1-(Benzotriazol-1-yl)-2-bromoethanone

Asiri, A.M.; Abo-Dya, N.E.; Arshad, M.N.; Shafiq, M.

doi:10.1107/S1600536812042900

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3179

doi:10.1107/S1600536812042900

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1-(Benzotriazol-1-yl)-2-bromoethanone

Abdullah M. Asiri,^a,^b Nader E. Abo-Dya,^c Muhammad Nadeem Arshad ^b ^* and Muhammad Shafiq ^d ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, ^bCenter of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, ^cDepartment of Pharmaceutical Organic Chemistry, Faculty of Pharmacy, Zagazig University, Zagazig, 44519, Egypt, and ^dDepartment of Chemistry, Government College University, Faisalabad 38040, Pakistan
^*Correspondence e-mail: mnachemist@hotmail.com, hafizshafique@hotmail.com

(Received 9 October 2012; accepted 14 October 2012; online 20 October 2012)

In the title compound C₈H₆BrN₃O, the benzotriazole ring is essentially planar (r.m.s. deviation = 0.0034 Å) and the bromoacetyl unit is twisted at a dihedral angle of 15.24 (16)° with respect to it. In the crystal, pairs of C—H⋯O hydrogen bondings result in the formation of inversion dimers, forming R₂²(12) rings, which are connected by further C—H⋯O interactions into chains extending along the b-axis direction.

Related literature

For the biological activity of the title compound, see: Nakagawa et al. (1973 ). For the crystal structure of a closely related compound, see: Selvarathy Grace et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₆BrN₃O
M_r = 240.07
Monoclinic, P 2₁ /n
a = 12.4815 (4) Å
b = 4.7207 (1) Å
c = 15.4780 (5) Å
β = 103.468 (3)°
V = 886.91 (4) Å³
Z = 4
Cu Kα radiation
μ = 6.02 mm⁻¹
T = 296 K
0.28 × 0.11 × 0.05 mm

Data collection

Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.284, T_max = 0.753
4362 measured reflections
1833 independent reflections
1507 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.141
S = 1.07
1833 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.93	2.50	3.266 (3)	139
C8—H8B⋯O1ⁱⁱ	0.97	2.47	3.413 (4)	163
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y+1, z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and X-SEED (Barbour, 2001 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812042900/pv2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042900/pv2595Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812042900/pv2595Isup3.cml

checkCIF report

Comment top

The title compound shows antitumor activity mediated by inhibition of ascites sarcoma 180 in mice (Nakagawa et al., 1973). Herein we report the crystal structure of the title compound.

The molecule of the title compound (Fig. 1) excluding Br1 atom is planer with r.m.s. deviation = 0.0367 Å; the Br1 atom is displaced from this plane by 0.489 (2) Å . The benzotriazole ring (C1–C6/N1–N3) is essentially planar with r.m.s.d = 0.0034 Å. The bromoacetyl moiety (Br1/C8/C7/O1) is twisted at a dihedral angle of 15.24 (16)° with respect to the benzotriazole ring. The structure of the title compound is stabilized by intermolecular hydrogen bonding interactions C5—H5···O1 resulting in dimers about inversion centers forming twelve membered ring motif R₂²(12) (Bernstein et al., 1995). The dimers are further connected through C8—H8B···O1 hydrogen bonding interactions resulting in chains of molecules extended along the b axis (Table 1 and Fig. 2).

Related literature top

For the biological activity of the title compound, see: Nakagawa et al. (1973). For crystal structure of a closely related compound, see: Selvarathy Grace et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A solution of thionyl chloride (0.4 mL, 5.5 mmol) and benzotriazole (1.79 g., 15 mmol) in methylene chloride (30 mL) was stirred at 293 K for 30 minutes. Bromoacetic acid (0.7 g., 5 mmol) was then added and the heterogeneous mixture was stirred for 2 hr. The solid was filtered and methylene chloride (50 mL) was added to the filtrate. The organic layer was extracted with saturated 4N HCl (3x, 15 mL), brine (2x, 5 mL) and dried over anhydrous Na₂SO₄. The crystals of the title compound suitable for X-ray crystallographic analysis were obtained by slow evaporation of methylene chloride (1.0 g, 83% yield).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and X-SEED (Barbour, 2001).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the C—-H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen- bonding were omitted for clarity.

1-(Benzotriazol-1-yl)-2-bromoethanone top

Crystal data top

C₈H₆BrN₃O	F(000) = 472
M_r = 240.07	D_x = 1.798 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 2295 reflections
a = 12.4815 (4) Å	θ = 3.6–76.0°
b = 4.7207 (1) Å	µ = 6.02 mm⁻¹
c = 15.4780 (5) Å	T = 296 K
β = 103.468 (3)°	Plate, colorless
V = 886.91 (4) Å³	0.28 × 0.11 × 0.05 mm
Z = 4

Data collection top

Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer	1833 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1507 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
ω scans	θ_max = 76.2°, θ_min = 4.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −15→12
T_min = 0.284, T_max = 0.753	k = −5→5
4362 measured reflections	l = −19→19

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0838P)² + 0.0945P] where P = (F_o² + 2F_c²)/3
1833 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₈H₆BrN₃O	V = 886.91 (4) Å³
M_r = 240.07	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 12.4815 (4) Å	µ = 6.02 mm⁻¹
b = 4.7207 (1) Å	T = 296 K
c = 15.4780 (5) Å	0.28 × 0.11 × 0.05 mm
β = 103.468 (3)°

Data collection top

Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer	1833 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	1507 reflections with I > 2σ(I)
T_min = 0.284, T_max = 0.753	R_int = 0.034
4362 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.07	Δρ_max = 0.43 e Å⁻³
1833 reflections	Δρ_min = −0.51 e Å⁻³
118 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 > 2sigma(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
Br1	0.84802 (3)	0.99732 (9)	−0.01180 (3)	0.0947 (2)
O1	0.63342 (16)	0.7775 (4)	0.02369 (12)	0.0717 (5)
N1	0.62518 (17)	1.0238 (4)	0.14622 (14)	0.0512 (5)
N2	0.67298 (17)	1.2209 (5)	0.20998 (14)	0.0603 (5)
N3	0.61989 (19)	1.2185 (5)	0.27134 (14)	0.0673 (6)
C1	0.5348 (2)	1.0227 (5)	0.25097 (18)	0.0582 (6)
C2	0.4553 (3)	0.9458 (7)	0.2965 (2)	0.0774 (8)
H2	0.4528	1.0294	0.3504	0.093*
C3	0.3809 (2)	0.7419 (8)	0.2586 (2)	0.0800 (9)
H3	0.3269	0.6862	0.2875	0.096*
C4	0.3843 (2)	0.6154 (7)	0.1776 (2)	0.0743 (7)
H4	0.3320	0.4787	0.1540	0.089*
C5	0.4624 (2)	0.6864 (5)	0.13167 (17)	0.0608 (6)
H5	0.4647	0.6012	0.0780	0.073*
C6	0.53792 (18)	0.8945 (5)	0.17058 (14)	0.0509 (5)
C7	0.6721 (2)	0.9628 (5)	0.07435 (16)	0.0518 (5)
C8	0.7682 (2)	1.1462 (6)	0.06834 (17)	0.0614 (6)
H8A	0.8172	1.1633	0.1268	0.074*
H8B	0.7419	1.3343	0.0489	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0844 (3)	0.1209 (5)	0.0895 (4)	0.00843 (18)	0.0419 (2)	−0.00526 (18)
O1	0.0855 (12)	0.0685 (12)	0.0622 (10)	−0.0108 (9)	0.0193 (9)	−0.0213 (9)
N1	0.0541 (10)	0.0483 (10)	0.0484 (10)	0.0024 (7)	0.0065 (8)	−0.0066 (7)
N2	0.0655 (11)	0.0525 (11)	0.0594 (11)	0.0003 (9)	0.0075 (9)	−0.0128 (9)
N3	0.0805 (13)	0.0640 (13)	0.0562 (11)	0.0053 (11)	0.0136 (10)	−0.0146 (9)
C1	0.0637 (14)	0.0573 (14)	0.0522 (13)	0.0132 (10)	0.0110 (11)	−0.0013 (9)
C2	0.087 (2)	0.0816 (19)	0.0684 (18)	0.0213 (16)	0.0281 (15)	0.0064 (14)
C3	0.0694 (15)	0.087 (2)	0.088 (2)	0.0074 (15)	0.0282 (15)	0.0204 (17)
C4	0.0606 (14)	0.0732 (18)	0.0864 (19)	−0.0028 (13)	0.0115 (13)	0.0139 (16)
C5	0.0592 (12)	0.0586 (14)	0.0600 (13)	−0.0012 (11)	0.0045 (10)	0.0011 (11)
C6	0.0535 (11)	0.0480 (11)	0.0486 (11)	0.0085 (9)	0.0066 (8)	0.0032 (9)
C7	0.0564 (12)	0.0495 (12)	0.0477 (12)	0.0042 (9)	0.0080 (9)	−0.0026 (8)
C8	0.0640 (13)	0.0619 (15)	0.0586 (13)	0.0006 (11)	0.0150 (10)	−0.0016 (11)

Geometric parameters (Å, º) top

Br1—C8	1.897 (3)	C2—H2	0.9300
O1—C7	1.199 (3)	C3—C4	1.398 (5)
N1—C6	1.376 (3)	C3—H3	0.9300
N1—N2	1.386 (3)	C4—C5	1.374 (4)
N1—C7	1.402 (3)	C4—H4	0.9300
N2—N3	1.279 (3)	C5—C6	1.397 (3)
N3—C1	1.388 (4)	C5—H5	0.9300
C1—C2	1.391 (5)	C7—C8	1.500 (4)
C1—C6	1.392 (3)	C8—H8A	0.9700
C2—C3	1.371 (5)	C8—H8B	0.9700

C6—N1—N2	109.9 (2)	C3—C4—H4	118.9
C6—N1—C7	129.1 (2)	C4—C5—C6	115.9 (3)
N2—N1—C7	120.8 (2)	C4—C5—H5	122.0
N3—N2—N1	108.2 (2)	C6—C5—H5	122.0
N2—N3—C1	109.8 (2)	N1—C6—C1	104.0 (2)
N3—C1—C2	131.0 (3)	N1—C6—C5	133.8 (2)
N3—C1—C6	108.2 (2)	C1—C6—C5	122.3 (2)
C2—C1—C6	120.7 (3)	O1—C7—N1	119.3 (2)
C3—C2—C1	117.3 (3)	O1—C7—C8	125.9 (2)
C3—C2—H2	121.4	N1—C7—C8	114.8 (2)
C1—C2—H2	121.4	C7—C8—Br1	112.09 (18)
C2—C3—C4	121.6 (3)	C7—C8—H8A	109.2
C2—C3—H3	119.2	Br1—C8—H8A	109.2
C4—C3—H3	119.2	C7—C8—H8B	109.2
C5—C4—C3	122.2 (3)	Br1—C8—H8B	109.2
C5—C4—H4	118.9	H8A—C8—H8B	107.9

C6—N1—N2—N3	0.0 (3)	C7—N1—C6—C5	−6.4 (4)
C7—N1—N2—N3	−174.6 (2)	N3—C1—C6—N1	−0.6 (3)
N1—N2—N3—C1	−0.4 (3)	C2—C1—C6—N1	179.7 (2)
N2—N3—C1—C2	−179.7 (3)	N3—C1—C6—C5	−179.9 (2)
N2—N3—C1—C6	0.6 (3)	C2—C1—C6—C5	0.4 (4)
N3—C1—C2—C3	180.0 (3)	C4—C5—C6—N1	−179.1 (2)
C6—C1—C2—C3	−0.4 (4)	C4—C5—C6—C1	0.0 (3)
C1—C2—C3—C4	0.0 (5)	C6—N1—C7—O1	1.4 (4)
C2—C3—C4—C5	0.4 (5)	N2—N1—C7—O1	174.8 (2)
C3—C4—C5—C6	−0.4 (4)	C6—N1—C7—C8	−179.3 (2)
N2—N1—C6—C1	0.4 (2)	N2—N1—C7—C8	−5.9 (3)
C7—N1—C6—C1	174.4 (2)	O1—C7—C8—Br1	−14.7 (3)
N2—N1—C6—C5	179.6 (2)	N1—C7—C8—Br1	166.13 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.93	2.50	3.266 (3)	139
C8—H8B···O1ⁱⁱ	0.97	2.47	3.413 (4)	163

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

Experimental details

Crystal data
Chemical formula	C₈H₆BrN₃O
M_r	240.07
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.4815 (4), 4.7207 (1), 15.4780 (5)
β (°)	103.468 (3)
V (Å³)	886.91 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	6.02
Crystal size (mm)	0.28 × 0.11 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.284, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	4362, 1833, 1507
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.141, 1.07
No. of reflections	1833
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.51

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 1999) and X-SEED (Barbour, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.93	2.50	3.266 (3)	139.2
C8—H8B···O1ⁱⁱ	0.97	2.47	3.413 (4)	163.2

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

Acknowledgements

The authors would like to thank the Deanship of Scientific Research at King Abdulaziz University for the support of this research via the Research Group Track of grant No. (3-102/428).

References

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