4-[(4-Hy­droxy­meth­yl-2H-1,2,3-triazol-2-yl)methyl]-6,8-dimethyl-2H-chromen-2-one

El-Khatatneh, N.; Chandra; Shamala, D.; Shivashankar, K.; Mahendra, M.

doi:10.1107/S2414314616016448

organic compounds

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Volume 1| Part 10| October 2016| x161644

https://doi.org/10.1107/S2414314616016448

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ADDENDA AND ERRATA

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4-[(4-Hydroxymethyl-2H-1,2,3-triazol-2-yl)methyl]-6,8-dimethyl-2H-chromen-2-one

Nasseem El-Khatatneh,^a Chandra,^a D. Shamala,^b K. Shivashankar ^b and M. Mahendra ^a ^*

^aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, and ^bDepartment of Chemistry, Central College Campus, Bangalore University, Bangalore 560 001, India
^*Correspondence e-mail: mahendra@physics.uni-mysore.ac.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 13 October 2016; accepted 15 October 2016; online 21 October 2016)

In the title compound, C₁₅H₁₅N₃O₃, the dihedral angle between the triazole ring and coumarin ring system [r.m.s. deviation = 0.040 Å] is 77.40 (6)°. The O atom of the hydroxymethyl group deviates from the triazole ring plane by 1.345 (1) Å. In the crystal, inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R²₂(22) loops; C—H⋯O and C—H⋯N interactions link the dimers into a three-dimensional network.

Keywords: crystal structure; chromene; triazole; hydrogen bonds.

CCDC reference: 1510042

Structure description

Coumarin derivatives represent an important class of natural and synthetic heterocycles that are often linked to a broad array of biological activities (Gaspar et al., 2015 ). As part of our ongoing studies of coumarin–triazole derivatives (El-Khatatneh et al., 2016 ), the title compound (Fig. 1) was synthesized and its crystal structure is now reported.

Figure 1
The molecular structure of the title compound with 50% probability displacement ellipsoids.

The dihedral angle between the triazole ring and coumarin ring system [r.m.s. deviation = 0.040 Å] is 77.40 (6)°. Key inter-ring torsion angles include 97.34 (15)° for N19—N15—C14—C13) and −173.30 (13)° for C6—C13—C14—N15. The O atom of the hydroxymethyl group is displaced from the triazole ring plane by 1.345 (1) Å.

In the crystal, inversion dimers linked by pairs of O—H⋯O hydrogen bonds (Table 1) generate R₂²(22) loops. The dimers are linked by weak C—H⋯O and C—H⋯N hydrogen bonds, generating a three-dimensional network (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O21—H21⋯O11ⁱ	0.82	2.10	2.9155 (19)	176
C14—H14A⋯N19ⁱⁱ	0.97	2.55	3.486 (2)	162
C14—H14B⋯N18ⁱⁱⁱ	0.97	2.41	3.344 (2)	162
C16—H16⋯O21ⁱⁱⁱ	0.93	2.47	3.284 (2)	146
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x+1, -y+2, -z+2; (iii) x+1, y, z.

Figure 2
The packing viewed along [100] with hydrogen bonds indicated by dashed lines.

Synthesis and crystallization

A mixture of propargyl alcohol (1.9 mmol), sodium azide (0.14 g, 2.0 mmol), copper(I) iodide (10 mol%) and triethylamine (0.19 g, 1.9 mmol) in 20 ml of acetone was taken in a round-bottom flask and stirred for 1 h. To this mixture, 4-bromomethylcoumarin (1.9 mmol) was added and the stirring continued for 8 h (the reaction was monitored by TLC). After the completion of the reaction, the copper catalyst was filtered through celite and the product was extracted with diethyl ether (3.10 ml). The solvent was removed under vacuum. The crude product was dried and recrystallized from ethyl acetate solution to give colourless blocks.

Yield 92%; colourless solid; m.p. 210–212 °C; IR (KBr, cm⁻¹): 1742 cm⁻¹ (lactone C=O), 3311 cm⁻¹ (OH); ¹H NMR (400 MHz, CDCl₃): δ 1.70 (s, 1H, OH), 2.37 (s, 3H, C₆—CH₃) 2.42 (s, 3H, C₈—CH₃) 4.83 (s, 2H, –CH₂O–), 5.43 (s, 1H, C₃—H), 5.70 (s, 2H, –CH₂N–), 7.21-7.24 (m, 1H, C₇—H), 7.60 (s, 1H, C₅—H), 7.75 (s, 1H, Tr—H) p.p.m. ¹³C NMR (100 MHz, DMSO-d₆): δ 15.0, 20.3, 49.0, 55.0, 113.0, 116.5, 122.0, 123.8, 125.3, 133.1, 134.5, 148.6, 149.5, 150.6, 159.5 p.p.m. Analysis C₁₅H₁₅N₃O₃. Calculated for: C, 63.15; H, 5.30; N, 14.73%. Found: C, 63.08; H, 5.26; N, 14.68%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃O₃
M_r	285.30
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	6.0265 (16), 11.062 (3), 11.848 (3)
α, β, γ (°)	108.812 (7), 103.950 (8), 100.848 (8)
V (Å³)	694.5 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.80
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker X8 Proteum
No. of measured, independent and observed [I > 2σ(I)] reflections	8218, 2217, 2142
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.587

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.114, 1.04
No. of reflections	2217
No. of parameters	194
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.14
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS (Sheldrick, 2008 ), SHELXL2016/4 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1510042

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616016448/hb4087sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016448/hb4087Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616016448/hb4087Isup3.cml

checkCIF report

Computing details top

4-[(4-Hydroxymethyl-2H-1,2,3-triazol-2-yl)methyl]-6,8-dimethyl-2H-chromen-2-one top

Crystal data top

C₁₅H₁₅N₃O₃	Z = 2
M_r = 285.30	F(000) = 300
Triclinic, P1	D_x = 1.364 Mg m⁻³
a = 6.0265 (16) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.062 (3) Å	Cell parameters from 2217 reflections
c = 11.848 (3) Å	θ = 7.2–64.7°
α = 108.812 (7)°	µ = 0.80 mm⁻¹
β = 103.950 (8)°	T = 293 K
γ = 100.848 (8)°	Block, colourless
V = 694.5 (3) Å³	0.30 × 0.20 × 0.10 mm

Data collection top

Bruker X8 Proteum diffractometer	2142 reflections with I > 2σ(I)
Radiation source: Bruker MicroStar microfocus rotating anode	R_int = 0.030
Helios multilayer optics monochromator	θ_max = 64.7°, θ_min = 7.2°
Detector resolution: 18.4 pixels mm^-1	h = −6→7
φ and ω scans	k = −12→12
8218 measured reflections	l = −13→13
2217 independent 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0622P)² + 0.126P] where P = (F_o² + 2F_c²)/3
2217 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.14 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)
O9	0.37402 (19)	0.76949 (10)	0.45209 (9)	0.0574 (3)
O21	−0.04447 (19)	1.36437 (12)	0.82987 (11)	0.0658 (3)
H21	−0.055031	1.305321	0.763928	0.099*
O11	0.0867 (2)	0.85556 (13)	0.39863 (11)	0.0757 (4)
C6	0.6271 (2)	0.84311 (13)	0.66749 (13)	0.0452 (3)
N19	0.2818 (2)	1.08969 (13)	0.92565 (13)	0.0596 (4)
N15	0.44456 (19)	1.12365 (11)	0.87345 (10)	0.0450 (3)
C13	0.5024 (2)	0.94266 (13)	0.70280 (13)	0.0458 (3)
C5	0.5580 (3)	0.75918 (14)	0.54097 (13)	0.0485 (3)
N18	0.1788 (2)	1.18550 (14)	0.94803 (13)	0.0598 (4)
C1	0.8117 (3)	0.82578 (14)	0.75347 (14)	0.0500 (4)
H1	0.860125	0.880475	0.838505	0.060*
C12	0.3208 (3)	0.94819 (14)	0.61462 (14)	0.0523 (4)
H12	0.240245	1.011061	0.638265	0.063*
C4	0.6663 (3)	0.66137 (15)	0.49641 (14)	0.0560 (4)
C2	0.9229 (3)	0.72895 (15)	0.71413 (15)	0.0542 (4)
C17	0.2756 (2)	1.28047 (13)	0.91088 (12)	0.0454 (3)
C20	0.1846 (3)	1.39858 (15)	0.91808 (14)	0.0556 (4)
H20A	0.178228	1.440812	1.002359	0.067*
H20B	0.295413	1.462794	0.903203	0.067*
C14	0.5903 (3)	1.03629 (14)	0.83948 (13)	0.0517 (4)
H14A	0.597759	0.983779	0.891184	0.062*
H14B	0.751444	1.090828	0.859203	0.062*
C10	0.2480 (3)	0.85893 (15)	0.48426 (14)	0.0552 (4)
C3	0.8477 (3)	0.64959 (16)	0.58574 (16)	0.0614 (4)
H3	0.923601	0.585243	0.558673	0.074*
C16	0.4471 (2)	1.24121 (13)	0.86378 (13)	0.0477 (3)
H16	0.545138	1.286513	0.831682	0.057*
C7	1.1162 (3)	0.70920 (19)	0.80743 (18)	0.0718 (5)
H7A	1.168804	0.636256	0.764247	0.108*	0.31 (2)
H7B	1.055076	0.689718	0.869294	0.108*	0.31 (2)
H7C	1.248294	0.789024	0.848366	0.108*	0.31 (2)
H7D	1.145979	0.773742	0.890357	0.108*	0.69 (2)
H7E	1.259707	0.720281	0.785311	0.108*	0.69 (2)
H7F	1.066488	0.620975	0.806239	0.108*	0.69 (2)
C8	0.5915 (4)	0.57393 (19)	0.35871 (16)	0.0760 (5)
H8A	0.690144	0.613072	0.319554	0.114*
H8B	0.427523	0.565734	0.318815	0.114*
H8C	0.609121	0.487213	0.349891	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O9	0.0673 (7)	0.0594 (6)	0.0445 (5)	0.0320 (5)	0.0145 (5)	0.0135 (4)
O21	0.0540 (6)	0.0732 (7)	0.0627 (7)	0.0362 (5)	0.0113 (5)	0.0124 (5)
O11	0.0765 (8)	0.0868 (8)	0.0507 (6)	0.0440 (7)	0.0024 (6)	0.0120 (6)
C6	0.0468 (7)	0.0422 (7)	0.0487 (7)	0.0192 (6)	0.0170 (6)	0.0156 (6)
N19	0.0560 (7)	0.0609 (7)	0.0744 (9)	0.0269 (6)	0.0276 (6)	0.0316 (6)
N15	0.0420 (6)	0.0456 (6)	0.0436 (6)	0.0198 (5)	0.0113 (5)	0.0105 (5)
C13	0.0457 (7)	0.0434 (7)	0.0477 (7)	0.0186 (6)	0.0143 (6)	0.0143 (6)
C5	0.0549 (8)	0.0481 (7)	0.0481 (8)	0.0228 (6)	0.0189 (6)	0.0197 (6)
N18	0.0546 (7)	0.0692 (8)	0.0696 (8)	0.0322 (6)	0.0297 (6)	0.0294 (7)
C1	0.0504 (8)	0.0486 (7)	0.0508 (8)	0.0237 (6)	0.0155 (6)	0.0144 (6)
C12	0.0518 (8)	0.0524 (8)	0.0514 (8)	0.0272 (6)	0.0136 (6)	0.0136 (6)
C4	0.0723 (10)	0.0526 (8)	0.0518 (8)	0.0309 (7)	0.0283 (7)	0.0180 (7)
C2	0.0564 (8)	0.0527 (8)	0.0607 (9)	0.0290 (7)	0.0213 (7)	0.0218 (7)
C17	0.0420 (7)	0.0472 (7)	0.0401 (7)	0.0183 (6)	0.0094 (5)	0.0082 (5)
C20	0.0553 (8)	0.0534 (8)	0.0509 (8)	0.0274 (6)	0.0126 (6)	0.0080 (6)
C14	0.0488 (8)	0.0502 (8)	0.0502 (8)	0.0271 (6)	0.0099 (6)	0.0093 (6)
C10	0.0560 (8)	0.0583 (8)	0.0493 (8)	0.0268 (7)	0.0117 (7)	0.0163 (7)
C3	0.0766 (11)	0.0591 (9)	0.0647 (9)	0.0434 (8)	0.0329 (8)	0.0237 (7)
C16	0.0467 (7)	0.0452 (7)	0.0535 (8)	0.0203 (6)	0.0196 (6)	0.0156 (6)
C7	0.0739 (11)	0.0756 (11)	0.0714 (11)	0.0479 (9)	0.0187 (9)	0.0242 (9)
C8	0.1070 (15)	0.0748 (11)	0.0542 (10)	0.0497 (11)	0.0331 (10)	0.0167 (8)

Geometric parameters (Å, º) top

O9—C10	1.3712 (18)	C4—C8	1.505 (2)
O9—C5	1.3833 (18)	C2—C3	1.395 (2)
O21—C20	1.4118 (18)	C2—C7	1.503 (2)
O21—H21	0.8200	C17—C16	1.3635 (19)
O11—C10	1.2089 (19)	C17—C20	1.4952 (19)
C6—C5	1.392 (2)	C20—H20A	0.9700
C6—C1	1.404 (2)	C20—H20B	0.9700
C6—C13	1.4554 (18)	C14—H14A	0.9700
N19—N18	1.3135 (18)	C14—H14B	0.9700
N19—N15	1.3375 (17)	C3—H3	0.9300
N15—C16	1.3395 (18)	C16—H16	0.9300
N15—C14	1.4513 (16)	C7—H7A	0.9600
C13—C12	1.345 (2)	C7—H7B	0.9600
C13—C14	1.5080 (19)	C7—H7C	0.9600
C5—C4	1.392 (2)	C7—H7D	0.9600
N18—C17	1.352 (2)	C7—H7E	0.9600
C1—C2	1.3829 (19)	C7—H7F	0.9600
C1—H1	0.9300	C8—H8A	0.9600
C12—C10	1.442 (2)	C8—H8B	0.9600
C12—H12	0.9300	C8—H8C	0.9600
C4—C3	1.384 (2)

C10—O9—C5	122.09 (11)	N15—C14—H14B	108.6
C20—O21—H21	109.5	C13—C14—H14B	108.6
C5—C6—C1	117.93 (12)	H14A—C14—H14B	107.6
C5—C6—C13	118.08 (12)	O11—C10—O9	115.82 (13)
C1—C6—C13	123.98 (12)	O11—C10—C12	126.45 (14)
N18—N19—N15	106.63 (11)	O9—C10—C12	117.73 (13)
N19—N15—C16	110.78 (11)	C4—C3—C2	123.61 (13)
N19—N15—C14	119.15 (12)	C4—C3—H3	118.2
C16—N15—C14	130.04 (12)	C2—C3—H3	118.2
C12—C13—C6	119.78 (12)	N15—C16—C17	105.51 (12)
C12—C13—C14	123.64 (12)	N15—C16—H16	127.2
C6—C13—C14	116.58 (11)	C17—C16—H16	127.2
O9—C5—C6	120.68 (12)	C2—C7—H7A	109.5
O9—C5—C4	116.33 (13)	C2—C7—H7B	109.5
C6—C5—C4	122.99 (13)	H7A—C7—H7B	109.5
N19—N18—C17	109.68 (12)	C2—C7—H7C	109.5
C2—C1—C6	121.27 (14)	H7A—C7—H7C	109.5
C2—C1—H1	119.4	H7B—C7—H7C	109.5
C6—C1—H1	119.4	C2—C7—H7D	109.5
C13—C12—C10	121.56 (13)	H7A—C7—H7D	141.1
C13—C12—H12	119.2	H7B—C7—H7D	56.3
C10—C12—H12	119.2	H7C—C7—H7D	56.3
C3—C4—C5	116.29 (14)	C2—C7—H7E	109.5
C3—C4—C8	121.84 (14)	H7A—C7—H7E	56.3
C5—C4—C8	121.87 (14)	H7B—C7—H7E	141.1
C1—C2—C3	117.89 (14)	H7C—C7—H7E	56.3
C1—C2—C7	120.78 (14)	H7D—C7—H7E	109.5
C3—C2—C7	121.33 (13)	C2—C7—H7F	109.5
N18—C17—C16	107.39 (12)	H7A—C7—H7F	56.3
N18—C17—C20	121.83 (13)	H7B—C7—H7F	56.3
C16—C17—C20	130.68 (14)	H7C—C7—H7F	141.1
O21—C20—C17	112.70 (12)	H7D—C7—H7F	109.5
O21—C20—H20A	109.1	H7E—C7—H7F	109.5
C17—C20—H20A	109.1	C4—C8—H8A	109.5
O21—C20—H20B	109.1	C4—C8—H8B	109.5
C17—C20—H20B	109.1	H8A—C8—H8B	109.5
H20A—C20—H20B	107.8	C4—C8—H8C	109.5
N15—C14—C13	114.71 (11)	H8A—C8—H8C	109.5
N15—C14—H14A	108.6	H8B—C8—H8C	109.5
C13—C14—H14A	108.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O11ⁱ	0.82	2.10	2.9155 (19)	176
C14—H14A···N19ⁱⁱ	0.97	2.55	3.486 (2)	162
C14—H14B···N18ⁱⁱⁱ	0.97	2.41	3.344 (2)	162
C16—H16···O21ⁱⁱⁱ	0.93	2.47	3.284 (2)	146

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

Acknowledgements

MM thanks UGC, New Delhi, Government of India, for awarding a project under the title F. No. 41–920/2012(SR) dated: 25–07–2012. SD is grateful to the Council of Scientific and Industrial Research, New Delhi, India, for financial assistance [Grant No. 02 (0172)/13/EMR-II].

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