026 (7) | −0.0149 (7) |
S4 | 0.0424 (6) | 0.0550 (8) | 0.0538 (7) | −0.0120 (5) | −0.0026 (5) | −0.0059 (6) |
S5 | 0.0366 (6) | 0.0653 (8) | 0.0546 (7) | −0.0112 (5) | 0.0080 (5) | −0.0144 (6) |
S6 | 0.0358 (6) | 0.0478 (7) | 0.0480 (7) | −0.0062 (5) | 0.0028 (5) | −0.0059 (5) |
S7 | 0.0473 (6) | 0.0595 (8) | 0.0585 (8) | −0.0079 (6) | −0.0036 (6) | −0.0135 (6) |
S8 | 0.0724 (9) | 0.0846 (11) | 0.0699 (9) | 0.0032 (7) | −0.0121 (7) | −0.0338 (8) |
S9 | 0.0519 (7) | 0.0708 (9) | 0.0477 (7) | −0.0024 (6) | 0.0049 (6) | −0.0142 (6) |
S10 | 0.0365 (6) | 0.0644 (8) | 0.0486 (7) | −0.0076 (5) | 0.0057 (5) | −0.0101 (6) |
C1 | 0.039 (2) | 0.041 (3) | 0.041 (2) | −0.0013 (19) | 0.0012 (19) | −0.001 (2) |
C2 | 0.056 (3) | 0.047 (3) | 0.036 (2) | −0.008 (2) | −0.006 (2) | 0.003 (2) |
C3 | 0.034 (2) | 0.045 (3) | 0.046 (3) | −0.0030 (19) | −0.0021 (19) | −0.003 (2) |
C4 | 0.038 (2) | 0.043 (3) | 0.037 (2) | −0.0011 (19) | −0.0062 (18) | 0.005 (2) |
C5 | 0.048 (2) | 0.048 (3) | 0.050 (3) | 0.012 (2) | −0.012 (2) | −0.007 (2) |
C6 | 0.040 (2) | 0.043 (3) | 0.040 (2) | 0.0031 (19) | −0.0016 (19) | 0.000 (2) |
C7 | 0.062 (3) | 0.071 (4) | 0.067 (4) | −0.007 (3) | 0.007 (3) | 0.009 (3) |
C8 | 0.067 (3) | 0.077 (4) | 0.071 (4) | 0.003 (3) | 0.007 (3) | 0.005 (3) |
C9 | 0.075 (4) | 0.067 (4) | 0.073 (4) | 0.005 (3) | −0.009 (3) | 0.007 (3) |
C10 | 0.067 (4) | 0.059 (4) | 0.075 (4) | −0.006 (3) | −0.015 (3) | 0.016 (3) |
C11 | 0.062 (3) | 0.059 (3) | 0.070 (4) | −0.008 (3) | −0.001 (3) | 0.019 (3) |
C12 | 0.078 (3) | 0.066 (4) | 0.065 (4) | −0.005 (3) | 0.007 (3) | 0.007 (3) |
C13 | 0.077 (4) | 0.060 (4) | 0.065 (4) | −0.002 (3) | −0.001 (3) | 0.005 (3) |
C14 | 0.082 (4) | 0.065 (4) | 0.074 (4) | 0.002 (3) | −0.009 (3) | 0.009 (3) |
C15 | 0.077 (4) | 0.068 (4) | 0.081 (4) | 0.002 (3) | −0.013 (3) | 0.003 (3) |
C16 | 0.096 (4) | 0.070 (4) | 0.083 (4) | −0.003 (3) | −0.008 (3) | 0.004 (3) |
C17 | 0.079 (4) | 0.059 (4) | 0.082 (4) | 0.000 (3) | −0.011 (3) | 0.011 (3) |
C18 | 0.076 (4) | 0.060 (4) | 0.077 (4) | −0.001 (3) | −0.009 (3) | 0.005 (3) |
N1 | 0.059 (3) | 0.060 (3) | 0.063 (3) | −0.007 (2) | 0.004 (2) | 0.012 (2) |
Br1 | 0.0988 (5) | 0.0863 (5) | 0.1987 (8) | −0.0306 (4) | −0.0005 (5) | 0.0174 (5) |
Ni1—S5 | 2.1504 (11) | C8—C9 | 1.356 (6) |
Ni1—S6 | 2.1609 (11) | C8—H8 | 0.9300 |
Ni1—S10 | 2.1664 (12) | C9—C10 | 1.345 (6) |
Ni1—S1 | 2.1707 (12) | C9—H9 | 0.9300 |
S1—C1 | 1.715 (4) | C10—C11 | 1.370 (6) |
S2—C2 | 1.724 (4) | C10—H10 | 0.9300 |
S2—C1 | 1.738 (4) | C11—N1 | 1.342 (5) |
S3—C2 | 1.644 (4) | C11—H11 | 0.9300 |
S4—C2 | 1.720 (4) | C12—N1 | 1.472 (5) |
S4—C3 | 1.747 (4) | C12—C13 | 1.503 (6) |
S5—C3 | 1.690 (4) | C12—H12A | 0.9700 |
S6—C4 | 1.707 (4) | C12—H12B | 0.9700 |
S7—C5 | 1.727 (4) | C13—C14 | 1.378 (6) |
S7—C4 | 1.741 (4) | C13—C18 | 1.380 (6) |
S8—C5 | 1.645 (4) | C14—C15 | 1.357 (6) |
S9—C5 | 1.718 (4) | C14—H14 | 0.9300 |
S9—C6 | 1.747 (4) | C15—C16 | 1.359 (6) |
S10—C6 | 1.702 (4) | C15—H15 | 0.9300 |
C1—C3 | 1.370 (5) | C16—C17 | 1.361 (6) |
C4—C6 | 1.365 (5) | C16—Br1 | 1.896 (5) |
C7—N1 | 1.344 (5) | C17—C18 | 1.380 (6) |
C7—C8 | 1.358 (6) | C17—H17 | 0.9300 |
C7—H7 | 0.9300 | C18—H18 | 0.9300 |
S5—Ni1—S6 | 178.09 (5) | C7—C8—H8 | 119.3 |
S5—Ni1—S10 | 85.25 (4) | C10—C9—C8 | 118.2 (5) |
S6—Ni1—S10 | 92.96 (4) | C10—C9—H9 | 120.9 |
S5—Ni1—S1 | 92.93 (4) | C8—C9—H9 | 120.9 |
S6—Ni1—S1 | 88.87 (4) | C9—C10—C11 | 120.0 (5) |
S10—Ni1—S1 | 177.60 (5) | C9—C10—H10 | 120.0 |
C1—S1—Ni1 | 101.94 (13) | C11—C10—H10 | 120.0 |
C2—S2—C1 | 97.93 (19) | N1—C11—C10 | 121.4 (5) |
C2—S4—C3 | 97.73 (18) | N1—C11—H11 | 119.3 |
C3—S5—Ni1 | 102.76 (13) | C10—C11—H11 | 119.3 |
C4—S6—Ni1 | 102.37 (13) | N1—C12—C13 | 114.1 (4) |
C5—S7—C4 | 97.57 (19) | N1—C12—H12A | 108.7 |
C5—S9—C6 | 97.41 (19) | C13—C12—H12A | 108.7 |
C6—S10—Ni1 | 101.90 (14) | N1—C12—H12B | 108.7 |
C3—C1—S1 | 120.6 (3) | C13—C12—H12B | 108.7 |
C3—C1—S2 | 115.6 (3) | H12A—C12—H12B | 107.6 |
S1—C1—S2 | 123.7 (2) | C14—C13—C18 | 119.6 (5) |
S3—C2—S4 | 122.2 (2) | C14—C13—C12 | 122.1 (5) |
S3—C2—S2 | 124.6 (2) | C18—C13—C12 | 118.3 (5) |
S4—C2—S2 | 113.2 (2) | C15—C14—C13 | 120.2 (5) |
C1—C3—S5 | 121.7 (3) | C15—C14—H14 | 119.9 |
C1—C3—S4 | 115.5 (3) | C13—C14—H14 | 119.9 |
S5—C3—S4 | 122.8 (2) | C14—C15—C16 | 119.7 (5) |
C6—C4—S6 | 120.8 (3) | C14—C15—H15 | 120.2 |
C6—C4—S7 | 115.6 (3) | C16—C15—H15 | 120.2 |
S6—C4—S7 | 123.6 (2) | C15—C16—C17 | 121.9 (5) |
S8—C5—S9 | 123.7 (3) | C15—C16—Br1 | 119.6 (4) |
S8—C5—S7 | 122.8 (2) | C17—C16—Br1 | 118.4 (4) |
S9—C5—S7 | 113.5 (2) | C16—C17—C18 | 118.6 (5) |
C4—C6—S10 | 121.9 (3) | C16—C17—H17 | 120.7 |
C4—C6—S9 | 115.9 (3) | C18—C17—H17 | 120.7 |
S10—C6—S9 | 122.2 (2) | C17—C18—C13 | 120.1 (5) |
N1—C7—C8 | 120.1 (5) | C17—C18—H18 | 120.0 |
N1—C7—H7 | 119.9 | C13—C18—H18 | 120.0 |
C8—C7—H7 | 119.9 | C11—N1—C7 | 118.7 (4) |
C9—C8—C7 | 121.5 (5) | C11—N1—C12 | 120.0 (4) |
C9—C8—H8 | 119.3 | C7—N1—C12 | 121.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···S3i | 0.93 | 2.70 | 3.557 (5) | 154 |
C11—H11···S5ii | 0.93 | 2.68 | 3.570 (5) | 161 |
C17—H17···S3iii | 0.93 | 2.85 | 3.773 (5) | 170 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x+1, y+1, z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H11BrN)[Ni(C3S5)2] |
Mr | 700.57 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.275 (1), 17.438 (3), 22.839 (3) |
β (°) | 91.87 (1) |
V (Å3) | 2497.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.22 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1990) |
Tmin, Tmax | 0.465, 0.523 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12855, 4626, 2953 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.079, 1.00 |
No. of reflections | 4626 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.29 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
Ni1—S5 | 2.1504 (11) | S5—C3 | 1.690 (4) |
Ni1—S6 | 2.1609 (11) | S6—C4 | 1.707 (4) |
Ni1—S10 | 2.1664 (12) | S7—C5 | 1.727 (4) |
Ni1—S1 | 2.1707 (12) | S7—C4 | 1.741 (4) |
S1—C1 | 1.715 (4) | S8—C5 | 1.645 (4) |
S2—C2 | 1.724 (4) | S9—C5 | 1.718 (4) |
S2—C1 | 1.738 (4) | S9—C6 | 1.747 (4) |
S3—C2 | 1.644 (4) | S10—C6 | 1.702 (4) |
S4—C2 | 1.720 (4) | C7—N1 | 1.344 (5) |
S4—C3 | 1.747 (4) | C16—Br1 | 1.896 (5) |
S5—Ni1—S6 | 178.09 (5) | S5—Ni1—S1 | 92.93 (4) |
S5—Ni1—S10 | 85.25 (4) | S6—Ni1—S1 | 88.87 (4) |
S6—Ni1—S10 | 92.96 (4) | S10—Ni1—S1 | 177.60 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···S3i | 0.93 | 2.70 | 3.557 (5) | 154 |
C11—H11···S5ii | 0.93 | 2.68 | 3.570 (5) | 161 |
C17—H17···S3iii | 0.93 | 2.85 | 3.773 (5) | 170 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x+1, y+1, z+1. |
A great deal of work has been reported on the synthesis and characterization of different types of bis-dithiolate metal complexes (dmit2− is 2-thioxo-1,3-dithiole-4,5-dithiolate). The studies on these bis-dithiolate metal compounds have been extended to other properties and utilization, such as conducting Langmuir–Blodgett films, unconventional magnetic properties, and non-linear optics (NLO). Recent tentative research works on the interplay of conducting, magnetic and NLO properties in such compounds are reported (Patrick, 1999).
In order to study the properties of interplay of magnetic, the title compound, (I), was synthesized. The crystal structure shows that the coordination around the NiIII atom is approximately planar [the Ni—S bond lengths range from 2.1504 (11) to 2.1707 (12) Å]. Two phenyl rings of different anions are parallel, while the pyridine ring is parallel with the Ni(dmit)2 plane.
There are two poles in the structure (Fig. 1). One is composited by Ni(dmit)2 anions, the other is composited by pyridine cations. Some non-classical hydrogen bonds (C—H···S) are found (Table 2). They range from 3.557 (5) to 3.773 (5) Å. The anions composite double deck layers. In these layers, there are some weak S···S and Ni···Ni interactions between layers and weak S···S interactions between different ions in the same layer (Fig. 2). All the S···S, Ni···Ni and non-classical hydrogen bonds extend the molecules into a three-dimensional supramolecular network structure.