




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810030977/bt5311sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810030977/bt5311Isup2.hkl |
CCDC reference: 792378
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.009 Å
- R factor = 0.067
- wR factor = 0.194
- Data-to-parameter ratio = 21.0
checkCIF/PLATON results
No syntax errors found
Alert level C SHFSU01_ALERT_2_C Test not performed. _refine_ls_shift/su_max and _refine_ls_shift/esd_max not present. Absolute value of the parameter shift to su ratio given 0.001 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 9 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 18 PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ? PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 29
Alert level G PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 15.14 PLAT432_ALERT_2_G Short Inter X...Y Contact O4B .. C1B .. 3.02 Ang. PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) .. 3 PLAT154_ALERT_1_G The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 22 PLAT931_ALERT_5_G Check Twin Law ( 0 0 1)[ ] Estimated BASF 0.28
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.
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).
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).
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).
C5H6BrN2+·C8H5O4− | Z = 4 |
Mr = 339.15 | F(000) = 680 |
Triclinic, P1 | Dx = 1.713 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0192 (4) Å | Cell parameters from 9951 reflections |
b = 10.2689 (5) Å | θ = 2.3–27.7° |
c = 14.4092 (6) Å | µ = 3.14 mm−1 |
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 |
Bruker SMART APEXII CCD area-detector diffractometer | 7631 independent reflections |
Radiation source: fine-focus sealed tube | 5583 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
φ and ω scans | θmax = 30.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −12→12 |
Tmin = 0.526, Tmax = 0.740 | k = −14→14 |
7631 measured reflections | l = −6→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.194 | H-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 parameters | Δρmax = 1.14 e Å−3 |
0 restraints | Δρmin = −1.25 e Å−3 |
C5H6BrN2+·C8H5O4− | γ = 87.845 (2)° |
Mr = 339.15 | V = 1314.72 (10) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.0192 (4) Å | Mo Kα radiation |
b = 10.2689 (5) Å | µ = 3.14 mm−1 |
c = 14.4092 (6) Å | T = 100 K |
α = 82.269 (2)° | 0.24 × 0.20 × 0.10 mm |
β = 83.969 (2)° |
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 = 0.740 | Rint = 0.000 |
7631 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.194 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0079P)2 + 15.1445P] where P = (Fo2 + 2Fc2)/3 |
7631 reflections | Δρmax = 1.14 e Å−3 |
364 parameters | Δρmin = −1.25 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Br1A | 0.79304 (8) | 0.52547 (8) | 0.47978 (5) | 0.03121 (19) | |
N1A | 0.6074 (6) | 0.6549 (5) | 0.7230 (4) | 0.0196 (10) | |
H1N1 | 0.6339 | 0.6324 | 0.7790 | 0.023* | |
N2A | 0.3893 (6) | 0.7645 (6) | 0.7726 (4) | 0.0236 (11) | |
H2NA | 0.2872 | 0.7862 | 0.7731 | 0.02 (2)* | |
H3NA | 0.4231 | 0.7281 | 0.8335 | 0.03 (2)* | |
C1A | 0.7009 (7) | 0.6012 (7) | 0.6581 (4) | 0.0223 (13) | |
H1AA | 0.7894 | 0.5596 | 0.6749 | 0.027* | |
C2A | 0.6649 (7) | 0.6083 (7) | 0.5678 (4) | 0.0223 (13) | |
C3A | 0.5324 (7) | 0.6715 (7) | 0.5428 (4) | 0.0243 (13) | |
H3AA | 0.5077 | 0.6766 | 0.4813 | 0.029* | |
C4A | 0.4383 (8) | 0.7262 (7) | 0.6095 (4) | 0.0244 (13) | |
H4AA | 0.3505 | 0.7696 | 0.5932 | 0.029* | |
C5A | 0.4765 (7) | 0.7158 (6) | 0.7033 (4) | 0.0206 (12) | |
H2O3 | 1.0538 | 0.7571 | 0.5815 | 0.031* | |
Br1B | 0.69848 (8) | 0.98559 (8) | 0.01879 (5) | 0.03200 (19) | |
N1B | 0.8885 (6) | 0.8524 (6) | 0.2596 (4) | 0.0221 (11) | |
H2N1 | 0.8515 | 0.8432 | 0.3223 | 0.027* | |
N2B | 1.0992 (7) | 0.7300 (6) | 0.2998 (4) | 0.0261 (12) | |
H3N2 | 1.2048 | 0.7046 | 0.2816 | 0.031* | |
H4N2 | 1.0882 | 0.7577 | 0.3502 | 0.031* | |
C1B | 0.7963 (7) | 0.9101 (7) | 0.1972 (4) | 0.0222 (13) | |
H1BA | 0.7119 | 0.9571 | 0.2180 | 0.027* | |
C2B | 0.8265 (7) | 0.8995 (7) | 0.1045 (4) | 0.0229 (13) | |
C3B | 0.9539 (8) | 0.8290 (7) | 0.0737 (5) | 0.0257 (14) | |
H3BA | 0.9755 | 0.8216 | 0.0101 | 0.031* | |
C4B | 1.0461 (8) | 0.7713 (7) | 0.1368 (4) | 0.0245 (13) | |
H4BA | 1.1305 | 0.7237 | 0.1168 | 0.029* | |
C5B | 1.0122 (7) | 0.7843 (7) | 0.2339 (4) | 0.0222 (13) | |
O1B | 0.7873 (6) | 0.9253 (6) | 0.4244 (3) | 0.0348 (13) | |
O2B | 0.9788 (5) | 0.8164 (5) | 0.4822 (3) | 0.0255 (10) | |
O3B | 1.0802 (6) | 0.7552 (5) | 0.6291 (3) | 0.0301 (11) | |
O4B | 1.0764 (6) | 0.8386 (5) | 0.7617 (3) | 0.0291 (11) | |
C10B | 0.8034 (7) | 0.9257 (6) | 0.5868 (4) | 0.0195 (12) | |
C6B | 0.7961 (8) | 0.9415 (7) | 0.7535 (4) | 0.0232 (13) | |
H6BA | 0.8386 | 0.9233 | 0.8101 | 0.028* | |
C7B | 0.6601 (8) | 1.0105 (7) | 0.7525 (5) | 0.0252 (13) | |
H7BA | 0.6122 | 1.0362 | 0.8077 | 0.030* | |
C8B | 0.5967 (8) | 1.0405 (7) | 0.6684 (5) | 0.0253 (13) | |
H8BA | 0.5074 | 1.0884 | 0.6663 | 0.030* | |
C9B | 0.6676 (7) | 0.9984 (7) | 0.5881 (4) | 0.0216 (12) | |
H9BA | 0.6239 | 1.0188 | 0.5321 | 0.026* | |
C11B | 0.8708 (7) | 0.8986 (6) | 0.6729 (4) | 0.0202 (12) | |
C12B | 0.8597 (7) | 0.8867 (6) | 0.4919 (4) | 0.0200 (12) | |
C13B | 1.0179 (7) | 0.8290 (7) | 0.6895 (5) | 0.0233 (13) | |
O1A | 0.4113 (6) | 0.6654 (5) | 1.2511 (3) | 0.0313 (11) | |
O2A | 0.3986 (6) | 0.7420 (5) | 1.1025 (3) | 0.0284 (11) | |
H1OA | 0.4630 | 0.7831 | 1.0627 | 0.043* | |
O3A | 0.5145 (5) | 0.6946 (5) | 0.9528 (3) | 0.0271 (10) | |
O4A | 0.7025 (6) | 0.5820 (6) | 0.8916 (3) | 0.0344 (13) | |
C6A | 0.8161 (7) | 0.5016 (7) | 1.0550 (4) | 0.0222 (13) | |
H6AB | 0.8572 | 0.4762 | 0.9981 | 0.027* | |
C7A | 0.8877 (7) | 0.4632 (7) | 1.1348 (5) | 0.0247 (13) | |
H7AB | 0.9766 | 0.4145 | 1.1309 | 0.030* | |
C8A | 0.8256 (8) | 0.4979 (7) | 1.2215 (4) | 0.0245 (13) | |
H8AB | 0.8736 | 0.4741 | 1.2755 | 0.029* | |
C9A | 0.6919 (7) | 0.5682 (6) | 1.2255 (4) | 0.0219 (12) | |
H9AB | 0.6506 | 0.5902 | 1.2834 | 0.026* | |
C10A | 0.6164 (7) | 0.6075 (6) | 1.1468 (4) | 0.0197 (12) | |
C11A | 0.6819 (7) | 0.5788 (6) | 1.0570 (4) | 0.0190 (12) | |
C12A | 0.4671 (8) | 0.6747 (7) | 1.1692 (5) | 0.0240 (13) | |
C13A | 0.6295 (7) | 0.6207 (7) | 0.9607 (4) | 0.0215 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.0271 (4) | 0.0455 (4) | 0.0232 (3) | −0.0034 (3) | 0.0011 (3) | −0.0148 (3) |
N1A | 0.022 (3) | 0.024 (3) | 0.013 (2) | −0.003 (2) | −0.0037 (19) | −0.0040 (19) |
N2A | 0.022 (3) | 0.030 (3) | 0.020 (3) | −0.001 (2) | −0.002 (2) | −0.006 (2) |
C1A | 0.020 (3) | 0.026 (3) | 0.021 (3) | −0.005 (2) | −0.002 (2) | −0.004 (2) |
C2A | 0.024 (3) | 0.030 (3) | 0.014 (3) | −0.008 (3) | 0.003 (2) | −0.008 (2) |
C3A | 0.026 (3) | 0.033 (4) | 0.017 (3) | −0.007 (3) | −0.006 (2) | −0.008 (3) |
C4A | 0.023 (3) | 0.030 (4) | 0.020 (3) | −0.005 (3) | −0.007 (2) | 0.000 (2) |
C5A | 0.022 (3) | 0.022 (3) | 0.019 (3) | −0.005 (2) | −0.003 (2) | −0.004 (2) |
Br1B | 0.0262 (4) | 0.0485 (5) | 0.0208 (3) | −0.0002 (3) | −0.0066 (3) | 0.0002 (3) |
N1B | 0.023 (3) | 0.028 (3) | 0.016 (2) | 0.000 (2) | 0.001 (2) | −0.006 (2) |
N2B | 0.028 (3) | 0.031 (3) | 0.019 (3) | 0.004 (2) | 0.000 (2) | −0.004 (2) |
C1B | 0.021 (3) | 0.024 (3) | 0.022 (3) | −0.005 (2) | −0.002 (2) | −0.004 (2) |
C2B | 0.022 (3) | 0.028 (3) | 0.020 (3) | −0.005 (3) | −0.004 (2) | −0.004 (2) |
C3B | 0.028 (3) | 0.030 (4) | 0.019 (3) | −0.006 (3) | 0.003 (2) | −0.009 (3) |
C4B | 0.026 (3) | 0.029 (3) | 0.018 (3) | 0.000 (3) | 0.003 (2) | −0.008 (2) |
C5B | 0.024 (3) | 0.023 (3) | 0.019 (3) | −0.005 (2) | 0.001 (2) | −0.002 (2) |
O1B | 0.036 (3) | 0.051 (3) | 0.018 (2) | 0.014 (3) | −0.007 (2) | −0.007 (2) |
O2B | 0.022 (2) | 0.033 (3) | 0.021 (2) | 0.0008 (19) | 0.0014 (18) | −0.0059 (19) |
O3B | 0.034 (3) | 0.037 (3) | 0.020 (2) | 0.012 (2) | −0.008 (2) | −0.007 (2) |
O4B | 0.029 (3) | 0.033 (3) | 0.028 (2) | 0.003 (2) | −0.014 (2) | −0.004 (2) |
C10B | 0.022 (3) | 0.021 (3) | 0.016 (3) | −0.003 (2) | −0.003 (2) | −0.001 (2) |
C6B | 0.033 (3) | 0.024 (3) | 0.014 (3) | 0.000 (3) | −0.005 (2) | −0.004 (2) |
C7B | 0.030 (3) | 0.027 (3) | 0.019 (3) | −0.003 (3) | 0.001 (3) | −0.008 (2) |
C8B | 0.023 (3) | 0.030 (4) | 0.024 (3) | 0.004 (3) | −0.001 (2) | −0.007 (3) |
C9B | 0.023 (3) | 0.027 (3) | 0.015 (3) | −0.002 (2) | −0.001 (2) | −0.002 (2) |
C11B | 0.022 (3) | 0.021 (3) | 0.018 (3) | −0.002 (2) | −0.001 (2) | −0.004 (2) |
C12B | 0.020 (3) | 0.023 (3) | 0.016 (3) | −0.002 (2) | −0.001 (2) | 0.000 (2) |
C13B | 0.020 (3) | 0.024 (3) | 0.026 (3) | 0.004 (2) | −0.008 (2) | −0.004 (2) |
O1A | 0.035 (3) | 0.033 (3) | 0.021 (2) | 0.008 (2) | 0.008 (2) | 0.002 (2) |
O2A | 0.030 (3) | 0.035 (3) | 0.018 (2) | 0.009 (2) | 0.0023 (18) | −0.0023 (19) |
O3A | 0.027 (2) | 0.036 (3) | 0.019 (2) | 0.010 (2) | −0.0050 (18) | −0.0047 (19) |
O4A | 0.033 (3) | 0.057 (4) | 0.013 (2) | 0.015 (3) | −0.0048 (19) | −0.005 (2) |
C6A | 0.021 (3) | 0.029 (3) | 0.016 (3) | 0.000 (3) | 0.003 (2) | −0.006 (2) |
C7A | 0.021 (3) | 0.028 (3) | 0.022 (3) | 0.002 (3) | 0.001 (2) | 0.002 (3) |
C8A | 0.026 (3) | 0.030 (3) | 0.018 (3) | −0.003 (3) | −0.005 (2) | 0.000 (2) |
C9A | 0.028 (3) | 0.023 (3) | 0.014 (3) | −0.002 (3) | 0.001 (2) | −0.004 (2) |
C10A | 0.023 (3) | 0.020 (3) | 0.016 (3) | 0.000 (2) | 0.002 (2) | −0.005 (2) |
C11A | 0.021 (3) | 0.022 (3) | 0.014 (3) | −0.002 (2) | 0.002 (2) | −0.004 (2) |
C12A | 0.028 (3) | 0.020 (3) | 0.024 (3) | 0.002 (3) | 0.001 (3) | −0.004 (2) |
C13A | 0.022 (3) | 0.028 (3) | 0.015 (3) | −0.004 (2) | −0.002 (2) | −0.002 (2) |
Br1A—C2A | 1.891 (6) | O3B—H2O3 | 0.7471 |
N1A—C1A | 1.352 (8) | O4B—C13B | 1.231 (8) |
N1A—C5A | 1.354 (8) | C10B—C9B | 1.410 (9) |
N1A—H1N1 | 0.8651 | C10B—C11B | 1.428 (8) |
N2A—C5A | 1.343 (8) | C10B—C12B | 1.508 (9) |
N2A—H2NA | 0.9388 | C6B—C7B | 1.394 (10) |
N2A—H3NA | 0.9814 | C6B—C11B | 1.396 (9) |
C1A—C2A | 1.366 (9) | C6B—H6BA | 0.9300 |
C1A—H1AA | 0.9300 | C7B—C8B | 1.385 (9) |
C2A—C3A | 1.396 (10) | C7B—H7BA | 0.9300 |
C3A—C4A | 1.378 (9) | C8B—C9B | 1.375 (9) |
C3A—H3AA | 0.9300 | C8B—H8BA | 0.9300 |
C4A—C5A | 1.418 (9) | C9B—H9BA | 0.9300 |
C4A—H4AA | 0.9300 | C11B—C13B | 1.510 (9) |
Br1B—C2B | 1.889 (7) | O1A—C12A | 1.226 (8) |
N1B—C5B | 1.340 (8) | O2A—C12A | 1.302 (8) |
N1B—C1B | 1.352 (8) | O2A—H1OA | 0.8532 |
N1B—H2N1 | 0.9235 | O3A—C13A | 1.267 (8) |
N2B—C5B | 1.345 (8) | O4A—C13A | 1.239 (8) |
N2B—H3N2 | 0.9952 | C6A—C7A | 1.381 (9) |
N2B—H4N2 | 0.8108 | C6A—C11A | 1.421 (9) |
C1B—C2B | 1.353 (9) | C6A—H6AB | 0.9300 |
C1B—H1BA | 0.9300 | C7A—C8A | 1.399 (9) |
C2B—C3B | 1.400 (10) | C7A—H7AB | 0.9300 |
C3B—C4B | 1.359 (10) | C8A—C9A | 1.382 (9) |
C3B—H3BA | 0.9300 | C8A—H8AB | 0.9300 |
C4B—C5B | 1.423 (9) | C9A—C10A | 1.389 (9) |
C4B—H4BA | 0.9300 | C9A—H9AB | 0.9300 |
O1B—C12B | 1.241 (8) | C10A—C11A | 1.428 (8) |
O2B—C12B | 1.277 (8) | C10A—C12A | 1.514 (9) |
O3B—C13B | 1.300 (8) | C11A—C13A | 1.515 (8) |
C1A—N1A—C5A | 123.1 (5) | C7B—C6B—C11B | 122.4 (6) |
C1A—N1A—H1N1 | 111.1 | C7B—C6B—H6BA | 118.8 |
C5A—N1A—H1N1 | 124.9 | C11B—C6B—H6BA | 118.8 |
C5A—N2A—H2NA | 126.7 | C8B—C7B—C6B | 119.4 (6) |
C5A—N2A—H3NA | 109.3 | C8B—C7B—H7BA | 120.3 |
H2NA—N2A—H3NA | 115.7 | C6B—C7B—H7BA | 120.3 |
N1A—C1A—C2A | 119.7 (6) | C9B—C8B—C7B | 119.2 (6) |
N1A—C1A—H1AA | 120.2 | C9B—C8B—H8BA | 120.4 |
C2A—C1A—H1AA | 120.2 | C7B—C8B—H8BA | 120.4 |
C1A—C2A—C3A | 119.9 (6) | C8B—C9B—C10B | 123.0 (6) |
C1A—C2A—Br1A | 118.9 (5) | C8B—C9B—H9BA | 118.5 |
C3A—C2A—Br1A | 121.1 (5) | C10B—C9B—H9BA | 118.5 |
C4A—C3A—C2A | 119.8 (6) | C6B—C11B—C10B | 118.3 (6) |
C4A—C3A—H3AA | 120.1 | C6B—C11B—C13B | 113.6 (6) |
C2A—C3A—H3AA | 120.1 | C10B—C11B—C13B | 128.2 (6) |
C3A—C4A—C5A | 119.4 (6) | O1B—C12B—O2B | 121.6 (6) |
C3A—C4A—H4AA | 120.3 | O1B—C12B—C10B | 118.0 (6) |
C5A—C4A—H4AA | 120.3 | O2B—C12B—C10B | 120.4 (6) |
N2A—C5A—N1A | 119.0 (6) | O4B—C13B—O3B | 120.1 (6) |
N2A—C5A—C4A | 122.9 (6) | O4B—C13B—C11B | 120.0 (6) |
N1A—C5A—C4A | 118.1 (6) | O3B—C13B—C11B | 119.9 (6) |
C5B—N1B—C1B | 122.7 (6) | C12A—O2A—H1OA | 108.9 |
C5B—N1B—H2N1 | 118.9 | C7A—C6A—C11A | 122.3 (6) |
C1B—N1B—H2N1 | 116.7 | C7A—C6A—H6AB | 118.9 |
C5B—N2B—H3N2 | 120.3 | C11A—C6A—H6AB | 118.9 |
C5B—N2B—H4N2 | 117.1 | C6A—C7A—C8A | 119.7 (6) |
H3N2—N2B—H4N2 | 112.4 | C6A—C7A—H7AB | 120.2 |
N1B—C1B—C2B | 120.1 (6) | C8A—C7A—H7AB | 120.2 |
N1B—C1B—H1BA | 120.0 | C9A—C8A—C7A | 119.0 (6) |
C2B—C1B—H1BA | 120.0 | C9A—C8A—H8AB | 120.5 |
C1B—C2B—C3B | 119.6 (6) | C7A—C8A—H8AB | 120.5 |
C1B—C2B—Br1B | 119.0 (5) | C8A—C9A—C10A | 122.8 (6) |
C3B—C2B—Br1B | 121.4 (5) | C8A—C9A—H9AB | 118.6 |
C4B—C3B—C2B | 120.0 (6) | C10A—C9A—H9AB | 118.6 |
C4B—C3B—H3BA | 120.0 | C9A—C10A—C11A | 119.0 (6) |
C2B—C3B—H3BA | 120.0 | C9A—C10A—C12A | 113.5 (5) |
C3B—C4B—C5B | 119.3 (6) | C11A—C10A—C12A | 127.5 (6) |
C3B—C4B—H4BA | 120.3 | C6A—C11A—C10A | 117.1 (6) |
C5B—C4B—H4BA | 120.3 | C6A—C11A—C13A | 113.9 (5) |
N1B—C5B—N2B | 119.5 (6) | C10A—C11A—C13A | 129.0 (6) |
N1B—C5B—C4B | 118.2 (6) | O1A—C12A—O2A | 120.2 (6) |
N2B—C5B—C4B | 122.2 (6) | O1A—C12A—C10A | 119.2 (6) |
C13B—O3B—H2O3 | 121.4 | O2A—C12A—C10A | 120.6 (6) |
C9B—C10B—C11B | 117.6 (6) | O4A—C13A—O3A | 122.0 (6) |
C9B—C10B—C12B | 114.3 (5) | O4A—C13A—C11A | 118.2 (6) |
C11B—C10B—C12B | 128.1 (6) | O3A—C13A—C11A | 119.8 (5) |
C5A—N1A—C1A—C2A | 0.5 (10) | C9B—C10B—C11B—C13B | −177.0 (6) |
N1A—C1A—C2A—C3A | 0.3 (10) | C12B—C10B—C11B—C13B | 2.7 (11) |
N1A—C1A—C2A—Br1A | −177.1 (5) | C9B—C10B—C12B—O1B | 2.9 (9) |
C1A—C2A—C3A—C4A | −0.1 (10) | C11B—C10B—C12B—O1B | −176.8 (6) |
Br1A—C2A—C3A—C4A | 177.3 (5) | C9B—C10B—C12B—O2B | −177.4 (6) |
C2A—C3A—C4A—C5A | −0.9 (10) | C11B—C10B—C12B—O2B | 2.9 (10) |
C1A—N1A—C5A—N2A | 178.9 (6) | C6B—C11B—C13B—O4B | −15.4 (9) |
C1A—N1A—C5A—C4A | −1.6 (9) | C10B—C11B—C13B—O4B | 163.8 (7) |
C3A—C4A—C5A—N2A | −178.8 (6) | C6B—C11B—C13B—O3B | 162.2 (6) |
C3A—C4A—C5A—N1A | 1.7 (10) | C10B—C11B—C13B—O3B | −18.6 (10) |
C5B—N1B—C1B—C2B | 0.5 (10) | C11A—C6A—C7A—C8A | 1.5 (10) |
N1B—C1B—C2B—C3B | −0.2 (10) | C6A—C7A—C8A—C9A | 1.2 (10) |
N1B—C1B—C2B—Br1B | −178.2 (5) | C7A—C8A—C9A—C10A | −0.7 (10) |
C1B—C2B—C3B—C4B | 0.2 (10) | C8A—C9A—C10A—C11A | −2.5 (10) |
Br1B—C2B—C3B—C4B | 178.1 (5) | C8A—C9A—C10A—C12A | 175.9 (6) |
C2B—C3B—C4B—C5B | −0.5 (10) | C7A—C6A—C11A—C10A | −4.6 (10) |
C1B—N1B—C5B—N2B | 179.7 (6) | C7A—C6A—C11A—C13A | 174.7 (6) |
C1B—N1B—C5B—C4B | −0.7 (10) | C9A—C10A—C11A—C6A | 5.0 (9) |
C3B—C4B—C5B—N1B | 0.7 (10) | C12A—C10A—C11A—C6A | −173.1 (6) |
C3B—C4B—C5B—N2B | −179.7 (7) | C9A—C10A—C11A—C13A | −174.2 (6) |
C11B—C6B—C7B—C8B | −1.2 (11) | C12A—C10A—C11A—C13A | 7.7 (11) |
C6B—C7B—C8B—C9B | 1.7 (10) | C9A—C10A—C12A—O1A | −14.9 (9) |
C7B—C8B—C9B—C10B | −0.2 (11) | C11A—C10A—C12A—O1A | 163.3 (7) |
C11B—C10B—C9B—C8B | −1.7 (10) | C9A—C10A—C12A—O2A | 164.9 (6) |
C12B—C10B—C9B—C8B | 178.5 (6) | C11A—C10A—C12A—O2A | −16.9 (10) |
C7B—C6B—C11B—C10B | −0.7 (10) | C6A—C11A—C13A—O4A | 2.3 (9) |
C7B—C6B—C11B—C13B | 178.5 (6) | C10A—C11A—C13A—O4A | −178.5 (7) |
C9B—C10B—C11B—C6B | 2.1 (9) | C6A—C11A—C13A—O3A | −177.0 (6) |
C12B—C10B—C11B—C6B | −178.2 (6) | C10A—C11A—C13A—O3A | 2.2 (10) |
D—H···A | D—H | H···A | D···A | 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. |
Experimental details
Crystal data | |
Chemical formula | C5H6BrN2+·C8H5O4− |
Mr | 339.15 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 1314.72 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.14 |
Crystal size (mm) | 0.24 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.526, 0.740 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7631, 7631, 5583 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.194, 1.09 |
No. of reflections | 7631 |
No. of parameters | 364 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0079P)2 + 15.1445P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.14, −1.25 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | 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. |
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]