organic compounds
2-Amino-4-methoxy-6-methylpyrimidinium hydrogen phthalate
aDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur 639 005, Tamil Nadu, India, bDepartment of Chemistry, Government Arts College, Tiruchirappalli 620 022, Tamil Nadu, India, and cDepartment of Chemistry, Mother Teresa Women's University, Kodaikanal 624 102, Tamil Nadu, India
*Correspondence e-mail: manavaibala@gmail.com
In the hydrogen phthalate anion of the title molecular salt, C6H10N3O+·C8H5O4−, the dihedral angles formed by the benzene ring and the mean planes of the –COOH and –COO− groups are 16.1 (3) and 19.8 (3)°, respectively. There is an intramolecular O—H⋯O hydrogen bond in the anion generating an S(7) ring motif. In the crystal, the protonated N atom of the pyrimidinium ring and the 2-amino group of the cation are hydrogen bonded to the carboxylate O atoms of the anion via a pair of N—H⋯O hydrogen bonds, forming an R22(8) ring motif. The ion pairs are further connected via N—H⋯O and C—H⋯O hydrogen bonds, forming ribbons parallel to the [01-1] direction. The ribbons are linked by off-set π–π stacking interactions [intercentroid distances = 3.8279 (16) and 3.6074 (15) Å], forming a three-dimensional structure.
Keywords: crystal structure; hydrogen phthalate anion; pyrimidinium cation; N—H⋯O hydrogen bonding; π–π interactions.
CCDC reference: 1479857
Structure description
Pyrimidine and aminopyrimidine derivatives are biologically very important compounds and they occur in nature as components of et al., 1993). For example, imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990). Pyrimidine derivatives have also been developed as antiviral agents, such as AZT, which is the most widely used anti-AIDS drug (Gilchrist, 1997). Phthalic acid forms hydrogen phthalate salts with various organic compounds. Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In order to study hydrogen-bonding interactions in such molecular salts, we report herein on the synthesis and structure of the title molecular salt.
such as cytosine, uracil and thymine. Pyrimidine derivatives have many applications in the areas of pesticide and pharmaceutical agents (CondonThe molecular structure of the title molecular salt is illustrated in Fig. 1. In the hydrogen phthalate anion, there is a strong intramolecular O4—H1O4⋯O3 hydrogen bond enclosing an S(7) ring (Fig. 1 and Table 1), which is a result of the negative charge-assisted effect described by Gilli et al. (1994). The proton transfers from the one of the carboxyl-group O atoms (O2) to atom N3 of form the 2-amino-4-methoxy-6-methylpyrimidinium cation, resulting in a widening of the C1—N3—C4 angle of the pyrimidinium ring to 121.2 (2)°, compared to the corresponding angle of 116.01 (18)° in neutral 2-amino-4-methoxy-6-methylpyrimidine (Glidewell et al., 2003). The 2-amino-4-methoxy-6-methylpyrimidinium cation is essentially planar, with a maximum deviation of 0.006 (3) Å for atom C3. The carboxylate group of the hydrogen phthalate anion is slightly twisted from the attached ring, with the dihedral angle between the C7–C12 ring and the O2/O3/C14 plane being 19.8 (3)°.
In the crystal, the protonated N atom (N1) and the 2-amino group (N2) are hydrogen bonded to carboxylate O atoms (O2 and O3) via a pair of intermolecular N3—H1N3⋯O2 and N2—H2N2⋯O3 hydrogen bonds, forming an (8) ring motif (Fig. 2 and Table 1). Furthermore, these motifs are connected via N2—H1N2⋯O5i and weak C6—H6A⋯O5ii hydrogen bonds (the symmetry codes are as in Table 1), forming ribbons parallel to the [01] direction. The is further stabilized by slipped parallel π–π interactions between inversion-related benzene rings of the anion [Cg1⋯Cg1iii = 3.8279 (16) Å, interplanar distance = 3.465 (1) Å and slippage = 1.626 Å; Cg1 is the centroid of the C7–C12 ring; symmetry code: (iii) −x + 1, −y + 2, −z + 2] and between inversion-related pyrimidinium rings of the cation [Cg2⋯Cg2iv = 3.6074 (15) Å, interplanar distance = 3.275 (1) Å and slippage = 1.513 Å; Cg2 is the centroid of the N1/N3/C1–C4 ring; symmetry code: (iv) −x, −y + 1, −z + 1], forming a three-dimensional structure.
Synthesis and crystallization
A hot methanol solution (20 ml) of 2-amino-4-methoxy-6-methylpyrimidine (69 mg, Aldrich) and phthalic acid (41 mg, Merck) was mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly to room temperature and crystals of the title salt appeared after a few days.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1479857
10.1107/S241431461600794X/su4043sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461600794X/su4043Isup2.hkl
Supporting information file. DOI: 10.1107/S241431461600794X/su4043Isup3.cml
A hot methanol solution (20 ml) of 2-amino-4-methoxy-6-methylpyrimidine (69 mg, Aldrich) and phthalic acid (41 mg, Merck) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly to room temperature and crystals of the title salt appeared after a few days.
Crystal data, data collection and structure
details are summarized in Table 2. O– and N-bound H atoms were located in difference Fourier maps. Atoms H1N3, H1N2 and H2N2 were refined freely, while atom H1O4 was refined with an O—H bond restraint of 0.82 (1) Å. C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. A rotating-group model was used for the methyl group.Pyrimidine and aminopyrimidine derivatives are biologically very important compounds and they occur in nature as components of
such as cytosine, uracil and thymine. Pyrimidine derivatives are very important molecules in biology and have many applications in the areas of pesticide and pharmaceutical agents (Condon et al., 1993). For example, imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990). Pyrimidine derivatives have also been developed as antiviral agents, such as AZT, which is the most widely used anti-AIDS drug (Gilchrist, 1997). Phthalic acid forms hydrogen phthalate salts with various organic compounds. Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In order to study hydrogen-bonding interactions in such molecular salts, we report herein on the synthesis and structure of the title molecular salt.The molecular structure of the title molecular salt is illustrated in Fig. 1. In the hydrogen phthalate anion, there is a strong intramolecular O4—H1O4···O3 hydrogen bond enclosing an S(7) ring (Fig. 1 and Table 1), which is a result of the negative charge-assisted effect described by Gilli et al. (1994). The proton transfers from the one of the carboxyl group O atoms (O2) to atom N3 of form the 2-amino-4-methoxy-6-methylpyrimidinium cation, resulting in the widening of the C1–N3–C4 angle of the pyrimidinium ring to 121.2 (2)°, compared to the corresponding angle of 116.01 (18)° in neutral 2-amino-4-methoxy-6- methylpyrimidine (Glidewell et al., 2003). The 2-amino-4-methoxy-6-methylpyrimidinium cation is essentially planar, with a maximum deviation of 0.006 (3) Å for atom C3. The carboxylate group of the hydrogen phthalate anion is slightly twisted from the attached ring, with the dihedral angle between the C7–C12 ring and the O2/O3/C14 plane being 19.8 (3)°.
In the crystal, the protonated N atom (N1) and the 2-amino group (N2) are hydrogen bonded to carboxylate O atoms (O2 and O3) via a pair of intermolecular N3—H1N3···O2 and N2—H2N2···O3 hydrogen bonds, forming an R22(8) ring motif (Fig. 2 and Table 1). Furthermore, these motifs are connected via N2—H1N2···O5i and weak C6—H6A···O5ii hydrogen bonds (the symmetry codes are as in Table 1), forming ribbons parallel to the [011] direction. The is further stabilized by slipped parallel π–π interactions between inversion-related benzene rings of the anion [Cg1···Cg1iii = 3.8279 (16) Å, interplanar distance = 3.465 (1) Å and slippage = 1.626 Å; Cg1 is the centroid of the C7–C12 ring; symmetry code: (iii) -x + 1, -y + 2, -z + 2] and between inversion-related pyrimidinium rings of the cation [Cg2···Cg2iv = 3.6074 (15) Å, interplanar distance = 3.275 (1) Å and slippage = 1.513 Å; Cg2 is the centroid of the N1/N3/C1–C4 ring; symmetry code: (iv) -x, -y + 1, -z + 1], forming a three-dimensional structure.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title molecular salt, showing the atom labelling and 50% probability displacement ellipsoids. | |
Fig. 2. The crystal packing of the title compound, viewed along the c axis. The H atoms not involved in the intermolecular interactions (dashed lines; see Table 1) have been omitted for clarity. |
C6H10N3O+·C8H5O4− | Z = 2 |
Mr = 305.29 | F(000) = 320 |
Triclinic, P1 | Dx = 1.461 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3951 (4) Å | Cell parameters from 3654 reflections |
b = 9.0021 (4) Å | θ = 2.8–29.5° |
c = 10.5163 (4) Å | µ = 0.11 mm−1 |
α = 97.298 (3)° | T = 100 K |
β = 92.096 (3)° | Plate, colourless |
γ = 90.4322 (18)° | 0.65 × 0.24 × 0.06 mm |
V = 693.90 (5) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 2391 independent reflections |
Radiation source: fine-focus sealed tube | 1802 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −8→8 |
Tmin = 0.931, Tmax = 0.994 | k = −10→10 |
9218 measured reflections | l = −12→12 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.209 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1227P)2 + 0.4813P] where P = (Fo2 + 2Fc2)/3 |
2391 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.37 e Å−3 |
1 restraint | Δρmin = −0.38 e Å−3 |
C6H10N3O+·C8H5O4− | γ = 90.4322 (18)° |
Mr = 305.29 | V = 693.90 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3951 (4) Å | Mo Kα radiation |
b = 9.0021 (4) Å | µ = 0.11 mm−1 |
c = 10.5163 (4) Å | T = 100 K |
α = 97.298 (3)° | 0.65 × 0.24 × 0.06 mm |
β = 92.096 (3)° |
Bruker SMART APEXII CCD area-detector diffractometer | 2391 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1802 reflections with I > 2σ(I) |
Tmin = 0.931, Tmax = 0.994 | Rint = 0.050 |
9218 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 1 restraint |
wR(F2) = 0.209 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.37 e Å−3 |
2391 reflections | Δρmin = −0.38 e Å−3 |
217 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems 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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.0588 (3) | 0.2684 (2) | 0.17366 (17) | 0.0215 (5) | |
O2 | 0.4117 (3) | 0.5765 (2) | 0.70319 (17) | 0.0240 (5) | |
O3 | 0.4156 (3) | 0.7964 (2) | 0.62996 (18) | 0.0263 (5) | |
O4 | 0.5952 (3) | 1.0238 (2) | 0.66349 (18) | 0.0252 (5) | |
O5 | 0.8160 (3) | 1.1196 (2) | 0.79417 (18) | 0.0262 (5) | |
N1 | 0.0956 (3) | 0.4729 (2) | 0.2777 (2) | 0.0184 (5) | |
N2 | 0.2541 (3) | 0.6709 (3) | 0.3901 (2) | 0.0214 (6) | |
N3 | 0.2275 (3) | 0.4535 (2) | 0.4839 (2) | 0.0192 (6) | |
C1 | 0.1924 (4) | 0.5324 (3) | 0.3839 (2) | 0.0188 (6) | |
C2 | 0.0351 (4) | 0.3341 (3) | 0.2767 (2) | 0.0179 (6) | |
C3 | 0.0649 (4) | 0.2466 (3) | 0.3776 (3) | 0.0202 (6) | |
H3A | 0.0172 | 0.1476 | 0.3729 | 0.024* | |
C4 | 0.1648 (4) | 0.3099 (3) | 0.4819 (3) | 0.0204 (6) | |
C5 | 0.2110 (4) | 0.2345 (3) | 0.5968 (3) | 0.0252 (7) | |
H5A | 0.3427 | 0.2354 | 0.6115 | 0.038* | |
H5B | 0.1662 | 0.1308 | 0.5825 | 0.038* | |
H5C | 0.1546 | 0.2879 | 0.6720 | 0.038* | |
C6 | −0.0780 (4) | 0.3558 (3) | 0.0676 (3) | 0.0232 (7) | |
H6A | −0.1421 | 0.2960 | −0.0049 | 0.035* | |
H6B | 0.0421 | 0.3842 | 0.0416 | 0.035* | |
H6C | −0.1469 | 0.4462 | 0.0942 | 0.035* | |
C7 | 0.5555 (3) | 0.7771 (3) | 0.8393 (3) | 0.0189 (6) | |
C8 | 0.5409 (4) | 0.6919 (3) | 0.9408 (3) | 0.0202 (6) | |
H8A | 0.4756 | 0.5996 | 0.9262 | 0.024* | |
C9 | 0.6175 (4) | 0.7366 (3) | 1.0616 (3) | 0.0224 (6) | |
H9A | 0.5996 | 0.6789 | 1.1298 | 0.027* | |
C10 | 0.7213 (4) | 0.8674 (3) | 1.0816 (3) | 0.0226 (7) | |
H10A | 0.7772 | 0.8987 | 1.1634 | 0.027* | |
C11 | 0.7428 (4) | 0.9514 (3) | 0.9827 (3) | 0.0223 (6) | |
H11A | 0.8174 | 1.0388 | 0.9971 | 0.027* | |
C12 | 0.6584 (3) | 0.9126 (3) | 0.8611 (3) | 0.0178 (6) | |
C13 | 0.6944 (4) | 1.0250 (3) | 0.7689 (3) | 0.0205 (6) | |
C14 | 0.4542 (4) | 0.7115 (3) | 0.7152 (3) | 0.0198 (6) | |
H1N3 | 0.292 (5) | 0.504 (4) | 0.556 (4) | 0.038 (10)* | |
H1N2 | 0.225 (5) | 0.725 (4) | 0.327 (4) | 0.039 (10)* | |
H2N2 | 0.311 (5) | 0.712 (4) | 0.468 (3) | 0.033 (9)* | |
H1O4 | 0.523 (4) | 0.952 (3) | 0.649 (4) | 0.056 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0247 (11) | 0.0213 (10) | 0.0179 (10) | −0.0043 (8) | −0.0049 (8) | 0.0024 (8) |
O2 | 0.0271 (11) | 0.0217 (11) | 0.0227 (11) | −0.0045 (8) | −0.0059 (9) | 0.0040 (8) |
O3 | 0.0313 (12) | 0.0238 (11) | 0.0243 (11) | −0.0068 (9) | −0.0107 (9) | 0.0086 (9) |
O4 | 0.0298 (12) | 0.0232 (11) | 0.0233 (11) | −0.0097 (9) | −0.0102 (9) | 0.0097 (9) |
O5 | 0.0303 (12) | 0.0229 (10) | 0.0259 (11) | −0.0101 (9) | −0.0060 (9) | 0.0079 (8) |
N1 | 0.0183 (12) | 0.0173 (11) | 0.0197 (12) | −0.0032 (9) | 0.0006 (9) | 0.0038 (9) |
N2 | 0.0260 (13) | 0.0197 (12) | 0.0187 (12) | −0.0053 (10) | −0.0039 (10) | 0.0045 (10) |
N3 | 0.0207 (12) | 0.0190 (12) | 0.0180 (12) | −0.0024 (9) | −0.0009 (10) | 0.0032 (9) |
C1 | 0.0165 (13) | 0.0220 (14) | 0.0183 (13) | −0.0007 (10) | −0.0002 (10) | 0.0039 (11) |
C2 | 0.0161 (13) | 0.0205 (13) | 0.0169 (13) | −0.0007 (10) | 0.0008 (11) | 0.0012 (11) |
C3 | 0.0218 (14) | 0.0173 (13) | 0.0219 (14) | −0.0026 (11) | −0.0012 (12) | 0.0048 (11) |
C4 | 0.0179 (14) | 0.0195 (14) | 0.0241 (14) | −0.0004 (11) | 0.0021 (11) | 0.0040 (11) |
C5 | 0.0279 (16) | 0.0245 (15) | 0.0241 (15) | −0.0021 (12) | −0.0026 (12) | 0.0076 (11) |
C6 | 0.0285 (15) | 0.0244 (15) | 0.0168 (13) | −0.0009 (12) | −0.0035 (11) | 0.0047 (11) |
C7 | 0.0140 (13) | 0.0210 (14) | 0.0221 (14) | 0.0002 (10) | −0.0017 (11) | 0.0055 (11) |
C8 | 0.0203 (14) | 0.0198 (13) | 0.0205 (14) | −0.0031 (11) | −0.0015 (11) | 0.0034 (11) |
C9 | 0.0247 (15) | 0.0234 (14) | 0.0202 (14) | −0.0002 (11) | −0.0006 (12) | 0.0080 (11) |
C10 | 0.0259 (15) | 0.0235 (14) | 0.0183 (14) | 0.0014 (12) | −0.0034 (11) | 0.0037 (11) |
C11 | 0.0221 (14) | 0.0201 (14) | 0.0243 (14) | −0.0034 (11) | −0.0040 (12) | 0.0030 (11) |
C12 | 0.0160 (13) | 0.0165 (13) | 0.0214 (14) | 0.0028 (10) | −0.0007 (11) | 0.0050 (10) |
C13 | 0.0211 (14) | 0.0191 (14) | 0.0208 (14) | −0.0003 (11) | −0.0013 (11) | 0.0010 (11) |
C14 | 0.0172 (13) | 0.0215 (14) | 0.0205 (14) | −0.0029 (11) | 0.0024 (11) | 0.0022 (11) |
O1—C2 | 1.335 (3) | C4—C5 | 1.490 (4) |
O1—C6 | 1.448 (3) | C5—H5A | 0.9800 |
O2—C14 | 1.243 (3) | C5—H5B | 0.9800 |
O3—C14 | 1.276 (3) | C5—H5C | 0.9800 |
O3—H1O4 | 1.588 (13) | C6—H6A | 0.9800 |
O4—C13 | 1.306 (3) | C6—H6B | 0.9800 |
O4—H1O4 | 0.834 (10) | C6—H6C | 0.9800 |
O5—C13 | 1.232 (3) | C7—C8 | 1.399 (4) |
N1—C2 | 1.323 (3) | C7—C12 | 1.421 (4) |
N1—C1 | 1.353 (3) | C7—C14 | 1.529 (4) |
N2—C1 | 1.318 (4) | C8—C9 | 1.382 (4) |
N2—H1N2 | 0.90 (4) | C8—H8A | 0.9500 |
N2—H2N2 | 0.94 (4) | C9—C10 | 1.390 (4) |
N3—C1 | 1.360 (3) | C9—H9A | 0.9500 |
N3—C4 | 1.367 (4) | C10—C11 | 1.374 (4) |
N3—H1N3 | 0.95 (4) | C10—H10A | 0.9500 |
C2—C3 | 1.412 (4) | C11—C12 | 1.405 (4) |
C3—C4 | 1.360 (4) | C11—H11A | 0.9500 |
C3—H3A | 0.9500 | C12—C13 | 1.516 (4) |
C2—O1—C6 | 115.7 (2) | O1—C6—H6B | 109.5 |
C14—O3—H1O4 | 114.1 (15) | H6A—C6—H6B | 109.5 |
C13—O4—H1O4 | 114 (3) | O1—C6—H6C | 109.5 |
C2—N1—C1 | 116.4 (2) | H6A—C6—H6C | 109.5 |
C1—N2—H1N2 | 120 (2) | H6B—C6—H6C | 109.5 |
C1—N2—H2N2 | 117 (2) | C8—C7—C12 | 118.2 (2) |
H1N2—N2—H2N2 | 123 (3) | C8—C7—C14 | 114.5 (2) |
C1—N3—C4 | 121.2 (2) | C12—C7—C14 | 127.3 (2) |
C1—N3—H1N3 | 117 (2) | C9—C8—C7 | 122.6 (3) |
C4—N3—H1N3 | 122 (2) | C9—C8—H8A | 118.7 |
N2—C1—N1 | 118.7 (2) | C7—C8—H8A | 118.7 |
N2—C1—N3 | 119.4 (2) | C8—C9—C10 | 118.9 (2) |
N1—C1—N3 | 121.9 (2) | C8—C9—H9A | 120.6 |
N1—C2—O1 | 119.2 (2) | C10—C9—H9A | 120.6 |
N1—C2—C3 | 124.6 (2) | C11—C10—C9 | 119.9 (3) |
O1—C2—C3 | 116.2 (2) | C11—C10—H10A | 120.0 |
C4—C3—C2 | 117.1 (2) | C9—C10—H10A | 120.0 |
C4—C3—H3A | 121.4 | C10—C11—C12 | 122.2 (2) |
C2—C3—H3A | 121.4 | C10—C11—H11A | 118.9 |
C3—C4—N3 | 118.7 (3) | C12—C11—H11A | 118.9 |
C3—C4—C5 | 124.7 (3) | C11—C12—C7 | 118.0 (2) |
N3—C4—C5 | 116.6 (2) | C11—C12—C13 | 113.1 (2) |
C4—C5—H5A | 109.5 | C7—C12—C13 | 128.9 (2) |
C4—C5—H5B | 109.5 | O5—C13—O4 | 119.6 (2) |
H5A—C5—H5B | 109.5 | O5—C13—C12 | 120.1 (2) |
C4—C5—H5C | 109.5 | O4—C13—C12 | 120.3 (2) |
H5A—C5—H5C | 109.5 | O2—C14—O3 | 123.0 (2) |
H5B—C5—H5C | 109.5 | O2—C14—C7 | 117.6 (2) |
O1—C6—H6A | 109.5 | O3—C14—C7 | 119.3 (2) |
C2—N1—C1—N2 | −179.3 (2) | C8—C9—C10—C11 | 1.4 (4) |
C2—N1—C1—N3 | 0.8 (4) | C9—C10—C11—C12 | 2.0 (4) |
C4—N3—C1—N2 | 179.4 (2) | C10—C11—C12—C7 | −3.4 (4) |
C4—N3—C1—N1 | −0.6 (4) | C10—C11—C12—C13 | 177.4 (2) |
C1—N1—C2—O1 | −178.9 (2) | C8—C7—C12—C11 | 1.3 (4) |
C1—N1—C2—C3 | 0.0 (4) | C14—C7—C12—C11 | −179.3 (2) |
C6—O1—C2—N1 | 3.0 (3) | C8—C7—C12—C13 | −179.6 (2) |
C6—O1—C2—C3 | −176.1 (2) | C14—C7—C12—C13 | −0.1 (4) |
N1—C2—C3—C4 | −0.8 (4) | C11—C12—C13—O5 | 14.3 (4) |
O1—C2—C3—C4 | 178.1 (2) | C7—C12—C13—O5 | −164.8 (3) |
C2—C3—C4—N3 | 0.9 (4) | C11—C12—C13—O4 | −164.6 (2) |
C2—C3—C4—C5 | −179.6 (2) | C7—C12—C13—O4 | 16.2 (4) |
C1—N3—C4—C3 | −0.3 (4) | C8—C7—C14—O2 | −18.8 (3) |
C1—N3—C4—C5 | −179.8 (2) | C12—C7—C14—O2 | 161.8 (3) |
C12—C7—C8—C9 | 2.1 (4) | C8—C7—C14—O3 | 160.6 (2) |
C14—C7—C8—C9 | −177.4 (2) | C12—C7—C14—O3 | −18.9 (4) |
C7—C8—C9—C10 | −3.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···O2 | 0.94 (4) | 1.80 (4) | 2.738 (3) | 172 (3) |
N2—H1N2···O5i | 0.89 (4) | 2.03 (4) | 2.907 (3) | 169 (3) |
N2—H2N2···O3 | 0.94 (3) | 1.91 (3) | 2.846 (3) | 177 (3) |
O4—H1O4···O3 | 0.83 (3) | 1.59 (3) | 2.413 (3) | 169 (3) |
C6—H6A···O5ii | 0.98 | 2.48 | 3.415 (4) | 158 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y−1, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···O2 | 0.94 (4) | 1.80 (4) | 2.738 (3) | 172 (3) |
N2—H1N2···O5i | 0.89 (4) | 2.03 (4) | 2.907 (3) | 169 (3) |
N2—H2N2···O3 | 0.94 (3) | 1.91 (3) | 2.846 (3) | 177 (3) |
O4—H1O4···O3 | 0.83 (3) | 1.59 (3) | 2.413 (3) | 169 (3) |
C6—H6A···O5ii | 0.98 | 2.48 | 3.415 (4) | 158 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y−1, z−1. |
Experimental details
Crystal data | |
Chemical formula | C6H10N3O+·C8H5O4− |
Mr | 305.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.3951 (4), 9.0021 (4), 10.5163 (4) |
α, β, γ (°) | 97.298 (3), 92.096 (3), 90.4322 (18) |
V (Å3) | 693.90 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.65 × 0.24 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.931, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9218, 2391, 1802 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.209, 1.12 |
No. of reflections | 2391 |
No. of parameters | 217 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.38 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Acknowledgements
RS thanks the Department of Science and Technology (DST), New Delhi, India, for financial support in the form of an INSPIRE fellowship (INSPIRE code No. IF131050).
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