Crystal structure of methyl 4-(4-hy­droxy­phen­yl)-6-methyl-2-oxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate monohydrate

Bairagi, K.M.; Venugopala, K.N.; Mondal, P.K.; Odhav, B.; Nayak, S.K.

doi:10.1107/S2056989016013359

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ISSN: 2056-9890

Volume 72| Part 9| September 2016| Pages 1335-1338

https://doi.org/10.1107/S2056989016013359

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Crystal structure of methyl 4-(4-hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate monohydrate

Keshab M. Bairagi,^a Katharigatta N. Venugopala,^b Pradip Kumar Mondal,^c Bharti Odhav ^b and Susanta K. Nayak ^a ^*

^aDepartment of Chemistry, Visvesvaraya National Institute of Technology, Nagpur, 440010, Maharashtra, India, ^bDepartment of Biotechnology and Food Technology, Durban University of Technology, Durban 4001, South Africa, and ^cDepartment of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462023, India
^*Correspondence e-mail:

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 July 2016; accepted 19 August 2016; online 26 August 2016)

The title hydrate, C₁₃H₁₄N₂O₄·H₂O, crystallizes with two formula units in the asymmetric unit (Z′ = 2). The dihedral angles between the planes of the tetrahydropyrimidine ring and the 4-hydroxyphenyl ring and ester group are 86.78 (4) and 6.81 (6)°, respectively, for one molecule and 89.35 (4) and 3.02 (4)° for the other. In the crystal, the organic molecules form a dimer, linked by a pair of N—H⋯O hydrogen bonds. The hydroxy groups of the organic molecules donate O—H⋯O hydrogen bonds to water molecules. Further, the hydroxy group accepts N—H⋯O hydrogen bonds from amides whereas the water molecules donate O—H⋯O hydrogen bonds to the both the amide and ester carbonyl groups. Other weak interactions, including C—H⋯O, C—H⋯π and π–π, further consolidate the packing, generating a three-dimensional network.

Keywords: crystal structure; DHPM derivative; monohydrate; Z′ = 2; hydrogen bonding.

CCDC reference: 1499989

1. Chemical context

Dihydropyrimidine (DHPM) derivatives are used in the treatment of disease as antiviral, antitumor, antibacterial and antimalarial agents, as first reported by the Italian chemist Pietro Biginelli in 1893 [Kappe (2000 ), Nayak et al. (2010 ) and references therein]. We have been working on the synthesis of various DHPM derivatives for better biological activities (Narayanaswamy et al., 2013 ; Nayak et al., 2011 ) and a wide range of applications (Nayak et al., 2009 , 2010). Here, we report the synthesis and single-crystal structure of the title compound, (I).

2. Structural commentary

Compound (I) crystallizes as a monohydrate with two formula units in the asymmetric unit (Z′ = 2), which may be supported by the formation of hydrogen bonds between the hydroxyphenyl group and the water molecule and dimer formation through N—H⋯O hydrogen bonds (Fig. 1). The dihedral angles between the planes of the six-membered tetrahydropyrimidine ring with its 4-hydroxyphenyl and ester substituents are 86.78 (4) and 6.81 (6)°, respectively, for the N1-containing molecule and 89.35 (4)° and 3.02 (4)°, respectively, for the other.

Figure 1
The asymmetric unit of the title compound with 50% probability ellipsoids. The double-dashed lines indicate hydrogen bonds.

3. Supramolecular features

In the crystal of (I), the DHPM molecules form dimers through N—H⋯O hydrogen bonds with an R₂²(8) graph-set motif (Fig. 2). The hydroxy groups of the dihydropyrimidine molecules donate O—H⋯O hydrogen bonds to water molecules, which may explain the preference for the monohydrated crystalline form. Further, the hydroxy group accepts N—H⋯O hydrogen bonds from amide groups whereas the water molecule donates O—H⋯O hydrogen bonds to the both the amide and ester carbonyl groups (Table 1). The key role of the water molecule in the hydrogen-bonding network is shown in Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C8–C13 and C21–C26 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O6	0.878 (19)	2.10 (2)	2.9762 (16)	173.1 (17)
N3—H3N⋯O1	0.88 (2)	1.98 (2)	2.8626 (16)	174 (2)
N2—H2N⋯O9ⁱ	0.89 (2)	2.02 (2)	2.8971 (19)	170.0 (18)
N4—H4N⋯O4ⁱⁱ	0.87 (2)	2.13 (2)	2.9738 (19)	163.4 (18)
O4—H1O⋯O5	0.87 (2)	1.78 (2)	2.6473 (16)	175 (2)
O9—H2O⋯O10	0.90 (2)	1.73 (2)	2.6189 (17)	174.7 (19)
O5—H4O⋯O2ⁱⁱⁱ	0.84 (2)	2.15 (2)	2.8549 (19)	141 (2)
O5—H3O⋯O1^iv	0.91 (3)	1.91 (3)	2.786 (2)	162 (2)
C20—H20C⋯O5^iv	1.00 (2)	2.56 (2)	3.332 (2)	133.7 (17)
C26—H26⋯O3^v	0.971 (17)	2.571 (18)	3.4607 (18)	152.4 (14)
C6—H6B⋯Cg2^vi	0.989 (19)	2.70 (2)	3.392 (2)	127.1 (16)
C19—H19C⋯Cg1^vii	0.98 (2)	2.84 (2)	3.395 (2)	116.5 (16)
Symmetry codes: (i) x-1, y-1, z-1; (ii) x+1, y+1, z+1; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z+1; (v) -x+1, -y+1, -z+2; (vi) x, y, z-1; (vii) x, y+1, z+1.

Figure 2
Crystal structure of title compound showing the dimers formed by N—H⋯O hydrogen bonds as well as the links to the water molecules, which donate O—H⋯O hydrogen bonds to the ester groups.

Figure 3
Three-dimensional crystal structure of the title compound showing the role of the water molecules in the hydrogen-bonding network.

Weak interactions including C—H⋯O, C—H⋯π and π⋯π [Cg1⋯Cg2(2 − x, 1 − y, 1 − z) = 3.652 (1) Å; Cg1 and Cg2 are the centroids of the C8–C13 and C21–C26 rings, respectively] help to consolidate the packing and a three-dimensional network arises.

4. Database survey

A search of the Cambridge structural Database (CSD) (Conquest Version 1.17; Groom et al., 2016 ) for methyl 4-(4-hydroxyphenyl)-6-methyl 2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate gave no hits; however, the crystal structures of sixteen hydroxyphenyl-substituted DHPM derivatives were found. These structures include four 2-hydroxyphenyl-substituted DHPM molecules, one 3-hydroxy-substituted and eleven 4-hydroxyphenyl-substituted DHPM molecules. It is interesting to note that five of the 4-hydroxyphenyl-substituted DHPM molecules prefer to crystallize in a hydrated form (ZOHFIN: Vishnevskii et al. 2014 ; VOJDOO: Das et al., 2008 ; VOJDOO01: Nayak et al., 2009; POWXIJ: Thenmozhi et al., 2009 ; XISMES: Liu et al., 2008 ). However, of these only ethyl 4-(4-hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5 carboxylate (VOJDOO: Das et al., 2008) crystallizes with a higher formula unit (Z′ > 1), i.e. its structure has three formula units in the asymmetric unit (Z′ = 3) in the monohydrated form. Hence, the title compound is the second member of this family of monohydrates to crystallize with higher formula units in the asymmetric unit (Z′ = 2). The CSD analysis clearly suggests that 4-hydroxy-substituted DHPM molecule are prone to crystallize in their hydrated form compared to 3-hydroxy or 2-hydroxy-substituted DHPM molecules; this may be due to the observed O—H⋯O hydrogen bonding with water molecule acceptors with the hydroxyl group in the preferred para position.

5. Synthesis and crystallization

The title compound was obtained by the reaction of three components, viz. methyl acetoacetate, 4-hydroxybenzaldehyde and urea in ethanol solution according to a reported procedure (Tumtin et al., 2010 ). The reaction progress was monitored by thin layer chromatography and after the completion of the reaction, the solvent was removed and the solid obtained was recrystallized from ethanol to obtain the pure product. Colorless single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in ethanol (yield 75%, m.p. 412.3 K). FT–IR ν_max cm⁻¹: 3379 (O—H), 3248 (N—H), 2963 (sp² C—H), 2845 (sp³ C—H), 1763 (C=O ester), 1682 (C=O amide), 1594 (C=C alkene), 1514 (C=C aromatic) and 1260 (C—O, ester).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were located in difference Fourier maps and freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂O₄·H₂O
M_r	280.28
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	10.7527 (6), 11.6731 (6), 12.4456 (7)
α, β, γ (°)	98.236 (2), 112.374 (1), 108.944 (2)
V (Å³)	1301.16 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.23 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII DUO
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.926, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	21716, 5116, 4387
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.099, 1.04
No. of reflections	5116
No. of parameters	489
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.28
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), Mercury (Farrugia, 2012 ) and ORTEP-3 for Windows (Macrae et al, 2008 ).

Supporting information

CCDC reference: 1499989

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016013359/hb7604sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016013359/hb7604Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016013359/hb7604Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al. (2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

Methyl 4-(4-hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate monohydrate top

Crystal data top

C₁₃H₁₄N₂O₄·H₂O	Z = 4
M_r = 280.28	F(000) = 592
Triclinic, P1	D_x = 1.431 Mg m⁻³
a = 10.7527 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6731 (6) Å	Cell parameters from 740 reflections
c = 12.4456 (7) Å	θ = 2.2–30.1°
α = 98.236 (2)°	µ = 0.11 mm⁻¹
β = 112.374 (1)°	T = 150 K
γ = 108.944 (2)°	Plate, colorless
V = 1301.16 (13) Å³	0.23 × 0.20 × 0.15 mm

Data collection top

Bruker Kappa APEXII DUO diffractometer	5116 independent reflections
Radiation source: fine-focus sealed tube	4387 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
T_min = 0.926, T_max = 0.934	k = −14→14
21716 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: difference Fourier map
wR(F²) = 0.099	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.046P)² + 0.5474P] where P = (F_o² + 2F_c²)/3
5116 reflections	(Δ/σ)_max = 0.001
489 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.28 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
C1	0.39164 (15)	0.54081 (12)	0.87596 (12)	0.0139 (3)
C2	0.60979 (15)	0.53784 (13)	0.86203 (12)	0.0148 (3)
C3	0.53110 (14)	0.42096 (12)	0.77764 (12)	0.0136 (3)
C4	0.36594 (14)	0.34937 (12)	0.73347 (12)	0.0133 (3)
C5	0.60417 (15)	0.35855 (12)	0.72784 (13)	0.0153 (3)
C6	0.56565 (17)	0.17576 (14)	0.58648 (15)	0.0209 (3)
C7	0.77354 (16)	0.61333 (15)	0.91932 (15)	0.0213 (3)
C8	0.26914 (14)	0.32159 (12)	0.59847 (12)	0.0135 (3)
C9	0.16677 (15)	0.19821 (12)	0.52680 (13)	0.0147 (3)
C10	0.07261 (15)	0.17160 (12)	0.40490 (13)	0.0153 (3)
C11	0.07936 (15)	0.26965 (13)	0.35266 (12)	0.0142 (3)
C12	0.18128 (15)	0.39416 (13)	0.42297 (13)	0.0155 (3)
C13	0.27411 (15)	0.41876 (13)	0.54497 (13)	0.0155 (3)
C14	0.62129 (15)	0.92206 (13)	1.09772 (12)	0.0144 (3)
C15	0.40117 (15)	0.90446 (13)	1.12011 (12)	0.0149 (3)
C16	0.46382 (15)	1.02900 (13)	1.18448 (12)	0.0149 (3)
C17	0.62246 (15)	1.11457 (12)	1.21918 (12)	0.0142 (3)
C18	0.37813 (15)	1.08432 (13)	1.22405 (13)	0.0179 (3)
C19	0.37283 (19)	1.26713 (15)	1.32473 (17)	0.0253 (3)
C20	0.24606 (16)	0.81093 (14)	1.07923 (14)	0.0209 (3)
C21	0.72322 (14)	1.15937 (12)	1.35558 (12)	0.0134 (3)
C22	0.81179 (15)	1.28805 (12)	1.41893 (13)	0.0154 (3)
C23	0.90581 (15)	1.32811 (12)	1.54268 (13)	0.0160 (3)
C24	0.91207 (14)	1.23915 (13)	1.60557 (12)	0.0146 (3)
C25	0.82479 (15)	1.10980 (13)	1.54369 (13)	0.0146 (3)
C26	0.73188 (14)	1.07151 (12)	1.41985 (13)	0.0140 (3)
N1	0.53814 (13)	0.59703 (11)	0.90574 (11)	0.0163 (3)
N2	0.31652 (13)	0.42046 (11)	0.80401 (11)	0.0153 (3)
N3	0.48323 (13)	0.85228 (11)	1.08401 (11)	0.0162 (3)
N4	0.68018 (13)	1.04716 (11)	1.15386 (11)	0.0154 (3)
O1	0.33372 (11)	0.59969 (9)	0.91804 (9)	0.0185 (2)
O2	0.73271 (11)	0.40171 (9)	0.74845 (10)	0.0225 (2)
O3	0.50735 (11)	0.24088 (9)	0.64955 (9)	0.0191 (2)
O4	−0.01614 (11)	0.23932 (9)	0.23188 (9)	0.0178 (2)
O5	−0.03765 (13)	0.44197 (10)	0.16905 (11)	0.0253 (3)
O6	0.68445 (10)	0.86842 (9)	1.05711 (9)	0.0181 (2)
O7	0.25613 (12)	1.02650 (11)	1.21377 (13)	0.0372 (3)
O8	0.45133 (11)	1.21067 (9)	1.27839 (10)	0.0215 (2)
O9	1.00441 (11)	1.28271 (9)	1.72845 (9)	0.0182 (2)
O10	1.02933 (13)	1.10134 (11)	1.82525 (11)	0.0279 (3)
H2	0.3460 (16)	0.2653 (14)	0.7513 (13)	0.012 (4)*
H4	0.6248 (16)	1.1903 (14)	1.1908 (14)	0.013 (4)*
H6C	0.801 (2)	0.695 (2)	0.9685 (19)	0.042 (6)*
H6A	0.6325 (19)	0.1504 (15)	0.6451 (15)	0.020 (4)*
H6B	0.618 (2)	0.2300 (17)	0.5497 (17)	0.032 (5)*
H7A	0.473 (2)	0.1020 (18)	0.5170 (18)	0.037 (5)*
H7B	0.810 (2)	0.6203 (19)	0.8581 (19)	0.043 (6)*
H7C	0.823 (2)	0.572 (2)	0.971 (2)	0.050 (6)*
H9	0.1627 (17)	0.1297 (15)	0.5647 (14)	0.014 (4)*
H10	0.0015 (18)	0.0858 (15)	0.3535 (15)	0.017 (4)*
H12	0.1873 (18)	0.4638 (16)	0.3874 (15)	0.023 (4)*
H13	0.3430 (18)	0.5067 (16)	0.5956 (15)	0.022 (4)*
H19A	0.272 (2)	1.2425 (19)	1.2587 (19)	0.041 (5)*
H19B	0.430 (2)	1.355 (2)	1.354 (2)	0.050 (6)*
H19C	0.369 (2)	1.2410 (18)	1.3956 (18)	0.035 (5)*
H20A	0.224 (2)	0.8036 (18)	1.1506 (19)	0.040 (5)*
H20B	0.176 (2)	0.8369 (18)	1.0264 (18)	0.035 (5)*
H20C	0.232 (2)	0.725 (2)	1.0365 (19)	0.043 (6)*
H22	0.8056 (18)	1.3477 (16)	1.3726 (15)	0.022 (4)*
H23	0.9677 (18)	1.4181 (16)	1.5872 (15)	0.019 (4)*
H25	0.8305 (18)	1.0473 (15)	1.5905 (15)	0.020 (4)*
H26	0.6728 (17)	0.9814 (15)	1.3765 (14)	0.014 (4)*
H1N	0.587 (2)	0.6755 (18)	0.9547 (16)	0.025 (4)*
H3N	0.442 (2)	0.7732 (19)	1.0363 (18)	0.034 (5)*
H2N	0.220 (2)	0.3872 (16)	0.7813 (16)	0.024 (4)*
H4N	0.769 (2)	1.0913 (17)	1.1660 (16)	0.025 (5)*
H1O	−0.017 (2)	0.308 (2)	0.2135 (19)	0.045 (6)*
H2O	1.007 (2)	1.218 (2)	1.759 (2)	0.047 (6)*
H3O	−0.126 (3)	0.447 (2)	0.147 (2)	0.049 (6)*
H4O	0.033 (2)	0.513 (2)	0.1929 (19)	0.040 (6)*
H5O	0.954 (3)	1.045 (2)	1.824 (2)	0.050 (6)*
H6O	1.115 (3)	1.097 (2)	1.870 (2)	0.048 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0135 (7)	0.0148 (6)	0.0126 (6)	0.0056 (5)	0.0053 (5)	0.0037 (5)
C2	0.0130 (7)	0.0171 (7)	0.0149 (7)	0.0068 (5)	0.0060 (5)	0.0064 (5)
C3	0.0112 (6)	0.0138 (6)	0.0153 (7)	0.0050 (5)	0.0053 (5)	0.0056 (5)
C4	0.0118 (6)	0.0104 (6)	0.0175 (7)	0.0041 (5)	0.0075 (5)	0.0021 (5)
C5	0.0140 (7)	0.0136 (6)	0.0176 (7)	0.0055 (5)	0.0065 (6)	0.0058 (5)
C6	0.0216 (8)	0.0187 (7)	0.0271 (8)	0.0102 (6)	0.0155 (7)	0.0031 (6)
C7	0.0136 (7)	0.0198 (7)	0.0219 (8)	0.0025 (6)	0.0057 (6)	−0.0002 (6)
C8	0.0104 (6)	0.0133 (6)	0.0171 (7)	0.0055 (5)	0.0071 (5)	0.0021 (5)
C9	0.0139 (7)	0.0123 (6)	0.0196 (7)	0.0061 (5)	0.0091 (6)	0.0039 (5)
C10	0.0120 (7)	0.0112 (6)	0.0192 (7)	0.0035 (5)	0.0067 (6)	−0.0008 (5)
C11	0.0111 (6)	0.0171 (7)	0.0147 (7)	0.0067 (5)	0.0066 (5)	0.0019 (5)
C12	0.0140 (7)	0.0137 (6)	0.0190 (7)	0.0056 (5)	0.0079 (6)	0.0051 (5)
C13	0.0112 (6)	0.0111 (6)	0.0201 (7)	0.0026 (5)	0.0061 (6)	0.0010 (5)
C14	0.0125 (6)	0.0160 (6)	0.0116 (6)	0.0059 (5)	0.0026 (5)	0.0034 (5)
C15	0.0121 (7)	0.0191 (7)	0.0117 (6)	0.0066 (5)	0.0038 (5)	0.0041 (5)
C16	0.0119 (7)	0.0173 (7)	0.0157 (7)	0.0063 (5)	0.0060 (5)	0.0052 (5)
C17	0.0137 (7)	0.0128 (6)	0.0169 (7)	0.0061 (5)	0.0074 (6)	0.0038 (5)
C18	0.0142 (7)	0.0180 (7)	0.0205 (7)	0.0067 (6)	0.0072 (6)	0.0050 (6)
C19	0.0263 (9)	0.0200 (8)	0.0398 (10)	0.0132 (7)	0.0224 (8)	0.0086 (7)
C20	0.0140 (7)	0.0191 (7)	0.0216 (8)	0.0023 (6)	0.0065 (6)	−0.0007 (6)
C21	0.0100 (6)	0.0131 (6)	0.0173 (7)	0.0048 (5)	0.0074 (5)	0.0015 (5)
C22	0.0150 (7)	0.0126 (6)	0.0207 (7)	0.0057 (5)	0.0104 (6)	0.0041 (5)
C23	0.0134 (7)	0.0098 (6)	0.0214 (7)	0.0021 (5)	0.0089 (6)	−0.0012 (5)
C24	0.0101 (6)	0.0163 (6)	0.0153 (7)	0.0050 (5)	0.0062 (5)	−0.0008 (5)
C25	0.0120 (6)	0.0142 (6)	0.0187 (7)	0.0058 (5)	0.0079 (6)	0.0041 (5)
C26	0.0110 (6)	0.0095 (6)	0.0190 (7)	0.0028 (5)	0.0068 (5)	0.0008 (5)
N1	0.0130 (6)	0.0115 (6)	0.0173 (6)	0.0017 (5)	0.0051 (5)	−0.0016 (5)
N2	0.0101 (6)	0.0147 (6)	0.0172 (6)	0.0030 (5)	0.0060 (5)	0.0001 (5)
N3	0.0128 (6)	0.0126 (6)	0.0178 (6)	0.0032 (5)	0.0053 (5)	−0.0005 (5)
N4	0.0119 (6)	0.0142 (6)	0.0175 (6)	0.0034 (5)	0.0071 (5)	0.0013 (5)
O1	0.0154 (5)	0.0168 (5)	0.0201 (5)	0.0061 (4)	0.0074 (4)	−0.0002 (4)
O2	0.0129 (5)	0.0211 (5)	0.0301 (6)	0.0053 (4)	0.0101 (4)	0.0021 (4)
O3	0.0158 (5)	0.0139 (5)	0.0264 (6)	0.0052 (4)	0.0114 (4)	0.0000 (4)
O4	0.0158 (5)	0.0165 (5)	0.0148 (5)	0.0042 (4)	0.0039 (4)	0.0023 (4)
O5	0.0141 (6)	0.0149 (5)	0.0356 (6)	0.0039 (5)	0.0036 (5)	0.0026 (5)
O6	0.0150 (5)	0.0169 (5)	0.0202 (5)	0.0072 (4)	0.0073 (4)	0.0008 (4)
O7	0.0200 (6)	0.0253 (6)	0.0613 (9)	0.0033 (5)	0.0247 (6)	−0.0035 (6)
O8	0.0200 (5)	0.0154 (5)	0.0342 (6)	0.0086 (4)	0.0173 (5)	0.0051 (4)
O9	0.0152 (5)	0.0160 (5)	0.0152 (5)	0.0027 (4)	0.0041 (4)	−0.0005 (4)
O10	0.0135 (6)	0.0255 (6)	0.0367 (7)	0.0048 (5)	0.0054 (5)	0.0119 (5)

Geometric parameters (Å, º) top

C1—O1	1.2481 (17)	C15—C20	1.4984 (19)
C1—N2	1.3342 (17)	C16—C18	1.4659 (19)
C1—N1	1.3653 (18)	C16—C17	1.5177 (19)
C2—C3	1.3579 (19)	C17—N4	1.4776 (17)
C2—N1	1.3872 (18)	C17—C21	1.5188 (19)
C2—C7	1.4973 (19)	C17—H4	0.994 (15)
C3—C5	1.4647 (19)	C18—O7	1.2105 (18)
C3—C4	1.5218 (18)	C18—O8	1.3444 (17)
C4—N2	1.4745 (17)	C19—O8	1.4499 (17)
C4—C8	1.5182 (19)	C19—H19A	0.99 (2)
C4—H2	1.009 (15)	C19—H19B	0.94 (2)
C5—O2	1.2127 (17)	C19—H19C	0.98 (2)
C5—O3	1.3548 (17)	C20—H20A	1.01 (2)
C6—O3	1.4491 (17)	C20—H20B	0.96 (2)
C6—H6A	0.968 (17)	C20—H20C	1.00 (2)
C6—H6B	0.989 (19)	C21—C26	1.3931 (19)
C6—H7A	1.03 (2)	C21—C22	1.3946 (19)
C7—H6C	0.95 (2)	C22—C23	1.384 (2)
C7—H7B	0.98 (2)	C22—H22	0.968 (17)
C7—H7C	0.96 (2)	C23—C24	1.391 (2)
C8—C9	1.3917 (19)	C23—H23	0.975 (17)
C8—C13	1.3918 (19)	C24—O9	1.3699 (17)
C9—C10	1.384 (2)	C24—C25	1.3965 (19)
C9—H9	0.982 (16)	C25—C26	1.383 (2)
C10—C11	1.3904 (19)	C25—H25	0.999 (17)
C10—H10	0.972 (16)	C26—H26	0.971 (16)
C11—O4	1.3696 (16)	N1—H1N	0.878 (19)
C11—C12	1.3966 (19)	N2—H2N	0.890 (19)
C12—C13	1.385 (2)	N3—H3N	0.88 (2)
C12—H12	0.976 (17)	N4—H4N	0.867 (19)
C13—H13	0.983 (17)	O4—H1O	0.86 (2)
C14—O6	1.2472 (17)	O5—H3O	0.91 (2)
C14—N4	1.3386 (18)	O5—H4O	0.83 (2)
C14—N3	1.3706 (18)	O9—H2O	0.90 (2)
C15—C16	1.3523 (19)	O10—H5O	0.86 (3)
C15—N3	1.3869 (18)	O10—H6O	0.90 (2)

O1—C1—N2	122.43 (12)	N4—C17—C16	109.46 (11)
O1—C1—N1	120.57 (12)	N4—C17—C21	109.83 (11)
N2—C1—N1	116.97 (12)	C16—C17—C21	113.17 (11)
C3—C2—N1	119.80 (12)	N4—C17—H4	106.2 (9)
C3—C2—C7	126.65 (13)	C16—C17—H4	109.2 (9)
N1—C2—C7	113.53 (12)	C21—C17—H4	108.7 (9)
C2—C3—C5	120.57 (12)	O7—C18—O8	121.30 (13)
C2—C3—C4	121.63 (12)	O7—C18—C16	126.02 (13)
C5—C3—C4	117.78 (11)	O8—C18—C16	112.66 (12)
N2—C4—C8	108.71 (10)	O8—C19—H19A	109.5 (12)
N2—C4—C3	109.65 (11)	O8—C19—H19B	106.2 (14)
C8—C4—C3	115.47 (11)	H19A—C19—H19B	112.9 (18)
N2—C4—H2	105.7 (9)	O8—C19—H19C	110.4 (11)
C8—C4—H2	107.5 (9)	H19A—C19—H19C	111.3 (16)
C3—C4—H2	109.4 (9)	H19B—C19—H19C	106.4 (17)
O2—C5—O3	121.53 (13)	C15—C20—H20A	111.6 (12)
O2—C5—C3	127.41 (13)	C15—C20—H20B	111.1 (12)
O3—C5—C3	111.05 (11)	H20A—C20—H20B	106.6 (16)
O3—C6—H6A	107.7 (10)	C15—C20—H20C	109.4 (12)
O3—C6—H6B	112.2 (11)	H20A—C20—H20C	107.8 (16)
H6A—C6—H6B	110.0 (14)	H20B—C20—H20C	110.3 (16)
O3—C6—H7A	103.6 (11)	C26—C21—C22	118.39 (13)
H6A—C6—H7A	115.1 (14)	C26—C21—C17	120.28 (12)
H6B—C6—H7A	108.1 (15)	C22—C21—C17	121.31 (12)
C2—C7—H6C	110.7 (12)	C23—C22—C21	121.08 (13)
C2—C7—H7B	112.1 (12)	C23—C22—H22	121.6 (10)
H6C—C7—H7B	109.6 (17)	C21—C22—H22	117.3 (10)
C2—C7—H7C	109.8 (13)	C22—C23—C24	119.74 (12)
H6C—C7—H7C	107.8 (18)	C22—C23—H23	121.3 (9)
H7B—C7—H7C	106.7 (17)	C24—C23—H23	119.0 (10)
C9—C8—C13	118.41 (13)	O9—C24—C23	118.02 (12)
C9—C8—C4	120.22 (12)	O9—C24—C25	121.92 (12)
C13—C8—C4	121.27 (12)	C23—C24—C25	120.06 (13)
C10—C9—C8	121.23 (13)	C26—C25—C24	119.37 (12)
C10—C9—H9	120.3 (9)	C26—C25—H25	121.7 (10)
C8—C9—H9	118.5 (9)	C24—C25—H25	118.9 (10)
C9—C10—C11	119.66 (12)	C25—C26—C21	121.36 (12)
C9—C10—H10	122.1 (9)	C25—C26—H26	119.4 (9)
C11—C10—H10	118.2 (9)	C21—C26—H26	119.3 (9)
O4—C11—C10	117.81 (12)	C1—N1—C2	123.79 (12)
O4—C11—C12	122.17 (12)	C1—N1—H1N	115.9 (12)
C10—C11—C12	120.02 (13)	C2—N1—H1N	120.3 (12)
C13—C12—C11	119.37 (13)	C1—N2—C4	126.69 (12)
C13—C12—H12	119.8 (10)	C1—N2—H2N	115.7 (11)
C11—C12—H12	120.8 (10)	C4—N2—H2N	115.6 (11)
C12—C13—C8	121.30 (12)	C14—N3—C15	123.93 (12)
C12—C13—H13	119.6 (10)	C14—N3—H3N	114.0 (13)
C8—C13—H13	119.1 (10)	C15—N3—H3N	120.9 (13)
O6—C14—N4	123.48 (13)	C14—N4—C17	126.51 (12)
O6—C14—N3	119.81 (12)	C14—N4—H4N	117.2 (12)
N4—C14—N3	116.70 (12)	C17—N4—H4N	115.1 (12)
C16—C15—N3	119.54 (12)	C5—O3—C6	115.32 (11)
C16—C15—C20	127.09 (13)	C11—O4—H1O	109.9 (14)
N3—C15—C20	113.36 (12)	H3O—O5—H4O	112.6 (19)
C15—C16—C18	119.77 (12)	C18—O8—C19	113.98 (11)
C15—C16—C17	122.02 (12)	C24—O9—H2O	111.0 (15)
C18—C16—C17	118.21 (12)	H5O—O10—H6O	113 (2)

N1—C2—C3—C5	178.24 (12)	C15—C16—C18—O8	−175.05 (12)
C7—C2—C3—C5	−3.6 (2)	C17—C16—C18—O8	5.71 (18)
N1—C2—C3—C4	−2.98 (19)	N4—C17—C21—C26	−68.68 (15)
C7—C2—C3—C4	175.15 (13)	C16—C17—C21—C26	53.97 (16)
C2—C3—C4—N2	−5.41 (17)	N4—C17—C21—C22	109.60 (14)
C5—C3—C4—N2	173.40 (11)	C16—C17—C21—C22	−127.75 (13)
C2—C3—C4—C8	117.77 (14)	C26—C21—C22—C23	−0.2 (2)
C5—C3—C4—C8	−63.42 (15)	C17—C21—C22—C23	−178.55 (12)
C2—C3—C5—O2	−3.9 (2)	C21—C22—C23—C24	−0.3 (2)
C4—C3—C5—O2	177.25 (13)	C22—C23—C24—O9	−178.78 (12)
C2—C3—C5—O3	177.24 (12)	C22—C23—C24—C25	0.6 (2)
C4—C3—C5—O3	−1.58 (17)	O9—C24—C25—C26	179.01 (12)
N2—C4—C8—C9	−108.73 (13)	C23—C24—C25—C26	−0.4 (2)
C3—C4—C8—C9	127.59 (13)	C24—C25—C26—C21	−0.2 (2)
N2—C4—C8—C13	67.52 (16)	C22—C21—C26—C25	0.5 (2)
C3—C4—C8—C13	−56.15 (17)	C17—C21—C26—C25	178.83 (12)
C13—C8—C9—C10	0.6 (2)	O1—C1—N1—C2	−179.62 (12)
C4—C8—C9—C10	176.94 (12)	N2—C1—N1—C2	2.45 (19)
C8—C9—C10—C11	−0.3 (2)	C3—C2—N1—C1	5.2 (2)
C9—C10—C11—O4	−179.75 (12)	C7—C2—N1—C1	−173.19 (13)
C9—C10—C11—C12	0.3 (2)	O1—C1—N2—C4	169.09 (12)
O4—C11—C12—C13	179.50 (12)	N1—C1—N2—C4	−13.0 (2)
C10—C11—C12—C13	−0.6 (2)	C8—C4—N2—C1	−113.04 (14)
C11—C12—C13—C8	0.8 (2)	C3—C4—N2—C1	14.04 (18)
C9—C8—C13—C12	−0.8 (2)	O6—C14—N3—C15	−176.36 (12)
C4—C8—C13—C12	−177.17 (12)	N4—C14—N3—C15	2.68 (19)
N3—C15—C16—C18	−179.33 (12)	C16—C15—N3—C14	−7.4 (2)
C20—C15—C16—C18	1.5 (2)	C20—C15—N3—C14	171.83 (12)
N3—C15—C16—C17	−0.1 (2)	O6—C14—N4—C17	−170.82 (12)
C20—C15—C16—C17	−179.25 (13)	N3—C14—N4—C17	10.18 (19)
C15—C16—C17—N4	10.20 (18)	C16—C17—N4—C14	−15.85 (18)
C18—C16—C17—N4	−170.57 (11)	C21—C17—N4—C14	108.97 (14)
C15—C16—C17—C21	−112.65 (14)	O2—C5—O3—C6	−4.45 (19)
C18—C16—C17—C21	66.57 (15)	C3—C5—O3—C6	174.46 (11)
C15—C16—C18—O7	6.7 (2)	O7—C18—O8—C19	1.7 (2)
C17—C16—C18—O7	−172.58 (15)	C16—C18—O8—C19	−176.70 (12)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C8–C13 and C21–C26 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O6	0.878 (19)	2.10 (2)	2.9762 (16)	173.1 (17)
N3—H3N···O1	0.88 (2)	1.98 (2)	2.8626 (16)	174 (2)
N2—H2N···O9ⁱ	0.89 (2)	2.02 (2)	2.8971 (19)	170.0 (18)
N4—H4N···O4ⁱⁱ	0.87 (2)	2.13 (2)	2.9738 (19)	163.4 (18)
O4—H1O···O5	0.87 (2)	1.78 (2)	2.6473 (16)	175 (2)
O9—H2O···O10	0.90 (2)	1.73 (2)	2.6189 (17)	174.7 (19)
O5—H4O···O2ⁱⁱⁱ	0.84 (2)	2.15 (2)	2.8549 (19)	141 (2)
O5—H3O···O1^iv	0.91 (3)	1.91 (3)	2.786 (2)	162 (2)
C20—H20C···O5^iv	1.00 (2)	2.56 (2)	3.332 (2)	133.7 (17)
C26—H26···O3^v	0.971 (17)	2.571 (18)	3.4607 (18)	152.4 (14)
C6—H6B···Cg2^vi	0.989 (19)	2.70 (2)	3.392 (2)	127.1 (16)
C19—H19C···Cg1^vii	0.98 (2)	2.84 (2)	3.395 (2)	116.5 (16)

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

Acknowledgements

This research was supported by the Visvesvaraya National Institute of Technology (VNIT), Nagpur, INDIA. We thank Dr D. Chopra, IISER, Bhopal, for the single-crystal X-ray data collection.

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