4-(1H-Benzimidazol-2-ylmeth­oxy)-3-meth­oxy­benzaldehyde tetra­hydrate

Jasinski, J.P.; Golen, J.A.; Samshuddin, S.; Narayana, B.; Yathirajan, H.S.

doi:10.1107/S1600536811027164

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages o2021-o2022

doi:10.1107/S1600536811027164

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4-(1H-Benzimidazol-2-ylmethoxy)-3-methoxybenzaldehyde tetrahydrate

Jerry P. Jasinski,^a ^* James A. Golen,^a S. Samshuddin,^b B. Narayana ^b and H. S. Yathirajan ^c

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 30 June 2011; accepted 6 July 2011; online 13 July 2011)

In the title compound, C₁₆H₁₄N₂O₃·4H₂O, the dihedral angle between the mean planes of the benzimidazole ring system and benzene ring is 2.9 (1)°. The aldehyde group is disordered over two sets of sites with refined occupancies of 0.559 (4) and 0.441 (4). In the crystal, extensive intermolecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds in concert with weak π–π stacking interactions [centroid–centroid distances = 3.6104 (9), 3.6288 (9) and 3.9167 (10) Å] create a three-dimensional network.

Related literature

For the pharmaceutical and biological activity of benzimidazole compounds, see: Pujar et al. (1988 ); Bouwman et al. (1990 ). For plant-protective agents in the field of pest control, see: Madkour et al. (2006 ). For related structures, see: Akkurt et al. (2011 ); Jian et al. (2003 ); Jasinski et al. (2010 , 2011 ); Odabaşoğlu et al. (2007). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₄N₂O₃·4H₂O
M_r = 354.36
Triclinic, $[P \overline 1]$
a = 6.8953 (6) Å
b = 11.4266 (13) Å
c = 11.7287 (14) Å
α = 107.965 (10)°
β = 90.906 (8)°
γ = 91.769 (8)°
V = 878.32 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.35 × 0.33 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ )' T_min = 0.964, T_max = 0.979
8245 measured reflections
4539 independent reflections
3499 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.152
S = 1.02
4539 reflections
273 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4WB⋯O5	0.84 (2)	1.98 (2)	2.809 (2)	170 (2)
O4—H4WA⋯O5ⁱ	0.87 (2)	2.04 (2)	2.880 (2)	162 (2)
O5—H5WB⋯N2	0.85 (1)	1.96 (2)	2.8003 (16)	171 (2)
O5—H5WA⋯O7ⁱⁱ	0.85 (2)	1.94 (2)	2.7882 (19)	171 (2)
O6—H6WA⋯O4ⁱⁱⁱ	0.85 (2)	2.16 (2)	2.996 (2)	171 (3)
O6—H6WB⋯O2	0.85 (2)	2.40 (2)	3.187 (3)	154 (3)
O7—H7WB⋯O4^iv	0.84 (2)	2.01 (2)	2.844 (2)	174 (2)
O7—H7WA⋯O3A	0.81 (2)	1.98 (2)	2.721 (3)	151 (2)
N1—H1N⋯O6	0.83 (1)	2.02 (1)	2.8152 (19)	160 (2)
Symmetry codes: (i) -x, -y+2, -z+1; (ii) x, y+1, z+1; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811027164/lh5279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027164/lh5279Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027164/lh5279Isup3.cml

checkCIF report

Comment top

The benzimidazole ring system and its related compounds play an important role in pharmaceutical and agricultural fields due to their broad spectrum of biological activities (Pujar et al., 1988, Bouwman et al., 1990). The synthesis of novel benzimidazole derivatives remains a main focus of medicinal research. Benzimidazoles are also useful as insecticides, acaricides, nematocides, herbicides and other plant-protective agents in the field of pest control (Madkour et al., 2006). In addition, benzimidazole derivatives have played a crucial role in the theoretical development of heterocyclic chemistry and are also used extensively in organic synthesis. The crystal structures of some benzimidazole derivatives viz., 2-chloromethyl-1H-benzimidazole nitrate (Jian et al., 2003) and 5-methoxy-1H-benzo[d]imidazole-2(3H)-thione (Odabaşoğlu et al., 2007) have been reported. In continuation of our work on the synthesis of benzimidazole containing aldehydes and their chalcones (Jasinski et al., 2010, 2011; Akkurt et al., 2011) and in view of the importance of benzimidazoles, the title compound, (I), was synthesized and its crystal structure is reported herein.

The molecular structure of the title compound is shown in Fig. 1. In (I) the dihedral angle between the mean planes of the benzimidazole ring system and benzene ring is 2.9 (1)°. The aldehyde group is disordered over two sets of sites corresponding to a rotation of approximately 180° about the C12-C16 bond with refined occupancies of 0.441 (4) and 0.559 (4). Bond distances are in normal ranges (Allen et al., 1987). Extensive O—H···O, O—H···N and N—H···O hydrogen bonds (Table 1) in concert with weak π–π stacking interactions (Table 2) create a 3-D network (Fig. 2).

Related literature top

For the pharmaceutical and biological activity of benzimidazole compounds, see: Pujar et al. (1988); Bouwman et al. (1990); For plant-protective agents in the field of pest control, see: Madkour et al. (2006). For related structures, see: Akkurt et al. (2011); Jian et al. (2003); Jasinski et al. (2010, 2011); Odabaşoğlu et al. (2007); For standard bond lengths, see: Allen et al. (1987).

Experimental top

Vanillin (1.52g, 0.01 mole) was dissolved in 30 mL of ethanolic KOH (0.56g, 0.01 mole) and the solution was stirred for 1 h. 2-chloromethyl-1H-benzimidazole (1.66g, 0.01 mole) was added with continuous stirring and refluxed for 5 h (Fig. 3). The reaction mixture was cooled to room temperature and poured into crushed ice. The solid products that separated out were filtered off and recrystallized in ethanol. Single crystals were grown from ethanol by the slow evaporation method which yielded the tetrahydrate of the product (m.p.: 381-382 K) with an yield of 46%.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Dashed lines represent O—H···O, O—H···N and N—H···O hydrogen bonds.
	Fig. 3. Reaction scheme of the title compound, (I).

4-(1H-Benzimidazol-2-ylmethoxy)-3-methoxybenzaldehyde tetrahydrate top

Crystal data top

C₁₆H₁₄N₂O₃·4H₂O	Z = 2
M_r = 354.36	F(000) = 376
Triclinic, P1	D_x = 1.340 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8953 (6) Å	Cell parameters from 4026 reflections
b = 11.4266 (13) Å	θ = 3.4–32.3°
c = 11.7287 (14) Å	µ = 0.11 mm⁻¹
α = 107.965 (10)°	T = 173 K
β = 90.906 (8)°	Block, pale yellow
γ = 91.769 (8)°	0.35 × 0.33 × 0.20 mm
V = 878.32 (16) Å³

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	4539 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3499 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 16.1500 pixels mm^-1	θ_max = 28.7°, θ_min = 3.4°
ω scans	h = −9→6
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)'	k = −15→12
T_min = 0.964, T_max = 0.979	l = −14→15
8245 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0835P)² + 0.139P] where P = (F_o² + 2F_c²)/3
4539 reflections	(Δ/σ)_max = 0.002
273 parameters	Δρ_max = 0.25 e Å⁻³
17 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₆H₁₄N₂O₃·4H₂O	γ = 91.769 (8)°
M_r = 354.36	V = 878.32 (16) Å³
Triclinic, P1	Z = 2
a = 6.8953 (6) Å	Mo Kα radiation
b = 11.4266 (13) Å	µ = 0.11 mm⁻¹
c = 11.7287 (14) Å	T = 173 K
α = 107.965 (10)°	0.35 × 0.33 × 0.20 mm
β = 90.906 (8)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	4539 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)'	3499 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.979	R_int = 0.016
8245 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	17 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.25 e Å⁻³
4539 reflections	Δρ_min = −0.36 e Å⁻³
273 parameters

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.25247 (16)	0.50917 (9)	0.48675 (9)	0.0433 (3)
O2	0.27855 (17)	0.27445 (9)	0.41320 (10)	0.0504 (3)
O3	0.3970 (4)	0.1784 (3)	−0.0482 (2)	0.0613 (10)	0.441 (4)
O3A	0.3989 (4)	0.3155 (2)	−0.0763 (2)	0.0688 (9)	0.559 (4)
O4	0.1293 (2)	0.86262 (11)	0.38472 (13)	0.0662 (4)
H4WB	0.161 (3)	0.8992 (19)	0.4568 (14)	0.079*
H4WA	0.045 (3)	0.9090 (19)	0.3647 (19)	0.079*
O5	0.18563 (19)	0.98294 (11)	0.63137 (12)	0.0599 (3)
H5WB	0.192 (3)	0.9297 (16)	0.6684 (18)	0.072*
H5WA	0.286 (3)	1.0304 (17)	0.6559 (18)	0.072*
O6	0.1819 (3)	0.33687 (14)	0.6899 (2)	0.0961 (6)
H6WA	0.101 (3)	0.276 (2)	0.674 (2)	0.115*
H6WB	0.246 (4)	0.326 (3)	0.626 (2)	0.115*
O7	0.4891 (2)	0.15864 (14)	−0.29388 (13)	0.0701 (4)
H7WB	0.603 (3)	0.158 (2)	−0.3182 (19)	0.084*
H7WA	0.493 (3)	0.192 (2)	−0.2216 (14)	0.084*
N1	0.18875 (16)	0.59173 (10)	0.72323 (11)	0.0364 (3)
H1N	0.192 (2)	0.5154 (12)	0.6960 (14)	0.044*
N2	0.19911 (17)	0.78893 (10)	0.72974 (10)	0.0386 (3)
C1	0.16508 (18)	0.65805 (12)	0.84166 (12)	0.0363 (3)
C2	0.1383 (2)	0.62248 (15)	0.94340 (14)	0.0462 (3)
H2A	0.1349	0.5383	0.9401	0.055*
C3	0.1168 (2)	0.71524 (17)	1.04909 (15)	0.0549 (4)
H3A	0.0961	0.6948	1.1207	0.066*
C4	0.1248 (3)	0.83881 (17)	1.05371 (15)	0.0588 (4)
H4A	0.1095	0.9004	1.1285	0.071*
C5	0.1541 (2)	0.87414 (14)	0.95290 (14)	0.0508 (4)
H5A	0.1614	0.9586	0.9573	0.061*
C6	0.17285 (18)	0.78171 (12)	0.84452 (12)	0.0375 (3)
C7	0.20690 (18)	0.67405 (11)	0.66209 (12)	0.0348 (3)
C8	0.2316 (2)	0.63843 (12)	0.53048 (12)	0.0407 (3)
H8A	0.1171	0.6617	0.4915	0.049*
H8B	0.3480	0.6816	0.5122	0.049*
C9	0.28517 (18)	0.46020 (12)	0.36761 (12)	0.0352 (3)
C10	0.3059 (2)	0.52749 (13)	0.28790 (13)	0.0413 (3)
H10A	0.2975	0.6145	0.3152	0.050*
C11	0.3390 (2)	0.46721 (14)	0.16864 (13)	0.0443 (3)
H11A	0.3551	0.5132	0.1141	0.053*
C12	0.34859 (19)	0.34084 (14)	0.12823 (13)	0.0418 (3)
C13	0.32778 (19)	0.27242 (13)	0.20786 (13)	0.0409 (3)
H13A	0.3346	0.1853	0.1796	0.049*
C14	0.29751 (18)	0.33106 (12)	0.32700 (13)	0.0375 (3)
C15	0.2914 (3)	0.14435 (14)	0.37694 (19)	0.0631 (5)
H15A	0.2866	0.1158	0.4476	0.095*
H15B	0.4139	0.1212	0.3363	0.095*
H15C	0.1825	0.1063	0.3219	0.095*
C16	0.3765 (19)	0.2805 (10)	0.0036 (9)	0.078 (5)	0.441 (4)
H16A	0.3785	0.3337	−0.0447	0.093*	0.441 (4)
C16A	0.3838 (12)	0.2765 (6)	0.0018 (4)	0.046 (2)	0.559 (4)
H16B	0.3959	0.1900	−0.0179	0.055*	0.559 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0595 (6)	0.0317 (5)	0.0400 (5)	0.0043 (4)	0.0048 (4)	0.0129 (4)
O2	0.0665 (7)	0.0350 (5)	0.0546 (6)	0.0035 (5)	0.0063 (5)	0.0206 (4)
O3	0.0618 (18)	0.064 (2)	0.0498 (16)	0.0027 (14)	0.0093 (12)	0.0047 (14)
O3A	0.0735 (16)	0.0759 (18)	0.0524 (14)	−0.0041 (12)	0.0180 (11)	0.0130 (12)
O4	0.0898 (10)	0.0485 (7)	0.0610 (8)	0.0035 (6)	0.0078 (7)	0.0177 (6)
O5	0.0660 (8)	0.0529 (7)	0.0692 (8)	−0.0063 (6)	−0.0137 (6)	0.0329 (6)
O6	0.0934 (13)	0.0469 (8)	0.1487 (18)	−0.0067 (8)	−0.0135 (11)	0.0330 (10)
O7	0.0674 (8)	0.0725 (9)	0.0644 (8)	−0.0059 (7)	0.0001 (7)	0.0131 (7)
N1	0.0372 (6)	0.0298 (5)	0.0432 (6)	−0.0010 (4)	−0.0011 (4)	0.0131 (5)
N2	0.0406 (6)	0.0322 (5)	0.0437 (6)	0.0043 (4)	0.0011 (5)	0.0126 (5)
C1	0.0276 (6)	0.0387 (6)	0.0441 (7)	0.0016 (5)	−0.0005 (5)	0.0149 (5)
C2	0.0415 (7)	0.0535 (8)	0.0491 (8)	−0.0006 (6)	−0.0005 (6)	0.0243 (7)
C3	0.0500 (9)	0.0739 (11)	0.0443 (8)	0.0067 (8)	0.0037 (7)	0.0229 (8)
C4	0.0606 (10)	0.0666 (11)	0.0439 (8)	0.0161 (8)	0.0049 (7)	0.0078 (7)
C5	0.0540 (9)	0.0436 (8)	0.0512 (9)	0.0139 (7)	0.0024 (7)	0.0083 (7)
C6	0.0310 (6)	0.0382 (7)	0.0439 (7)	0.0058 (5)	0.0007 (5)	0.0133 (5)
C7	0.0308 (6)	0.0327 (6)	0.0430 (7)	0.0003 (5)	−0.0015 (5)	0.0149 (5)
C8	0.0506 (8)	0.0315 (6)	0.0411 (7)	0.0011 (5)	0.0005 (6)	0.0128 (5)
C9	0.0326 (6)	0.0345 (6)	0.0394 (7)	0.0016 (5)	0.0006 (5)	0.0127 (5)
C10	0.0445 (7)	0.0350 (6)	0.0470 (7)	0.0024 (5)	0.0018 (6)	0.0162 (6)
C11	0.0419 (7)	0.0502 (8)	0.0461 (8)	0.0026 (6)	0.0031 (6)	0.0225 (6)
C12	0.0310 (6)	0.0509 (8)	0.0411 (7)	0.0033 (5)	0.0037 (5)	0.0104 (6)
C13	0.0324 (6)	0.0355 (6)	0.0516 (8)	0.0024 (5)	0.0024 (6)	0.0087 (6)
C14	0.0316 (6)	0.0342 (6)	0.0490 (8)	0.0015 (5)	0.0009 (5)	0.0162 (6)
C15	0.0776 (12)	0.0351 (8)	0.0826 (13)	0.0022 (8)	0.0069 (10)	0.0266 (8)
C16	0.039 (6)	0.085 (9)	0.116 (9)	−0.005 (5)	−0.002 (5)	0.042 (7)
C16A	0.042 (4)	0.060 (4)	0.0252 (19)	0.007 (3)	0.011 (2)	−0.004 (2)

Geometric parameters (Å, º) top

O1—C9	1.3609 (17)	C3—H3A	0.9500
O1—C8	1.4190 (16)	C4—C5	1.378 (2)
O2—C14	1.3638 (17)	C4—H4A	0.9500
O2—C15	1.4206 (18)	C5—C6	1.390 (2)
O3—C16	1.151 (8)	C5—H5A	0.9500
O3A—C16A	1.140 (7)	C7—C8	1.4840 (19)
O4—H4WB	0.841 (15)	C8—H8A	0.9900
O4—H4WA	0.873 (15)	C8—H8B	0.9900
O5—H5WB	0.851 (14)	C9—C10	1.3880 (19)
O5—H5WA	0.853 (15)	C9—C14	1.4097 (18)
O6—H6WA	0.845 (16)	C10—C11	1.381 (2)
O6—H6WB	0.850 (16)	C10—H10A	0.9500
O7—H7WB	0.838 (15)	C11—C12	1.378 (2)
O7—H7WA	0.814 (15)	C11—H11A	0.9500
N1—C7	1.3514 (16)	C12—C13	1.397 (2)
N1—C1	1.3768 (18)	C12—C16	1.430 (9)
N1—H1N	0.832 (13)	C12—C16A	1.466 (4)
N2—C7	1.3110 (17)	C13—C14	1.373 (2)
N2—C6	1.3881 (18)	C13—H13A	0.9500
C1—C2	1.387 (2)	C15—H15A	0.9800
C1—C6	1.4023 (18)	C15—H15B	0.9800
C2—C3	1.374 (2)	C15—H15C	0.9800
C2—H2A	0.9500	C16—H16A	0.9500
C3—C4	1.396 (3)	C16A—H16B	0.9500

C9—O1—C8	116.72 (10)	C7—C8—H8B	110.0
C14—O2—C15	117.42 (13)	H8A—C8—H8B	108.4
H4WB—O4—H4WA	105.6 (17)	O1—C9—C10	124.95 (12)
H5WB—O5—H5WA	104.9 (17)	O1—C9—C14	114.89 (11)
H6WA—O6—H6WB	105 (2)	C10—C9—C14	120.15 (13)
H7WB—O7—H7WA	107.6 (19)	C11—C10—C9	119.63 (13)
C7—N1—C1	106.93 (11)	C11—C10—H10A	120.2
C7—N1—H1N	127.5 (11)	C9—C10—H10A	120.2
C1—N1—H1N	125.5 (11)	C12—C11—C10	120.42 (13)
C7—N2—C6	104.49 (11)	C12—C11—H11A	119.8
N1—C1—C2	132.25 (13)	C10—C11—H11A	119.8
N1—C1—C6	105.01 (11)	C11—C12—C13	120.31 (13)
C2—C1—C6	122.74 (13)	C11—C12—C16	119.2 (5)
C3—C2—C1	116.54 (14)	C13—C12—C16	120.4 (5)
C3—C2—H2A	121.7	C11—C12—C16A	120.6 (3)
C1—C2—H2A	121.7	C13—C12—C16A	119.1 (3)
C2—C3—C4	121.51 (15)	C14—C13—C12	120.00 (13)
C2—C3—H3A	119.2	C14—C13—H13A	120.0
C4—C3—H3A	119.2	C12—C13—H13A	120.0
C5—C4—C3	121.91 (16)	O2—C14—C13	125.26 (12)
C5—C4—H4A	119.0	O2—C14—C9	115.26 (12)
C3—C4—H4A	119.0	C13—C14—C9	119.48 (12)
C4—C5—C6	117.59 (15)	O2—C15—H15A	109.5
C4—C5—H5A	121.2	O2—C15—H15B	109.5
C6—C5—H5A	121.2	H15A—C15—H15B	109.5
N2—C6—C5	130.48 (13)	O2—C15—H15C	109.5
N2—C6—C1	109.82 (12)	H15A—C15—H15C	109.5
C5—C6—C1	119.70 (13)	H15B—C15—H15C	109.5
N2—C7—N1	113.74 (12)	O3—C16—C12	131.0 (10)
N2—C7—C8	122.82 (11)	O3—C16—H16A	114.5
N1—C7—C8	123.43 (11)	C12—C16—H16A	114.5
O1—C8—C7	108.39 (10)	O3A—C16A—C12	129.3 (5)
O1—C8—H8A	110.0	O3A—C16A—H16B	115.4
C7—C8—H8A	110.0	C12—C16A—H16B	115.4
O1—C8—H8B	110.0

C7—N1—C1—C2	179.33 (14)	O1—C9—C10—C11	179.95 (13)
C7—N1—C1—C6	−0.62 (14)	C14—C9—C10—C11	−0.1 (2)
N1—C1—C2—C3	−179.16 (14)	C9—C10—C11—C12	0.9 (2)
C6—C1—C2—C3	0.8 (2)	C10—C11—C12—C13	−0.9 (2)
C1—C2—C3—C4	−1.0 (2)	C10—C11—C12—C16	177.9 (6)
C2—C3—C4—C5	0.1 (3)	C10—C11—C12—C16A	−179.9 (4)
C3—C4—C5—C6	1.0 (3)	C11—C12—C13—C14	0.0 (2)
C7—N2—C6—C5	−179.88 (14)	C16—C12—C13—C14	−178.8 (6)
C7—N2—C6—C1	−0.13 (14)	C16A—C12—C13—C14	179.0 (4)
C4—C5—C6—N2	178.55 (14)	C15—O2—C14—C13	0.1 (2)
C4—C5—C6—C1	−1.2 (2)	C15—O2—C14—C9	−179.54 (13)
N1—C1—C6—N2	0.47 (14)	C12—C13—C14—O2	−178.79 (12)
C2—C1—C6—N2	−179.48 (12)	C12—C13—C14—C9	0.8 (2)
N1—C1—C6—C5	−179.75 (12)	O1—C9—C14—O2	−1.17 (17)
C2—C1—C6—C5	0.3 (2)	C10—C9—C14—O2	178.85 (12)
C6—N2—C7—N1	−0.28 (15)	O1—C9—C14—C13	179.18 (11)
C6—N2—C7—C8	179.19 (12)	C10—C9—C14—C13	−0.81 (19)
C1—N1—C7—N2	0.59 (15)	C11—C12—C16—O3	176.2 (10)
C1—N1—C7—C8	−178.88 (12)	C13—C12—C16—O3	−4.9 (16)
C9—O1—C8—C7	−177.26 (11)	C16A—C12—C16—O3	50 (19)
N2—C7—C8—O1	174.58 (12)	C11—C12—C16A—O3A	−3.5 (10)
N1—C7—C8—O1	−6.00 (18)	C13—C12—C16A—O3A	177.5 (6)
C8—O1—C9—C10	2.33 (19)	C16—C12—C16A—O3A	51 (20)
C8—O1—C9—C14	−177.65 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4WB···O5	0.84 (2)	1.98 (2)	2.809 (2)	170 (2)
O4—H4WA···O5ⁱ	0.87 (2)	2.04 (2)	2.880 (2)	162 (2)
O5—H5WB···N2	0.85 (1)	1.96 (2)	2.8003 (16)	171 (2)
O5—H5WA···O7ⁱⁱ	0.85 (2)	1.94 (2)	2.7882 (19)	171 (2)
O6—H6WA···O4ⁱⁱⁱ	0.85 (2)	2.16 (2)	2.996 (2)	171 (3)
O6—H6WB···O2	0.85 (2)	2.40 (2)	3.187 (3)	154 (3)
O7—H7WB···O4^iv	0.84 (2)	2.01 (2)	2.844 (2)	174 (2)
O7—H7WA···O3A	0.81 (2)	1.98 (2)	2.721 (3)	151 (2)
N1—H1N···O6	0.83 (1)	2.02 (1)	2.8152 (19)	160 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₂O₃·4H₂O
M_r	354.36
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.8953 (6), 11.4266 (13), 11.7287 (14)
α, β, γ (°)	107.965 (10), 90.906 (8), 91.769 (8)
V (Å³)	878.32 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.33 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)'
T_min, T_max	0.964, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	8245, 4539, 3499
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.152, 1.02
No. of reflections	4539
No. of parameters	273
No. of restraints	17
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.36

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4WB···O5	0.841 (15)	1.976 (16)	2.809 (2)	170 (2)
O4—H4WA···O5ⁱ	0.873 (15)	2.037 (17)	2.880 (2)	162 (2)
O5—H5WB···N2	0.851 (14)	1.956 (15)	2.8003 (16)	171 (2)
O5—H5WA···O7ⁱⁱ	0.853 (15)	1.943 (15)	2.7882 (19)	170.7 (19)
O6—H6WA···O4ⁱⁱⁱ	0.845 (16)	2.159 (17)	2.996 (2)	171 (3)
O6—H6WB···O2	0.850 (16)	2.40 (2)	3.187 (3)	154 (3)
O7—H7WB···O4^iv	0.838 (15)	2.009 (16)	2.844 (2)	174 (2)
O7—H7WA···O3A	0.814 (15)	1.982 (17)	2.721 (3)	151 (2)
N1—H1N···O6	0.832 (13)	2.018 (14)	2.8152 (19)	160.1 (16)

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

Cg···Cg π stacking interactions, Cg1, Cg2 and Cg3 are the centroids of rings N1/C1/C6/N2/C7, C1-C6 and C9-C14, respectively; [Symmetry codes: (i) -x,1-y, 1-z; (ii) 1-x, 1-y, 1-z ] top

CgX···CgY	Cg···Cg (Å)	CgX···Perp (Å)	CgY···Perp (Å)
Cg1···Cg3ⁱ	3.6104 (9)	-3.4276 (5)	-3.4041 (5)
Cg1···Cg3ⁱⁱ	3.6288 (9)	3.3426 (5)	3.4101 (5)
Cg2···Cg3ⁱ	3.9167 (10)	-3.4841 (6)	-3.4068 (5)

Acknowledgements

BN thanks Mangalore University for the research facilities and the UGC SAP for financial assistance for the purchase of chemicals. HSY thanks the UOM for the facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

Akkurt, M., Baktır, Z., Samshuddin, S., Narayana, B. & Yathirajan, H. S. (2011). Acta Cryst. E67, o1088–o1089. Web of Science CSD CrossRef IUCr Journals Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bouwman, E., Driessen, W. L. & Reedijk, J. (1990). Coord. Chem. Rev. 104, 143–172. CrossRef CAS Web of Science Google Scholar
Jasinski, J. P., Braley, A. N., Samshuddin, S., Narayana, B. & Yathirajan, H. S. (2010). Acta Cryst. E66, o2052. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jasinski, J. P., Miller, W. M., Samshuddin, S., Narayana, B. & Yathirajan, H. S. (2011). Acta Cryst. E67, o834–o835. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jian, F. F., Bei, F. L., Wang, X. & Lu, L. D. (2003). Chinese J. Struct. Chem. 22, 382–386. CAS Google Scholar
Madkour, H. M. F., Farag, A. A., Ramses, S. S. & Ibrahiem, N. A. A. (2006). Phosphorus Sulfur Silicon 181, 255–265. Web of Science CrossRef CAS Google Scholar
Odabaşoğlu, M., Büyükgüngör, O., Narayana, B., Vijesh, A. M. & Yathirajan, H. S. (2007). Acta Cryst. E63, o3199–o3200. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Pujar, M. A., Bharamgoudar, T. D. & Sathyanarayana, D. N. (1988). Transition Met. Chem. 13, 423–425. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar