Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015969/ob6172sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015969/ob6172Isup2.hkl |
CCDC reference: 198950
Crystals of (I) were obtained by slow evaporation from an acetonitrile solution of 1,2,3-benzotriazole with 2-chloro-4-nitrobenzoic acid with molar ratio of 1:1.
H atoms were found in difference Fourier maps and refined isotropically. Refined distances: C—H = 0.89 (3) − 1.03 (4), O—H = 0.78 (4) and N—H = 0.95 (4) Å.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare, et al. 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN for Windows.
C7H4ClNO4·C6H5N3 | F(000) = 656.00 |
Mr = 320.69 | Dx = 1.558 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.0590 (15) Å | θ = 10.5–12.5° |
b = 11.7721 (13) Å | µ = 0.30 mm−1 |
c = 16.4853 (17) Å | T = 300 K |
β = 93.717 (13)° | Prismatic, colorless |
V = 1367.0 (4) Å3 | 0.40 × 0.30 × 0.25 mm |
Z = 4 |
Rigaku AFC-5R diffractometer | 1816 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.020 |
Graphite monochromator | θmax = 27.5°, θmin = 2.1° |
ω–2θ scans | h = −1→9 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→15 |
Tmin = 0.913, Tmax = 0.927 | l = −21→21 |
3894 measured reflections | 3 standard reflections every 97 reflections |
3134 independent reflections | intensity decay: 1.4% |
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 | All H-atom parameters refined |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + 0.6722P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
3134 reflections | Δρmax = 0.25 e Å−3 |
236 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 4.7 (11)×10-3 |
C7H4ClNO4·C6H5N3 | V = 1367.0 (4) Å3 |
Mr = 320.69 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.0590 (15) Å | µ = 0.30 mm−1 |
b = 11.7721 (13) Å | T = 300 K |
c = 16.4853 (17) Å | 0.40 × 0.30 × 0.25 mm |
β = 93.717 (13)° |
Rigaku AFC-5R diffractometer | 1816 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.913, Tmax = 0.927 | 3 standard reflections every 97 reflections |
3894 measured reflections | intensity decay: 1.4% |
3134 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.132 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.25 e Å−3 |
3134 reflections | Δρmin = −0.23 e Å−3 |
236 parameters |
Experimental. The scan width was (1.73 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 3 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | 0.38055 (15) | 0.51916 (6) | 0.64808 (5) | 0.0581 (3) | |
O1 | 0.3549 (4) | 0.2435 (2) | 0.82590 (14) | 0.0724 (9) | |
O2 | 0.4708 (4) | 0.41516 (18) | 0.80647 (13) | 0.0680 (8) | |
O3 | 0.3291 (5) | 0.2687 (2) | 0.39476 (13) | 0.0903 (11) | |
O4 | 0.3893 (4) | 0.09565 (19) | 0.42854 (13) | 0.0726 (8) | |
N1 | 0.3657 (4) | 0.1950 (2) | 0.44490 (15) | 0.0514 (7) | |
N2 | 0.3769 (4) | 0.2854 (2) | 0.98486 (14) | 0.0533 (7) | |
N3 | 0.3953 (5) | 0.3916 (2) | 1.00574 (15) | 0.0600 (8) | |
N4 | 0.4115 (4) | 0.3974 (2) | 1.08682 (16) | 0.0530 (8) | |
C1 | 0.3985 (4) | 0.2946 (2) | 0.69216 (16) | 0.0369 (7) | |
C2 | 0.3887 (4) | 0.3751 (2) | 0.63032 (16) | 0.0375 (7) | |
C3 | 0.3785 (5) | 0.3416 (2) | 0.54951 (17) | 0.0409 (7) | |
C4 | 0.3780 (4) | 0.2282 (2) | 0.53154 (16) | 0.0397 (7) | |
C5 | 0.3874 (5) | 0.1449 (2) | 0.59007 (18) | 0.0441 (7) | |
C6 | 0.3971 (5) | 0.1798 (2) | 0.67076 (18) | 0.0442 (8) | |
C7 | 0.4109 (5) | 0.3263 (2) | 0.78078 (16) | 0.0434 (7) | |
C8 | 0.4035 (4) | 0.2920 (2) | 1.12031 (16) | 0.0401 (7) | |
C9 | 0.4128 (5) | 0.2515 (3) | 1.20022 (18) | 0.0516 (9) | |
C10 | 0.4004 (5) | 0.1374 (3) | 1.2092 (2) | 0.0565 (9) | |
C11 | 0.3807 (5) | 0.0632 (3) | 1.1426 (2) | 0.0591 (9) | |
C12 | 0.3692 (5) | 0.1032 (3) | 1.0646 (2) | 0.0516 (9) | |
C13 | 0.3811 (4) | 0.2195 (2) | 1.05411 (16) | 0.0388 (7) | |
H1 | 0.368 (4) | 0.392 (2) | 0.5099 (15) | 0.033 (7)* | |
H2 | 0.385 (4) | 0.066 (2) | 0.5739 (16) | 0.047 (8)* | |
H3 | 0.408 (4) | 0.130 (2) | 0.7132 (16) | 0.037 (8)* | |
H4 | 0.370 (7) | 0.254 (4) | 0.872 (3) | 0.109 (17)* | |
H5 | 0.428 (6) | 0.470 (3) | 1.112 (2) | 0.096 (14)* | |
H6 | 0.433 (5) | 0.298 (3) | 1.2423 (19) | 0.061 (10)* | |
H7 | 0.407 (5) | 0.102 (3) | 1.266 (2) | 0.088 (12)* | |
H8 | 0.373 (4) | −0.015 (3) | 1.1547 (17) | 0.047 (8)* | |
H9 | 0.360 (5) | 0.052 (3) | 1.023 (2) | 0.072 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0957 (7) | 0.0265 (3) | 0.0514 (4) | −0.0006 (4) | −0.0012 (4) | −0.0044 (3) |
O1 | 0.128 (3) | 0.0560 (14) | 0.0322 (11) | −0.0316 (16) | −0.0025 (14) | 0.0019 (11) |
O2 | 0.114 (2) | 0.0458 (13) | 0.0436 (12) | −0.0215 (14) | 0.0032 (13) | −0.0104 (10) |
O3 | 0.177 (3) | 0.0561 (15) | 0.0382 (12) | −0.0105 (18) | 0.0093 (17) | −0.0014 (11) |
O4 | 0.111 (2) | 0.0508 (14) | 0.0555 (14) | 0.0127 (14) | 0.0034 (15) | −0.0230 (11) |
N1 | 0.070 (2) | 0.0471 (15) | 0.0374 (13) | −0.0061 (14) | 0.0068 (13) | −0.0077 (12) |
N2 | 0.079 (2) | 0.0463 (15) | 0.0338 (13) | −0.0107 (15) | −0.0017 (13) | 0.0009 (11) |
N3 | 0.088 (2) | 0.0467 (16) | 0.0443 (15) | −0.0108 (15) | −0.0079 (15) | 0.0049 (12) |
N4 | 0.076 (2) | 0.0358 (13) | 0.0456 (14) | −0.0014 (14) | −0.0075 (14) | −0.0061 (11) |
C1 | 0.0415 (18) | 0.0323 (13) | 0.0364 (14) | −0.0014 (13) | −0.0007 (13) | −0.0025 (11) |
C2 | 0.0445 (19) | 0.0266 (12) | 0.0415 (15) | −0.0016 (13) | 0.0025 (14) | −0.0043 (11) |
C3 | 0.052 (2) | 0.0332 (14) | 0.0376 (15) | −0.0025 (14) | 0.0062 (14) | −0.0008 (12) |
C4 | 0.0436 (18) | 0.0384 (15) | 0.0376 (15) | −0.0024 (14) | 0.0057 (13) | −0.0085 (12) |
C5 | 0.055 (2) | 0.0304 (14) | 0.0471 (16) | 0.0029 (14) | 0.0042 (15) | −0.0077 (12) |
C6 | 0.060 (2) | 0.0311 (14) | 0.0413 (16) | 0.0018 (14) | −0.0005 (15) | 0.0018 (12) |
C7 | 0.057 (2) | 0.0379 (16) | 0.0350 (14) | −0.0033 (15) | −0.0001 (14) | −0.0036 (12) |
C8 | 0.0410 (18) | 0.0418 (15) | 0.0374 (14) | −0.0007 (14) | 0.0018 (13) | −0.0050 (12) |
C9 | 0.058 (2) | 0.064 (2) | 0.0326 (15) | 0.0011 (19) | 0.0013 (15) | −0.0045 (15) |
C10 | 0.055 (2) | 0.068 (2) | 0.0462 (18) | −0.0038 (19) | 0.0022 (16) | 0.0165 (17) |
C11 | 0.060 (2) | 0.0468 (18) | 0.070 (2) | −0.0041 (19) | 0.0025 (18) | 0.0155 (18) |
C12 | 0.062 (2) | 0.0385 (16) | 0.0539 (19) | −0.0037 (16) | −0.0002 (17) | −0.0064 (15) |
C13 | 0.0431 (18) | 0.0399 (15) | 0.0331 (13) | −0.0018 (14) | 0.0013 (13) | −0.0022 (11) |
Cl—C2 | 1.723 (3) | C3—C4 | 1.367 (4) |
O1—C7 | 1.303 (4) | C3—H1 | 0.89 (3) |
O1—H4 | 0.78 (4) | C4—C5 | 1.374 (4) |
O2—C7 | 1.196 (3) | C5—C6 | 1.390 (4) |
O3—N1 | 1.215 (3) | C5—H2 | 0.97 (3) |
O4—N1 | 1.214 (3) | C6—H3 | 0.91 (3) |
N1—C4 | 1.478 (3) | C8—C13 | 1.387 (4) |
N2—N3 | 1.302 (3) | C8—C9 | 1.398 (4) |
N2—C13 | 1.379 (3) | C9—C10 | 1.356 (5) |
N3—N4 | 1.336 (3) | C9—H6 | 0.89 (3) |
N4—C8 | 1.360 (4) | C10—C11 | 1.403 (5) |
N4—H5 | 0.95 (4) | C10—H7 | 1.03 (4) |
C1—C2 | 1.391 (4) | C11—C12 | 1.368 (5) |
C1—C6 | 1.396 (4) | C11—H8 | 0.95 (3) |
C1—C7 | 1.505 (4) | C12—C13 | 1.383 (4) |
C2—C3 | 1.387 (4) | C12—H9 | 0.91 (3) |
Cl···O1i | 3.164 (3) | O4···C5vi | 3.265 (4) |
Cl···O3ii | 3.335 (3) | N2···C7 | 3.425 (4) |
O1···N2 | 2.661 (3) | N3···N3iii | 2.962 (4) |
O2···N4iii | 2.909 (3) | N3···N4iii | 3.260 (4) |
O3···C9iv | 3.305 (4) | N4···C5vii | 3.393 (5) |
O4···N4v | 3.154 (4) | C1···C9viii | 3.482 (5) |
C7—O1—H4 | 115 (3) | C5—C6—C1 | 121.8 (3) |
O4—N1—O3 | 124.3 (3) | C5—C6—H3 | 122.5 (16) |
O4—N1—C4 | 118.0 (2) | C1—C6—H3 | 115.6 (16) |
O3—N1—C4 | 117.7 (2) | O2—C7—O1 | 124.5 (3) |
N3—N2—C13 | 109.0 (2) | O2—C7—C1 | 123.9 (3) |
N2—N3—N4 | 108.3 (2) | O1—C7—C1 | 111.6 (2) |
N3—N4—C8 | 110.9 (2) | N4—C8—C13 | 104.3 (2) |
N3—N4—H5 | 118 (2) | N4—C8—C9 | 133.8 (3) |
C8—N4—H5 | 131 (2) | C13—C8—C9 | 121.8 (3) |
C2—C1—C6 | 118.4 (2) | C10—C9—C8 | 116.2 (3) |
C2—C1—C7 | 122.6 (2) | C10—C9—H6 | 122 (2) |
C6—C1—C7 | 119.0 (2) | C8—C9—H6 | 122 (2) |
C3—C2—C1 | 120.5 (2) | C9—C10—C11 | 122.4 (3) |
C3—C2—Cl | 116.3 (2) | C9—C10—H7 | 120 (2) |
C1—C2—Cl | 123.2 (2) | C11—C10—H7 | 117 (2) |
C4—C3—C2 | 119.0 (3) | C12—C11—C10 | 121.2 (3) |
C4—C3—H1 | 120.1 (17) | C12—C11—H8 | 122.2 (18) |
C2—C3—H1 | 120.9 (17) | C10—C11—H8 | 116.5 (18) |
C3—C4—C5 | 123.0 (3) | C11—C12—C13 | 117.2 (3) |
C3—C4—N1 | 117.8 (3) | C11—C12—H9 | 119 (2) |
C5—C4—N1 | 119.1 (2) | C13—C12—H9 | 124 (2) |
C4—C5—C6 | 117.2 (3) | N2—C13—C12 | 131.4 (3) |
C4—C5—H2 | 119.6 (17) | N2—C13—C8 | 107.5 (2) |
C6—C5—H2 | 123.2 (17) | C12—C13—C8 | 121.1 (3) |
C13—N2—N3—N4 | 0.0 (4) | C2—C1—C7—O2 | −24.0 (5) |
N2—N3—N4—C8 | −0.1 (4) | C6—C1—C7—O2 | 155.9 (3) |
C6—C1—C2—C3 | −0.2 (5) | C2—C1—C7—O1 | 158.3 (3) |
C7—C1—C2—C3 | 179.6 (3) | C6—C1—C7—O1 | −21.8 (4) |
C6—C1—C2—Cl | 177.6 (2) | N3—N4—C8—C13 | 0.1 (4) |
C7—C1—C2—Cl | −2.6 (4) | N3—N4—C8—C9 | −179.8 (4) |
C1—C2—C3—C4 | 0.0 (5) | N4—C8—C9—C10 | −179.5 (4) |
Cl—C2—C3—C4 | −177.9 (2) | C13—C8—C9—C10 | 0.6 (5) |
C2—C3—C4—C5 | −0.1 (5) | C8—C9—C10—C11 | 0.4 (6) |
C2—C3—C4—N1 | 179.6 (3) | C9—C10—C11—C12 | −1.3 (6) |
O4—N1—C4—C3 | 170.9 (3) | C10—C11—C12—C13 | 1.1 (6) |
O3—N1—C4—C3 | −10.5 (5) | N3—N2—C13—C12 | −179.3 (4) |
O4—N1—C4—C5 | −9.5 (5) | N3—N2—C13—C8 | 0.0 (4) |
O3—N1—C4—C5 | 169.2 (3) | C11—C12—C13—N2 | 179.1 (3) |
C3—C4—C5—C6 | 0.2 (5) | C11—C12—C13—C8 | −0.1 (5) |
N1—C4—C5—C6 | −179.4 (3) | N4—C8—C13—N2 | 0.0 (4) |
C4—C5—C6—C1 | −0.4 (5) | C9—C8—C13—N2 | 179.9 (3) |
C2—C1—C6—C5 | 0.4 (5) | N4—C8—C13—C12 | 179.3 (3) |
C7—C1—C6—C5 | −179.4 (3) | C9—C8—C13—C12 | −0.7 (5) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x, y, z−1; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x+1, −y, −z+1; (vii) x+1/2, −y+1/2, z+1/2; (viii) x−1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H4···N2 | 0.77 (5) | 1.89 (5) | 2.661 (3) | 173 (5) |
N4—H5···O2iii | 0.95 (4) | 2.00 (3) | 2.909 (3) | 158 (3) |
C5—H2···O4vi | 0.97 (2) | 2.48 (3) | 3.265 (4) | 138 (2) |
Symmetry codes: (iii) −x+1, −y+1, −z+2; (vi) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C7H4ClNO4·C6H5N3 |
Mr | 320.69 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 300 |
a, b, c (Å) | 7.0590 (15), 11.7721 (13), 16.4853 (17) |
β (°) | 93.717 (13) |
V (Å3) | 1367.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.40 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.913, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3894, 3134, 1816 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.132, 1.06 |
No. of reflections | 3134 |
No. of parameters | 236 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), SIR92 (Altomare, et al. 1993), SHELXL97 (Sheldrick, 1997), TEXSAN for Windows.
Cl—C2 | 1.723 (3) | N2—N3 | 1.302 (3) |
O1—C7 | 1.303 (4) | N2—C13 | 1.379 (3) |
O2—C7 | 1.196 (3) | N3—N4 | 1.336 (3) |
O3—N1 | 1.215 (3) | N4—C8 | 1.360 (4) |
O4—N1 | 1.214 (3) | C1—C7 | 1.505 (4) |
N1—C4 | 1.478 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H4···N2 | 0.77 (5) | 1.89 (5) | 2.661 (3) | 173 (5) |
N4—H5···O2i | 0.95 (4) | 2.00 (3) | 2.909 (3) | 158 (3) |
C5—H2···O4ii | 0.97 (2) | 2.48 (3) | 3.265 (4) | 138 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1. |
The title compound, (I), was investigated as part of a study on D—H···A hydrogen bonding (D = N, O or C; A = N, O or Cl) in chloro-and nitro-substituted benzoic acid-amine systems (Ishida et al., 2001a,b,c,d,e). In the crystal, two acid and two base components are held together by short O—H···N hydrogen bonds and relatively long N—H···O hydrogen bonds (Table 2) to afford a centrosymmetric macro ring with graph-set descriptor R44(16) (Bernstein et al., 1995) (Fig. 1), which is similar to that found in benzotriazole 3-nitrobenzoic acid (Hashizume et al., 2001). The dihedral angle between the nitro group and the benzene ring is 10.03 (19)°, and that between the carboxyl group and the benzene ring is 22.79 (17)°. A C—H···O hydrogen bond (C5—H2···O4ii; Table 2) connects the hydrogen-bonded rings, resulting in the formation of molecular ribbon running parallel to the [011] direction (Fig. 2). The ribbons, related by a twofold screw axis, are stacked along the a axis. A short contact [Cl···O1iii, 3.164 (3) Å; symmetry code: (iii) 1/2 − x, 1/2 + y, 3/2 − z] is observed between the ribbons.