N,N′-[Methyl­enedi(3,5-dimethyl-o-phenyl­ene)]diphthalimide

In the structure of the title compound, C₃₃H₂₆N₂O₄, two phthalimide units are symmetrically linked by a bis­(3,5-dimethyl­phen­yl)methane bridge. The methyl­ene C atom of this bridge lies on a twofold rotation axis. The dihedral angle between the planes of the two central benzene rings is 61.4 (4)°. The terminal isoindole group is approximately planar, with an r.m.s. deviation of atoms from the mean plane of 0.012 Å and a dihedral angle of 75.3 (14)° with the attached benzene ring. An extensive network of C—H...O hydrogen bonds stabilizes the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.049
• wR factor = 0.135
• Data-to-parameter ratio = 9.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C14
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.59
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9A    ..  O2      ..       2.67 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.99
           From the CIF: _reflns_number_total               1762
           Count of symmetry unique reflns         1761
           Completeness (_total/calc)            100.06%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         1
           Fraction of Friedel pairs measured     0.001
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Bisimides are heterocyclic compounds, some of which have biological activity (Rich et al., 1975). Moreover, they are synthetic precursors with applications in organic synthesis (Degenhardt et al., 2002), polymer synthesis (Mallakpour & Kowsari, 2004), supramolecular chemistry (Zhang et al., 1999), and for the development of new materials (Langhals & Kirner, 2000) and molecular electronic devices (Yakimov & Forrest, 2002).

Following our studies on the synthesis of bisimides derivatives, (Li et al., 2007) we report here the structure of the title compound (I), Fig. 1. In the compound, two phthalimide units are symmetrically linked by a bis(3,5-dimethylphenyl)methane bridge. The methylene C atom of this bridge lies on a twofold rotation axis. The dihedral angle between the planes of the two central benzene rings is 61.4 (4)°. The terminal isoindole group is approximately planar with 0.012 Å r.m.s. deviation of atoms from the best fit plane and makes a dihedral angle of 75.3 (14)° with the attached benzene ring. Compared to a similar structure (Li et al., 2007), the packing pattern is different which may result from the methyl groups on the two central benzene rings. This is because the hydrogen atoms of the methyl groups form weak intermolecular C—H···O hydrogen bonds which contribute to the stability of the structure (Table 1).

Related literature

For details of the biological activity and uses of bis(imide) derivatives, see: Rich et al. (1975); Degenhardt et al. (2002); Mallakpour & Kowsari (2004); Zhang et al. (1999); Langhals & Kirner (2000); Yakimov & Forrest (2002). For a related structure, see: Li et al. (2007).

S2. Experimental

A solution of phthaloyl dichoride (420, 2 mmol) was added slowly over a period of 10 min to a solution of 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylbenzenamine (510 mg, 2 mmol) in dichloromethane (25 ml) at 273 K to yield a light yellow precipitate. Triethylamine (5 ml) was then added to dissolve the precipitate which became a yellow suspension after stirring for 12 h. The compound was filtered and dried to give (I), (yield 350 mg, 68%). Single crystals of (I) were obtained by recrystallization from DMF at room temperature.

S3. Refinement

In the absence of significant anomalous dispersion effects, Friedel pairs were merged. All H atoms were initially located in a difference Fourier map and then included with constrained bond lengths and isotropic displacement parameters: C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids (arbitrary spheres for H atoms). Atoms labelled a are related to other atoms by the symmetry operation x + 1, -y + 1, z

N,N'-[Methylenedi(3,5-dimethyl-o-phenylene)]diphthalimide

Crystal data

C33H26N2O4	F(000) = 540
Mr = 514.56	Dx = 1.227 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 1971 reflections
a = 16.221 (3) Å	θ = 2.4–20.7°
b = 8.4722 (18) Å	µ = 0.08 mm^−1
c = 10.136 (2) Å	T = 292 K
V = 1392.9 (5) Å^3	Block, colourless
Z = 2	0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer	1223 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 27.0°, θmin = 2.0°
φ and ω scans	h = −19→20
9315 measured reflections	k = −10→10
1762 independent reflections	l = −12→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0778P)^2 + 0.0282P] where P = (Fo^2 + 2Fc^2)/3
1762 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.11270 (12)	0.3874 (3)	0.8973 (2)	0.0822 (7)
C4	0.36944 (16)	0.5785 (4)	0.9058 (3)	0.0676 (8)
H4	0.3816	0.6821	0.9291	0.081*
C6	0.29729 (15)	0.5483 (3)	0.8366 (3)	0.0638 (7)
C7	0.28176 (15)	0.3923 (4)	0.8016 (3)	0.0613 (7)
C2	0.42398 (14)	0.4605 (4)	0.9415 (3)	0.0654 (8)
C10	0.12854 (15)	0.3540 (3)	0.7854 (3)	0.0650 (7)
N1	0.20752 (12)	0.3573 (3)	0.7307 (2)	0.0687 (7)
C1	0.5000	0.5000	1.0209 (4)	0.0820 (13)
H1A	0.4874	0.5891	1.0776	0.098*	0.50
H1B	0.5126	0.4109	1.0776	0.098*	0.50
C5	0.33479 (17)	0.2697 (4)	0.8357 (3)	0.0705 (8)
C3	0.40569 (16)	0.3082 (4)	0.9057 (3)	0.0718 (8)
H3	0.4420	0.2280	0.9290	0.086*
C11	0.07252 (16)	0.3054 (4)	0.6778 (3)	0.0690 (8)
O2	0.26424 (14)	0.3205 (6)	0.5260 (3)	0.1490 (16)
C17	−0.01132 (17)	0.2809 (4)	0.6786 (3)	0.0855 (10)
H17	−0.0421	0.2949	0.7552	0.103*
C13	0.20528 (17)	0.3221 (5)	0.5960 (3)	0.0971 (12)
C12	0.11783 (17)	0.2860 (5)	0.5650 (3)	0.0870 (10)
C16	−0.0480 (2)	0.2354 (5)	0.5634 (5)	0.1075 (12)
H16	−0.1046	0.2184	0.5612	0.129*
C8	0.3160 (2)	0.1013 (5)	0.8045 (5)	0.1101 (13)
H8A	0.3557	0.0344	0.8471	0.165*
H8B	0.3187	0.0856	0.7108	0.165*
H8C	0.2618	0.0758	0.8356	0.165*
C9	0.23849 (19)	0.6788 (4)	0.8031 (4)	0.0868 (10)
H9A	0.2287	0.6794	0.7097	0.130*
H9B	0.2618	0.7781	0.8293	0.130*
H9C	0.1874	0.6624	0.8488	0.130*
C14	0.0814 (2)	0.2415 (7)	0.4501 (4)	0.1268 (17)
H14	0.1120	0.2298	0.3732	0.152*
C15	−0.0023 (3)	0.2143 (6)	0.4510 (4)	0.1265 (16)
H15	−0.0283	0.1811	0.3741	0.152*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0570 (11)	0.1194 (17)	0.0702 (14)	−0.0088 (11)	0.0105 (10)	−0.0066 (13)
C4	0.0482 (14)	0.0855 (18)	0.0692 (18)	−0.0171 (13)	0.0017 (13)	0.0010 (15)
C6	0.0462 (14)	0.0812 (19)	0.0640 (16)	−0.0096 (13)	0.0021 (13)	0.0086 (14)
C7	0.0359 (12)	0.089 (2)	0.0591 (16)	−0.0094 (12)	0.0029 (11)	0.0000 (14)
C2	0.0359 (12)	0.108 (2)	0.0526 (14)	−0.0085 (14)	0.0054 (11)	0.0045 (16)
C10	0.0437 (13)	0.0829 (18)	0.0685 (18)	−0.0066 (13)	0.0054 (13)	−0.0023 (15)
N1	0.0407 (11)	0.1025 (17)	0.0629 (14)	−0.0096 (12)	0.0018 (10)	−0.0099 (13)
C1	0.0447 (19)	0.145 (4)	0.056 (2)	−0.013 (2)	0.000	0.000
C5	0.0526 (15)	0.083 (2)	0.0753 (19)	−0.0060 (14)	0.0059 (15)	−0.0026 (16)
C3	0.0451 (14)	0.097 (2)	0.0737 (19)	0.0052 (14)	0.0008 (13)	0.0075 (18)
C11	0.0431 (13)	0.0869 (19)	0.0768 (19)	−0.0027 (13)	−0.0025 (14)	−0.0072 (17)
O2	0.0531 (13)	0.310 (5)	0.0842 (17)	−0.017 (2)	0.0157 (13)	−0.054 (2)
C17	0.0418 (15)	0.111 (2)	0.104 (2)	−0.0021 (16)	−0.0051 (17)	0.000 (2)
C13	0.0441 (15)	0.171 (3)	0.076 (2)	−0.007 (2)	0.0060 (15)	−0.032 (2)
C12	0.0462 (15)	0.143 (3)	0.072 (2)	−0.0026 (17)	−0.0051 (15)	−0.017 (2)
C16	0.0493 (17)	0.144 (3)	0.129 (3)	−0.0055 (19)	−0.022 (2)	−0.016 (3)
C8	0.087 (2)	0.092 (2)	0.151 (4)	−0.0020 (19)	−0.008 (3)	−0.019 (3)
C9	0.0641 (18)	0.089 (2)	0.107 (3)	−0.0053 (16)	−0.0040 (18)	0.017 (2)
C14	0.072 (2)	0.223 (5)	0.085 (2)	−0.004 (3)	−0.009 (2)	−0.043 (3)
C15	0.074 (2)	0.194 (4)	0.111 (3)	0.000 (3)	−0.037 (3)	−0.051 (3)

Geometric parameters (Å, º)

O1—C10	1.197 (3)	C11—C12	1.369 (4)
C4—C2	1.383 (4)	C11—C17	1.376 (4)
C4—C6	1.388 (4)	O2—C13	1.191 (4)
C4—H4	0.9300	C17—C16	1.366 (5)
C6—C7	1.392 (4)	C17—H17	0.9300
C6—C9	1.499 (4)	C13—C12	1.485 (4)
C7—C5	1.392 (4)	C12—C14	1.360 (5)
C7—N1	1.434 (3)	C16—C15	1.370 (6)
C2—C3	1.373 (4)	C16—H16	0.9300
C2—C1	1.510 (3)	C8—H8A	0.9600
C10—N1	1.396 (3)	C8—H8B	0.9600
C10—C11	1.478 (4)	C8—H8C	0.9600
N1—C13	1.397 (4)	C9—H9A	0.9600
C1—C2^i	1.510 (3)	C9—H9B	0.9600
C1—H1A	0.9700	C9—H9C	0.9600
C1—H1B	0.9700	C14—C15	1.377 (6)
C5—C3	1.390 (4)	C14—H14	0.9300
C5—C8	1.492 (5)	C15—H15	0.9300
C3—H3	0.9300
C2—C4—C6	122.6 (3)	C17—C11—C10	130.2 (3)
C2—C4—H4	118.7	C16—C17—C11	117.9 (3)
C6—C4—H4	118.7	C16—C17—H17	121.1
C4—C6—C7	117.1 (3)	C11—C17—H17	121.1
C4—C6—C9	121.0 (3)	O2—C13—N1	124.3 (3)
C7—C6—C9	121.8 (2)	O2—C13—C12	129.7 (3)
C6—C7—C5	122.2 (2)	N1—C13—C12	106.0 (2)
C6—C7—N1	118.5 (3)	C14—C12—C11	121.0 (3)
C5—C7—N1	119.3 (3)	C14—C12—C13	130.8 (3)
C3—C2—C4	118.1 (2)	C11—C12—C13	108.1 (3)
C3—C2—C1	121.7 (2)	C17—C16—C15	120.8 (3)
C4—C2—C1	120.1 (3)	C17—C16—H16	119.6
O1—C10—N1	124.7 (3)	C15—C16—H16	119.6
O1—C10—C11	129.3 (2)	C5—C8—H8A	109.5
N1—C10—C11	106.0 (2)	C5—C8—H8B	109.5
C10—N1—C13	111.1 (2)	H8A—C8—H8B	109.5
C10—N1—C7	125.1 (2)	C5—C8—H8C	109.5
C13—N1—C7	123.8 (2)	H8A—C8—H8C	109.5
C2^i—C1—C2	115.6 (3)	H8B—C8—H8C	109.5
C2^i—C1—H1A	108.4	C6—C9—H9A	109.5
C2—C1—H1A	108.4	C6—C9—H9B	109.5
C2^i—C1—H1B	108.4	H9A—C9—H9B	109.5
C2—C1—H1B	108.4	C6—C9—H9C	109.5
H1A—C1—H1B	107.4	H9A—C9—H9C	109.5
C3—C5—C7	117.6 (3)	H9B—C9—H9C	109.5
C3—C5—C8	120.1 (3)	C12—C14—C15	118.0 (4)
C7—C5—C8	122.3 (3)	C12—C14—H14	121.0
C2—C3—C5	122.3 (3)	C15—C14—H14	121.0
C2—C3—H3	118.8	C16—C15—C14	121.1 (4)
C5—C3—H3	118.8	C16—C15—H15	119.5
C12—C11—C17	121.2 (3)	C14—C15—H15	119.5
C12—C11—C10	108.6 (2)
C2—C4—C6—C7	−1.0 (4)	C8—C5—C3—C2	−177.2 (3)
C2—C4—C6—C9	178.2 (3)	O1—C10—C11—C12	177.3 (3)
C4—C6—C7—C5	1.1 (4)	N1—C10—C11—C12	−1.6 (4)
C9—C6—C7—C5	−178.1 (3)	O1—C10—C11—C17	−2.4 (6)
C4—C6—C7—N1	179.7 (2)	N1—C10—C11—C17	178.7 (3)
C9—C6—C7—N1	0.5 (4)	C12—C11—C17—C16	0.5 (5)
C6—C4—C2—C3	0.5 (4)	C10—C11—C17—C16	−179.8 (3)
C6—C4—C2—C1	−177.9 (3)	C10—N1—C13—O2	178.3 (4)
O1—C10—N1—C13	−176.1 (3)	C7—N1—C13—O2	−1.5 (7)
C11—C10—N1—C13	2.8 (4)	C10—N1—C13—C12	−2.9 (4)
O1—C10—N1—C7	3.7 (5)	C7—N1—C13—C12	177.2 (3)
C11—C10—N1—C7	−177.3 (3)	C17—C11—C12—C14	−0.1 (6)
C6—C7—N1—C10	−74.6 (4)	C10—C11—C12—C14	−179.9 (4)
C5—C7—N1—C10	103.9 (3)	C17—C11—C12—C13	179.6 (3)
C6—C7—N1—C13	105.2 (4)	C10—C11—C12—C13	−0.2 (4)
C5—C7—N1—C13	−76.2 (4)	O2—C13—C12—C14	0.1 (8)
C3—C2—C1—C2^i	91.2 (3)	N1—C13—C12—C14	−178.5 (4)
C4—C2—C1—C2^i	−90.4 (3)	O2—C13—C12—C11	−179.5 (5)
C6—C7—C5—C3	−0.8 (4)	N1—C13—C12—C11	1.9 (5)
N1—C7—C5—C3	−179.4 (2)	C11—C17—C16—C15	0.3 (6)
C6—C7—C5—C8	176.7 (3)	C11—C12—C14—C15	−0.9 (7)
N1—C7—C5—C8	−1.9 (5)	C13—C12—C14—C15	179.4 (5)
C4—C2—C3—C5	−0.2 (4)	C17—C16—C15—C14	−1.4 (8)
C1—C2—C3—C5	178.2 (3)	C12—C14—C15—C16	1.7 (8)
C7—C5—C3—C2	0.3 (4)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^ii	0.93	2.48	3.304 (4)	148
C16—H16···O2^iii	0.93	2.33	3.213 (4)	159
C9—H9A···O2^iv	0.96	2.67	3.545 (4)	151

Symmetry codes: (ii) −x+1/2, y+1/2, −z+2; (iii) x−1/2, −y+1/2, −z+1; (iv) −x+1/2, y+1/2, −z+1.