organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

2-Amino-5-bromo­pyridinium 2-carb­­oxy­benzoate

aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: hkfun@usm.my

(Received 26 July 2010; accepted 3 August 2010; online 11 August 2010)

The asymmetric unit of the title compound, C5H6BrN2+·C8H5O4, consists of two crystallographically independent 2-amino-5-bromo­pyridinium cations (A and B) and two 2-carb­oxy­benzoate anions (A and B). Each 2-amino-5-bromo­pyridinium cation is approximately planar, with a maximum deviation of 0.047 (1) Å in cation A and 0.027 (1) Å in cation B. The 2-amino-5-bromo­pyridinium unit in cation A is inclined at dihedral angles of 4.9 (3) and 2.2 (3)° with the phenyl rings of the A and B 2-carb­oxy­benzoate anions, respectively. The corresponding angles for cation B are 3.0 (3) and 5.6 (3)°. The mol­ecular structure is stabilized by an intra­molecular O—H⋯O hydrogen bond,which generates an S(7) ring motif. The cations and anions are linked via inter­molecular N—H⋯O and C—H⋯O hydrogen bonds, generating R22(8) ring motifs. In the crystal packing, mol­ecules are linked into wave-like chains along [001] via adjacent ring motifs. Short inter­molecular distances between the phenyl and pyridine rings [3.613 (4) and 3.641 (4) Å] indicate the existence of ππ inter­actions. The crystal structure is a non-merohedral twin with a contribution of 0.271 (3) of the minor component.

Related literature

For applications of phthalic acid, see: Dale et al. (2004[Dale, S. H., Elsegood, M. R. J., Hemmings, M. & Wilkinson, A. L. (2004). CrystEngComm, 6, 207-214.]); Ballabh et al. (2005[Ballabh, A., Trivedi, D. R. & Dastidar, P. (2005). Cryst. Growth Des. 5, 1548-1553.]). For related structures, see: Schuckmann et al. (1978[Schuckmann, W., Fuess, H. & Bats, J. W. (1978). Acta Cryst. B34, 3754-3756.]); Küppers (1978[Küppers, H. (1978). Acta Cryst. B34, 3763-3765.]); Jessen & Küppers (1991[Jessen, S. M. & Küppers, H. (1991). J. Mol. Struct. 263, 247-265.]); Quah et al. (2008[Quah, C. K., Jebas, S. R. & Fun, H.-K. (2008). Acta Cryst. E64, o1878-o1879.], 2010a[Quah, C. K., Hemamalini, M. & Fun, H.-K. (2010a). Acta Cryst. E66, o1932.],b[Quah, C. K., Hemamalini, M. & Fun, H.-K. (2010b). Acta Cryst. E66, o1935-o1936.]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C5H6BrN2+·C8H5O4

  • Mr = 339.15

  • Triclinic, [P \overline 1]

  • a = 9.0192 (4) Å

  • b = 10.2689 (5) Å

  • c = 14.4092 (6) Å

  • α = 82.269 (2)°

  • β = 83.969 (2)°

  • γ = 87.845 (2)°

  • V = 1314.72 (10) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.14 mm−1

  • T = 100 K

  • 0.24 × 0.20 × 0.10 mm

Data collection
  • Bruker SMART APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.526, Tmax = 0.740

  • 7631 measured reflections

  • 7631 independent reflections

  • 5583 reflections with I > 2σ(I)

Refinement
  • R[F2 > 2σ(F2)] = 0.067

  • wR(F2) = 0.194

  • S = 1.09

  • 7631 reflections

  • 364 parameters

  • H-atom parameters constrained

  • Δρmax = 1.14 e Å−3

  • Δρmin = −1.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1A—H1N1⋯O4A 0.86 1.80 2.664 (7) 176
N2A—H2NA⋯O4Bi 0.94 1.97 2.910 (8) 175
N2A—H3NA⋯O3A 0.98 1.97 2.930 (7) 167
O3B—H2O3⋯O2B 0.75 1.68 2.391 (6) 159
N1B—H2N1⋯O1B 0.92 1.82 2.647 (7) 147
N2B—H3N2⋯O1Aii 1.00 1.91 2.903 (8) 176
N2B—H4N2⋯O2B 0.81 2.20 2.971 (7) 160
C4A—H4AA⋯O3Bi 0.93 2.44 3.219 (9) 141
C4B—H4BA⋯O2Aii 0.93 2.42 3.175 (9) 139
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z-1.

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Phthalic acid forms hydrogen phthalate salts with various organic and other compounds. The crystal structures of hydrogen phthalates include calcium phthalate monohydrate (Schuckmann et al., 1978), lithium hydrogen phthalate monohydrate (Küppers, 1978) and tetramethylammonium hydrogen phthalate (Jessen & Küppers, 1991) have been reported in the literature. Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In this paper, the hydrogen-bonding patterns of 2-amino-5-bromopyridinium hydrogenphthalate, (I), are discussed.

The asymmetric unit of the title compound consists of two crystallographically independent 2-amino-5-bromopyridinium cations (A and B) and two 2-carboxybenzoate anions (A and B). The bond lengths (Allen et al., 1987) and angles in the title compound (Fig. 1) are within normal ranges and comparable with the related structures (Quah et al., 2008, 2010a, b). Each 2-amino-5-bromopyridinium cation is approximately planar, with a maximum deviation of 0.047 (1) Å for atom Br1A in cation A and 0.027 (1) Å for atom Br1B in cation B. The 2-amino-5-bromopyridinium in cation A is inclined at dihedral angles of 4.9 (3) and 2.2 (3)° with the C6A—C11A and C6B—C11B phenyl rings, respectively. The correspondence angles for cation B are 3.0 (3) and 5.6 (3)°. The molecular structure is stabilized by an intramolecular O3B—H2O3···O2B hydrogen bond which generates an S(7) ring motif (Bernstein et al., 1995).

The cations and anions are linked via intermolecular N–H···O and C–H···O hydrogen bonds (Table 1), generating R22(8) ring motifs. In the crystal packing (Fig. 2), the molecules are linked into one-dimensional wave-like chains along [001] via adjacent ring motifs. The crystal packing is further consolidated by π-π stacking interactions between the centroids of C6A—C11A (Cg1), N1B/C1B—C5B (Cg2) rings and C6B—C11B (Cg3), N1A/C1A—C5A (Cg4) rings, with Cg1···Cg2iii and Cg3···Cg4 distances of 3.613 (4) and 3.641 (4) Å, respectively [symmetry code: (iii) x, y, 1 + z]

Related literature top

For applications of phthalic acid, see: Dale et al. (2004); Ballabh et al. (2005). For related structures, see: Schuckmann et al. (1978); Küppers (1978); Jessen & Küppers (1991); Quah et al. (2008, 2010a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A hot methanol solution (20 ml) of 2-amino-5-bromopyridine (86 mg, Aldrich) and phthalic acid (83 mg, Merck) was mixed and warmed over a magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared after a few days.

Refinement top

O– and N– bound H atoms were located in a difference Fourier map and refined using a riding model with O–H = 0.7471–0.8532 Å and N–H = 0.8108–0.9952 Å]. The rest of the hydrogen atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C). The crystal structure is a non-merohedral twin, a contribution of 0.271 (3) of the minor component. The twin law is (-1 0 0 / 0 -1 0 /-0.320 -0.367 1).

Structure description top

Phthalic acid forms hydrogen phthalate salts with various organic and other compounds. The crystal structures of hydrogen phthalates include calcium phthalate monohydrate (Schuckmann et al., 1978), lithium hydrogen phthalate monohydrate (Küppers, 1978) and tetramethylammonium hydrogen phthalate (Jessen & Küppers, 1991) have been reported in the literature. Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In this paper, the hydrogen-bonding patterns of 2-amino-5-bromopyridinium hydrogenphthalate, (I), are discussed.

The asymmetric unit of the title compound consists of two crystallographically independent 2-amino-5-bromopyridinium cations (A and B) and two 2-carboxybenzoate anions (A and B). The bond lengths (Allen et al., 1987) and angles in the title compound (Fig. 1) are within normal ranges and comparable with the related structures (Quah et al., 2008, 2010a, b). Each 2-amino-5-bromopyridinium cation is approximately planar, with a maximum deviation of 0.047 (1) Å for atom Br1A in cation A and 0.027 (1) Å for atom Br1B in cation B. The 2-amino-5-bromopyridinium in cation A is inclined at dihedral angles of 4.9 (3) and 2.2 (3)° with the C6A—C11A and C6B—C11B phenyl rings, respectively. The correspondence angles for cation B are 3.0 (3) and 5.6 (3)°. The molecular structure is stabilized by an intramolecular O3B—H2O3···O2B hydrogen bond which generates an S(7) ring motif (Bernstein et al., 1995).

The cations and anions are linked via intermolecular N–H···O and C–H···O hydrogen bonds (Table 1), generating R22(8) ring motifs. In the crystal packing (Fig. 2), the molecules are linked into one-dimensional wave-like chains along [001] via adjacent ring motifs. The crystal packing is further consolidated by π-π stacking interactions between the centroids of C6A—C11A (Cg1), N1B/C1B—C5B (Cg2) rings and C6B—C11B (Cg3), N1A/C1A—C5A (Cg4) rings, with Cg1···Cg2iii and Cg3···Cg4 distances of 3.613 (4) and 3.641 (4) Å, respectively [symmetry code: (iii) x, y, 1 + z]

For applications of phthalic acid, see: Dale et al. (2004); Ballabh et al. (2005). For related structures, see: Schuckmann et al. (1978); Küppers (1978); Jessen & Küppers (1991); Quah et al. (2008, 2010a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. Intramolecular interactions are shown in dashed lines.
[Figure 2] Fig. 2. The crystal structure of the title compound viewed along the b axis. H atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.
2-Amino-5-bromopyridinium 2-carboxybenzoate top
Crystal data top
C5H6BrN2+·C8H5O4Z = 4
Mr = 339.15F(000) = 680
Triclinic, P1Dx = 1.713 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0192 (4) ÅCell parameters from 9951 reflections
b = 10.2689 (5) Åθ = 2.3–27.7°
c = 14.4092 (6) ŵ = 3.14 mm1
α = 82.269 (2)°T = 100 K
β = 83.969 (2)°Block, colourless
γ = 87.845 (2)°0.24 × 0.20 × 0.10 mm
V = 1314.72 (10) Å3
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
7631 independent reflections
Radiation source: fine-focus sealed tube5583 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.000
φ and ω scansθmax = 30.0°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1212
Tmin = 0.526, Tmax = 0.740k = 1414
7631 measured reflectionsl = 620
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.194H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0079P)2 + 15.1445P]
where P = (Fo2 + 2Fc2)/3
7631 reflections(Δ/σ)max < 0.001
364 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = 1.25 e Å3
Crystal data top
C5H6BrN2+·C8H5O4γ = 87.845 (2)°
Mr = 339.15V = 1314.72 (10) Å3
Triclinic, P1Z = 4
a = 9.0192 (4) ÅMo Kα radiation
b = 10.2689 (5) ŵ = 3.14 mm1
c = 14.4092 (6) ÅT = 100 K
α = 82.269 (2)°0.24 × 0.20 × 0.10 mm
β = 83.969 (2)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
7631 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
5583 reflections with I > 2σ(I)
Tmin = 0.526, Tmax = 0.740Rint = 0.000
7631 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.194H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0079P)2 + 15.1445P]
where P = (Fo2 + 2Fc2)/3
7631 reflectionsΔρmax = 1.14 e Å3
364 parametersΔρmin = 1.25 e Å3
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
xyzUiso*/Ueq
Br1A0.79304 (8)0.52547 (8)0.47978 (5)0.03121 (19)
N1A0.6074 (6)0.6549 (5)0.7230 (4)0.0196 (10)
H1N10.63390.63240.77900.023*
N2A0.3893 (6)0.7645 (6)0.7726 (4)0.0236 (11)
H2NA0.28720.78620.77310.02 (2)*
H3NA0.42310.72810.83350.03 (2)*
C1A0.7009 (7)0.6012 (7)0.6581 (4)0.0223 (13)
H1AA0.78940.55960.67490.027*
C2A0.6649 (7)0.6083 (7)0.5678 (4)0.0223 (13)
C3A0.5324 (7)0.6715 (7)0.5428 (4)0.0243 (13)
H3AA0.50770.67660.48130.029*
C4A0.4383 (8)0.7262 (7)0.6095 (4)0.0244 (13)
H4AA0.35050.76960.59320.029*
C5A0.4765 (7)0.7158 (6)0.7033 (4)0.0206 (12)
H2O31.05380.75710.58150.031*
Br1B0.69848 (8)0.98559 (8)0.01879 (5)0.03200 (19)
N1B0.8885 (6)0.8524 (6)0.2596 (4)0.0221 (11)
H2N10.85150.84320.32230.027*
N2B1.0992 (7)0.7300 (6)0.2998 (4)0.0261 (12)
H3N21.20480.70460.28160.031*
H4N21.08820.75770.35020.031*
C1B0.7963 (7)0.9101 (7)0.1972 (4)0.0222 (13)
H1BA0.71190.95710.21800.027*
C2B0.8265 (7)0.8995 (7)0.1045 (4)0.0229 (13)
C3B0.9539 (8)0.8290 (7)0.0737 (5)0.0257 (14)
H3BA0.97550.82160.01010.031*
C4B1.0461 (8)0.7713 (7)0.1368 (4)0.0245 (13)
H4BA1.13050.72370.11680.029*
C5B1.0122 (7)0.7843 (7)0.2339 (4)0.0222 (13)
O1B0.7873 (6)0.9253 (6)0.4244 (3)0.0348 (13)
O2B0.9788 (5)0.8164 (5)0.4822 (3)0.0255 (10)
O3B1.0802 (6)0.7552 (5)0.6291 (3)0.0301 (11)
O4B1.0764 (6)0.8386 (5)0.7617 (3)0.0291 (11)
C10B0.8034 (7)0.9257 (6)0.5868 (4)0.0195 (12)
C6B0.7961 (8)0.9415 (7)0.7535 (4)0.0232 (13)
H6BA0.83860.92330.81010.028*
C7B0.6601 (8)1.0105 (7)0.7525 (5)0.0252 (13)
H7BA0.61221.03620.80770.030*
C8B0.5967 (8)1.0405 (7)0.6684 (5)0.0253 (13)
H8BA0.50741.08840.66630.030*
C9B0.6676 (7)0.9984 (7)0.5881 (4)0.0216 (12)
H9BA0.62391.01880.53210.026*
C11B0.8708 (7)0.8986 (6)0.6729 (4)0.0202 (12)
C12B0.8597 (7)0.8867 (6)0.4919 (4)0.0200 (12)
C13B1.0179 (7)0.8290 (7)0.6895 (5)0.0233 (13)
O1A0.4113 (6)0.6654 (5)1.2511 (3)0.0313 (11)
O2A0.3986 (6)0.7420 (5)1.1025 (3)0.0284 (11)
H1OA0.46300.78311.06270.043*
O3A0.5145 (5)0.6946 (5)0.9528 (3)0.0271 (10)
O4A0.7025 (6)0.5820 (6)0.8916 (3)0.0344 (13)
C6A0.8161 (7)0.5016 (7)1.0550 (4)0.0222 (13)
H6AB0.85720.47620.99810.027*
C7A0.8877 (7)0.4632 (7)1.1348 (5)0.0247 (13)
H7AB0.97660.41451.13090.030*
C8A0.8256 (8)0.4979 (7)1.2215 (4)0.0245 (13)
H8AB0.87360.47411.27550.029*
C9A0.6919 (7)0.5682 (6)1.2255 (4)0.0219 (12)
H9AB0.65060.59021.28340.026*
C10A0.6164 (7)0.6075 (6)1.1468 (4)0.0197 (12)
C11A0.6819 (7)0.5788 (6)1.0570 (4)0.0190 (12)
C12A0.4671 (8)0.6747 (7)1.1692 (5)0.0240 (13)
C13A0.6295 (7)0.6207 (7)0.9607 (4)0.0215 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0271 (4)0.0455 (4)0.0232 (3)0.0034 (3)0.0011 (3)0.0148 (3)
N1A0.022 (3)0.024 (3)0.013 (2)0.003 (2)0.0037 (19)0.0040 (19)
N2A0.022 (3)0.030 (3)0.020 (3)0.001 (2)0.002 (2)0.006 (2)
C1A0.020 (3)0.026 (3)0.021 (3)0.005 (2)0.002 (2)0.004 (2)
C2A0.024 (3)0.030 (3)0.014 (3)0.008 (3)0.003 (2)0.008 (2)
C3A0.026 (3)0.033 (4)0.017 (3)0.007 (3)0.006 (2)0.008 (3)
C4A0.023 (3)0.030 (4)0.020 (3)0.005 (3)0.007 (2)0.000 (2)
C5A0.022 (3)0.022 (3)0.019 (3)0.005 (2)0.003 (2)0.004 (2)
Br1B0.0262 (4)0.0485 (5)0.0208 (3)0.0002 (3)0.0066 (3)0.0002 (3)
N1B0.023 (3)0.028 (3)0.016 (2)0.000 (2)0.001 (2)0.006 (2)
N2B0.028 (3)0.031 (3)0.019 (3)0.004 (2)0.000 (2)0.004 (2)
C1B0.021 (3)0.024 (3)0.022 (3)0.005 (2)0.002 (2)0.004 (2)
C2B0.022 (3)0.028 (3)0.020 (3)0.005 (3)0.004 (2)0.004 (2)
C3B0.028 (3)0.030 (4)0.019 (3)0.006 (3)0.003 (2)0.009 (3)
C4B0.026 (3)0.029 (3)0.018 (3)0.000 (3)0.003 (2)0.008 (2)
C5B0.024 (3)0.023 (3)0.019 (3)0.005 (2)0.001 (2)0.002 (2)
O1B0.036 (3)0.051 (3)0.018 (2)0.014 (3)0.007 (2)0.007 (2)
O2B0.022 (2)0.033 (3)0.021 (2)0.0008 (19)0.0014 (18)0.0059 (19)
O3B0.034 (3)0.037 (3)0.020 (2)0.012 (2)0.008 (2)0.007 (2)
O4B0.029 (3)0.033 (3)0.028 (2)0.003 (2)0.014 (2)0.004 (2)
C10B0.022 (3)0.021 (3)0.016 (3)0.003 (2)0.003 (2)0.001 (2)
C6B0.033 (3)0.024 (3)0.014 (3)0.000 (3)0.005 (2)0.004 (2)
C7B0.030 (3)0.027 (3)0.019 (3)0.003 (3)0.001 (3)0.008 (2)
C8B0.023 (3)0.030 (4)0.024 (3)0.004 (3)0.001 (2)0.007 (3)
C9B0.023 (3)0.027 (3)0.015 (3)0.002 (2)0.001 (2)0.002 (2)
C11B0.022 (3)0.021 (3)0.018 (3)0.002 (2)0.001 (2)0.004 (2)
C12B0.020 (3)0.023 (3)0.016 (3)0.002 (2)0.001 (2)0.000 (2)
C13B0.020 (3)0.024 (3)0.026 (3)0.004 (2)0.008 (2)0.004 (2)
O1A0.035 (3)0.033 (3)0.021 (2)0.008 (2)0.008 (2)0.002 (2)
O2A0.030 (3)0.035 (3)0.018 (2)0.009 (2)0.0023 (18)0.0023 (19)
O3A0.027 (2)0.036 (3)0.019 (2)0.010 (2)0.0050 (18)0.0047 (19)
O4A0.033 (3)0.057 (4)0.013 (2)0.015 (3)0.0048 (19)0.005 (2)
C6A0.021 (3)0.029 (3)0.016 (3)0.000 (3)0.003 (2)0.006 (2)
C7A0.021 (3)0.028 (3)0.022 (3)0.002 (3)0.001 (2)0.002 (3)
C8A0.026 (3)0.030 (3)0.018 (3)0.003 (3)0.005 (2)0.000 (2)
C9A0.028 (3)0.023 (3)0.014 (3)0.002 (3)0.001 (2)0.004 (2)
C10A0.023 (3)0.020 (3)0.016 (3)0.000 (2)0.002 (2)0.005 (2)
C11A0.021 (3)0.022 (3)0.014 (3)0.002 (2)0.002 (2)0.004 (2)
C12A0.028 (3)0.020 (3)0.024 (3)0.002 (3)0.001 (3)0.004 (2)
C13A0.022 (3)0.028 (3)0.015 (3)0.004 (2)0.002 (2)0.002 (2)
Geometric parameters (Å, º) top
Br1A—C2A1.891 (6)O3B—H2O30.7471
N1A—C1A1.352 (8)O4B—C13B1.231 (8)
N1A—C5A1.354 (8)C10B—C9B1.410 (9)
N1A—H1N10.8651C10B—C11B1.428 (8)
N2A—C5A1.343 (8)C10B—C12B1.508 (9)
N2A—H2NA0.9388C6B—C7B1.394 (10)
N2A—H3NA0.9814C6B—C11B1.396 (9)
C1A—C2A1.366 (9)C6B—H6BA0.9300
C1A—H1AA0.9300C7B—C8B1.385 (9)
C2A—C3A1.396 (10)C7B—H7BA0.9300
C3A—C4A1.378 (9)C8B—C9B1.375 (9)
C3A—H3AA0.9300C8B—H8BA0.9300
C4A—C5A1.418 (9)C9B—H9BA0.9300
C4A—H4AA0.9300C11B—C13B1.510 (9)
Br1B—C2B1.889 (7)O1A—C12A1.226 (8)
N1B—C5B1.340 (8)O2A—C12A1.302 (8)
N1B—C1B1.352 (8)O2A—H1OA0.8532
N1B—H2N10.9235O3A—C13A1.267 (8)
N2B—C5B1.345 (8)O4A—C13A1.239 (8)
N2B—H3N20.9952C6A—C7A1.381 (9)
N2B—H4N20.8108C6A—C11A1.421 (9)
C1B—C2B1.353 (9)C6A—H6AB0.9300
C1B—H1BA0.9300C7A—C8A1.399 (9)
C2B—C3B1.400 (10)C7A—H7AB0.9300
C3B—C4B1.359 (10)C8A—C9A1.382 (9)
C3B—H3BA0.9300C8A—H8AB0.9300
C4B—C5B1.423 (9)C9A—C10A1.389 (9)
C4B—H4BA0.9300C9A—H9AB0.9300
O1B—C12B1.241 (8)C10A—C11A1.428 (8)
O2B—C12B1.277 (8)C10A—C12A1.514 (9)
O3B—C13B1.300 (8)C11A—C13A1.515 (8)
C1A—N1A—C5A123.1 (5)C7B—C6B—C11B122.4 (6)
C1A—N1A—H1N1111.1C7B—C6B—H6BA118.8
C5A—N1A—H1N1124.9C11B—C6B—H6BA118.8
C5A—N2A—H2NA126.7C8B—C7B—C6B119.4 (6)
C5A—N2A—H3NA109.3C8B—C7B—H7BA120.3
H2NA—N2A—H3NA115.7C6B—C7B—H7BA120.3
N1A—C1A—C2A119.7 (6)C9B—C8B—C7B119.2 (6)
N1A—C1A—H1AA120.2C9B—C8B—H8BA120.4
C2A—C1A—H1AA120.2C7B—C8B—H8BA120.4
C1A—C2A—C3A119.9 (6)C8B—C9B—C10B123.0 (6)
C1A—C2A—Br1A118.9 (5)C8B—C9B—H9BA118.5
C3A—C2A—Br1A121.1 (5)C10B—C9B—H9BA118.5
C4A—C3A—C2A119.8 (6)C6B—C11B—C10B118.3 (6)
C4A—C3A—H3AA120.1C6B—C11B—C13B113.6 (6)
C2A—C3A—H3AA120.1C10B—C11B—C13B128.2 (6)
C3A—C4A—C5A119.4 (6)O1B—C12B—O2B121.6 (6)
C3A—C4A—H4AA120.3O1B—C12B—C10B118.0 (6)
C5A—C4A—H4AA120.3O2B—C12B—C10B120.4 (6)
N2A—C5A—N1A119.0 (6)O4B—C13B—O3B120.1 (6)
N2A—C5A—C4A122.9 (6)O4B—C13B—C11B120.0 (6)
N1A—C5A—C4A118.1 (6)O3B—C13B—C11B119.9 (6)
C5B—N1B—C1B122.7 (6)C12A—O2A—H1OA108.9
C5B—N1B—H2N1118.9C7A—C6A—C11A122.3 (6)
C1B—N1B—H2N1116.7C7A—C6A—H6AB118.9
C5B—N2B—H3N2120.3C11A—C6A—H6AB118.9
C5B—N2B—H4N2117.1C6A—C7A—C8A119.7 (6)
H3N2—N2B—H4N2112.4C6A—C7A—H7AB120.2
N1B—C1B—C2B120.1 (6)C8A—C7A—H7AB120.2
N1B—C1B—H1BA120.0C9A—C8A—C7A119.0 (6)
C2B—C1B—H1BA120.0C9A—C8A—H8AB120.5
C1B—C2B—C3B119.6 (6)C7A—C8A—H8AB120.5
C1B—C2B—Br1B119.0 (5)C8A—C9A—C10A122.8 (6)
C3B—C2B—Br1B121.4 (5)C8A—C9A—H9AB118.6
C4B—C3B—C2B120.0 (6)C10A—C9A—H9AB118.6
C4B—C3B—H3BA120.0C9A—C10A—C11A119.0 (6)
C2B—C3B—H3BA120.0C9A—C10A—C12A113.5 (5)
C3B—C4B—C5B119.3 (6)C11A—C10A—C12A127.5 (6)
C3B—C4B—H4BA120.3C6A—C11A—C10A117.1 (6)
C5B—C4B—H4BA120.3C6A—C11A—C13A113.9 (5)
N1B—C5B—N2B119.5 (6)C10A—C11A—C13A129.0 (6)
N1B—C5B—C4B118.2 (6)O1A—C12A—O2A120.2 (6)
N2B—C5B—C4B122.2 (6)O1A—C12A—C10A119.2 (6)
C13B—O3B—H2O3121.4O2A—C12A—C10A120.6 (6)
C9B—C10B—C11B117.6 (6)O4A—C13A—O3A122.0 (6)
C9B—C10B—C12B114.3 (5)O4A—C13A—C11A118.2 (6)
C11B—C10B—C12B128.1 (6)O3A—C13A—C11A119.8 (5)
C5A—N1A—C1A—C2A0.5 (10)C9B—C10B—C11B—C13B177.0 (6)
N1A—C1A—C2A—C3A0.3 (10)C12B—C10B—C11B—C13B2.7 (11)
N1A—C1A—C2A—Br1A177.1 (5)C9B—C10B—C12B—O1B2.9 (9)
C1A—C2A—C3A—C4A0.1 (10)C11B—C10B—C12B—O1B176.8 (6)
Br1A—C2A—C3A—C4A177.3 (5)C9B—C10B—C12B—O2B177.4 (6)
C2A—C3A—C4A—C5A0.9 (10)C11B—C10B—C12B—O2B2.9 (10)
C1A—N1A—C5A—N2A178.9 (6)C6B—C11B—C13B—O4B15.4 (9)
C1A—N1A—C5A—C4A1.6 (9)C10B—C11B—C13B—O4B163.8 (7)
C3A—C4A—C5A—N2A178.8 (6)C6B—C11B—C13B—O3B162.2 (6)
C3A—C4A—C5A—N1A1.7 (10)C10B—C11B—C13B—O3B18.6 (10)
C5B—N1B—C1B—C2B0.5 (10)C11A—C6A—C7A—C8A1.5 (10)
N1B—C1B—C2B—C3B0.2 (10)C6A—C7A—C8A—C9A1.2 (10)
N1B—C1B—C2B—Br1B178.2 (5)C7A—C8A—C9A—C10A0.7 (10)
C1B—C2B—C3B—C4B0.2 (10)C8A—C9A—C10A—C11A2.5 (10)
Br1B—C2B—C3B—C4B178.1 (5)C8A—C9A—C10A—C12A175.9 (6)
C2B—C3B—C4B—C5B0.5 (10)C7A—C6A—C11A—C10A4.6 (10)
C1B—N1B—C5B—N2B179.7 (6)C7A—C6A—C11A—C13A174.7 (6)
C1B—N1B—C5B—C4B0.7 (10)C9A—C10A—C11A—C6A5.0 (9)
C3B—C4B—C5B—N1B0.7 (10)C12A—C10A—C11A—C6A173.1 (6)
C3B—C4B—C5B—N2B179.7 (7)C9A—C10A—C11A—C13A174.2 (6)
C11B—C6B—C7B—C8B1.2 (11)C12A—C10A—C11A—C13A7.7 (11)
C6B—C7B—C8B—C9B1.7 (10)C9A—C10A—C12A—O1A14.9 (9)
C7B—C8B—C9B—C10B0.2 (11)C11A—C10A—C12A—O1A163.3 (7)
C11B—C10B—C9B—C8B1.7 (10)C9A—C10A—C12A—O2A164.9 (6)
C12B—C10B—C9B—C8B178.5 (6)C11A—C10A—C12A—O2A16.9 (10)
C7B—C6B—C11B—C10B0.7 (10)C6A—C11A—C13A—O4A2.3 (9)
C7B—C6B—C11B—C13B178.5 (6)C10A—C11A—C13A—O4A178.5 (7)
C9B—C10B—C11B—C6B2.1 (9)C6A—C11A—C13A—O3A177.0 (6)
C12B—C10B—C11B—C6B178.2 (6)C10A—C11A—C13A—O3A2.2 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1N1···O4A0.861.802.664 (7)176
N2A—H2NA···O4Bi0.941.972.910 (8)175
N2A—H3NA···O3A0.981.972.930 (7)167
O3B—H2O3···O2B0.751.682.391 (6)159
N1B—H2N1···O1B0.921.822.647 (7)147
N2B—H3N2···O1Aii1.001.912.903 (8)176
N2B—H4N2···O2B0.812.202.971 (7)160
C4A—H4AA···O3Bi0.932.443.219 (9)141
C4B—H4BA···O2Aii0.932.423.175 (9)139
Symmetry codes: (i) x1, y, z; (ii) x+1, y, z1.

Experimental details

Crystal data
Chemical formulaC5H6BrN2+·C8H5O4
Mr339.15
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)9.0192 (4), 10.2689 (5), 14.4092 (6)
α, β, γ (°)82.269 (2), 83.969 (2), 87.845 (2)
V3)1314.72 (10)
Z4
Radiation typeMo Kα
µ (mm1)3.14
Crystal size (mm)0.24 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.526, 0.740
No. of measured, independent and
observed [I > 2σ(I)] reflections
7631, 7631, 5583
Rint0.000
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.194, 1.09
No. of reflections7631
No. of parameters364
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0079P)2 + 15.1445P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.14, 1.25

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1N1···O4A0.861.802.664 (7)176
N2A—H2NA···O4Bi0.941.972.910 (8)175
N2A—H3NA···O3A0.981.972.930 (7)167
O3B—H2O3···O2B0.751.682.391 (6)159
N1B—H2N1···O1B0.921.822.647 (7)147
N2B—H3N2···O1Aii1.001.912.903 (8)176
N2B—H4N2···O2B0.812.202.971 (7)160
C4A—H4AA···O3Bi0.932.443.219 (9)141
C4B—H4BA···O2Aii0.932.423.175 (9)139
Symmetry codes: (i) x1, y, z; (ii) x+1, y, z1.
 

Footnotes

Thomson Reuters ResearcherID: A-5525-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ also thanks USM for the award of a USM fellowship and HM also thanks USM for the award of a post­doctoral fellowship.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CSD CrossRef Web of Science Google Scholar
First citationBallabh, A., Trivedi, D. R. & Dastidar, P. (2005). Cryst. Growth Des. 5, 1548–1553.  Web of Science CSD CrossRef Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationDale, S. H., Elsegood, M. R. J., Hemmings, M. & Wilkinson, A. L. (2004). CrystEngComm, 6, 207–214.  Web of Science CSD CrossRef CAS Google Scholar
First citationJessen, S. M. & Küppers, H. (1991). J. Mol. Struct. 263, 247–265.  CSD CrossRef CAS Web of Science Google Scholar
First citationKüppers, H. (1978). Acta Cryst. B34, 3763–3765.  CSD CrossRef IUCr Journals Web of Science Google Scholar
First citationQuah, C. K., Hemamalini, M. & Fun, H.-K. (2010a). Acta Cryst. E66, o1932.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationQuah, C. K., Hemamalini, M. & Fun, H.-K. (2010b). Acta Cryst. E66, o1935–o1936.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationQuah, C. K., Jebas, S. R. & Fun, H.-K. (2008). Acta Cryst. E64, o1878–o1879.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSchuckmann, W., Fuess, H. & Bats, J. W. (1978). Acta Cryst. B34, 3754–3756.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds