Structures of tetrathiabenzoquinone derivatives and the order-disorder phase transition

The tetrathiabenzoquinone derivatives 2,3,7,8-tetrahydro-benzo[1,2-b:4,5-b']bis[1,4]dithiin-5,10-dione (1), C₁₀H₈O₂S₄, and 3,4,9,10-tetrahydro-2H,8H-benzo[1,2-b:4,5-b']bis[1,4]dithiepin-6,12-dione (2), C₁₂H₁₂O₂S₄, have attracted attention as new organic pigments. Compound (1) has also been known to exhibit a large third-order non-linear susceptibility. In order to study the electronic structure in the solid state, the crystal structure has been investigated. Compound (1) was found to possess two crystal phases. Phase I is a room-temperature phase in which the molecular conformation is disordered. The other phase II is an ordered phase found at 223 K. Compound (2) is found to be isomorphous with (1) (phase II). Both (1) and (2) form characteristic one-dimensional molecular columns along the stacking c axis and two-dimensional or quasi two-dimensional molecular sheets parallel to the ab plane. Several close van der Waals contacts were observed between the neighboring molecules. Compound (1) was also found to undergo a reversible order-disorder phase transition at ca 265-269 K by X-ray diffraction as well as differential scanning calorimetry.

Computing details

For all compounds, data collection: Rigaku/AFC Diffractometer Control; cell refinement: Rigaku/AFC Diffractometer Control; data reduction: TEXSAN; program(s) used to solve structure: SIR92(Altomare et al., 1994); program(s) used to refine structure: TEXSAN. Molecular graphics: ORTEPII(Johnson, 1976) for 1phaseI; ORTEP II(Johnson, 1976) for 1phaseII, (2). For all compounds, software used to prepare material for publication: TEXSAN.

Figures

(1phaseI) 2,3,7,8-tetrahydro-benzo[1,2 - b:4,5 - b']bis[1,4]dithiin-5,10-dione

Crystal data

C10H8O2S4	F(000) = 592.00
Mr = 288.41	Dx = 1.703 Mg m^−3
Orthorhombic, Ibam	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -I 2 2c	Cell parameters from 22 reflections
a = 9.441 (2) Å	θ = 12.5–14.8°
b = 16.583 (2) Å	µ = 0.82 mm^−1
c = 7.184 (3) Å	T = 296 K
V = 1124.8 (5) Å^3	Prismatic, dark red
Z = 4	0.25 × 0.08 × 0.05 mm

Data collection

Rigaku AFC7R diffractometer	522 reflections with I > 2.0σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω–2θ scans	h = 0→12
Absorption correction: ψ scan ψ scan	k = 0→21
Tmin = 0.959, Tmax = 1.000	l = 0→9
703 measured reflections	3 standard reflections every 150 reflections
703 independent reflections	intensity decay: 0.04%

Refinement

Refinement on F	0 constraints
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo) + 0.00164|Fo|^2]
wR(F^2) = 0.050	(Δ/σ)max = 0.005
S = 1.00	Δρmax = 0.23 e Å^−3
522 reflections	Δρmin = −0.17 e Å^−3
56 parameters	Extinction correction: Zachariasen(1967) type 2 Gaussian isotropic
0 restraints	Extinction coefficient: 0.002 (2)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S(1)	0.16733 (8)	0.02006 (4)	0.0000	0.0691 (3)
S(2)	0.39990 (9)	0.18324 (4)	0.0000	0.0635 (3)
O(1)	0.3206 (2)	−0.1224 (1)	0.0000	0.0625 (6)
C(1)	0.4040 (2)	−0.0660 (2)	0.0000	0.0415 (6)
C(2)	0.3504 (3)	0.0179 (1)	0.0000	0.0413 (6)
C(3)	0.4420 (3)	0.0808 (1)	0.0000	0.0419 (6)
C(4)	0.1299 (5)	0.1247 (3)	0.0611 (7)	0.065 (1)	0.50
C(5)	0.2141 (4)	0.1801 (2)	−0.0624 (7)	0.065 (1)	0.50
H(4a)	0.0316	0.1351	0.0449	0.0788*	0.50
H(4b)	0.1550	0.1338	0.1874	0.0788*	0.50
H(5a)	0.1762	0.2330	−0.0529	0.0778*	0.50
H(5b)	0.2062	0.1619	−0.1875	0.0778*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S(1)	0.0265 (4)	0.0441 (5)	0.1366 (9)	−0.0004 (2)	0.0000	0.0000
S(2)	0.0397 (4)	0.0296 (4)	0.1212 (8)	0.0018 (2)	0.0000	0.0000
O(1)	0.035 (1)	0.0359 (10)	0.116 (2)	−0.0078 (7)	0.0000	0.0000
C(1)	0.029 (1)	0.033 (1)	0.062 (2)	−0.0028 (8)	0.0000	0.0000
C(2)	0.027 (1)	0.033 (1)	0.065 (1)	0.0009 (8)	0.0000	0.0000
C(3)	0.030 (1)	0.030 (1)	0.066 (2)	−0.0002 (9)	0.0000	0.0000
C(4)	0.036 (2)	0.047 (2)	0.113 (5)	0.007 (1)	0.004 (2)	−0.005 (2)
C(5)	0.042 (2)	0.042 (2)	0.110 (5)	0.012 (2)	−0.002 (2)	0.008 (2)

Geometric parameters (Å, º)

S(1)—C(2)	1.729 (3)	C(4)—C(5)	1.505 (6)
S(1)—C(4)	1.824 (4)	C(4)—C(5)^i	1.216 (6)
S(1)—C(4)^i	1.824 (4)	C(4)—H(4a)	0.951
S(2)—C(3)	1.744 (2)	C(4)—H(4a)^i	1.213
S(2)—C(5)	1.811 (4)	C(4)—H(4b)	0.950
S(2)—C(5)^i	1.811 (4)	C(5)—C(5)^i	0.896 (10)
O(1)—C(1)	1.222 (3)	C(5)—H(4b)^i	1.307
C(1)—C(2)	1.481 (3)	C(5)—H(5a)	0.950
C(1)—C(3)^ii	1.475 (3)	C(5)—H(5a)^i	1.258
C(2)—C(3)	1.356 (3)	C(5)—H(5b)	0.951
C(4)—C(4)^i	0.88 (1)
S(1)···S(1)^iii	3.229 (2)	O(1)···C(5)^viii	3.437 (5)
S(1)···S(1)^iv	3.6531 (2)	O(1)···C(5)^ix	3.437 (5)
O(1)···C(4)^v	3.631 (5)	O(1)···H(5a)^vii	2.43
O(1)···C(5)^vi	3.321 (4)	C(1)···C(3)^iv	3.6182 (4)
O(1)···C(5)^vii	3.321 (4)	C(2)···C(2)^iv	3.6407 (7)
C(2)—S(1)—C(4)	102.3 (1)	C(5)^i—C(4)—H(4b)	73.1 (4)
C(2)—S(1)—C(4)^i	102.3 (1)	H(4a)—C(4)—H(4a)^i	31.9 (2)
C(4)—S(1)—C(4)^i	27.9 (3)	H(4a)—C(4)—H(4b)	109.4 (4)
C(3)—S(2)—C(5)	101.1 (1)	H(4a)^i—C(4)—H(4b)	140.2 (4)
C(3)—S(2)—C(5)^i	101.1 (1)	S(2)—C(5)—C(4)	112.5 (3)
C(5)—S(2)—C(5)^i	28.6 (3)	S(2)—C(5)—C(4)^i	130.8 (3)
O(1)—C(1)—C(2)	119.9 (2)	S(2)—C(5)—C(5)^i	75.7 (2)
O(1)—C(1)—C(3)^ii	120.5 (2)	S(2)—C(5)—H(4b)^i	126.9 (3)
C(2)—C(1)—C(3)^ii	119.6 (2)	S(2)—C(5)—H(5a)	108.7 (3)
S(1)—C(2)—C(1)	111.2 (2)	S(2)—C(5)—H(5a)^i	95.3 (3)
S(1)—C(2)—C(3)	128.4 (2)	S(2)—C(5)—H(5b)	108.6 (3)
C(1)—C(2)—C(3)	120.4 (2)	C(4)—C(5)—C(4)^i	35.7 (4)
S(2)—C(3)—C(1)^ii	112.8 (2)	C(4)—C(5)—C(5)^i	53.9 (2)
S(2)—C(3)—C(2)	127.2 (2)	C(4)—C(5)—H(4b)^i	79.7 (3)
C(1)^ii—C(3)—C(2)	120.1 (2)	C(4)—C(5)—H(5a)	108.8 (4)
S(1)—C(4)—C(4)^i	76.1 (2)	C(4)—C(5)—H(5a)^i	83.6 (3)
S(1)—C(4)—C(5)	109.7 (3)	C(4)—C(5)—H(5b)	108.7 (4)
S(1)—C(4)—C(5)^i	126.5 (3)	C(4)^i—C(5)—C(5)^i	89.6 (3)
S(1)—C(4)—H(4a)	109.4 (3)	C(4)^i—C(5)—H(4b)^i	44.0 (3)
S(1)—C(4)—H(4a)^i	97.6 (3)	C(4)^i—C(5)—H(5a)	116.9 (4)
S(1)—C(4)—H(4b)	109.5 (3)	C(4)^i—C(5)—H(5a)^i	109.7 (4)
C(4)^i—C(4)—C(5)	53.9 (2)	C(4)^i—C(5)—H(5b)	73.4 (4)
C(4)^i—C(4)—C(5)^i	90.4 (3)	C(5)^i—C(5)—H(4b)^i	133.4 (2)
C(4)^i—C(4)—H(4a)	83.0 (3)	C(5)^i—C(5)—H(5a)	85.9 (3)
C(4)^i—C(4)—H(4a)^i	51.1 (2)	C(5)^i—C(5)—H(5a)^i	48.9 (2)
C(4)^i—C(4)—H(4b)	162.8 (3)	C(5)^i—C(5)—H(5b)	160.9 (2)
C(5)—C(4)—C(5)^i	36.5 (4)	H(4b)^i—C(5)—H(5a)	115.6 (4)
C(5)—C(4)—H(4a)	109.4 (4)	H(4b)^i—C(5)—H(5a)^i	137.8 (3)
C(5)—C(4)—H(4a)^i	87.0 (3)	H(4b)^i—C(5)—H(5b)	29.6 (1)
C(5)—C(4)—H(4b)	109.5 (4)	H(5a)—C(5)—H(5a)^i	37.0 (2)
C(5)^i—C(4)—H(4a)	120.1 (4)	H(5a)—C(5)—H(5b)	109.4 (4)
C(5)^i—C(4)—H(4a)^i	113.4 (4)	H(5a)^i—C(5)—H(5b)	145.2 (4)
S(1)—C(2)—C(1)—O(1)	0.0	O(1)—C(1)—C(3)^ii—C(2)^ii	180.0
S(1)—C(2)—C(1)—C(3)^ii	180.0	C(1)—C(2)—S(1)—C(4)	165.7 (2)
S(1)—C(2)—C(3)—S(2)	0.0	C(1)—C(2)—S(1)—C(4)^i	−165.7 (2)
S(1)—C(2)—C(3)—C(1)^ii	180.0	C(1)—C(3)^ii—S(2)^ii—C(5)^ii	165.4 (2)
S(1)—C(4)—C(4)^i—C(5)	−127.6 (3)	C(1)—C(3)^ii—S(2)^ii—C(5)^x	−165.4 (2)
S(1)—C(4)—C(4)^i—C(5)^i	−127.6 (3)	C(2)—S(1)—C(4)—C(4)^i	93.11 (5)
S(1)—C(4)—C(5)—S(2)	−74.7 (3)	C(2)—S(1)—C(4)—C(5)	50.3 (3)
S(1)—C(4)—C(5)—C(4)^i	54.7 (3)	C(2)—S(1)—C(4)—C(5)^i	13.1 (5)
S(1)—C(4)—C(5)—C(5)^i	−125.3 (3)	C(2)—S(1)—C(4)^i—C(4)	−93.11 (5)
S(1)—C(4)—C(5)^i—S(2)	2.4 (8)	C(2)—S(1)—C(4)^i—C(5)	−13.1 (5)
S(1)—C(4)—C(5)^i—C(4)^i	72.9 (4)	C(2)—S(1)—C(4)^i—C(5)^i	−50.3 (3)
S(1)—C(4)—C(5)^i—C(5)	72.9 (4)	C(2)—C(3)—S(2)—C(5)	−14.6 (2)
S(1)—C(4)^i—C(4)—C(5)	127.6 (3)	C(2)—C(3)—S(2)—C(5)^i	14.6 (2)
S(1)—C(4)^i—C(4)—C(5)^i	127.6 (3)	C(3)—S(2)—C(5)—C(4)	52.7 (3)
S(1)—C(4)^i—C(5)—S(2)	−2.4 (8)	C(3)—S(2)—C(5)—C(4)^i	16.2 (6)
S(1)—C(4)^i—C(5)—C(4)	−72.9 (4)	C(3)—S(2)—C(5)—C(5)^i	92.88 (5)
S(1)—C(4)^i—C(5)—C(5)^i	−72.9 (4)	C(3)—S(2)—C(5)^i—C(4)	−16.2 (6)
S(1)—C(4)^i—C(5)^i—S(2)	74.7 (3)	C(3)—S(2)—C(5)^i—C(4)^i	−52.7 (3)
S(1)—C(4)^i—C(5)^i—C(4)	−54.7 (3)	C(3)—S(2)—C(5)^i—C(5)	−92.88 (5)
S(1)—C(4)^i—C(5)^i—C(5)	125.3 (3)	C(3)—C(2)—S(1)—C(4)	−14.3 (2)
S(2)—C(3)—C(1)^ii—O(1)^ii	0.0	C(3)—C(2)—S(1)—C(4)^i	14.3 (2)
S(2)—C(3)—C(1)^ii—C(2)^ii	180.0	C(4)—S(1)—C(4)^i—C(5)	80.0 (5)
S(2)—C(3)—C(2)—C(1)	180.0	C(4)—S(1)—C(4)^i—C(5)^i	42.8 (3)
S(2)—C(5)—C(4)—C(4)^i	−129.4 (3)	C(4)—C(4)^i—C(5)—C(5)^i	0.0
S(2)—C(5)—C(4)—C(5)^i	50.6 (3)	C(4)—C(4)^i—C(5)^i—C(5)	180.0
S(2)—C(5)—C(4)^i—C(4)	70.5 (5)	C(4)—C(5)—S(2)—C(5)^i	−40.1 (3)
S(2)—C(5)—C(4)^i—C(5)^i	70.5 (5)	C(4)—C(5)—C(4)^i—C(5)^i	0.0
S(2)—C(5)—C(5)^i—C(4)	−132.5 (3)	C(4)—C(5)—C(5)^i—C(4)^i	0.0
S(2)—C(5)—C(5)^i—C(4)^i	−132.5 (3)	C(4)—C(5)^i—S(2)—C(5)	76.7 (6)
S(2)—C(5)^i—C(4)—C(4)^i	−70.5 (5)	C(4)—C(5)^i—C(4)^i—C(5)	180.0
S(2)—C(5)^i—C(4)—C(5)	−70.5 (5)	C(4)—C(5)^i—C(5)—C(4)^i	0.0
S(2)—C(5)^i—C(4)^i—C(4)	129.4 (3)	C(5)—C(4)—C(4)^i—C(5)^i	0.0
S(2)—C(5)^i—C(4)^i—C(5)	−50.6 (3)	C(5)—C(4)—C(5)^i—C(4)^i	0.0
S(2)—C(5)^i—C(5)—C(4)	132.5 (3)	C(5)—C(4)^i—C(4)—C(5)^i	0.0
S(2)—C(5)^i—C(5)—C(4)^i	132.5 (3)	C(5)—C(4)^i—C(5)^i—C(4)	−180.0
O(1)—C(1)—C(2)—C(3)	180.0

Symmetry codes: (i) x, y, −z; (ii) −x+1, −y, z; (iii) −x, −y, z; (iv) x, −y, −z+1/2; (v) x, −y, z−1/2; (vi) −x+1/2, y−1/2, −z; (vii) −x+1/2, y−1/2, z; (viii) x, −y, −z−1/2; (ix) x, −y, z+1/2; (x) −x+1, −y, −z.

(1phaseII) 2,3,7,8-tetrahydro-benzo[1,2 - b:4,5 - b']bis[1,4]dithiin-5,10-dione

Crystal data

C10H8O2S4	F(000) = 592.00
Mr = 288.41	Dx = 1.749 Mg m^−3
Orthorhombic, Pccn	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 25 reflections
a = 9.401 (4) Å	θ = 23.4–28.1°
b = 16.515 (3) Å	µ = 7.81 mm^−1
c = 7.053 (4) Å	T = 223 K
V = 1095.0 (8) Å^3	Prismatic, dark red
Z = 4	0.12 × 0.09 × 0.07 mm

Data collection

Rigaku AFC7R diffractometer	729 reflections with I > 2.0σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.000
Graphite monochromator	θmax = 70.1°, θmin = 2.7°
ω–2θ scans	h = 0→11
Absorption correction: ψ scan (North, Phillips & Mathews, 1968)	k = 0→20
Tmin = 0.664, Tmax = 1.000	l = 0→8
1037 measured reflections	3 standard reflections every 150 reflections
1037 independent reflections	intensity decay: −2.4%

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.073	H-atom parameters not refined
wR(F^2) = 0.104	w = 1/[σ^2(Fo) + 0.00384|Fo|^2]
S = 1.38	(Δ/σ)max = 0.021
729 reflections	Δρmax = 0.89 e Å^−3
73 parameters	Δρmin = −0.62 e Å^−3

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

	x	y	z	Uiso*/Ueq
S(1)	0.8509 (1)	0.06611 (9)	0.2867 (3)	0.0575 (5)
S(2)	1.0835 (1)	0.23039 (8)	0.3276 (3)	0.0583 (5)
O(1)	0.5693 (4)	0.1275 (3)	0.2949 (7)	0.057 (1)
C(1)	0.6550 (5)	0.1841 (3)	0.3006 (9)	0.045 (1)
C(2)	0.8095 (6)	0.1682 (3)	0.2992 (9)	0.044 (1)
C(3)	0.9001 (6)	0.2325 (3)	0.3083 (10)	0.048 (2)
C(4)	1.0385 (6)	0.0705 (4)	0.236 (1)	0.061 (2)
C(5)	1.1205 (6)	0.1251 (4)	0.366 (1)	0.062 (2)
H(4a)	1.0764	0.0173	0.2457	0.0734*
H(4b)	1.0503	0.0895	0.1094	0.0734*
H(5a)	1.2193	0.1160	0.3467	0.0743*
H(5b)	1.0964	0.1119	0.4933	0.0743*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S(1)	0.0292 (8)	0.0304 (9)	0.113 (1)	0.0007 (5)	0.0005 (7)	0.0000 (7)
S(2)	0.0215 (8)	0.0414 (9)	0.112 (1)	−0.0002 (5)	−0.0037 (7)	0.0000 (8)
O(1)	0.025 (2)	0.034 (2)	0.111 (4)	−0.003 (2)	−0.001 (2)	0.002 (2)
C(1)	0.024 (2)	0.035 (3)	0.076 (4)	0.001 (2)	0.001 (2)	0.001 (3)
C(2)	0.026 (2)	0.034 (3)	0.073 (4)	0.001 (2)	0.001 (2)	0.001 (2)
C(3)	0.022 (2)	0.044 (3)	0.079 (4)	0.000 (2)	0.002 (2)	0.002 (3)
C(4)	0.027 (3)	0.040 (3)	0.117 (6)	0.006 (3)	0.004 (3)	−0.011 (3)
C(5)	0.028 (3)	0.044 (3)	0.115 (5)	0.003 (2)	0.000 (3)	0.008 (4)

Geometric parameters (Å, º)

S(1)—C(2)	1.733 (5)	C(2)—C(3)	1.363 (8)
S(1)—C(4)	1.801 (6)	C(4)—C(5)	1.502 (10)
S(2)—C(3)	1.730 (6)	C(4)—H(4a)	0.950
S(2)—C(5)	1.795 (6)	C(4)—H(4b)	0.950
O(1)—C(1)	1.235 (6)	C(5)—H(5a)	0.950
C(1)—C(2)	1.476 (7)	C(5)—H(5b)	0.950
C(1)—C(3)^i	1.472 (8)
S(2)···S(2)^ii	3.196 (3)	O(1)···H(4a)^v	2.41
S(2)···S(2)^iii	3.5854 (5)	C(1)···C(2)^vi	3.542 (9)
S(2)···S(2)^iv	3.5854 (5)	C(1)···C(2)^vii	3.562 (9)
O(1)···C(4)^v	3.289 (8)	C(3)···C(3)^iii	3.573 (2)
O(1)···C(4)^vi	3.40 (1)	C(3)···C(3)^iv	3.573 (2)
O(1)···C(5)^vii	3.511 (9)
C(2)—S(1)—C(4)	101.0 (3)	S(1)—C(4)—H(4a)	108.4 (5)
C(3)—S(2)—C(5)	103.0 (3)	S(1)—C(4)—H(4b)	108.4 (5)
O(1)—C(1)—C(2)	120.5 (5)	C(5)—C(4)—H(4a)	108.4 (6)
O(1)—C(1)—C(3)^i	118.7 (5)	C(5)—C(4)—H(4b)	108.4 (6)
C(2)—C(1)—C(3)^i	120.8 (5)	H(4a)—C(4)—H(4b)	109.5 (7)
S(1)—C(2)—C(1)	113.2 (4)	S(2)—C(5)—C(4)	112.9 (5)
S(1)—C(2)—C(3)	128.3 (5)	S(2)—C(5)—H(5a)	108.6 (5)
C(1)—C(2)—C(3)	118.4 (5)	S(2)—C(5)—H(5b)	108.6 (5)
S(2)—C(3)—C(1)^i	111.9 (4)	C(4)—C(5)—H(5a)	108.6 (7)
S(2)—C(3)—C(2)	127.6 (4)	C(4)—C(5)—H(5b)	108.6 (6)
C(1)^i—C(3)—C(2)	120.5 (5)	H(5a)—C(5)—H(5b)	109.4 (7)
S(1)—C(4)—C(5)	113.8 (5)
S(1)—C(2)—C(1)—O(1)	0.6 (9)	O(1)—C(1)—C(2)—C(3)	−179.1 (6)
S(1)—C(2)—C(1)—C(3)^i	−179.2 (5)	O(1)—C(1)—C(3)^i—C(2)^i	−174.6 (7)
S(1)—C(2)—C(3)—S(2)	−5.2 (9)	C(1)—C(2)—S(1)—C(4)	168.0 (5)
S(1)—C(2)—C(3)—C(1)^i	174.4 (5)	C(1)—C(3)^i—S(2)^i—C(5)^i	172.5 (5)
S(1)—C(4)—C(5)—S(2)	−70.8 (6)	C(2)—S(1)—C(4)—C(5)	50.0 (6)
S(2)—C(3)—C(1)^i—O(1)^i	5.0 (8)	C(2)—C(3)—S(2)—C(5)	−7.9 (7)
S(2)—C(3)—C(1)^i—C(2)^i	−175.2 (5)	C(3)—S(2)—C(5)—C(4)	45.0 (6)
S(2)—C(3)—C(2)—C(1)	174.5 (5)	C(3)—C(2)—S(1)—C(4)	−12.4 (7)

Symmetry codes: (i) −x+3/2, −y+1/2, z; (ii) −x+5/2, −y+1/2, z; (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2; (v) x−1/2, −y, −z+1/2; (vi) −x+3/2, y, z+1/2; (vii) −x+3/2, y, z−1/2.

(2) 3,4,9,10-tetrahydro-2H,8H-benzo[1,2 - b:4,5 - b']bis[1,4] dithiepin-6,12-dione

Crystal data

C12H12O2S4	F(000) = 656.00
Mr = 316.47	Dx = 1.602 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 25 reflections
a = 9.758 (2) Å	θ = 14.7–15.0°
b = 16.846 (2) Å	µ = 0.71 mm^−1
c = 7.981 (2) Å	T = 296 K
V = 1312.0 (3) Å^3	Prismatic, dark orange
Z = 4	0.80 × 0.30 × 0.15 mm

Data collection

Rigaku AFC7R diffractometer	1264 reflections with I > 2.0σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω–2θ scans	h = 0→12
Absorption correction: ψ scan (North, Phillips & Mathews, 1968)	k = 0→21
Tmin = 0.836, Tmax = 1.000	l = 0→10
1510 measured reflections	3 standard reflections every 150 reflections
1510 independent reflections	intensity decay: −0.1%

Refinement

Refinement on F	0 constraints
Least-squares matrix: full	Only H-atom coordinates refined
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo) + 0.00346|Fo|^2]
wR(F^2) = 0.066	(Δ/σ)max = 0.034
S = 1.05	Δρmax = 0.35 e Å^−3
1264 reflections	Δρmin = −0.28 e Å^−3
107 parameters	Extinction correction: Zachariasen(1967) type 2 Gaussian isotropic
0 restraints	Extinction coefficient: 0.027 (5)

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

	x	y	z	Uiso*/Ueq
S(1)	0.36463 (5)	0.07390 (3)	0.21954 (8)	0.0513 (2)
S(2)	0.57316 (4)	0.24539 (3)	0.12550 (6)	0.0452 (2)
O(1)	0.0931 (2)	0.12265 (9)	0.1824 (2)	0.0529 (4)
C(1)	0.1659 (2)	0.1813 (1)	0.1779 (2)	0.0360 (4)
C(2)	0.3180 (2)	0.1727 (1)	0.1862 (2)	0.0355 (4)
C(3)	0.3966 (2)	0.2382 (1)	0.1637 (2)	0.0355 (4)
C(4)	0.5401 (3)	0.0796 (1)	0.2920 (3)	0.0502 (6)
C(5)	0.6448 (2)	0.0855 (2)	0.1527 (3)	0.0510 (6)
C(6)	0.6116 (2)	0.1506 (1)	0.0302 (3)	0.0489 (5)
H(4a)	0.552 (3)	0.041 (2)	0.363 (3)	0.066 (8)*
H(4b)	0.552 (3)	0.127 (2)	0.378 (3)	0.059 (7)*
H(5a)	0.740 (3)	0.102 (2)	0.205 (4)	0.063 (7)*
H(5b)	0.651 (2)	0.032 (2)	0.104 (3)	0.053 (7)*
H(6a)	0.542 (3)	0.139 (1)	−0.038 (3)	0.049 (6)*
H(6b)	0.686 (3)	0.165 (2)	−0.032 (3)	0.052 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S(1)	0.0488 (4)	0.0280 (4)	0.0773 (5)	0.0025 (2)	−0.0002 (2)	−0.0011 (2)
S(2)	0.0322 (4)	0.0460 (4)	0.0575 (4)	−0.0003 (2)	0.0040 (2)	0.0051 (2)
O(1)	0.0404 (7)	0.0330 (8)	0.085 (1)	−0.0069 (6)	0.0053 (7)	−0.0085 (7)
C(1)	0.0355 (8)	0.0309 (8)	0.0415 (8)	−0.0027 (6)	0.0032 (7)	−0.0053 (6)
C(2)	0.0338 (8)	0.0308 (8)	0.0420 (8)	0.0021 (6)	0.0007 (6)	−0.0021 (6)
C(3)	0.0322 (7)	0.0347 (9)	0.0394 (8)	−0.0005 (6)	0.0000 (7)	0.0020 (7)
C(4)	0.056 (1)	0.039 (1)	0.055 (1)	0.0123 (9)	−0.0086 (9)	−0.0014 (8)
C(5)	0.046 (1)	0.050 (1)	0.058 (1)	0.0153 (8)	−0.0087 (8)	−0.0141 (10)
C(6)	0.0387 (9)	0.065 (1)	0.0433 (9)	0.0084 (8)	−0.0003 (9)	−0.0092 (9)

Geometric parameters (Å, º)

S(1)—C(2)	1.746 (2)	C(4)—C(5)	1.513 (3)
S(1)—C(4)	1.810 (2)	C(4)—H(4a)	0.88 (3)
S(2)—C(3)	1.754 (2)	C(4)—H(4b)	1.06 (3)
S(2)—C(6)	1.807 (2)	C(5)—C(6)	1.506 (3)
O(1)—C(1)	1.217 (2)	C(5)—H(5a)	1.05 (3)
C(1)—C(2)	1.493 (3)	C(5)—H(5b)	0.98 (3)
C(1)—C(3)^i	1.491 (3)	C(6)—H(6a)	0.89 (3)
C(2)—C(3)	1.355 (3)	C(6)—H(6b)	0.91 (3)
S(1)···H(5b)^ii	3.08 (2)	C(1)···H(6a)^iv	3.12 (3)
S(1)···H(5b)^iii	3.14 (3)	C(1)···H(4b)^viii	3.33 (3)
S(1)···H(5a)^ii	3.27 (3)	C(3)···C(3)^vii	4.0106 (4)
S(1)···C(5)^ii	3.585 (2)	C(3)···H(6a)^vii	3.46 (3)
S(1)···O(1)^iv	3.807 (2)	C(3)···H(4b)^v	3.55 (3)
S(2)···H(4b)^v	2.92 (3)	C(4)···H(6b)^x	3.34 (3)
S(2)···H(6b)^vi	3.07 (3)	C(4)···H(4a)^xi	3.54 (3)
S(2)···H(5a)^vi	3.21 (3)	C(5)···H(6b)^x	3.29 (3)
S(2)···H(6b)^vii	3.31 (2)	C(6)···H(5a)^xii	3.09 (3)
S(2)···H(6a)^vii	3.34 (2)	C(6)···H(4b)^xii	3.52 (3)
S(2)···S(2)^vii	3.994 (3)	H(4a)···H(4a)^xi	2.77 (6)
S(2)···S(2)^vi	3.455 (1)	H(4a)···H(6b)^x	3.40 (4)
O(1)···H(6a)^iv	2.61 (3)	H(4a)···H(5b)^x	3.48 (4)
O(1)···H(4a)^ii	2.80 (3)	H(4a)···H(5a)^x	3.55 (4)
O(1)···H(4b)^viii	2.81 (2)	H(4b)···H(6b)^x	2.73 (4)
O(1)···H(5b)^ii	3.16 (3)	H(4b)···H(5a)^x	3.33 (4)
O(1)···H(4a)^viii	3.23 (3)	H(5a)···H(6a)^x	3.03 (4)
O(1)···C(6)^iv	3.452 (3)	H(5a)···H(5b)^x	3.56 (4)
O(1)···C(4)^ii	3.452 (3)	H(5b)···H(6a)^iii	3.47 (3)
O(1)···C(4)^viii	3.453 (3)	H(5b)···H(5b)^iii	3.55 (5)
O(1)···H(5a)^ix	3.47 (3)	H(6b)···H(6b)^vi	3.13 (5)
C(1)···C(2)^viii	3.930 (2)
C(2)—S(1)—C(4)	104.16 (9)	C(5)—C(4)—H(4b)	110 (1)
C(3)—S(2)—C(6)	102.44 (10)	H(4a)—C(4)—H(4b)	97 (2)
O(1)—C(1)—C(2)	120.0 (2)	C(4)—C(5)—C(6)	112.3 (2)
O(1)—C(1)—C(3)^i	120.1 (2)	C(4)—C(5)—H(5a)	108 (1)
C(2)—C(1)—C(3)^i	119.9 (2)	C(4)—C(5)—H(5b)	105 (1)
S(1)—C(2)—C(1)	111.0 (1)	C(6)—C(5)—H(5a)	104 (1)
S(1)—C(2)—C(3)	130.4 (1)	C(6)—C(5)—H(5b)	115 (1)
C(1)—C(2)—C(3)	118.5 (2)	H(5a)—C(5)—H(5b)	110 (1)
S(2)—C(3)—C(1)^i	110.6 (1)	S(2)—C(6)—C(5)	114.5 (2)
S(2)—C(3)—C(2)	129.4 (1)	S(2)—C(6)—H(6a)	107 (1)
C(1)^i—C(3)—C(2)	119.9 (2)	S(2)—C(6)—H(6b)	99 (1)
S(1)—C(4)—C(5)	114.0 (2)	C(5)—C(6)—H(6a)	113 (1)
S(1)—C(4)—H(4a)	107 (1)	C(5)—C(6)—H(6b)	111 (1)
S(1)—C(4)—H(4b)	110 (1)	H(6a)—C(6)—H(6b)	109 (2)
C(5)—C(4)—H(4a)	115 (1)
S(1)—C(2)—C(1)—O(1)	−5.0 (2)	O(1)—C(1)—C(2)—C(3)	173.3 (2)
S(1)—C(2)—C(1)—C(3)^i	175.2 (1)	O(1)—C(1)—C(3)^i—C(2)^i	169.2 (2)
S(1)—C(2)—C(3)—S(2)	11.7 (3)	C(1)—C(2)—S(1)—C(4)	−162.2 (1)
S(1)—C(2)—C(3)—C(1)^i	−165.4 (1)	C(1)—C(3)^i—S(2)^i—C(6)^i	−157.5 (1)
S(1)—C(4)—C(5)—C(6)	51.4 (2)	C(2)—S(1)—C(4)—C(5)	−83.7 (2)
S(2)—C(3)—C(1)^i—O(1)^i	−8.4 (2)	C(2)—C(3)—S(2)—C(6)	25.2 (2)
S(2)—C(3)—C(1)^i—C(2)^i	171.4 (1)	C(3)—S(2)—C(6)—C(5)	−87.3 (2)
S(2)—C(3)—C(2)—C(1)	−166.2 (1)	C(3)—C(2)—S(1)—C(4)	19.7 (2)
S(2)—C(6)—C(5)—C(4)	49.3 (2)

Symmetry codes: (i) −x+1/2, −y+1/2, z; (ii) x−1/2, −y, −z+1/2; (iii) −x+1, −y, −z; (iv) −x+1/2, y, z+1/2; (v) x, −y+1/2, z−1/2; (vi) −x+3/2, −y+1/2, z; (vii) x, −y+1/2, z+1/2; (viii) −x+1/2, y, z−1/2; (ix) x−1, y, z; (x) −x+3/2, y, z+1/2; (xi) −x+1, −y, −z+1; (xii) −x+3/2, y, z−1/2.