Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008961/ob6238sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008961/ob62382sup2.hkl |
CCDC reference: 214805
Key indicators
- Single-crystal X-ray study
- T = 93 K
- Mean (C-C) = 0.003 Å
- R factor = 0.043
- wR factor = 0.101
- Data-to-parameter ratio = 21.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound, (2), was prepared according to the procedure of Kobayashi et al. (2002), and recrystallized from methanol to give colorless blocks.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Fig. 1. A view of the title compound, (2), showing the atom-labelling scheme and 50% displacement ellipsoids for non-H atoms. |
C11H10N2S2 | F(000) = 488.00 |
Mr = 234.33 | Dx = 1.523 Mg m−3 |
Monoclinic, P21/c | Melting point: 444 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.7107 Å |
a = 7.700 (2) Å | Cell parameters from 10963 reflections |
b = 19.601 (5) Å | θ = 3.0–30.0° |
c = 7.332 (2) Å | µ = 0.48 mm−1 |
β = 112.58 (2)° | T = 93 K |
V = 1021.8 (5) Å3 | Block, colorless |
Z = 4 | 0.15 × 0.10 × 0.05 mm |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 2255 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.034 |
ω scans | θmax = 30.0° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→10 |
Tmin = 0.879, Tmax = 0.976 | k = −27→26 |
12265 measured reflections | l = −10→10 |
2979 independent reflections |
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.101 | (Δ/σ)max = 0.0002 |
S = 1.02 | Δρmax = 0.69 e Å−3 |
2969 reflections | Δρmin = −0.27 e Å−3 |
136 parameters |
C11H10N2S2 | V = 1021.8 (5) Å3 |
Mr = 234.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.700 (2) Å | µ = 0.48 mm−1 |
b = 19.601 (5) Å | T = 93 K |
c = 7.332 (2) Å | 0.15 × 0.10 × 0.05 mm |
β = 112.58 (2)° |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 2979 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2255 reflections with F2 > 2σ(F2) |
Tmin = 0.879, Tmax = 0.976 | Rint = 0.034 |
12265 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 136 parameters |
wR(F2) = 0.101 | H-atom parameters not refined |
S = 1.02 | Δρmax = 0.69 e Å−3 |
2969 reflections | Δρmin = −0.27 e Å−3 |
Refinement. Refinement using reflections with F2 > −3.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.77185 (7) | 0.69813 (3) | 0.84722 (8) | 0.0180 (1) | |
S6 | 0.26015 (7) | 0.46034 (2) | 0.45873 (7) | 0.0142 (1) | |
N4 | 0.2836 (2) | 0.62489 (8) | 0.8129 (2) | 0.0131 (3) | |
N9 | 0.2245 (2) | 0.66101 (8) | 0.4729 (2) | 0.0128 (4) | |
C2 | 0.7892 (3) | 0.6589 (1) | 1.0647 (3) | 0.0180 (4) | |
C3 | 0.6215 (3) | 0.63271 (10) | 1.0528 (3) | 0.0157 (4) | |
C5 | 0.2550 (3) | 0.55097 (9) | 0.7655 (3) | 0.0131 (4) | |
C7 | 0.2474 (3) | 0.4966 (1) | 0.2395 (3) | 0.0157 (4) | |
C8 | 0.2354 (3) | 0.5662 (1) | 0.2430 (3) | 0.0145 (4) | |
C10 | 0.4067 (3) | 0.6971 (1) | 0.5264 (3) | 0.0149 (4) | |
C11 | 0.5355 (3) | 0.67843 (10) | 0.7346 (3) | 0.0139 (4) | |
C12 | 0.4761 (3) | 0.64410 (10) | 0.8628 (3) | 0.0131 (4) | |
C13 | 0.2490 (3) | 0.53886 (9) | 0.5597 (3) | 0.0115 (4) | |
C14 | 0.2376 (2) | 0.59025 (10) | 0.4287 (3) | 0.0117 (4) | |
C15 | 0.1636 (3) | 0.66537 (10) | 0.6405 (3) | 0.0142 (4) | |
H2 | 0.9023 | 0.6560 | 1.1789 | 0.0216* | |
H3 | 0.6032 | 0.6096 | 1.1579 | 0.0189* | |
H5a | 0.3558 | 0.5257 | 0.8580 | 0.0158* | |
H5b | 0.1397 | 0.5366 | 0.7721 | 0.0158* | |
H7 | 0.2487 | 0.4713 | 0.1295 | 0.0188* | |
H8 | 0.2266 | 0.5951 | 0.1357 | 0.0174* | |
H10a | 0.4639 | 0.6842 | 0.4375 | 0.0179* | |
H10b | 0.3856 | 0.7450 | 0.5184 | 0.0179* | |
H15a | 0.0381 | 0.6490 | 0.5986 | 0.0170* | |
H15b | 0.1678 | 0.7118 | 0.6793 | 0.0170* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0145 (2) | 0.0187 (2) | 0.0187 (2) | −0.0030 (2) | 0.0042 (2) | −0.0010 (2) |
S6 | 0.0157 (2) | 0.0125 (2) | 0.0138 (2) | −0.0002 (2) | 0.0051 (2) | −0.0006 (2) |
N4 | 0.0144 (7) | 0.0132 (7) | 0.0112 (7) | 0.0011 (6) | 0.0044 (6) | −0.0001 (6) |
N9 | 0.0153 (7) | 0.0111 (7) | 0.0120 (7) | 0.0002 (6) | 0.0053 (6) | 0.0010 (6) |
C2 | 0.0170 (9) | 0.0171 (9) | 0.0160 (9) | 0.0033 (7) | 0.0021 (7) | −0.0007 (7) |
C3 | 0.0194 (9) | 0.0145 (8) | 0.0110 (8) | 0.0033 (7) | 0.0033 (7) | −0.0006 (6) |
C5 | 0.0158 (8) | 0.0129 (8) | 0.0114 (8) | 0.0001 (6) | 0.0060 (7) | 0.0025 (6) |
C7 | 0.0161 (9) | 0.0206 (9) | 0.0118 (8) | −0.0003 (7) | 0.0069 (7) | −0.0022 (7) |
C8 | 0.0139 (8) | 0.0191 (9) | 0.0103 (8) | 0.0002 (7) | 0.0047 (7) | 0.0000 (7) |
C10 | 0.0172 (9) | 0.0144 (8) | 0.0127 (8) | −0.0016 (7) | 0.0053 (7) | 0.0014 (7) |
C11 | 0.0138 (8) | 0.0131 (8) | 0.0138 (8) | −0.0006 (6) | 0.0040 (7) | −0.0006 (7) |
C12 | 0.0142 (8) | 0.0119 (8) | 0.0124 (8) | 0.0010 (6) | 0.0043 (7) | −0.0013 (6) |
C13 | 0.0123 (8) | 0.0114 (7) | 0.0105 (7) | 0.0002 (6) | 0.0039 (6) | −0.0002 (6) |
C14 | 0.0113 (8) | 0.0132 (8) | 0.0096 (7) | 0.0013 (6) | 0.0030 (6) | 0.0007 (6) |
C15 | 0.0139 (8) | 0.0149 (8) | 0.0127 (8) | 0.0024 (7) | 0.0039 (7) | 0.0002 (7) |
S1—C2 | 1.728 (2) | C5—C13 | 1.511 (3) |
S1—C11 | 1.729 (2) | C5—H5a | 0.950 |
S6—C7 | 1.726 (2) | C5—H5b | 0.950 |
S6—C13 | 1.724 (2) | C7—C8 | 1.368 (3) |
N4—C5 | 1.486 (2) | C7—H7 | 0.950 |
N4—C12 | 1.433 (2) | C8—C14 | 1.434 (3) |
N4—C15 | 1.478 (2) | C8—H8 | 0.950 |
N9—C10 | 1.483 (3) | C10—C11 | 1.512 (3) |
N9—C14 | 1.437 (2) | C10—H10a | 0.950 |
N9—C15 | 1.477 (2) | C10—H10b | 0.950 |
C2—C3 | 1.362 (3) | C11—C12 | 1.370 (3) |
C2—H2 | 0.950 | C13—C14 | 1.371 (3) |
C3—C12 | 1.430 (3) | C15—H15a | 0.950 |
C3—H3 | 0.950 | C15—H15b | 0.950 |
S1···C2i | 3.517 (2) | C5···C8ii | 3.574 (3) |
N4···C8ii | 3.508 (3) | C10···C12i | 3.450 (3) |
N9···C2iii | 3.534 (3) | ||
C2—S1—C11 | 92.04 (10) | C14—C8—H8 | 124.2 |
C7—S6—C13 | 92.17 (9) | N9—C10—C11 | 109.8 (2) |
C5—N4—C12 | 111.2 (1) | N9—C10—H10a | 109.4 |
C5—N4—C15 | 109.6 (1) | N9—C10—H10b | 109.4 |
C12—N4—C15 | 108.8 (2) | C11—C10—H10a | 109.4 |
C10—N9—C14 | 112.3 (1) | C11—C10—H10b | 109.4 |
C10—N9—C15 | 108.8 (1) | H10a—C10—H10b | 109.5 |
C14—N9—C15 | 108.4 (1) | S1—C11—C10 | 126.2 (1) |
S1—C2—C3 | 111.9 (1) | S1—C11—C12 | 110.5 (1) |
S1—C2—H2 | 124.0 | C10—C11—C12 | 123.3 (2) |
C3—C2—H2 | 124.0 | N4—C12—C3 | 123.6 (2) |
C2—C3—C12 | 111.9 (2) | N4—C12—C11 | 122.6 (2) |
C2—C3—H3 | 124.1 | C3—C12—C11 | 113.7 (2) |
C12—C3—H3 | 124.1 | S6—C13—C5 | 125.6 (1) |
N4—C5—C13 | 109.3 (1) | S6—C13—C14 | 110.8 (1) |
N4—C5—H5a | 109.5 | C5—C13—C14 | 123.6 (2) |
N4—C5—H5b | 109.5 | N9—C14—C8 | 123.7 (2) |
C13—C5—H5a | 109.5 | N9—C14—C13 | 122.8 (2) |
C13—C5—H5b | 109.5 | C8—C14—C13 | 113.4 (2) |
H5a—C5—H5b | 109.5 | N4—C15—N9 | 112.7 (2) |
S6—C7—C8 | 111.9 (1) | N4—C15—H15a | 108.7 |
S6—C7—H7 | 124.0 | N4—C15—H15b | 108.7 |
C8—C7—H7 | 124.1 | N9—C15—H15a | 108.7 |
C7—C8—C14 | 111.7 (2) | N9—C15—H15b | 108.7 |
C7—C8—H8 | 124.2 | H15a—C15—H15b | 109.5 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y, z+1; (iii) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C11H10N2S2 |
Mr | 234.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 93 |
a, b, c (Å) | 7.700 (2), 19.601 (5), 7.332 (2) |
β (°) | 112.58 (2) |
V (Å3) | 1021.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.15 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.879, 0.976 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 12265, 2979, 2255 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.101, 1.02 |
No. of reflections | 2969 |
No. of parameters | 136 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.69, −0.27 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), TEXSAN (Molecular Structure Corporation & Rigaku, 1999), SIR97 (Altomare et al., 1999), TEXSAN, ORTEPII (Johnson, 1976).
S1—C2 | 1.728 (2) | N9—C15 | 1.477 (2) |
S1—C11 | 1.729 (2) | C2—C3 | 1.362 (3) |
S6—C7 | 1.726 (2) | C3—C12 | 1.430 (3) |
S6—C13 | 1.724 (2) | C5—C13 | 1.511 (3) |
N4—C5 | 1.486 (2) | C7—C8 | 1.368 (3) |
N4—C12 | 1.433 (2) | C8—C14 | 1.434 (3) |
N4—C15 | 1.478 (2) | C10—C11 | 1.512 (3) |
N9—C10 | 1.483 (3) | C11—C12 | 1.370 (3) |
N9—C14 | 1.437 (2) | C13—C14 | 1.371 (3) |
Tröger's base, (1), and its analogues have been recently received much attention as a basic skeleton to construct molecular receptors, due to the rigid structure and the concave shape (Demeunynck & Tatibouët, 1999). However, Tröger's base and its analogues exhibit various values of the dihedral (hinge) angles between two aromatic rings depending on the fused aromatic rings and their substituents, in spite of the rigid bicyclic skeleton (Demeunynck & Tatibouët, 1999). For example, the dihedral angle of (1) was reported as being 92.9 (2) and 97.4 (2)° (Wilcox, 1985; Sucholeiki et al., 1988). The angles vary from 88.6 (1) to 104.01 (6)°, depending on the substituents of the benzene ring. The dihedral angles of heteroaromatic analogues, such as pyrazole [96.4 (4)°; Cudero et al., 1997] and porphyrin (81.0 and 89.7°; Crossley et al., 1995) were also reported.
We recently reported the synthesis of the title compound, (2) (Kobayashi et al., 2002), which is the first example of a thiophene analogue of the Tröger's base. An X-ray crystal structure determination of (2) was undertaken in order to estimate the concave space as well as the dihedral angle between two thiophene rings.
No significant difference of the bond lengths and angles for the thiophene ring of (2) was observed when compared with those previously reported for thiophene (Nygaard et al., 1969) and a thiophene fused with a norbornadiene skeleton (Kobayashi et al., 1993). The dihedral angle between two thiophene rings was found to be 100.73 (7)°, which is slightly larger than that of the Tröger's base. Therefore, it is of interest to synthesize molecular receptors constructed with (2) and to investigate the effect of the concave space for selective binding. The synthetic study toward new molecular receptors will be reported elsewhere in due course.