Crystal structure of N,N′-di­benzyl­pyromellitic diimide

Im, H.; Moon, S.-H.; Kim, T.H.; Park, K.-M.

doi:10.1107/S2056989016017710

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Volume 72| Part 12| December 2016| Pages 1809-1811

https://doi.org/10.1107/S2056989016017710

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Crystal structure of N,N′-dibenzylpyromellitic diimide

Hansu Im,^a Suk-Hee Moon,^b Tae Ho Kim ^a ^* and Ki-Min Park ^a ^*

^aResearch Institute of Natural Science and Department of Chemistry, Gyeongsang National University, Jinju 52828, Republic of Korea, and ^bDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, kmpark@gnu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 3 November 2016; accepted 7 November 2016; online 15 November 2016)

The title compound, C₂₄H₁₆N₂O₄ [systematic name: 2,6-dibenzylpyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone], consists of a central pyromellitic diimide moiety with terminal benzyl groups at the N-atom positions. The molecule is located about an inversion centre, so the asymmetric unit contains one half-molecule. In the molecule, both terminal phenyl groups, tilted by 72.97 (4)° with respect to the mean plane of the central pyromellitic diimide moiety (r.m.s. deviation = 0.0145 Å), are oriented away from each other, forming an elongated S-shaped conformation. In the crystal, molecules are connected via weak C—H⋯O hydrogen bonds and C—H⋯π interactions, resulting in the formation of supramolecular layers extending parallel to the ab plane.

Keywords: crystal structure; pyromellitic diimide derivative; hydrogen bonding; two-dimensional network.

CCDC reference: 1515263

1. Chemical context

As a result of their potential applications in organic photovoltaics (Huang et al., 2014 ) and as molecular electronic devices (Guo et al., 2014 ) and energy storage devices (Song et al., 2010 ), several π-conjugated, redox-active aromatic diimides including pyromellitic diimides, naphthalene diimides and perylene diimides have received considerable attention from materials chemists. Additionally, π-conjugated aromatic diimides and their derivatives are used as rigid structural components in supramolecular assemblies for the exploitation of supramolecular interactions such as hydrogen-bonding and halogen–π interactions (Hay & Custelcean, 2009 ; Lu et al., 2007 ; Gamez et al., 2007 ). Recently, our group reported a copper(I) coordination polymer with a pyromellitic diimide ligand, namely N,N′-bis[3-(methylthio)propyl]pyromellitic diimide, and revealed the presence of halogen–π interactions between the chlorine atoms of a dichloromethane solvent molecule of crystallization and pyromellitic diimide rings (Park et al., 2011 ). In an extension of our studies of pyromellitic diimide derivatives, we have prepared the title compound by the reaction of pyromellitic dianhydride with 2-phenyethylamine and we report its crystal structure here.

2. Structural commentary

The molecular structure of the title compound consists of a central pyromellitic diimide ring system with terminal benzyl groups on each of the inversion-related nitrogen atoms (Fig. 1). As the molecule is located about a crystallographic inversion centre, the asymmetric unit of the compound comprises one half-molecule. Short intramolecular C—H⋯O contacts (Table 1) enclose S(5) rings and may contribute to the planarity of the pyromellitic diimide ring system (r.m.s. deviation = 0.0145 Å). The two terminal phenyl groups in the molecule are oriented away from each other, forming an elongated S-shaped conformation. The terminal phenyl ring is tilted by 72.97 (4)° with respect to the mean plane of the central pyromellitic diimide moiety.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1	0.99	2.53	2.917 (2)	103
C12—H12⋯O2ⁱ	0.95	2.45	3.401 (2)	178
C7—H7B⋯Cg1ⁱⁱ	0.99	2.60	3.478 (2)	148
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z.

Figure 1
A view of the molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius and yellow dashed lines represent the intramolecular C—H⋯O short contacts. [Symmetry code; (i) −x + 2, −y + 1, −z.]

3. Supramolecular features

In the crystal, adjacent molecules are connected by weak C12—H12⋯O2 hydrogen bonds, Table 1 (yellow dashed lines in Fig. 2), forming inversion dimers. Inversion symmetry links these into a chain propagating along [ $[\overline{1}]$ 10]. Neighboring chains are linked through intermolecular C—H⋯π interactions between a methylene H atom and the terminal phenyl ring, resulting in the formation of supramolecular layers extending parallel to the ab plane (black dashed lines in Fig. 3 and Table 1). These layers are separated from each other by 3.104 (3) Å. No intermolecular π–π interactions are found between the pyromellitic diimide moieties.

Figure 2
Chains of the title compound formed through intermolecular C—H⋯O hydrogen bonds (yellow dashed lines).

Figure 3
Supramolecular layers of the title compound formed through intermolecular C—H⋯π interactions (black dashed lines) between the chains generated by intermolecular C—H⋯O hydrogen bonds (yellow dashed lines). H atoms not involved in intermolecular interactions have been omitted for clarity.

4. Synthesis and crystallization

The title compound was synthesized by the reaction of pyromellitic dianhydride with 2-phenylethylamine according to a literature procedure (Kang et al., 2015 ). X-ray quality single crystals were obtained by slow evaporation of a dichloromethane solution of the title compound.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically with d(C—H) = 0.95 Å for Csp²—H and 0.99 Å for methylene, and were refined as riding with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₁₆N₂O₄
M_r	396.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	6.1500 (5), 4.7475 (3), 31.002 (2)
β (°)	90.461 (3)
V (Å³)	905.14 (11)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.06 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker 2013 )
T_min, T_max	0.661, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	4593, 2016, 1444
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.119, 1.04
No. of reflections	2016
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXTL (Sheldrick 2008 ), SHELXL2014 (Sheldrick, 2015 ) and DIAMOND (Brandenburg, 2010 ).

Supporting information

CCDC reference: 1515263

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989016017710/sj5513sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016017710/sj5513Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016017710/sj5513Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); 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).

2,6-Dibenzylpyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone top

Crystal data top

C₂₄H₁₆N₂O₄	F(000) = 412
M_r = 396.39	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.1500 (5) Å	Cell parameters from 874 reflections
b = 4.7475 (3) Å	θ = 2.6–24.8°
c = 31.002 (2) Å	µ = 0.10 mm⁻¹
β = 90.461 (3)°	T = 173 K
V = 905.14 (11) Å³	Needle, colourless
Z = 2	0.50 × 0.06 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	1444 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.034
Absorption correction: multi-scan (SADABS; Bruker 2013)	θ_max = 27.5°, θ_min = 1.3°
T_min = 0.661, T_max = 0.746	h = −6→7
4593 measured reflections	k = −2→6
2016 independent reflections	l = −38→40

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0529P)² + 0.089P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2016 reflections	Δρ_max = 0.25 e Å⁻³
136 parameters	Δρ_min = −0.22 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.9145 (2)	0.9617 (3)	0.09759 (4)	0.0314 (4)
O2	0.4737 (2)	0.2514 (3)	0.04921 (4)	0.0282 (3)
N1	0.6589 (2)	0.6176 (3)	0.08217 (5)	0.0218 (4)
C1	0.2783 (3)	0.3279 (4)	0.15445 (6)	0.0303 (5)
H1	0.1617	0.3659	0.1350	0.036*
C2	0.2505 (4)	0.1311 (4)	0.18711 (7)	0.0363 (5)
H2	0.1157	0.0354	0.1901	0.044*
C3	0.4206 (4)	0.0760 (4)	0.21524 (7)	0.0399 (6)
H3	0.4021	−0.0568	0.2378	0.048*
C4	0.6175 (4)	0.2130 (4)	0.21071 (6)	0.0356 (5)
H4	0.7346	0.1724	0.2299	0.043*
C5	0.6439 (3)	0.4094 (4)	0.17812 (6)	0.0298 (5)
H5	0.7792	0.5036	0.1751	0.036*
C6	0.4739 (3)	0.4699 (4)	0.14973 (6)	0.0233 (4)
C7	0.4994 (3)	0.6895 (4)	0.11523 (6)	0.0252 (4)
H7A	0.3565	0.7201	0.1011	0.030*
H7B	0.5432	0.8691	0.1290	0.030*
C8	0.8499 (3)	0.7687 (3)	0.07548 (6)	0.0213 (4)
C9	0.9507 (3)	0.6455 (3)	0.03618 (5)	0.0199 (4)
C10	0.8168 (3)	0.4283 (3)	0.02169 (5)	0.0186 (4)
C11	0.6279 (3)	0.4093 (3)	0.05118 (5)	0.0211 (4)
C12	1.1389 (3)	0.7249 (3)	0.01520 (5)	0.0202 (4)
H12	1.2303	0.8725	0.0253	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0344 (9)	0.0305 (7)	0.0293 (7)	−0.0060 (6)	0.0023 (6)	−0.0098 (6)
O2	0.0247 (8)	0.0285 (7)	0.0316 (7)	−0.0056 (6)	0.0030 (6)	−0.0014 (6)
N1	0.0230 (9)	0.0219 (7)	0.0204 (8)	0.0001 (6)	0.0034 (6)	−0.0008 (6)
C1	0.0264 (11)	0.0300 (9)	0.0346 (11)	0.0002 (8)	0.0036 (9)	−0.0041 (9)
C2	0.0402 (14)	0.0287 (10)	0.0401 (12)	−0.0023 (10)	0.0169 (10)	−0.0015 (10)
C3	0.0580 (17)	0.0307 (10)	0.0313 (12)	0.0042 (11)	0.0151 (11)	0.0035 (9)
C4	0.0460 (14)	0.0341 (10)	0.0267 (10)	0.0039 (10)	−0.0045 (9)	0.0039 (9)
C5	0.0301 (12)	0.0315 (9)	0.0279 (10)	−0.0028 (9)	−0.0009 (9)	−0.0003 (9)
C6	0.0258 (11)	0.0228 (8)	0.0214 (9)	0.0009 (8)	0.0049 (8)	−0.0046 (7)
C7	0.0248 (11)	0.0269 (9)	0.0240 (9)	0.0025 (8)	0.0043 (8)	−0.0009 (8)
C8	0.0227 (10)	0.0198 (8)	0.0214 (9)	0.0011 (7)	−0.0010 (8)	0.0016 (7)
C9	0.0211 (10)	0.0184 (8)	0.0202 (9)	0.0011 (7)	−0.0025 (7)	0.0010 (7)
C10	0.0187 (9)	0.0181 (7)	0.0190 (8)	0.0005 (7)	0.0001 (7)	0.0024 (7)
C11	0.0239 (10)	0.0194 (8)	0.0199 (9)	0.0012 (8)	−0.0021 (7)	0.0027 (7)
C12	0.0229 (11)	0.0182 (7)	0.0195 (9)	−0.0014 (7)	−0.0019 (7)	0.0005 (7)

Geometric parameters (Å, º) top

O1—C8	1.210 (2)	C4—H4	0.9500
O2—C11	1.210 (2)	C5—C6	1.391 (2)
N1—C11	1.391 (2)	C5—H5	0.9500
N1—C8	1.393 (2)	C6—C7	1.503 (2)
N1—C7	1.465 (2)	C7—H7A	0.9900
C1—C6	1.387 (3)	C7—H7B	0.9900
C1—C2	1.389 (3)	C8—C9	1.491 (2)
C1—H1	0.9500	C9—C12	1.385 (2)
C2—C3	1.382 (3)	C9—C10	1.392 (2)
C2—H2	0.9500	C10—C12ⁱ	1.384 (2)
C3—C4	1.383 (3)	C10—C11	1.487 (3)
C3—H3	0.9500	C12—C10ⁱ	1.384 (2)
C4—C5	1.385 (3)	C12—H12	0.9500

C11—N1—C8	111.98 (15)	N1—C7—C6	114.25 (14)
C11—N1—C7	124.05 (15)	N1—C7—H7A	108.7
C8—N1—C7	123.68 (14)	C6—C7—H7A	108.7
C6—C1—C2	121.05 (19)	N1—C7—H7B	108.7
C6—C1—H1	119.5	C6—C7—H7B	108.7
C2—C1—H1	119.5	H7A—C7—H7B	107.6
C3—C2—C1	119.4 (2)	O1—C8—N1	125.37 (17)
C3—C2—H2	120.3	O1—C8—C9	128.58 (17)
C1—C2—H2	120.3	N1—C8—C9	106.04 (14)
C2—C3—C4	120.40 (19)	C12—C9—C10	122.98 (16)
C2—C3—H3	119.8	C12—C9—C8	129.19 (15)
C4—C3—H3	119.8	C10—C9—C8	107.81 (16)
C3—C4—C5	119.9 (2)	C12ⁱ—C10—C9	122.44 (16)
C3—C4—H4	120.1	C12ⁱ—C10—C11	129.49 (16)
C5—C4—H4	120.1	C9—C10—C11	108.03 (15)
C4—C5—C6	120.59 (19)	O2—C11—N1	125.35 (18)
C4—C5—H5	119.7	O2—C11—C10	128.50 (16)
C6—C5—H5	119.7	N1—C11—C10	106.14 (15)
C1—C6—C5	118.72 (17)	C10ⁱ—C12—C9	114.59 (15)
C1—C6—C7	120.50 (17)	C10ⁱ—C12—H12	122.7
C5—C6—C7	120.77 (17)	C9—C12—H12	122.7

C6—C1—C2—C3	−0.1 (3)	N1—C8—C9—C12	178.00 (17)
C1—C2—C3—C4	−0.7 (3)	O1—C8—C9—C10	−179.63 (17)
C2—C3—C4—C5	0.8 (3)	N1—C8—C9—C10	−0.36 (18)
C3—C4—C5—C6	−0.2 (3)	C12—C9—C10—C12ⁱ	−0.4 (3)
C2—C1—C6—C5	0.7 (3)	C8—C9—C10—C12ⁱ	178.05 (15)
C2—C1—C6—C7	−177.86 (17)	C12—C9—C10—C11	−178.18 (15)
C4—C5—C6—C1	−0.6 (3)	C8—C9—C10—C11	0.31 (18)
C4—C5—C6—C7	178.03 (17)	C8—N1—C11—O2	−178.89 (16)
C11—N1—C7—C6	71.0 (2)	C7—N1—C11—O2	−4.8 (3)
C8—N1—C7—C6	−115.62 (18)	C8—N1—C11—C10	−0.08 (18)
C1—C6—C7—N1	−115.50 (19)	C7—N1—C11—C10	173.99 (14)
C5—C6—C7—N1	65.9 (2)	C12ⁱ—C10—C11—O2	1.1 (3)
C11—N1—C8—O1	179.57 (16)	C9—C10—C11—O2	178.61 (17)
C7—N1—C8—O1	5.5 (3)	C12ⁱ—C10—C11—N1	−177.67 (16)
C11—N1—C8—C9	0.27 (18)	C9—C10—C11—N1	−0.15 (18)
C7—N1—C8—C9	−173.83 (14)	C10—C9—C12—C10ⁱ	0.4 (3)
O1—C8—C9—C12	−1.3 (3)	C8—C9—C12—C10ⁱ	−177.73 (16)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1	0.99	2.53	2.917 (2)	103
C12—H12···O2ⁱⁱ	0.95	2.45	3.401 (2)	178
C7—H7B···Cg1ⁱⁱⁱ	0.99	2.60	3.478 (2)	148

Symmetry codes: (ii) x+1, y+1, z; (iii) x, y+1, z.

Acknowledgements

This work was supported from the National Research Foundation of Korea (NRF) project (2012R1A4A1027750 and 2015R1D1A3A01020410).

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