Crystal structure of (E)-N′-(3,4-di­hydroxy­benzyl­idene)-4-hy­droxy­benzohydrazide

Chantrapromma, S.; Kwong, H.C.; Prachumrat, P.; Kobkeatthawin, T.; Chia, T.S.; Quah, C.K.

doi:10.1107/S2056989019010442

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1280-1283

https://doi.org/10.1107/S2056989019010442

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Crystal structure of (E)-N′-(3,4-dihydroxybenzylidene)-4-hydroxybenzohydrazide¹

Suchada Chantrapromma,^a ^*‡ Huey Chong Kwong,^b Patcharawadee Prachumrat,^a Thawanrat Kobkeatthawin,^a Tze Shyang Chia ^c and Ching Kheng Quah ^c

^aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, ^bDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

Edited by H. Ishida, Okayama University, Japan (Received 22 June 2019; accepted 22 July 2019; online 28 July 2019)

In the title benzohydrazide derivative, C₁₄H₁₂N₂O₄, the azomethine C=N double bond has an E configuration. The hydrazide connecting bridge, (C=O)—(NH)—N=(CH), is nearly planar with C—C—N—N and C—N—N=C torsion angles of −177.33 (10) and −174.98 (12)°, respectively. The 4-hydroxyphenyl and 3,4-dihydroxyphenyl rings are slightly twisted, making a dihedral angle of 9.18 (6)°. In the crystal, molecules are connected by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network, while further consolidated via π–π interactions [centroid–centroid distances = 3.6480 (8) and 3.7607 (8) Å]. The conformation is compared to those of related benzylidene-4-hydroxybenzohydrazide derivatives.

Keywords: crystal structure; hydrazide; molecular conformation; antioxidant; α-glucosidase inhibitory.

CCDC reference: 1942396

1. Chemical context

Hydrazides and hydrazones are important synthons for several transformations and have gained importance because of their various biological and clinical applications (Narasimhan et al., 2010 ). Benzohydrazide derivatives containing an azomethine (–NHN=CH–) group have been reported to possess diverse biological activities such as antitumor (Xia et al., 2007 ; Kumari & Bansal, 2018 ), antioxidant (Aziz et al., 2014 ), antitubercular and antimicrobial (Maheswari & Manjula, 2015 ) and α-glucosidase inhibition (Taha et al., 2015 ) activities. The interesting biological activities of benzohydrazides led us to synthesize several benzohydrazides to study their bioactivities (Fun et al., 2011 ; Horkaew et al., 2011 ; Chantrapromma et al., 2016 ), including the title compound (I), which was found to exhibit antioxidant activity with an IC₅₀ value of 0.035 ± 0.004 mM (ascorbic acid used as the reference standard; Thaipong et al., 2006 ) and α-glucosidase inhibitory activity with an IC₅₀ value of 0.014 ± 0.001 mM (acarbose as the reference standard; Bachhawat et al., 2011 ).

2. Structural commentary

The title hydrazide derivative, (I), consists of a 4-hydroxyphenyl ring, a 3,4-dihydroxyphenyl ring and a hydrazide (C=O)—(NH)—N=(CH) connecting bridge (Fig. 1). The C6—C7, C7—N1 and C8—C9 bond lengths of 1.4861 (15), 1.3385 (17) and 1.4584 (16) Å, respectively, confirm their single-bond character, whereas the C7=O2 and N2=C8 bond lengths of 1.2403 (15) and 1.2738 (17) Å, respectively, confirm the presence of the double bonds. The sp²-hybridized character of atoms C7 and C8 is further supported by the bond angles C6—C7—N1 [116.49 (11)°] and N2—C8—C9 [120.86 (12)°]. The bond lengths and angles of the central hydrazide connecting bridge are consistent with those in related structures (Fun et al., 2011; Chantrapromma et al., 2016). The molecule exhibits an E configuration with respect to the azomethine C=N double bond. As the torsion angle C6—C7—N1—N2 [−177.33 (10)°] and C7—N1—N2—C8 [−174.98 (12)°] are both in an anti-periplanar conformation, the overall conformation for the hydrazide connecting bridge is almost planar. Furthermore, the 4-hydroxyphenyl and 3,4-dihydroxyphenyl rings are also coplanar to the corresponding azomethine and carbonyl double bonds, with torsion angles N2—C8—C9—C10 [−0.76 (19)°] and C5—C6—C7—O2 [−1.18 (19)°] both in a syn-periplanar conformation. Those torsion angles result in an overall flat shape of the title compound with the dihedral angle between the terminal benzene rings being 9.18 (6)°.

Figure 1
The molecular structure of the title compound with the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

3. Supramolecular features

In the crystal, molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds (Table 1) into a three-dimensional network. Molecules are connected into infinite chains along [101] through an O4—H1O4⋯O1ⁱⁱⁱ hydrogen bond and those chains are further connected into two-dimensional plates parallel to the ac plane via N1—H1N1⋯O3ⁱ and O1—H1O1⋯O2ⁱ hydrogen bonds with an R₂²(18) ring motif (Fig. 2a and 3a; symmetry codes as in Table 1). Those plate are interconnected via an O3—H1O3⋯O2ⁱⁱ hydrogen bond with an R₂²(20) ring motif, forming a three-dimensional network (Fig. 2b and 3b; symmetry code as in Table 1). In addition, the molecules are further stabilized by π–π interactions involving both aromatic rings with Cg1⋯Cg2^iv = 3.6480 (8) Å and Cg1⋯Cg2^v = 3.7607 (8) Å [symmetry codes: (iv) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (v) 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 aromatic rings, respectively.]

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2ⁱ	0.80 (2)	1.92 (2)	2.7203 (15)	171 (2)
O3—H1O3⋯O2ⁱⁱ	0.88 (2)	2.17 (2)	3.0276 (13)	163 (2)
O4—H1O4⋯O1ⁱⁱⁱ	0.82 (2)	1.93 (2)	2.7379 (16)	166 (2)
N1—H1N1⋯O3ⁱ	0.87 (2)	2.24 (2)	3.0017 (16)	146.1 (19)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) x-1, y, z-1.

Figure 2
(a) A partial packing diagram of the title compound, showing a two-dimensional plate formed by O—H⋯O and N—H⋯O hydrogen bonds (cyan dotted lines). [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iii) x − 1, y, z − 1.] (b) A partial packing diagram of the title compound with additional O—H⋯O hydrogen bonds (magenta dotted lines). [Symmetry code: (ii) −x + 1, −y + 1, −z.] Hydrogen atoms not involved in with these interactions are omitted for clarity.

Figure 3
A view of dimers with (a) R₂²(18) and (b) R₂²(20) ring motifs. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) −x + 1, −y + 1, −z.]

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.40, last update May 2019; Groom et al., 2016 ) using (E)-N′-benzenylidene-4-hydroxybenzohydrazide as the reference moiety resulted in 31 structures with different substituents at the benzylidenyl ring. The different substituent (R) together with selected torsion angles, τ₁ (C5—C6—C7—O2), τ₂ (C6—C7—N1—N2), τ₃ (C7—N1—N2—C8) and τ₄ (N2—C8—C9—C10) as shown in Fig. 4, and the dihedral angle between the terminal aromatic rings are summarized in Table 2. The torsion angles τ₂ and τ₃ are anti-periplanar (151.7–179.8°), showing that the hydrazide connecting bridges are nearly planar. As for the torsion angle τ₄, all structures adopt a syn-periplanar conformation (0.6–19.6°). Similar to the title compound, the τ₁ torsion angles for most of the structures are syn-periplanar (2.0–29.1°). However, there are three outliers (CEDBAQ, HUCWOS and PAQJID) whose τ₁ torsion angles are syn-clinal (34.9–50.9°). By comparing the dihedral angles, the structures can be divided into planar compounds (dihedral angle = 2.5–29.3°) and non-planar compounds (dihedral angle = 30.5–77.3°). In general, as the hydrazide-connecting bridges are nearly planar, relatively flat τ₁ and τ₄ torsion angles are observed in the former compounds, while relatively twisted τ₁ and τ₄ torsion angles are observed in the latter.

Table 2
Selected torsion angles (°) and the dihedral angle (°) between the terminal benzene rings

Compound	R	τ₁	τ₂	τ₃	τ₄	Dihedral angle
Planar
(I)	3,4-dihydroxyphenyl	−1.2	−177.3	−175.0	−0.8	9.2
ABALIA (Fun et al., 2011)	3-hydroxy-4-methoxyphenyl	3.2	178.4	170.1	−14.2	24.2
CECZOB (Subashini et al., 2012 )	4-chlorophenyl	26.1	−174.4	166.6	−8.9	5.8
CECZUH (Subashini et al., 2012)	4-bromophenyl	25.6	−174.9	169.0	−7.2	9.8
ESOTUD (Chantrapromma et al., 2016)	3-methoxyphenyl	−19.4, 20.7	−173.5, −177.8	−175.7, −173.0	1.2, 0.6	24.0, 29.3
HOZBII (Li & Ban, 2009 )	4-nitrophenyl	2.0	177.7	178.3	−0.6	2.5
IJUKEE (Zhang, 2011 )	4-hydroxy-3-nitrophenyl	−7.2	−177.0	−179.3	6.0	5.5
IRAXEF (Sánchez-Lozano et al., 2011 )	2,4-dihydroxyphenyl	−7.7	−177.8	−177.2	−4.1	6.9
MOZPEX (Ren, 2009 )	3,5-dichloro-2-hydroxyphenyl	12.3	178.7	−179.4	−7.3	5.1
ROFMOP (Xue et al., 2008 )	3-bromo-5-chloro-2-hydroxyphenyl	−2.3	175.9	−176.5	−1.3	3.0
TEWLAL (Ayyannan et al., 2016 )	5-bromo-2-hydroxyphenyl	−15.7	−173.6	168.9	3.1	27.0
WACVON (Shalash et al., 2010 )	4-hydroxy-3-methoxyphenyl	−34.2	−175.5	174.7	15.4	28.6
WACXOP (Huang, 2010 )	2,4-dichlorophenyl	−14.3	−179.8	−175.0	3.0	7.0
YAGYAI (Horkaew et al., 2011)	3,4,5-trimethoxyphenyl	−10.6	172.2	175.8	2.8	19.4
YIFPAF (Salhin et al., 2007 )	2-hydroxyphenyl	18.8	179.5	178.7	3.3	21.7
ZAPKOS (Hou, 2012 )	3-nitrophenyl	−14.6	169.4	177.4	13.8	9.2
ZIPLAO (Prachumrat et al., 2018 )	2,3-dimethoxyphenyl	9.6	−175.3	172.9	−1.3	9.3
Non-planar
CABWUA (Meng et al., 2014 )	2-hydroxy-5-methylphenyl	18.4	−178.5	−169.8	8.0	40.8
CEDBAQ (Subashini et al., 2012)	4-(diethylamino)phenyl	34.9	−178.5	−151.7	8.75	77.3
HUCVIL (Hao, 2009 )	2-chlorophenyl	−22.5	−179.2	177.4	−4.2	30.5
HUCWOS (Shi, 2009 )	4-methoxyphenyl	−50.9	−177.5	174.8	9.2	46.6
MOSPEQ (Qiu, 2009 )	5-chloro-2-hydroxyphenyl	19.0	−178.5	−170.9	7.59	40.2
PAQJID (Gopal Reddy et al., 2017 )	4-ethylphenyl	−39.9	171.1	173.9	7.4	49.9
PAWVUG (Rassem et al., 2012a )	2-methoxyphenyl	29.1	−166.8	−175.1	19.2	66.6
PEDGOW (Saad et al., 2012 )	3-chlorophenyl	−21.1	179.5	175.3	−9.3	39.0
XEBYUA (Rassem et al., 2012b )	2-hydroxy-4-methoxyphenyl	28.7	178.1	−169.8	1.3	40.6

Figure 4
General chemical diagram, showing torsion angles τ₁, τ₂, τ₃ and τ₄ in the benzylidene-4-hydroxybenzohydrazide derivative.

5. Synthesis and crystallization

The title compound (I) was prepared by dissolving 4-hydroxybenzohydrazide (2 mmol, 0.30 g) in ethanol (10 ml). A solution of 3,4-dihydroxybenzaldehyde (2 mmol, 0.28 g) in ethanol (10 ml) was then added to the reaction. The mixture was refluxed for 6 h and the white solid of the product that appeared was collected by filtration, washed with ethanol and dried in air. Colourless single crystals of (I) were obtained after recrystallization from methanol at room temperature for several days.

M.p. 572–573 K. UV–Vis (MeOH) λ_max 213, 327 nm; FT–IR (KBr) ν (cm⁻¹): 3121 (O—H stretching), 2800 (C—H aromatic stretching), 1615 (amide C=O stretching), 1570 (C=N stretching), 1506 (C=C stretching of aromatic compound) cm⁻¹; ¹H NMR (300 MHz, d₆-DMSO) δ 11.39 (s, 1H, NH), 10.10 (s, 1H, Ar—OH), 8.23 (s, 1H, N=CH), 7.77 (d, J = 8.4 Hz, 2H, Ar—H), 6.84 (d, J = 8.4, 2H, Ar—H), 9.33 (s, 2H, Ar—OH), 7.22 (s, 1H, Ar—H), 6.90 (d, J = 7.8 Hz, 1H, Ar—H), 6.77 (d, J = 8.1 Hz, 1H, Ar—H).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C). All O- and N-bound H atoms were located in a difference-Fourier map and refined freely [O—H = 0.80 (2)–0.88 (2) Å and N—H = 0.87 (2) Å].

Table 3
Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₄
M_r	272.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.5352 (8), 7.1711 (5), 15.0606 (10)
β (°)	108.548 (2)
V (Å³)	1181.10 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.80 × 0.21 × 0.07

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.924, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	22559, 3200, 2453
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.161, 1.05
No. of reflections	3200
No. of parameters	197
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1942396

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010442/is5518sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010442/is5518Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010442/is5518Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXL2013 (Sheldrick, 2015) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) and PLATON (Spek, 2009).

(E)-N'-(3,4-Dihydroxybenzylidene)-4-hydroxybenzohydrazide top

Crystal data top

C₁₄H₁₂N₂O₄	F(000) = 568
M_r = 272.26	D_x = 1.531 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.5352 (8) Å	Cell parameters from 6293 reflections
b = 7.1711 (5) Å	θ = 2.9–29.2°
c = 15.0606 (10) Å	µ = 0.11 mm⁻¹
β = 108.548 (2)°	T = 296 K
V = 1181.10 (14) Å³	Plate, colourless
Z = 4	0.80 × 0.21 × 0.07 mm

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3200 independent reflections
Radiation source: fine-focus sealed tube	2453 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 29.2°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −15→15
T_min = 0.924, T_max = 0.954	k = −9→9
22559 measured reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0999P)² + 0.1317P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3200 reflections	Δρ_max = 0.35 e Å⁻³
197 parameters	Δρ_min = −0.18 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	0.87093 (9)	0.31797 (18)	0.75119 (6)	0.0493 (3)
O2	0.72990 (8)	0.42338 (15)	0.31133 (6)	0.0439 (3)
O3	0.36583 (9)	0.37514 (15)	−0.12560 (6)	0.0432 (3)
O4	0.11997 (10)	0.35694 (18)	−0.18715 (7)	0.0547 (3)
N1	0.54178 (10)	0.37659 (17)	0.32223 (7)	0.0392 (3)
N2	0.48862 (10)	0.38068 (17)	0.22612 (7)	0.0387 (3)
C1	0.64041 (11)	0.3493 (2)	0.52044 (8)	0.0360 (3)
H1A	0.555998	0.341901	0.493279	0.043*
C2	0.69125 (11)	0.32969 (19)	0.61626 (8)	0.0370 (3)
H2A	0.641478	0.308993	0.653221	0.044*
C3	0.81673 (12)	0.34105 (19)	0.65681 (8)	0.0359 (3)
C4	0.89049 (12)	0.3773 (2)	0.60204 (9)	0.0429 (3)
H4A	0.974622	0.389056	0.629625	0.051*
C5	0.83860 (12)	0.3960 (2)	0.50639 (9)	0.0398 (3)
H5A	0.888474	0.419686	0.469812	0.048*
C6	0.71320 (11)	0.38002 (16)	0.46381 (8)	0.0312 (3)
C7	0.66306 (11)	0.39454 (18)	0.36014 (8)	0.0334 (3)
C8	0.37218 (12)	0.37651 (18)	0.19709 (8)	0.0357 (3)
H8A	0.329660	0.374477	0.240199	0.043*
C9	0.30468 (12)	0.37489 (17)	0.09713 (8)	0.0332 (3)
C10	0.36617 (11)	0.38007 (18)	0.03124 (8)	0.0339 (3)
H10A	0.451058	0.387612	0.051040	0.041*
C11	0.30251 (11)	0.37414 (17)	−0.06263 (8)	0.0332 (3)
C12	0.17505 (12)	0.36368 (19)	−0.09316 (9)	0.0377 (3)
C13	0.11375 (12)	0.3624 (2)	−0.02790 (9)	0.0434 (3)
H13A	0.028756	0.358471	−0.047790	0.052*
C14	0.17809 (12)	0.3669 (2)	0.06705 (9)	0.0400 (3)
H14A	0.136252	0.364586	0.110600	0.048*
H1O1	0.8288 (18)	0.256 (3)	0.7732 (15)	0.074 (6)*
H1O3	0.324 (2)	0.421 (3)	−0.1808 (16)	0.092 (7)*
H1O4	0.046 (2)	0.345 (3)	−0.1964 (16)	0.085 (7)*
H1N1	0.4954 (19)	0.342 (3)	0.3546 (14)	0.069 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0364 (5)	0.0836 (8)	0.0215 (4)	−0.0105 (5)	0.0004 (4)	0.0057 (4)
O2	0.0376 (5)	0.0700 (7)	0.0267 (4)	−0.0036 (4)	0.0139 (4)	−0.0016 (4)
O3	0.0344 (5)	0.0719 (7)	0.0236 (4)	0.0037 (4)	0.0095 (4)	0.0026 (4)
O4	0.0352 (6)	0.0991 (9)	0.0227 (5)	−0.0083 (5)	−0.0009 (4)	0.0033 (5)
N1	0.0326 (6)	0.0651 (7)	0.0185 (5)	−0.0038 (5)	0.0060 (4)	0.0023 (4)
N2	0.0380 (6)	0.0576 (7)	0.0182 (5)	−0.0033 (5)	0.0056 (4)	0.0010 (4)
C1	0.0254 (6)	0.0554 (7)	0.0248 (6)	−0.0019 (5)	0.0046 (4)	−0.0004 (5)
C2	0.0319 (6)	0.0558 (8)	0.0232 (6)	−0.0014 (5)	0.0086 (5)	0.0005 (5)
C3	0.0335 (6)	0.0485 (7)	0.0220 (5)	−0.0024 (5)	0.0037 (5)	−0.0001 (5)
C4	0.0272 (6)	0.0688 (9)	0.0289 (6)	−0.0039 (6)	0.0037 (5)	0.0022 (6)
C5	0.0307 (6)	0.0611 (8)	0.0284 (6)	−0.0029 (5)	0.0105 (5)	0.0014 (5)
C6	0.0300 (6)	0.0411 (6)	0.0213 (5)	0.0007 (4)	0.0063 (4)	−0.0010 (4)
C7	0.0337 (6)	0.0440 (7)	0.0222 (6)	−0.0001 (5)	0.0086 (5)	−0.0019 (4)
C8	0.0352 (7)	0.0481 (7)	0.0231 (6)	0.0003 (5)	0.0081 (5)	0.0012 (5)
C9	0.0332 (6)	0.0416 (6)	0.0219 (5)	0.0005 (5)	0.0046 (5)	0.0009 (4)
C10	0.0261 (5)	0.0492 (7)	0.0234 (6)	0.0004 (5)	0.0038 (4)	−0.0001 (5)
C11	0.0311 (6)	0.0443 (7)	0.0234 (5)	0.0008 (5)	0.0073 (4)	0.0010 (4)
C12	0.0313 (6)	0.0521 (7)	0.0243 (6)	−0.0013 (5)	0.0012 (5)	0.0026 (5)
C13	0.0255 (6)	0.0686 (9)	0.0321 (7)	−0.0003 (5)	0.0038 (5)	0.0046 (6)
C14	0.0329 (6)	0.0582 (8)	0.0298 (6)	0.0015 (5)	0.0110 (5)	0.0037 (5)

Geometric parameters (Å, º) top

O1—C3	1.3688 (14)	C4—C5	1.3794 (18)
O1—H1O1	0.80 (2)	C4—H4A	0.9300
O2—C7	1.2403 (15)	C5—C6	1.3880 (18)
O3—C11	1.3688 (15)	C5—H5A	0.9300
O3—H1O3	0.88 (2)	C6—C7	1.4861 (15)
O4—C12	1.3556 (15)	C8—C9	1.4584 (16)
O4—H1O4	0.83 (3)	C8—H8A	0.9300
N1—C7	1.3385 (17)	C9—C14	1.3856 (18)
N1—N2	1.3811 (14)	C9—C10	1.3918 (17)
N1—H1N1	0.87 (2)	C10—C11	1.3709 (16)
N2—C8	1.2738 (17)	C10—H10A	0.9300
C1—C2	1.3812 (16)	C11—C12	1.3959 (18)
C1—C6	1.3916 (17)	C12—C13	1.3815 (19)
C1—H1A	0.9300	C13—C14	1.3861 (17)
C2—C3	1.3828 (18)	C13—H13A	0.9300
C2—H2A	0.9300	C14—H14A	0.9300
C3—C4	1.3852 (19)

C3—O1—H1O1	111.0 (15)	O2—C7—N1	121.71 (11)
C11—O3—H1O3	113.5 (15)	O2—C7—C6	121.79 (11)
C12—O4—H1O4	107.2 (16)	N1—C7—C6	116.49 (11)
C7—N1—N2	120.02 (11)	N2—C8—C9	120.86 (12)
C7—N1—H1N1	122.4 (13)	N2—C8—H8A	119.6
N2—N1—H1N1	116.6 (13)	C9—C8—H8A	119.6
C8—N2—N1	115.30 (11)	C14—C9—C10	119.41 (11)
C2—C1—C6	121.20 (11)	C14—C9—C8	119.93 (12)
C2—C1—H1A	119.4	C10—C9—C8	120.66 (11)
C6—C1—H1A	119.4	C11—C10—C9	120.47 (11)
C1—C2—C3	119.49 (11)	C11—C10—H10A	119.8
C1—C2—H2A	120.3	C9—C10—H10A	119.8
C3—C2—H2A	120.3	O3—C11—C10	119.04 (11)
O1—C3—C2	121.31 (12)	O3—C11—C12	120.68 (11)
O1—C3—C4	118.49 (11)	C10—C11—C12	120.26 (11)
C2—C3—C4	120.20 (11)	O4—C12—C13	124.53 (12)
C5—C4—C3	119.69 (12)	O4—C12—C11	116.14 (12)
C5—C4—H4A	120.2	C13—C12—C11	119.33 (11)
C3—C4—H4A	120.2	C12—C13—C14	120.43 (12)
C4—C5—C6	121.12 (12)	C12—C13—H13A	119.8
C4—C5—H5A	119.4	C14—C13—H13A	119.8
C6—C5—H5A	119.4	C9—C14—C13	120.07 (12)
C5—C6—C1	118.24 (11)	C9—C14—H14A	120.0
C5—C6—C7	118.67 (11)	C13—C14—H14A	120.0
C1—C6—C7	123.09 (11)

C7—N1—N2—C8	−174.98 (12)	N1—N2—C8—C9	−178.29 (10)
C6—C1—C2—C3	0.1 (2)	N2—C8—C9—C14	178.83 (12)
C1—C2—C3—O1	−178.44 (12)	N2—C8—C9—C10	−0.76 (19)
C1—C2—C3—C4	1.9 (2)	C14—C9—C10—C11	−1.11 (18)
O1—C3—C4—C5	178.19 (13)	C8—C9—C10—C11	178.47 (11)
C2—C3—C4—C5	−2.1 (2)	C9—C10—C11—O3	−178.51 (12)
C3—C4—C5—C6	0.3 (2)	C9—C10—C11—C12	0.29 (19)
C4—C5—C6—C1	1.6 (2)	O3—C11—C12—O4	−0.71 (19)
C4—C5—C6—C7	−177.78 (12)	C10—C11—C12—O4	−179.50 (12)
C2—C1—C6—C5	−1.9 (2)	O3—C11—C12—C13	179.81 (13)
C2—C1—C6—C7	177.51 (12)	C10—C11—C12—C13	1.03 (19)
N2—N1—C7—O2	3.3 (2)	O4—C12—C13—C14	179.03 (13)
N2—N1—C7—C6	−177.33 (10)	C11—C12—C13—C14	−1.5 (2)
C5—C6—C7—O2	−1.18 (19)	C10—C9—C14—C13	0.60 (19)
C1—C6—C7—O2	179.44 (13)	C8—C9—C14—C13	−178.99 (12)
C5—C6—C7—N1	179.42 (12)	C12—C13—C14—C9	0.7 (2)
C1—C6—C7—N1	0.04 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	0.80 (2)	1.92 (2)	2.7203 (15)	171 (2)
O3—H1O3···O2ⁱⁱ	0.88 (2)	2.17 (2)	3.0276 (13)	163 (2)
O4—H1O4···O1ⁱⁱⁱ	0.82 (2)	1.93 (2)	2.7379 (16)	166 (2)
N1—H1N1···O3ⁱ	0.87 (2)	2.24 (2)	3.0017 (16)	146.1 (19)

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

Selected torsion angles (°) and the dihedral angle (°) between the terminal benzene rings top

Compound	R	τ₁	τ₂	τ₃	τ₄	Dihedral angle
Planar
(I)	3,4-dihydroxyphenyl	-1.2	-177.3	-175.0	-0.8	9.2
ABALIA (Fun et al., 2011)	3-hydroxy-4-methoxyphenyl	3.2	178.4	170.1	-14.2	24.2
CECZOB (Subashini et al., 2012)	4-chlorophenyl	26.1	-174.4	166.6	-8.9	5.8
CECZUH (Subashini et al., 2012)	4-bromophenyl	25.6	-174.9	169.0	-7.2	9.8
ESOTUD (Chantrapromma et al., 2016)	3-methoxyphenyl	-19.4, 20.7	-173.5, -177.8	-175.7, -173.0	1.2, 0.6	24.0, 29.3
HOZBII (Li & Ban, 2009)	4-nitrophenyl	2.0	177.7	178.3	-0.6	2.5
IJUKEE (Zhang, 2011)	4-hydroxy-3-nitrophenyl	-7.2	-177.0	-179.3	6.0	5.5
IRAXEF (Sánchez-Lozano et al., 2011)	2,4-dihydroxyphenyl	-7.7	-177.8	-177.2	-4.1	6.9
MOZPEX (Ren, 2009)	3,5-dichloro-2-hydroxyphenyl	12.3	178.7	-179.4	-7.3	5.1
ROFMOP (Xue et al., 2008)	3-bromo-5-chloro-2-hydroxyphenyl	-2.3	175.9	-176.5	-1.3	3.0
TEWLAL (Ayyannan et al., 2016)	5-bromo-2-hydroxyphenyl	-15.7	-173.6	168.9	3.1	27.0
WACVON (Shalash et al., 2010)	4-hydroxy-3-methoxyphenyl	-34.2	-175.5	174.7	15.4	28.6
WACXOP (Huang, 2010)	2,4-dichlorophenyl	-14.3	-179.8	-175.0	3.0	7.0
YAGYAI (Horkaew et al., 2011)	3,4,5-trimethoxyphenyl	-10.6	172.2	175.8	2.8	19.4
YIFPAF (Salhin et al., 2007)	2-hydroxyphenyl	18.8	179.5	178.7	3.3	21.7
ZAPKOS (Hou, 2012)	3-nitrophenyl	-14.6	169.4	177.4	13.8	9.2
ZIPLAO (Prachumrat et al., 2018)	2,3-dimethoxyphenyl	9.6	-175.3	172.9	-1.3	9.3
Non-planar
CABWUA (Meng et al., 2014)	2-hydroxy-5-methylphenyl	18.4	-178.5	-169.8	8.0	40.8
CEDBAQ (Subashini et al., 2012)	4-(diethylamino)phenyl	34.9	-178.5	-151.7	8.75	77.3
HUCVIL (Hao, 2009)	2-chlorophenyl	-22.5	-179.2	177.4	-4.2	30.5
HUCWOS (Shi, 2009)	4-methoxyphenyl	-50.9	-177.5	174.8	9.2	46.6
MOSPEQ (Qiu, 2009)	5-chloro-2-hydroxyphenyl	19.0	-178.5	-170.9	7.59	40.2
PAQJID (Gopal Reddy et al., 2017)	4-ethylphenyl	-39.9	171.1	173.9	7.4	49.9
PAWVUG (Rassem et al., 2012a)	2-methoxyphenyl	29.1	-166.8	-175.1	19.2	66.6
PEDGOW (Saad et al., 2012)	3-chlorophenyl	-21.1	179.5	175.3	-9.3	39.0
XEBYUA (Rassem et al., 2012b)	2-hydroxy-4-methoxyphenyl	28.7	178.1	-169.8	1.3	40.6

Footnotes

¹This paper is dedicated to Her Royal Highness Princess Chulabhorn Krom Phra Srisavangavadhana of Thailand for her contributions to science on the occasion of her 62th birthday, which fell on July 4th, 2019.

‡Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

The authors thank Prince of Songkla University for research grant (SCI590716S). PP thanks the Graduate School, Prince of Songkla University for partial financial support. The authors extend their appreciation to the Universiti Sains Malaysia for the research facilities.

Funding information

The authors thank Prince of Songkla University for research grant (SCI590716S). PP thanks the Graduate School, Prince of Songkla University for partial financial support.

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