Supra­molecular hydrogen-bonding patterns in the N(9)—H protonated and N(7)—H tautomeric form of an N6-benzoyl­adenine salt: N6-benzoyl­adeninium nitrate

Karthikeyan, A.; Jeeva Jasmine, N.; Thomas Muthiah, P.; Perdih, F.

doi:10.1107/S2056989015024871

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 140-143

doi:10.1107/S2056989015024871

Open

access

Supramolecular hydrogen-bonding patterns in the N(9)—H protonated and N(7)—H tautomeric form of an N⁶-benzoyladenine salt: N⁶-benzoyladeninium nitrate

Ammasai Karthikeyan,^a Nithianantham Jeeva Jasmine,^a Packianathan Thomas Muthiah ^a ^* and Franc Perdih ^b

^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

Edited by J. Simpson, University of Otago, New Zealand (Received 9 December 2015; accepted 29 December 2015; online 9 January 2016)

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 asymmetric unit 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 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 crystal structure 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.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+1, -y, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iii) $[-x+1, -y, z-{\script{1\over 2}}]$ .

Figure 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.

3. Supramolecular features

In the crystal structure 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. 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, − $[{1\over 2}]$ + 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) $[{1\over 2}]$ + x, $[{1\over 2}]$ − 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.

Figure 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

Figure 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, − $[{1\over 2}]$ + z; (ii) $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, z.

Figure 4
Overall packing in (I)

viewed along the a-axis direction. Hydrogen bonds are drawn as light-blue dashed lines.

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 crystal structure (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 refinement 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 U_iso(H) = 1.2U_eq(C, N).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₅O⁺·NO₃⁻
M_r	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 )
T_min, T_max	0.791, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4891, 2559, 2080
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14
Computer programs: CrysAlis PRO (Agilent, 2013), SIR97 (Altomare, 1999 ), SHELXL2014/7 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1444600

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015024871/sj5489sup1.cif

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

checkCIF report

Chemical context top

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).

Structural commentary top

The asymmetric unit 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 crystal structure 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.

Supramolecular features top

In the crystal structure 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. 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.

Database Survey top

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 crystal structure (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.

Synthesis and crystallization top

Refinement top

Structure description top

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 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 crystal structure (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.

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: 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).

Figures top

	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.

N⁶-benzoyladeninium nitrate top

Crystal data top

C₁₂H₁₀N₅O⁺·NO₃⁻	D_x = 1.536 Mg m⁻³
M_r = 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

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	2080 reflections with I > 2σ(I)
Detector resolution: 10.4933 pixels mm^-1	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −16→11
T_min = 0.791, T_max = 1.000	k = −13→9
4891 measured reflections	l = −12→12
2559 independent reflections

Refinement top

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(F_o²) + (0.0412P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.19 e Å⁻³
2559 reflections	Δρ_min = −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)

Crystal data top

C₁₂H₁₀N₅O⁺·NO₃⁻	V = 1306.71 (17) Å³
M_r = 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

Data collection top

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)
T_min = 0.791, T_max = 1.000	R_int = 0.021
4891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.097	H-atom parameters constrained
S = 1.10	Δρ_max = 0.19 e Å⁻³
2559 reflections	Δρ_min = −0.14 e Å⁻³
200 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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⁻
M_r	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)
T_min, T_max	0.791, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4891, 2559, 2080
R_int	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
Δρ_max, Δρ_min (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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 140-143

doi:10.1107/S2056989015024871

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)