2-(Benzotriazol-1-ylmethyl­amino)­benzoic acid

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

doi:10.1107/S160053680800740X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o735

doi:10.1107/S160053680800740X

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2-(Benzotriazol-1-ylmethylamino)benzoic acid

Yao Wang,^a Mai-Hua Yin ^a and Guo-Fang Zhang ^a ^*

^aKey Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi'an 710062, People's Republic of China
^*Correspondence e-mail: gfzhang@snnu.edu.cn

(Received 27 February 2008; accepted 18 March 2008; online 20 March 2008)

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 ); Zhang, Dou et al. (2007 ); Zhang et al. (2006 ); Zhang, Zhou et al. (2007 ).

Experimental

Crystal data

C₁₄H₁₂N₄O₂
M_r = 268.28
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.047
wR(F²) = 0.117
S = 1.02
2388 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯N3ⁱ	0.82	1.95	2.746 (3)	165
C7—H7A⋯O1ⁱⁱ	0.97	2.40	3.214 (3)	141
C12—H12⋯Cg2ⁱⁱⁱ	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. Cg2 is the centroid of the C1–C6 ring.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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: SHELXTL.

Supporting information

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

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

checkCIF report

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 U_iso(H) = 1.5U_eq(O) and 1.2U_eq(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

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

C₁₄H₁₂N₄O₂	F(000) = 560
M_r = 268.28	D_x = 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) Å³	Block, colourless
Z = 4	0.19 × 0.16 × 0.07 mm

Data collection top

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

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0885P)² + 0.2074P] where P = (F_o² + 2F_c²)/3
2388 reflections	(Δ/σ)_max < 0.001
186 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₂N₄O₂	V = 1285.8 (12) Å³
M_r = 268.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.225 (6) Å	µ = 0.10 mm⁻¹
b = 15.669 (8) Å	T = 291 K
c = 8.098 (4) Å	0.19 × 0.16 × 0.07 mm
β = 97.671 (7)°

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)
T_min = 0.982, T_max = 0.993	R_int = 0.053
9692 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.14 e Å⁻³
2388 reflections	Δρ_min = −0.17 e Å⁻³
186 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

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···N3ⁱ	0.82	1.95	2.746 (3)	165
C7—H7A···O1ⁱⁱ	0.97	2.40	3.214 (3)	141
C12—H12···Cg2ⁱⁱⁱ	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.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₄O₂
M_r	268.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	10.225 (6), 15.669 (8), 8.098 (4)
β (°)	97.671 (7)
V (Å³)	1285.8 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.19 × 0.16 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.982, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	9692, 2388, 1438
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.117, 1.02
No. of reflections	2388
No. of parameters	186
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.17

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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···N3ⁱ	0.82	1.95	2.746 (3)	164.9
C7—H7A···O1ⁱⁱ	0.97	2.40	3.214 (3)	141
C12—H12···Cg2ⁱⁱⁱ	0.93	2.9367	3.836 (3)	163.02

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

Acknowledgements

We thank Shaanxi Normal University for research grants.

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