1H-Benzotriazole–4-hy­droxy­benzoic acid (1/1)

Thirunavukkarasu, A.; Silambarasan, A.; Chakkaravarthi, G.; Mohankumar, R.; Umarani, P.R.

doi:10.1107/S1600536813026767

organic compounds

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Volume 69| Part 11| November 2013| Page o1605

doi:10.1107/S1600536813026767

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1H-Benzotriazole–4-hydroxybenzoic acid (1/1)

A. Thirunavukkarasu,^a A. Silambarasan,^a G. Chakkaravarthi,^b ^* R. Mohankumar ^c and P. R. Umarani ^d ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^cDepartment of Physics, Presidency College, Chennai 600 005, India, and ^dKunthavai Naacchiyaar Govt. Arts College (W), Thanjavur 613 007, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, kan_uma6@yahoo.com

(Received 23 September 2013; accepted 29 September 2013; online 2 October 2013)

The asymmetric unit of the title compound, C₆H₅N₃·C₇H₆O₃, comprises independent benzotriazole and 4-hydroxybenzoic acid molecules. The dihedral angle between the benzene ring and the benzotriazole ring system is 15.18 (7)°. The mean plane of the carboxyl group is twisted at an angle of 18.55 (1)° with respect to the benzene ring. The crystal structure is stabilized by weak intermolecular N—H⋯N, O—H⋯N, O—H⋯O and C—H⋯O interactions, forming a three-dimensional network.

CCDC reference: 963643

Related literature

For biological activities of benzotriazole derivates, see: Dubey et al. (2011 ); Gaikwad, et al. (2012 ). For reported structures, see: Sieroń (2007 ); Sudhahar et al.(2013 ); Yang et al. (2010 ).

Experimental

Crystal data

C₆H₅N₃·C₇H₆O₃
M_r = 257.25
Orthorhombic, P n a 2₁
a = 17.3634 (13) Å
b = 11.4669 (9) Å
c = 6.0818 (4) Å
V = 1210.91 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 0.976
6611 measured reflections
2195 independent reflections
1925 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.074
S = 1.04
2195 reflections
174 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.86	2.20	2.982 (2)	152
O2—H2A⋯N3ⁱⁱ	0.82	1.87	2.6817 (19)	169
O3—H3A⋯O1ⁱⁱⁱ	0.82	1.88	2.6912 (17)	171
C13—H13⋯O3^iv	0.93	2.49	3.373 (2)	159
Symmetry codes: (i) $[-x, -y+2, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+1]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y, z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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: SHELXL97.

Supporting information

CCDC reference: 963643

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813026767/vm2200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026767/vm2200Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813026767/vm2200Isup3.cml

checkCIF report

Comment top

Benzotriazole derivates exhibit numerous essential bioactivitities, especially in antitubercular and antimicrobial (Dubey et al., 2011; Gaikwad et al., 2012) activities. We herewith report the crystal structure of the title compound (I) (Fig.1). The geometric parameters are comparable with reported structures (Sieroń , 2007; Sudhahar et al., 2013; Yang et al., 2010).

The benzene ring (C1-C6) is planar, with the maximum deviation of 0.010 (2) Å. The dihedral angle between the benzene ring and benzotriazole ring system is 15.18 (7)°. The mean plane of carboxyl group is twisted at an angle of 18.55 (1)° with the benzene ring. The crystal structure is stabilized by weak intermolecular N—H···N, O—H···N, O—H···O, C—H···O (Table 1 & Fig. 2) interactions to form a three dimensional network.

Related literature top

For biological activities of benzotriazole derivates, see: Dubey et al. (2011); Gaikwad, et al. (2012). For reported structures, see: Sieroń (2007); Sudhahar et al.(2013); Yang et al. (2010).

Experimental top

Benzotriazole (C₆H₅N₃, 1.1913 g) and p-hydroxy benzoic acid (C₇H₆O₃, 1.3812 g) were mixed in equimolar ratio in methanol and the prepared solution was allowed for slow evaporation at room temperature. Good quality crystals suitable for X-ray intensity data collection were collected in a period of 10 days.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down c axis. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

1H-Benzotriazole–4-hydroxybenzoic acid (1/1) top

Crystal data top

C₆H₅N₃·C₇H₆O₃	F(000) = 536
M_r = 257.25	D_x = 1.411 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2578 reflections
a = 17.3634 (13) Å	θ = 2.1–25.2°
b = 11.4669 (9) Å	µ = 0.10 mm⁻¹
c = 6.0818 (4) Å	T = 295 K
V = 1210.91 (15) Å³	Block, colourless
Z = 4	0.30 × 0.26 × 0.24 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2195 independent reflections
Radiation source: fine-focus sealed tube	1925 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω and ϕ scan	θ_max = 26.8°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→22
T_min = 0.970, T_max = 0.976	k = −13→14
6611 measured reflections	l = −7→4

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0362P)² + 0.0577P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2195 reflections	Δρ_max = 0.15 e Å⁻³
174 parameters	Δρ_min = −0.11 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (2)

Crystal data top

C₆H₅N₃·C₇H₆O₃	V = 1210.91 (15) Å³
M_r = 257.25	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 17.3634 (13) Å	µ = 0.10 mm⁻¹
b = 11.4669 (9) Å	T = 295 K
c = 6.0818 (4) Å	0.30 × 0.26 × 0.24 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2195 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1925 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.976	R_int = 0.033
6611 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.074	H-atom parameters constrained
S = 1.04	Δρ_max = 0.15 e Å⁻³
2195 reflections	Δρ_min = −0.11 e Å⁻³
174 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
C7	0.37669 (8)	0.74471 (13)	0.7594 (3)	0.0363 (4)
C4	0.32444 (9)	0.79794 (14)	0.5984 (3)	0.0353 (4)
C3	0.30244 (10)	0.73727 (15)	0.4112 (3)	0.0457 (4)
H3	0.3204	0.6617	0.3895	0.055*
C2	0.25482 (10)	0.78675 (16)	0.2581 (3)	0.0492 (5)
H2	0.2416	0.7452	0.1323	0.059*
C1	0.22618 (9)	0.89793 (15)	0.2887 (3)	0.0385 (4)
C6	0.24605 (9)	0.95891 (15)	0.4762 (3)	0.0417 (4)
H6	0.2261	1.0331	0.4997	0.050*
C5	0.29535 (10)	0.91033 (14)	0.6286 (3)	0.0419 (4)
H5	0.3093	0.9528	0.7527	0.050*
N2	−0.00946 (8)	0.88952 (13)	0.2498 (3)	0.0477 (4)
C9	0.03383 (9)	0.72630 (14)	0.3824 (3)	0.0345 (4)
C8	0.05616 (10)	0.81341 (14)	0.5280 (3)	0.0366 (4)
C13	0.09730 (10)	0.78968 (17)	0.7199 (3)	0.0485 (5)
H13	0.1117	0.8480	0.8178	0.058*
C12	0.11490 (10)	0.67520 (17)	0.7544 (4)	0.0539 (5)
H12	0.1419	0.6551	0.8809	0.065*
C11	0.09398 (12)	0.58653 (16)	0.6071 (3)	0.0521 (5)
H11	0.1083	0.5101	0.6375	0.062*
C10	0.05347 (10)	0.60939 (14)	0.4216 (3)	0.0459 (4)
H10	0.0393	0.5504	0.3248	0.055*
N3	−0.00650 (8)	0.77773 (12)	0.2146 (2)	0.0418 (3)
N1	0.02792 (8)	0.91193 (12)	0.4377 (3)	0.0456 (4)
H1	0.0332	0.9803	0.4935	0.055*
O1	0.38942 (6)	0.63969 (10)	0.7712 (2)	0.0472 (3)
O2	0.40973 (7)	0.81933 (10)	0.8925 (2)	0.0504 (3)
H2A	0.4380	0.7843	0.9779	0.076*
O3	0.17907 (8)	0.94246 (11)	0.13231 (19)	0.0531 (4)
H3A	0.1627	1.0060	0.1729	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0366 (8)	0.0325 (9)	0.0398 (9)	−0.0021 (6)	0.0031 (7)	−0.0020 (9)
C4	0.0346 (8)	0.0338 (8)	0.0376 (9)	−0.0022 (6)	0.0022 (7)	−0.0032 (7)
C3	0.0509 (10)	0.0377 (9)	0.0485 (11)	0.0083 (7)	−0.0051 (9)	−0.0119 (10)
C2	0.0575 (10)	0.0467 (10)	0.0434 (11)	0.0084 (8)	−0.0093 (10)	−0.0186 (9)
C1	0.0391 (8)	0.0405 (9)	0.0359 (9)	0.0005 (7)	−0.0001 (7)	−0.0029 (8)
C6	0.0480 (9)	0.0303 (8)	0.0468 (10)	0.0029 (7)	−0.0041 (8)	−0.0082 (7)
C5	0.0463 (9)	0.0375 (9)	0.0418 (10)	−0.0014 (7)	−0.0062 (8)	−0.0101 (8)
N2	0.0591 (9)	0.0351 (8)	0.0488 (9)	−0.0029 (6)	−0.0070 (8)	0.0017 (7)
C9	0.0379 (8)	0.0318 (8)	0.0336 (9)	−0.0030 (6)	−0.0001 (7)	−0.0033 (7)
C8	0.0397 (9)	0.0324 (9)	0.0376 (9)	−0.0030 (7)	0.0033 (7)	−0.0053 (7)
C13	0.0527 (10)	0.0538 (12)	0.0391 (10)	−0.0031 (8)	−0.0053 (8)	−0.0128 (10)
C12	0.0563 (11)	0.0610 (12)	0.0445 (11)	0.0052 (9)	−0.0124 (10)	0.0009 (11)
C11	0.0582 (11)	0.0405 (11)	0.0574 (12)	0.0063 (8)	−0.0091 (10)	0.0023 (10)
C10	0.0524 (10)	0.0326 (9)	0.0528 (12)	−0.0006 (7)	−0.0056 (10)	−0.0074 (9)
N3	0.0519 (8)	0.0330 (8)	0.0406 (8)	−0.0022 (6)	−0.0058 (7)	−0.0004 (7)
N1	0.0587 (9)	0.0295 (7)	0.0486 (9)	−0.0043 (6)	−0.0009 (8)	−0.0086 (7)
O1	0.0533 (7)	0.0323 (7)	0.0560 (8)	0.0004 (5)	−0.0065 (6)	−0.0008 (7)
O2	0.0630 (7)	0.0339 (7)	0.0542 (8)	0.0015 (5)	−0.0221 (7)	−0.0036 (6)
O3	0.0654 (8)	0.0509 (8)	0.0430 (7)	0.0145 (6)	−0.0147 (6)	−0.0089 (6)

Geometric parameters (Å, º) top

C7—O1	1.2265 (18)	C9—N3	1.371 (2)
C7—O2	1.3102 (19)	C9—C8	1.390 (2)
C7—C4	1.468 (2)	C9—C10	1.404 (2)
C4—C3	1.388 (2)	C8—N1	1.348 (2)
C4—C5	1.396 (2)	C8—C13	1.395 (3)
C3—C2	1.369 (2)	C13—C12	1.364 (3)
C3—H3	0.9300	C13—H13	0.9300
C2—C1	1.381 (2)	C12—C11	1.403 (3)
C2—H2	0.9300	C12—H12	0.9300
C1—O3	1.3545 (19)	C11—C10	1.355 (3)
C1—C6	1.381 (2)	C11—H11	0.9300
C6—C5	1.380 (2)	C10—H10	0.9300
C6—H6	0.9300	N1—H1	0.8600
C5—H5	0.9300	O2—H2A	0.8200
N2—N3	1.3008 (19)	O3—H3A	0.8200
N2—N1	1.339 (2)

O1—C7—O2	121.74 (15)	N3—C9—C10	131.39 (15)
O1—C7—C4	123.97 (15)	C8—C9—C10	120.69 (16)
O2—C7—C4	114.28 (13)	N1—C8—C9	103.95 (15)
C3—C4—C5	118.12 (15)	N1—C8—C13	133.65 (17)
C3—C4—C7	120.59 (15)	C9—C8—C13	122.39 (16)
C5—C4—C7	121.30 (15)	C12—C13—C8	115.53 (17)
C2—C3—C4	121.11 (16)	C12—C13—H13	122.2
C2—C3—H3	119.4	C8—C13—H13	122.2
C4—C3—H3	119.4	C13—C12—C11	122.75 (19)
C3—C2—C1	120.55 (16)	C13—C12—H12	118.6
C3—C2—H2	119.7	C11—C12—H12	118.6
C1—C2—H2	119.7	C10—C11—C12	121.73 (17)
O3—C1—C2	118.07 (15)	C10—C11—H11	119.1
O3—C1—C6	122.67 (15)	C12—C11—H11	119.1
C2—C1—C6	119.26 (16)	C11—C10—C9	116.89 (16)
C5—C6—C1	120.36 (15)	C11—C10—H10	121.6
C5—C6—H6	119.8	C9—C10—H10	121.6
C1—C6—H6	119.8	N2—N3—C9	108.75 (14)
C6—C5—C4	120.56 (15)	N2—N1—C8	111.29 (14)
C6—C5—H5	119.7	N2—N1—H1	124.4
C4—C5—H5	119.7	C8—N1—H1	124.4
N3—N2—N1	108.09 (14)	C7—O2—H2A	109.5
N3—C9—C8	107.91 (14)	C1—O3—H3A	109.5

O1—C7—C4—C3	−18.0 (2)	N3—C9—C8—C13	178.84 (16)
O2—C7—C4—C3	161.82 (15)	C10—C9—C8—C13	−1.3 (3)
O1—C7—C4—C5	161.86 (16)	N1—C8—C13—C12	179.32 (19)
O2—C7—C4—C5	−18.3 (2)	C9—C8—C13—C12	0.6 (3)
C5—C4—C3—C2	1.3 (3)	C8—C13—C12—C11	0.6 (3)
C7—C4—C3—C2	−178.86 (17)	C13—C12—C11—C10	−1.2 (3)
C4—C3—C2—C1	−1.3 (3)	C12—C11—C10—C9	0.5 (3)
C3—C2—C1—O3	−179.75 (16)	N3—C9—C10—C11	−179.47 (17)
C3—C2—C1—C6	−0.1 (3)	C8—C9—C10—C11	0.6 (2)
O3—C1—C6—C5	−178.87 (16)	N1—N2—N3—C9	−0.20 (18)
C2—C1—C6—C5	1.5 (3)	C8—C9—N3—N2	0.25 (18)
C1—C6—C5—C4	−1.5 (3)	C10—C9—N3—N2	−179.65 (18)
C3—C4—C5—C6	0.1 (2)	N3—N2—N1—C8	0.09 (19)
C7—C4—C5—C6	−179.74 (16)	C9—C8—N1—N2	0.06 (18)
N3—C9—C8—N1	−0.18 (17)	C13—C8—N1—N2	−178.79 (18)
C10—C9—C8—N1	179.72 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.20	2.982 (2)	152
O2—H2A···N3ⁱⁱ	0.82	1.87	2.6817 (19)	169
O3—H3A···O1ⁱⁱⁱ	0.82	1.88	2.6912 (17)	171
C13—H13···O3^iv	0.93	2.49	3.373 (2)	159

Symmetry codes: (i) −x, −y+2, z+1/2; (ii) x+1/2, −y+3/2, z+1; (iii) −x+1/2, y+1/2, z−1/2; (iv) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.20	2.982 (2)	152
O2—H2A···N3ⁱⁱ	0.82	1.87	2.6817 (19)	169
O3—H3A···O1ⁱⁱⁱ	0.82	1.88	2.6912 (17)	171
C13—H13···O3^iv	0.93	2.49	3.373 (2)	159

Symmetry codes: (i) −x, −y+2, z+1/2; (ii) x+1/2, −y+3/2, z+1; (iii) −x+1/2, y+1/2, z−1/2; (iv) x, y, z+1.

Acknowledgements

The authors thanks SAIF, IIT, Madras, for data collection.

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