Crystal structure of 2,6-di-benzyl-pyrrolo-[3,4-f]iso-indole-1,3,5,7(2H,6H)-tetra-thione.

The title compound, C24H16N2S4, consists of a central pyromellitic di-imide substituted with an S atom and terminal benzyl groups. The mol-ecule lies on a crystallographic inversion centre so that the asymmetric unit contains half of the mol-ecule. The mol-ecule was prepared by thio-nation of N,N'-di-benzyl-pyromellitic di-imide 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, mol-ecules are connected by C-H⋯π inter-actions and weak short S⋯S contacts, forming supra-molecular 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).

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 crystal structure here.

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 asymmetric unit 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.

Figure 1

The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius and yellow dashed lines represent intra­molecular C—H⋯S short contacts. Unlabelled atoms are generated by the symmetry operation (−x + 2, −y + 1, −z).

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 ring.

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⋯Cg1i	0.99	2.66	3.498 (3)	142

Symmetry code: (i) .

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 ▸).

Figure 2

Inter­molecular C—H⋯π inter­actions (yellow dashed lines) forming one-dimensional loop chains.

Figure 3

The packing diagram for the title compound, showing the two-dimensional network formed by C—H⋯π inter­actions (yellow dashed lines) and weak short S⋯S contacts (black dashed lines). H atoms not involved in inter­molecular inter­actions have been omitted for clarity.

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 column chromatography (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.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and U iso(H) = 1.2U eq(C) for aromatic C—H groups, and C—H = 0.99 Å and U iso(H) = 1.2U eq(C) for Csp 3—H groups. Non-merohedral twinning was identified in the crystal (TwinRotMat within PLATON; Spek, 2009 ▸); the twin law 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).

Table 2

Experimental details

Crystal data
Chemical formula	C24H16N2S4
M r	460.63
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	173
a, b, c (Å)	6.8571 (4), 4.7724 (3), 32.0010 (17)
β (°)	95.916 (4)
V (Å3)	1041.65 (11)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.47
Crystal size (mm)	0.43 × 0.34 × 0.01
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.646, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	1829, 1829, 1640
R int	0.059
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.089, 1.05
No. of reflections	1829
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.26, −0.23

Computer programs: APEX2 (Bruker, 2014 ▸), SAINT (Bruker, 2014 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 2010 ▸), SHELXTL (Sheldrick, 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017012154/hg5493sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017012154/hg5493Isup2.hkl

CCDC reference: 1570214

Additional supporting information: crystallographic information; 3D view; checkCIF report

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)

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