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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2433–o2434.
Published online 2010 August 28. doi:  10.1107/S1600536810032903
PMCID: PMC3008098

2,6-Diamino­pyridinium 2-carb­oxy­benzoate

Abstract

In the crystal of the title mol­ecular salt, C5H8N3 +·C8H5O4 , the diamino­pyridine cation and the phthalate anion are linked by a pair of N—H(...)O hydrogen bonds. Within the phthalate anion, an almost symmetrical O—H(...)O hydrogen bond is observed. The ion pairs are linked by further N—H(...)O hydrogen bonds, generating a two-dimensional network lying parallel to (10An external file that holds a picture, illustration, etc.
Object name is e-66-o2433-efi1.jpg).

Related literature

For background to 2,6-diamino­pyridines, see: Abu Zuhri & Cox (1989 [triangle]); Inuzuka & Fujimoto (1990 [triangle]); El-Mossalamy (2001 [triangle]). For background and the biological activity of phthalic acid, see: Brike et al. (2002 [triangle]); Yamamoto et al. (1990 [triangle]). For related structures: see: Büyükgüngör & Odabąsoğlu (2006 [triangle]); Al-Dajani et al. (2009 [triangle]); Raissi Shabari et al. (2010 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2433-scheme1.jpg

Experimental

Crystal data

  • C5H8N3 +·C8H5O4
  • M r = 275.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2433-efi2.jpg
  • a = 32.332 (11) Å
  • b = 3.7246 (14) Å
  • c = 24.184 (8) Å
  • β = 123.036 (6)°
  • V = 2441.5 (15) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 100 K
  • 0.47 × 0.10 × 0.03 mm

Data collection

  • Bruker APEXII DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.948, T max = 0.996
  • 5492 measured reflections
  • 2757 independent reflections
  • 1869 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.197
  • S = 1.06
  • 2757 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.40 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032903/hb5557sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032903/hb5557Isup2.hkl

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

Acknowledgments

NM gratefully acknowledges funding from Universiti Sains Malaysia (USM) under the University Research Grant (No. 1001/PFARMASI/815025) and HHA gratefully acknowledges funding from Universiti Sains Malaysia (USM) under the University Research Grant (No. 1001/PKIMIA/811142). HKF thanks Universiti Sains Malaysia for the Research University Golden Goose grant (No. 1001/PFIZIK/811012).

supplementary crystallographic information

Comment

Phthalic acid is an aromatic dicarboxylic acid which can be used for the preparation of many organic and inorganic compounds such as dyes, perfumes and phthalates(Brike et al. 2002). Some of its derivatives have anti-tumor promoting action (Yamamoto et al. 1990). The diaminopyridine have an important role in the preparation of aromatic azo dyes (Abu Zuhri & Cox, 1989; Inuzuka & Fujimoto, 1990) and in many polarographic investigations (El-Mossalamy, 2001).

All geometrical parameters in the title compound, C5H8N3+.C8H5O4-,(I), are within normal ranges and are comparable with the related structures (Büyükgüngör & Odabąsoǧlu, 2006; Al-Dajani et al., 2009; Shabari et al., 2010). In the crystal structure, the anion and the cation were linked by N1—H1A···O3 and N2—H2A···O4 interactions. In the phthalate anion, a strong intramolecular interaction of O2—H1O2···O3 was observed. Intermolecular N—H···O hydrogen bonds (Table 1) further contribute to the stabilization of crystal structure, forming an infinite two-dimensional network parallel to the (101) plane.

Experimental

In a round bottom flask, 25ml of THF was mixed with 2,6-diaminopyridine (0.01 mol, 1.1 g) with stirring. Phthalic anhydrate (0.01 mol, 1.5 g) was dissolved in THF and then added in small portions into the round bottom flask and refluxed for 2 hours. The gray precipitate formed was filtrated and washed with THF. Brown plates of (I) were formed by dissolving the precipitate in hot water and letting it to cool at room temperature. The crystals was then filtered and dried at 60°C.

Refinement

O-bound H atoms were located from a difference Fourier map and refined as riding with Uiso(H) = 1.5Ueq(O).The remaining H atoms were positioned geometrically [N–H = 0.86Å, C–H = 0.93 Å and refined using a riding model, with Uiso(H) = 1.2Ueq(N,C)].

Figures

Fig. 1.
The molecular structure of (I), showing 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius. Dashed lines indicate the intermolecular hydrogen bonds.
Fig. 2.
The crystal packing of (I) viewed down the b axis. Dashed lines indicate hydrogen bonds. H atoms not involved in the hydrogen bond interactions have been omitted for clarity.

Crystal data

C5H8N3+·C8H5O4F(000) = 1152
Mr = 275.26Dx = 1.498 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 975 reflections
a = 32.332 (11) Åθ = 3.8–28.1°
b = 3.7246 (14) ŵ = 0.11 mm1
c = 24.184 (8) ÅT = 100 K
β = 123.036 (6)°Plate, brown
V = 2441.5 (15) Å30.47 × 0.10 × 0.03 mm
Z = 8

Data collection

Bruker APEXII DUO CCD area-detector diffractometer2757 independent reflections
Radiation source: fine-focus sealed tube1869 reflections with I > 2σ(I)
graphiteRint = 0.041
[var phi] and ω scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −36→42
Tmin = 0.948, Tmax = 0.996k = −4→4
5492 measured reflectionsl = −31→27

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.1138P)2] where P = (Fo2 + 2Fc2)/3
2757 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

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 esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
N10.09892 (7)0.9810 (6)0.16036 (9)0.0153 (5)
H1A0.11090.89740.13880.018*
N20.02334 (7)0.8089 (7)0.07262 (10)0.0195 (5)
H2A0.03810.73290.05420.023*
H2B−0.00820.78820.05260.023*
N30.17839 (7)1.1355 (7)0.24299 (10)0.0210 (5)
H3A0.18831.04870.21920.025*
H3B0.19931.22680.28100.025*
C10.04920 (8)0.9585 (7)0.13210 (11)0.0158 (5)
C20.02953 (9)1.0896 (8)0.16702 (11)0.0179 (6)
H2C−0.00421.07540.14940.021*
C30.06092 (9)1.2402 (8)0.22794 (12)0.0191 (6)
H3C0.04781.33090.25100.023*
C40.11140 (9)1.2624 (8)0.25640 (11)0.0169 (5)
H4A0.13191.36360.29800.020*
C50.13083 (8)1.1287 (7)0.22106 (11)0.0153 (5)
O10.26121 (6)−0.0595 (6)0.12827 (8)0.0228 (5)
O20.21888 (6)0.2628 (6)0.15685 (7)0.0191 (4)
H1O20.18160.41810.12250.029*
O30.14264 (6)0.6094 (5)0.10279 (8)0.0193 (5)
O40.06986 (6)0.5317 (6)0.01065 (9)0.0272 (5)
C60.18695 (8)0.1875 (7)0.03925 (11)0.0148 (5)
C70.20221 (9)0.0642 (8)−0.00144 (12)0.0170 (5)
H7A0.2336−0.03360.01790.020*
C80.17220 (9)0.0825 (8)−0.06960 (12)0.0193 (6)
H8A0.18360.0045−0.09550.023*
C90.12537 (9)0.2173 (8)−0.09827 (11)0.0195 (6)
H9A0.10450.2259−0.14400.023*
C100.10903 (9)0.3408 (7)−0.05943 (11)0.0159 (5)
H10A0.07720.4316−0.07970.019*
C110.13903 (8)0.3330 (7)0.00959 (11)0.0145 (5)
C120.11507 (8)0.4977 (7)0.04302 (11)0.0161 (5)
C130.22537 (8)0.1262 (7)0.11219 (11)0.0154 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0160 (10)0.0203 (12)0.0105 (9)0.0010 (9)0.0079 (8)−0.0016 (9)
N20.0140 (9)0.0278 (13)0.0146 (9)−0.0007 (10)0.0066 (8)−0.0046 (10)
N30.0140 (9)0.0340 (15)0.0135 (9)−0.0008 (10)0.0064 (8)−0.0042 (10)
C10.0162 (11)0.0156 (13)0.0147 (10)0.0007 (10)0.0079 (9)0.0025 (10)
C20.0162 (11)0.0185 (14)0.0181 (11)0.0005 (11)0.0089 (10)0.0018 (11)
C30.0236 (12)0.0207 (14)0.0175 (11)0.0051 (12)0.0141 (10)0.0020 (11)
C40.0196 (11)0.0175 (13)0.0136 (11)−0.0001 (11)0.0091 (10)−0.0004 (11)
C50.0170 (11)0.0148 (13)0.0111 (10)−0.0031 (10)0.0057 (9)−0.0006 (10)
O10.0190 (9)0.0286 (11)0.0184 (8)0.0056 (9)0.0085 (7)0.0023 (9)
O20.0170 (8)0.0274 (11)0.0127 (8)0.0010 (8)0.0078 (7)−0.0007 (8)
O30.0155 (8)0.0272 (11)0.0151 (8)0.0011 (8)0.0084 (7)−0.0045 (8)
O40.0152 (9)0.0409 (13)0.0235 (9)−0.0007 (9)0.0092 (7)−0.0105 (10)
C60.0147 (10)0.0162 (13)0.0134 (10)−0.0004 (10)0.0076 (9)0.0005 (10)
C70.0161 (11)0.0185 (13)0.0184 (11)−0.0018 (11)0.0107 (9)−0.0010 (11)
C80.0261 (13)0.0192 (14)0.0191 (11)−0.0028 (12)0.0166 (10)−0.0008 (11)
C90.0209 (12)0.0205 (14)0.0126 (10)−0.0037 (11)0.0062 (9)−0.0003 (11)
C100.0141 (10)0.0156 (13)0.0162 (11)−0.0024 (10)0.0072 (9)−0.0013 (10)
C110.0153 (10)0.0127 (12)0.0162 (11)−0.0016 (10)0.0090 (9)−0.0017 (10)
C120.0159 (11)0.0176 (14)0.0161 (11)−0.0023 (11)0.0095 (9)−0.0015 (11)
C130.0141 (10)0.0166 (13)0.0161 (11)−0.0004 (10)0.0086 (9)0.0020 (10)

Geometric parameters (Å, °)

N1—C11.364 (3)O2—C131.310 (3)
N1—C51.368 (3)O2—H1O21.1764
N1—H1A0.8600O3—C121.285 (3)
N2—C11.329 (3)O3—H1O21.2919
N2—H2A0.8600O4—C121.232 (3)
N2—H2B0.8600C6—C71.397 (3)
N3—C51.326 (3)C6—C111.413 (3)
N3—H3A0.8600C6—C131.522 (3)
N3—H3B0.8600C7—C81.385 (3)
C1—C21.393 (3)C7—H7A0.9300
C2—C31.373 (3)C8—C91.372 (3)
C2—H2C0.9300C8—H8A0.9300
C3—C41.386 (3)C9—C101.383 (3)
C3—H3C0.9300C9—H9A0.9300
C4—C51.399 (3)C10—C111.401 (3)
C4—H4A0.9300C10—H10A0.9300
O1—C131.217 (3)C11—C121.521 (3)
C1—N1—C5123.8 (2)C12—O3—H1O2100.1
C1—N1—H1A118.1C7—C6—C11118.6 (2)
C5—N1—H1A118.1C7—C6—C13112.8 (2)
C1—N2—H2A120.0C11—C6—C13128.5 (2)
C1—N2—H2B120.0C8—C7—C6122.3 (2)
H2A—N2—H2B120.0C8—C7—H7A118.8
C5—N3—H3A120.0C6—C7—H7A118.8
C5—N3—H3B120.0C9—C8—C7118.9 (2)
H3A—N3—H3B120.0C9—C8—H8A120.5
N2—C1—N1116.2 (2)C7—C8—H8A120.5
N2—C1—C2125.2 (2)C8—C9—C10120.2 (2)
N1—C1—C2118.5 (2)C8—C9—H9A119.9
C3—C2—C1118.6 (2)C10—C9—H9A119.9
C3—C2—H2C120.7C9—C10—C11122.0 (2)
C1—C2—H2C120.7C9—C10—H10A119.0
C2—C3—C4122.6 (2)C11—C10—H10A119.0
C2—C3—H3C118.7C10—C11—C6117.9 (2)
C4—C3—H3C118.7C10—C11—C12113.7 (2)
C3—C4—C5118.3 (2)C6—C11—C12128.3 (2)
C3—C4—H4A120.8O4—C12—O3122.4 (2)
C5—C4—H4A120.8O4—C12—C11118.4 (2)
N3—C5—N1118.0 (2)O3—C12—C11119.1 (2)
N3—C5—C4123.9 (2)O1—C13—O2120.6 (2)
N1—C5—C4118.1 (2)O1—C13—C6119.3 (2)
C13—O2—H1O299.9O2—C13—C6120.0 (2)
C5—N1—C1—N2179.6 (2)C9—C10—C11—C6−1.2 (4)
C5—N1—C1—C2−0.7 (4)C9—C10—C11—C12177.1 (2)
N2—C1—C2—C3−179.5 (3)C7—C6—C11—C100.9 (4)
N1—C1—C2—C30.9 (4)C13—C6—C11—C10−175.8 (2)
C1—C2—C3—C4−0.9 (4)C7—C6—C11—C12−177.1 (3)
C2—C3—C4—C50.7 (4)C13—C6—C11—C126.2 (4)
C1—N1—C5—N3−179.8 (2)C10—C11—C12—O419.0 (4)
C1—N1—C5—C40.5 (4)C6—C11—C12—O4−162.9 (3)
C3—C4—C5—N3179.8 (3)C10—C11—C12—O3−158.2 (2)
C3—C4—C5—N1−0.4 (4)C6—C11—C12—O319.9 (4)
C11—C6—C7—C80.5 (4)C7—C6—C13—O1−9.9 (3)
C13—C6—C7—C8177.8 (3)C11—C6—C13—O1167.0 (3)
C6—C7—C8—C9−1.8 (4)C7—C6—C13—O2172.4 (2)
C7—C8—C9—C101.6 (4)C11—C6—C13—O2−10.8 (4)
C8—C9—C10—C11−0.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H1O2···O31.181.292.437 (3)162
N1—H1A···O30.861.982.828 (3)167
N2—H2A···O40.861.982.834 (3)177
N2—H2B···O4i0.862.102.851 (3)145
N3—H3A···O2ii0.862.353.042 (3)138
N3—H3B···O1iii0.862.012.858 (3)171

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5557).

References

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