A new polymorph of 2-(2H-benzotriazol-2-yl)acetic acid.

A new polymorph of 2-(benzotriazol-2-yl)acetic acid, C(8)H(7)N(3)O(2), crystallizes in the space group C2/c (Z = 8). The non-planar mol-ecule has a synplanar conformation of the carb-oxy group. The crystal structure features helices parallel to the b axis sustained by O-H⋯N hydrogen bonding which are similar to those in the known polymorph [Giordano & Zagari (1978 ▶). J. Chem. Soc. Perkin Trans. 2, pp. 312-315]. However, in the title structure, columns are formed by π-π stacking inter-actions between benzotriazole fragments of centrosymmetrically related adjacent mol-ecules [centroid-centroid distances = 3.593 (10) and 3.381 (10) Å] whereas π-π stacking inter-actions are not observed in the other polymorph. In the crystal of the title compound, C-H⋯O inter-actions are also observed.

Related literature

For general background to the biological activity of benzotriazole derivatives, see: Hirokawa et al. (1998 ▶); Yu et al. (2003 ▶); Kopanska et al. (2004 ▶). For the previously reported polymorph, see: Giordano & Zagari (1978 ▶).

Experimental

Crystal data

C8H7N3O2

M = 177.17

Monoclinic,

a = 11.719 (9) Å

b = 8.308 (3) Å

c = 17.246 (5) Å

β = 96.703 (5)°

V = 1667.6 (15) Å3

Z = 8

Cu Kα radiation

μ = 0.89 mm−1

T = 293 K

0.40 × 0.32 × 0.28 mm

Data collection

Oxford Diffraction Xcalibur, Ruby diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.181, T max = 1.000

4907 measured reflections

1488 independent reflections

1235 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.100

S = 1.04

1488 reflections

120 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.12 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812036768/ds2205sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036768/ds2205Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812036768/ds2205Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H7N3O2	F(000) = 736
Mr = 177.17	Dx = 1.411 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 408 reflections
a = 11.719 (9) Å	θ = 5.2–43.7°
b = 8.308 (3) Å	µ = 0.89 mm−1
c = 17.246 (5) Å	T = 293 K
β = 96.703 (5)°	Block, colourless
V = 1667.6 (15) Å3	0.40 × 0.32 × 0.28 mm
Z = 8

Oxford Diffraction Xcalibur, Ruby diffractometer	1488 independent reflections
Radiation source: fine-focus sealed tube	1235 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10.2576 pixels mm-1	θmax = 67.1°, θmin = 5.2°
ω scans	h = −12→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −9→9
Tmin = 0.181, Tmax = 1.000	l = −20→19
4907 measured reflections

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)] = 0.036	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0576P)2 + 0.4124P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1488 reflections	Δρmax = 0.15 e Å−3
120 parameters	Δρmin = −0.12 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0012 (3)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

	x	y	z	Uiso*/Ueq
C1	0.55191 (14)	0.2934 (2)	−0.01273 (10)	0.0573 (4)
H1	0.5107	0.2146	0.0103	0.069*
C2	0.52406 (16)	0.3401 (2)	−0.08830 (10)	0.0713 (6)
H2	0.4617	0.2915	−0.1175	0.086*
C3	0.58612 (18)	0.4597 (3)	−0.12416 (10)	0.0763 (6)
H3	0.5632	0.4868	−0.1760	0.092*
C4	0.67792 (18)	0.5361 (2)	−0.08543 (9)	0.0682 (5)
H4	0.7186	0.6142	−0.1094	0.082*
C5	0.70856 (14)	0.49131 (18)	−0.00695 (8)	0.0511 (4)
C6	0.64717 (12)	0.37216 (17)	0.02830 (8)	0.0454 (4)
C7	0.85382 (12)	0.48491 (19)	0.18123 (8)	0.0517 (4)
H7A	0.9296	0.5179	0.1701	0.062*
H7B	0.8618	0.3840	0.2096	0.062*
C8	0.80584 (12)	0.61084 (19)	0.23154 (8)	0.0480 (4)
N1	0.79426 (11)	0.54651 (15)	0.04583 (7)	0.0542 (4)
N2	0.78104 (10)	0.46083 (14)	0.10872 (7)	0.0468 (3)
N3	0.69527 (10)	0.35514 (14)	0.10293 (6)	0.0457 (3)
O1	0.87531 (9)	0.63393 (16)	0.29596 (6)	0.0666 (4)
H1A	0.8481	0.7025	0.3227	0.100*
O2	0.71669 (10)	0.67914 (16)	0.21507 (6)	0.0672 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0544 (9)	0.0607 (10)	0.0547 (9)	0.0124 (7)	−0.0024 (7)	−0.0122 (7)
C2	0.0694 (11)	0.0844 (13)	0.0551 (10)	0.0264 (10)	−0.0136 (8)	−0.0231 (9)
C3	0.1008 (15)	0.0870 (13)	0.0384 (9)	0.0391 (12)	−0.0026 (9)	−0.0039 (9)
C4	0.0975 (13)	0.0652 (10)	0.0433 (9)	0.0255 (10)	0.0145 (9)	0.0059 (8)
C5	0.0650 (9)	0.0475 (8)	0.0414 (8)	0.0153 (7)	0.0087 (6)	−0.0012 (6)
C6	0.0507 (8)	0.0468 (8)	0.0383 (7)	0.0133 (6)	0.0031 (6)	−0.0038 (6)
C7	0.0471 (8)	0.0582 (9)	0.0482 (9)	0.0004 (7)	−0.0008 (6)	−0.0039 (7)
C8	0.0475 (8)	0.0574 (9)	0.0386 (7)	−0.0016 (7)	0.0026 (6)	0.0013 (6)
N1	0.0677 (8)	0.0487 (7)	0.0479 (7)	0.0021 (6)	0.0132 (6)	0.0007 (5)
N2	0.0512 (7)	0.0488 (7)	0.0403 (6)	0.0007 (5)	0.0046 (5)	−0.0023 (5)
N3	0.0477 (7)	0.0483 (7)	0.0403 (6)	0.0032 (5)	0.0027 (5)	−0.0008 (5)
O1	0.0524 (6)	0.0924 (9)	0.0518 (7)	0.0143 (6)	−0.0069 (5)	−0.0215 (6)
O2	0.0643 (7)	0.0858 (9)	0.0482 (6)	0.0216 (6)	−0.0072 (5)	−0.0114 (6)

C1—C2	1.362 (3)	C6—N3	1.3510 (17)
C1—C6	1.411 (2)	C7—N2	1.4431 (18)
C1—H1	0.9300	C7—C8	1.509 (2)
C2—C3	1.415 (3)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C4	1.356 (3)	C8—O2	1.1937 (19)
C3—H3	0.9300	C8—O1	1.3126 (17)
C4—C5	1.409 (2)	N1—N2	1.3214 (17)
C4—H4	0.9300	N2—N3	1.3296 (17)
C5—N1	1.354 (2)	O1—H1A	0.8200
C5—C6	1.403 (2)
C2—C1—C6	115.77 (18)	C5—C6—C1	121.70 (14)
C2—C1—H1	122.1	N2—C7—C8	111.85 (12)
C6—C1—H1	122.1	N2—C7—H7A	109.2
C1—C2—C3	122.69 (18)	C8—C7—H7A	109.2
C1—C2—H2	118.7	N2—C7—H7B	109.2
C3—C2—H2	118.7	C8—C7—H7B	109.2
C4—C3—C2	122.14 (17)	H7A—C7—H7B	107.9
C4—C3—H3	118.9	O2—C8—O1	124.82 (14)
C2—C3—H3	118.9	O2—C8—C7	124.56 (13)
C3—C4—C5	116.61 (18)	O1—C8—C7	110.62 (13)
C3—C4—H4	121.7	N2—N1—C5	102.73 (13)
C5—C4—H4	121.7	N1—N2—N3	117.02 (11)
N1—C5—C6	108.97 (13)	N1—N2—C7	121.50 (13)
N1—C5—C4	129.93 (17)	N3—N2—C7	121.45 (12)
C6—C5—C4	121.10 (16)	N2—N3—C6	103.30 (11)
N3—C6—C5	107.98 (13)	C8—O1—H1A	109.5
N3—C6—C1	130.32 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3i	0.82	1.91	2.7273 (17)	171
C2—H2···O2ii	0.93	2.54	3.365 (3)	148
C7—H7A···O1iii	0.97	2.49	3.387 (3)	154
C7—H7B···O2iv	0.97	2.39	3.268 (3)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N3i	0.82	1.91	2.7273 (17)	171
C2—H2⋯O2ii	0.93	2.54	3.365 (3)	148
C7—H7A⋯O1iii	0.97	2.49	3.387 (3)	154
C7—H7B⋯O2iv	0.97	2.39	3.268 (3)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .