organic compounds
1-Benzyl-1H-benzotriazole 3-oxide monohydrate
aDepartment of Chemistry, Popes College, Sawyerpuram 628 251, Tamilnadu, India, bDepartment of Physics, Sethupathy Government Arts College, Ramanathapuram 623 502, Tamilnadu, India, and cInstitut für Organische Chemie, Universität Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
*Correspondence e-mail: b_ravidurai@yahoo.com
In the title hydrate, C13H11N3O·H2O, the benzotriazole ring system is planar (r.m.s. deviation = 0.007 Å) and is almost orthogonal to the phenyl ring to which it is linked by a methylene group, forming a dihedral angle of 81.87 (15)°. In the crystal, molecules are linked into chains along [001] by O—H⋯O hydrogen bonds. The chains are consolidated into a three-dimensional architecture by C—H⋯O, C—H⋯π and π–π [centroid–centroid distance between the five- and six-membered rings of the benzotriazole ring system = 3.595 (3) Å] interactions.
Related literature
For the biological activity of benzotriazole derivatives, see: Kopańska et al. (2005); Sarala et al. (2007). For their applications, see: Kopec et al. (2008); Krawczyk & Gdaniec (2005); Smith et al. (2001); Sha et al. (1996). For a related structure, see: Selvarathy Grace et al. (2012).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812044868/tk5165sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044868/tk5165Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044868/tk5165Isup3.cml
A mixture of sodium salt of 1-hydroxyl benzotriazole (0.157 g, 1 mmol) and benzyl chloride (0.126 g, 1 mmol) in a mixture comprising ethanol, water and sodium ethoxide (10 ml) were heated at 333 K with continuous stirring for 6 h. The mixture was kept aside for slow evaporation. After a week, crystals suitable for X-ray diffraction were obtained.
H atoms were positioned geometrically [C—H = 0.95 (aromatic) or 0.99 Å (methylene); O—H= 0.82–0.85 Å] and refined using a riding model, with Uiso(H) = 1.2-1.5Ueq(C,O).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).C13H11N3O·H2O | F(000) = 512 |
Mr = 243.26 | Dx = 1.321 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 1403 reflections |
a = 12.556 (5) Å | θ = 2.5–20.2° |
b = 20.881 (8) Å | µ = 0.09 mm−1 |
c = 4.6651 (18) Å | T = 173 K |
V = 1223.1 (8) Å3 | Needle, colourless |
Z = 4 | 0.40 × 0.05 × 0.04 mm |
Bruker SMART APEXII diffractometer | 1118 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.132 |
Graphite monochromator | θmax = 28.2°, θmin = 1.9° |
CCD scan | h = −16→16 |
15911 measured reflections | k = −27→27 |
1677 independent reflections | l = −6→6 |
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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0825P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
1677 reflections | Δρmax = 0.19 e Å−3 |
164 parameters | Δρmin = −0.24 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: 0.038 (6) |
C13H11N3O·H2O | V = 1223.1 (8) Å3 |
Mr = 243.26 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.556 (5) Å | µ = 0.09 mm−1 |
b = 20.881 (8) Å | T = 173 K |
c = 4.6651 (18) Å | 0.40 × 0.05 × 0.04 mm |
Bruker SMART APEXII diffractometer | 1118 reflections with I > 2σ(I) |
15911 measured reflections | Rint = 0.132 |
1677 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 1 restraint |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.19 e Å−3 |
1677 reflections | Δρmin = −0.24 e Å−3 |
164 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3160 (2) | 0.27237 (12) | 0.6604 (7) | 0.0335 (7) | |
N2 | 0.4106 (2) | 0.25008 (13) | 0.5616 (7) | 0.0372 (7) | |
N3 | 0.4253 (2) | 0.19473 (13) | 0.6976 (8) | 0.0389 (8) | |
C4 | 0.3429 (3) | 0.18041 (15) | 0.8807 (9) | 0.0343 (8) | |
C5 | 0.3241 (3) | 0.12821 (16) | 1.0631 (10) | 0.0455 (10) | |
H5 | 0.3720 | 0.0931 | 1.0769 | 0.055* | |
C6 | 0.2315 (3) | 0.13125 (18) | 1.2207 (10) | 0.0524 (11) | |
H6 | 0.2153 | 0.0974 | 1.3495 | 0.063* | |
C7 | 0.1594 (3) | 0.18339 (18) | 1.1969 (10) | 0.0464 (9) | |
H7 | 0.0962 | 0.1829 | 1.3089 | 0.056* | |
C8 | 0.1776 (3) | 0.23429 (16) | 1.0183 (8) | 0.0380 (9) | |
H8 | 0.1293 | 0.2692 | 1.0038 | 0.046* | |
C9 | 0.2720 (3) | 0.23174 (14) | 0.8583 (8) | 0.0301 (8) | |
C10 | 0.2800 (3) | 0.33671 (14) | 0.5809 (9) | 0.0344 (8) | |
H10A | 0.2019 | 0.3360 | 0.5514 | 0.041* | |
H10B | 0.3137 | 0.3492 | 0.3974 | 0.041* | |
C11 | 0.3069 (3) | 0.38601 (15) | 0.8068 (8) | 0.0310 (8) | |
C12 | 0.2259 (3) | 0.42481 (15) | 0.9188 (9) | 0.0364 (8) | |
H12 | 0.1545 | 0.4193 | 0.8558 | 0.044* | |
C13 | 0.2499 (3) | 0.47148 (15) | 1.1226 (9) | 0.0419 (9) | |
H13 | 0.1948 | 0.4979 | 1.1972 | 0.050* | |
C14 | 0.3532 (3) | 0.47944 (16) | 1.2161 (10) | 0.0423 (9) | |
H14 | 0.3693 | 0.5115 | 1.3539 | 0.051* | |
C15 | 0.4335 (3) | 0.44073 (16) | 1.1095 (9) | 0.0396 (9) | |
H15 | 0.5044 | 0.4458 | 1.1767 | 0.048* | |
C16 | 0.4107 (3) | 0.39448 (16) | 0.9047 (9) | 0.0377 (8) | |
H16 | 0.4663 | 0.3684 | 0.8308 | 0.045* | |
O17 | 0.51045 (19) | 0.16046 (12) | 0.6496 (9) | 0.0576 (10) | |
O1W | 0.4934 (2) | 0.03436 (11) | 0.4506 (7) | 0.0472 (7) | |
H1W | 0.4943 | 0.0098 | 0.5883 | 0.071* | |
H2W | 0.4986 | 0.0728 | 0.5103 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0399 (15) | 0.0262 (13) | 0.0344 (17) | 0.0007 (12) | −0.0016 (14) | 0.0040 (13) |
N2 | 0.0383 (15) | 0.0306 (13) | 0.0426 (18) | 0.0002 (13) | 0.0004 (15) | −0.0061 (14) |
N3 | 0.0389 (15) | 0.0276 (13) | 0.0503 (19) | 0.0033 (12) | −0.0076 (16) | −0.0087 (15) |
C4 | 0.0400 (18) | 0.0240 (15) | 0.039 (2) | −0.0013 (14) | −0.0091 (18) | −0.0034 (16) |
C5 | 0.063 (2) | 0.0263 (16) | 0.048 (2) | −0.0027 (17) | −0.021 (2) | 0.0027 (18) |
C6 | 0.080 (3) | 0.034 (2) | 0.043 (2) | −0.017 (2) | −0.018 (3) | 0.0126 (19) |
C7 | 0.056 (2) | 0.043 (2) | 0.039 (2) | −0.0120 (17) | −0.003 (2) | 0.008 (2) |
C8 | 0.044 (2) | 0.0316 (18) | 0.038 (2) | −0.0022 (15) | −0.0036 (18) | 0.0001 (16) |
C9 | 0.0396 (18) | 0.0241 (14) | 0.0268 (19) | −0.0015 (13) | −0.0043 (16) | 0.0025 (14) |
C10 | 0.045 (2) | 0.0259 (15) | 0.0321 (19) | 0.0012 (14) | −0.0032 (17) | 0.0053 (15) |
C11 | 0.0410 (18) | 0.0214 (14) | 0.0304 (18) | −0.0046 (14) | −0.0022 (16) | 0.0067 (14) |
C12 | 0.0353 (17) | 0.0297 (15) | 0.044 (2) | 0.0020 (14) | −0.0066 (18) | 0.0010 (17) |
C13 | 0.0461 (19) | 0.0287 (16) | 0.051 (3) | 0.0061 (15) | −0.005 (2) | −0.0025 (18) |
C14 | 0.056 (2) | 0.0299 (16) | 0.041 (2) | −0.0108 (16) | −0.001 (2) | −0.0005 (18) |
C15 | 0.0401 (19) | 0.0376 (17) | 0.041 (2) | −0.0109 (16) | −0.0017 (18) | 0.0010 (17) |
C16 | 0.0376 (18) | 0.0372 (17) | 0.038 (2) | 0.0002 (15) | 0.0028 (17) | 0.0048 (17) |
O17 | 0.0404 (14) | 0.0367 (13) | 0.096 (3) | 0.0084 (11) | −0.0063 (17) | −0.0224 (18) |
O1W | 0.0745 (18) | 0.0287 (12) | 0.0382 (15) | −0.0030 (12) | −0.0035 (14) | −0.0018 (12) |
N1—N2 | 1.356 (4) | C10—H10A | 0.9900 |
N1—C9 | 1.370 (4) | C10—H10B | 0.9900 |
N1—C10 | 1.465 (4) | C11—C16 | 1.393 (5) |
N2—N3 | 1.331 (4) | C11—C12 | 1.401 (5) |
N3—O17 | 1.306 (4) | C12—C13 | 1.394 (5) |
N3—C4 | 1.374 (5) | C12—H12 | 0.9500 |
C4—C9 | 1.398 (4) | C13—C14 | 1.379 (5) |
C4—C5 | 1.403 (5) | C13—H13 | 0.9500 |
C5—C6 | 1.377 (6) | C14—C15 | 1.385 (5) |
C5—H5 | 0.9500 | C14—H14 | 0.9500 |
C6—C7 | 1.421 (6) | C15—C16 | 1.389 (5) |
C6—H6 | 0.9500 | C15—H15 | 0.9500 |
C7—C8 | 1.370 (5) | C16—H16 | 0.9500 |
C7—H7 | 0.9500 | O1W—H1W | 0.8225 |
C8—C9 | 1.401 (5) | O1W—H2W | 0.8519 |
C8—H8 | 0.9500 | ||
N2—N1—C9 | 111.7 (3) | N1—C10—C11 | 112.3 (3) |
N2—N1—C10 | 119.9 (3) | N1—C10—H10A | 109.1 |
C9—N1—C10 | 127.8 (3) | C11—C10—H10A | 109.1 |
N3—N2—N1 | 104.9 (3) | N1—C10—H10B | 109.1 |
O17—N3—N2 | 120.5 (3) | C11—C10—H10B | 109.1 |
O17—N3—C4 | 127.1 (3) | H10A—C10—H10B | 107.9 |
N2—N3—C4 | 112.4 (3) | C16—C11—C12 | 118.9 (3) |
N3—C4—C9 | 105.4 (3) | C16—C11—C10 | 121.6 (3) |
N3—C4—C5 | 132.3 (3) | C12—C11—C10 | 119.5 (3) |
C9—C4—C5 | 122.3 (3) | C13—C12—C11 | 120.1 (3) |
C6—C5—C4 | 115.5 (3) | C13—C12—H12 | 119.9 |
C6—C5—H5 | 122.3 | C11—C12—H12 | 119.9 |
C4—C5—H5 | 122.3 | C14—C13—C12 | 120.2 (3) |
C5—C6—C7 | 122.1 (4) | C14—C13—H13 | 119.9 |
C5—C6—H6 | 118.9 | C12—C13—H13 | 119.9 |
C7—C6—H6 | 118.9 | C13—C14—C15 | 120.1 (4) |
C8—C7—C6 | 122.4 (4) | C13—C14—H14 | 120.0 |
C8—C7—H7 | 118.8 | C15—C14—H14 | 120.0 |
C6—C7—H7 | 118.8 | C14—C15—C16 | 120.2 (3) |
C7—C8—C9 | 115.9 (3) | C14—C15—H15 | 119.9 |
C7—C8—H8 | 122.1 | C16—C15—H15 | 119.9 |
C9—C8—H8 | 122.1 | C15—C16—C11 | 120.5 (3) |
N1—C9—C4 | 105.5 (3) | C15—C16—H16 | 119.8 |
N1—C9—C8 | 132.6 (3) | C11—C16—H16 | 119.8 |
C4—C9—C8 | 121.9 (3) | H1W—O1W—H2W | 109.4 |
C9—N1—N2—N3 | 0.5 (4) | C5—C4—C9—N1 | −179.4 (3) |
C10—N1—N2—N3 | 172.9 (3) | N3—C4—C9—C8 | −179.3 (3) |
N1—N2—N3—O17 | 179.9 (3) | C5—C4—C9—C8 | 0.3 (5) |
N1—N2—N3—C4 | 0.2 (4) | C7—C8—C9—N1 | 179.4 (4) |
O17—N3—C4—C9 | 179.6 (3) | C7—C8—C9—C4 | −0.1 (5) |
N2—N3—C4—C9 | −0.8 (4) | N2—N1—C10—C11 | −96.1 (4) |
O17—N3—C4—C5 | 0.0 (7) | C9—N1—C10—C11 | 74.9 (4) |
N2—N3—C4—C5 | 179.6 (4) | N1—C10—C11—C16 | 54.8 (4) |
N3—C4—C5—C6 | 178.9 (4) | N1—C10—C11—C12 | −126.0 (3) |
C9—C4—C5—C6 | −0.6 (5) | C16—C11—C12—C13 | 0.7 (5) |
C4—C5—C6—C7 | 0.8 (6) | C10—C11—C12—C13 | −178.6 (3) |
C5—C6—C7—C8 | −0.7 (6) | C11—C12—C13—C14 | −0.4 (6) |
C6—C7—C8—C9 | 0.3 (6) | C12—C13—C14—C15 | −0.5 (6) |
N2—N1—C9—C4 | −1.0 (4) | C13—C14—C15—C16 | 1.0 (6) |
C10—N1—C9—C4 | −172.6 (3) | C14—C15—C16—C11 | −0.7 (6) |
N2—N1—C9—C8 | 179.5 (4) | C12—C11—C16—C15 | −0.1 (5) |
C10—N1—C9—C8 | 7.8 (6) | C10—C11—C16—C15 | 179.1 (3) |
N3—C4—C9—N1 | 1.0 (4) |
Cg1 is the centroid of the C11–C16 phenyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O1Wi | 0.82 | 1.93 | 2.744 (3) | 169 |
O1W—H2W···O17 | 0.85 | 1.95 | 2.800 (3) | 180 |
C10—H10A···O17ii | 0.99 | 2.45 | 3.400 (5) | 161 |
C10—H10B···Cg3iii | 0.99 | 2.51 | 3.382 (4) | 147 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) x−1/2, −y+1/2, z; (iii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C13H11N3O·H2O |
Mr | 243.26 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 173 |
a, b, c (Å) | 12.556 (5), 20.881 (8), 4.6651 (18) |
V (Å3) | 1223.1 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.05 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART APEXII diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15911, 1677, 1118 |
Rint | 0.132 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.140, 0.98 |
No. of reflections | 1677 |
No. of parameters | 164 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.24 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).
Cg1 is the centroid of the C11–C16 phenyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O1Wi | 0.82 | 1.93 | 2.744 (3) | 169 |
O1W—H2W···O17 | 0.85 | 1.95 | 2.800 (3) | 180 |
C10—H10A···O17ii | 0.99 | 2.45 | 3.400 (5) | 161 |
C10—H10B···Cg3iii | 0.99 | 2.51 | 3.382 (4) | 147 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) x−1/2, −y+1/2, z; (iii) x, y, z−1. |
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Benzotriazole derivatives show biological activities such as anti-inflammatory, diuretic, anti-viral and anti-hypertensive (Kopańska et al., 2005; Sarala et al., 2007). They have been used as a corrosion inhibitor, anti-freeze agent, ultraviolet light stabilizer for plastics and as an anti-foggant in photography (Krawczyk & Gdaniec, 2005; Smith et al., 2001). N-aryloxy derivatives of benzotriazole have anti-mycobacterial activity (Kopec et al., 2008). Benzotriazole possessing three vicinal N atoms, is used as an anti-fouling and anti-wear reagent (Sha et al., 1996). Due to the above mentioned applications of benzotriazole, we have systematically synthesised and investigated the structures of novel benzotriazole derivatives. We have already reported the crystal structure of 1-(benzyl)-1H-benzotriazole (Selvarathy Grace et al., 2012). Here, we report the crystal structure of the title compound (I).
The benzotriazole ring in (I), Fig 1, is essentially planar with the maximum deviation from planarity being 0.010 (3) Å for atom N3. The mean plane of the benzotriazole ring (N1–N3,C4–C9) forms a dihedral angle of 81.87 (15) Å with the mean plane of the phenyl ring (C11–C16).
The molecules are linked into a one dimensional chain along [001] by O—H···O hydrogen bonds, Table 1 and Fig. 2. The crystal packing is stabilized by π–π stacking interactions with the centroid-centroid distance of 3.595 (3) Å [symmetry code: x, y, -1+z], together with C—H···O and C—H···π interactions, Table 1.