4,5,9,10-Tetra­hydro-4,9-methano­dithieno­[3,2-b:3',2'-f][1,5]­diazo­cine

In the title compound, C₁₁H₁₀N₂S₂, which is the first thio­phene analogue of Tröger's base, the dihedral angle between the two thio­phene rings is 100.73 (7)°.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](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

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S1. Comment

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.

S2. Experimental

The title compound, (2), was prepared according to the procedure of Kobayashi et al. (2002), and recrystallized from methanol to give colorless blocks.

Computing details

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.

Figures

Fig. 1. A view of the title compound, (2), showing the atom-labelling scheme and 50% displacement ellipsoids for non-H atoms.

(2)

Crystal data

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) Å^3	Block, colorless
Z = 4	0.15 × 0.10 × 0.05 mm

Data collection

Rigaku R-AXIS RAPID Imaging Plate diffractometer	2255 reflections with F^2 > 2σ(F^2)
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

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.057P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

Special details

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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···C2^i	3.517 (2)	C5···C8^ii	3.574 (3)
N4···C8^ii	3.508 (3)	C10···C12^i	3.450 (3)
N9···C2^iii	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.