4-(5-Bromo-1,3-dioxoisoindolin-2-yl)­benzoic acid N,N-dimethyl­formamide solvate

Liang, Z.-P.; Li, J.; Hua, Y.; Wang, H.-L.

doi:10.1107/S1600536807025913

4-(5-Bromo-1,3-dioxoisoindolin-2-yl)benzoic acid N,N-dimethylformamide solvate

Z.-P. Liang, J. Li, Y. Hua and H.-L. Wang

In the crystal structure of the title compound, C₁₅H₈BrNO₄·C₃H₇NO, the constituent species interact by C—H

O and O—H

O hydrogen bonds. The dihedral angle between the phthalimide group and the benzene ring is 51.4 (2)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025913/hb2427sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025913/hb2427Isup2.hkl Contains datablock I

CCDC reference: 654853

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.005 Å
R factor = 0.040
wR factor = 0.118
Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N2
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  Br1     ..       3.49 Ang.

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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

Comment top

Phthalimides and N-substituted phthalimides are an important class of compounds because of their interesting biological activities. Phthalimides have also served as starting materials and intermediates for the syntheses of alkaloids and pharmacophores. The asymmetric unit of (I) contains one 4-(5-bromo-1,3-dioxoisoindolin-2-yl)benzoic acid (BDA) molecule and one dimethylformamide (DMF) solvent molecule (Fig. 1).

The bond lengths and angles in (I) agree with those in the similar compound 4-phthalimidobenzoic acid N,N-dimethylformamide solvate (Liang et al., 2006). The phthalimide group in (I) is essentially planar, with a mean deviation of 0.033 (3) Å. The dihedral angle between the phthalimide group and the C9—C14 benzene ring is 51.4 (2) °. The crystal structure of (I) is stabilized by an O—H···O hydrogen bond which connects the BDA and DMF molecules and by a C—H···O hydrogen bond which links the BDA molecules together (Fig. 2 and Table 1).

Related literature top

For a related structure, see: Liang et al. (2006).

Experimental top

A mixture of 5-bromoisobenzofuran-1,3-dione (0.01 mol) and 4-aminobenzoic acid (0.01 mol) in acetic acid (20 ml) was refluxed for 4 h. After cooling, filtration and drying, the compound 4-(5-bromo-1,3-dioxoisoindolin-2-yl)benzoic acid was obtained. 10 mg of this compound was dissolved in DMF (7 ml), and the solution was then allowed to evaporate at room temperature; colorless single crystals of (I) were formed after 12 d.

Structure description top

For a related structure, see: Liang et al. (2006).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Figures top

	Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. The crystal packing of (I), viewed along the a axis. Hydrogen bonds are indicated by dashed lines.

4-(5-Bromo-1,3-dioxoisoindolin-2-yl)benzoic acid N,N-dimethylformamide solvate top

Crystal data top

C₁₅H₈BrNO₄·C₃H₇NO	Z = 2
M_r = 419.23	F(000) = 424
Triclinic, P1	D_x = 1.583 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9686 (9) Å	Cell parameters from 2063 reflections
b = 8.3214 (12) Å	θ = 2.6–26.1°
c = 19.058 (3) Å	µ = 2.37 mm⁻¹
α = 101.231 (2)°	T = 294 K
β = 93.417 (3)°	Block, colorless
γ = 107.273 (2)°	0.26 × 0.22 × 0.12 mm
V = 879.6 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	3561 independent reflections
Radiation source: fine-focus sealed tube	2643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 26.4°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −7→7
T_min = 0.578, T_max = 0.764	k = −10→10
5114 measured reflections	l = −15→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.061P)² + 0.029P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.002
3561 reflections	Δρ_max = 0.40 e Å⁻³
239 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.062 (4)

Crystal data top

C₁₅H₈BrNO₄·C₃H₇NO	γ = 107.273 (2)°
M_r = 419.23	V = 879.6 (2) Å³
Triclinic, P1	Z = 2
a = 5.9686 (9) Å	Mo Kα radiation
b = 8.3214 (12) Å	µ = 2.37 mm⁻¹
c = 19.058 (3) Å	T = 294 K
α = 101.231 (2)°	0.26 × 0.22 × 0.12 mm
β = 93.417 (3)°

Data collection top

Bruker SMART CCD diffractometer	3561 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2643 reflections with I > 2σ(I)
T_min = 0.578, T_max = 0.764	R_int = 0.022
5114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.13	Δρ_max = 0.40 e Å⁻³
3561 reflections	Δρ_min = −0.42 e Å⁻³
239 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	−0.43214 (7)	0.20856 (4)	0.48540 (2)	0.0632 (2)
O1	−0.1509 (4)	0.8323 (3)	0.37081 (13)	0.0516 (6)
O2	0.3821 (4)	0.5901 (3)	0.26776 (14)	0.0597 (6)
O3	0.7047 (4)	1.3643 (3)	0.17597 (14)	0.0619 (7)
H3	0.7489	1.4260	0.1475	0.093*
O4	0.3495 (4)	1.3123 (3)	0.11588 (13)	0.0604 (6)
N1	0.1307 (4)	0.7455 (3)	0.30854 (14)	0.0405 (6)
C1	−0.0493 (5)	0.7278 (4)	0.35266 (16)	0.0390 (7)
C2	−0.0781 (5)	0.5619 (4)	0.37446 (16)	0.0369 (6)
C3	−0.2363 (5)	0.4823 (4)	0.41681 (17)	0.0415 (7)
H3A	−0.3506	0.5283	0.4351	0.050*
C4	−0.2140 (6)	0.3285 (4)	0.43040 (17)	0.0442 (7)
C5	−0.0431 (6)	0.2596 (4)	0.40437 (17)	0.0469 (8)
H5	−0.0324	0.1581	0.4156	0.056*
C6	0.1121 (6)	0.3415 (4)	0.36169 (17)	0.0443 (7)
H6	0.2279	0.2968	0.3438	0.053*
C7	0.0890 (5)	0.4929 (4)	0.34652 (16)	0.0399 (7)
C8	0.2262 (6)	0.6062 (4)	0.30239 (18)	0.0429 (7)
C9	0.2166 (5)	0.8872 (4)	0.27445 (16)	0.0374 (7)
C10	0.0590 (5)	0.9331 (4)	0.23213 (16)	0.0398 (7)
H10	−0.1025	0.8760	0.2275	0.048*
C11	0.1456 (5)	1.0653 (4)	0.19680 (16)	0.0406 (7)
H11	0.0410	1.0969	0.1684	0.049*
C12	0.3859 (5)	1.1507 (4)	0.20329 (15)	0.0359 (6)
C13	0.5403 (5)	1.1039 (4)	0.24672 (17)	0.0426 (7)
H13	0.7019	1.1609	0.2517	0.051*
C14	0.4556 (5)	0.9732 (4)	0.28260 (17)	0.0425 (7)
H14	0.5595	0.9436	0.3121	0.051*
C15	0.4749 (5)	1.2844 (4)	0.16040 (17)	0.0430 (7)
O5	−0.1165 (4)	0.5819 (3)	0.09856 (14)	0.0597 (6)
N2	0.2246 (4)	0.7231 (4)	0.06190 (15)	0.0479 (7)
C16	0.0984 (6)	0.6147 (4)	0.09704 (18)	0.0497 (8)
H16	0.1766	0.5586	0.1226	0.060*
C17	0.1156 (6)	0.8105 (5)	0.0182 (2)	0.0603 (9)
H17A	−0.0530	0.7689	0.0173	0.090*
H17B	0.1554	0.7881	−0.0300	0.090*
H17C	0.1721	0.9325	0.0384	0.090*
C18	0.4768 (7)	0.7532 (7)	0.0622 (3)	0.0818 (13)
H18A	0.5272	0.6866	0.0920	0.123*
H18B	0.5599	0.8736	0.0808	0.123*
H18C	0.5102	0.7193	0.0138	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0765 (3)	0.0469 (2)	0.0669 (3)	0.00944 (18)	0.01407 (19)	0.02855 (19)
O1	0.0564 (13)	0.0408 (12)	0.0702 (16)	0.0257 (11)	0.0207 (12)	0.0218 (11)
O2	0.0655 (15)	0.0520 (14)	0.0746 (17)	0.0320 (12)	0.0304 (13)	0.0169 (12)
O3	0.0464 (13)	0.0750 (17)	0.0739 (18)	0.0141 (12)	0.0162 (12)	0.0443 (14)
O4	0.0634 (15)	0.0670 (16)	0.0588 (15)	0.0195 (12)	0.0041 (12)	0.0350 (13)
N1	0.0437 (14)	0.0333 (13)	0.0491 (15)	0.0152 (11)	0.0108 (12)	0.0136 (11)
C1	0.0420 (16)	0.0320 (15)	0.0457 (18)	0.0150 (13)	0.0036 (14)	0.0103 (13)
C2	0.0414 (15)	0.0314 (14)	0.0398 (17)	0.0142 (12)	0.0018 (13)	0.0087 (12)
C3	0.0427 (16)	0.0351 (16)	0.0478 (18)	0.0124 (13)	0.0059 (14)	0.0114 (14)
C4	0.0550 (18)	0.0310 (15)	0.0424 (18)	0.0064 (13)	−0.0025 (14)	0.0125 (13)
C5	0.059 (2)	0.0298 (15)	0.052 (2)	0.0165 (14)	−0.0048 (16)	0.0097 (14)
C6	0.0519 (18)	0.0313 (15)	0.0508 (19)	0.0181 (13)	0.0017 (15)	0.0054 (14)
C7	0.0439 (16)	0.0299 (14)	0.0447 (18)	0.0121 (12)	−0.0010 (14)	0.0070 (13)
C8	0.0476 (17)	0.0331 (15)	0.0499 (19)	0.0161 (13)	0.0064 (15)	0.0083 (14)
C9	0.0437 (16)	0.0327 (15)	0.0399 (16)	0.0157 (12)	0.0087 (13)	0.0107 (13)
C10	0.0336 (14)	0.0418 (16)	0.0436 (17)	0.0115 (12)	0.0035 (13)	0.0093 (14)
C11	0.0419 (16)	0.0467 (17)	0.0391 (17)	0.0195 (13)	0.0039 (13)	0.0147 (14)
C12	0.0384 (15)	0.0390 (15)	0.0344 (16)	0.0163 (12)	0.0079 (12)	0.0103 (13)
C13	0.0338 (15)	0.0483 (18)	0.0462 (18)	0.0099 (13)	0.0046 (13)	0.0164 (15)
C14	0.0376 (16)	0.0460 (17)	0.0467 (18)	0.0144 (13)	−0.0010 (13)	0.0168 (15)
C15	0.0487 (18)	0.0422 (17)	0.0429 (18)	0.0165 (14)	0.0146 (14)	0.0144 (14)
O5	0.0533 (14)	0.0570 (15)	0.0764 (18)	0.0148 (11)	0.0215 (12)	0.0325 (13)
N2	0.0406 (14)	0.0561 (17)	0.0522 (17)	0.0185 (12)	0.0119 (12)	0.0176 (14)
C16	0.062 (2)	0.0484 (19)	0.049 (2)	0.0273 (16)	0.0127 (16)	0.0164 (16)
C17	0.060 (2)	0.067 (2)	0.065 (2)	0.0222 (18)	0.0136 (18)	0.034 (2)
C18	0.045 (2)	0.115 (4)	0.090 (3)	0.029 (2)	0.018 (2)	0.024 (3)

Geometric parameters (Å, º) top

Br1—C4	1.895 (3)	C9—C10	1.387 (4)
O1—C1	1.210 (3)	C10—C11	1.387 (4)
O2—C8	1.197 (4)	C10—H10	0.9300
O3—C15	1.321 (4)	C11—C12	1.385 (4)
O3—H3	0.8200	C11—H11	0.9300
O4—C15	1.199 (4)	C12—C13	1.391 (4)
N1—C1	1.395 (4)	C12—C15	1.497 (4)
N1—C8	1.425 (4)	C13—C14	1.382 (4)
N1—C9	1.433 (3)	C13—H13	0.9300
C1—C2	1.484 (4)	C14—H14	0.9300
C2—C7	1.375 (4)	O5—C16	1.233 (4)
C2—C3	1.382 (4)	N2—C16	1.312 (4)
C3—C4	1.396 (4)	N2—C17	1.448 (4)
C3—H3A	0.9300	N2—C18	1.450 (4)
C4—C5	1.383 (5)	C16—H16	0.9300
C5—C6	1.384 (4)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C6—C7	1.389 (4)	C17—H17C	0.9600
C6—H6	0.9300	C18—H18A	0.9600
C7—C8	1.483 (4)	C18—H18B	0.9600
C9—C14	1.377 (4)	C18—H18C	0.9600

C15—O3—H3	109.5	C12—C11—C10	120.8 (3)
C1—N1—C8	111.7 (2)	C12—C11—H11	119.6
C1—N1—C9	125.2 (2)	C10—C11—H11	119.6
C8—N1—C9	123.1 (2)	C11—C12—C13	119.0 (3)
O1—C1—N1	125.7 (3)	C11—C12—C15	119.4 (3)
O1—C1—C2	128.4 (3)	C13—C12—C15	121.5 (3)
N1—C1—C2	105.8 (2)	C14—C13—C12	120.6 (3)
C7—C2—C3	122.2 (3)	C14—C13—H13	119.7
C7—C2—C1	108.7 (3)	C12—C13—H13	119.7
C3—C2—C1	129.1 (3)	C9—C14—C13	119.6 (3)
C2—C3—C4	115.9 (3)	C9—C14—H14	120.2
C2—C3—H3A	122.1	C13—C14—H14	120.2
C4—C3—H3A	122.1	O4—C15—O3	124.2 (3)
C5—C4—C3	122.8 (3)	O4—C15—C12	122.9 (3)
C5—C4—Br1	119.2 (2)	O3—C15—C12	112.8 (3)
C3—C4—Br1	118.1 (3)	C16—N2—C17	121.3 (3)
C4—C5—C6	120.1 (3)	C16—N2—C18	121.3 (3)
C4—C5—H5	119.9	C17—N2—C18	117.3 (3)
C6—C5—H5	119.9	O5—C16—N2	124.7 (3)
C5—C6—C7	117.7 (3)	O5—C16—H16	117.6
C5—C6—H6	121.1	N2—C16—H16	117.6
C7—C6—H6	121.1	N2—C17—H17A	109.5
C2—C7—C6	121.3 (3)	N2—C17—H17B	109.5
C2—C7—C8	109.0 (2)	H17A—C17—H17B	109.5
C6—C7—C8	129.7 (3)	N2—C17—H17C	109.5
O2—C8—N1	125.2 (3)	H17A—C17—H17C	109.5
O2—C8—C7	130.0 (3)	H17B—C17—H17C	109.5
N1—C8—C7	104.8 (3)	N2—C18—H18A	109.5
C14—C9—C10	120.8 (3)	N2—C18—H18B	109.5
C14—C9—N1	119.5 (2)	H18A—C18—H18B	109.5
C10—C9—N1	119.7 (3)	N2—C18—H18C	109.5
C11—C10—C9	119.1 (3)	H18A—C18—H18C	109.5
C11—C10—H10	120.4	H18B—C18—H18C	109.5
C9—C10—H10	120.4

C8—N1—C1—O1	175.1 (3)	C2—C7—C8—O2	−177.9 (3)
C9—N1—C1—O1	−3.3 (5)	C6—C7—C8—O2	3.0 (6)
C8—N1—C1—C2	−2.1 (3)	C2—C7—C8—N1	1.4 (3)
C9—N1—C1—C2	179.4 (2)	C6—C7—C8—N1	−177.6 (3)
O1—C1—C2—C7	−174.2 (3)	C1—N1—C9—C14	128.3 (3)
N1—C1—C2—C7	3.0 (3)	C8—N1—C9—C14	−50.0 (4)
O1—C1—C2—C3	4.4 (5)	C1—N1—C9—C10	−53.4 (4)
N1—C1—C2—C3	−178.5 (3)	C8—N1—C9—C10	128.3 (3)
C7—C2—C3—C4	0.9 (4)	C14—C9—C10—C11	1.2 (4)
C1—C2—C3—C4	−177.4 (3)	N1—C9—C10—C11	−177.1 (3)
C2—C3—C4—C5	0.9 (4)	C9—C10—C11—C12	0.1 (4)
C2—C3—C4—Br1	−177.9 (2)	C10—C11—C12—C13	−0.9 (4)
C3—C4—C5—C6	−1.3 (5)	C10—C11—C12—C15	175.8 (3)
Br1—C4—C5—C6	177.4 (2)	C11—C12—C13—C14	0.4 (5)
C4—C5—C6—C7	0.0 (5)	C15—C12—C13—C14	−176.2 (3)
C3—C2—C7—C6	−2.2 (5)	C10—C9—C14—C13	−1.7 (5)
C1—C2—C7—C6	176.4 (3)	N1—C9—C14—C13	176.6 (3)
C3—C2—C7—C8	178.6 (3)	C12—C13—C14—C9	0.9 (5)
C1—C2—C7—C8	−2.7 (3)	C11—C12—C15—O4	−6.1 (5)
C5—C6—C7—C2	1.7 (4)	C13—C12—C15—O4	170.5 (3)
C5—C6—C7—C8	−179.3 (3)	C11—C12—C15—O3	175.2 (3)
C1—N1—C8—O2	180.0 (3)	C13—C12—C15—O3	−8.2 (4)
C9—N1—C8—O2	−1.5 (5)	C17—N2—C16—O5	−2.6 (5)
C1—N1—C8—C7	0.5 (3)	C18—N2—C16—O5	−179.3 (4)
C9—N1—C8—C7	179.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.82	1.77	2.583 (3)	170
C5—H5···O1ⁱⁱ	0.93	2.54	3.343 (4)	144
C14—H14···O1ⁱⁱⁱ	0.93	2.49	3.413 (4)	170
C16—H16···O4ⁱⁱ	0.93	2.54	3.352 (4)	146
C18—H18A···O5ⁱⁱⁱ	0.96	2.53	3.262 (5)	133

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

Experimental details

Crystal data
Chemical formula	C₁₅H₈BrNO₄·C₃H₇NO
M_r	419.23
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	5.9686 (9), 8.3214 (12), 19.058 (3)
α, β, γ (°)	101.231 (2), 93.417 (3), 107.273 (2)
V (Å³)	879.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.37
Crystal size (mm)	0.26 × 0.22 × 0.12

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.578, 0.764
No. of measured, independent and observed [I > 2σ(I)] reflections	5114, 3561, 2643
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 1.13
No. of reflections	3561
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.42

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.