research communications
f]isoindole-1,3,5,7(2H,6H)-tetrathione
of 2,6-dibenzylpyrrolo[3,4-aDepartment of Chemistry (BK21 plus) and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 52828, Republic of Korea, and bDirector of Planning Center, Gyeongsang National University Academy and Industry Collaboration, 501 Jinjudaero, Jinjusi 52828, Republic of Korea
*Correspondence e-mail: woo@gnu.ac.kr
The title compound, C24H16N2S4, consists of a central pyromellitic diimide substituted with an S atom and terminal benzyl groups. The molecule lies on a crystallographic inversion centre so that the contains half of the molecule. The molecule was prepared by thionation of N,N′-dibenzylpyromellitic diimide with Lawesson's reagent and has an S-shaped conformation similar to other compounds of this type. The phenyl groups are tilted by 72.69 (8)° with respect to the plane of the central arene ring. In the crystal, molecules are connected by C—H⋯π interactions and weak short S⋯S contacts, forming supramolecular layers extending paralled to the ab plane. The crystal studied was found to be non-merohedrally twinned, with the minor component being 0.113 (3).
CCDC reference: 1570214
1. Chemical context
Recently, pyromellitic diimide derivatives have been spotlighted due to their use in energy-storage materials (Nalluri et al. 2016). They also show potential applications in photovoltaic devices (Kanosue et al., 2016) and organic semiconductors (Zheng et al., 2008). Not only pyromellitic diimide derivatives, but also pyromellitic diimides substituted with sulfur have potential applications in organic semiconductors (Yang et al., 2015). We have reported copper(I) coordination polymers based on pyromellitic diimide derivatives (Park et al., 2011), which showed colour change owing to intermolecular halogen–π interactions. In addition, we have found that reversible solvent exchange and crystal transformations were possible in the crystals (Kang et al., 2015). In an extension of previous research, we have synthesized the pyromellitic diimide in which the O atoms are replaced with S atoms, by the reaction of N,N′-dibenzylpyromellitic diimide with Lawesson's reagent, and report its here.
2. Structural commentary
The molecular structure of the title compound consists of a central pyromellitic diimide substituted with S atoms and two terminal benzyl groups (Fig. 1). The molecule possesses a crystallographic inversion centre and thus the of the title compound is composed of half a molecule. The molecule exhibits an intramolecular C6—H6B⋯S2 short contact (Table 1). In the molecule, the terminal phenyl groups point in opposite directions and their planes are tilted by 72.69 (8)° with respect to the plane of the central arene ring, forming an elongated S-shaped molecule.
3. Supramolecular features
In the crystal, C6—H6B⋯Cg1i (Cg1 is the centroid of the C7–C12 ring) interactions between neighbouring molecules generate a one-dimensional loop chain (yellow dashed lines in Fig. 2, and Table 1). Moreover, adjacent molecules are connected by a weak short S1⋯ S2 contact [3.5921 (10) Å], resulting in the formation of a two-dimensional network (yellow and black dashed lines in Fig. 3).
4. Synthesis and crystallization
N,N′-Dibenzylpyromellitic diimide was synthesized by the reaction of pyromellitic dianhydride with 2-phenylethylamine according to the literature procedure of Im et al. (2017). To a stirred solution of N,N′-dibenzylpyromellitic diimide (0.25 g, 0.63 mmol) in anhydrous toluene (100 ml) was added Lawesson's reagent (2.00 g, 4.90 mmol), and the resulting mixture was stirred under reflux for 36 h. It was then cooled to room temperature and concentrated in vacuo, followed by purification by silica-gel flash (CH2Cl2–n-hexane, 1:3 v/v). Crystals suitable for X-ray diffaction analysis were obtained by slow evaporation of a dichloromethane solution of the title compound.
5. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H groups, and C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for Csp3—H groups. Non-merohedral was identified in the crystal (TwinRotMat within PLATON; Spek, 2009); the is −0.999 0 0.002, 0 −1 0, 1 0 0.999 and the final refined BASF parameter was determined to be 0.113 (3).
details are summarized in Table 2Supporting information
CCDC reference: 1570214
https://doi.org/10.1107/S2056989017012154/hg5493sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017012154/hg5493Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).C24H16N2S4 | F(000) = 476 |
Mr = 460.63 | Dx = 1.469 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8571 (4) Å | Cell parameters from 3915 reflections |
b = 4.7724 (3) Å | θ = 2.6–25.5° |
c = 32.0010 (17) Å | µ = 0.47 mm−1 |
β = 95.916 (4)° | T = 173 K |
V = 1041.65 (11) Å3 | Plate, brown |
Z = 2 | 0.43 × 0.34 × 0.01 mm |
Bruker APEXII CCD diffractometer | 1640 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.059 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | θmax = 25.0°, θmin = 1.3° |
Tmin = 0.646, Tmax = 0.746 | h = −8→8 |
1829 measured reflections | k = −5→5 |
1829 independent reflections | l = −6→38 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.037P)2 + 0.6197P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1829 reflections | Δρmax = 0.26 e Å−3 |
137 parameters | Δρmin = −0.23 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component twin |
x | y | z | Uiso*/Ueq | ||
S1 | 0.50612 (10) | 0.30438 (16) | 0.05735 (2) | 0.0259 (2) | |
S2 | 1.10897 (11) | 0.99091 (17) | 0.10558 (2) | 0.0299 (2) | |
N1 | 0.7913 (3) | 0.6607 (5) | 0.08677 (6) | 0.0192 (5) | |
C1 | 0.7132 (4) | 0.4707 (6) | 0.05665 (7) | 0.0189 (6) | |
C2 | 0.9678 (4) | 0.7718 (6) | 0.07722 (7) | 0.0199 (6) | |
C3 | 1.0046 (4) | 0.6467 (6) | 0.03656 (7) | 0.0182 (6) | |
C4 | 0.8521 (4) | 0.4592 (6) | 0.02468 (7) | 0.0184 (6) | |
C5 | 1.1572 (4) | 0.6945 (6) | 0.01231 (7) | 0.0199 (6) | |
H5 | 1.2604 | 0.8225 | 0.0204 | 0.024* | |
C6 | 0.6888 (4) | 0.7471 (6) | 0.12291 (8) | 0.0232 (6) | |
H6A | 0.5503 | 0.7888 | 0.1130 | 0.028* | |
H6B | 0.7493 | 0.9218 | 0.1348 | 0.028* | |
C7 | 0.6944 (4) | 0.5277 (6) | 0.15724 (8) | 0.0235 (6) | |
C8 | 0.5208 (5) | 0.4058 (6) | 0.16745 (9) | 0.0300 (7) | |
H8 | 0.3993 | 0.4576 | 0.1525 | 0.036* | |
C9 | 0.5252 (5) | 0.2086 (7) | 0.19950 (10) | 0.0411 (9) | |
H9 | 0.4069 | 0.1252 | 0.2064 | 0.049* | |
C10 | 0.7023 (5) | 0.1345 (7) | 0.22125 (9) | 0.0423 (9) | |
H10 | 0.7052 | 0.0004 | 0.2433 | 0.051* | |
C11 | 0.8741 (5) | 0.2531 (7) | 0.21127 (9) | 0.0383 (8) | |
H11 | 0.9952 | 0.2000 | 0.2263 | 0.046* | |
C12 | 0.8711 (4) | 0.4503 (6) | 0.17935 (8) | 0.0289 (7) | |
H12 | 0.9901 | 0.5326 | 0.1726 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0227 (3) | 0.0291 (4) | 0.0261 (3) | −0.0078 (3) | 0.0038 (3) | 0.0008 (3) |
S2 | 0.0311 (4) | 0.0301 (5) | 0.0291 (4) | −0.0100 (3) | 0.0063 (3) | −0.0092 (3) |
N1 | 0.0213 (11) | 0.0168 (13) | 0.0198 (10) | −0.0010 (10) | 0.0041 (9) | 0.0010 (9) |
C1 | 0.0212 (13) | 0.0160 (15) | 0.0193 (12) | 0.0008 (11) | 0.0013 (10) | 0.0051 (11) |
C2 | 0.0235 (14) | 0.0158 (16) | 0.0210 (12) | 0.0014 (12) | 0.0046 (10) | 0.0024 (11) |
C3 | 0.0208 (13) | 0.0153 (15) | 0.0184 (12) | 0.0035 (12) | 0.0022 (10) | 0.0026 (11) |
C4 | 0.0196 (13) | 0.0156 (16) | 0.0202 (12) | −0.0001 (11) | 0.0024 (10) | 0.0046 (11) |
C5 | 0.0208 (13) | 0.0177 (16) | 0.0209 (13) | −0.0005 (12) | 0.0012 (10) | 0.0021 (11) |
C6 | 0.0279 (14) | 0.0180 (17) | 0.0249 (13) | 0.0020 (12) | 0.0089 (11) | −0.0020 (12) |
C7 | 0.0359 (16) | 0.0163 (16) | 0.0197 (12) | −0.0004 (13) | 0.0094 (11) | −0.0036 (11) |
C8 | 0.0359 (16) | 0.0259 (19) | 0.0304 (15) | −0.0014 (14) | 0.0145 (13) | −0.0022 (13) |
C9 | 0.057 (2) | 0.029 (2) | 0.0427 (17) | −0.0066 (17) | 0.0301 (16) | −0.0013 (15) |
C10 | 0.070 (2) | 0.032 (2) | 0.0276 (16) | −0.0005 (18) | 0.0169 (16) | 0.0040 (14) |
C11 | 0.053 (2) | 0.033 (2) | 0.0273 (15) | 0.0034 (17) | 0.0005 (14) | 0.0030 (14) |
C12 | 0.0365 (16) | 0.0238 (18) | 0.0272 (14) | −0.0037 (14) | 0.0068 (12) | −0.0010 (13) |
S1—C1 | 1.629 (3) | C6—H6A | 0.9900 |
S2—C2 | 1.635 (3) | C6—H6B | 0.9900 |
N1—C2 | 1.384 (3) | C7—C12 | 1.388 (4) |
N1—C1 | 1.390 (3) | C7—C8 | 1.394 (4) |
N1—C6 | 1.473 (3) | C8—C9 | 1.390 (4) |
C1—C4 | 1.469 (3) | C8—H8 | 0.9500 |
C2—C3 | 1.477 (3) | C9—C10 | 1.382 (5) |
C3—C5 | 1.384 (4) | C9—H9 | 0.9500 |
C3—C4 | 1.399 (4) | C10—C11 | 1.374 (5) |
C4—C5i | 1.388 (3) | C10—H10 | 0.9500 |
C5—C4i | 1.388 (3) | C11—C12 | 1.388 (4) |
C5—H5 | 0.9500 | C11—H11 | 0.9500 |
C6—C7 | 1.515 (4) | C12—H12 | 0.9500 |
C2—N1—C1 | 112.3 (2) | N1—C6—H6B | 108.9 |
C2—N1—C6 | 124.4 (2) | C7—C6—H6B | 108.9 |
C1—N1—C6 | 123.1 (2) | H6A—C6—H6B | 107.7 |
N1—C1—C4 | 106.0 (2) | C12—C7—C8 | 119.4 (3) |
N1—C1—S1 | 125.63 (19) | C12—C7—C6 | 120.6 (2) |
C4—C1—S1 | 128.3 (2) | C8—C7—C6 | 120.0 (2) |
N1—C2—C3 | 105.8 (2) | C9—C8—C7 | 120.1 (3) |
N1—C2—S2 | 127.14 (19) | C9—C8—H8 | 120.0 |
C3—C2—S2 | 127.06 (19) | C7—C8—H8 | 120.0 |
C5—C3—C4 | 122.7 (2) | C10—C9—C8 | 119.7 (3) |
C5—C3—C2 | 129.4 (2) | C10—C9—H9 | 120.1 |
C4—C3—C2 | 107.9 (2) | C8—C9—H9 | 120.1 |
C5i—C4—C3 | 122.5 (2) | C11—C10—C9 | 120.5 (3) |
C5i—C4—C1 | 129.6 (2) | C11—C10—H10 | 119.8 |
C3—C4—C1 | 107.9 (2) | C9—C10—H10 | 119.8 |
C3—C5—C4i | 114.8 (2) | C10—C11—C12 | 120.2 (3) |
C3—C5—H5 | 122.6 | C10—C11—H11 | 119.9 |
C4i—C5—H5 | 122.6 | C12—C11—H11 | 119.9 |
N1—C6—C7 | 113.4 (2) | C11—C12—C7 | 120.1 (3) |
N1—C6—H6A | 108.9 | C11—C12—H12 | 119.9 |
C7—C6—H6A | 108.9 | C7—C12—H12 | 119.9 |
C2—N1—C1—C4 | −0.2 (3) | S1—C1—C4—C5i | −0.3 (4) |
C6—N1—C1—C4 | 175.6 (2) | N1—C1—C4—C3 | −1.2 (3) |
C2—N1—C1—S1 | −178.89 (19) | S1—C1—C4—C3 | 177.4 (2) |
C6—N1—C1—S1 | −3.1 (3) | C4—C3—C5—C4i | −0.3 (4) |
C1—N1—C2—C3 | 1.5 (3) | C2—C3—C5—C4i | −180.0 (2) |
C6—N1—C2—C3 | −174.3 (2) | C2—N1—C6—C7 | −108.7 (3) |
C1—N1—C2—S2 | −177.3 (2) | C1—N1—C6—C7 | 76.0 (3) |
C6—N1—C2—S2 | 7.0 (4) | N1—C6—C7—C12 | 64.7 (3) |
N1—C2—C3—C5 | 177.5 (3) | N1—C6—C7—C8 | −116.7 (3) |
S2—C2—C3—C5 | −3.8 (4) | C12—C7—C8—C9 | 0.0 (4) |
N1—C2—C3—C4 | −2.2 (3) | C6—C7—C8—C9 | −178.7 (3) |
S2—C2—C3—C4 | 176.5 (2) | C7—C8—C9—C10 | 0.1 (5) |
C5—C3—C4—C5i | 0.3 (4) | C8—C9—C10—C11 | −0.3 (5) |
C2—C3—C4—C5i | −180.0 (2) | C9—C10—C11—C12 | 0.4 (5) |
C5—C3—C4—C1 | −177.6 (2) | C10—C11—C12—C7 | −0.3 (5) |
C2—C3—C4—C1 | 2.1 (3) | C8—C7—C12—C11 | 0.1 (4) |
N1—C1—C4—C5i | −179.0 (3) | C6—C7—C12—C11 | 178.8 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···S2 | 0.99 | 2.75 | 3.208 (3) | 109 |
C6—H6B···Cg1ii | 0.99 | 2.66 | 3.498 (3) | 142 |
Symmetry code: (ii) x, y+1, z. |
Funding information
Funding for this research was provided by: Ministry of Education, Science and Technology (Basic Science Program through the National Research Foundation of Korea (NRF); grant No. 2015R1D1A4A01020317); Ministry of Trade, Industry and Energy (MOTIE, Korea), Industrial Human Resources and Skill Development Program (award No. N0001415, Display Expert Training Project for Advanced Display equipments and components engineer).
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