research communications
Supramolecular hydrogen-bonding patterns in the N(9)—H protonated and N(7)—H tautomeric form of an N6-benzoyladenine salt: N6-benzoyladeninium nitrate
aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620024, Tamilnadu, India, and bFaculty of Chemistry and Chemical Technology, University of Ljubljana, Vecna pot 113, PO Box 537, SI-1000 Ljubljana, Slovenia
*Correspondence e-mail: tommtrichy@yahoo.co.in
In the title molecular salt, C12H10N5O+·NO3−, the adenine unit has an N9-protonated N(7)—H tautomeric form with non-protonated N1 and N3 atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°. The typical intramolecular N7—H⋯O hydrogen bond with an S(7) graph-set motif is also present. The benzoyladeninium cations also form base pairs through N—H⋯O and C—H⋯N hydrogen bonds involving the Watson–Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supramolecular ribbon with R22(9) rings. Benzoyladeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N—H⋯O hydrogen bonds to generate a second ribbon motif. These ribbons together with π–π stacking interactions between the phenyl ring and the five- and six-membered adenine rings of adjacent molecules generate a three-dimensional supramolecular architecture.
Keywords: crystal structure; N6-benzoyl adenine; nitrate anion; hydrogen bonding; supramolecular architecture.
CCDC reference: 1444600
1. Chemical context
Non-covalent interactions, such as hydrogen bonding, halogen bonding and π–π interactions play major roles in molecular recognition and pharmaceutical drug design processes (Desiraju, 1989; Perumalla & Sun, 2014). N6-substituted adenine compounds continue to attract interest due to their biological activity as they can act as plant hormones and have anti-allergenic, antibacterial, antiviral and antifungal properties (Hall, 1973; McHugh & Erxleben, 2011). N6-substituted adenine compounds also exhibit an extensive variety of hydrogen-bonding patterns and supramolecular architectures (Raghunathan & Pattabhi, 1981; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; McHugh & Erxleben, 2011; Jennifer et al., 2014). The present investigation deals with the nitrate salt of N9-protonated benzoyladenine (I). Nitrate ions are known to play pivotal roles in hydrogen bonded supramolecular architectures, as they have three oxygen atoms to act as good hydrogen bond acceptors (Murugesan et al., 1997; Cherouana et al., 2003; Balasubramani et al., 2005; Nirmalram et al., 2011).
2. Structural commentary
The consists of one N6-benzoyladeninium cation and one nitrate anion, Fig. 1. In this salt, the N6-benzoyladenine moiety is found in the N(7)—H tautomeric form with N9 protonated and N1, N3 non-protonated. The internal angles at N7 [C8—N7—C5 = 108.9 (2)°] and N9 [C8—N9—C4 = 107.9 (2)°] are similar as both carry hydrogen atoms (Raghunathan & Pattabhi, 1981; Raghunathan et al., 1983; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; García-Terán et al., 2004; Bo et al., 2006). The internal angles at N1 [C6—N1—C2 = 118.9 (3)°] and N3 [C4—N3—C2 = 111.0 (3)°] agree with those reported for the neutral six-membered rings in other ademine structures (Raghunathan & Pattabhi, 1981; Karthikeyan et al., 2015). An intramolecular N7—H7⋯O1 hydrogen bond (Table 1) is observed on the Hoogsteen face of the purine ring with the benzoyl oxygen atom, generating an S(7) ring motif. A similar bond was found in the of the neutral N6-benzoyl adenine (Raghunathan & Pattabhi, 1981). The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°, and the C6—N6—C10—C11 torsion angle is −168.8 (2). The bond lengths and bond angles for the nitrate anion are in good agreement with literature values (Nirmalram et al., 2011). Tables comparing dihedral and torsion angles in the title compound with those in related structures appear in the supporting information.
of compound (I)3. Supramolecular features
In the , the benzoyladeninium cations form base pairs via N—H⋯O and C—H⋯N hydrogen bonds (Table 1) involving the N1 and N6 atoms on the Watson–Crick face of the adenine ring system and the C16 and O1 atoms of the benzoyl ring of an adjacent benzoyladeninium cation. These result in the formation of a supramolecular ribbon based on R22(9) rings, Fig. 2a. The benzoyladeninum cations are also bridged by the O3 oxygen atoms of the nitrate anion, which acts as a bifurcated acceptor, forming N9—H9⋯O3 and N7—H7⋯O3 hydrogen bonds to generate a second ribbon motif, Fig. 2b. π–π stacking interactions occur between the one face of the C11–C16 phenyl ring and the C4/C5/N7/C8/N9 imidazole ring with a relatively short centroid-to-centroid separation Cg1⋯Cg3i = 3.4919 (17) Å [symmetry code: (i) 1 − x, −y, − + z]. The other face of the phenyl ring makes offset π–π contacts with both the imidazole [Cg1⋯Cg3ii = 3.7213 (17) Å] and the pyrimidine rings [Cg2⋯Cg3ii = 3.5362 (16) Å; symmetry code (ii) + x, − y, z], Fig. 3. Cg1, Cg2 and Cg3 are the centroids of the imidazole, pyrimidine and phenyl rings, respectively. Similar contacts are found in related structures (Raghunathan & Pattabhi, 1981; Karthikeyan et al., 2015). These various contacts combine to generate a three-dimensional supramolecular architecture Fig. 4.
of (I)4. Database Survey
The crystal structures of a number of N6-substituted adenines, adeninium salts and their metal complexes have been investigated in a variety of crystalline environments. Neutral molecules include N6-benzyladenine (Raghunathan et al., 1983), N6-furfuryladenine (Soriano-Garcia & Parthasarathy, 1977) and N6-benzoyladenine (Raghunathan & Pattabhi, 1981). Recently our group reported the formation of two co-crystals, N6-benzoyladenine–3-hydroxypyridinium-2-carboxylate (1:1) and N6-benzoyladenine–DL-tartaric acid (1:1). In these, the benzoyladenine molecule has a conformation similar to that reported for the neutral benzoyladenine (Karthikeyan et al., 2015). N6-benzyladeninum salts with a wide variety of counter-anions have also been reported (Umadevi et al., 2001; Xia et al., 2010; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; McHugh & Erxleben, 2011; Stanley et al., 2003). A variety of metal complexes of neutral N6-benzyl/furfuryladenines have been reported (Jennifer et al., 2014), while structures of copper complexes of N6-furfuryladeninium (Umadevi et al., 2002) and N6-benzyladeninium (Balasubramanian et al., 1996) are also known.
5. Synthesis and crystallization
To a hot methanol solution of N6-benzolyadenine (60 mg), a few drops of nitric acid were added. The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week colourless prismatic crystals of (I) were obtained.
6. Refinement
Crystal data, data collection and structure . Hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N).
details are summarized in Table 2Supporting information
CCDC reference: 1444600
10.1107/S2056989015024871/sj5489sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015024871/sj5489Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015024871/sj5489Isup3.pdf
Supporting information file. DOI: 10.1107/S2056989015024871/sj5489Isup4.cml
Non-covalent interactions, such as hydrogen bonding, halogen bonding and π–π interactions play major roles in molecular recognition and pharmaceutical drug design processes (Desiraju, 1989; Perumalla & Sun, 2014). N6-substituted adenine compounds continue to attract interest due to their biological activity as they can act as plant hormones and have anti-allergenic, antibacterial, antiviral and antifungal properties (Hall, 1973; McHugh & Erxleben, 2011). N6-substituted adenine compounds also exhibit an extensive variety of hydrogen-bonding patterns and supramolecular architectures (Raghunathan & Pattabhi, 1981; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; McHugh & Erxleben, 2011; Jennifer et al., 2014). The present investigation deals with the nitrate salt of N9protonated benzoyladenine (I). Nitrate ions are known to play pivotal roles in hydrogen bonded supramolecular architectures, as they have three oxygen atoms to act as good hydrogen bond acceptors (Murugesan et al., 1997; Cherouana et al., 2003; Balasubramani et al., 2005; Nirmalram et al., 2011).
The
of compound (I) consists of one N6-benzoyladeninium cation and one nitrate anion, Fig. 1. In this salt, the N6-benzoyladenine moiety is found in the N7—H tautomeric form with N9 protonated and N1, N3 non-protonated. The internal angles at N7 [C8—N7—C5 = 108.9 (2)°] and N9 [C8—N9—C4 = 107.9 (2)°] are similar as both carry hydrogen atoms (Raghunathan & Pattabhi, 1981; Raghunathan et al., 1983; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; García-Terán et al., 2004; Bo et al.,2006). The internal angles at N1 [C6—N1—C2 = 118.9 (3)°] and N3 [C4—N3—C2 = 111.0 (3)°] agree with those reported for the neutral six-membered rings in other ademine structures (Raghunathan & Pattabhi, 1981; Karthikeyan et al., 2015). An intramolecular N7—H7···O1 hydrogen bond (Table 1) is observed on the Hoogsteen face of the purine ring with the benzoyl oxygen atom, generating an S(7) ring motif. A similar bond was found in the of the neutral N6-benzoyl adenine (Raghunathan & Pattabhi, 1981). The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°, and the C6—N6—C10—C11 torsion angle is is −168.8 (2). The bond lengths and bond angles for the nitrate anion are in good agreement with literature values (Nirmalram et al., 2011). Tables comparing dihedral and torsion angles in the title compound with those in related structures appear in the supporting information.In the π–π stacking interactions occur between the one face of the C11–C16 phenyl ring and the C4/C5/N7/C8/N9 imidazole ring with a relatively short centroid-to-centroid separation Cg1···Cg3i = 3.4919 (17) Å [symmetry code: (i) 1 − x, −y, −1/2 + z]. The other face of the phenyl ring makes offset π–π contacts with both the imidazole [Cg1···Cg3ii = 3.7213 (17) Å] and the pyrimidine rings [Cg2···Cg3ii = 3.5362 (16) Å; symmetry code (ii) 1/2 + x, 1/2 − y, z], Fig. 3. Cg1, Cg2 and Cg3 are the centroids of the imidazole, pyrimidine and phenyl rings, respectively. Similar contacts are found in related structures (Raghunathan & Pattabhi, 1981; Karthikeyan et al., 2015). These various contacts combine to generate a three-dimensional supramolecular architecture Fig. 4.
of (I), the benzoyladeninium cations form base pairs via N—H···O and C—H···N hydrogen bonds (Table 1) involving the N1 and N6 atoms on the Watson–Crick face of the adenine ring system and the C16 and O1 atoms of the benzoyl ring of an adjacent benzoyladeninium cation. These result in the formation of a supramolecular ribbon based on R22(9) rings, Fig. 2a. The benzoyladeninum cations are also bridged by the O3 oxygen atoms of the nitrate anion, which acts as a bifurcated acceptor, forming N9—H9···O3 and N7—H7···O3 hydrogen bonds to generate a second ribbon motif, Fig. 2b.The crystal structures of a number of N6-substituted adenines, adeninium salts and their metal complexes have been investigated in a variety of crystalline environments. Neutral molecules include N6-benzyladenine (Raghunathan et al., 1983), N6-furfuryladenine (Soriano-Garcia & Parthasarathy, 1977) and N6-benzoyladenine (Raghunathan & Pattabhi, 1981). Recently our group reported the formation of two co-crystals, N6-benzoyladenine–3-hydroxypyridinium-2-carboxylate (1:1) and N6-benzoyladenine–DL-tartaric acid (1:1). In these, the benzoyladenine molecule has a conformation similar to that reported for the neutral benzoyladenine
(Karthikeyan et al., 2015). N6-benzyladeninum salts with a wide variety of counter-anions have also been reported (Umadevi et al., 2001; Xia et al., 2010; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; McHugh & Erxleben, 2011; Stanley et al., 2003). A variety of metal complexes of neutral N6-benzyl/furfuryladenines have been reported (Jennifer et al., 2014), while structures of copper complexes of N6-furfuryladeninium (Umadevi et al., 2002) and N6-benzyladeninium (Balasubramanian et al., 1996) are also known.To a hot methanol solution of N6-benzolyadenine (60 mg), a few drops of nitric acid were added. The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week colourless prismatic crystals of (I) were obtained.
Crystal data, data collection and structure
details are summarized in Table 2. Hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N).Non-covalent interactions, such as hydrogen bonding, halogen bonding and π–π interactions play major roles in molecular recognition and pharmaceutical drug design processes (Desiraju, 1989; Perumalla & Sun, 2014). N6-substituted adenine compounds continue to attract interest due to their biological activity as they can act as plant hormones and have anti-allergenic, antibacterial, antiviral and antifungal properties (Hall, 1973; McHugh & Erxleben, 2011). N6-substituted adenine compounds also exhibit an extensive variety of hydrogen-bonding patterns and supramolecular architectures (Raghunathan & Pattabhi, 1981; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; McHugh & Erxleben, 2011; Jennifer et al., 2014). The present investigation deals with the nitrate salt of N9protonated benzoyladenine (I). Nitrate ions are known to play pivotal roles in hydrogen bonded supramolecular architectures, as they have three oxygen atoms to act as good hydrogen bond acceptors (Murugesan et al., 1997; Cherouana et al., 2003; Balasubramani et al., 2005; Nirmalram et al., 2011).
The
of compound (I) consists of one N6-benzoyladeninium cation and one nitrate anion, Fig. 1. In this salt, the N6-benzoyladenine moiety is found in the N7—H tautomeric form with N9 protonated and N1, N3 non-protonated. The internal angles at N7 [C8—N7—C5 = 108.9 (2)°] and N9 [C8—N9—C4 = 107.9 (2)°] are similar as both carry hydrogen atoms (Raghunathan & Pattabhi, 1981; Raghunathan et al., 1983; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; García-Terán et al., 2004; Bo et al.,2006). The internal angles at N1 [C6—N1—C2 = 118.9 (3)°] and N3 [C4—N3—C2 = 111.0 (3)°] agree with those reported for the neutral six-membered rings in other ademine structures (Raghunathan & Pattabhi, 1981; Karthikeyan et al., 2015). An intramolecular N7—H7···O1 hydrogen bond (Table 1) is observed on the Hoogsteen face of the purine ring with the benzoyl oxygen atom, generating an S(7) ring motif. A similar bond was found in the of the neutral N6-benzoyl adenine (Raghunathan & Pattabhi, 1981). The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°, and the C6—N6—C10—C11 torsion angle is is −168.8 (2). The bond lengths and bond angles for the nitrate anion are in good agreement with literature values (Nirmalram et al., 2011). Tables comparing dihedral and torsion angles in the title compound with those in related structures appear in the supporting information.In the π–π stacking interactions occur between the one face of the C11–C16 phenyl ring and the C4/C5/N7/C8/N9 imidazole ring with a relatively short centroid-to-centroid separation Cg1···Cg3i = 3.4919 (17) Å [symmetry code: (i) 1 − x, −y, −1/2 + z]. The other face of the phenyl ring makes offset π–π contacts with both the imidazole [Cg1···Cg3ii = 3.7213 (17) Å] and the pyrimidine rings [Cg2···Cg3ii = 3.5362 (16) Å; symmetry code (ii) 1/2 + x, 1/2 − y, z], Fig. 3. Cg1, Cg2 and Cg3 are the centroids of the imidazole, pyrimidine and phenyl rings, respectively. Similar contacts are found in related structures (Raghunathan & Pattabhi, 1981; Karthikeyan et al., 2015). These various contacts combine to generate a three-dimensional supramolecular architecture Fig. 4.
of (I), the benzoyladeninium cations form base pairs via N—H···O and C—H···N hydrogen bonds (Table 1) involving the N1 and N6 atoms on the Watson–Crick face of the adenine ring system and the C16 and O1 atoms of the benzoyl ring of an adjacent benzoyladeninium cation. These result in the formation of a supramolecular ribbon based on R22(9) rings, Fig. 2a. The benzoyladeninum cations are also bridged by the O3 oxygen atoms of the nitrate anion, which acts as a bifurcated acceptor, forming N9—H9···O3 and N7—H7···O3 hydrogen bonds to generate a second ribbon motif, Fig. 2b.The crystal structures of a number of N6-substituted adenines, adeninium salts and their metal complexes have been investigated in a variety of crystalline environments. Neutral molecules include N6-benzyladenine (Raghunathan et al., 1983), N6-furfuryladenine (Soriano-Garcia & Parthasarathy, 1977) and N6-benzoyladenine (Raghunathan & Pattabhi, 1981). Recently our group reported the formation of two co-crystals, N6-benzoyladenine–3-hydroxypyridinium-2-carboxylate (1:1) and N6-benzoyladenine–DL-tartaric acid (1:1). In these, the benzoyladenine molecule has a conformation similar to that reported for the neutral benzoyladenine
(Karthikeyan et al., 2015). N6-benzyladeninum salts with a wide variety of counter-anions have also been reported (Umadevi et al., 2001; Xia et al., 2010; Nirmalram et al., 2011; Tamilselvi & Muthiah, 2011; McHugh & Erxleben, 2011; Stanley et al., 2003). A variety of metal complexes of neutral N6-benzyl/furfuryladenines have been reported (Jennifer et al., 2014), while structures of copper complexes of N6-furfuryladeninium (Umadevi et al., 2002) and N6-benzyladeninium (Balasubramanian et al., 1996) are also known.To a hot methanol solution of N6-benzolyadenine (60 mg), a few drops of nitric acid were added. The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week colourless prismatic crystals of (I) were obtained.
detailsCrystal data, data collection and structure
details are summarized in Table 2. Hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N).Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SIR97 (Altomare, 1999); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009), Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).Fig. 1. The asymmetric unit of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines represent hydrogen bonds. | |
Fig. 2. A view of two supramolecular ribbons of (I). (a) A view of adeninium–benzoyl interactions via N—H···O and C—H···N hydrogen bonding, forming a supramolecular ribbon. (b) A view of adeninum cations bridged by one of the oxygen atoms of the nitrate anion via N9—H9···O3 and N7—H7···O3 hydrogen bonds (purple dashed lines), generating a second type of ribbon motif. The phenyl groups and H atoms not involved in hydrogen bonding have been omitted for clarity. The symmetry codes are as given in Table 1. | |
Fig. 3. A view of π–π stacking interactions in (I). Cg1 is the centroid of the imidazole ring, Cg2 that of the pyrimidine ring, Cg3 that of the phenyl ring. Dashed lines indicate stacking interactions. Symmetry codes: (i) 1 − x, −y, −1/2 + z; (ii) 1/2 + x, 1/2 − y, z. | |
Fig. 4. Overall packing in (I) viewed along the a-axis direction. Hydrogen bonds are drawn as light-blue dashed lines. |
C12H10N5O+·NO3− | Dx = 1.536 Mg m−3 |
Mr = 302.26 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1553 reflections |
a = 12.7949 (10) Å | θ = 3.7–27.6° |
b = 10.5639 (9) Å | µ = 0.12 mm−1 |
c = 9.6676 (6) Å | T = 293 K |
V = 1306.71 (17) Å3 | Prism, colorless |
Z = 4 | 0.33 × 0.30 × 0.20 mm |
F(000) = 624 |
Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer | 2080 reflections with I > 2σ(I) |
Detector resolution: 10.4933 pixels mm-1 | Rint = 0.021 |
ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | h = −16→11 |
Tmin = 0.791, Tmax = 1.000 | k = −13→9 |
4891 measured reflections | l = −12→12 |
2559 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0412P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.19 e Å−3 |
2559 reflections | Δρmin = −0.14 e Å−3 |
200 parameters | Extinction correction: SHELXL2014/7 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0092 (16) |
C12H10N5O+·NO3− | V = 1306.71 (17) Å3 |
Mr = 302.26 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.7949 (10) Å | µ = 0.12 mm−1 |
b = 10.5639 (9) Å | T = 293 K |
c = 9.6676 (6) Å | 0.33 × 0.30 × 0.20 mm |
Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer | 2559 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | 2080 reflections with I > 2σ(I) |
Tmin = 0.791, Tmax = 1.000 | Rint = 0.021 |
4891 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 1 restraint |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.19 e Å−3 |
2559 reflections | Δρmin = −0.14 e Å−3 |
200 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.7324 (2) | 0.0197 (2) | 0.8356 (3) | 0.0543 (7) | |
N3 | 0.8848 (2) | 0.0766 (2) | 0.7035 (3) | 0.0546 (7) | |
N6 | 0.56197 (18) | 0.0580 (2) | 0.7771 (2) | 0.0458 (6) | |
H6 | 0.5487 | 0.0479 | 0.8637 | 0.055* | |
N7 | 0.67166 (18) | 0.1685 (2) | 0.5004 (2) | 0.0437 (6) | |
H7 | 0.6070 | 0.1798 | 0.4795 | 0.052* | |
N9 | 0.84001 (19) | 0.1733 (2) | 0.4852 (2) | 0.0467 (6) | |
H9 | 0.9016 | 0.1874 | 0.4532 | 0.056* | |
O1 | 0.48787 (16) | 0.0648 (2) | 0.5649 (2) | 0.0540 (6) | |
C2 | 0.8360 (3) | 0.0298 (3) | 0.8128 (4) | 0.0591 (9) | |
H2 | 0.8789 | 0.0000 | 0.8833 | 0.071* | |
C4 | 0.8168 (2) | 0.1171 (2) | 0.6093 (3) | 0.0425 (7) | |
C5 | 0.7080 (2) | 0.1128 (2) | 0.6197 (3) | 0.0379 (6) | |
C6 | 0.6665 (2) | 0.0629 (2) | 0.7404 (3) | 0.0420 (7) | |
C8 | 0.7516 (2) | 0.2016 (3) | 0.4239 (3) | 0.0478 (7) | |
H8 | 0.7463 | 0.2400 | 0.3376 | 0.057* | |
C10 | 0.4770 (2) | 0.0675 (2) | 0.6908 (3) | 0.0405 (6) | |
C11 | 0.3735 (2) | 0.0836 (2) | 0.7561 (3) | 0.0406 (6) | |
C12 | 0.3614 (2) | 0.1411 (3) | 0.8840 (3) | 0.0471 (7) | |
H12 | 0.4197 | 0.1645 | 0.9354 | 0.056* | |
C13 | 0.2615 (3) | 0.1635 (3) | 0.9351 (3) | 0.0559 (8) | |
H13 | 0.2532 | 0.2035 | 1.0201 | 0.067* | |
C14 | 0.1755 (3) | 0.1272 (3) | 0.8610 (4) | 0.0580 (8) | |
H14 | 0.1090 | 0.1420 | 0.8963 | 0.070* | |
C15 | 0.1868 (3) | 0.0689 (3) | 0.7344 (4) | 0.0581 (9) | |
H15 | 0.1280 | 0.0437 | 0.6848 | 0.070* | |
C16 | 0.2852 (2) | 0.0480 (3) | 0.6814 (3) | 0.0483 (7) | |
H16 | 0.2928 | 0.0100 | 0.5952 | 0.058* | |
N10 | 0.5040 (2) | 0.2616 (3) | 0.2263 (3) | 0.0563 (7) | |
O2 | 0.5789 (2) | 0.2331 (3) | 0.1545 (3) | 0.0904 (9) | |
O3 | 0.51791 (16) | 0.2830 (2) | 0.3540 (2) | 0.0660 (7) | |
O4 | 0.4156 (2) | 0.2712 (3) | 0.1814 (3) | 0.0993 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0528 (16) | 0.0628 (16) | 0.0473 (14) | 0.0062 (12) | −0.0050 (13) | 0.0127 (14) |
N3 | 0.0460 (14) | 0.0608 (14) | 0.0571 (17) | 0.0070 (13) | −0.0043 (15) | 0.0027 (15) |
N6 | 0.0458 (13) | 0.0589 (14) | 0.0326 (12) | −0.0001 (11) | 0.0032 (12) | 0.0047 (11) |
N7 | 0.0400 (13) | 0.0536 (13) | 0.0375 (13) | −0.0021 (11) | 0.0002 (11) | 0.0048 (11) |
N9 | 0.0399 (13) | 0.0549 (13) | 0.0452 (14) | −0.0060 (11) | 0.0022 (12) | −0.0012 (12) |
O1 | 0.0503 (12) | 0.0780 (15) | 0.0338 (11) | −0.0144 (11) | 0.0053 (10) | −0.0019 (10) |
C2 | 0.055 (2) | 0.068 (2) | 0.054 (2) | 0.0108 (16) | −0.0108 (17) | 0.0123 (17) |
C4 | 0.0442 (15) | 0.0420 (13) | 0.0415 (16) | 0.0011 (13) | 0.0011 (14) | −0.0050 (14) |
C5 | 0.0403 (14) | 0.0390 (12) | 0.0344 (13) | 0.0004 (12) | 0.0004 (13) | −0.0039 (12) |
C6 | 0.0448 (14) | 0.0439 (14) | 0.0375 (15) | 0.0027 (12) | −0.0021 (15) | −0.0002 (13) |
C8 | 0.0484 (17) | 0.0536 (15) | 0.0412 (16) | −0.0086 (14) | 0.0019 (14) | 0.0024 (14) |
C10 | 0.0430 (15) | 0.0427 (14) | 0.0357 (15) | −0.0027 (12) | 0.0024 (13) | 0.0008 (13) |
C11 | 0.0443 (15) | 0.0428 (13) | 0.0347 (13) | −0.0008 (12) | 0.0049 (13) | 0.0066 (12) |
C12 | 0.0512 (16) | 0.0514 (15) | 0.0386 (15) | 0.0021 (14) | 0.0031 (15) | 0.0021 (14) |
C13 | 0.066 (2) | 0.0601 (18) | 0.0417 (17) | 0.0105 (17) | 0.0136 (16) | 0.0033 (16) |
C14 | 0.0522 (19) | 0.0625 (18) | 0.059 (2) | 0.0077 (16) | 0.0137 (18) | 0.0131 (18) |
C15 | 0.0493 (18) | 0.0646 (18) | 0.060 (2) | −0.0075 (16) | 0.0022 (18) | 0.0105 (18) |
C16 | 0.0494 (18) | 0.0532 (15) | 0.0425 (15) | −0.0033 (14) | 0.0018 (16) | 0.0036 (15) |
N10 | 0.0528 (17) | 0.0612 (15) | 0.0549 (16) | 0.0087 (14) | 0.0073 (15) | 0.0001 (13) |
O2 | 0.0774 (17) | 0.1083 (19) | 0.086 (2) | 0.0132 (16) | 0.0372 (16) | −0.0060 (17) |
O3 | 0.0484 (13) | 0.1011 (18) | 0.0485 (13) | 0.0120 (12) | −0.0007 (11) | 0.0072 (14) |
O4 | 0.0652 (16) | 0.159 (3) | 0.0738 (18) | 0.0326 (19) | −0.0219 (15) | −0.0447 (19) |
N1—C6 | 1.330 (4) | C8—H8 | 0.9300 |
N1—C2 | 1.347 (4) | C10—C11 | 1.477 (4) |
N3—C2 | 1.323 (4) | C11—C12 | 1.386 (4) |
N3—C4 | 1.330 (4) | C11—C16 | 1.393 (4) |
N6—C10 | 1.374 (4) | C12—C13 | 1.390 (4) |
N6—C6 | 1.384 (4) | C12—H12 | 0.9300 |
N6—H6 | 0.8600 | C13—C14 | 1.367 (5) |
N7—C8 | 1.309 (3) | C13—H13 | 0.9300 |
N7—C5 | 1.376 (3) | C14—C15 | 1.378 (5) |
N7—H7 | 0.8600 | C14—H14 | 0.9300 |
N9—C8 | 1.312 (4) | C15—C16 | 1.378 (4) |
N9—C4 | 1.371 (4) | C15—H15 | 0.9300 |
N9—H9 | 0.8600 | C16—H16 | 0.9300 |
O1—C10 | 1.226 (3) | N10—O4 | 1.216 (3) |
C2—H2 | 0.9300 | N10—O2 | 1.222 (3) |
C4—C5 | 1.397 (4) | N10—O3 | 1.268 (4) |
C5—C6 | 1.386 (4) | ||
C6—N1—C2 | 118.9 (3) | N9—C8—H8 | 124.5 |
C2—N3—C4 | 111.0 (3) | O1—C10—N6 | 120.8 (3) |
C10—N6—C6 | 127.3 (2) | O1—C10—C11 | 121.9 (3) |
C10—N6—H6 | 116.4 | N6—C10—C11 | 117.3 (2) |
C6—N6—H6 | 116.4 | C12—C11—C16 | 119.3 (3) |
C8—N7—C5 | 108.9 (2) | C12—C11—C10 | 122.2 (3) |
C8—N7—H7 | 125.6 | C16—C11—C10 | 118.3 (3) |
C5—N7—H7 | 125.6 | C11—C12—C13 | 119.6 (3) |
C8—N9—C4 | 107.9 (3) | C11—C12—H12 | 120.2 |
C8—N9—H9 | 126.0 | C13—C12—H12 | 120.2 |
C4—N9—H9 | 126.0 | C14—C13—C12 | 120.4 (3) |
N3—C2—N1 | 128.6 (3) | C14—C13—H13 | 119.8 |
N3—C2—H2 | 115.7 | C12—C13—H13 | 119.8 |
N1—C2—H2 | 115.7 | C13—C14—C15 | 120.4 (3) |
N3—C4—N9 | 126.7 (3) | C13—C14—H14 | 119.8 |
N3—C4—C5 | 126.3 (3) | C15—C14—H14 | 119.8 |
N9—C4—C5 | 107.0 (2) | C16—C15—C14 | 119.8 (3) |
N7—C5—C6 | 137.6 (3) | C16—C15—H15 | 120.1 |
N7—C5—C4 | 105.2 (2) | C14—C15—H15 | 120.1 |
C6—C5—C4 | 117.1 (3) | C15—C16—C11 | 120.4 (3) |
N1—C6—N6 | 115.0 (2) | C15—C16—H16 | 119.8 |
N1—C6—C5 | 118.0 (2) | C11—C16—H16 | 119.8 |
N6—C6—C5 | 126.9 (3) | O4—N10—O2 | 123.2 (3) |
N7—C8—N9 | 110.9 (3) | O4—N10—O3 | 117.6 (3) |
N7—C8—H8 | 124.5 | O2—N10—O3 | 119.1 (3) |
C4—N3—C2—N1 | 0.3 (5) | N7—C5—C6—N6 | −1.3 (5) |
C6—N1—C2—N3 | −1.4 (5) | C4—C5—C6—N6 | 174.9 (3) |
C2—N3—C4—N9 | 178.5 (3) | C5—N7—C8—N9 | −0.9 (3) |
C2—N3—C4—C5 | −0.1 (4) | C4—N9—C8—N7 | 0.5 (3) |
C8—N9—C4—N3 | −178.7 (3) | C6—N6—C10—O1 | 9.9 (4) |
C8—N9—C4—C5 | 0.1 (3) | C6—N6—C10—C11 | −168.8 (2) |
C8—N7—C5—C6 | 177.4 (3) | O1—C10—C11—C12 | −150.8 (3) |
C8—N7—C5—C4 | 1.0 (3) | N6—C10—C11—C12 | 27.9 (4) |
N3—C4—C5—N7 | 178.2 (3) | O1—C10—C11—C16 | 24.4 (4) |
N9—C4—C5—N7 | −0.6 (3) | N6—C10—C11—C16 | −156.9 (2) |
N3—C4—C5—C6 | 0.9 (4) | C16—C11—C12—C13 | −0.7 (4) |
N9—C4—C5—C6 | −178.0 (2) | C10—C11—C12—C13 | 174.5 (3) |
C2—N1—C6—N6 | −175.0 (3) | C11—C12—C13—C14 | 1.2 (4) |
C2—N1—C6—C5 | 2.1 (4) | C12—C13—C14—C15 | −0.5 (5) |
C10—N6—C6—N1 | −163.5 (2) | C13—C14—C15—C16 | −0.6 (4) |
C10—N6—C6—C5 | 19.7 (4) | C14—C15—C16—C11 | 1.1 (4) |
N7—C5—C6—N1 | −178.0 (3) | C12—C11—C16—C15 | −0.4 (4) |
C4—C5—C6—N1 | −1.9 (4) | C10—C11—C16—C15 | −175.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···O1i | 0.86 | 2.33 | 3.135 (3) | 156 |
N7—H7···O1 | 0.86 | 2.12 | 2.668 (3) | 121 |
N7—H7···O3 | 0.86 | 1.99 | 2.709 (3) | 140 |
N9—H9···O3ii | 0.86 | 1.80 | 2.646 (3) | 169 |
C16—H16···N1iii | 0.93 | 2.55 | 3.426 (4) | 157 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) x+1/2, −y+1/2, z; (iii) −x+1, −y, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···O1i | 0.86 | 2.33 | 3.135 (3) | 156 |
N7—H7···O1 | 0.86 | 2.12 | 2.668 (3) | 121 |
N7—H7···O3 | 0.86 | 1.99 | 2.709 (3) | 140 |
N9—H9···O3ii | 0.86 | 1.80 | 2.646 (3) | 169 |
C16—H16···N1iii | 0.93 | 2.55 | 3.426 (4) | 157 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) x+1/2, −y+1/2, z; (iii) −x+1, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H10N5O+·NO3− |
Mr | 302.26 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 293 |
a, b, c (Å) | 12.7949 (10), 10.5639 (9), 9.6676 (6) |
V (Å3) | 1306.71 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.33 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Agilent SuperNova, Dual, Cu at zero, Atlas |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2013) |
Tmin, Tmax | 0.791, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4891, 2559, 2080 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.10 |
No. of reflections | 2559 |
No. of parameters | 200 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.14 |
Computer programs: CrysAlis PRO (Agilent, 2013), SIR97 (Altomare, 1999), SHELXL2014/7 (Sheldrick, 2015), PLATON (Spek, 2009), Mercury (Macrae et al., 2008).
Acknowledgements
AK and NJJ thank the UGC–SAP and UGC–BSR India for the award of an RFSMS. PTM is thankful to the UGC, New Delhi, for a UGC–BSR one-time grant to Faculty. FP thanks the Slovenian Research Agency for financial support (P1–0230–0175), as well as the EN–FIST Centre of Excellence, Trg Osvobodilne fronte 13, 1000 Ljubljana, Slovenia, for use of the SuperNova diffractometer.
References
Agilent (2013). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England. Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Balasubramani, K., Muthiah, P. T., Rychlewska, U. & Plutecka, A. (2005). Acta Cryst. C61, o586–o588. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Balasubramanian, T., Muthiah, P. T., Ananthasaravanan, & Mazumdar, S. K. (1996). J. Inorg. Biochem. 63, 175–181. Google Scholar
Bo, Y., Cheng, K., Bi, S. & Zhang, S.-S. (2006). Acta Cryst. E62, o4174–o4175. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cherouana, A., Bouchouit, K., Bendjeddou, L. & Benali-Cherif, N. (2003). Acta Cryst. E59, o983–o985. Web of Science CSD CrossRef IUCr Journals Google Scholar
Desiraju, G. R. (1989). Crystal engineering: the design of organic solids. Amsterdam: Elsevier. Google Scholar
García-Terán, J. P., Castillo, O., Luque, A., García-Couceiro, U., Román, P. & Lloret, F. (2004). Inorg. Chem. 43, 5761–5770. Web of Science PubMed Google Scholar
Hall, R. H. (1973). Annu. Rev. Plant Physiol. 24, 415–444. CrossRef CAS Web of Science Google Scholar
Jennifer, S. J., Thomas Muthiah, P. & Tamilselvi, D. (2014). Chem. Cent. J. 8, 58. Web of Science CSD CrossRef PubMed Google Scholar
Karthikeyan, A., Swinton Darious, R., Thomas Muthiah, P. & Perdih, F. (2015). Acta Cryst. C71, 985–990. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
McHugh, C. & Erxleben, A. (2011). Cryst. Growth Des. 11, 5096–5104. Web of Science CSD CrossRef CAS Google Scholar
Murugesan, S. & Muthiah, P. T. (1997). Acta Cryst. C53, 763–764. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Nirmalram, J. S., Tamilselvi, D. & Muthiah, P. T. (2011). J. Chem. Crystallogr. 41, 864–867. Web of Science CSD CrossRef CAS Google Scholar
Perumalla, S. R. & Sun, C. C. (2014). J. Pharm. Sci. 103, 1126–1132. Web of Science CrossRef CAS PubMed Google Scholar
Raghunathan, S. & Pattabhi, V. (1981). Acta Cryst. B37, 1670–1673. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Raghunathan, S., Sinha, B. K., Pattabhi, V. & Gabe, E. J. (1983). Acta Cryst. C39, 1545–1547. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Soriano-Garcia, M. & Parthasarathy, R. (1977). Acta Cryst. B33, 2674–2677. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stanley, N., Muthiah, P. T. & Geib, S. J. (2003). Acta Cryst. C59, o27–o29. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Tamilselvi, D. & Muthiah, P. T. (2011). Acta Cryst. C67, o192–o194. Web of Science CSD CrossRef IUCr Journals Google Scholar
Umadevi, B., Stanley, N., Muthiah, P. T., Bocelli, G. & Cantoni, A. (2001). Acta Cryst. E57, o881–o883. Web of Science CSD CrossRef IUCr Journals Google Scholar
Umadevi, B., Stanley, N., Muthiah, P. T. & Varghese, B. (2002). Indian J. Chem. A41, 737–740. Google Scholar
Xia, M., Ma, K. & Zhu, Y. (2010). J. Chem. Crystallogr. 40, 634–638. Web of Science CSD CrossRef CAS 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.