2-(Benzotriazol-1-ylmethyl­amino)­benzoic acid

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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.048
• wR factor = 0.118
• Data-to-parameter ratio = 12.8

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S1. 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).

Related literature

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

S2. 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 U_iso(H) = 1.5U_eq(O) and 1.2U_eq(C).

Computing details

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

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

Crystal data

C14H12N4O2	F(000) = 560
Mr = 268.28	Dx = 1.386 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.225 (6) Å	Cell parameters from 1098 reflections
b = 15.669 (8) Å	θ = 2.4–21.9°
c = 8.098 (4) Å	µ = 0.10 mm^−1
β = 97.671 (7)°	T = 291 K
V = 1285.8 (12) Å^3	Block, colourless
Z = 4	0.19 × 0.16 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2388 independent reflections
Radiation source: fine-focus sealed tube	1438 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ϕ and ω scans	θmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.982, Tmax = 0.993	k = −18→18
9692 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0885P)^2 + 0.2074P] where P = (Fo^2 + 2Fc^2)/3
2388 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

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 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.37616 (15)	0.01777 (11)	0.3049 (2)	0.0594 (5)
O2	0.23657 (15)	0.05486 (12)	0.0817 (2)	0.0609 (5)
H2	0.1845	0.0294	0.1327	0.091*
N1	0.85744 (16)	0.01883 (12)	0.3449 (2)	0.0414 (5)
N2	0.95246 (18)	0.05227 (13)	0.2642 (2)	0.0511 (5)
N3	1.02834 (18)	−0.00961 (14)	0.2240 (2)	0.0539 (6)
N4	0.62976 (19)	0.06560 (14)	0.3142 (3)	0.0488 (6)
C1	0.8708 (2)	−0.06775 (14)	0.3566 (3)	0.0393 (5)
C2	0.8006 (2)	−0.13078 (16)	0.4280 (3)	0.0506 (6)
H2A	0.7279	−0.1185	0.4818	0.061*
C3	0.8460 (3)	−0.21219 (17)	0.4134 (3)	0.0635 (8)
H3	0.8022	−0.2567	0.4586	0.076*
C4	0.9558 (3)	−0.23133 (19)	0.3332 (4)	0.0723 (9)
H4	0.9827	−0.2878	0.3270	0.087*
C5	1.0235 (3)	−0.16907 (19)	0.2644 (4)	0.0657 (8)
H5	1.0957	−0.1820	0.2103	0.079*
C6	0.9808 (2)	−0.08513 (16)	0.2776 (3)	0.0462 (6)
C7	0.7583 (2)	0.07434 (15)	0.4056 (3)	0.0479 (6)
H7A	0.7538	0.0612	0.5218	0.057*
H7B	0.7864	0.1333	0.3995	0.057*
C8	0.5883 (2)	0.10492 (13)	0.1642 (3)	0.0377 (5)
C9	0.6766 (2)	0.15121 (14)	0.0805 (3)	0.0488 (6)
H9	0.7650	0.1547	0.1257	0.059*
C10	0.6343 (2)	0.19133 (15)	−0.0668 (3)	0.0578 (7)
H10	0.6946	0.2223	−0.1192	0.069*
C11	0.5051 (3)	0.18711 (16)	−0.1397 (3)	0.0595 (7)
H11	0.4774	0.2150	−0.2396	0.071*
C12	0.4182 (2)	0.14051 (15)	−0.0609 (3)	0.0489 (6)
H12	0.3310	0.1361	−0.1103	0.059*
C13	0.4559 (2)	0.09968 (13)	0.0902 (3)	0.0372 (5)
C14	0.3554 (2)	0.05360 (15)	0.1695 (3)	0.0441 (6)
H4D	0.568 (2)	0.0420 (16)	0.360 (3)	0.068 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0421 (10)	0.0791 (13)	0.0586 (12)	−0.0032 (9)	0.0122 (9)	0.0203 (10)
O2	0.0344 (9)	0.0840 (14)	0.0641 (12)	−0.0085 (9)	0.0054 (9)	0.0151 (10)
N1	0.0287 (10)	0.0482 (12)	0.0475 (12)	−0.0040 (9)	0.0062 (9)	0.0045 (9)
N2	0.0332 (11)	0.0629 (14)	0.0563 (13)	−0.0067 (10)	0.0030 (10)	0.0090 (11)
N3	0.0342 (11)	0.0726 (15)	0.0552 (13)	−0.0018 (11)	0.0078 (10)	0.0039 (11)
N4	0.0306 (11)	0.0626 (14)	0.0532 (14)	−0.0003 (10)	0.0050 (10)	0.0160 (11)
C1	0.0350 (12)	0.0427 (14)	0.0385 (13)	−0.0007 (11)	−0.0010 (10)	−0.0001 (11)
C2	0.0447 (14)	0.0559 (16)	0.0507 (16)	−0.0061 (13)	0.0050 (12)	0.0067 (13)
C3	0.0670 (19)	0.0527 (18)	0.0670 (19)	−0.0078 (15)	−0.0056 (15)	0.0064 (14)
C4	0.077 (2)	0.0529 (18)	0.082 (2)	0.0130 (16)	−0.0071 (18)	−0.0084 (16)
C5	0.0532 (17)	0.073 (2)	0.070 (2)	0.0111 (15)	0.0053 (14)	−0.0125 (16)
C6	0.0351 (13)	0.0555 (16)	0.0465 (15)	−0.0006 (12)	0.0000 (11)	−0.0029 (12)
C7	0.0418 (14)	0.0496 (15)	0.0520 (15)	0.0025 (12)	0.0055 (11)	0.0017 (12)
C8	0.0368 (12)	0.0336 (12)	0.0436 (14)	0.0024 (10)	0.0094 (11)	0.0011 (10)
C9	0.0360 (13)	0.0501 (15)	0.0611 (17)	−0.0038 (11)	0.0100 (12)	0.0061 (13)
C10	0.0503 (16)	0.0570 (17)	0.0695 (19)	−0.0034 (13)	0.0205 (14)	0.0208 (14)
C11	0.0541 (17)	0.0657 (18)	0.0584 (17)	−0.0023 (14)	0.0061 (13)	0.0207 (14)
C12	0.0406 (13)	0.0565 (16)	0.0488 (15)	−0.0017 (12)	0.0030 (12)	0.0026 (13)
C13	0.0320 (12)	0.0379 (13)	0.0429 (14)	0.0023 (10)	0.0096 (10)	−0.0019 (10)
C14	0.0360 (13)	0.0460 (15)	0.0512 (16)	0.0025 (11)	0.0088 (12)	−0.0011 (12)

Geometric parameters (Å, º)

O1—C14	1.225 (3)	C4—C5	1.358 (4)
O2—C14	1.323 (3)	C4—H4	0.9300
O2—H2	0.8200	C5—C6	1.394 (4)
N1—N2	1.347 (2)	C5—H5	0.9300
N1—C1	1.365 (3)	C7—H7A	0.9700
N1—C7	1.470 (3)	C7—H7B	0.9700
N2—N3	1.310 (3)	C8—C9	1.402 (3)
N3—C6	1.371 (3)	C8—C13	1.408 (3)
N4—C8	1.377 (3)	C9—C10	1.367 (3)
N4—C7	1.426 (3)	C9—H9	0.9300
N4—H4D	0.86 (2)	C10—C11	1.375 (3)
C1—C2	1.391 (3)	C10—H10	0.9300
C1—C6	1.393 (3)	C11—C12	1.372 (3)
C2—C3	1.368 (3)	C11—H11	0.9300
C2—H2A	0.9300	C12—C13	1.389 (3)
C3—C4	1.402 (4)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.472 (3)
C14—O2—H2	109.5	N4—C7—N1	113.5 (2)
N2—N1—C1	110.39 (18)	N4—C7—H7A	108.9
N2—N1—C7	120.44 (19)	N1—C7—H7A	108.9
C1—N1—C7	129.17 (18)	N4—C7—H7B	108.9
N3—N2—N1	108.78 (18)	N1—C7—H7B	108.9
N2—N3—C6	108.27 (18)	H7A—C7—H7B	107.7
C8—N4—C7	124.7 (2)	N4—C8—C9	121.1 (2)
C8—N4—H4D	114.7 (18)	N4—C8—C13	121.0 (2)
C7—N4—H4D	119.7 (18)	C9—C8—C13	118.0 (2)
N1—C1—C2	133.0 (2)	C10—C9—C8	120.7 (2)
N1—C1—C6	104.0 (2)	C10—C9—H9	119.6
C2—C1—C6	123.0 (2)	C8—C9—H9	119.6
C3—C2—C1	115.2 (2)	C9—C10—C11	121.8 (2)
C3—C2—H2A	122.4	C9—C10—H10	119.1
C1—C2—H2A	122.4	C11—C10—H10	119.1
C2—C3—C4	122.8 (3)	C12—C11—C10	118.1 (2)
C2—C3—H3	118.6	C12—C11—H11	121.0
C4—C3—H3	118.6	C10—C11—H11	121.0
C5—C4—C3	121.3 (3)	C11—C12—C13	122.3 (2)
C5—C4—H4	119.3	C11—C12—H12	118.9
C3—C4—H4	119.3	C13—C12—H12	118.9
C4—C5—C6	117.7 (3)	C12—C13—C8	119.1 (2)
C4—C5—H5	121.2	C12—C13—C14	118.8 (2)
C6—C5—H5	121.2	C8—C13—C14	122.1 (2)
N3—C6—C1	108.6 (2)	O1—C14—O2	121.7 (2)
N3—C6—C5	131.4 (2)	O1—C14—C13	124.6 (2)
C1—C6—C5	120.0 (2)	O2—C14—C13	113.8 (2)
C1—N1—N2—N3	−0.6 (2)	C8—N4—C7—N1	−81.5 (3)
C7—N1—N2—N3	179.61 (18)	N2—N1—C7—N4	109.0 (2)
N1—N2—N3—C6	0.8 (2)	C1—N1—C7—N4	−70.8 (3)
N2—N1—C1—C2	179.3 (2)	C7—N4—C8—C9	6.5 (3)
C7—N1—C1—C2	−0.9 (4)	C7—N4—C8—C13	−173.6 (2)
N2—N1—C1—C6	0.1 (2)	N4—C8—C9—C10	−178.8 (2)
C7—N1—C1—C6	179.9 (2)	C13—C8—C9—C10	1.3 (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—C4	0.3 (4)	C10—C11—C12—C13	1.5 (4)
C2—C3—C4—C5	−0.2 (4)	C11—C12—C13—C8	−1.1 (3)
C3—C4—C5—C6	0.6 (4)	C11—C12—C13—C14	177.8 (2)
N2—N3—C6—C1	−0.8 (2)	N4—C8—C13—C12	179.8 (2)
N2—N3—C6—C5	179.0 (2)	C9—C8—C13—C12	−0.3 (3)
N1—C1—C6—N3	0.4 (2)	N4—C8—C13—C14	1.0 (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—C5	1.3 (3)	C8—C13—C14—O1	1.4 (3)
C4—C5—C6—N3	179.1 (2)	C12—C13—C14—O2	1.6 (3)
C4—C5—C6—C1	−1.2 (4)	C8—C13—C14—O2	−179.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4D···O1	0.86 (2)	1.99 (3)	2.691 (3)	138 (2)
O2—H2···N3^i	0.82	1.95	2.746 (3)	165
C7—H7A···O1^ii	0.97	2.40	3.214 (3)	141
C12—H12···Cg2^iii	0.93	2.94	3.836 (3)	163

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