Supra­molecular hydrogen-bonding patterns in a 1:1 co-crystal of the N(7)—H tautomeric form of N6-benzoyl­adenine with 4-hy­droxy­benzoic acid

Swinton Darious, R.; Thomas Muthiah, P.; Perdih, F.

doi:10.1107/S2056989017002171

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ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 383-386

https://doi.org/10.1107/S2056989017002171

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Supramolecular hydrogen-bonding patterns in a 1:1 co-crystal of the N(7)—H tautomeric form of N⁶-benzoyladenine with 4-hydroxybenzoic acid

Robert Swinton Darious,^a Packianathan Thomas Muthiah ^a ^* and Franc Perdih ^b

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India, and ^bFaculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, PO Box 537, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: tommtrichy@yahoo.co.in

Edited by P. C. Healy, Griffith University, Australia (Received 7 February 2017; accepted 9 February 2017; online 17 February 2017)

The asymmetric unit of the title co-crystal, C₁₂H₉N₅O·C₇H₆O₃, contains one molecule of N⁶-benzoyladenine (BA) and one molecule of 4-hydroxybenzoic acid (HBA). The N⁶-benzoyladenine (BA) has an N(7)—H tautomeric form with nonprotonated N-1 and N-3 atoms. This tautomeric form is stabilized by a typical intramolecular N—H⋯O hydrogen bond between the carbonyl (C=O) group and the N(7)—H hydrogen on the Hoogsteen face of the purine ring, forming a graph-set S(7) ring motif. The primary robust R₂²(8) ring motif is formed in the Watson–Crick face via N—H⋯O and O—H⋯N hydrogen bonds (involving N1, N6—H and the carboxyl group of HBA). Weak interactions, such as, C—H⋯π and π–π are also observed in this crystal structure.

Keywords: crystal structure; hydrogen bond; dihedral angle; coplanar; supramolecular interaction.

CCDC reference: 1531929

1. Chemical context

Adenine is one of the major nucleobases and some of its N⁶-derivatives have plant hormone (kinetin) (Tr). They also offer a variety of hydrogen-bonding donor and acceptor sites (McHugh & Erxleben, 2011 ; Imaz et al., 2011 ). 4-Hydroxybenzoic acid is also a promising hydrogen-bond donor with the ability to form co-crystals with other organic molecules (Vishweshwar et al., 2003 ). It is used as an antimicrobial paraben (Barker & Frost, 2001 ). The present study investigates co-crystal formation between N⁶- benzoyladenine and 4-hydroxybenzoic acid.

2. Structural commentary

In the title co-crystal (I), the asymmetric unit contains one N⁶-benzoyladenine (BA) molecule and one 4-hydroxybenzoic acid (HBA) molecule (Fig. 1). The bond angle at N7 [C8—N7—C5 = 106.93 (17)°] is wider than at N9 [C8—N9—C4 = 104.19 (16)°]. In addition, the C8—N7 bond [1.343 (2)Å] is longer than C8—N9 [1.319 (3) Å]. These values agree with those reported earlier for the crystal structure of N⁶-benzoyladenine (Raghunathan & Pattabhi, 1981 ). In the title co-crystal, the N⁶-benzoyladenine also exists in the N(7)—H tautomeric form with non-protonated N1, N3 and N9 atoms. In the crystal structures of N⁶-benzoyladenine (Raghunathan & Pattabhi, 1981), N⁶-benzoyladenine-3-hydroxypyridinium-2-carboxylate (1:1) and N⁶-benzoyl adenine-DL-tartaric acid (1:1) (Karthikeyan et al., 2015 ), N⁶-benzoyladeninium nitrate (1:1) (Karthikeyan et al., 2016 ), N⁶-benzoyl adenine–adipic acid (1:0.5) (Swinton Darious et al., 2016 ) and the title compound (I), the N⁶-substituent is distal to the N1 and syn to the adenine nitrogen atom N7. This may be due to the participation of the N7 atom in N7—H7⋯O1A intramolecular hydrogen bond (Table 1) with an S(7) ring motif in the Hoogsteen face. In contrast, it may be noted that in the crystal structure of N⁶-benzyladenine, (where no intramolecular hydrogen bond is present) the N⁶-substituent is syn to N1 and distal to N7 and the adenine moiety exists in the N(9)—H tautomeric form (Raghunathan et al., 1983 ). The dihedral angle between the benzene ring and the carboxyl group of HBA is 1.5 (3)°, indicating that the benzene ring and the carboxyl group are nearly coplanar. A comparison of dihedral angles and the C6—N6—C10—C11 torsion angle reported for various N⁶-benzoyladenine-containing crystal structures is given in Table 2.

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C11–C16 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1	0.82	1.92	2.737 (2)	172
O4—H4⋯N9ⁱ	0.82	1.98	2.784 (2)	168
N6—H6⋯O3	0.86	1.94	2.778 (2)	166
N7—H7⋯O1	0.86	2.14	2.726 (2)	126
N7—H7⋯O1ⁱⁱ	0.86	2.36	3.164 (2)	155
C8—H8⋯Cg3ⁱⁱ	0.93	2.77	3.646 (2)	157
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+2, -z+1.

Table 2
Comparison of dihedral angles and torsion angles (°) for various N⁶-benzoyladenine-containing crystal structures

Pyrimidine ring: N1/C2/N3/C4–C6; imidazole ring of adenine: C4/C5/N7/C8/N9; purine ring system: N1/C2/N3/C4–C6/N7/C8/N9; benzene ring: C11–C16; amide: N6/H6/C10/O1.

Compound	pyrimidine/imidazole	purine/benzene	purine/amide	benzene/amide	C6—N6—C10—C11
N⁶-benzoyladenine–DL-tartaric acid^a	2.26 (10)	9.77 (8)	2.93 (18)	11.35 (9)	−179.08 (17)
N⁶-benzoyladenine–3-hydroxypridinium-2-carboxylate^a	3.00 (9)	0.94 (8)	21.20 (17)	21.45 (18)	−176.24 (16)
N⁶-benzoyladeninium nitrate^b	1.34 (14)	52.25 (12)	23.7 (2)	29.2 (2)	−168.8 (2)
N⁶-benzoyladenine–adipic acid^c	0.33 (8)	26.71 (7)	10.8 (7)	23.0 (7)	173.08 (14)
N⁶-benzoyladenine–4-hydroxybenzoic acid^d	0.24 (12)	70.80 (11)	11.71 (19)	59.4 (2)	−177.91 (18)
References: (a) Karthikeyan et al. (2015); (b) Karthikeyan et al. (2016); (c) Swinton Darious et al. (2016); (d) this study.

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

The robust $[R_{2}^{2}]$ (8) ring motif is formed in the Watson–Crick face (N1 and N6 atoms) via N—H⋯O and O—H⋯N hydrogen bonds involving the carboxyl group of HBA. The N7 atom is a bifurcated donor and the carbonyl oxygen atom acts as a double acceptor for the N—H⋯O hydrogen bonds. Inversion-related BA molecules form dimers through an array of hydrogen bonds, generating ring motifs, and these dimers are doubly bridged by inversion-related HBA molecules (Fig. 2). A large R₆⁶(32) supramolecular ring is formed along the c-axis direction. A weak C8—H8⋯π interaction is also present. Further consolidation of the structure is provided by homo and hetero π–π stacking interactions [Cg1⋯Cg5( $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z) = 3.5580 (13) Å, Cg2⋯Cg5( $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z) = 3.6508 (12) Å; Cg1, Cg2 and Cg5 are the centroids of the imidazole ring, the pyrimidine ring and the benzene ring of HBA, respectively] (Fig. 3).

Figure 2
The formation of a supramolecular three-dimensional large ring structure in the title compound.

Figure 3
A view of the homo/hetero-stacking interactions in the title compound.

4. Database survey

The neutral molecule N⁶-benzoyladenine was first reported by Raghunathan & Pattabhi (1981). Various salts and co-crystals of N⁶-benzoyladenine have also been reported: N⁶-benzoyladenine–3-hydroxypyridinium-2-carboxylate (1:1) and N⁶-benzoyladenine–DL-tartaric acid (1:1) (Karthikeyan et al., 2015), N⁶-benzoyladeninium nitrate (1:1) (Karthikeyan et al., 2015), N⁶-benzoyladenine–adipic acid (1:0.5) (Swinton Darious et al., 2016). Similarly, various co-crystals of HBA have been reported: 2-amino-4,6-dimethylpyrimidine–4-hydroxybenzoic acid (Balasubramani et al., 2006 ), 4-hydroxybenzoic acid–1H-imidazole (Wang et al., 2009 ), 2-amino-5-bromopyridine–4-hydroxybenzoic acid (Quah et al., 2010 ) and 4,6-dimethoxy-2-(methylsulfanyl)-pyrimidine–4-hydroxybenzoic acid (Thanigaimani et al., 2012 ).

5. Synthesis and crystallization

The title co-crystal was prepared by mixing a hot ethanol solution of N⁶-benzoyladenine (30 mg) and 4-hydroxybenzoic acid (35 mg) in an equimolar ratio in a total volume of 30 mL. The mixture was warmed over a water bath for 30 min, filtered, and left aside for a few days. Colourless plate-shaped crystals were collected from the mother solution following slow cooling at room temperature.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. 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, N—H = 0.86 and O—H = 0.82 Å, and with U_iso(H) = kU_eq(C,N,O), where k = 1.5 for hydroxy and 1.2 for all other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₂H₉N₅O·C₇H₆O₃
M_r	377.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.7579 (5), 6.7930 (3), 17.2873 (5)
β (°)	91.287 (3)
V (Å³)	1732.62 (11)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.88
Crystal size (mm)	0.20 × 0.15 × 0.03

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.597, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6790, 3284, 2457
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.161, 1.02
No. of reflections	3284
No. of parameters	256
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.30
Computer programs: CrysAlis PRO (Agilent, 2013), SUPERFLIP (Palatinus & Chapuis, 2007 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1531929

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002171/hg5481sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002171/hg5481Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017002171/hg5481Isup3.cml

checkCIF report

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: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

N⁶-Benzoyladenine–4-hydroxybenzoic acid (1/1) top

Crystal data top

C₁₂H₉N₅O·C₇H₆O₃	F(000) = 784
M_r = 377.36	D_x = 1.447 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 14.7579 (5) Å	Cell parameters from 2120 reflections
b = 6.7930 (3) Å	θ = 3.9–74.6°
c = 17.2873 (5) Å	µ = 0.88 mm⁻¹
β = 91.287 (3)°	T = 293 K
V = 1732.62 (11) Å³	Plate, colorless
Z = 4	0.20 × 0.15 × 0.03 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	3284 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2457 reflections with I > 2σ(I)
Detector resolution: 10.4933 pixels mm^-1	R_int = 0.028
ω scans	θ_max = 70.1°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −12→17
T_min = 0.597, T_max = 1.000	k = −8→7
6790 measured reflections	l = −19→21

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.053	w = 1/[σ²(F_o²) + (0.0934P)² + 0.2078P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.161	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.44 e Å⁻³
3284 reflections	Δρ_min = −0.30 e Å⁻³
256 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0007 (2)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.42682 (11)	1.0650 (3)	0.54392 (9)	0.0705 (6)
N1	0.39444 (11)	0.9505 (3)	0.78054 (9)	0.0441 (4)
N3	0.54449 (12)	0.9582 (3)	0.83693 (10)	0.0507 (5)
N6	0.35504 (10)	0.9706 (2)	0.65248 (9)	0.0398 (4)
H6	0.3024	0.9381	0.6686	0.048*
N7	0.57481 (11)	0.9980 (3)	0.63742 (10)	0.0428 (4)
H7	0.5598	1.0053	0.5892	0.051*
N9	0.66312 (11)	0.9887 (3)	0.74394 (11)	0.0466 (4)
C2	0.45586 (14)	0.9466 (4)	0.84004 (12)	0.0522 (6)
H2	0.4322	0.9340	0.8892	0.063*
C4	0.57400 (13)	0.9747 (3)	0.76459 (12)	0.0402 (4)
C6	0.42445 (13)	0.9683 (3)	0.70853 (11)	0.0362 (4)
C5	0.51711 (12)	0.9806 (3)	0.69794 (11)	0.0357 (4)
C8	0.65938 (13)	1.0017 (3)	0.66780 (13)	0.0473 (5)
H8	0.7107	1.0125	0.6378	0.057*
C10	0.35828 (13)	1.0163 (3)	0.57653 (12)	0.0430 (5)
C11	0.26848 (13)	1.0088 (3)	0.53510 (11)	0.0448 (5)
C12	0.21996 (19)	0.8373 (5)	0.53086 (16)	0.0774 (8)
H12	0.2415	0.7252	0.5561	0.093*
C13	0.1393 (2)	0.8303 (7)	0.4892 (2)	0.1083 (14)
H13	0.1075	0.7124	0.4847	0.130*
C14	0.1062 (2)	0.9956 (7)	0.45466 (18)	0.0950 (13)
H14	0.0510	0.9908	0.4277	0.114*
C15	0.15326 (18)	1.1700 (6)	0.45909 (15)	0.0828 (10)
H15	0.1297	1.2828	0.4356	0.099*
C16	0.23613 (16)	1.1771 (4)	0.49876 (14)	0.0621 (6)
H16	0.2694	1.2933	0.5009	0.075*
O2	0.22103 (10)	0.9691 (3)	0.83296 (9)	0.0563 (4)
H2A	0.2718	0.9530	0.8157	0.084*
O3	0.18126 (10)	0.9349 (4)	0.70936 (9)	0.0734 (6)
O4	−0.20332 (10)	1.0061 (3)	0.86009 (10)	0.0608 (5)
H4	−0.2373	0.9926	0.8223	0.091*
C17	0.15996 (13)	0.9583 (3)	0.77584 (11)	0.0409 (4)
C18	0.06559 (12)	0.9737 (3)	0.79947 (11)	0.0366 (4)
C19	0.04097 (14)	1.0009 (3)	0.87579 (11)	0.0435 (5)
H19	0.0857	1.0112	0.9143	0.052*
C20	−0.04879 (14)	1.0128 (4)	0.89506 (12)	0.0499 (5)
H20	−0.0643	1.0314	0.9464	0.060*
C21	−0.11692 (13)	0.9970 (3)	0.83780 (12)	0.0425 (5)
C22	−0.09232 (13)	0.9722 (3)	0.76111 (12)	0.0437 (5)
H22	−0.1368	0.9637	0.7223	0.052*
C23	−0.00281 (13)	0.9602 (3)	0.74278 (12)	0.0433 (5)
H23	0.0127	0.9427	0.6914	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0375 (9)	0.1294 (16)	0.0446 (8)	−0.0059 (9)	−0.0021 (6)	0.0179 (9)
N1	0.0314 (8)	0.0663 (11)	0.0343 (8)	0.0027 (7)	−0.0060 (6)	−0.0018 (7)
N3	0.0361 (9)	0.0755 (12)	0.0400 (9)	0.0026 (8)	−0.0107 (7)	−0.0030 (8)
N6	0.0240 (8)	0.0597 (10)	0.0353 (8)	−0.0021 (6)	−0.0076 (6)	0.0019 (7)
N7	0.0287 (8)	0.0592 (10)	0.0403 (9)	−0.0002 (7)	−0.0034 (6)	0.0011 (7)
N9	0.0264 (8)	0.0624 (11)	0.0503 (10)	0.0015 (7)	−0.0087 (7)	−0.0032 (8)
C2	0.0379 (11)	0.0841 (16)	0.0344 (9)	0.0035 (10)	−0.0064 (8)	−0.0016 (10)
C4	0.0302 (10)	0.0476 (10)	0.0424 (10)	0.0019 (7)	−0.0097 (7)	−0.0034 (8)
C6	0.0296 (9)	0.0430 (10)	0.0355 (9)	0.0010 (7)	−0.0078 (7)	−0.0021 (7)
C5	0.0302 (9)	0.0401 (9)	0.0365 (9)	0.0011 (7)	−0.0061 (7)	−0.0012 (7)
C8	0.0259 (10)	0.0649 (13)	0.0511 (12)	0.0005 (8)	−0.0012 (8)	0.0007 (10)
C10	0.0301 (10)	0.0615 (12)	0.0372 (10)	0.0017 (8)	−0.0048 (7)	0.0011 (9)
C11	0.0311 (10)	0.0710 (13)	0.0320 (9)	0.0012 (9)	−0.0061 (7)	0.0023 (9)
C12	0.0706 (17)	0.0902 (19)	0.0699 (16)	−0.0204 (15)	−0.0324 (13)	0.0151 (15)
C13	0.086 (2)	0.150 (3)	0.086 (2)	−0.053 (2)	−0.0499 (18)	0.030 (2)
C14	0.0481 (15)	0.182 (4)	0.0536 (15)	−0.0141 (19)	−0.0213 (12)	0.0164 (19)
C15	0.0563 (15)	0.135 (3)	0.0564 (14)	0.0353 (18)	−0.0098 (11)	0.0172 (17)
C16	0.0517 (13)	0.0784 (16)	0.0558 (12)	0.0135 (12)	−0.0075 (10)	0.0073 (12)
O2	0.0294 (7)	0.0975 (12)	0.0416 (8)	−0.0001 (7)	−0.0052 (6)	−0.0040 (8)
O3	0.0339 (8)	0.1439 (18)	0.0425 (8)	−0.0016 (9)	−0.0009 (6)	−0.0160 (10)
O4	0.0290 (8)	0.1037 (14)	0.0497 (9)	0.0011 (7)	−0.0003 (6)	−0.0057 (9)
C17	0.0317 (10)	0.0510 (11)	0.0398 (10)	−0.0015 (8)	−0.0052 (7)	−0.0014 (8)
C18	0.0308 (10)	0.0403 (9)	0.0383 (9)	−0.0009 (7)	−0.0051 (7)	0.0018 (7)
C19	0.0332 (10)	0.0621 (12)	0.0350 (9)	−0.0004 (8)	−0.0078 (7)	0.0008 (8)
C20	0.0349 (10)	0.0822 (15)	0.0324 (9)	0.0006 (10)	−0.0023 (8)	0.0000 (10)
C21	0.0294 (10)	0.0540 (11)	0.0439 (10)	−0.0002 (8)	−0.0034 (8)	0.0009 (9)
C22	0.0330 (10)	0.0578 (12)	0.0397 (10)	0.0009 (8)	−0.0092 (7)	−0.0036 (9)
C23	0.0346 (10)	0.0602 (12)	0.0349 (9)	0.0014 (8)	−0.0060 (7)	−0.0029 (9)

Geometric parameters (Å, º) top

O1—C10	1.215 (3)	C13—H13	0.9300
N1—C6	1.336 (3)	C14—C15	1.375 (5)
N1—C2	1.356 (2)	C14—H14	0.9300
N3—C2	1.313 (3)	C15—C16	1.389 (3)
N3—C4	1.338 (3)	C15—H15	0.9300
N6—C10	1.351 (3)	C16—H16	0.9300
N6—C6	1.394 (2)	O2—C17	1.324 (2)
N6—H6	0.8600	O2—H2A	0.8200
N7—C8	1.343 (2)	O3—C17	1.209 (3)
N7—C5	1.369 (3)	O4—C21	1.342 (3)
N7—H7	0.8600	O4—H4	0.8200
N9—C8	1.319 (3)	C17—C18	1.464 (3)
N9—C4	1.374 (3)	C18—C19	1.389 (3)
C2—H2	0.9300	C18—C23	1.394 (2)
C4—C5	1.411 (2)	C19—C20	1.376 (3)
C6—C5	1.386 (3)	C19—H19	0.9300
C8—H8	0.9300	C20—C21	1.399 (3)
C10—C11	1.493 (3)	C20—H20	0.9300
C11—C12	1.369 (4)	C21—C22	1.393 (3)
C11—C16	1.384 (3)	C22—C23	1.368 (3)
C12—C13	1.379 (3)	C22—H22	0.9300
C12—H12	0.9300	C23—H23	0.9300
C13—C14	1.357 (5)

C6—N1—C2	118.60 (18)	C14—C13—H13	120.0
C2—N3—C4	112.88 (17)	C12—C13—H13	120.0
C10—N6—C6	129.53 (17)	C13—C14—C15	120.8 (3)
C10—N6—H6	115.2	C13—C14—H14	119.6
C6—N6—H6	115.2	C15—C14—H14	119.6
C8—N7—C5	106.93 (17)	C14—C15—C16	119.7 (3)
C8—N7—H7	126.5	C14—C15—H15	120.2
C5—N7—H7	126.5	C16—C15—H15	120.2
C8—N9—C4	104.19 (16)	C11—C16—C15	119.1 (3)
N3—C2—N1	128.1 (2)	C11—C16—H16	120.4
N3—C2—H2	115.9	C15—C16—H16	120.4
N1—C2—H2	115.9	C17—O2—H2A	109.5
N3—C4—N9	125.60 (17)	C21—O4—H4	109.5
N3—C4—C5	124.43 (18)	O3—C17—O2	121.96 (18)
N9—C4—C5	109.97 (18)	O3—C17—C18	122.96 (17)
N1—C6—C5	118.50 (16)	O2—C17—C18	115.08 (18)
N1—C6—N6	113.25 (17)	C19—C18—C23	118.42 (18)
C5—C6—N6	128.25 (18)	C19—C18—C17	123.06 (17)
N7—C5—C6	137.61 (17)	C23—C18—C17	118.53 (18)
N7—C5—C4	104.93 (16)	C20—C19—C18	120.79 (18)
C6—C5—C4	117.46 (18)	C20—C19—H19	119.6
N9—C8—N7	113.98 (18)	C18—C19—H19	119.6
N9—C8—H8	123.0	C19—C20—C21	120.3 (2)
N7—C8—H8	123.0	C19—C20—H20	119.8
O1—C10—N6	124.15 (18)	C21—C20—H20	119.8
O1—C10—C11	121.74 (18)	O4—C21—C22	123.28 (18)
N6—C10—C11	114.07 (17)	O4—C21—C20	117.8 (2)
C12—C11—C16	120.3 (2)	C22—C21—C20	118.97 (19)
C12—C11—C10	120.8 (2)	C23—C22—C21	120.10 (17)
C16—C11—C10	118.9 (2)	C23—C22—H22	119.9
C11—C12—C13	120.1 (3)	C21—C22—H22	119.9
C11—C12—H12	119.9	C22—C23—C18	121.40 (19)
C13—C12—H12	119.9	C22—C23—H23	119.3
C14—C13—C12	119.9 (3)	C18—C23—H23	119.3

C4—N3—C2—N1	−0.4 (4)	N6—C10—C11—C12	−60.8 (3)
C6—N1—C2—N3	0.0 (4)	O1—C10—C11—C16	−56.9 (3)
C2—N3—C4—N9	−179.7 (2)	N6—C10—C11—C16	121.2 (2)
C2—N3—C4—C5	0.4 (3)	C16—C11—C12—C13	1.1 (5)
C8—N9—C4—N3	179.9 (2)	C10—C11—C12—C13	−176.8 (3)
C8—N9—C4—C5	−0.2 (2)	C11—C12—C13—C14	−2.4 (6)
C2—N1—C6—C5	0.4 (3)	C12—C13—C14—C15	1.6 (6)
C2—N1—C6—N6	−179.98 (19)	C13—C14—C15—C16	0.6 (5)
C10—N6—C6—N1	168.6 (2)	C12—C11—C16—C15	1.0 (4)
C10—N6—C6—C5	−11.9 (3)	C10—C11—C16—C15	179.0 (2)
C8—N7—C5—C6	−179.9 (2)	C14—C15—C16—C11	−1.9 (4)
C8—N7—C5—C4	0.0 (2)	O3—C17—C18—C19	−179.9 (2)
N1—C6—C5—N7	179.6 (2)	O2—C17—C18—C19	1.0 (3)
N6—C6—C5—N7	0.0 (4)	O3—C17—C18—C23	0.2 (3)
N1—C6—C5—C4	−0.4 (3)	O2—C17—C18—C23	−178.92 (19)
N6—C6—C5—C4	−179.93 (18)	C23—C18—C19—C20	0.5 (3)
N3—C4—C5—N7	179.99 (19)	C17—C18—C19—C20	−179.43 (19)
N9—C4—C5—N7	0.1 (2)	C18—C19—C20—C21	0.2 (3)
N3—C4—C5—C6	0.0 (3)	C19—C20—C21—O4	178.8 (2)
N9—C4—C5—C6	−179.93 (16)	C19—C20—C21—C22	−1.0 (3)
C4—N9—C8—N7	0.2 (2)	O4—C21—C22—C23	−178.7 (2)
C5—N7—C8—N9	−0.2 (2)	C20—C21—C22—C23	1.1 (3)
C6—N6—C10—O1	0.1 (4)	C21—C22—C23—C18	−0.4 (3)
C6—N6—C10—C11	−177.92 (19)	C19—C18—C23—C22	−0.3 (3)
O1—C10—C11—C12	121.1 (3)	C17—C18—C23—C22	179.55 (19)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C11–C16 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1	0.82	1.92	2.737 (2)	172
O4—H4···N9ⁱ	0.82	1.98	2.784 (2)	168
N6—H6···O3	0.86	1.94	2.778 (2)	166
N7—H7···O1	0.86	2.14	2.726 (2)	126
N7—H7···O1ⁱⁱ	0.86	2.36	3.164 (2)	155
C8—H8···Cg3ⁱⁱ	0.93	2.77	3.646 (2)	157

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

Comparison of dihedral angles and torsion angles (°) for various N⁶-benzoyladenine-containing crystal structures top

Pyrimidine ring: N1/C2/N3/C4–C6; imidazole ring of adenine: C4/C5/N7/C8/N9; purine ring system: N1/C2/N3/C4–C6/N7/C8/N9; benzene ring: C11–C16; amide: N6/H6/C10/O1.

Compound	pyrimidine/imidazole	purine/benzene	purine/amide	benzene/amide	C6—N6—C10—C11
N⁶-benzoyladenine–DL-tartaric acid^a	2.26 (10)	9.77 (8)	2.93 (18)	11.35 (9)	-179.08 (17)
N⁶-benzoyladenine–3-hydroxypridinium-2-carboxylate^a	3.00 (9)	0.94 (8)	21.20 (17)	21.45 (18)	-176.24 (16)
N⁶-benzoyladeninium nitrate^b	1.34 (14)	52.25 (12)	23.7 (2)	29.2 (2)	-168.8 (2)
N⁶-benzoyladenine–adipic acid^c	0.33 (8)	26.71 (7)	10.8 (7)	23.0 (7)	173.08 (14)
N⁶-benzoyladenine–4-hydroxybenzoic acid^d	0.24 (12)	70.80 (11)	11.71 (19)	59.4 (2)	-177.91 (18)

References: (a) Karthikeyan et al. (2015); (b) Karthikeyan et al. (2016); (c) Swinton Darious et al. (2016); (d) this study.

Acknowledgements

RSD thanks the 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, Ljubljana, Slovenia, for the use of the SuperNova diffractometer.

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