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Acta Cryst. (2008). E64, o735    [ doi:10.1107/S160053680800740X ]

2-(Benzotriazol-1-ylmethylamino)benzoic acid

Y. Wang, M.-H. Yin and G.-F. Zhang

Abstract top

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...[pi] interactions.

Comment top

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).

Related literature top

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

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom numbering scheme and dislacement ellipsoids drawn at the 50% probability level.
2-(Benzotriazol-1-ylmethylamino)benzoic acid top
Crystal data top
C14H12N4O2F000 = 560
Mr = 268.28Dx = 1.386 Mg m−3
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 mm−1
β = 97.671 (7)ºT = 291 (2) K
V = 1285.8 (12) Å3Block, colourless
Z = 40.19 × 0.16 × 0.07 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2388 independent reflections
Radiation source: fine-focus sealed tube1438 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
T = 291(2) Kθmax = 25.5º
φ 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 top
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 Å−3
186 parametersΔρmin = −0.17 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C14H12N4O2V = 1285.8 (12) Å3
Mr = 268.28Z = 4
Monoclinic, P21/cMo Kα
a = 10.225 (6) ŵ = 0.10 mm−1
b = 15.669 (8) ÅT = 291 (2) K
c = 8.098 (4) Å0.19 × 0.16 × 0.07 mm
β = 97.671 (7)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2388 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1438 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.993Rint = 0.053
9692 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047186 parameters
wR(F2) = 0.117H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.14 e Å−3
2388 reflectionsΔρmin = −0.17 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

We thank Shaanxi Normal University for research grants.

references
References top

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