organic papers
o2302
Wanet al. C21H15ClN4O3 doi:10.1107/S1600536806017065 Acta Cryst.(2006). E62, o2302–o2303
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
2-(1
H
-1,2,3-Benzotriazol-1-ylmethyl)-1-(4-chloro-benzoyl)ethyl nicotinate
Jun Wan,aZheng-Zhong Peng,b Xue-Mei Li,bPing-Kai Ouyanga and Shu-Sheng Zhanga*
aCollege of Life Science and Pharmaceutical
Engineering, Nanjing University of Technology, 210093 Nanjing, Jiangsu, People’s Republic of China, andbCollege of Chemistry and Molecular
Engineering, Qingdao University of Science and Technology, 266042 Qingdao, Shandong, People’s Republic of China
Correspondence e-mail: shushzhang@126.com
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.043
wRfactor = 0.089
Data-to-parameter ratio = 14.4
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 24 April 2006 Accepted 9 May 2006
#2006 International Union of Crystallography All rights reserved
In the title compound, C21H15ClN4O3, molecules are linked
into chains along thebaxis by C—H O hydrogen bonds. The chains are further connected by intermolecular C—H O hydrogen bonds, forming two-dimensional layers parallel to theabplane.
Comment
We have recently reported the structure of 2-(1H-1,2,3-benzotriazol-1-ylmethyl)-1-benzoylethyl 4-chlorobenzoate, (II) (Wanet al., 2006). In our ongoing studies of benzotriazole compounds, the title compound, (I), was obtained.
The bond lengths and angles in (I) show normal values (Allenet al., 1987) and are comparable to those found in (II). The benzotriazole system is essentially planar, with a dihedral angle of 1.0 (2) between the triazole (A, atoms N1–N3/C10/
C15) and benzene rings (B, atoms C10–C15). The dihedral angles between the mean plane of the benzotriazole system and ringsC (atoms C1–C6) andD(atoms N4/C17–C21) are 6.9 (1) and 71.1 (1), respectively. The dihedral angle between
ringsCandDis 74.4 (1).
There exists an intramolecular C21—H21A O2 hydrogen bond, forming a five-membered ring. In the crystal structure, molecules of (I) are linked into chains along thebaxis by C— H O hydrogen bonds. Further C—H O interactions connect the chains into two-dimensional layers parallel to the abplane (Fig. 2 and Table 2 for geometry values and symmetry code).
Experimental
anhydrous magnesium sulfate and the chloroform solution filtered. After cooling with ice–water, an acetone solution (10 ml) of nicotinic acid (3.1 g, 0.02 mol) and triethylamine (2.8 ml) were added. The mixture was stirred at room temperature for about 2 h, then filtered, concentrated and purified by flash column chromatography (silica gel, petroleum ether–ethyl acetate, 3:1 v/v) to afford the title compound. Single crystals were obtained by slow evaporation of a petroleum ether–ethyl acetate (1:1v/v) solution at room temperature over a period of one week.
Crystal data
C21H15ClN4O3
Mr= 406.82
Orthorhombic,Pca21 a= 18.820 (2) A˚ b= 5.3367 (6) A˚ c= 19.027 (2) A˚ V= 1911.0 (4) A˚3
Z= 4
Dx= 1.414 Mg m 3
MoKradiation
= 0.23 mm1 T= 293 (2) K Column, colourless 0.400.190.10 mm
Data collection
Siemens SMART 1000 CCD area-detector diffractometer
!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.913,Tmax= 0.977
10277 measured reflections 3763 independent reflections 2880 reflections withI> 2(I) Rint= 0.036
max= 26.1
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.043
wR(F2) = 0.089
S= 1.01 3763 reflections 262 parameters
H-atom parameters constrained
w= 1/[2
(Fo2) + (0.036P)2
+ 0.0701P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.19 e A˚
3
min=0.12 e A˚
3
Absolute structure: Flack (1983), 1811 Friedel pairs
Flack parameter: 0.01 (7)
Table 1
Selected bond lengths (A˚ ).
Cl1—C3 1.732 (3) O1—C7 1.212 (3) O2—C16 1.356 (3) O2—C8 1.437 (3)
O3—C16 1.194 (3) C7—C8 1.520 (4) C8—C9 1.525 (4)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C9—H9B O1i 0.97 2.57 3.058 (3) 111 C13—H13A O3ii
0.93 2.49 3.351 (4) 155 C21—H21A O2 0.93 2.39 2.739 (4) 102
Symmetry codes: (i)x;y1;z; (ii)x1 2;yþ3;z.
All H atoms were located in difference Fourier maps and constrained to ride on their parent atoms, with C—H = 0.93–0.98 A˚ andUiso(H) = 1.2Ueq(C).
Data collection:SMART(Siemens, 1996); cell refinement:SAINT
(Siemens, 1996); data reduction:SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL,PARST(Nardelli, 1995) andPLATON(Spek, 2003).
This project was supported by the Special Project of Qingdao for Leadership of Science and Technology (No. 05–2-JC-80) and the Outstanding Adult-Young Scientific Research Encouraging Foundation of Shandong Province (No. 2005BS04007).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Flack, H. D. (1983).Acta Cryst.A39, 876–881. Nardelli, M. (1995).J. Appl. Cryst.28, 659.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997).SHELXTL. Version 5.1. Bruker AXS Inc., Madison,
Wisconsin, USA.
Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.
[image:2.610.44.295.70.243.2] [image:2.610.46.297.291.496.2]Wan, J., Peng, Z.-Z., Li, X.-M. & Zhang, S.-S. (2006).Acta Cryst.E62, o634– o636.
Figure 1
The structure of the compound (I), showing 50% probability displace-ment ellipsoids and the atom-numbering scheme.
Figure 2
supporting information
sup-1 Acta Cryst. (2006). E62, o2302–o2303
supporting information
Acta Cryst. (2006). E62, o2302–o2303 [https://doi.org/10.1107/S1600536806017065]
2-(1
H
-1,2,3-Benzotriazol-1-ylmethyl)-1-(4-chlorobenzoyl)ethyl nicotinate
Jun Wan, Zheng-Zhong Peng, Xue-Mei Li, Ping-Kai Ouyang and Shu-Sheng Zhang
2-(1H-1,2,3-Benzotriazol-1-ylmethyl)-1-(4-chlorobenzoyl)ethyl nicotinate
Crystal data C21H15ClN4O3
Mr = 406.82
Orthorhombic, Pca21
Hall symbol: P 2c -2ac a = 18.820 (2) Å b = 5.3367 (6) Å c = 19.027 (2) Å V = 1911.0 (4) Å3
Z = 4
F(000) = 840 Dx = 1.414 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1989 reflections θ = 3.0–20.9°
µ = 0.23 mm−1
T = 293 K
Column, colourless 0.40 × 0.19 × 0.10 mm
Data collection
Siemens SMART 1000 CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 8.33 pixels mm-1
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.913, Tmax = 0.977
10277 measured reflections 3763 independent reflections 2880 reflections with I > 2σ(I) Rint = 0.036
θmax = 26.1°, θmin = 2.1°
h = −17→23 k = −6→6 l = −23→23
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.043
wR(F2) = 0.089
S = 1.01 3763 reflections 262 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.036P)2 + 0.0701P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.19 e Å−3
Δρmin = −0.12 e Å−3
Absolute structure: Flack (1983), 1811 Friedel pairs
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 (Å2)
x y z Uiso*/Ueq
supporting information
sup-3 Acta Cryst. (2006). E62, o2302–o2303
C17 0.28422 (14) 1.4591 (5) 0.51739 (13) 0.0470 (6) C18 0.32881 (16) 1.5671 (6) 0.46915 (16) 0.0758 (9) H18A 0.3754 1.5115 0.4647 0.091* C19 0.3041 (2) 1.7579 (7) 0.42753 (18) 0.0818 (10) H19A 0.3333 1.8325 0.3941 0.098* C20 0.23668 (19) 1.8347 (6) 0.43612 (17) 0.0760 (10) H20A 0.2210 1.9666 0.4082 0.091* C21 0.21599 (17) 1.5499 (6) 0.52124 (17) 0.0694 (9) H21A 0.1854 1.4766 0.5537 0.083*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cl1 0.0825 (6) 0.1024 (7) 0.0773 (5) 0.0155 (5) −0.0322 (5) 0.0053 (5) O1 0.0779 (13) 0.0344 (11) 0.0660 (11) 0.0038 (9) −0.0131 (10) 0.0064 (9) O2 0.0458 (11) 0.0522 (10) 0.0497 (10) 0.0018 (9) −0.0021 (8) 0.0093 (8) O3 0.0509 (12) 0.0860 (15) 0.0636 (12) 0.0164 (10) 0.0078 (10) 0.0157 (11) N1 0.0494 (13) 0.0499 (13) 0.0487 (13) 0.0010 (10) 0.0032 (11) 0.0076 (11) N2 0.0671 (17) 0.0770 (18) 0.0477 (14) 0.0072 (15) 0.0034 (12) 0.0030 (13) N3 0.0721 (18) 0.0817 (19) 0.0633 (17) 0.0110 (15) 0.0103 (15) −0.0080 (14) N4 0.0724 (18) 0.094 (2) 0.099 (2) 0.0158 (15) −0.0082 (17) 0.0373 (19) C1 0.0562 (17) 0.0413 (15) 0.0572 (17) 0.0050 (13) 0.0022 (14) −0.0017 (13) C2 0.0699 (19) 0.0602 (19) 0.0474 (16) 0.0015 (16) −0.0042 (15) −0.0037 (14) C3 0.0460 (15) 0.0609 (19) 0.0563 (17) 0.0019 (14) −0.0076 (13) 0.0089 (15) C4 0.0470 (17) 0.0466 (17) 0.0666 (19) 0.0068 (12) −0.0055 (14) 0.0029 (14) C5 0.0534 (15) 0.0392 (14) 0.0535 (15) 0.0034 (12) 0.0008 (13) −0.0005 (12) C6 0.0422 (13) 0.0340 (14) 0.0451 (14) 0.0000 (11) 0.0014 (11) 0.0058 (11) C7 0.0474 (14) 0.0305 (14) 0.0474 (14) 0.0052 (11) 0.0084 (12) 0.0046 (11) C8 0.0512 (15) 0.0355 (13) 0.0461 (13) 0.0073 (12) −0.0004 (12) 0.0029 (12) C9 0.0538 (16) 0.0353 (15) 0.0632 (16) 0.0001 (12) 0.0011 (14) 0.0083 (13) C10 0.0421 (15) 0.0490 (16) 0.0500 (16) −0.0047 (12) 0.0065 (13) 0.0093 (13) C11 0.0541 (18) 0.075 (2) 0.063 (2) −0.0042 (16) 0.0015 (16) −0.0001 (17) C12 0.055 (2) 0.116 (3) 0.068 (2) 0.010 (2) −0.0093 (17) 0.015 (2) C13 0.056 (2) 0.092 (3) 0.101 (3) 0.0208 (18) 0.009 (2) 0.029 (2) C14 0.063 (2) 0.064 (2) 0.097 (3) 0.0131 (16) 0.022 (2) 0.0128 (19) C15 0.0519 (17) 0.0522 (18) 0.0632 (19) 0.0047 (14) 0.0161 (15) 0.0052 (15) C16 0.0450 (15) 0.0518 (16) 0.0445 (15) 0.0026 (13) 0.0017 (13) −0.0016 (13) C17 0.0527 (16) 0.0502 (16) 0.0381 (13) 0.0011 (13) −0.0022 (12) 0.0003 (12) C18 0.072 (2) 0.088 (2) 0.068 (2) 0.0220 (18) 0.0167 (18) 0.0224 (19) C19 0.095 (3) 0.088 (3) 0.0622 (19) 0.006 (2) 0.0110 (19) 0.0291 (19) C20 0.104 (3) 0.064 (2) 0.060 (2) 0.005 (2) −0.018 (2) 0.0165 (16) C21 0.0583 (18) 0.081 (2) 0.069 (2) −0.0015 (17) −0.0011 (16) 0.0216 (18)
Geometric parameters (Å, º)
O2—C8 1.437 (3) C9—H9B 0.9700 O3—C16 1.194 (3) C10—C15 1.382 (4) N1—C10 1.361 (3) C10—C11 1.386 (4) N1—N2 1.363 (3) C11—C12 1.384 (5) N1—C9 1.443 (3) C11—H11A 0.9300 N2—N3 1.303 (3) C12—C13 1.393 (5) N3—C15 1.373 (4) C12—H12A 0.9300 N4—C20 1.335 (4) C13—C14 1.350 (5) N4—C21 1.336 (4) C13—H13A 0.9300 C1—C2 1.374 (4) C14—C15 1.396 (4) C1—C6 1.392 (4) C14—H14A 0.9300 C1—H1A 0.9300 C16—C17 1.479 (4) C2—C3 1.378 (4) C17—C18 1.371 (4) C2—H2B 0.9300 C17—C21 1.375 (4) C3—C4 1.372 (4) C18—C19 1.372 (4) C4—C5 1.381 (4) C18—H18A 0.9300 C4—H4B 0.9300 C19—C20 1.343 (5) C5—C6 1.388 (3) C19—H19A 0.9300 C5—H5A 0.9300 C20—H20A 0.9300 C6—C7 1.480 (3) C21—H21A 0.9300 C7—C8 1.520 (4)
supporting information
sup-5 Acta Cryst. (2006). E62, o2302–o2303
O1—C7—C8 119.3 (2) C17—C18—C19 119.4 (3) C6—C7—C8 120.2 (2) C17—C18—H18A 120.3 O2—C8—C7 108.34 (18) C19—C18—H18A 120.3 O2—C8—C9 106.3 (2) C20—C19—C18 118.5 (3) C7—C8—C9 112.1 (2) C20—C19—H19A 120.8 O2—C8—H8A 110.0 C18—C19—H19A 120.8 C7—C8—H8A 110.0 N4—C20—C19 125.0 (3) C9—C8—H8A 110.0 N4—C20—H20A 117.5 N1—C9—C8 112.3 (2) C19—C20—H20A 117.5 N1—C9—H9A 109.1 N4—C21—C17 124.6 (3) C8—C9—H9A 109.1 N4—C21—H21A 117.7 N1—C9—H9B 109.1 C17—C21—H21A 117.7
C10—N1—N2—N3 0.6 (3) N2—N1—C10—C11 −178.6 (3) C9—N1—N2—N3 171.6 (2) C9—N1—C10—C11 11.8 (5) N1—N2—N3—C15 −1.0 (3) N1—C10—C11—C12 179.4 (3) C6—C1—C2—C3 0.3 (4) C15—C10—C11—C12 0.9 (4) C1—C2—C3—C4 0.4 (4) C10—C11—C12—C13 0.5 (5) C1—C2—C3—Cl1 179.8 (2) C11—C12—C13—C14 −1.4 (5) C2—C3—C4—C5 −1.5 (4) C12—C13—C14—C15 0.8 (5) Cl1—C3—C4—C5 179.1 (2) N2—N3—C15—C10 1.1 (3) C3—C4—C5—C6 1.9 (4) N2—N3—C15—C14 −179.3 (3) C4—C5—C6—C1 −1.3 (4) N1—C10—C15—N3 −0.7 (3) C4—C5—C6—C7 175.0 (2) C11—C10—C15—N3 178.2 (2) C2—C1—C6—C5 0.2 (4) N1—C10—C15—C14 179.6 (3) C2—C1—C6—C7 −176.2 (2) C11—C10—C15—C14 −1.5 (4) C5—C6—C7—O1 −149.1 (2) C13—C14—C15—N3 −179.0 (3) C1—C6—C7—O1 27.1 (4) C13—C14—C15—C10 0.6 (4) C5—C6—C7—C8 34.4 (3) C8—O2—C16—O3 16.8 (3) C1—C6—C7—C8 −149.4 (2) C8—O2—C16—C17 −161.64 (19) C16—O2—C8—C7 65.7 (3) O3—C16—C17—C18 4.0 (4) C16—O2—C8—C9 −173.7 (2) O2—C16—C17—C18 −177.6 (2) O1—C7—C8—O2 16.2 (3) O3—C16—C17—C21 −171.8 (3) C6—C7—C8—O2 −167.3 (2) O2—C16—C17—C21 6.6 (4) O1—C7—C8—C9 −100.8 (3) C21—C17—C18—C19 0.1 (5) C6—C7—C8—C9 75.8 (3) C16—C17—C18—C19 −176.0 (3) C10—N1—C9—C8 83.9 (3) C17—C18—C19—C20 0.7 (5) N2—N1—C9—C8 −84.9 (3) C21—N4—C20—C19 0.9 (5) O2—C8—C9—N1 −62.2 (3) C18—C19—C20—N4 −1.3 (6) C7—C8—C9—N1 55.9 (3) C20—N4—C21—C17 0.0 (5) N2—N1—C10—C15 0.1 (3) C18—C17—C21—N4 −0.4 (5) C9—N1—C10—C15 −169.4 (2) C16—C17—C21—N4 175.5 (3)
Hydrogen-bond geometry (Å, º)
C13—H13A···O3ii 0.93 2.49 3.351 (4) 155
C21—H21A···O2 0.93 2.39 2.739 (4) 102