C. P. Sakthidharan,
R. Niewa,
D. A. Zherebtsov,
F. V. Podgornov,
Y. V. Matveychuk,
E. V. Bartashevich,
S. A. Nayfert,
S. A. Adonin,
M. V. Gavrilyak,
V. A. Boronin,
M. A. Polozov,
S. Karthikeyan,
M. Sarojadevi,
K. Rajakumar and
P. Prabunathan The structures of the red polymorph (space group P1) and the black polymorph (space group P21/c) of 4,4′-dimethyl-6,6′-dichlorothioindigo were solved from single-crystal samples. For both polymorphs, the spatial stacking of the flat molecules is driven by π-stacking and noncovalent interactions within the layers. Spectroscopic (UV–vis, IR and photoluminescence) and thermal properties of the red polymorph were investigated experimentally. The bandgap of this polymorph was estimated as 2.08 eV at room temperature. It is demonstrated that the electric conductivity of the red polymorph follows the hopping mechanism.
Supporting information
CCDC references: 2000467; 2000468
For both structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Crystal data top
C18H10Cl2O2S2 | F(000) = 400 |
Mr = 393.28 | Dx = 1.740 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 4.6455 (3) Å | Cell parameters from 1880 reflections |
b = 15.9427 (8) Å | θ = 2.4–28.3° |
c = 10.1908 (6) Å | µ = 0.72 mm−1 |
β = 95.846 (4)° | T = 130 K |
V = 750.82 (8) Å3 | Black needle, black |
Z = 2 | 0.35 × 0.11 × 0.08 mm |
Data collection top
BRUKER AXS (Kappa APEX II Duo) diffractometer | 1410 reflections with I > 2σ(I) |
Radiation source: conventional tube | Rint = 0.056 |
Graphite monochromator | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan Blessing, 1995 | h = −6→6 |
Tmin = 0.788, Tmax = 0.948 | k = −21→21 |
12979 measured reflections | l = −13→13 |
1882 independent reflections | |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.201 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.107P)2 + 2.7825P] where P = (Fo2 + 2Fc2)/3 |
1882 reflections | (Δ/σ)max = 0.002 |
115 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −1.31 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.2746 (2) | 0.54976 (6) | 0.35512 (10) | 0.0121 (3) | |
Cl1 | 0.8916 (3) | 0.39280 (9) | −0.00068 (13) | 0.0337 (4) | |
O1 | −0.0020 (6) | 0.34048 (17) | 0.4845 (3) | 0.0160 (6) | |
C2 | 0.4055 (8) | 0.4608 (2) | 0.2771 (4) | 0.0123 (8) | |
C3 | 0.5920 (8) | 0.4662 (3) | 0.1779 (4) | 0.0139 (8) | |
H3 | 0.6591 | 0.5186 | 0.1488 | 0.016 (12)* | |
C4 | 0.3911 (9) | 0.3087 (2) | 0.2646 (4) | 0.0140 (8) | |
C5 | 0.5771 (9) | 0.3137 (3) | 0.1649 (4) | 0.0158 (8) | |
H5 | 0.6380 | 0.2639 | 0.1246 | 0.019 (13)* | |
C6 | 0.3085 (8) | 0.3837 (2) | 0.3201 (4) | 0.0120 (7) | |
C7 | 0.0834 (8) | 0.4858 (2) | 0.4533 (4) | 0.0111 (7) | |
C9 | 0.6729 (8) | 0.3913 (3) | 0.1248 (4) | 0.0164 (8) | |
C10 | 0.2851 (9) | 0.2253 (3) | 0.3056 (5) | 0.0189 (9) | |
H10A | 0.3599 | 0.1813 | 0.2512 | 0.043 (18)* | |
H10B | 0.0731 | 0.2246 | 0.2941 | 0.06 (2)* | |
H10C | 0.3528 | 0.2153 | 0.3986 | 0.05 (2)* | |
C11 | 0.1172 (8) | 0.3945 (2) | 0.4246 (4) | 0.0115 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0126 (5) | 0.0118 (4) | 0.0126 (5) | 0.0004 (3) | 0.0042 (3) | −0.0006 (4) |
Cl1 | 0.0283 (7) | 0.0453 (8) | 0.0287 (7) | 0.0051 (5) | 0.0093 (5) | −0.0022 (5) |
O1 | 0.0210 (15) | 0.0108 (13) | 0.0168 (15) | 0.0000 (11) | 0.0047 (11) | −0.0001 (11) |
C2 | 0.0082 (17) | 0.0157 (18) | 0.0131 (19) | 0.0000 (13) | 0.0006 (14) | −0.0027 (14) |
C3 | 0.0103 (18) | 0.0192 (19) | 0.0125 (19) | 0.0010 (14) | 0.0030 (14) | 0.0003 (15) |
C4 | 0.0137 (18) | 0.0159 (18) | 0.0117 (19) | 0.0054 (14) | −0.0015 (15) | −0.0013 (15) |
C5 | 0.0158 (19) | 0.019 (2) | 0.0122 (19) | 0.0081 (15) | 0.0004 (15) | −0.0050 (15) |
C6 | 0.0105 (17) | 0.0145 (18) | 0.0110 (18) | 0.0022 (14) | 0.0004 (14) | −0.0012 (14) |
C7 | 0.0102 (16) | 0.0116 (17) | 0.0114 (18) | 0.0009 (13) | 0.0002 (14) | 0.0016 (14) |
C9 | 0.0107 (18) | 0.028 (2) | 0.0103 (19) | 0.0032 (15) | 0.0013 (14) | −0.0041 (16) |
C10 | 0.022 (2) | 0.0146 (19) | 0.020 (2) | 0.0052 (15) | 0.0025 (17) | −0.0009 (16) |
C11 | 0.0093 (16) | 0.0131 (17) | 0.0118 (18) | 0.0030 (13) | −0.0008 (14) | −0.0019 (14) |
Geometric parameters (Å, º) top
S1—C7 | 1.735 (4) | C4—C10 | 1.492 (6) |
S1—C2 | 1.764 (4) | C5—C9 | 1.390 (6) |
Cl1—C9 | 1.713 (4) | C5—H5 | 0.9500 |
O1—C11 | 1.221 (5) | C6—C11 | 1.465 (5) |
C2—C6 | 1.395 (5) | C7—C7i | 1.365 (7) |
C2—C3 | 1.399 (5) | C7—C11 | 1.495 (5) |
C3—C9 | 1.379 (6) | C10—H10A | 0.9800 |
C3—H3 | 0.9500 | C10—H10B | 0.9800 |
C4—C6 | 1.394 (5) | C10—H10C | 0.9800 |
C4—C5 | 1.402 (6) | | |
| | | |
C7—S1—C2 | 90.41 (18) | C7i—C7—C11 | 122.6 (4) |
C6—C2—C3 | 121.6 (4) | C7i—C7—S1 | 124.5 (4) |
C6—C2—S1 | 115.5 (3) | C11—C7—S1 | 112.9 (3) |
C3—C2—S1 | 122.9 (3) | C3—C9—C5 | 123.2 (4) |
C9—C3—C2 | 116.3 (4) | C3—C9—Cl1 | 119.1 (3) |
C9—C3—H3 | 121.8 | C5—C9—Cl1 | 117.6 (3) |
C2—C3—H3 | 121.8 | C4—C10—H10A | 109.5 |
C6—C4—C5 | 117.4 (4) | C4—C10—H10B | 109.5 |
C6—C4—C10 | 122.6 (4) | H10A—C10—H10B | 109.5 |
C5—C4—C10 | 120.0 (4) | C4—C10—H10C | 109.5 |
C9—C5—C4 | 120.2 (4) | H10A—C10—H10C | 109.5 |
C9—C5—H5 | 119.9 | H10B—C10—H10C | 109.5 |
C4—C5—H5 | 119.9 | O1—C11—C6 | 128.3 (4) |
C4—C6—C2 | 121.2 (4) | O1—C11—C7 | 121.8 (3) |
C4—C6—C11 | 127.5 (4) | C6—C11—C7 | 109.9 (3) |
C2—C6—C11 | 111.3 (3) | | |
Symmetry code: (i) −x, −y+1, −z+1. |
Crystal data top
C18H10Cl2O2S2 | Z = 1 |
Mr = 393.28 | F(000) = 200 |
Triclinic, P1 | Dx = 1.714 Mg m−3 |
a = 3.8612 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 8.8249 (3) Å | Cell parameters from 1288 reflections |
c = 11.2319 (5) Å | θ = 4.0–66.5° |
α = 94.972 (3)° | µ = 6.47 mm−1 |
β = 92.244 (3)° | T = 130 K |
γ = 90.968 (3)° | Red needle, red |
V = 380.91 (3) Å3 | 0.17 × 0.04 × 0.03 mm |
Data collection top
BRUKER AXS (Kappa APEX II Duo) diffractometer | 1141 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 66.6°, θmin = 4.0° |
Absorption correction: multi-scan Blessing 1995 | h = −4→4 |
Tmin = 0.409, Tmax = 0.820 | k = −8→10 |
5028 measured reflections | l = −12→13 |
1290 independent reflections | |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.72 | w = 1/[σ2(Fo2) + (0.0653P)2 + 0.9825P] where P = (Fo2 + 2Fc2)/3 |
1290 reflections | (Δ/σ)max = 0.001 |
115 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.75448 (14) | 1.07494 (6) | 0.83555 (5) | 0.01482 (19) | |
Cl4 | 0.11393 (15) | 0.75465 (6) | 0.44718 (5) | 0.02008 (19) | |
O2 | 0.9293 (4) | 0.71215 (18) | 0.99625 (15) | 0.0192 (4) | |
C1 | 0.4183 (6) | 0.9049 (3) | 0.6432 (2) | 0.0154 (5) | |
H1 | 0.3780 | 0.9958 | 0.6058 | 0.018 (7)* | |
C3 | 0.9117 (6) | 0.9700 (3) | 0.9499 (2) | 0.0136 (5) | |
C4 | 0.5212 (6) | 0.6313 (3) | 0.7568 (2) | 0.0146 (5) | |
C5 | 0.8327 (6) | 0.8034 (3) | 0.9265 (2) | 0.0146 (5) | |
C6 | 0.3118 (6) | 0.7640 (3) | 0.5898 (2) | 0.0160 (5) | |
C7 | 0.5879 (6) | 0.9063 (3) | 0.7551 (2) | 0.0150 (5) | |
C8 | 0.6397 (6) | 0.7732 (3) | 0.8113 (2) | 0.0146 (5) | |
C9 | 0.3587 (6) | 0.6290 (3) | 0.6439 (2) | 0.0162 (5) | |
H9 | 0.2791 | 0.5351 | 0.6035 | 0.022 (7)* | |
C10 | 0.5632 (7) | 0.4874 (3) | 0.8172 (2) | 0.0196 (5) | |
H10A | 0.4709 | 0.4011 | 0.7639 | 0.042 (9)* | |
H10B | 0.4365 | 0.4946 | 0.8913 | 0.024 (7)* | |
H10C | 0.8096 | 0.4724 | 0.8359 | 0.036 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0165 (3) | 0.0119 (3) | 0.0156 (3) | −0.0004 (2) | −0.0026 (2) | 0.0005 (2) |
Cl4 | 0.0218 (3) | 0.0208 (3) | 0.0168 (3) | −0.0023 (2) | −0.0056 (2) | 0.0004 (2) |
O2 | 0.0220 (9) | 0.0157 (8) | 0.0196 (9) | 0.0006 (7) | −0.0040 (7) | 0.0021 (7) |
C1 | 0.0148 (11) | 0.0149 (12) | 0.0172 (12) | 0.0018 (9) | 0.0011 (10) | 0.0043 (9) |
C3 | 0.0117 (11) | 0.0128 (11) | 0.0164 (11) | 0.0013 (9) | 0.0017 (9) | 0.0013 (9) |
C4 | 0.0120 (11) | 0.0154 (11) | 0.0165 (12) | 0.0015 (9) | 0.0035 (9) | 0.0003 (9) |
C5 | 0.0125 (11) | 0.0158 (11) | 0.0156 (12) | 0.0012 (9) | 0.0027 (9) | 0.0003 (9) |
C6 | 0.0110 (11) | 0.0218 (12) | 0.0147 (12) | −0.0021 (9) | −0.0003 (9) | −0.0011 (9) |
C7 | 0.0110 (11) | 0.0164 (11) | 0.0174 (12) | −0.0003 (9) | 0.0020 (9) | −0.0007 (9) |
C8 | 0.0123 (11) | 0.0154 (11) | 0.0160 (12) | 0.0005 (9) | 0.0021 (9) | 0.0003 (9) |
C9 | 0.0153 (11) | 0.0135 (11) | 0.0192 (12) | −0.0013 (9) | 0.0010 (9) | −0.0022 (9) |
C10 | 0.0241 (13) | 0.0129 (11) | 0.0215 (13) | −0.0019 (10) | −0.0032 (10) | 0.0022 (9) |
Geometric parameters (Å, º) top
S1—C3 | 1.744 (2) | C4—C8 | 1.407 (3) |
S1—C7 | 1.771 (2) | C4—C10 | 1.499 (3) |
Cl4—C6 | 1.742 (2) | C5—C8 | 1.469 (3) |
O2—C5 | 1.224 (3) | C6—C9 | 1.395 (3) |
C1—C6 | 1.382 (3) | C7—C8 | 1.394 (3) |
C1—C7 | 1.393 (3) | C9—H9 | 0.9500 |
C1—H1 | 0.9500 | C10—H10A | 0.9800 |
C3—C3i | 1.355 (5) | C10—H10B | 0.9800 |
C3—C5 | 1.495 (3) | C10—H10C | 0.9800 |
C4—C9 | 1.391 (3) | | |
| | | |
C3—S1—C7 | 90.39 (11) | C1—C7—C8 | 121.8 (2) |
C6—C1—C7 | 116.3 (2) | C1—C7—S1 | 122.94 (18) |
C6—C1—H1 | 121.8 | C8—C7—S1 | 115.24 (18) |
C7—C1—H1 | 121.8 | C7—C8—C4 | 121.0 (2) |
C3i—C3—C5 | 122.5 (3) | C7—C8—C5 | 111.7 (2) |
C3i—C3—S1 | 124.7 (2) | C4—C8—C5 | 127.3 (2) |
C5—C3—S1 | 112.84 (17) | C4—C9—C6 | 120.3 (2) |
C9—C4—C8 | 117.3 (2) | C4—C9—H9 | 119.8 |
C9—C4—C10 | 120.7 (2) | C6—C9—H9 | 119.8 |
C8—C4—C10 | 122.0 (2) | C4—C10—H10A | 109.5 |
O2—C5—C8 | 128.4 (2) | C4—C10—H10B | 109.5 |
O2—C5—C3 | 121.8 (2) | H10A—C10—H10B | 109.5 |
C8—C5—C3 | 109.9 (2) | C4—C10—H10C | 109.5 |
C1—C6—C9 | 123.2 (2) | H10A—C10—H10C | 109.5 |
C1—C6—Cl4 | 118.29 (19) | H10B—C10—H10C | 109.5 |
C9—C6—Cl4 | 118.56 (18) | | |
Symmetry code: (i) −x+2, −y+2, −z+2. |