Crystal structure of 4-(2-hy­droxy-3-meth­oxy­benzyl­amino)­benzoic acid di­methyl­formamide monosolvate monohydrate

Faizi, M.S.H.; Kamaal, S.; Ali, A.; Ahmad, M.; Golenya, I.A.

doi:10.1107/S2056989019005103

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 646-649

https://doi.org/10.1107/S2056989019005103

Open

access

Crystal structure of 4-(2-hydroxy-3-methoxybenzylamino)benzoic acid dimethylformamide monosolvate monohydrate

Md. Serajul Haque Faizi,^a ^* Saima Kamaal,^b Arif Ali,^b Musheer Ahmad ^b and Irina A. Golenya ^c ^*

^aDepartment of Chemistry, Langat Singh College, B. R. A. Bihar University, Muzaffarpur, Bihar, 842001, India, ^bDepartment of Applied Chemistry, Faculty of Engineering & Technology, Aligarh, Muslim University, Aligarh, UP 202002, India, and ^cNational Taras Shevchenko University, Department of Chemistry, Volodymyrska, str., 64, 01601, Kyiv, Ukraine
^*Correspondence e-mail: faizichemiitg@gmail.com, igolenya@ua.fm

Edited by M. Weil, Vienna University of Technology, Austria (Received 21 February 2019; accepted 14 April 2019; online 18 April 2019)

The title compound, C₁₅H₁₅NO₄·C₃H₇NO·H₂O, a secondary amine molecule, is accompanied by one equivalent of water and one equivalent of dimethylformamide (DMF) as solvents. The molecule is non-planar, with a C_aryl—CH₂—NH—C_aryl torsion angle of −66.3 (3)°. In the crystal, O—H⋯O and N—H⋯O hydrogen-bonding interactions between the amine molecules and the two types of solvent molecule result in the formation of a layered structure extending parallel to (010).

Keywords: crystal structure; 2-hydroxy-3-methoxy-benzaldehyde; 4-aminobenzoic acid (PABA); secondary amine; hydrogen bonding; vanillin derivative; dimethylformamide solvate.

CCDC reference: 1909944

1. Chemical context

Vanillin and vanillin derivatives are used in food and non-food applications, in fragrances and as flavouring agents for pharmaceutical products (Hocking, 1997 ; Walton et al., 2003 ). Synthetic vanillin is used as an intermediate in the chemical and pharmaceutical industries for the production of herbicides, antifoaming agents and drugs, such as papaverine, L-dopa and L-methyldopa, as well as antimicrobial agents such as trimethoprim (Fitzgerald et al., 2005 ), and as a bacterial co-factor involved in the synthesis of folic acid (Robinson, 1966 ). Another example is benzocaine, the ethyl ester of p-aminobenzoic acid, which is a local anaesthetic. The mechanism includes inhibiting voltage-dependent sodium channels on the nerve membrane, which results in stopping the signal propagation (Neumcke et al., 1981 ). The title compound (1) was synthesized by reduction of reported (E)-4-(2-hydroxy-3-methoxybenzylideneamino)benzoic acid with sodium borohydride and crystallizes as a water and dimethylformamide solvate. The latter Schiff base is formed by condensation of 4-aminobenzoic acid with o-vanilline.

In this context and as part of an ongoing structural study of Schiff bases and secondary amines for their utilization in the synthesis of new organic compounds and the application of excited-state proton transfer and fluorescent chemosensors (Faizi et al., 2016a ,b , 2018a ,b ; Kumar et al., 2018 ; Mukherjee et al., 2018 ), we report here the molecular and crystal structure of (1), C₁₅H₁₅NO₄·C₃H₇NO·H₂O.

2. Structural commentary

Compound (1) crystallizes in space group Pbca with one molecule of 4-(2-hydroxy-3-methoxybenzylamino)benzoic acid and one molecule each of DMF and water in the asymmetric unit (Fig. 1). The secondary amine has two substituted aromatic rings at either end of the —CH₂—NH— linkage. As a result of the C_aryl—CH₂—NH— C_aryl torsion angle of −66.3 (3)°, the molecular shape of the title compound is bent around the central C8—N1 bond. The secondary amine N atom (N1) has a practically trigonal-planar configuration deviating by 0.02 (1) Å from the mean plane of the adjacent atoms, and N1—C5 is apparently less conjugated with the C2–C7 benzenecarboxylic acid ring. For comparison, the reported C—N distance in the crystal structure of the ethyl 4-[(E)-(4-hydroxy-3-methoxybenzylidene)amino]benzoate Schiff base is 1.274 (2) Å (Ling et al., 2016 ), and in the zwitterionic form it is 1.312 Å (Kamaal et al., 2018 ). The benzene rings C2–C7 and C9–C14 are roughly perpendicular to each another, with a dihedral angle of 88.15 (10)° between them.

Figure 1
The structures of the molecular entities in the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 40% probability level. Intermolecular O—H_water⋯O_amide and C—H_methyl⋯N_amine hydrogen bonds involving the water and dimethylformamide solvent molecules are shown as dashed lines (see Table 1

for numerical details).

The C16=O5 bond length in the dimethlyformamide solvent is 1.246 (2) Å, which is slightly longer than reported [1.2309 (17) Å (Fernandes et al., 2007 ) or 1.2373 (18) Å (Elgemeie et al., 2015 )] for other dimethylformamide solvates. In (1), the C13—O4 bond length to the methoxy group is 1.366 (2) Å.

3. Supramolecular features

The water and dimethylformamide solvent molecules stabilize the packing within the crystal structure through hydrogen bonding. The molecules of dimethylformamide, 4-(2-hydroxy-3-methoxybenzylamino)benzoic acid and water are linked through _hydroxyO3—H3⋯O6_water, _amineN1—H1⋯O6_water, _waterO6—H6B⋯O5_amide, _waterO6—H6B⋯O1_carboxyate and O2—H2⋯O5_amide hydrogen bonds (Table 1, Fig. 2) into a layered structure extending parallel to (010) (Fig. 3). Further C—H⋯O interactions (Table 1) between the methyl group of the methoxy functionality and the carboxylate group consolidate the packing.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15C⋯O1ⁱ	0.96	2.50	3.329 (3)	145
N1—H1⋯O6ⁱⁱⁱ	0.89 (2)	2.05 (2)	2.936 (2)	175 (2)
O2—H2⋯O5^iv	0.90 (3)	1.70 (3)	2.591 (2)	171 (3)
O3—H3⋯O6^v	0.88 (3)	1.90 (3)	2.739 (2)	158 (3)
O6—H6A⋯O1^vi	0.85 (3)	1.94 (3)	2.776 (2)	172 (3)
O6—H6B⋯O5	0.88 (3)	1.91 (3)	2.785 (2)	178 (3)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y+1, -z+1; (v) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
A view of hydrogen-bonding interactions around the water molecule in the title structure.

Figure 3
A partial view of the title structure projected along the a axis to emphasize the crystal packing. Dashed lines indicate hydrogen bonds (see Table 1

for numerical details).

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.39; Groom et al., 2016 ) gave eleven hits for reduced Schiff bases containing a C_aryl—CH₂—NH— C_aryl moiety. In direct comparison with the title compound, there are two examples of very similar compounds reported in the literature: ethyl 4-{[(2-hydroxyphenyl)methyl]amino}benzoate, (I) (WEFQEG; Salman et al., 2017 ), and ethyl 4-[(3,5-di-tert-butyl-2-hydroxybenzyl) amino]benzoate, (II) (VABTAV; Shakir et al., 2010 ). There is also a related compound, viz. ethyl 4-[(2-hydroxybenzyl)amino]benzoate, in which the 3-methoxy group in the title compound is replaced by a hydrogen atom and the carboxylic acid is replaced by an ester. Other related structures based on a benzylidene–phenyl–amine moiety are n-propyl 4-[2-(4,6-dimethoxypyrimidin-2-yloxy)benzylamino]benzoate, (III) (ILAGIL; Wu et al., 2003 ), and [4-(2-hydroxybenzylamino)benzoato-κO]triphenyltin(IV), (IV) (WENXAP; Jiang et al., 2006 ). The torsion angle C_aryl—CH₂—NH—C_aryl in the title compound [−66.3 (3)°] compares well to those in I (73.68°), II (77.38°) and IV (−87.28°), despite the difference in substituent groups.

5. Synthesis and crystallization

To a hot stirred solution of 4-aminobenzoic acid (PABA) (1.00 g, 7.2 mmol) in methanol (15 ml) was added vanillin (1.11 g, 7.2 mmol). The resultant mixture was then heated under reflux. After an hour, a precipitate was formed. The reaction mixture was heated for about a further 30 minutes for completion of the reaction, which was monitored through TLC. The reaction mixture was then cooled to room temperature, filtered and washed with hot methanol. It was then dried in vacuo to give (E)-4-(2-hydroxy-3-methoxybenzylideneamino) benzoic acid in 78% yield. The latter (1.00 g, 3.7 mmol) was dissolved in 25 ml of methanol and reduced by addition of excess sodium borohydride (0.28 g, 7.4 mmol). The solution was stirred until the yellow colour disappeared. Then the solution was diluted with 8–10 times the volume of water and the pH was adjusted to 6 by addition of 12%_wt HCl. The white precipitate was collected and dried in air. Colourless single crystals of the title compound, suitable for X-ray analysis, were obtained by slow evaporation of a dimethylformamide solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N—H and O—H hydrogen atoms were located in difference-Fourier maps and were freely refined, while the C-bound H atoms were included in calculated positions and treated as riding, with fixed C—H = 0.93 Å, and U_iso(H) = 1.2U_eq(C,N).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₄·C₃H₇NO·H₂O
M_r	364.39
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	11.5504 (7), 13.8047 (7), 22.3899 (12)
V (Å³)	3570.1 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.39 × 0.24 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	40928, 3165, 2321
R_int	0.106
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.113, 1.05
No. of reflections	3165
No. of parameters	258
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25
Computer programs: APEX2 (Bruker, 2014 ), SAINT (Bruker, 2014), SHELXT2015 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1909944

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005103/wm5490sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005103/wm5490Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019005103/wm5490Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2015 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

4-(2-Hydroxy-3-methoxybenzylamino)benzoic acid dimethylformamide monosolvate monohydrate top

Crystal data top

C₁₅H₁₅NO₄·C₃H₇NO·H₂O	D_x = 1.356 Mg m⁻³
M_r = 364.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 6409 reflections
a = 11.5504 (7) Å	θ = 2.3–28.2°
b = 13.8047 (7) Å	µ = 0.10 mm⁻¹
c = 22.3899 (12) Å	T = 100 K
V = 3570.1 (3) Å³	Block, colorless
Z = 8	0.39 × 0.24 × 0.17 mm
F(000) = 1552

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.106
φ and ω scans	θ_max = 25.1°, θ_min = 2.9°
40928 measured reflections	h = −13→13
3165 independent reflections	k = −16→16
2321 reflections with I > 2σ(I)	l = −26→26

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0393P)² + 2.7178P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3165 reflections	Δρ_max = 0.25 e Å⁻³
258 parameters	Δρ_min = −0.25 e Å⁻³

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	0.97909 (13)	0.64576 (11)	0.53644 (7)	0.0253 (4)
O2	1.07571 (14)	0.62871 (12)	0.45097 (7)	0.0283 (4)
O3	0.71716 (14)	0.70129 (10)	0.18430 (7)	0.0252 (4)
O4	0.76784 (13)	0.88000 (10)	0.14629 (6)	0.0225 (4)
N1	0.56965 (16)	0.64392 (13)	0.34340 (8)	0.0202 (4)
C1	0.97938 (19)	0.63895 (15)	0.48187 (10)	0.0203 (5)
C2	0.87414 (18)	0.64213 (15)	0.44484 (9)	0.0191 (5)
C3	0.76483 (19)	0.64465 (15)	0.47181 (10)	0.0205 (5)
H3A	0.759163	0.644607	0.513245	0.025*
C4	0.66632 (18)	0.64718 (15)	0.43802 (9)	0.0195 (5)
H4	0.594711	0.649520	0.456958	0.023*
C5	0.67081 (18)	0.64633 (14)	0.37540 (9)	0.0182 (5)
C6	0.78028 (18)	0.64468 (15)	0.34804 (9)	0.0209 (5)
H6	0.786010	0.645126	0.306608	0.025*
C7	0.87952 (18)	0.64238 (15)	0.38257 (10)	0.0204 (5)
H7	0.951416	0.640972	0.363889	0.024*
C8	0.56478 (18)	0.66082 (15)	0.27954 (9)	0.0198 (5)
H8A	0.487059	0.646580	0.265676	0.024*
H8B	0.617048	0.615927	0.259956	0.024*
C9	0.59608 (18)	0.76308 (15)	0.26052 (9)	0.0183 (5)
C10	0.54893 (18)	0.84270 (15)	0.29065 (9)	0.0204 (5)
H10	0.499734	0.832750	0.322951	0.024*
C11	0.57492 (18)	0.93582 (15)	0.27275 (9)	0.0216 (5)
H11	0.543392	0.988120	0.293264	0.026*
C12	0.64763 (18)	0.95228 (15)	0.22444 (9)	0.0204 (5)
H12	0.664327	1.015250	0.212442	0.024*
C13	0.69509 (18)	0.87437 (15)	0.19427 (9)	0.0184 (5)
C14	0.66910 (18)	0.77913 (15)	0.21267 (9)	0.0185 (5)
C15	0.8038 (2)	0.97495 (15)	0.12804 (10)	0.0246 (5)
H15A	0.838277	1.007996	0.161321	0.037*
H15B	0.737862	1.010846	0.114248	0.037*
H15C	0.859436	0.969537	0.096352	0.037*
O5	0.73401 (13)	0.39240 (11)	0.48915 (6)	0.0232 (4)
N2	0.63766 (15)	0.39534 (12)	0.40067 (8)	0.0197 (4)
C16	0.73235 (19)	0.38897 (15)	0.43356 (10)	0.0207 (5)
H16	0.802632	0.381408	0.413834	0.025*
C17	0.64116 (19)	0.39045 (16)	0.33595 (9)	0.0233 (5)
H17A	0.718785	0.376788	0.323146	0.035*
H17B	0.616637	0.451334	0.319537	0.035*
H17C	0.590384	0.340011	0.322353	0.035*
C18	0.52415 (19)	0.40815 (18)	0.42793 (10)	0.0287 (6)
H18A	0.533133	0.419569	0.469968	0.043*
H18B	0.478642	0.350798	0.421860	0.043*
H18C	0.485877	0.462530	0.409914	0.043*
O6	0.63671 (14)	0.30090 (13)	0.58799 (7)	0.0227 (4)
H1	0.506 (2)	0.6567 (16)	0.3644 (10)	0.025 (6)*
H2	1.138 (3)	0.623 (2)	0.4752 (13)	0.060 (10)*
H3	0.759 (2)	0.7170 (19)	0.1528 (12)	0.045 (8)*
H6A	0.607 (2)	0.250 (2)	0.5735 (12)	0.044 (9)*
H6B	0.667 (2)	0.329 (2)	0.5565 (13)	0.047 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0240 (9)	0.0326 (9)	0.0193 (9)	0.0028 (7)	−0.0005 (7)	0.0003 (7)
O2	0.0179 (9)	0.0423 (10)	0.0247 (9)	0.0061 (7)	0.0004 (7)	−0.0053 (7)
O3	0.0359 (10)	0.0164 (8)	0.0234 (9)	0.0002 (7)	0.0095 (7)	−0.0016 (7)
O4	0.0277 (9)	0.0182 (8)	0.0217 (8)	−0.0013 (6)	0.0070 (7)	0.0019 (6)
N1	0.0190 (10)	0.0251 (10)	0.0165 (10)	0.0002 (8)	0.0014 (8)	0.0014 (8)
C1	0.0243 (12)	0.0164 (11)	0.0202 (13)	0.0024 (9)	0.0011 (9)	−0.0017 (9)
C2	0.0218 (12)	0.0156 (11)	0.0199 (12)	0.0009 (9)	−0.0004 (9)	−0.0008 (9)
C3	0.0255 (12)	0.0185 (12)	0.0175 (11)	−0.0009 (9)	0.0026 (9)	0.0010 (9)
C4	0.0178 (11)	0.0206 (12)	0.0199 (12)	−0.0018 (9)	0.0038 (9)	0.0000 (9)
C5	0.0212 (12)	0.0117 (10)	0.0216 (12)	−0.0006 (9)	0.0001 (9)	0.0005 (8)
C6	0.0254 (12)	0.0204 (12)	0.0169 (11)	0.0017 (9)	0.0019 (9)	−0.0016 (9)
C7	0.0189 (11)	0.0182 (11)	0.0240 (12)	0.0013 (9)	0.0042 (9)	−0.0020 (9)
C8	0.0195 (11)	0.0225 (12)	0.0173 (11)	−0.0023 (9)	0.0003 (9)	−0.0003 (9)
C9	0.0171 (11)	0.0192 (11)	0.0185 (11)	−0.0019 (9)	−0.0053 (9)	0.0009 (9)
C10	0.0182 (11)	0.0233 (12)	0.0196 (12)	0.0014 (9)	0.0003 (9)	0.0006 (9)
C11	0.0215 (12)	0.0192 (12)	0.0242 (12)	0.0054 (9)	−0.0002 (9)	−0.0029 (9)
C12	0.0208 (11)	0.0157 (11)	0.0246 (12)	0.0013 (9)	−0.0031 (9)	0.0011 (9)
C13	0.0175 (11)	0.0223 (12)	0.0156 (11)	0.0003 (9)	−0.0020 (9)	0.0001 (9)
C14	0.0200 (11)	0.0184 (11)	0.0170 (11)	0.0013 (9)	−0.0009 (9)	−0.0029 (9)
C15	0.0290 (13)	0.0181 (12)	0.0265 (13)	−0.0025 (10)	0.0044 (10)	0.0042 (9)
O5	0.0247 (8)	0.0262 (9)	0.0188 (8)	0.0007 (7)	−0.0020 (6)	0.0019 (7)
N2	0.0198 (10)	0.0194 (10)	0.0198 (10)	0.0007 (7)	0.0014 (8)	0.0010 (7)
C16	0.0211 (12)	0.0169 (11)	0.0241 (13)	0.0006 (9)	0.0018 (9)	0.0011 (9)
C17	0.0246 (12)	0.0266 (13)	0.0186 (12)	0.0026 (10)	−0.0003 (9)	0.0006 (9)
C18	0.0207 (12)	0.0386 (14)	0.0267 (13)	0.0027 (10)	0.0038 (10)	0.0013 (11)
O6	0.0226 (8)	0.0265 (9)	0.0190 (9)	−0.0021 (7)	0.0003 (7)	0.0005 (7)

Geometric parameters (Å, º) top

O1—C1	1.225 (2)	C9—C10	1.400 (3)
O2—C1	1.318 (3)	C10—C11	1.380 (3)
O2—H2	0.90 (3)	C10—H10	0.9300
O3—C14	1.366 (2)	C11—C12	1.388 (3)
O3—H3	0.88 (3)	C11—H11	0.9300
O4—C13	1.366 (2)	C12—C13	1.383 (3)
O4—C15	1.434 (2)	C12—H12	0.9300
N1—C5	1.371 (3)	C13—C14	1.410 (3)
N1—C8	1.450 (3)	C15—H15A	0.9600
N1—H1	0.89 (2)	C15—H15B	0.9600
C1—C2	1.472 (3)	C15—H15C	0.9600
C2—C7	1.396 (3)	O5—C16	1.246 (2)
C2—C3	1.400 (3)	N2—C16	1.321 (3)
C3—C4	1.367 (3)	N2—C17	1.451 (3)
C3—H3A	0.9300	N2—C18	1.457 (3)
C4—C5	1.403 (3)	C16—H16	0.9300
C4—H4	0.9300	C17—H17A	0.9600
C5—C6	1.405 (3)	C17—H17B	0.9600
C6—C7	1.383 (3)	C17—H17C	0.9600
C6—H6	0.9300	C18—H18A	0.9600
C7—H7	0.9300	C18—H18B	0.9600
C8—C9	1.518 (3)	C18—H18C	0.9600
C8—H8A	0.9700	O6—H6A	0.85 (3)
C8—H8B	0.9700	O6—H6B	0.88 (3)
C9—C14	1.382 (3)

C1—O2—H2	111.3 (19)	C9—C10—H10	119.8
C14—O3—H3	113.6 (18)	C10—C11—C12	120.70 (19)
C13—O4—C15	117.01 (16)	C10—C11—H11	119.6
C5—N1—C8	122.99 (18)	C12—C11—H11	119.6
C5—N1—H1	115.1 (15)	C13—C12—C11	119.53 (19)
C8—N1—H1	117.1 (15)	C13—C12—H12	120.2
O1—C1—O2	122.3 (2)	C11—C12—H12	120.2
O1—C1—C2	123.9 (2)	O4—C13—C12	125.70 (19)
O2—C1—C2	113.87 (18)	O4—C13—C14	114.44 (17)
C7—C2—C3	118.1 (2)	C12—C13—C14	119.87 (19)
C7—C2—C1	121.73 (19)	O3—C14—C9	118.85 (18)
C3—C2—C1	120.17 (19)	O3—C14—C13	120.74 (18)
C4—C3—C2	120.8 (2)	C9—C14—C13	120.40 (19)
C4—C3—H3A	119.6	O4—C15—H15A	109.5
C2—C3—H3A	119.6	O4—C15—H15B	109.5
C3—C4—C5	121.5 (2)	H15A—C15—H15B	109.5
C3—C4—H4	119.3	O4—C15—H15C	109.5
C5—C4—H4	119.3	H15A—C15—H15C	109.5
N1—C5—C4	119.40 (19)	H15B—C15—H15C	109.5
N1—C5—C6	122.59 (19)	C16—N2—C17	122.02 (18)
C4—C5—C6	118.0 (2)	C16—N2—C18	121.30 (18)
C7—C6—C5	120.2 (2)	C17—N2—C18	116.68 (18)
C7—C6—H6	119.9	O5—C16—N2	124.5 (2)
C5—C6—H6	119.9	O5—C16—H16	117.7
C6—C7—C2	121.4 (2)	N2—C16—H16	117.7
C6—C7—H7	119.3	N2—C17—H17A	109.5
C2—C7—H7	119.3	N2—C17—H17B	109.5
N1—C8—C9	114.65 (17)	H17A—C17—H17B	109.5
N1—C8—H8A	108.6	N2—C17—H17C	109.5
C9—C8—H8A	108.6	H17A—C17—H17C	109.5
N1—C8—H8B	108.6	H17B—C17—H17C	109.5
C9—C8—H8B	108.6	N2—C18—H18A	109.5
H8A—C8—H8B	107.6	N2—C18—H18B	109.5
C14—C9—C10	119.03 (19)	H18A—C18—H18B	109.5
C14—C9—C8	120.80 (19)	N2—C18—H18C	109.5
C10—C9—C8	120.15 (19)	H18A—C18—H18C	109.5
C11—C10—C9	120.5 (2)	H18B—C18—H18C	109.5
C11—C10—H10	119.8	H6A—O6—H6B	103 (2)

O1—C1—C2—C7	174.4 (2)	C14—C9—C10—C11	0.1 (3)
O2—C1—C2—C7	−5.1 (3)	C8—C9—C10—C11	−178.52 (19)
O1—C1—C2—C3	−5.8 (3)	C9—C10—C11—C12	0.4 (3)
O2—C1—C2—C3	174.68 (19)	C10—C11—C12—C13	−0.5 (3)
C7—C2—C3—C4	0.1 (3)	C15—O4—C13—C12	4.2 (3)
C1—C2—C3—C4	−179.70 (19)	C15—O4—C13—C14	−175.82 (18)
C2—C3—C4—C5	0.7 (3)	C11—C12—C13—O4	−179.86 (19)
C8—N1—C5—C4	168.25 (18)	C11—C12—C13—C14	0.1 (3)
C8—N1—C5—C6	−14.0 (3)	C10—C9—C14—O3	178.43 (18)
C3—C4—C5—N1	176.67 (19)	C8—C9—C14—O3	−3.0 (3)
C3—C4—C5—C6	−1.2 (3)	C10—C9—C14—C13	−0.4 (3)
N1—C5—C6—C7	−176.78 (19)	C8—C9—C14—C13	178.20 (19)
C4—C5—C6—C7	1.0 (3)	O4—C13—C14—O3	1.5 (3)
C5—C6—C7—C2	−0.3 (3)	C12—C13—C14—O3	−178.52 (19)
C3—C2—C7—C6	−0.2 (3)	O4—C13—C14—C9	−179.71 (18)
C1—C2—C7—C6	179.53 (19)	C12—C13—C14—C9	0.3 (3)
C5—N1—C8—C9	−66.3 (3)	C17—N2—C16—O5	−179.74 (19)
N1—C8—C9—C14	135.2 (2)	C18—N2—C16—O5	0.6 (3)
N1—C8—C9—C10	−46.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15C···O1ⁱ	0.96	2.50	3.329 (3)	145
C15—H15C···O2ⁱⁱ	0.96	2.55	3.094 (3)	116
N1—H1···O6ⁱⁱⁱ	0.89 (2)	2.05 (2)	2.936 (2)	175 (2)
O2—H2···O5^iv	0.90 (3)	1.70 (3)	2.591 (2)	171 (3)
O3—H3···O6^v	0.88 (3)	1.90 (3)	2.739 (2)	158 (3)
O6—H6A···O1^vi	0.85 (3)	1.94 (3)	2.776 (2)	172 (3)
O6—H6B···O5	0.88 (3)	1.91 (3)	2.785 (2)	178 (3)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+1, −z+1; (v) −x+3/2, −y+1, z−1/2; (vi) −x+3/2, y−1/2, z.

Acknowledgements

The Department of Applied Chemistry, Aligarh Muslim University, Aligarh and the Department of Chemistry, L. S. College, B. R. A. Bihar University, are acknowledged for providing laboratory facilities.

Funding information

Funding for this research was provided by: UGC (grant to Musheer Ahmad).

References

Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elgemeie, G. H., Mohamed, R. A., Hussein, H. A. & Jones, P. G. (2015). Acta Cryst. E71, 1322–1324. Web of Science CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H., Alam, M. J., Haque, A., Ahmad, S., Shahid, M. & Ahmad, M. (2018a). J. Mol. Struct. 1156, 457–464. Web of Science CSD CrossRef CAS Google Scholar
Faizi, M. S. H., Ali, A. & Potaskalov, V. A. (2016a). Acta Cryst. E72, 1366–1369. Web of Science CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H., Dege, N. & Iskenderov, T. S. (2018b). Acta Cryst. E74, 410–413. Web of Science CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H., Gupta, S., Mohan, V. K., Jain, K. V. & Sen, P. (2016b). Sens. Actuators B Chem. 222, 15–20. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fernandes, P., Florence, A. J., Fabbiani, F., David, W. I. F. & Shankland, K. (2007). Acta Cryst. E63, o4861. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fitzgerald, D. J., Stratford, M., Gasson, M. J. & Narbad, A. (2005). J. Agric. Food Chem. 53, 1769–1775. Web of Science CrossRef PubMed CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hocking, M. B. (1997). J. Chem. Educ. 74, 1055–1059. CrossRef CAS Web of Science Google Scholar
Jiang, H., Ma, J.-F. & Zhang, W.-L. (2006). Acta Cryst. E62, m2745–m2746. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kamaal, S., Faizi, M. S. H., Ali, A., Ahmad, M. & Iskenderov, T. (2018). Acta Cryst. E74, 1847–1850. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kumar, M., Kumar, A., Faizi, M. S. H., Kumar, S., Singh, M. K., Sahu, S. K., Kishor, S. & John, R. P. (2018). Sens. Actuators B Chem. 260, 888–899. Web of Science CrossRef CAS Google Scholar
Ling, J., Kavuru, P., Wojtas, L. & Chadwick, K. (2016). Acta Cryst. E72, 951–954. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mukherjee, P., Das, A., Faizi, M. S. H. & Sen, P. (2018). Chemistry Select, 3, 3787–3796. CAS Google Scholar
Neumcke, B., Schwarz, W. & Stampfli, R. (1981). Pflugers Arch. 390, 230–236. CrossRef CAS PubMed Web of Science Google Scholar
Robinson, F. A. (1966). The Vitamin Co-factors of Enzyme Systems, pp. 541–662 London: Pergamon. Google Scholar
Salman, M., Abu-Yamin, A. A., Sarairah, I., Ibrahim, A. & Aldamen, M. A. (2017). Z. Kristallogr. 232, 631–632. CAS Google Scholar
Shakir, R. M., Ariffin, A. & Ng, S. W. (2010). Acta Cryst. E66, o2916. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Walton, N. J., Mayer, M. J. & Narbad, A. (2003). Phytochemistry, 63, 505–515. Web of Science CrossRef PubMed CAS Google Scholar
Wu, J., Zhang, P.-Z., Lu, L., Yu, Q.-S., Hu, X.-R. & Gu, J.-M. (2003). Chin. J. Struct. Chem. 22, 613–616. 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.