5,6-Di­hydro-1,4-dithiine-2,3-di­carb­oxy­lic anhydride

Bullock, O.; Rice, S.; Bond, M.R.

doi:10.1107/S2414314623006478

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 8| August 2023| x230647

https://doi.org/10.1107/S2414314623006478

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5,6-Dihydro-1,4-dithiine-2,3-dicarboxylic anhydride

Olivia Bullock,^a Sarah Rice ^a and Marcus R. Bond ^a ^*

^aDepartment of Chemistry and Physics, Southeast Missouri State University, Cape Girardeau, MO 63701, USA
^*Correspondence e-mail: mbond@semo.edu

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 19 July 2023; accepted 25 July 2023; online 4 August 2023)

In the title compound (systematic name: 2,3-dihydro-1,4-dithiino[2,3-c]furan-5,7-dione), C₆H₄O₃S₂, the observed geometry agrees well with those of its phthalamide, thieno and hydroxy analogs, and with a calculated geometry obtained by density functional theory (DFT) calculations. Specific structural features are an S—C—C—S torsion angle of −70.39 (17)° and S—C bonds to sp²-hybridized C atoms approximately 0.1 Å shorter than those to sp³-hybridized C atoms. Unlike the extended structures of the analogs, there are no directed intermolecular interactions and the head-to-tail rows of molecules that are a prominent structural motif of the packing can be rationalized in terms of optimized dipole–dipole interactions.

Keywords: crystal structure; fused ring; heterocycle; dithiine; anhydride.

CCDC reference: 2284875

Structure description

The unit-cell parameters for the title compound have been reported previously [Grabowski, 1968 ; Cambridge Structural Database (CSD; Groom et al., 2016 ) refcode QQQDIA], but atomic coordinates are not available. Related compounds with reported three-dimensional atomic coordinates are the phthalamide (DTHPIM; Kirfel et al., 1975 ), the thieno (ZUHQUQ; Skabara et al., 2003 ) and the monohydroxy (USUMOL; Kurbangalieva et al., 2010 ) analogs, all of which are reported to crystallize in the monoclinic space groups P2₁/c or P2₁/n. We report here the three-dimensional structure of 5,6-dihydro-1,4-dithiine-2,3-dicarboxylic anhydride, which crystallizes in the triclinic space group P $[\overline{1}]$ with unit-cell parameters in agreement with those reported by Grabowski.

The molecule (Fig. 1) consists of furandione and dihydro-1,4-dithiine rings fused by a common carbon–carbon double bond (atoms C3 and C4) and is largely planar (r.m.s. deviation of 0.044 Å from the mean plane for all atoms except the CH₂ groups). The CH₂ groups are twisted about the molecular plane in order to reduce angle strain, with C1 0.323 (3) Å above and C2 0.528 (3) Å below, and an S1—C1—C2—S2 torsion angle of −70.39 (17)°. The S—C bond lengths are 0.096 (7) Å shorter for bonds to sp²-hybridized C atoms than to those with sp³-hybridization (Table 1). The interior bond angles within the furandione ring are close to idealized values for a uniform pentagon, ranging from 107.44 (17) to 108.36 (18)°. The O=C—O angles have expected values of 121–122° for an sp²-hybridized center, while the external O=C—C angles average 130.2 (7)° in order to accommodate the geometry of the planar ring. These details agree well with the geometrical parameters for maleic anhydride [MLEICA (Marsh et al., 1962 ) and MLEICA01 (Lutz, 2001 )].

Table 1
Selected geometric parameters (Å, °)

S1—C1	1.805 (2)	C3—C5	1.469 (3)
S1—C3	1.7136 (19)	C4—C6	1.472 (3)
S2—C2	1.817 (2)	O1—C5	1.193 (3)
S2—C4	1.7160 (19)	O2—C5	1.376 (3)
C1—C2	1.510 (3)	O2—C6	1.386 (3)
C3—C4	1.345 (3)	O3—C6	1.186 (3)

C1—S1—C3	99.54 (10)	C3—C4—C6	107.44 (17)
C2—S2—C4	98.30 (10)	O1—C5—C3	129.7 (2)
S1—C1—C2	114.41 (15)	O2—C5—C3	108.36 (18)
C1—C2—S2	115.01 (15)	O1—C5—O2	121.98 (19)
S1—C3—C4	131.57 (14)	O2—C6—C4	108.13 (18)
S1—C3—C5	120.60 (16)	O3—C6—C4	130.7 (2)
C4—C3—C5	107.83 (17)	O2—C6—O3	121.2 (2)
C3—C4—S2	129.27 (14)	C5—O2—C6	108.14 (15)
C6—C4—S2	123.28 (16)

Figure 1
Displacement ellipsoid plot at the 50% probability level of the formula unit of the title compound, showing labels for non-H atoms.

The geometrical details for the related compounds listed above agree closely with those of the title compound. In particular, the S—C—C—S torsion-angle magnitudes range from 68.10 to 70.75° and the S—C bond lengths to sp²-hybridized C atoms average 0.087 (14) Å shorter than those to sp³-hybridized C atoms, with the phthalamide analog providing the closest agreement [average sp³–sp² bond length difference = 0.0995 (7) Å]. A DFT geometry optimization in vacuo [B3LYP functional, cc-pTVZ basis set; GAMESS (Schmidt et al., 1993 )] yields similar results, with an S—C—C—S torsion angle of −69.6° and S—C bond lengths of 1.730 and 1.829 Å to sp²- and sp³-hybridized C atoms, respectively. An electrostatic potential plot with the optimized molecule visible is presented in Fig. 2.

Figure 2
Electrostatic potential plot of the title molecule with the optimized geometry visible. Red represents the most negatively charged regions, while blue represents the most positively charged.

The unit-cell packing of the title compound consists of sheets of molecules lying parallel to (11 $[\overline{2}]$ ), with neighboring sheets related by inversion. The molecular planes are approximately coplanar with the sheet, with molecules forming head-to-tail rows parallel to [1 $[\overline{1}]$ 0] within the sheet. Neighboring rows within the sheet have opposite orientations, while rows on neighboring sheets straddle each other. This packing differs from that of similar molecules, where directed hydrogen bonding or short S⋯O contacts feature prominently, with the head-to-tail rows of molecules in the title compound rationalized in terms of optimized dipole–dipole interactions. A ball-and-stick diagram of a sheet is presented in Fig. 3 and a unit-cell packing diagram viewed edge on to the sheets is presented in Fig. 4.

Figure 3
Ball-and stick diagram of the sheet structure viewed perpendiciular to (11 $[\overline{2}]$ ).

Figure 4
Ball-and-stick packing diagram of a unit cell, with axis labels viewed along [1 $[\overline{1}]$ 0], showing the stacking of four sheets to generate the three-dimensional structure.

Synthesis and crystallization

5,6-Dihydro-1,4-dithiin-2,3-dicarboxylic anhydride (98+%) was purchased from Fisher Scientific and recrystalized by slow evaporation at room temperature from tetrahydrofuran solution to yield yellow block-like crystals.

Refinement

Crystal data, data collection, and structure refinement details are listed in Table 2. The final structure refinement was carried out within the OLEX2 system via Hirshfeld atom refinement with nonspherical atomic form factors using NoSpherA2 (Kleemiss et al., 2021 ; Midgley et al., 2021 ) derived from electron density from DFT calculations using ORCA (B3LYP functional, def2-SVP basis set; Neese, 2022 ). All atoms were refined anisotropically.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₄O₃S₂
M_r	188.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	295
a, b, c (Å)	5.398 (1), 7.5537 (15), 9.2566 (18)
α, β, γ (°)	89.273 (6), 87.361 (6), 75.701 (5)
V (Å³)	365.36 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.68
Crystal size (mm)	0.42 × 0.38 × 0.17

Data collection
Diffractometer	Bruker D8 Quest Eco
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.648, 0.746
No. of measured, independent and observed [I ≥ 2u(I)] reflections	16978, 1669, 1338
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.074, 1.11
No. of reflections	1669
No. of parameters	136
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.25
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), olex2.refine (Bourhis et al., 2015 ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2020 ), WebMO (Schmidt & Polik, 2016 ), and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2284875

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314623006478/hb4438sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006478/hb4438Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006478/hb4438Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b) and olex2.refine (Bourhis et al., 2015); molecular graphics: OLEX2 1(Dolomanov et al., 2009), Mercury (Macrae et al., 2020) and WebMO (Schmidt & Polik, 2016); software used to prepare material for publication: publCIF (Westrip, 2010).

5,6-Dihydro-1,4-dithiine-2,3-dicarboxylic anhydride top

Crystal data top

C₆H₄O₃S₂	Z = 2
M_r = 188.23	F(000) = 192.603
Triclinic, P1	D_x = 1.711 Mg m⁻³
a = 5.398 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.5537 (15) Å	Cell parameters from 7641 reflections
c = 9.2566 (18) Å	θ = 2.8–27.4°
α = 89.273 (6)°	µ = 0.68 mm⁻¹
β = 87.361 (6)°	T = 295 K
γ = 75.701 (5)°	Plate, yellow
V = 365.36 (12) Å³	0.42 × 0.38 × 0.17 mm

Data collection top

Bruker D8 Quest Eco diffractometer	1338 reflections with I ≥ 2u(I)
φ and ω scans	R_int = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 27.6°, θ_min = 3.6°
T_min = 0.648, T_max = 0.746	h = −7→7
16978 measured reflections	k = −9→9
1669 independent reflections	l = −12→12

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Primary atom site location: dual
R[F² > 2σ(F²)] = 0.033	All H-atom parameters refined
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0229P)² + 0.1706P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.0002
1669 reflections	Δρ_max = 0.45 e Å⁻³
136 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.87227 (9)	0.35661 (7)	0.38382 (6)	0.04127 (16)
S2	0.45568 (10)	0.23942 (8)	0.13318 (6)	0.04824 (17)
C1	0.8444 (5)	0.1333 (3)	0.3315 (2)	0.0440 (5)
H1a	1.028 (5)	0.039 (4)	0.347 (3)	0.091 (10)
H1b	0.700 (5)	0.098 (3)	0.400 (3)	0.072 (8)
C2	0.7794 (4)	0.1195 (3)	0.1758 (2)	0.0440 (5)
H2a	0.793 (6)	−0.019 (4)	0.152 (3)	0.086 (9)
H2b	0.909 (5)	0.169 (4)	0.102 (3)	0.064 (8)
C3	0.6129 (3)	0.4890 (2)	0.3010 (2)	0.0338 (4)
C4	0.4505 (3)	0.4463 (2)	0.2093 (2)	0.0347 (4)
C5	0.5328 (4)	0.6869 (3)	0.3268 (2)	0.0457 (5)
C6	0.2545 (4)	0.6150 (3)	0.1802 (2)	0.0478 (5)
O1	0.6268 (4)	0.7808 (2)	0.3987 (2)	0.0682 (5)
O2	0.3162 (3)	0.75751 (18)	0.25156 (17)	0.0558 (4)
O3	0.0695 (3)	0.6399 (2)	0.11090 (19)	0.0695 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0364 (3)	0.0389 (3)	0.0489 (3)	−0.0100 (2)	−0.0021 (2)	−0.0005 (2)
S2	0.0401 (3)	0.0441 (3)	0.0610 (4)	−0.0107 (2)	−0.0014 (2)	−0.0144 (3)
C1	0.0523 (14)	0.0263 (10)	0.0484 (13)	−0.0007 (10)	0.0016 (11)	0.0030 (9)
H1a	0.08 (2)	0.057 (19)	0.10 (2)	0.045 (17)	−0.031 (18)	0.019 (17)
H1b	0.09 (2)	0.033 (15)	0.10 (2)	−0.030 (15)	0.015 (18)	−0.009 (15)
C2	0.0464 (12)	0.0299 (11)	0.0496 (13)	0.0014 (9)	0.0061 (10)	−0.0076 (10)
H2a	0.13 (3)	0.038 (16)	0.09 (2)	−0.012 (17)	0.007 (18)	−0.021 (15)
H2b	0.053 (17)	0.076 (19)	0.060 (17)	−0.013 (15)	0.022 (13)	0.014 (15)
C3	0.0335 (9)	0.0236 (9)	0.0427 (10)	−0.0055 (7)	0.0074 (8)	−0.0008 (8)
C4	0.0306 (9)	0.0281 (9)	0.0415 (10)	−0.0011 (7)	0.0060 (8)	0.0003 (8)
C5	0.0551 (13)	0.0245 (10)	0.0556 (13)	−0.0096 (9)	0.0171 (10)	−0.0021 (9)
C6	0.0370 (11)	0.0442 (12)	0.0528 (12)	0.0054 (9)	0.0076 (10)	0.0118 (10)
O1	0.0867 (13)	0.0358 (9)	0.0862 (12)	−0.0262 (9)	0.0178 (10)	−0.0185 (9)
O2	0.0611 (10)	0.0270 (7)	0.0673 (10)	0.0084 (7)	0.0161 (8)	0.0070 (7)
O3	0.0467 (9)	0.0712 (12)	0.0784 (12)	0.0086 (8)	−0.0076 (9)	0.0218 (10)

Geometric parameters (Å, º) top

S1—C1	1.805 (2)	C2—H2b	1.08 (2)
S1—C3	1.7136 (19)	C3—C4	1.345 (3)
S2—C2	1.817 (2)	C3—C5	1.469 (3)
S2—C4	1.7160 (19)	C4—C6	1.472 (3)
C1—H1a	1.08 (2)	O1—C5	1.193 (3)
C1—H1b	1.06 (2)	O2—C5	1.376 (3)
C1—C2	1.510 (3)	O2—C6	1.386 (3)
C2—H2a	1.06 (2)	O3—C6	1.186 (3)

C1—S1—C3	99.54 (10)	S1—C3—C4	131.57 (14)
C2—S2—C4	98.30 (10)	S1—C3—C5	120.60 (16)
S1—C1—H1a	107.2 (15)	C4—C3—C5	107.83 (17)
S1—C1—H1b	108.1 (12)	C3—C4—S2	129.27 (14)
H1a—C1—H1b	110 (2)	C6—C4—S2	123.28 (16)
S1—C1—C2	114.41 (15)	C3—C4—C6	107.44 (17)
C2—C1—H1a	107.8 (16)	O1—C5—C3	129.7 (2)
C2—C1—H1b	108.9 (15)	O2—C5—C3	108.36 (18)
C1—C2—S2	115.01 (15)	O1—C5—O2	121.98 (19)
S2—C2—H2a	105.1 (17)	O2—C6—C4	108.13 (18)
S2—C2—H2b	107.5 (13)	O3—C6—C4	130.7 (2)
C1—C2—H2a	108.8 (16)	O2—C6—O3	121.2 (2)
C1—C2—H2b	111.8 (14)	C5—O2—C6	108.14 (15)
H2a—C2—H2b	108 (2)

S1—C1—C2—S2	−70.39 (17)	S2—C4—C6—O3	4.1 (2)
S1—C3—C4—S2	−3.9 (2)	C3—C4—C6—O2	3.05 (16)
S1—C3—C4—C6	176.69 (19)	C3—C4—C6—O3	−176.50 (17)
S1—C3—C5—O1	1.95 (19)	C3—C5—O2—C6	0.24 (18)
S1—C3—C5—O2	−177.86 (15)	C4—C6—O2—C5	−1.95 (18)
S2—C4—C3—C5	176.57 (18)	C5—O2—C6—O3	177.65 (17)
S2—C4—C6—O2	−176.39 (17)

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