research communications
of 3-methylpyridinium picrate: a triclinic polymorph
aPG and Research Department of Chemistry, Seethalakshmi Ramaswami College, Tiruchirappalli 620 002, Tamil Nadu, India
*Correspondence e-mail: kalaivbalaj@yahoo.co.in
The title molecular salt, C6H8N+·C6H2N3O7− (systematic name: 3-methylpyridinium 2,4,6-trinitrophenolate), crystallizes in the triclinic P-1. The of the monoclinic polymorph (space group P21/n) has been reported [Stilinovic & Kaitner (2011). Cryst. Growth Des. 11, 4110–4119]. In the crystal, the anion and cation are linked via bifurcated N—H⋯(O,O) hydrogen bonds, enclosing an R12(6) graph-set motif. These units are linked via C—H⋯O hydrogen bonds, forming a three-dimensional framework. Within the framework there are π–π interactions present, involving inversion-related picrate anions and inversion-related pyridinium cations, with inter-centroid distances of 3.7389 (14) and 3.560 (2) Å, respectively.
Keywords: crystal structure; 3-methylpyridinium picrate; triclinic polymorph; π–π stacking; anticonvulsant activity..
CCDC reference: 1417794
1. Chemical context
Stilinovic & Kaitner (2011) have synthesized a series of 20 crystalline of pyridine derivatives and through single crystal X-ray diffraction studies revealed the presence of a common synthon. They reported the of the monoclinic polymorph of the title molecular salt: P21/n.
The observation that the presence of more than one heterocyclic component in a molecule enhances the biological response and thermal stability encouraged us to synthesize several new carbon-bonded anionic sigma complexes from chloronitro-aromatic compounds and pyrimidine derivatives in the presence of pyridine bases (Babykala et al., 2014; Buvaneswari & Kalaivani, 2013; Mangaiyarkarasi & Kalaivani, 2013; Manickkam & Kalaivani, 2011, 2014; Sridevi & Kalaivani, 2012). Surprisingly, when we made an attempt to synthesize a similar type of complex from the electron-deficient chloronitroaromatic compound (picryl chloride), an imidazole derivative (hydantoin) and 3-methylpyridine, the title salt crystallized from the medium (ethanol) instead of the expected carbon-bonded anionic sigma complex.
2. Structural commentary
The molecular structure of the title molecular salt is shown in Fig. 1. The anion and cation are linked via bifurcated N—H⋯(O,O) hydrogen bonds, enclosing an (6) graph-set motif (Fig. 1 and Table 1). In the picrate anion, the two nitro groups flanking the C—O− bond are oriented differently. Nitro group O1/N1/O2, involved in N—H⋯O hydrogen bonds as noted above, is inclined to the benzene ring by 6.7 (3)°, while nitro group O5/N3/O6 is inclined to the benzene ring by 70.07 (3)°, probably to alleviate steric crowding. The third nitro group (O3/N2/O4), para with respect to the C—O− bond, deviates only slightly from the benzene ring, making a dihedral angle of 6.6 (3)°.
3. Supramolecular features
In the crystal, the anionic and cationic hydrogen-bonded units are linked via C—H⋯O hydrogen bonds, forming a three-dimensional structure (Figs. 2 and 3, and Table 1). Within this framework there are slipped parallel π–π interactions present, involving inversion-related picrate anions [inter-centroid distance = 3.7389 (14) Å, inter-planar distance = 3.5829 (8) Å, slippage = 1.069 Å] and inversion-related pyridinium cations [inter-centroid distance = 3.560 (2) Å, inter-planar distance = 3.5548 (14) Å, slippage = 0.422 Å].
4. Anticonvulsant activity
The anticonvulsant activity of synthesized 3-methylpyridinium picrate has been measured by employing the maximal electro shock (MES) method (Bhattacharya & Chakrabarti, 1998; Misra et al., 1973). Different stages of convulsion such as tonic flexion, tonic extensor, clonus convulsion, stupor and recovery/death have been examined. Though all phases are reduced, noticeable decrease is observed in the clonus phase and hence the title molecule may be a potent agent for controlling myoclonic type epilepsy in the future.
5. Database survey
A search of the Cambridge Structural Database (Version 5.36, last update May 2015; Groom & Allen, 2014) yielded 40 hits for meta- or para-substituted pyridinium picrate salts. In the picrate anions, the average dihedral angle of the nitro group para to the C—O− bond with respect to the benzene ring is ca 6°, while for the two nitro groups on either side of the C—O− bond the dihedral angles are both ca 26–28°. In the title compound, the latter two dihedral angles are quite different being 6.7 (3) and 70.07 (3)°. In the monoclinic polymorph (UBEFEO; Stilinovic & Kaitner, 2011), these three dihedal angle are ca 3.60, 6.92 and 13.83°, respectively, and the cation and anion are also linked via bifurcated N—H⋯(O,O) hydrogen bonds.
6. Synthesis and crystallization
Picryl chloride [2.56 g (0.01 mol)] was dissolved in 30 ml of rectified spirit and mixed with hydantoin [1.00 g (0.01 mol)] in 30 ml of rectified spirit. After mixing these solutions, 3 ml of 3-methylpyridine (0.03 mol) was added and the temperature of the mixture was raised to 313 K. At this temperature, the mixture was stirred for 5 to 6 h. The solution was then cooled to room temperature, filtered and the filtrate kept at 298 K. After a period of 4 weeks, dark shiny maroon-red–coloured crystals formed from the solution. The crystals were filtered, powdered and dried. The dry solid was washed with 50 ml of dry ether (5 ml for each aliquot) and recrystallized from rectified spirit (yield: 60%; m.p. 483 K).
7. Refinement
Crystal data, data collection and structure . The NH H atom was located in a difference Fourier map and freely refined. The C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.93–0.96 Å with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2Supporting information
CCDC reference: 1417794
10.1107/S2056989015017090/su5205sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017090/su5205Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017090/su5205Isup3.cml
Stilinovic & Kaitner (2011) have synthesized a series of 20 crystalline
of pyridine derivatives and through single crystal X-ray diffraction studies revealed the presence of a common synthon. They reported the of the monoclinic polymorph of the title molecular salt: P21/n.The observation that the presence of more than one heterocyclic component in a molecule enhances the biological response and thermal stability encouraged us to synthesize several new carbon-bonded anionic sigma complexes from chloronitro-aromatic compounds and pyrimidine derivatives in the presence of pyridine bases (Babykala et al., 2014; Buvaneswari & Kalaivani, 2013; Mangaiyarkarasi & Kalaivani, 2013; Manickkam & Kalaivani, 2011, 2014; Sridevi & Kalaivani, 2012). Surprisingly, when we made an attempt to synthesize a similar type of complex from the electron-deficient chloronitroaromatic compound (picryl chloride), an imidazole derivative (hydantoin) and 3-methylpyridine, the title salt crystallized from the medium (ethanol) instead of the expected carbon-bonded anionic sigma complex.
The molecular structure of the title molecular salt is shown in Fig. 1. The anion and cation are linked via bifurcated N—H···(O,O) hydrogen bonds, enclosing an R21(6) graph-set motif (Fig. 1 and Table 1). In the picrate anion, the two nitro groups flanking the C—O- bond are oriented differently. Nitro group O1/N1/O2, involved in N—H···O hydrogen bonds as noted above, is inclined to the benzene ring by 6.7 (3)°, while nitro group O5/N3/O6 is inclined to the benzene ring by 70.07 (3)°, probably to alleviate steric crowding. The third nitro group (O3/N2/O4), para with respect to the C—O- bond, deviates only slightly from the benzene ring, making a dihedral angle of 6.6 (3)°.
In the crystal, the anionic and cationic hydrogen-bonded units are linked via C—H···O hydrogen bonds, forming a three-dimensional structure (Figs. 2 and 3, and Table 1). Within this framework there are slipped parallel π–π interactions present, involving inversion-related picrate anions [inter-centroid distance = 3.7389 (14) Å, inter-planar distance = 3.5829 (8) Å, slippage = 1.069 Å] and inversion-related pyridinium cations [inter-centroid distance = 3.560 (2) Å, inter-planar distance = 3.5548 (14) Å, slippage = 0.422 Å].
The anticonvulsant activity of synthesized 3-methylpyridinium picrate has been measured by employing the maximal electro shock (MES) method (Bhattacharya & Chakrabarti, 1998; Misra et al., 1973). Different stages of convulsion such as tonic flexion, tonic extensor, clonus convulsion, stupor and recovery/death have been examined. Though all phases are reduced, noticeable decrease is observed in the clonus phase and hence the title molecule may be a potent agent for controlling myoclonic type epilepsy in the future.
A search of the Cambridge Structural Database (Version 5.36, last update May 2015; Groom & Allen, 2014) yielded 40 hits for meta- or para-substituted pyridinium picrate salts. In the picrate anions, the average dihedral angle of the nitro group para to the C—O- bond with respect to the benzene ring is ca 6°, while for the two nitro groups on either side of the C—O- bond the dihedral angles are both ca 26–28°. In the title compound, the latter two dihedral angles are quite different being 6.7 (3) and 70.07 (3)°. In the monoclinic polymorph (UBEFEO; Stilinovic & Kaitner, 2011), these three dihedal angle are ca 3.60, 6.92 and 13.83°, respectively, and the cation and anion are also linked via bifurcated N—H···(O,O) hydrogen bonds.
Picryl chloride [2.56 g (0.01 mol)] was dissolved in 30 ml of rectified spirit and mixed with hydantoin [1.00 g (0.01 mol)] in 30 ml of rectified spirit. After mixing these solutions, 3 ml of 3-methylpyridine (0.03 mol) was added and the temperature of the mixture was raised to 313 K. At this temperature, the mixture was stirred for 5 to 6 h. The solution was then cooled to room temperature, filtered and the filtrate kept at 298 K. After a period of 4 weeks, dark shiny maroon-red–coloured crystals formed from the solution. The crystals were filtered, powdered and dried. The dry solid was washed with 50 ml of dry ether (5 ml for each aliquot) and recrystallized from rectified spirit (yield: 60 %; m.p.: 483 K).
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).Fig. 1. A view of the molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown as dashed lines (see Table 1). | |
Fig. 2. A view along the b axis of the crystal packing of the title molecular salt. Hydrogen bonds are shown as dashed lines (see Table 1), and H atoms not involved in these interactions have been omitted for clarity. | |
Fig. 3. A view along the a axis of the crystal packing of the title molecular salt. Hydrogen bonds are shown as dashed lines (see Table 1), and H atoms not involved in these interactions have been omitted for clarity. |
C6H8N+·C6H2N3O7− | Z = 2 |
Mr = 322.24 | F(000) = 332 |
Triclinic, P1 | Dx = 1.590 Mg m−3 |
a = 8.1224 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7016 (5) Å | Cell parameters from 5179 reflections |
c = 11.3161 (6) Å | θ = 2.7–26.9° |
α = 98.239 (3)° | µ = 0.13 mm−1 |
β = 100.318 (3)° | T = 293 K |
γ = 117.635 (3)° | Block, red |
V = 673.17 (7) Å3 | 0.35 × 0.30 × 0.25 mm |
Bruker Kappa APEXII CCD diffractometer | 2374 independent reflections |
Radiation source: fine-focus sealed tube | 1717 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω and φ scan | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −9→9 |
Tmin = 0.952, Tmax = 0.969 | k = −10→10 |
13299 measured reflections | l = −13→13 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.5934P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2374 reflections | Δρmax = 0.24 e Å−3 |
212 parameters | Δρmin = −0.25 e Å−3 |
C6H8N+·C6H2N3O7− | γ = 117.635 (3)° |
Mr = 322.24 | V = 673.17 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1224 (5) Å | Mo Kα radiation |
b = 8.7016 (5) Å | µ = 0.13 mm−1 |
c = 11.3161 (6) Å | T = 293 K |
α = 98.239 (3)° | 0.35 × 0.30 × 0.25 mm |
β = 100.318 (3)° |
Bruker Kappa APEXII CCD diffractometer | 2374 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1717 reflections with I > 2σ(I) |
Tmin = 0.952, Tmax = 0.969 | Rint = 0.029 |
13299 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.24 e Å−3 |
2374 reflections | Δρmin = −0.25 e Å−3 |
212 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6227 (3) | 0.5359 (3) | 0.3281 (2) | 0.0338 (5) | |
C2 | 0.8010 (3) | 0.6555 (3) | 0.4224 (2) | 0.0342 (5) | |
C3 | 0.8216 (3) | 0.7875 (3) | 0.5161 (2) | 0.0371 (6) | |
H3 | 0.9405 | 0.8616 | 0.5755 | 0.044* | |
C4 | 0.6675 (3) | 0.8101 (3) | 0.5224 (2) | 0.0356 (6) | |
C5 | 0.4892 (3) | 0.7045 (3) | 0.4328 (2) | 0.0352 (6) | |
H5 | 0.3854 | 0.7222 | 0.4356 | 0.042* | |
C6 | 0.4730 (3) | 0.5752 (3) | 0.3417 (2) | 0.0320 (5) | |
C7 | 0.7112 (4) | 0.0619 (4) | 0.1648 (3) | 0.0537 (7) | |
H7 | 0.6806 | 0.0272 | 0.2355 | 0.064* | |
C8 | 0.7330 (4) | −0.0490 (4) | 0.0772 (2) | 0.0441 (6) | |
C9 | 0.7774 (4) | 0.0108 (4) | −0.0253 (2) | 0.0460 (7) | |
H9 | 0.7911 | −0.0610 | −0.0875 | 0.055* | |
C10 | 0.8018 (4) | 0.1739 (4) | −0.0378 (3) | 0.0516 (7) | |
H10 | 0.8335 | 0.2132 | −0.1071 | 0.062* | |
C11 | 0.7792 (4) | 0.2771 (4) | 0.0525 (3) | 0.0530 (7) | |
H11 | 0.7960 | 0.3885 | 0.0460 | 0.064* | |
C12 | 0.7062 (5) | −0.2262 (4) | 0.0915 (3) | 0.0683 (9) | |
H12A | 0.7274 | −0.2835 | 0.0214 | 0.102* | |
H12B | 0.7972 | −0.2084 | 0.1665 | 0.102* | |
H12C | 0.5769 | −0.3007 | 0.0957 | 0.102* | |
N1 | 0.9729 (3) | 0.6445 (3) | 0.4219 (2) | 0.0495 (6) | |
N2 | 0.6903 (3) | 0.9444 (3) | 0.6245 (2) | 0.0461 (6) | |
N3 | 0.2906 (3) | 0.4686 (3) | 0.24334 (19) | 0.0398 (5) | |
N4 | 0.7332 (3) | 0.2180 (4) | 0.1493 (2) | 0.0549 (7) | |
O1 | 0.9718 (3) | 0.5443 (3) | 0.3360 (3) | 0.0885 (9) | |
O2 | 1.1190 (3) | 0.7419 (4) | 0.5074 (2) | 0.0792 (8) | |
O3 | 0.8528 (3) | 1.0446 (3) | 0.69676 (19) | 0.0630 (6) | |
O4 | 0.5489 (3) | 0.9540 (3) | 0.6359 (2) | 0.0670 (6) | |
O5 | 0.2505 (3) | 0.5433 (3) | 0.1711 (2) | 0.0799 (7) | |
O6 | 0.1909 (3) | 0.3122 (3) | 0.2365 (2) | 0.0673 (6) | |
O7 | 0.5902 (3) | 0.4101 (3) | 0.24116 (17) | 0.0518 (5) | |
H4A | 0.712 (6) | 0.291 (5) | 0.205 (4) | 0.093 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0374 (13) | 0.0393 (13) | 0.0313 (12) | 0.0242 (11) | 0.0115 (10) | 0.0080 (10) |
C2 | 0.0287 (12) | 0.0393 (13) | 0.0389 (13) | 0.0200 (10) | 0.0124 (10) | 0.0079 (10) |
C3 | 0.0301 (13) | 0.0386 (13) | 0.0358 (13) | 0.0136 (10) | 0.0085 (10) | 0.0050 (10) |
C4 | 0.0384 (14) | 0.0339 (12) | 0.0345 (12) | 0.0186 (11) | 0.0138 (11) | 0.0031 (10) |
C5 | 0.0361 (13) | 0.0396 (13) | 0.0381 (13) | 0.0246 (11) | 0.0141 (11) | 0.0084 (11) |
C6 | 0.0310 (12) | 0.0372 (12) | 0.0302 (12) | 0.0203 (10) | 0.0074 (10) | 0.0063 (10) |
C7 | 0.0408 (16) | 0.072 (2) | 0.0438 (15) | 0.0268 (14) | 0.0152 (12) | 0.0057 (14) |
C8 | 0.0328 (13) | 0.0488 (15) | 0.0427 (15) | 0.0188 (12) | 0.0067 (11) | 0.0002 (12) |
C9 | 0.0453 (15) | 0.0493 (15) | 0.0403 (14) | 0.0272 (13) | 0.0078 (12) | −0.0050 (12) |
C10 | 0.0584 (18) | 0.0547 (17) | 0.0434 (15) | 0.0330 (14) | 0.0112 (13) | 0.0048 (13) |
C11 | 0.0496 (17) | 0.0504 (16) | 0.0557 (18) | 0.0304 (14) | 0.0038 (14) | −0.0005 (14) |
C12 | 0.067 (2) | 0.062 (2) | 0.076 (2) | 0.0307 (17) | 0.0222 (18) | 0.0207 (17) |
N1 | 0.0350 (13) | 0.0548 (14) | 0.0596 (15) | 0.0254 (11) | 0.0136 (11) | 0.0064 (12) |
N2 | 0.0503 (14) | 0.0424 (12) | 0.0428 (12) | 0.0233 (11) | 0.0148 (11) | 0.0009 (10) |
N3 | 0.0386 (12) | 0.0480 (13) | 0.0360 (11) | 0.0269 (11) | 0.0076 (9) | 0.0048 (10) |
N4 | 0.0416 (13) | 0.0639 (16) | 0.0530 (15) | 0.0316 (12) | 0.0076 (11) | −0.0137 (13) |
O1 | 0.0459 (13) | 0.0855 (16) | 0.114 (2) | 0.0365 (12) | 0.0156 (13) | −0.0352 (15) |
O2 | 0.0415 (12) | 0.116 (2) | 0.0693 (15) | 0.0458 (13) | −0.0011 (11) | −0.0092 (14) |
O3 | 0.0572 (13) | 0.0555 (12) | 0.0524 (12) | 0.0195 (10) | 0.0083 (10) | −0.0134 (10) |
O4 | 0.0646 (14) | 0.0736 (14) | 0.0663 (14) | 0.0430 (12) | 0.0233 (11) | −0.0078 (11) |
O5 | 0.0700 (16) | 0.0835 (16) | 0.0718 (15) | 0.0343 (13) | −0.0089 (12) | 0.0310 (13) |
O6 | 0.0546 (13) | 0.0478 (13) | 0.0684 (14) | 0.0122 (10) | −0.0058 (10) | 0.0049 (10) |
O7 | 0.0504 (11) | 0.0585 (12) | 0.0472 (11) | 0.0367 (10) | 0.0068 (9) | −0.0093 (9) |
C1—O7 | 1.251 (3) | C9—C10 | 1.371 (4) |
C1—C2 | 1.432 (3) | C9—H9 | 0.9300 |
C1—C6 | 1.434 (3) | C10—C11 | 1.357 (4) |
C2—C3 | 1.372 (3) | C10—H10 | 0.9300 |
C2—N1 | 1.444 (3) | C11—N4 | 1.318 (4) |
C3—C4 | 1.366 (3) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—H12A | 0.9600 |
C4—C5 | 1.394 (3) | C12—H12B | 0.9600 |
C4—N2 | 1.439 (3) | C12—H12C | 0.9600 |
C5—C6 | 1.351 (3) | N1—O1 | 1.205 (3) |
C5—H5 | 0.9300 | N1—O2 | 1.218 (3) |
C6—N3 | 1.461 (3) | N2—O4 | 1.217 (3) |
C7—N4 | 1.326 (4) | N2—O3 | 1.230 (3) |
C7—C8 | 1.375 (4) | N3—O6 | 1.199 (3) |
C7—H7 | 0.9300 | N3—O5 | 1.205 (3) |
C8—C9 | 1.377 (4) | N4—H4A | 0.93 (4) |
C8—C12 | 1.491 (4) | ||
O7—C1—C2 | 127.4 (2) | C8—C9—H9 | 119.3 |
O7—C1—C6 | 120.7 (2) | C11—C10—C9 | 119.0 (3) |
C2—C1—C6 | 111.90 (19) | C11—C10—H10 | 120.5 |
C3—C2—C1 | 123.2 (2) | C9—C10—H10 | 120.5 |
C3—C2—N1 | 116.0 (2) | N4—C11—C10 | 119.4 (3) |
C1—C2—N1 | 120.8 (2) | N4—C11—H11 | 120.3 |
C4—C3—C2 | 120.0 (2) | C10—C11—H11 | 120.3 |
C4—C3—H3 | 120.0 | C8—C12—H12A | 109.5 |
C2—C3—H3 | 120.0 | C8—C12—H12B | 109.5 |
C3—C4—C5 | 121.2 (2) | H12A—C12—H12B | 109.5 |
C3—C4—N2 | 119.0 (2) | C8—C12—H12C | 109.5 |
C5—C4—N2 | 119.7 (2) | H12A—C12—H12C | 109.5 |
C6—C5—C4 | 117.4 (2) | H12B—C12—H12C | 109.5 |
C6—C5—H5 | 121.3 | O1—N1—O2 | 121.1 (2) |
C4—C5—H5 | 121.3 | O1—N1—C2 | 120.0 (2) |
C5—C6—C1 | 126.1 (2) | O2—N1—C2 | 118.8 (2) |
C5—C6—N3 | 118.5 (2) | O4—N2—O3 | 122.8 (2) |
C1—C6—N3 | 115.36 (19) | O4—N2—C4 | 119.0 (2) |
N4—C7—C8 | 120.7 (3) | O3—N2—C4 | 118.2 (2) |
N4—C7—H7 | 119.6 | O6—N3—O5 | 123.3 (2) |
C8—C7—H7 | 119.6 | O6—N3—C6 | 119.3 (2) |
C7—C8—C9 | 116.5 (3) | O5—N3—C6 | 117.4 (2) |
C7—C8—C12 | 121.8 (3) | C11—N4—C7 | 123.0 (2) |
C9—C8—C12 | 121.8 (2) | C11—N4—H4A | 115 (2) |
C10—C9—C8 | 121.5 (2) | C7—N4—H4A | 122 (2) |
C10—C9—H9 | 119.3 | ||
O7—C1—C2—C3 | −178.4 (2) | C7—C8—C9—C10 | 1.2 (4) |
C6—C1—C2—C3 | 1.9 (3) | C12—C8—C9—C10 | −180.0 (3) |
O7—C1—C2—N1 | 2.7 (4) | C8—C9—C10—C11 | −0.8 (4) |
C6—C1—C2—N1 | −177.0 (2) | C9—C10—C11—N4 | −0.4 (4) |
C1—C2—C3—C4 | −0.2 (4) | C3—C2—N1—O1 | −172.7 (3) |
N1—C2—C3—C4 | 178.7 (2) | C1—C2—N1—O1 | 6.3 (4) |
C2—C3—C4—C5 | −1.9 (4) | C3—C2—N1—O2 | 5.0 (4) |
C2—C3—C4—N2 | 177.4 (2) | C1—C2—N1—O2 | −176.0 (3) |
C3—C4—C5—C6 | 2.0 (4) | C3—C4—N2—O4 | −173.7 (2) |
N2—C4—C5—C6 | −177.3 (2) | C5—C4—N2—O4 | 5.6 (4) |
C4—C5—C6—C1 | 0.0 (4) | C3—C4—N2—O3 | 6.1 (4) |
C4—C5—C6—N3 | −177.0 (2) | C5—C4—N2—O3 | −174.6 (2) |
O7—C1—C6—C5 | 178.5 (2) | C5—C6—N3—O6 | −112.1 (3) |
C2—C1—C6—C5 | −1.8 (3) | C1—C6—N3—O6 | 70.5 (3) |
O7—C1—C6—N3 | −4.4 (3) | C5—C6—N3—O5 | 69.4 (3) |
C2—C1—C6—N3 | 175.3 (2) | C1—C6—N3—O5 | −108.0 (3) |
N4—C7—C8—C9 | −0.3 (4) | C10—C11—N4—C7 | 1.4 (4) |
N4—C7—C8—C12 | −179.1 (3) | C8—C7—N4—C11 | −1.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1 | 0.93 (4) | 2.27 (4) | 2.827 (4) | 118 (4) |
N4—H4A···O7 | 0.93 (4) | 1.79 (5) | 2.638 (4) | 152 (4) |
C5—H5···O2i | 0.93 | 2.51 | 3.406 (4) | 162 |
C10—H10···O3ii | 0.93 | 2.55 | 3.220 (4) | 129 |
C12—H12B···O3iii | 0.96 | 2.56 | 3.414 (5) | 149 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z−1; (iii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1 | 0.93 (4) | 2.27 (4) | 2.827 (4) | 118 (4) |
N4—H4A···O7 | 0.93 (4) | 1.79 (5) | 2.638 (4) | 152 (4) |
C5—H5···O2i | 0.93 | 2.51 | 3.406 (4) | 162 |
C10—H10···O3ii | 0.93 | 2.55 | 3.220 (4) | 129 |
C12—H12B···O3iii | 0.96 | 2.56 | 3.414 (5) | 149 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z−1; (iii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C6H8N+·C6H2N3O7− |
Mr | 322.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.1224 (5), 8.7016 (5), 11.3161 (6) |
α, β, γ (°) | 98.239 (3), 100.318 (3), 117.635 (3) |
V (Å3) | 673.17 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.952, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13299, 2374, 1717 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.131, 1.07 |
No. of reflections | 2374 |
No. of parameters | 212 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.25 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
Acknowledgements
The authors are thankful to the DST–SERB, New Delhi, for financial support and the SAIF, IIT Madras, Chennai, for the single crystal XRD data collection.
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