2-(3,5-Dibromo-2-hydroxy­benzyl­ideneamino)isoindole-1,3-dione

In the title mol­ecule, C₁₅H₈Br₂N₂O₃, the dihedral angle between the benzene ring and the isoindole ring system is 4.9 (1)°. An intra­molecular O—H...N hydrogen bond stabilizes the mol­ecular structure and inter­molecular C—H...O hydrogen bonds link the mol­ecules into a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.059
• wR factor = 0.126
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br2    ..  O2      ..       3.29 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   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
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988),the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I).

In the molecular structure of (I) (Fig. 1), the expected geometric parameters are observed. The benzene ring system (C1—C6) is planar, with an r.m.s. deviation for the fitted atoms of 0.0056 (6) Å, as is the isoindole ring (C8—C15/N1), with an r.m.s. deviation of 0.0063 (5) Å. The dihedral angle between these two planes is 4.9 (1)°. An intramolecular O—H···N hydrogen bond stabilizes the molecular structure, and intermolecular C—H···O hydrogen bond link the molecules into a three-dimensional framework, as illustrated in Fig.2.

Related literature

For related literature, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

S2. Experimental

An anhydrous ethanol solution (50 ml) of 3,5-dibromo-2-hydroxy- benzaldehyde (2.78 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of 2-amino-isoindole-1,3-dione (1.62 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N₂, whereupon a red solution appeared. The solvent was removed and the residue was recrystallized from anhydrous ethanol. The product was isolated and then dried in vacuo to give pure compound (I) in 91% yield. Red single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.

S3. Refinement

The hydroxyl H atom was found in a difference Fourier map and refined freely. C-bound H atoms were included in calculated positions, with C—H = 0.95 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2005); software used to prepare material for publication: CrystalStructure.

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of (I), viewed down the b axis. Hydrogen bonds are indicated by dashed lines.

2-(3,5-Dibromo-2-hydroxybenzylideneamino)isoindole-1,3-dione

Crystal data

C15H8Br2N2O3	F(000) = 1648
Mr = 424.05	Dx = 1.981 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4946 reflections
a = 16.8495 (9) Å	θ = 2.6–25.0°
b = 7.2320 (3) Å	µ = 5.71 mm^−1
c = 23.3405 (11) Å	T = 113 K
V = 2844.2 (2) Å^3	Prism, red
Z = 8	0.20 × 0.08 × 0.06 mm

Data collection

Rigaku Saturn diffractometer	2513 independent reflections
Radiation source: rotating anode	2427 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.067
Detector resolution: 14.63 pixels mm^-1	θmax = 25.0°, θmin = 1.7°
ω scans	h = −20→19
Absorption correction: multi-scan (Jacobson, 1998)	k = −8→8
Tmin = 0.395, Tmax = 0.726	l = −27→26
20003 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0257P)^2 + 33.0268P] where P = (Fo^2 + 2Fc^2)/3
2513 reflections	(Δ/σ)max = 0.001
203 parameters	Δρmax = 1.08 e Å^−3
1 restraint	Δρmin = −1.36 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
Br2	0.51772 (4)	0.89425 (9)	0.62815 (3)	0.0188 (2)
Br1	0.28824 (5)	0.65005 (13)	0.46789 (3)	0.0352 (3)
O1	0.4297 (3)	0.6161 (7)	0.39257 (19)	0.0189 (10)
H1	0.468 (3)	0.585 (11)	0.374 (3)	0.028*
N2	0.5809 (3)	0.6040 (8)	0.3697 (2)	0.0176 (12)
O2	0.5523 (3)	0.4722 (7)	0.26039 (19)	0.0202 (11)
C11	0.7913 (4)	0.3648 (9)	0.1776 (3)	0.0163 (14)
H11	0.8038	0.3194	0.1405	0.020*
C10	0.7122 (4)	0.3830 (9)	0.1933 (3)	0.0171 (14)
H10	0.6704	0.3505	0.1678	0.021*
C6	0.5326 (4)	0.7088 (9)	0.4591 (3)	0.0157 (14)
C5	0.5513 (4)	0.7713 (9)	0.5143 (3)	0.0165 (14)
H5	0.6052	0.7896	0.5249	0.020*
N1	0.6408 (3)	0.5580 (7)	0.3326 (2)	0.0119 (11)
O3	0.7580 (3)	0.6294 (7)	0.38100 (19)	0.0251 (12)
C9	0.6966 (4)	0.4512 (8)	0.2483 (3)	0.0128 (13)
C1	0.4524 (4)	0.6784 (9)	0.4442 (3)	0.0161 (14)
C7	0.5968 (4)	0.6680 (9)	0.4197 (3)	0.0172 (14)
H7	0.6504	0.6884	0.4309	0.021*
C14	0.7583 (4)	0.4983 (9)	0.2851 (3)	0.0138 (13)
C4	0.4917 (4)	0.8061 (9)	0.5535 (3)	0.0163 (14)
C3	0.4128 (4)	0.7761 (9)	0.5402 (3)	0.0159 (14)
H3	0.3723	0.7989	0.5676	0.019*
C2	0.3943 (4)	0.7120 (10)	0.4860 (3)	0.0175 (14)
C8	0.6195 (4)	0.4884 (9)	0.2770 (3)	0.0152 (14)
C12	0.8533 (4)	0.4117 (9)	0.2151 (3)	0.0183 (14)
H12	0.9068	0.3980	0.2030	0.022*
C15	0.7245 (4)	0.5694 (9)	0.3394 (3)	0.0155 (14)
C13	0.8370 (4)	0.4780 (9)	0.2699 (3)	0.0171 (14)
H13	0.8785	0.5083	0.2958	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br2	0.0230 (4)	0.0225 (4)	0.0107 (3)	0.0054 (3)	−0.0009 (3)	−0.0016 (3)
Br1	0.0221 (4)	0.0516 (5)	0.0319 (5)	−0.0006 (4)	−0.0008 (3)	−0.0080 (4)
O1	0.020 (3)	0.024 (3)	0.012 (2)	0.001 (2)	−0.0026 (19)	−0.005 (2)
N2	0.023 (3)	0.018 (3)	0.012 (3)	0.005 (3)	0.001 (2)	−0.003 (2)
O2	0.014 (3)	0.031 (3)	0.015 (2)	−0.003 (2)	0.000 (2)	−0.002 (2)
C11	0.018 (3)	0.018 (3)	0.013 (3)	0.001 (3)	0.004 (3)	−0.002 (3)
C10	0.026 (4)	0.015 (3)	0.010 (3)	0.000 (3)	−0.001 (3)	0.004 (3)
C6	0.013 (3)	0.018 (3)	0.016 (3)	0.000 (3)	0.001 (3)	0.002 (3)
C5	0.015 (3)	0.017 (3)	0.018 (3)	0.002 (3)	0.000 (3)	0.002 (3)
N1	0.011 (3)	0.014 (3)	0.010 (3)	0.001 (2)	0.000 (2)	−0.002 (2)
O3	0.016 (2)	0.042 (3)	0.017 (2)	0.001 (2)	−0.003 (2)	−0.013 (2)
C9	0.010 (3)	0.012 (3)	0.016 (3)	0.000 (3)	0.001 (3)	0.000 (3)
C1	0.022 (4)	0.017 (3)	0.009 (3)	−0.001 (3)	−0.002 (3)	0.000 (3)
C7	0.021 (4)	0.014 (3)	0.017 (3)	0.002 (3)	0.000 (3)	0.000 (3)
C14	0.014 (3)	0.017 (3)	0.010 (3)	0.000 (3)	0.000 (3)	0.004 (3)
C4	0.019 (4)	0.015 (3)	0.015 (3)	0.003 (3)	−0.003 (3)	0.004 (3)
C3	0.017 (3)	0.016 (3)	0.015 (3)	0.003 (3)	0.008 (3)	0.000 (3)
C2	0.011 (3)	0.024 (4)	0.018 (3)	0.000 (3)	−0.002 (3)	0.000 (3)
C8	0.019 (4)	0.012 (3)	0.014 (3)	0.002 (3)	−0.001 (3)	0.003 (3)
C12	0.019 (4)	0.016 (3)	0.020 (3)	0.001 (3)	0.004 (3)	0.002 (3)
C15	0.016 (3)	0.014 (3)	0.017 (3)	−0.003 (3)	0.000 (3)	0.000 (3)
C13	0.016 (3)	0.019 (3)	0.016 (3)	−0.001 (3)	−0.002 (3)	−0.003 (3)

Geometric parameters (Å, º)

Br2—C4	1.906 (7)	C5—H5	0.9500
Br1—C2	1.891 (6)	N1—C15	1.423 (8)
O1—C1	1.343 (8)	N1—C8	1.438 (8)
O1—H1	0.81 (3)	O3—C15	1.202 (8)
N2—C7	1.284 (8)	C9—C14	1.391 (9)
N2—N1	1.370 (7)	C9—C8	1.487 (9)
O2—C8	1.203 (8)	C1—C2	1.402 (9)
C11—C10	1.389 (9)	C7—H7	0.9500
C11—C12	1.404 (9)	C14—C13	1.381 (9)
C11—H11	0.9500	C14—C15	1.482 (9)
C10—C9	1.400 (9)	C4—C3	1.383 (9)
C10—H10	0.9500	C3—C2	1.382 (9)
C6—C5	1.402 (9)	C3—H3	0.9500
C6—C1	1.412 (9)	C12—C13	1.392 (9)
C6—C7	1.451 (9)	C12—H12	0.9500
C5—C4	1.382 (9)	C13—H13	0.9500
C1—O1—H1	111 (6)	C6—C7—H7	120.2
C7—N2—N1	120.5 (6)	C13—C14—C9	122.1 (6)
C10—C11—C12	121.8 (6)	C13—C14—C15	128.8 (6)
C10—C11—H11	119.1	C9—C14—C15	109.1 (6)
C12—C11—H11	119.1	C5—C4—C3	121.4 (6)
C11—C10—C9	117.0 (6)	C5—C4—Br2	119.9 (5)
C11—C10—H10	121.5	C3—C4—Br2	118.7 (5)
C9—C10—H10	121.5	C2—C3—C4	118.4 (6)
C5—C6—C1	119.5 (6)	C2—C3—H3	120.8
C5—C6—C7	118.6 (6)	C4—C3—H3	120.8
C1—C6—C7	121.8 (6)	C3—C2—C1	122.5 (6)
C4—C5—C6	120.2 (6)	C3—C2—Br1	119.8 (5)
C4—C5—H5	119.9	C1—C2—Br1	117.6 (5)
C6—C5—H5	119.9	O2—C8—N1	124.1 (6)
N2—N1—C15	130.3 (5)	O2—C8—C9	131.3 (6)
N2—N1—C8	118.1 (5)	N1—C8—C9	104.6 (5)
C15—N1—C8	111.6 (5)	C13—C12—C11	120.6 (6)
C14—C9—C10	120.9 (6)	C13—C12—H12	119.7
C14—C9—C8	109.2 (6)	C11—C12—H12	119.7
C10—C9—C8	129.9 (6)	O3—C15—N1	125.1 (6)
O1—C1—C2	118.9 (6)	O3—C15—C14	129.5 (6)
O1—C1—C6	123.0 (6)	N1—C15—C14	105.4 (5)
C2—C1—C6	118.0 (6)	C14—C13—C12	117.6 (6)
N2—C7—C6	119.5 (6)	C14—C13—H13	121.2
N2—C7—H7	120.2	C12—C13—H13	121.2
C12—C11—C10—C9	0.3 (10)	O1—C1—C2—C3	−180.0 (6)
C1—C6—C5—C4	−1.3 (10)	C6—C1—C2—C3	1.1 (10)
C7—C6—C5—C4	−178.0 (6)	O1—C1—C2—Br1	4.3 (9)
C7—N2—N1—C15	−0.4 (10)	C6—C1—C2—Br1	−174.6 (5)
C7—N2—N1—C8	−179.5 (6)	N2—N1—C8—O2	1.9 (9)
C11—C10—C9—C14	0.0 (9)	C15—N1—C8—O2	−177.4 (6)
C11—C10—C9—C8	179.1 (6)	N2—N1—C8—C9	−179.6 (5)
C5—C6—C1—O1	−179.0 (6)	C15—N1—C8—C9	1.1 (7)
C7—C6—C1—O1	−2.3 (10)	C14—C9—C8—O2	177.9 (7)
C5—C6—C1—C2	−0.1 (10)	C10—C9—C8—O2	−1.3 (12)
C7—C6—C1—C2	176.5 (6)	C14—C9—C8—N1	−0.4 (7)
N1—N2—C7—C6	−177.6 (6)	C10—C9—C8—N1	−179.6 (6)
C5—C6—C7—N2	177.4 (6)	C10—C11—C12—C13	0.2 (10)
C1—C6—C7—N2	0.7 (10)	N2—N1—C15—O3	−2.1 (11)
C10—C9—C14—C13	−0.8 (10)	C8—N1—C15—O3	177.1 (6)
C8—C9—C14—C13	179.9 (6)	N2—N1—C15—C14	179.4 (6)
C10—C9—C14—C15	178.9 (6)	C8—N1—C15—C14	−1.4 (7)
C8—C9—C14—C15	−0.4 (7)	C13—C14—C15—O3	2.4 (12)
C6—C5—C4—C3	1.8 (10)	C9—C14—C15—O3	−177.3 (7)
C6—C5—C4—Br2	−179.1 (5)	C13—C14—C15—N1	−179.2 (7)
C5—C4—C3—C2	−0.8 (10)	C9—C14—C15—N1	1.1 (7)
Br2—C4—C3—C2	−179.9 (5)	C9—C14—C13—C12	1.3 (10)
C4—C3—C2—C1	−0.6 (10)	C15—C14—C13—C12	−178.3 (6)
C4—C3—C2—Br1	174.9 (5)	C11—C12—C13—C14	−1.0 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.81 (3)	1.92 (6)	2.605 (7)	143 (8)
C3—H3···O3^i	0.95	2.33	3.264 (8)	169

Symmetry code: (i) x−1/2, −y+3/2, −z+1.