Synthesis of di­thia­fulvene–quinone donor–acceptor systems: isolation of a Michael adduct

π-Conjugated donor–acceptor systems based on di­thia­fulvene (DTF) donor units and various acceptor units have attracted attention for their linear and nonlinear optical properties. The reaction between p-benzo­quinone and a 1,3-di­thiole phospho­nium salt, deprotonated by lithium hexa­methyl­disilazide (LiHMDS), gave a product mixture from which the Michael adduct [systematic name: dimethyl 2-(3-hy­droxy-6-oxo­cyclo­hexa-2,4-dien-1-yl­idene)-2H-1,3-di­thiole-4,5-di­carboxyl­ate], C₁₃H₁₀O₆S₂, was isolated. It is likely that one of the unidentified products obtained previously by others from related reactions could be a similar Michael adduct.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Dimethyl 2-(3-hydroxy-6-oxocyclohexa-2,4-dien-1-ylidene)-2H-1,3-dithiole-4,5-dicarboxylate

Crystal data

C13H10O6S2	Dx = 1.660 Mg m^−3
Mr = 326.35	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 4173 reflections
a = 12.2352 (8) Å	θ = 2.3–26.4°
b = 26.1845 (18) Å	µ = 0.43 mm^−1
c = 4.0769 (3) Å	T = 123 K
V = 1306.13 (16) Å^3	Needle, purple
Z = 4	0.52 × 0.44 × 0.08 mm
F(000) = 673.3777

Data collection

Bruker APEXII CCD diffractometer	2240 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.120
Absorption correction: multi-scan (SADABS; Bruker, 2001)	θmax = 26.4°, θmin = 2.3°
Tmin = 0.661, Tmax = 0.746	h = −17→15
24110 measured reflections	k = −37→35
2662 independent reflections	l = −5→5

Refinement

Refinement on F^2	8 constraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0373P)^2 + 0.0555P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.077	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.34 e Å^−3
2662 reflections	Δρmin = −0.34 e Å^−3
203 parameters	Absolute structure: Flack (1983), 1135 Friedel pairs
0 restraints	Absolute structure parameter: −0.02 (10)

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

	x	y	z	Uiso*/Ueq
C7	−0.8038 (2)	−0.33428 (9)	−0.2357 (6)	0.0159 (6)
C13	−0.4182 (2)	−0.42916 (9)	−0.8236 (8)	0.0240 (6)
H13a	−0.4314 (6)	−0.4262 (6)	−1.0600 (8)	0.0360 (9)*
H13b	−0.3531 (3)	−0.4094 (4)	−0.765 (3)	0.0360 (9)*
H13c	−0.4068 (9)	−0.4651 (2)	−0.766 (3)	0.0360 (9)*
C11	−0.8388 (2)	−0.55891 (10)	−0.6949 (7)	0.0264 (7)
H11a	−0.8467 (14)	−0.5551 (3)	−0.9329 (9)	0.0396 (10)*
H11b	−0.7874 (8)	−0.58667 (17)	−0.648 (4)	0.0396 (10)*
H11c	−0.9101 (8)	−0.5669 (4)	−0.598 (3)	0.0396 (10)*
C6	−0.8296 (2)	−0.29035 (9)	−0.0622 (6)	0.0157 (6)
C4	−0.9623 (2)	−0.24188 (10)	0.2628 (6)	0.0194 (7)
C1	−0.7496 (2)	−0.25089 (10)	0.0049 (6)	0.0175 (6)
C10	−0.8502 (2)	−0.47026 (10)	−0.6535 (6)	0.0184 (6)
C8	−0.6981 (2)	−0.40558 (9)	−0.5393 (6)	0.0155 (6)
C2	−0.7777 (2)	−0.21004 (9)	0.1914 (7)	0.0184 (6)
C5	−0.9398 (2)	−0.28515 (9)	0.0575 (6)	0.0186 (6)
C12	−0.6082 (2)	−0.43157 (10)	−0.7180 (6)	0.0167 (6)
C9	−0.8024 (2)	−0.42187 (9)	−0.5175 (6)	0.0173 (6)
C3	−0.8857 (2)	−0.20660 (10)	0.3274 (7)	0.0213 (6)
O2	−1.01144 (15)	−0.31835 (7)	−0.0171 (4)	0.0221 (4)
O6	−0.51254 (14)	−0.40944 (6)	−0.6447 (4)	0.0191 (4)
O5	−0.62028 (15)	−0.46607 (7)	−0.9059 (5)	0.0268 (5)
O4	−0.79753 (15)	−0.51150 (6)	−0.5554 (4)	0.0226 (5)
O1	−0.70915 (16)	−0.17081 (7)	0.2655 (5)	0.0252 (5)
O3	−0.93031 (17)	−0.46953 (6)	−0.8224 (5)	0.0361 (5)
S1	−0.67086 (5)	−0.34633 (2)	−0.36298 (14)	0.01603 (15)
S2	−0.89720 (5)	−0.38103 (2)	−0.33327 (15)	0.01772 (15)
H1a	−0.646 (3)	−0.1768 (11)	0.188 (10)	0.043400*
H3	−0.900 (3)	−0.1758 (11)	0.459 (8)	0.041500*
H4	−1.034 (3)	−0.2386 (11)	0.365 (9)	0.046300*
H1	−0.679 (3)	−0.2559 (11)	−0.081 (9)	0.036300*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C7	0.0089 (13)	0.0194 (13)	0.0195 (15)	−0.0006 (10)	0.0012 (11)	0.0078 (11)
C13	0.0123 (13)	0.0307 (13)	0.0289 (16)	0.0032 (10)	0.0063 (16)	0.0015 (16)
C11	0.0226 (16)	0.0208 (14)	0.0359 (18)	−0.0043 (12)	−0.0033 (14)	−0.0043 (13)
C6	0.0123 (14)	0.0190 (13)	0.0157 (15)	0.0036 (10)	−0.0003 (12)	0.0050 (12)
C4	0.0108 (14)	0.0261 (15)	0.0212 (16)	0.0037 (12)	0.0050 (11)	0.0044 (12)
C1	0.0107 (13)	0.0218 (14)	0.0200 (15)	0.0035 (11)	0.0038 (12)	0.0061 (11)
C10	0.0159 (15)	0.0218 (14)	0.0174 (15)	−0.0020 (11)	−0.0006 (13)	0.0060 (12)
C8	0.0134 (14)	0.0157 (13)	0.0175 (15)	−0.0020 (11)	−0.0040 (12)	0.0032 (11)
C2	0.0142 (12)	0.0176 (12)	0.0235 (16)	0.0010 (10)	−0.0000 (14)	0.0044 (13)
C5	0.0132 (14)	0.0223 (14)	0.0202 (16)	0.0017 (11)	−0.0022 (11)	0.0100 (11)
C12	0.0133 (14)	0.0182 (13)	0.0185 (14)	−0.0027 (11)	−0.0018 (11)	0.0060 (12)
C9	0.0160 (15)	0.0187 (13)	0.0173 (15)	−0.0003 (10)	−0.0034 (12)	0.0050 (12)
C3	0.0189 (15)	0.0231 (15)	0.0220 (16)	0.0072 (12)	0.0052 (13)	0.0068 (13)
O2	0.0120 (10)	0.0245 (10)	0.0299 (11)	−0.0007 (8)	0.0031 (9)	0.0041 (9)
O6	0.0116 (10)	0.0208 (9)	0.0248 (11)	0.0001 (7)	0.0015 (8)	−0.0037 (9)
O5	0.0233 (10)	0.0285 (10)	0.0286 (13)	−0.0038 (8)	0.0017 (10)	−0.0092 (10)
O4	0.0183 (11)	0.0151 (9)	0.0346 (13)	−0.0026 (8)	−0.0083 (9)	0.0017 (9)
O1	0.0149 (10)	0.0220 (9)	0.0386 (14)	0.0002 (9)	0.0065 (9)	−0.0048 (9)
O3	0.0338 (12)	0.0263 (10)	0.0483 (14)	−0.0083 (8)	−0.0277 (14)	0.0126 (13)
S1	0.0094 (3)	0.0166 (3)	0.0221 (3)	−0.0003 (2)	0.0016 (3)	0.0016 (4)
S2	0.0102 (3)	0.0200 (3)	0.0230 (4)	−0.0016 (2)	−0.0003 (4)	0.0056 (4)

Geometric parameters (Å, º)

C7—C6	1.387 (3)	C1—C2	1.357 (4)
C7—S1	1.736 (3)	C1—H1	0.95 (3)
C7—S2	1.721 (3)	C10—C9	1.502 (4)
C13—H13a	0.9800	C10—O4	1.320 (3)
C13—H13b	0.9800	C10—O3	1.198 (3)
C13—H13c	0.9800	C8—C12	1.485 (4)
C13—O6	1.460 (3)	C8—C9	1.348 (3)
C11—H11a	0.9800	C8—S1	1.742 (2)
C11—H11b	0.9800	C2—C3	1.435 (4)
C11—H11c	0.9800	C2—O1	1.360 (3)
C11—O4	1.456 (3)	C5—O2	1.272 (3)
C6—C1	1.449 (4)	C12—O6	1.340 (3)
C6—C5	1.440 (4)	C12—O5	1.194 (3)
C4—C5	1.435 (4)	C9—S2	1.747 (3)
C4—C3	1.342 (4)	C3—H3	0.98 (3)
C4—H4	0.97 (3)	O1—H1a	0.85 (3)
S1—C7—C6	121.11 (19)	O3—C10—C9	121.2 (2)
S2—C7—C6	123.8 (2)	O3—C10—O4	125.9 (2)
S2—C7—S1	115.08 (14)	C9—C8—C12	126.1 (2)
H13b—C13—H13a	109.5	S1—C8—C12	117.96 (19)
H13c—C13—H13a	109.5	S1—C8—C9	115.83 (19)
H13c—C13—H13b	109.5	C3—C2—C1	120.0 (2)
O6—C13—H13a	109.5	O1—C2—C1	124.3 (2)
O6—C13—H13b	109.5	O1—C2—C3	115.8 (2)
O6—C13—H13c	109.5	C4—C5—C6	116.9 (2)
H11b—C11—H11a	109.5	O2—C5—C6	120.0 (2)
H11c—C11—H11a	109.5	O2—C5—C4	123.1 (2)
H11c—C11—H11b	109.5	O6—C12—C8	109.9 (2)
O4—C11—H11a	109.5	O5—C12—C8	124.8 (2)
O4—C11—H11b	109.5	O5—C12—O6	125.3 (3)
O4—C11—H11c	109.5	C8—C9—C10	127.7 (2)
C1—C6—C7	122.3 (2)	S2—C9—C10	114.57 (19)
C5—C6—C7	117.7 (2)	S2—C9—C8	117.59 (19)
C5—C6—C1	120.1 (2)	C2—C3—C4	121.6 (3)
C3—C4—C5	121.6 (3)	H3—C3—C4	123.0 (18)
H4—C4—C5	119.6 (18)	H3—C3—C2	115.3 (18)
H4—C4—C3	118.8 (19)	C12—O6—C13	115.2 (2)
C2—C1—C6	119.8 (2)	C10—O4—C11	114.2 (2)
H1—C1—C6	116.8 (19)	H1a—O1—C2	110 (2)
H1—C1—C2	123.4 (19)	C8—S1—C7	96.07 (12)
O4—C10—C9	112.8 (2)	C9—S2—C7	95.36 (12)