4-Bromo­anilinium hydrogen phthalate

Abstract

In the anion of the title compound, C₆H₇BrN⁺·C₈H₅O₄ ⁻, the dihedral angles formed by the benzene ring and the mean planes of the –COOH and –COO⁻ groups are 20.6 (3) and 83.2 (3)°, respectively. In the crystal, inter­molecular N—H⋯O and O—H⋯O hydrogen bonds connect the cations and anions, forming a two-dimensional network parallel to (001).

Related literature

For applications of phthalimides and N-substituted phthalimides, see: Lima et al. (2002 ▶). For the crystal structures of 4-chloro­anilinium, 2-hy­droxy­anilinium and 3-hy­droxy­anilinium hydrogen phthalates, see: Jagan & Sivakumar (2009 ▶).

Experimental

Crystal data

• C₆H₇BrN⁺·C₈H₅O₄ ⁻

• M _r = 338.16

• Monoclinic,

• a = 13.0890 (14) Å

• b = 7.6670 (7) Å

• c = 14.6900 (14) Å

• β = 106.671 (1)°

• V = 1412.2 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 2.92 mm⁻¹

• T = 298 K

• 0.41 × 0.37 × 0.18 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.380, T _max = 0.621

• 3555 measured reflections

• 2364 independent reflections

• 1659 reflections with I > 2σ(I)

• R _int = 0.045

Refinement

• R[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 0.127

• S = 0.94

• 2364 reflections

• 186 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.82 e Å⁻³

• Δρ_min = −0.51 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1027 Friedel pairs

• Flack parameter: 0.012 (16)

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811017727/lh5245Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3i	0.80 (6)	1.76 (6)	2.518 (6)	158 (7)
N1—H1C⋯O4	0.89	2.37	2.962 (7)	125
N1—H1C⋯O1ii	0.89	2.13	2.916 (7)	147
N1—H1B⋯O4iii	0.89	1.96	2.804 (7)	159
N1—H1A⋯O3iv	0.89	1.96	2.828 (6)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

Phthalimides and N-substituted phthalimides are animportant class of compounds because of their interesting biological activities (Lima et al., 2002). 4-Bromoanilinium hydrogen phthalate is an intermediate in the preparation of N-substituted phthalimides. The crystal structures of 4-chloroanilinium, 2-hydroxyanilinium and 3-hydroxyanilinium hydrogen phthalates have already been reported (Jagan & Sivakumar, 2009). In this paper, the structure of the title compound is reported. The asymmetric unit of the title compound (I) contains one 4-bromoanilinium cation and one hydrogen phthalate anion (Fig. 1). The dihedral angles formed by the benzene ring and the mean planes of the —COOH and —COO^- groups are 20.6 (3) and 83.2 (3) °, respectively. In the crystal, intermolecular N—H···O and O—H···O hydrogen bonds connect cations and anions to form a two-dimensional network parallel to (001) (Fig. 2).

Experimental

A mixture of phthalic anhydride (1.52 g, 0.01 mol) and 4-bromoaniline (1.72 g, 0.01 mol) in 20 ml ethanol(95%) solution was refluxed for 0.5 h. The solution was kept at room temperature for 7 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.

Refinement

H atoms bonded to C and N were initially located in difference maps and then refined in a riding-model approximation with C—H = 0.93 Å and N—H = 0.89 Å and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(N). The H atom bonded to O was refined independently with an isotropic displacment parameter.

Figures

Fig. 1.

The asymmetric unit of (I), drawn with 30% probability ellipsoids.

Fig. 2.

Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines.

Crystal data

C6H7BrN+·C8H5O4−	F(000) = 680
Mr = 338.16	Dx = 1.590 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 1173 reflections
a = 13.0890 (14) Å	θ = 2.9–20.8°
b = 7.6670 (7) Å	µ = 2.92 mm−1
c = 14.6900 (14) Å	T = 298 K
β = 106.671 (1)°	Block, colorless
V = 1412.2 (2) Å3	0.41 × 0.37 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2364 independent reflections
Radiation source: fine-focus sealed tube	1659 reflections with I > 2σ(I)
graphite	Rint = 0.045
φ and ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −13→15
Tmin = 0.380, Tmax = 0.621	k = −8→9
3555 measured reflections	l = −17→13

Refinement

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)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0642P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94	(Δ/σ)max < 0.001
2364 reflections	Δρmax = 0.82 e Å−3
186 parameters	Δρmin = −0.51 e Å−3
1 restraint	Absolute structure: Flack (1983), 1027 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.012 (16)

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
Br1	0.16160 (6)	0.43398 (15)	0.05674 (5)	0.0677 (3)
N1	0.3761 (4)	−0.0249 (6)	0.4004 (3)	0.0329 (13)
H1A	0.3407	−0.1253	0.3952	0.049*
H1B	0.3731	0.0303	0.4528	0.049*
H1C	0.4438	−0.0462	0.4035	0.049*
O1	0.5651 (4)	0.7623 (6)	0.4163 (4)	0.0553 (16)
O2	0.6767 (3)	0.5378 (6)	0.4617 (4)	0.0377 (12)
H2	0.699 (4)	0.569 (9)	0.516 (4)	0.03 (2)*
O3	0.7303 (3)	0.1975 (5)	0.3875 (3)	0.0324 (10)
O4	0.5788 (4)	0.1691 (7)	0.4309 (4)	0.0385 (12)
C1	0.5990 (5)	0.6178 (9)	0.4009 (6)	0.0345 (18)
C2	0.6314 (5)	0.2287 (7)	0.3804 (5)	0.0255 (15)
C3	0.5581 (5)	0.5282 (9)	0.3075 (6)	0.0307 (17)
C4	0.5732 (5)	0.3475 (9)	0.2962 (5)	0.0297 (17)
C5	0.5343 (5)	0.2691 (11)	0.2082 (5)	0.044 (2)
H5	0.5446	0.1504	0.2013	0.053*
C6	0.4791 (6)	0.3685 (13)	0.1293 (6)	0.056 (3)
H6	0.4520	0.3151	0.0704	0.067*
C7	0.4648 (6)	0.5461 (13)	0.1385 (7)	0.056 (2)
H7	0.4297	0.6127	0.0859	0.067*
C8	0.5031 (5)	0.6231 (10)	0.2269 (6)	0.043 (2)
H8	0.4920	0.7418	0.2329	0.052*
C9	0.3276 (4)	0.0844 (8)	0.3171 (4)	0.0305 (15)
C10	0.3175 (5)	0.2651 (8)	0.3301 (5)	0.0342 (16)
H10	0.3433	0.3149	0.3901	0.041*
C11	0.2688 (4)	0.3668 (9)	0.2525 (5)	0.0403 (17)
H11	0.2614	0.4862	0.2598	0.048*
C12	0.2314 (5)	0.2920 (9)	0.1649 (5)	0.0378 (17)
C13	0.2417 (5)	0.1129 (9)	0.1509 (5)	0.0425 (17)
H13	0.2166	0.0638	0.0908	0.051*
C14	0.2908 (4)	0.0107 (8)	0.2296 (5)	0.0356 (16)
H14	0.2983	−0.1086	0.2223	0.043*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0717 (5)	0.0667 (6)	0.0567 (5)	0.0124 (6)	0.0056 (3)	0.0159 (6)
N1	0.033 (2)	0.020 (3)	0.047 (3)	−0.002 (2)	0.013 (2)	−0.003 (2)
O1	0.052 (3)	0.027 (3)	0.082 (4)	0.015 (2)	0.011 (3)	−0.012 (3)
O2	0.035 (2)	0.024 (2)	0.045 (3)	0.0035 (19)	−0.002 (2)	−0.009 (2)
O3	0.025 (2)	0.021 (2)	0.050 (3)	0.0016 (17)	0.0098 (19)	0.001 (2)
O4	0.033 (2)	0.040 (3)	0.043 (3)	−0.007 (2)	0.013 (2)	0.004 (2)
C1	0.019 (3)	0.030 (4)	0.055 (5)	0.002 (3)	0.011 (3)	0.005 (3)
C2	0.029 (4)	0.011 (3)	0.036 (4)	−0.002 (2)	0.008 (3)	−0.007 (2)
C3	0.016 (3)	0.036 (4)	0.040 (4)	0.004 (3)	0.007 (3)	0.007 (3)
C4	0.032 (4)	0.022 (4)	0.034 (5)	−0.004 (3)	0.006 (3)	0.007 (3)
C5	0.043 (4)	0.043 (5)	0.044 (5)	−0.007 (3)	0.009 (4)	−0.004 (4)
C6	0.043 (4)	0.074 (7)	0.044 (5)	−0.013 (4)	0.001 (4)	−0.002 (4)
C7	0.039 (4)	0.066 (7)	0.054 (6)	−0.008 (4)	−0.001 (4)	0.017 (5)
C8	0.033 (4)	0.027 (4)	0.063 (6)	0.003 (3)	0.003 (4)	0.014 (4)
C9	0.021 (3)	0.035 (4)	0.037 (4)	−0.003 (3)	0.010 (3)	0.008 (3)
C10	0.032 (3)	0.030 (4)	0.038 (4)	−0.002 (3)	0.005 (3)	−0.004 (3)
C11	0.036 (3)	0.034 (4)	0.050 (5)	0.005 (3)	0.012 (3)	0.005 (3)
C12	0.033 (3)	0.041 (5)	0.038 (4)	0.003 (3)	0.007 (3)	0.008 (3)
C13	0.036 (4)	0.052 (5)	0.038 (4)	−0.004 (3)	0.008 (3)	−0.007 (3)
C14	0.037 (3)	0.024 (4)	0.045 (4)	0.000 (3)	0.012 (3)	−0.006 (3)

Geometric parameters (Å, °)

Br1—C12	1.927 (6)	C5—H5	0.9300
N1—C9	1.468 (8)	C6—C7	1.386 (12)
N1—H1A	0.8900	C6—H6	0.9300
N1—H1B	0.8900	C7—C8	1.382 (11)
N1—H1C	0.8900	C7—H7	0.9300
O1—C1	1.238 (8)	C8—H8	0.9300
O2—C1	1.299 (8)	C9—C14	1.359 (8)
O2—H2	0.80 (6)	C9—C10	1.410 (9)
O3—C2	1.292 (7)	C10—C11	1.377 (9)
O4—C2	1.236 (8)	C10—H10	0.9300
C1—C3	1.490 (11)	C11—C12	1.365 (9)
C2—C4	1.548 (9)	C11—H11	0.9300
C3—C8	1.400 (10)	C12—C13	1.400 (10)
C3—C4	1.415 (8)	C13—C14	1.392 (9)
C4—C5	1.385 (11)	C13—H13	0.9300
C5—C6	1.402 (12)	C14—H14	0.9300
C9—N1—H1A	109.5	C8—C7—C6	119.2 (9)
C9—N1—H1B	109.5	C8—C7—H7	120.4
H1A—N1—H1B	109.5	C6—C7—H7	120.4
C9—N1—H1C	109.5	C7—C8—C3	122.2 (8)
H1A—N1—H1C	109.5	C7—C8—H8	118.9
H1B—N1—H1C	109.5	C3—C8—H8	118.9
C1—O2—H2	122 (5)	C14—C9—C10	121.0 (6)
O1—C1—O2	123.2 (7)	C14—C9—N1	120.1 (6)
O1—C1—C3	121.9 (7)	C10—C9—N1	118.9 (6)
O2—C1—C3	114.8 (6)	C11—C10—C9	118.9 (6)
O4—C2—O3	127.0 (6)	C11—C10—H10	120.5
O4—C2—C4	117.8 (6)	C9—C10—H10	120.5
O3—C2—C4	115.2 (5)	C12—C11—C10	119.9 (6)
C8—C3—C4	117.7 (8)	C12—C11—H11	120.1
C8—C3—C1	120.1 (7)	C10—C11—H11	120.1
C4—C3—C1	122.2 (7)	C11—C12—C13	121.8 (6)
C5—C4—C3	120.5 (8)	C11—C12—Br1	119.8 (5)
C5—C4—C2	117.1 (6)	C13—C12—Br1	118.4 (5)
C3—C4—C2	122.4 (7)	C14—C13—C12	118.1 (6)
C4—C5—C6	120.0 (8)	C14—C13—H13	121.0
C4—C5—H5	120.0	C12—C13—H13	121.0
C6—C5—H5	120.0	C9—C14—C13	120.4 (6)
C7—C6—C5	120.3 (9)	C9—C14—H14	119.8
C7—C6—H6	119.8	C13—C14—H14	119.8
C5—C6—H6	119.8
O1—C1—C3—C8	18.0 (10)	C5—C6—C7—C8	−1.6 (13)
O2—C1—C3—C8	−157.9 (6)	C6—C7—C8—C3	1.3 (12)
O1—C1—C3—C4	−162.5 (7)	C4—C3—C8—C7	−0.3 (10)
O2—C1—C3—C4	21.7 (9)	C1—C3—C8—C7	179.3 (7)
C8—C3—C4—C5	−0.2 (10)	C14—C9—C10—C11	0.4 (9)
C1—C3—C4—C5	−179.8 (6)	N1—C9—C10—C11	−177.8 (5)
C8—C3—C4—C2	−179.1 (5)	C9—C10—C11—C12	0.0 (9)
C1—C3—C4—C2	1.3 (10)	C10—C11—C12—C13	−0.5 (10)
O4—C2—C4—C5	−95.0 (7)	C10—C11—C12—Br1	179.2 (4)
O3—C2—C4—C5	82.4 (7)	C11—C12—C13—C14	0.7 (9)
O4—C2—C4—C3	83.9 (8)	Br1—C12—C13—C14	−179.0 (4)
O3—C2—C4—C3	−98.7 (7)	C10—C9—C14—C13	−0.2 (8)
C3—C4—C5—C6	−0.1 (11)	N1—C9—C14—C13	178.0 (5)
C2—C4—C5—C6	178.9 (6)	C12—C13—C14—C9	−0.3 (9)
C4—C5—C6—C7	1.0 (12)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3i	0.80 (6)	1.76 (6)	2.518 (6)	158 (7)
N1—H1C···O4	0.89	2.37	2.962 (7)	125
N1—H1C···O1ii	0.89	2.13	2.916 (7)	147
N1—H1B···O4iii	0.89	1.96	2.804 (7)	159
N1—H1A···O3iv	0.89	1.96	2.828 (6)	164

Symmetry codes: (i) −x+3/2, y+1/2, −z+1; (ii) x, y−1, z; (iii) −x+1, y, −z+1; (iv) x−1/2, y−1/2, z.