4-Bromo­anilinium hydrogen phthalate

Liang, Z.P.

doi:10.1107/S1600536811017727

organic compounds

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Volume 67| Part 6| June 2011| Page o1430

doi:10.1107/S1600536811017727

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4-Bromoanilinium hydrogen phthalate

Zu Pei Liang ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: lzpwfu@163.com

(Received 29 April 2011; accepted 11 May 2011; online 14 May 2011)

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, C 2
a = 13.0890 (14) Å
b = 7.6670 (7) Å
c = 14.6900 (14) Å
β = 106.671 (1)°
V = 1412.2 (2) Å³
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[F² > 2σ(F²)] = 0.054
wR(F²) = 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)

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⋯O3^iv	0.89	1.96	2.828 (6)	164
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y-1, z; (iii) -x+1, y, -z+1; (iv) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017727/lh5245sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017727/lh5245Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811017727/lh5245Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

	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.

4-Bromoanilinium 2-carboxybenzoate top

Crystal data top

C₆H₇BrN⁺·C₈H₅O₄⁻	F(000) = 680
M_r = 338.16	D_x = 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 top

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

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)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0642P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max < 0.001
2364 reflections	Δρ_max = 0.82 e Å⁻³
186 parameters	Δρ_min = −0.51 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1027 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.012 (16)

Crystal data top

C₆H₇BrN⁺·C₈H₅O₄⁻	V = 1412.2 (2) Å³
M_r = 338.16	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 13.0890 (14) Å	µ = 2.92 mm⁻¹
b = 7.6670 (7) Å	T = 298 K
c = 14.6900 (14) Å	0.41 × 0.37 × 0.18 mm
β = 106.671 (1)°

Data collection top

Bruker SMART CCD diffractometer	2364 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1659 reflections with I > 2σ(I)
T_min = 0.380, T_max = 0.621	R_int = 0.045
3555 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.127	Δρ_max = 0.82 e Å⁻³
S = 0.94	Δρ_min = −0.51 e Å⁻³
2364 reflections	Absolute structure: Flack (1983), 1027 Friedel pairs
186 parameters	Absolute structure parameter: 0.012 (16)
1 restraint

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	0.16160 (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 (Å²) top

	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, º) top

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, º) top

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···O3^iv	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.

Experimental details

Crystal data
Chemical formula	C₆H₇BrN⁺·C₈H₅O₄⁻
M_r	338.16
Crystal system, space group	Monoclinic, C2
Temperature (K)	298
a, b, c (Å)	13.0890 (14), 7.6670 (7), 14.6900 (14)
β (°)	106.671 (1)
V (Å³)	1412.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.92
Crystal size (mm)	0.41 × 0.37 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.380, 0.621
No. of measured, independent and observed [I > 2σ(I)] reflections	3555, 2364, 1659
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.127, 0.94
No. of reflections	2364
No. of parameters	186
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.51
Absolute structure	Flack (1983), 1027 Friedel pairs
Absolute structure parameter	0.012 (16)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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···O3^iv	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.

Acknowledgements

The author thanks Shandong Provincial Natural Science Foundation, China (ZR2010BM033) for support.

References

Bruker (1997). SADABS, SMART and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jagan, R. & Sivakumar, K. (2009). Acta Cryst. C65, o414–o418. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lima, L. M., Castro, P., Machado, A. L., Frage, C. A. M., Lugniur, C., Moraes, V. L. G. & Barreiro, E. (2002). J. Biol. Org. Med. Chem. 10, 3067–3073. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar