Crystal structure of methyl 2-[5-(2-hy­droxy­phen­yl)-2H-tetra­zol-2-yl]acetate

Lee, S.G.; Ryu, J.Y.; Lee, J.

doi:10.1107/S205698901701698X

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Volume 73| Part 12| December 2017| Pages 1971-1973

https://doi.org/10.1107/S205698901701698X

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Crystal structure of methyl 2-[5-(2-hydroxyphenyl)-2H-tetrazol-2-yl]acetate

Seul Gi Lee,^a Ji Yeon Ryu ^a and Junseong Lee ^a ^*

^aDepartment of Chemistry, Chonnam National University, Gwangju, 61186, Republic of Korea
^*Correspondence e-mail: leespy@chonnam.ac.kr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 November 2017; accepted 26 November 2017; online 30 November 2017)

The title compound, C₁₀H₁₀N₄O₃, was synthesized by the esterification of hydroxyphenyl tetrazole. There is an intramolecular O—H⋯N hydrogen bond present involving the hydroxy group and the tetrazole ring. The tetrazole ring is inclined to the phenol ring by 2.85 (13)°, while the methyl acetate group is almost normal to the tetrazole ring, making a dihedral angle of 82.61 (14)°. In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers. Within the dimers, the phenol rings are linked by offset π–π interactions [intercentroid distance = 3.759 (2) Å]. There are no further significant intermolecular interactions present in the crystal. The hydroxy group is disordered about positions 2 and 6 on the benzene ring, with a refined occupancy ratio of 0.531 (5):0.469 (5).

Keywords: crystal structure; tetrazole; hydroxyphenyl tetrazole; hydrogen bonding; offset π–π interactions.

CCDC reference: 1587621

1. Chemical context

Tetrazole ligands are useful building blocks for the construction of high-dimensional metal–organic frameworks by providing various binding modes toward metal centers (Karaghiosoff et al., 2009 ; Liu et al., 2013 ). Recently, we have used 5-(2-hydroxyphenyl)tetrazole as a chelating multidentate ligand and reported several interesting compounds (Park et al., 2015 ; 2014 ). It provides strong [N,O] chelation to metal centers with various additional binding modes. As part of a project on the study of the substitution effects on the tetrazole ring on the self-assembly behaviour in solution, as well as in the solid state, we have synthesized a number of substituted hydroxyphenyl tetrazole complexes. The substitution of the tetrazole group may promote supramolecular interaction by weak interactions, such as hydrogen bonding. The reaction between hydroxyphenyl tetrazole and bromo acetate methyl ester in the presence of potassium carbonate gave three isomeric products. Using column chromatography, the major product was isolated and its molecular structure was determined unambiguously by X-ray crystallography. We report herein, the synthesis and crystal structure of this compound.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The structure analysis confirms the nature of the major product of the reaction, which yielded three isomeric compounds as described in Section 5, Synthesis and crystallization. The title molecule consists of a tetrazole ring (N1–N4/C1) and a phenol ring (C2–C7), which are connected by an intramolecular O—H⋯N hydrogen bond (Fig. 1, Table 1) and inclined to one another by 2.85 (13)°. The planar methyl acetate group [O2/O3/C8–C10; maximum deviation of 0.037 (2) Å for atom O2] is inclined to the tetrazole ring by 82.61 (14)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84	1.91	2.659 (4)	148
C5—H5⋯O3ⁱ	0.95	2.57	3.472 (3)	158
Symmetry code: (i) -x+1, -y, -z+1.

Figure 1
A view of the molecular structure of the title compound, with the atom labelling and 30% probability displacement ellipsoids. The intramolecular O—H⋯N hydrogen bond (see Table 1

) is indicated by a dashed line. Only the major component of the disordered OH group, in position 2, is shown.

3. Supramolecular features

In the crystal, the molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(22) loop (Table 1, Fig. 2). Within the dimers, the phenol rings are linked by offset π–π interactions [Cg⋯Cgⁱ = 3.759 (2) Å, interplanar distance = 3.526 (1) Å, slippage 1.305 Å; Cg is the centroid of the C2–C7 phenol ring, symmetry code: (i) −x + 1, −y, −z + 1]. There are no further significant intermolecular interactions present in the crystal.

Figure 2
A view along the a axis of the crystal packing of the title compound. The intra- and intermolecular hydrogen bonds (see Table 1

) are indicated by dashed lines. The offset π–π interactions are shown as dashed double arrows. Only H atoms H1 and H5, and the major component of the disordered OH group in position 2, have been included.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016 ) for the methyl 2-(5-phenyl-2H-tetrazol-2-yl)acetate skeleton revealed only two hits, viz. ethyl (Z)-3-phenyl-2-(5-phenyl-2H-tetrazol-2-yl)-2-propenoate (SAKVIM; Ramazani et al., 2017 ) and methyl (5-phenyl-2H-tetrazol-2-yl)acetate (WUKNUN; Saeed et al., 2015 ). In WUKNUN, the 5-phenyl substituent is inclined to the tetrazole ring by 3.89 (7)°, compared to 2.85 (13)° in the title compound. In contrast, the corresponding dihedral angle in SAKVIM is 19.97 (16)°. The methyl/ethyl acetate groups are inclined to the plane of the tetrazole ring by 84.99 (7)° in WUKNUN and 84.57 (7)° in SAKVIM, similar to the value observed in the title compound, viz. 82.61 (14)°.

5. Synthesis and crystallization

The synthesis of the title compound is illustrated in Fig. 3. 2-(2H-Tetrazol-5-yl)phenol (100 mg, 0.62 mmol) and potassium carbonate (85.0 mg, 0.62 mmol) were dissolved in acetonitrile at 273 K while stirring for 30 min. To the resulting solution methyl 2-bromoacetate (207 µl, 2.18 mmol) was added and stirring was continued for 24 h. The white solid that was obtained was filtered and the solvent removed under reduced pressure. The residue was purified by column chromatography on silica gel using ether:hexane (2:3) as eluent. Three isomeric compounds were obtained, as shown in Fig. 3. The major product (I) (yield = 59%), was recrystallized in dichloromethane and yielded needle-like colourless crystals of the title compound. Spectroscopic data: ¹H NMR (CDCl₃, 400MHz): δ = 9.59 (s, 1H, OH), 8.06 (d, 1H, Ph), 7.41 (t, 1H, Ph), 7.11 (d, 1H, Ph), 6.99 (t, 1H, Ph), 5.51 (s, 2H), 3.85 (s, 3H). ¹³C NMR (125 MHz, CDCl₃): 165.06, 164.68, 156.42, 132.44, 127.50, 120.06, 117.62, 53.41, 53.38 ppm.

Figure 3
Reaction scheme for the synthesis of the title compound, (I)

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxy group is disordered about positions 2 and 6 on the phenol ring, with a refined occupancy ratio of 0.531 (5):0.469 (5). All the H atoms were included in calculated positions using a riding model: O—H = 0.84 Å, C-H = 0.95–1.00 Å with U_iso(H) = 1.5 U_eq(O-hydroxyl, C-methyl) and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄O₃
M_r	234.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.060 (2), 8.2538 (17), 13.536 (3)
β (°)	104.479 (10)
V (Å³)	1088.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.15 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.987, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	14003, 2372, 1252
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.137, 1.02
No. of reflections	2372
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.17
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1587621

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S205698901701698X/su5409sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901701698X/su5409Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901701698X/su5409Isup3.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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Methyl 2-[5-(2-hydroxyphenyl)-2H-tetrazol-2-yl]acetate top

Crystal data top

C₁₀H₁₀N₄O₃	F(000) = 488
M_r = 234.22	D_x = 1.430 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.060 (2) Å	Cell parameters from 3134 reflections
b = 8.2538 (17) Å	θ = 2.9–24.3°
c = 13.536 (3) Å	µ = 0.11 mm⁻¹
β = 104.479 (10)°	T = 100 K
V = 1088.2 (4) Å³	Needle, colourless
Z = 4	0.15 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1252 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.044
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.2°, θ_min = 2.1°
T_min = 0.987, T_max = 0.989	h = −12→12
14003 measured reflections	k = −10→10
2372 independent reflections	l = −17→17

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0479P)² + 0.3171P] where P = (F_o² + 2F_c²)/3
2372 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.17 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	Occ. (<1)
O1	0.3781 (3)	0.2337 (4)	0.3644 (3)	0.0745 (14)	0.531 (5)
H1	0.4534	0.2755	0.3623	0.112*	0.531 (5)
O2	0.92819 (16)	0.46762 (19)	0.26859 (14)	0.0718 (5)
O3	0.92563 (18)	0.2756 (2)	0.38419 (16)	0.0879 (6)
O1A	0.5939 (5)	0.1877 (6)	0.7094 (3)	0.1031 (19)	0.469 (5)
H1A	0.6557	0.2377	0.6900	0.155*	0.469 (5)
N1	0.61929 (19)	0.3786 (2)	0.43476 (16)	0.0618 (5)
N2	0.7415 (2)	0.4500 (2)	0.46016 (19)	0.0679 (6)
N3	0.8043 (2)	0.4384 (3)	0.5571 (2)	0.0890 (7)
N4	0.7203 (2)	0.3567 (3)	0.59958 (17)	0.0826 (7)
C1	0.6085 (2)	0.3209 (3)	0.5240 (2)	0.0574 (6)
C2	0.4922 (2)	0.2276 (2)	0.53816 (19)	0.0555 (6)
C3	0.4899 (3)	0.1677 (3)	0.6336 (3)	0.0749 (7)
H3	0.5638	0.1911	0.6908	0.090*	0.531 (5)
C4	0.3811 (4)	0.0744 (3)	0.6462 (3)	0.0916 (10)
H4	0.3810	0.0334	0.7117	0.110*
C5	0.2743 (3)	0.0412 (3)	0.5647 (3)	0.0913 (10)
H5	0.2001	−0.0237	0.5734	0.110*
C6	0.2733 (3)	0.1010 (3)	0.4701 (3)	0.0831 (8)
H6	0.1978	0.0790	0.4137	0.100*
C7	0.3818 (3)	0.1929 (3)	0.4565 (2)	0.0652 (7)
H7	0.3808	0.2330	0.3905	0.078*	0.469 (5)
C8	0.8045 (3)	0.5246 (3)	0.3866 (2)	0.0778 (8)
H8A	0.8619	0.6170	0.4189	0.093*
H8B	0.7322	0.5670	0.3288	0.093*
C9	0.8923 (2)	0.4048 (3)	0.3474 (2)	0.0635 (7)
C10	1.0223 (3)	0.3749 (3)	0.2257 (2)	0.0834 (8)
H10A	1.0402	0.4334	0.1674	0.125*
H10B	0.9817	0.2691	0.2031	0.125*
H10C	1.1087	0.3594	0.2776	0.125*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.063 (2)	0.086 (3)	0.071 (3)	−0.0122 (18)	0.0098 (17)	0.0043 (19)
O2	0.0666 (11)	0.0501 (10)	0.1035 (13)	0.0043 (8)	0.0303 (10)	0.0086 (10)
O3	0.0893 (13)	0.0446 (10)	0.1425 (17)	0.0147 (9)	0.0529 (12)	0.0194 (11)
O1A	0.127 (4)	0.118 (4)	0.062 (3)	0.006 (3)	0.018 (3)	0.011 (3)
N1	0.0533 (12)	0.0445 (11)	0.0897 (15)	0.0028 (10)	0.0215 (11)	−0.0002 (11)
N2	0.0570 (13)	0.0463 (12)	0.1035 (18)	0.0007 (10)	0.0260 (13)	−0.0040 (12)
N3	0.0684 (15)	0.0838 (18)	0.111 (2)	−0.0131 (14)	0.0151 (15)	−0.0115 (16)
N4	0.0699 (15)	0.0835 (16)	0.0897 (17)	−0.0084 (13)	0.0113 (13)	−0.0090 (13)
C1	0.0534 (15)	0.0414 (12)	0.0779 (17)	0.0082 (11)	0.0172 (13)	−0.0068 (13)
C2	0.0568 (14)	0.0374 (12)	0.0754 (17)	0.0095 (11)	0.0225 (13)	−0.0017 (12)
C3	0.085 (2)	0.0605 (17)	0.082 (2)	0.0139 (15)	0.0271 (18)	0.0054 (16)
C4	0.118 (3)	0.0586 (18)	0.119 (3)	0.0109 (19)	0.069 (2)	0.0116 (18)
C5	0.096 (2)	0.0504 (17)	0.151 (3)	−0.0090 (16)	0.074 (2)	−0.015 (2)
C6	0.0686 (18)	0.0668 (18)	0.121 (3)	−0.0077 (15)	0.0376 (17)	−0.0194 (18)
C7	0.0604 (16)	0.0517 (15)	0.088 (2)	0.0008 (12)	0.0273 (15)	−0.0047 (14)
C8	0.0703 (16)	0.0433 (14)	0.130 (2)	0.0011 (12)	0.0439 (17)	0.0049 (15)
C9	0.0474 (13)	0.0384 (13)	0.106 (2)	−0.0044 (11)	0.0219 (13)	−0.0004 (14)
C10	0.0779 (18)	0.0708 (18)	0.110 (2)	0.0042 (15)	0.0398 (16)	−0.0052 (16)

Geometric parameters (Å, º) top

O1—C7	1.282 (4)	N4—C1	1.351 (3)
O2—C9	1.315 (3)	C1—C2	1.452 (3)
O2—C10	1.447 (3)	C2—C7	1.387 (3)
O3—C9	1.190 (3)	C2—C3	1.388 (3)
O1A—C3	1.280 (5)	C3—C4	1.383 (4)
N1—C1	1.328 (3)	C4—C5	1.362 (4)
N1—N2	1.329 (3)	C5—C6	1.370 (4)
N2—N3	1.310 (3)	C6—C7	1.378 (3)
N2—C8	1.445 (3)	C8—C9	1.508 (3)
N3—N4	1.319 (3)

C9—O2—C10	117.19 (18)	O1A—C3—C4	119.1 (4)
C1—N1—N2	101.8 (2)	O1A—C3—C2	119.9 (3)
N3—N2—N1	114.2 (2)	C4—C3—C2	120.7 (3)
N3—N2—C8	122.4 (2)	C5—C4—C3	120.0 (3)
N1—N2—C8	123.2 (2)	C4—C5—C6	120.3 (3)
N2—N3—N4	105.9 (2)	C5—C6—C7	120.1 (3)
N3—N4—C1	106.5 (2)	O1—C7—C6	116.2 (3)
N1—C1—N4	111.6 (2)	O1—C7—C2	122.9 (3)
N1—C1—C2	124.2 (2)	C6—C7—C2	120.7 (3)
N4—C1—C2	124.2 (2)	N2—C8—C9	111.09 (19)
C7—C2—C3	118.1 (2)	O3—C9—O2	126.0 (2)
C7—C2—C1	121.0 (2)	O3—C9—C8	124.7 (2)
C3—C2—C1	120.8 (2)	O2—C9—C8	109.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.91	2.659 (4)	148
C5—H5···O3ⁱ	0.95	2.57	3.472 (3)	158

Symmetry code: (i) −x+1, −y, −z+1.

Funding information

We acknowledge financial support from the Basic Science Research Program (2016R1D1A1B03930507) and the BRL Program (2015R1A4A1041036) of the National Research Foundation of Korea (NRF), funded by the Ministry of Science, ICT & Future Planning and Education.

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