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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o735.
Published online 2008 March 20. doi:  10.1107/S160053680800740X
PMCID: PMC2960979

2-(Benzotriazol-1-ylmethyl­amino)­benzoic acid

Abstract

The title compound, C14H12N4O2, a new N,O,N′-tridentate ligand, is V-shaped with the mean plane through the benzotriazole system [planar to within 0.013 (2) Å] inclined by 67.7 (1)° to the mean plane through the benzene ring. In the mol­ecule there is an intra­molecular N—H(...)O hydrogen bond involving the amine H atom and the carbonyl O atom. In the crystal structure, symmtry-related mol­ecules are connected by inter­molecular O—H(...)N and C—H(...)O hydrogen bonds and C—H(...)π inter­actions.

Related literature

For related literature, see: Trofimenko (1993 [triangle]); Zhang, Dou et al. (2007 [triangle]); Zhang et al. (2006 [triangle]); Zhang, Zhou et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o735-scheme1.jpg

Experimental

Crystal data

  • C14H12N4O2
  • M r = 268.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o735-efi1.jpg
  • a = 10.225 (6) Å
  • b = 15.669 (8) Å
  • c = 8.098 (4) Å
  • β = 97.671 (7)°
  • V = 1285.8 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 291 (2) K
  • 0.19 × 0.16 × 0.07 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.982, T max = 0.993
  • 9692 measured reflections
  • 2388 independent reflections
  • 1438 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.117
  • S = 1.02
  • 2388 reflections
  • 186 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800740X/su2045sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800740X/su2045Isup2.hkl

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

Acknowledgments

We thank Shaanxi Normal University for research grants.

supplementary crystallographic information

Comment

In last decades, extensive investigations have been undertaken to design and synthesize pyrazole-based tridentate ligands, with the aim of mimiking structures and functions of some metalloenzymes (Trofimenko, 1993). Our interests have been focused on the design and syntheses of flexible N,O,N ligands derived from pyrazoles and triazoles since a certain flexibility might afford coordination versitality of the ligands. We have therefore designed and synthesized a number of such ligands as well as their transition-metal complexes (Zhang, Dou et al., 2007; Zhang, Yin et al., 2006; Zhang, Zhou et al., 2007). Here we report on the structure of a new N,O,N tridentate ligand, 2-(benzotriazolylmethylamino)benzoic acid.

The molecular structure of the title compound is illustrated in Fig. 1. Details of the hydrogen bonding and C—H···\p interactions are given in Table 1. The molecule is V-shaped with the best plane through the benzotriazole moiety (planar to within 0.013 (2) Å) inclined by 67.7 (1)° to the best plane through the benzene ring (C8—C13). In the molecule there is an intra-molecular N—H···O hydrogen bond involving the amine (N4) hydrogen, H4D, and the carbonyl O-atom, O1 (Table 1).

In the crystal structure symmetry related molecules form dimers via C—H···π interactions involving C12—H12 and the benzene ring [(C1—C6 = Cg2iii]. Adjacent molecules are linked by O2—H2···N3i hydrogen bonds to form zigzag chains parallel to the a axis, and these chains are further linked by C7—H7A···O1ii intermolecular hydrogen bonds (Table 1).

Experimental

The NH hydrogen atom was located from a difference Fourier map and freely refined, N—H = 0.86 (2) Å. The remainder of the H-atoms were included in calculated positions and treated as riding atoms: O—H = 0.82 Å and C—H = 0.93 - 0.97 \%A, with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(C).

Figures

Fig. 1.
Molecular structure of the title compound showing the atom numbering scheme and dislacement ellipsoids drawn at the 50% probability level.

Crystal data

C14H12N4O2F000 = 560
Mr = 268.28Dx = 1.386 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
a = 10.225 (6) ÅCell parameters from 1098 reflections
b = 15.669 (8) Åθ = 2.4–21.9º
c = 8.098 (4) ŵ = 0.10 mm1
β = 97.671 (7)ºT = 291 (2) K
V = 1285.8 (12) Å3Block, colourless
Z = 40.19 × 0.16 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer2388 independent reflections
Radiation source: fine-focus sealed tube1438 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
T = 291(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.982, Tmax = 0.993k = −18→18
9692 measured reflectionsl = −9→9

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.0885P)2 + 0.2074P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2388 reflectionsΔρmax = 0.14 e Å3
186 parametersΔρmin = −0.17 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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)

xyzUiso*/Ueq
O10.37616 (15)0.01777 (11)0.3049 (2)0.0594 (5)
O20.23657 (15)0.05486 (12)0.0817 (2)0.0609 (5)
H20.18450.02940.13270.091*
N10.85744 (16)0.01883 (12)0.3449 (2)0.0414 (5)
N20.95246 (18)0.05227 (13)0.2642 (2)0.0511 (5)
N31.02834 (18)−0.00961 (14)0.2240 (2)0.0539 (6)
N40.62976 (19)0.06560 (14)0.3142 (3)0.0488 (6)
C10.8708 (2)−0.06775 (14)0.3566 (3)0.0393 (5)
C20.8006 (2)−0.13078 (16)0.4280 (3)0.0506 (6)
H2A0.7279−0.11850.48180.061*
C30.8460 (3)−0.21219 (17)0.4134 (3)0.0635 (8)
H30.8022−0.25670.45860.076*
C40.9558 (3)−0.23133 (19)0.3332 (4)0.0723 (9)
H40.9827−0.28780.32700.087*
C51.0235 (3)−0.16907 (19)0.2644 (4)0.0657 (8)
H51.0957−0.18200.21030.079*
C60.9808 (2)−0.08513 (16)0.2776 (3)0.0462 (6)
C70.7583 (2)0.07434 (15)0.4056 (3)0.0479 (6)
H7A0.75380.06120.52180.057*
H7B0.78640.13330.39950.057*
C80.5883 (2)0.10492 (13)0.1642 (3)0.0377 (5)
C90.6766 (2)0.15121 (14)0.0805 (3)0.0488 (6)
H90.76500.15470.12570.059*
C100.6343 (2)0.19133 (15)−0.0668 (3)0.0578 (7)
H100.69460.2223−0.11920.069*
C110.5051 (3)0.18711 (16)−0.1397 (3)0.0595 (7)
H110.47740.2150−0.23960.071*
C120.4182 (2)0.14051 (15)−0.0609 (3)0.0489 (6)
H120.33100.1361−0.11030.059*
C130.4559 (2)0.09968 (13)0.0902 (3)0.0372 (5)
C140.3554 (2)0.05360 (15)0.1695 (3)0.0441 (6)
H4D0.568 (2)0.0420 (16)0.360 (3)0.068 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0421 (10)0.0791 (13)0.0586 (12)−0.0032 (9)0.0122 (9)0.0203 (10)
O20.0344 (9)0.0840 (14)0.0641 (12)−0.0085 (9)0.0054 (9)0.0151 (10)
N10.0287 (10)0.0482 (12)0.0475 (12)−0.0040 (9)0.0062 (9)0.0045 (9)
N20.0332 (11)0.0629 (14)0.0563 (13)−0.0067 (10)0.0030 (10)0.0090 (11)
N30.0342 (11)0.0726 (15)0.0552 (13)−0.0018 (11)0.0078 (10)0.0039 (11)
N40.0306 (11)0.0626 (14)0.0532 (14)−0.0003 (10)0.0050 (10)0.0160 (11)
C10.0350 (12)0.0427 (14)0.0385 (13)−0.0007 (11)−0.0010 (10)−0.0001 (11)
C20.0447 (14)0.0559 (16)0.0507 (16)−0.0061 (13)0.0050 (12)0.0067 (13)
C30.0670 (19)0.0527 (18)0.0670 (19)−0.0078 (15)−0.0056 (15)0.0064 (14)
C40.077 (2)0.0529 (18)0.082 (2)0.0130 (16)−0.0071 (18)−0.0084 (16)
C50.0532 (17)0.073 (2)0.070 (2)0.0111 (15)0.0053 (14)−0.0125 (16)
C60.0351 (13)0.0555 (16)0.0465 (15)−0.0006 (12)0.0000 (11)−0.0029 (12)
C70.0418 (14)0.0496 (15)0.0520 (15)0.0025 (12)0.0055 (11)0.0017 (12)
C80.0368 (12)0.0336 (12)0.0436 (14)0.0024 (10)0.0094 (11)0.0011 (10)
C90.0360 (13)0.0501 (15)0.0611 (17)−0.0038 (11)0.0100 (12)0.0061 (13)
C100.0503 (16)0.0570 (17)0.0695 (19)−0.0034 (13)0.0205 (14)0.0208 (14)
C110.0541 (17)0.0657 (18)0.0584 (17)−0.0023 (14)0.0061 (13)0.0207 (14)
C120.0406 (13)0.0565 (16)0.0488 (15)−0.0017 (12)0.0030 (12)0.0026 (13)
C130.0320 (12)0.0379 (13)0.0429 (14)0.0023 (10)0.0096 (10)−0.0019 (10)
C140.0360 (13)0.0460 (15)0.0512 (16)0.0025 (11)0.0088 (12)−0.0011 (12)

Geometric parameters (Å, °)

O1—C141.225 (3)C4—C51.358 (4)
O2—C141.323 (3)C4—H40.9300
O2—H20.8200C5—C61.394 (4)
N1—N21.347 (2)C5—H50.9300
N1—C11.365 (3)C7—H7A0.9700
N1—C71.470 (3)C7—H7B0.9700
N2—N31.310 (3)C8—C91.402 (3)
N3—C61.371 (3)C8—C131.408 (3)
N4—C81.377 (3)C9—C101.367 (3)
N4—C71.426 (3)C9—H90.9300
N4—H4D0.86 (2)C10—C111.375 (3)
C1—C21.391 (3)C10—H100.9300
C1—C61.393 (3)C11—C121.372 (3)
C2—C31.368 (3)C11—H110.9300
C2—H2A0.9300C12—C131.389 (3)
C3—C41.402 (4)C12—H120.9300
C3—H30.9300C13—C141.472 (3)
C14—O2—H2109.5N4—C7—N1113.5 (2)
N2—N1—C1110.39 (18)N4—C7—H7A108.9
N2—N1—C7120.44 (19)N1—C7—H7A108.9
C1—N1—C7129.17 (18)N4—C7—H7B108.9
N3—N2—N1108.78 (18)N1—C7—H7B108.9
N2—N3—C6108.27 (18)H7A—C7—H7B107.7
C8—N4—C7124.7 (2)N4—C8—C9121.1 (2)
C8—N4—H4D114.7 (18)N4—C8—C13121.0 (2)
C7—N4—H4D119.7 (18)C9—C8—C13118.0 (2)
N1—C1—C2133.0 (2)C10—C9—C8120.7 (2)
N1—C1—C6104.0 (2)C10—C9—H9119.6
C2—C1—C6123.0 (2)C8—C9—H9119.6
C3—C2—C1115.2 (2)C9—C10—C11121.8 (2)
C3—C2—H2A122.4C9—C10—H10119.1
C1—C2—H2A122.4C11—C10—H10119.1
C2—C3—C4122.8 (3)C12—C11—C10118.1 (2)
C2—C3—H3118.6C12—C11—H11121.0
C4—C3—H3118.6C10—C11—H11121.0
C5—C4—C3121.3 (3)C11—C12—C13122.3 (2)
C5—C4—H4119.3C11—C12—H12118.9
C3—C4—H4119.3C13—C12—H12118.9
C4—C5—C6117.7 (3)C12—C13—C8119.1 (2)
C4—C5—H5121.2C12—C13—C14118.8 (2)
C6—C5—H5121.2C8—C13—C14122.1 (2)
N3—C6—C1108.6 (2)O1—C14—O2121.7 (2)
N3—C6—C5131.4 (2)O1—C14—C13124.6 (2)
C1—C6—C5120.0 (2)O2—C14—C13113.8 (2)
C1—N1—N2—N3−0.6 (2)C8—N4—C7—N1−81.5 (3)
C7—N1—N2—N3179.61 (18)N2—N1—C7—N4109.0 (2)
N1—N2—N3—C60.8 (2)C1—N1—C7—N4−70.8 (3)
N2—N1—C1—C2179.3 (2)C7—N4—C8—C96.5 (3)
C7—N1—C1—C2−0.9 (4)C7—N4—C8—C13−173.6 (2)
N2—N1—C1—C60.1 (2)N4—C8—C9—C10−178.8 (2)
C7—N1—C1—C6179.9 (2)C13—C8—C9—C101.3 (3)
N1—C1—C2—C3−179.9 (2)C8—C9—C10—C11−0.9 (4)
C6—C1—C2—C3−0.9 (3)C9—C10—C11—C12−0.5 (4)
C1—C2—C3—C40.3 (4)C10—C11—C12—C131.5 (4)
C2—C3—C4—C5−0.2 (4)C11—C12—C13—C8−1.1 (3)
C3—C4—C5—C60.6 (4)C11—C12—C13—C14177.8 (2)
N2—N3—C6—C1−0.8 (2)N4—C8—C13—C12179.8 (2)
N2—N3—C6—C5179.0 (2)C9—C8—C13—C12−0.3 (3)
N1—C1—C6—N30.4 (2)N4—C8—C13—C141.0 (3)
C2—C1—C6—N3−178.9 (2)C9—C8—C13—C14−179.1 (2)
N1—C1—C6—C5−179.4 (2)C12—C13—C14—O1−177.4 (2)
C2—C1—C6—C51.3 (3)C8—C13—C14—O11.4 (3)
C4—C5—C6—N3179.1 (2)C12—C13—C14—O21.6 (3)
C4—C5—C6—C1−1.2 (4)C8—C13—C14—O2−179.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4D···O10.86 (2)1.99 (3)2.691 (3)138 (2)
O2—H2···N3i0.821.952.746 (3)165
C7—H7A···O1ii0.972.403.214 (3)141
C12—H12···Cg2iii0.932.943.836 (3)163

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2045).

References

  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Trofimenko, S. (1993). Chem. Rev.93, 943–980.
  • Zhang, G.-F., Dou, Y.-L., She, J.-B. & Yin, M.-H. (2007). J. Chem. Crystallogr.37, 63–69.
  • Zhang, G.-F., Yin, M.-H., Dou, Y.-L., Zhao, S.-M. & Liu, H.-Q. (2006). Acta Cryst. E62, o4812–o4813.
  • Zhang, G.-F., Zhou, Q.-P., Dou, Y.-L., Wang, Y. & Wu, L.-P. (2007). Z. Anorg. Allg. Chem.633, 2104–2108.

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