research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 261-265
doi:10.1107/S2056989016001493

Crystal structures of methyl (E)-3-(2-chloro­phen­yl)-2-({2-[(E)-2-nitro­vin­yl]phen­­oxy}meth­yl)acrylate and methyl (E)-2-({4-chloro-2-[(E)-2-nitro­vin­yl]phen­­oxy}meth­yl)-3-(2-chloro­phen­yl)acrylate

CROSSMARK_Color_square_no_text.svg
G. Vimala,a N. Poomathi,b P. T. Perumalb and A. SubbiahPandia*

aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and bOrganic Chemistry, CSIR – Central Leather Research Institute, Adyar, Chennai 600 020, India
*Correspondence e-mail: aspandian59@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 15 December 2015; accepted 23 January 2016; online 30 January 2016)

The title compounds, C19H16ClNO5, (I), and C19H15Cl2NO5, (II), both crystallize in the monoclinic space group P21/n. They differ essentially in the orientation of the methyl acetate group, with the C=O bond directed towards the NO2 group in (I) but away from it in (II). In compound (I), the mean plane of the methyl acrylate unit is planar, with a maximum deviation of 0.0044 (2) Å for the methyl C atom, while in (II) this deviation is 0.0147 Å. The inter­planar angles between the two aromatic rings are 74.87 (9) and 75.65 (2)° for compounds (I) and (II), respectively. In both compounds, the methyl acrylate and nitro­vinyl groups each adopt an E conformation about the C=C bond. In the crystal of (I), mol­ecules are linked by C—H⋯O hydrogen bonds forming chains along the b axis. The chains are linked via C—H⋯Cl hydrogen bonds, forming sheets parallel to the ab plane. The sheets are linked via C—H⋯π inter­actions, forming a three-dimensional structure. In the crystal of (II), mol­ecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R22(30) ring motif. The dimers are linked via C—H⋯O hydrogen bonds, forming sheets parallel to the ac plane and enclosing R44(28) ring motifs. The sheets are linked via parallel slipped π–π inter­actions (inter­centroid distances are both ca 3.86 Å), forming a three-dimensional structure.

CCDC references: 1449405; 1449404

1. Chemical context

Recently, 2-cyano­acrylates have been used extensively as agrochemicals because of their unique mechanism of action and good environmental profiles (Govindan et al., 2011[Govindan, E., SakthiMurugesan, K., Srinivasan, J., Bakthadoss, M. & SubbiahPandi, A. (2011). Acta Cryst. E67, o2753.]). Phenyl acrylates and their derivatives are important compounds because of their agrochemical and medical applications (De Fraine & Martin, 1991[De Fraine, P. J. & Martin, A. (1991). US Patent 5 055 471.]). Cinnamic acid derivatives have received attention in medicinal research as traditional as well as recently synthetic anti­tumor agents (De et al., 2011[De, P., Baltas, M. & Bedos-Belval, F. (2011). Curr. Med. Chem. 18, 1672-1703.]). They also possess significant anti­bacterial activity against Staphylococcus aureus (Xiao et al., 2008[Xiao, Z.-P., Fang, R.-Q., Li, H.-Q., Xue, J.-Y., Zheng, Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. 43, 1828-1836.]). In addition, different substitutions on the basic moiety lead to various pharmacological activities, such as anti-oxidant, hepatoprotective, anxiolytic, insect repellent, anti­diabetic and anti­cholesterolemic (Sharma, 2011[Sharma, P. (2011). J. Chem. Pharm. Res. 3, 403-423.]). Against this background, the title compounds were synthesized and we report herein on their crystal structures.

2. Structural commentary

The title compounds, (I)[link] and (II)[link], crystallized in the monoclinic space group P21/n with Z = 4; their mol­ecular structures are illustrated in Figs. 1[link] and 2[link], respectively. In compound (I)[link], the methyl acrylate unit is essentially planar, with a maximum deviation of 0.0044 (2) Å for atom C12, and forms dihedral angles of 84.04 (9) and 50.23 (9)° with the benzene rings (C3–C8) and (C14–C19), respectively. Likewise, in compound (II)[link], the methyl acrylate unit is essentially planar, with a maximum deviation of 0.0147 (2) Å for atom C12, and forms dihedral angle of 73.20 (9) and 42.81 (9)° with benzene rings (C3–C8) and (C14–C19), respectively. In compound (I)[link], the rings (C3–C8) and (C14–C19) are almost normal to one another, making a dihedral angle of 74.87 (9)°. In the case of compound (II)[link], the corresponding dihedral angle is 75.65 (2)°. The title mol­ecules exhibit structural similarities with the related structure, (Z)-methyl 3-(2,4-di­chloro­phen­yl)-2-[(2-formyl­phen­oxy)meth­yl]acrylate (Gangadharan et al., 2011[Gangadharan, R., Sethusankar, K., Selvakumar, R. & Bakthadoss, M. (2011). Acta Cryst. E67, o2738.]).

[Scheme 1]
[Figure 1]
Figure 1
The mol­ecular structure of compound (I)[link], showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
The mol­ecular structure of compound (II)[link], showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

The methyl acrylate moieties adopt an extended conformation, as is evident from the torsion angles O4—C11—C10—C13 = 170.6 (2)°, O5—C11—C10—C13 = −8.5 (2)°, C9—C10—C11—O4 = −5.5 (2)° and C9—C10—C11—O5 = 175.5 (1)° for compound (I)[link], while the corresponding angles in compound (II)[link] are −2.9 (5), 177.7 (3), 173.0 (3) and −6.3 (4)°, respectively. The extended conformation is supported by the fact that the bond angles involving the carbonyl O atoms are invariably enlarged (Schweizer & Dunitz, 1982[Schweizer, W. B. & Dunitz, J. D. (1982). Helv. Chim. Acta, 65, 1547-1554.]).

The significant difference in the bond lengths O5—C11 and O5—C12, which are 1.324 (2) and 1.444 (2) Å, respectively, for compound (I)[link], and 1.328 (4) and 1.440 (4) Å, respectively, for compound (II)[link], can be attributed to a partial contribution from the O−—C=O+—C resonance structures of the O5—C11(=O4)—C10 group (Merlino et al., 1971[Merlino, S. (1971). Acta Cryst. B27, 2491-2492.]). This feature, commonly observed for the carb­oxy­lic ester group of substit­uents in various compounds gives average values of 1.340 and 1.447 Å, respectively (Varghese et al., 1986[Varghese, B., Srinivasan, S., Padmanabhan, P. V. & Ramadas, S. R. (1986). Acta Cryst. C42, 1544-1546.]).

In both compounds, the nitro­vinyl groups [C2=C1—N1(O1,O2)], have an E conformation about the C2=C1 bond. In (I)[link], its mean plane makes a dihedral angle of 2.025 (9)° with the benzene ring (C3–C8) to which it is attached, while in compound (II)[link], the corresponding dihedral angle is much larger, at 14.78 (16) °.

3. Supra­molecular features

In the crystal of (I)[link], adjacent mol­ecules are linked by C—H⋯O hydrogen bonds forming chains along the b-axis direction (Table 1[link] and Fig. 3[link]). The chains are linked via C—H⋯Cl hydrogen bonds, forming sheets parallel to the ab plane (Fig. 4[link] and Table 1[link]). The sheets are linked via C—H⋯π inter­actions, forming a three-dimensional structure (Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

Cg2 is the centroid of the C14–C19 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C12—H12A⋯O1i 0.96 2.45 3.406 (2) 172
C2—H2⋯Cl1ii 0.93 2.85 3.7515 (16) 165
C13—H13⋯Cg2iii 0.93 2.91 3.5828 (16) 130
Symmetry codes: (i) [-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) -x+2, -y+1, -z-3.
[Figure 3]
Figure 3
A partial view of the crystal structure of compound (I)[link], showing the hydrogen-bonded (dashed lines) zigzag chains propagating along [010]; see Table 1[link].
[Figure 4]
Figure 4
The crystal packing of compound (I)[link], viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1[link]).

In compound (II)[link], mol­ecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers enclosing an R22(30) ring motif (Table 2[link] and Fig. 5[link]). The dimers are linked by further C—H⋯O hydrogen bonds, forming sheets parallel to the ac plane and enclosing R44(28) ring motifs (Table 2[link] and Fig. 5[link]). The sheets are linked via slipped parallel π–π inter­actions, forming a three-dimensional structure, Fig. 6[link] [Cg1⋯Cg1i = 3.863 (2) Å, inter-planar distance = 3.487 (1) Å, slippage 1.662 Å; Cg1 is the centroid of ring C3–C8; symmetry code: (i) −x + 1, −y, z + 1, and Cg2⋯Cg2ii = 3.861 (2) Å, inter-planar distance = 3.506 (2) Å, slippage = 1.617 Å; Cg2 is the centroid of ring C14–C19; symmetry code: (ii) −x + 1, −y, −z + 2].

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C6—H6⋯O4i 0.93 2.56 3.371 (4) 146
C7—H7⋯O2ii 0.93 2.58 3.476 (4) 161
C18—H18⋯O1iii 0.93 2.60 3.485 (5) 160
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) x-1, y, z; (iii) -x+1, -y, -z+2.
[Figure 5]
Figure 5
A partial view of the crystal packing of compound (II)[link], viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 2[link]).
[Figure 6]
Figure 6
The crystal packing of compound (II)[link], viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1[link]).

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.37, November 2015; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) for the substructure methyl (E)-2-(phen­oxy­meth­yl)-3-phenyl­acrylate gave 12 hits. There is a great variety in the dihedral angle involving the two aromatic rings; from a minimum of ca 47.2° in (E)-methyl 2-({2-eth­oxy-6-[(E)-(hy­droxy­imino)­meth­yl]phen­oxy}meth­yl)-3-phenyl­acrylate (CSD code: ZARDAT; Govindan et al., 2012[Govindan, E., Ganesh, G., Srinivasan, J., Bakthadoss, M. & SubbiahPandi, A. (2012). Acta Cryst. E68, o1373.]) to a maximum of ca 88.4° in methyl (E)-2-[(2-nitro­phen­oxy)meth­yl]-3-phenyl­acrylate (CSD code: PAWFIE; Anuradha et al., 2012[Anuradha, T., Devaraj, A., Seshadri, P. R. & Bakthadoss, M. (2012). Acta Cryst. E68, o1748.]). In the title compounds, this dihedral angle is 74.87 (9)° in (I)[link] and 75.65 (2)° in (II)[link].

5. Synthesis and crystallization

The title compounds were prepared in a similar manner using a mixture of methyl (E)-3-(2-chloro­phen­yl)-2-{[2-(2,2-di­cyano­vin­yl)phen­oxy]meth­yl}acrylate (1 mmol) for compound (I)[link], and methyl (E)-2-{[4-chloro-2-(2,2-di­cyano­vin­yl)phen­oxy]meth­yl}-3-(2-chloro­phen­yl)acrylate (1 mol) for compound (II)[link], dissolved in nitro­methane (5 mol) in toluene (3 ml) with a catalytic amount of cinchona alkaloid (0.005 mmol %). The resulting solutions were stirred for 4 h at room temperature. The consumption of the starting materials was monitored by TLC. After completion of the reaction, DMAP (0.020 mol %) and di-tert-butyl dicarbonate (1.2 equiv) were added and the solutions of the corresponding crude products were stirred at 318–323 K for 2 h, followed by TLC (20% EtOAc and petroleum ether). The solvents were removed under reduced pressure and the residues purified by column chromatography on silica gel (3:97%, ethyl­acetate and petroleum ether) to afford pure products. The purified compounds were recrystallized from ethanol, by slow evaporation of the solvent, yielding block-like crystals of compounds (I)[link] and (II)[link], suitable for X ray diffraction analysis.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C-meth­yl) and 1.2Ueq(C) for other H atoms.

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C19H16ClNO5 C19H15Cl2NO5
Mr 373.78 408.22
Crystal system, space group Monoclinic, P21/n Monoclinic, P21/n
Temperature (K) 293 293
a, b, c (Å) 9.0152 (3), 13.6579 (4), 14.6366 (4) 9.2372 (3), 14.5027 (5), 14.4830 (5)
β (°) 102.176 (1) 94.521 (2)
V (Å3) 1761.64 (9) 1934.17 (11)
Z 4 4
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.25 0.37
Crystal size (mm) 0.27 × 0.24 × 0.18 0.28 × 0.22 × 0.19
 
Data collection
Diffractometer Bruker Kappa APEXII CCD Bruker Kappa APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.935, 0.935 0.942, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections 15968, 4365, 3186 12108, 3481, 2382
Rint 0.019 0.029
(sin θ/λ)max (Å−1) 0.667 0.600
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.109, 1.04 0.055, 0.143, 1.04
No. of reflections 4365 3481
No. of parameters 236 245
H-atom treatment H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.23, −0.23 0.57, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Supporting information

CCDC references: 1449405; 1449404

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S2056989016001493/su5265sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016001493/su5265Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989016001493/su5265IIsup3.hkl

Supporting information file. DOI: 10.1107/S2056989016001493/su5265Isup4.cml

Supporting information file. DOI: 10.1107/S2056989016001493/su5265IIsup5.cml

checkCIF report


Chemical context top

Recently, 2-cyano­acrylates have been used extensively as agrochemicals because of their unique mechanism of action and good environmental profiles (Govindan et al., 2011). Phenyl acrylates and their derivatives are important compounds because of their agrochemical and medical applications (De Fraine & Martin, 1991). Cinnamic acid derivatives have received attention in medicinal research as traditional as well as recently synthetic anti­tumor agents (De et al., 2011). They also possess significant anti­bacterial activity against Staphylococcus aureus (Xiao et al., 2008). In addition, different substitutions on the basic moiety lead to various pharmacological activities, such as anti-oxidant, hepatoprotective, anxiolytic, insect repellent, anti­diabetic and anti­cholesterolemic (Sharma, 2011). Against this background, the title compounds were synthesized and we report herein on their crystal structures.

Structural commentary top

The title compounds, (I) and (II), crystallized in the monoclinic space group P21/n with Z = 4; their molecular structures are illustrated in Figs. 1 and 2, respectively. In compound (I), the methyl acrylate unit is essentially planar, with a maximum deviation of 0.0044 (2) Å for atom C12, and forms dihedral angles of 84.04 (9) and 50.23 (9)° with the benzene rings (C3–C8) and (C14–C19), respectively. Likewise, in compound (II), the methyl acrylate unit is essentially planar, with a maximum deviation of 0.0147 (2) Å for atom C12, and forms dihedral angle of 73.20 (9) and 42.81 (9)° with benzene rings (C3–C8) and (C14–C19), respectively. In compound (I), the rings (C3–C8) and (C14–C19) are almost normal to one another, making a dihedral angle of 74.87 (9)°. In the case of compound (II), the corresponding dihedral angle is 75.65 (2)°. The title molecules exhibit structural similarities with the related structure, (Z)-methyl 3-(2,4-di­chloro­phenyl)-2-[(2-formyl­phen­oxy)­methyl]­acrylate (Gangadharan et al., 2011).

The methyl acrylate moieties adopt an extended conformation, as is evident from the torsion angles O4—C11—C10—C13 = 170.6 (2)°, O5—C11—C10—C13 = −8.5 (2)°, C9—C10—C11—O4 = −5.5 (2)° and C9—C10—C11—O5 = 175.5 (1)° for compound (I), while the corresponding angles in compound (II) are −2.9 (5), 177.7 (3), 173.0 (3) and −6.3 (4)°, respectively. The extended conformation is supported by the fact that the bond angles involving the carbonyl O atoms are invariably enlarged (Schweizer & Dunitz, 1982).

The significant difference in the bond lengths O5—C11 and O5—C12, which are 1.324 (2) and 1.444 (2) Å, respectively, for compound (I), and 1.328 (4) and 1.440 (4) Å, respectively, for compound (II), can be attributed to a partial contribution from the O−—C═O+—C resonance structures of the O5—C11(═O4)—C10 group (Merlino et al., 1971). This feature, commonly observed for the carb­oxy­lic ester group of substituents in various compounds gives average values of 1.340 and 1.447 Å, respectively (Varghese et al., 1986).

In both compounds, the nitro­vinyl groups [C2═C1—N1(O1,O2)], have an E conformation about the C2═C1 bond. In (I), its mean plane makes a dihedral angle of 2.025 (9) ° with the benzene ring (C3–C8) to which it is attached, while in compound (II), the corresponding dihedral angle is much larger, at 14.78 (16) °.

Supra­molecular features top

In the crystal of (I), adjacent molecules are linked by C—H···O hydrogen bonds forming chains along the b-axis direction (Table 1 and Fig. 3). The chains are linked via C—H···Cl hydrogen bonds, forming sheets parallel to the ab plane (Fig. 4 and Table 1). The sheets are linked via C—H···π inter­actions, forming a three-dimensional structure (Table 1).

In compound (II), molecules are linked by pairs of C—H···O hydrogen bonds, forming inversion dimers enclosing an R22(30) ring motif (Table 2 and Fig. 5). The dimers are linked by further C—H···O hydrogen bonds, forming sheets parallel to the ac plane and enclosing R44(28) ring motifs (Table 2 and Fig. 5). The sheets are linked via slipped parallel π–π inter­actions, forming a three-dimensional structure, Fig. 6 [Cg1···Cg1i = 3.863 (2) Å, inter-planar distance = 3.487 (1) Å, slippage 1.662 Å; Cg1 is the centroid of ring C3–C8; symmetry code: (i) −x + 1, −y, z + 1, and Cg2···Cg2ii = 3.861 (2) Å, inter-planar distance = 3.506 (2) Å, slippage = 1.617 Å; Cg2 is the centroid of ring C14–C19; symmetry code: (ii) −x + 1, −y, −z + 2].

Database survey top

\ A search of the Cambridge Structural Database (CSD, Version 5.37, November 2015; Groom & Allen, 2014) for the substructure methyl (E)-2-(phen­oxy­methyl)-3-phenyl­acrylate gave 12 hits. There is a great variety in the dihedral angle involving the two aromatic rings; from a minimum of ca 47.2° in (E)-methyl 2-({2-eth­oxy-6-[(E)-(hy­droxy­imino)­methyl]­phen­oxy}­methyl)-3-\ phenyl­acrylate (CSD code: ZARDAT; Govindan et al., 2012) to a maximum of ca 88.4° in methyl (E)-2-[(2-nitro­phen­oxy)­methyl]-3-phenyl­acrylate (CSD code: PAWFIE; Anuradha et al., 2012). In the title compounds, this dihedral angle is 74.87 (9)° in (I) and 75.65 (2)° in (II).

Synthesis and crystallization top

\ The title compounds were prepared in a similar manner using a mixture of methyl (E)-3-(2-chloro­phenyl)-2-{[2-(2,2-di­cyano­vinyl)­phen­oxy]­methyl}­acrylate (1 mmol) for compound (I), and methyl (E)-2-{[4-chloro-2-(2,2-di­cyano­vinyl)­phen­oxy]­methyl}-3-(2-\ chloro­phenyl)­acrylate (1 mol) for compound (II), dissolved in nitro­methane (5 mol) in toluene (3 ml) with a catalytic amount of cinchona alkaloid (0.005 mmol %). The resulting solutions were stirred for 4 h at room temperature. The consumption of the starting materials was monitored by TLC. After completion of the reaction, DMAP (0.020 mol %) and di-tert-butyl dicarbonate (1.2 equiv) were added and the solutions of the corresponding crude products were stirred at 318–323 K for 2 h, followed by TLC (20% EtOAc and petroleum ether). The solvents were removed under reduced pressure and the residues purified by column chromatography on silica gel (3:97%, ethyl­acetate and petroleum ether) to afford pure products. The purified compounds were recrystallized from ethanol, by slow evaporation of the solvent, yielding block-like crystals of compounds (I) and (II), suitable for X ray diffraction analysis.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.

Structure description top

Recently, 2-cyano­acrylates have been used extensively as agrochemicals because of their unique mechanism of action and good environmental profiles (Govindan et al., 2011). Phenyl acrylates and their derivatives are important compounds because of their agrochemical and medical applications (De Fraine & Martin, 1991). Cinnamic acid derivatives have received attention in medicinal research as traditional as well as recently synthetic anti­tumor agents (De et al., 2011). They also possess significant anti­bacterial activity against Staphylococcus aureus (Xiao et al., 2008). In addition, different substitutions on the basic moiety lead to various pharmacological activities, such as anti-oxidant, hepatoprotective, anxiolytic, insect repellent, anti­diabetic and anti­cholesterolemic (Sharma, 2011). Against this background, the title compounds were synthesized and we report herein on their crystal structures.

The title compounds, (I) and (II), crystallized in the monoclinic space group P21/n with Z = 4; their molecular structures are illustrated in Figs. 1 and 2, respectively. In compound (I), the methyl acrylate unit is essentially planar, with a maximum deviation of 0.0044 (2) Å for atom C12, and forms dihedral angles of 84.04 (9) and 50.23 (9)° with the benzene rings (C3–C8) and (C14–C19), respectively. Likewise, in compound (II), the methyl acrylate unit is essentially planar, with a maximum deviation of 0.0147 (2) Å for atom C12, and forms dihedral angle of 73.20 (9) and 42.81 (9)° with benzene rings (C3–C8) and (C14–C19), respectively. In compound (I), the rings (C3–C8) and (C14–C19) are almost normal to one another, making a dihedral angle of 74.87 (9)°. In the case of compound (II), the corresponding dihedral angle is 75.65 (2)°. The title molecules exhibit structural similarities with the related structure, (Z)-methyl 3-(2,4-di­chloro­phenyl)-2-[(2-formyl­phen­oxy)­methyl]­acrylate (Gangadharan et al., 2011).

The methyl acrylate moieties adopt an extended conformation, as is evident from the torsion angles O4—C11—C10—C13 = 170.6 (2)°, O5—C11—C10—C13 = −8.5 (2)°, C9—C10—C11—O4 = −5.5 (2)° and C9—C10—C11—O5 = 175.5 (1)° for compound (I), while the corresponding angles in compound (II) are −2.9 (5), 177.7 (3), 173.0 (3) and −6.3 (4)°, respectively. The extended conformation is supported by the fact that the bond angles involving the carbonyl O atoms are invariably enlarged (Schweizer & Dunitz, 1982).

The significant difference in the bond lengths O5—C11 and O5—C12, which are 1.324 (2) and 1.444 (2) Å, respectively, for compound (I), and 1.328 (4) and 1.440 (4) Å, respectively, for compound (II), can be attributed to a partial contribution from the O−—C═O+—C resonance structures of the O5—C11(═O4)—C10 group (Merlino et al., 1971). This feature, commonly observed for the carb­oxy­lic ester group of substituents in various compounds gives average values of 1.340 and 1.447 Å, respectively (Varghese et al., 1986).

In both compounds, the nitro­vinyl groups [C2═C1—N1(O1,O2)], have an E conformation about the C2═C1 bond. In (I), its mean plane makes a dihedral angle of 2.025 (9) ° with the benzene ring (C3–C8) to which it is attached, while in compound (II), the corresponding dihedral angle is much larger, at 14.78 (16) °.

In the crystal of (I), adjacent molecules are linked by C—H···O hydrogen bonds forming chains along the b-axis direction (Table 1 and Fig. 3). The chains are linked via C—H···Cl hydrogen bonds, forming sheets parallel to the ab plane (Fig. 4 and Table 1). The sheets are linked via C—H···π inter­actions, forming a three-dimensional structure (Table 1).

In compound (II), molecules are linked by pairs of C—H···O hydrogen bonds, forming inversion dimers enclosing an R22(30) ring motif (Table 2 and Fig. 5). The dimers are linked by further C—H···O hydrogen bonds, forming sheets parallel to the ac plane and enclosing R44(28) ring motifs (Table 2 and Fig. 5). The sheets are linked via slipped parallel π–π inter­actions, forming a three-dimensional structure, Fig. 6 [Cg1···Cg1i = 3.863 (2) Å, inter-planar distance = 3.487 (1) Å, slippage 1.662 Å; Cg1 is the centroid of ring C3–C8; symmetry code: (i) −x + 1, −y, z + 1, and Cg2···Cg2ii = 3.861 (2) Å, inter-planar distance = 3.506 (2) Å, slippage = 1.617 Å; Cg2 is the centroid of ring C14–C19; symmetry code: (ii) −x + 1, −y, −z + 2].

\ A search of the Cambridge Structural Database (CSD, Version 5.37, November 2015; Groom & Allen, 2014) for the substructure methyl (E)-2-(phen­oxy­methyl)-3-phenyl­acrylate gave 12 hits. There is a great variety in the dihedral angle involving the two aromatic rings; from a minimum of ca 47.2° in (E)-methyl 2-({2-eth­oxy-6-[(E)-(hy­droxy­imino)­methyl]­phen­oxy}­methyl)-3-\ phenyl­acrylate (CSD code: ZARDAT; Govindan et al., 2012) to a maximum of ca 88.4° in methyl (E)-2-[(2-nitro­phen­oxy)­methyl]-3-phenyl­acrylate (CSD code: PAWFIE; Anuradha et al., 2012). In the title compounds, this dihedral angle is 74.87 (9)° in (I) and 75.65 (2)° in (II).

Synthesis and crystallization top

\ The title compounds were prepared in a similar manner using a mixture of methyl (E)-3-(2-chloro­phenyl)-2-{[2-(2,2-di­cyano­vinyl)­phen­oxy]­methyl}­acrylate (1 mmol) for compound (I), and methyl (E)-2-{[4-chloro-2-(2,2-di­cyano­vinyl)­phen­oxy]­methyl}-3-(2-\ chloro­phenyl)­acrylate (1 mol) for compound (II), dissolved in nitro­methane (5 mol) in toluene (3 ml) with a catalytic amount of cinchona alkaloid (0.005 mmol %). The resulting solutions were stirred for 4 h at room temperature. The consumption of the starting materials was monitored by TLC. After completion of the reaction, DMAP (0.020 mol %) and di-tert-butyl dicarbonate (1.2 equiv) were added and the solutions of the corresponding crude products were stirred at 318–323 K for 2 h, followed by TLC (20% EtOAc and petroleum ether). The solvents were removed under reduced pressure and the residues purified by column chromatography on silica gel (3:97%, ethyl­acetate and petroleum ether) to afford pure products. The purified compounds were recrystallized from ethanol, by slow evaporation of the solvent, yielding block-like crystals of compounds (I) and (II), suitable for X ray diffraction analysis.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of compound (II), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A partial view of the crystal structure of compound (I), showing the hydrogen-bonded (dashed lines) zigzag chains propagating along [010]; see Table 1.
[Figure 4] Fig. 4. The crystal packing of compound (I), viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1).
[Figure 5] Fig. 5. A partial view of the crystal packing of compound (II), viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 2).
[Figure 6] Fig. 6. The crystal packing of compound (II), viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1).
(I) Methyl (E)-3-(2-chlorophenyl)-2-({2-[(E)-2-nitrovinyl]phenoxy}methyl)acrylate top
Crystal data top
C19H16ClNO5F(000) = 776
Mr = 373.78Dx = 1.409 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.0152 (3) ÅCell parameters from 2595 reflections
b = 13.6579 (4) Åθ = 2.1–25.0°
c = 14.6366 (4) ŵ = 0.25 mm−1
β = 102.176 (1)°T = 293 K
V = 1761.64 (9) Å3Block, colourless
Z = 40.27 × 0.24 × 0.18 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		4365 independent reflections
Radiation source: fine-focus sealed tube3186 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω and φ scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −9→12
Tmin = 0.935, Tmax = 0.935k = −9→18
15968 measured reflectionsl = −19→19
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.0464P)2 + 0.4238P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
4365 reflectionsΔρmax = 0.23 e Å−3
236 parametersΔρmin = −0.23 e Å−3
Crystal data top
C19H16ClNO5V = 1761.64 (9) Å3
Mr = 373.78Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.0152 (3) ŵ = 0.25 mm−1
b = 13.6579 (4) ÅT = 293 K
c = 14.6366 (4) Å0.27 × 0.24 × 0.18 mm
β = 102.176 (1)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer		4365 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		3186 reflections with I > 2σ(I)
Tmin = 0.935, Tmax = 0.935Rint = 0.019
15968 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.04Δρmax = 0.23 e Å−3
4365 reflectionsΔρmin = −0.23 e Å−3
236 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.94245 (6)0.33362 (3)1.09845 (3)0.06629 (16)
O11.02396 (17)0.69069 (14)0.66665 (11)0.0909 (5)
O20.88624 (18)0.72882 (13)0.53405 (12)0.0931 (5)
O30.63790 (11)0.47698 (8)0.70425 (7)0.0448 (3)
O40.81629 (15)0.27705 (11)0.67330 (8)0.0732 (4)
O51.02681 (12)0.29776 (9)0.78215 (8)0.0572 (3)
N10.90607 (17)0.68625 (11)0.60846 (11)0.0562 (4)
C10.78561 (18)0.62664 (12)0.63151 (11)0.0480 (4)
H10.80590.58420.68230.058*
C20.64741 (18)0.63313 (11)0.57985 (10)0.0454 (4)
H20.63730.67540.52910.054*
C30.50814 (17)0.58452 (11)0.58984 (9)0.0420 (3)
C40.3720 (2)0.61704 (14)0.53395 (11)0.0553 (4)
H40.37380.66820.49230.066*
C50.2351 (2)0.57515 (15)0.53901 (13)0.0645 (5)
H50.14560.59850.50180.077*
C60.2317 (2)0.49857 (15)0.59942 (13)0.0624 (5)
H60.13920.47020.60290.075*
C70.36441 (18)0.46297 (13)0.65535 (11)0.0512 (4)
H70.36100.41050.69530.061*
C80.50191 (17)0.50605 (11)0.65131 (9)0.0404 (3)
C90.64005 (16)0.39327 (11)0.76435 (10)0.0415 (3)
H9A0.59310.33750.72850.050*
H9B0.58440.40740.81270.050*
C100.80192 (16)0.37129 (10)0.80709 (9)0.0371 (3)
C110.88048 (18)0.31119 (11)0.74673 (10)0.0421 (3)
C121.1079 (2)0.23635 (15)0.72892 (14)0.0658 (5)
H12A1.21070.22810.76270.099*
H12B1.10780.26660.66970.099*
H12C1.05930.17360.71900.099*
C130.87143 (16)0.39681 (10)0.89424 (9)0.0387 (3)
H130.97010.37440.91520.046*
C140.80700 (16)0.45658 (11)0.95956 (10)0.0401 (3)
C150.72385 (19)0.54180 (12)0.93057 (11)0.0503 (4)
H150.70680.55990.86800.060*
C160.6666 (2)0.59956 (14)0.99228 (13)0.0595 (4)
H160.61180.65580.97130.071*
C170.6908 (2)0.57362 (15)1.08512 (13)0.0616 (5)
H170.65090.61201.12660.074*
C180.7739 (2)0.49116 (14)1.11704 (11)0.0566 (4)
H180.79070.47401.17990.068*
C190.83196 (18)0.43422 (11)1.05485 (10)0.0448 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0968 (4)0.0562 (3)0.0402 (2)0.0052 (2)0.0017 (2)0.00662 (18)
O10.0637 (9)0.1316 (15)0.0765 (10)−0.0259 (9)0.0127 (8)−0.0043 (10)
O20.0839 (10)0.0980 (12)0.1021 (12)−0.0038 (9)0.0300 (9)0.0478 (10)
O30.0423 (6)0.0458 (6)0.0437 (5)0.0003 (5)0.0033 (4)0.0125 (5)
O40.0721 (8)0.0937 (10)0.0474 (7)0.0174 (7)−0.0020 (6)−0.0269 (7)
O50.0500 (7)0.0665 (8)0.0533 (7)0.0096 (6)0.0071 (5)−0.0167 (6)
N10.0609 (10)0.0516 (8)0.0611 (9)0.0006 (7)0.0237 (8)−0.0041 (7)
C10.0572 (10)0.0432 (8)0.0456 (8)0.0012 (7)0.0154 (7)0.0017 (7)
C20.0615 (10)0.0366 (8)0.0392 (7)0.0090 (7)0.0131 (7)0.0024 (6)
C30.0519 (9)0.0397 (8)0.0332 (7)0.0087 (6)0.0060 (6)−0.0041 (6)
C40.0617 (11)0.0563 (10)0.0435 (8)0.0161 (8)0.0007 (7)0.0005 (7)
C50.0525 (11)0.0774 (13)0.0558 (10)0.0168 (9)−0.0065 (8)−0.0059 (10)
C60.0430 (9)0.0790 (13)0.0621 (11)−0.0005 (9)0.0038 (8)−0.0137 (10)
C70.0489 (9)0.0589 (10)0.0447 (8)−0.0015 (8)0.0077 (7)−0.0020 (7)
C80.0437 (8)0.0436 (8)0.0325 (7)0.0051 (6)0.0045 (6)−0.0055 (6)
C90.0457 (8)0.0394 (8)0.0387 (7)−0.0033 (6)0.0074 (6)0.0042 (6)
C100.0456 (8)0.0313 (7)0.0345 (7)−0.0012 (6)0.0089 (6)0.0048 (5)
C110.0532 (9)0.0383 (8)0.0341 (7)0.0024 (6)0.0079 (6)0.0036 (6)
C120.0612 (11)0.0704 (12)0.0683 (11)0.0132 (9)0.0196 (9)−0.0120 (10)
C130.0440 (8)0.0355 (7)0.0362 (7)0.0002 (6)0.0075 (6)0.0045 (6)
C140.0433 (8)0.0398 (8)0.0373 (7)−0.0053 (6)0.0089 (6)−0.0030 (6)
C150.0577 (10)0.0482 (9)0.0452 (8)0.0031 (7)0.0110 (7)−0.0020 (7)
C160.0591 (11)0.0536 (10)0.0671 (11)0.0078 (8)0.0165 (9)−0.0100 (9)
C170.0613 (11)0.0664 (12)0.0635 (11)−0.0070 (9)0.0277 (9)−0.0227 (9)
C180.0688 (11)0.0644 (11)0.0405 (8)−0.0168 (9)0.0203 (8)−0.0109 (8)
C190.0515 (9)0.0438 (8)0.0386 (7)−0.0101 (7)0.0082 (6)−0.0037 (6)
Geometric parameters (Å, º) top
Cl1—C191.7377 (17)C7—H70.9300
O1—N11.2152 (19)C9—C101.492 (2)
O2—N11.214 (2)C9—H9A0.9700
O3—C81.3639 (17)C9—H9B0.9700
O3—C91.4403 (17)C10—C131.3431 (19)
O4—C111.2022 (18)C10—C111.490 (2)
O5—C111.3244 (19)C12—H12A0.9600
O5—C121.444 (2)C12—H12B0.9600
N1—C11.453 (2)C12—H12C0.9600
C1—C21.317 (2)C13—C141.467 (2)
C1—H10.9300C13—H130.9300
C2—C31.455 (2)C14—C191.399 (2)
C2—H20.9300C14—C151.401 (2)
C3—C41.396 (2)C15—C161.379 (2)
C3—C81.408 (2)C15—H150.9300
C4—C51.376 (3)C16—C171.376 (3)
C4—H40.9300C16—H160.9300
C5—C61.374 (3)C17—C181.378 (3)
C5—H50.9300C17—H170.9300
C6—C71.388 (2)C18—C191.381 (2)
C6—H60.9300C18—H180.9300
C7—C81.385 (2)
C8—O3—C9118.21 (11)H9A—C9—H9B108.5
C11—O5—C12116.44 (13)C13—C10—C11121.41 (13)
O2—N1—O1123.12 (17)C13—C10—C9124.41 (13)
O2—N1—C1120.05 (16)C11—C10—C9114.05 (12)
O1—N1—C1116.83 (15)O4—C11—O5123.24 (14)
C2—C1—N1119.47 (15)O4—C11—C10122.99 (15)
C2—C1—H1120.3O5—C11—C10113.77 (12)
N1—C1—H1120.3O5—C12—H12A109.5
C1—C2—C3130.07 (15)O5—C12—H12B109.5
C1—C2—H2115.0H12A—C12—H12B109.5
C3—C2—H2115.0O5—C12—H12C109.5
C4—C3—C8117.89 (15)H12A—C12—H12C109.5
C4—C3—C2117.83 (15)H12B—C12—H12C109.5
C8—C3—C2124.27 (13)C10—C13—C14126.43 (14)
C5—C4—C3121.58 (17)C10—C13—H13116.8
C5—C4—H4119.2C14—C13—H13116.8
C3—C4—H4119.2C19—C14—C15116.54 (14)
C6—C5—C4119.57 (16)C19—C14—C13121.72 (14)
C6—C5—H5120.2C15—C14—C13121.67 (13)
C4—C5—H5120.2C16—C15—C14121.82 (16)
C5—C6—C7120.82 (18)C16—C15—H15119.1
C5—C6—H6119.6C14—C15—H15119.1
C7—C6—H6119.6C17—C16—C15119.73 (17)
C8—C7—C6119.63 (17)C17—C16—H16120.1
C8—C7—H7120.2C15—C16—H16120.1
C6—C7—H7120.2C16—C17—C18120.45 (16)
O3—C8—C7123.89 (14)C16—C17—H17119.8
O3—C8—C3115.62 (13)C18—C17—H17119.8
C7—C8—C3120.49 (14)C17—C18—C19119.40 (16)
O3—C9—C10107.56 (11)C17—C18—H18120.3
O3—C9—H9A110.2C19—C18—H18120.3
C10—C9—H9A110.2C18—C19—C14122.04 (16)
O3—C9—H9B110.2C18—C19—Cl1118.07 (13)
C10—C9—H9B110.2C14—C19—Cl1119.87 (12)
O2—N1—C1—C2−12.4 (2)C12—O5—C11—O4−1.8 (2)
O1—N1—C1—C2167.54 (17)C12—O5—C11—C10177.29 (14)
N1—C1—C2—C3−177.77 (14)C13—C10—C11—O4170.56 (15)
C1—C2—C3—C4169.58 (16)C9—C10—C11—O4−5.5 (2)
C1—C2—C3—C8−11.3 (3)C13—C10—C11—O5−8.5 (2)
C8—C3—C4—C50.8 (2)C9—C10—C11—O5175.47 (12)
C2—C3—C4—C5−179.97 (15)C11—C10—C13—C14179.10 (13)
C3—C4—C5—C6−0.9 (3)C9—C10—C13—C14−5.3 (2)
C4—C5—C6—C70.0 (3)C10—C13—C14—C19139.80 (16)
C5—C6—C7—C81.0 (3)C10—C13—C14—C15−43.5 (2)
C9—O3—C8—C73.4 (2)C19—C14—C15—C16−1.4 (2)
C9—O3—C8—C3−176.32 (12)C13—C14—C15—C16−178.25 (15)
C6—C7—C8—O3179.22 (14)C14—C15—C16—C170.0 (3)
C6—C7—C8—C3−1.0 (2)C15—C16—C17—C181.0 (3)
C4—C3—C8—O3179.92 (13)C16—C17—C18—C19−0.4 (3)
C2—C3—C8—O30.8 (2)C17—C18—C19—C14−1.1 (2)
C4—C3—C8—C70.2 (2)C17—C18—C19—Cl1177.47 (13)
C2—C3—C8—C7−178.99 (14)C15—C14—C19—C182.0 (2)
C8—O3—C9—C10174.75 (12)C13—C14—C19—C18178.82 (14)
O3—C9—C10—C13100.78 (15)C15—C14—C19—Cl1−176.57 (12)
O3—C9—C10—C11−83.34 (14)C13—C14—C19—Cl10.3 (2)
Hydrogen-bond geometry (Å, º) top
Cg2 is the centroid of the C14–C19 ring.
D—H···AD—HH···AD···AD—H···A
C12—H12A···O1i0.962.453.406 (2)172
C2—H2···Cl1ii0.932.853.7515 (16)165
C13—H13···Cg2iii0.932.913.5828 (16)130
Symmetry codes: (i) −x+5/2, y−1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+2, −y+1, −z−3.
(II) Methyl (E)-2-({4-chloro-2-[(E)-2-nitrovinyl]phenoxy}methyl)-3-(2-chlorophenyl)acrylate top
Crystal data top
C19H15Cl2NO5F(000) = 840
Mr = 408.22Dx = 1.402 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.2372 (3) ÅCell parameters from 2355 reflections
b = 14.5027 (5) Åθ = 2.0–25.0°
c = 14.4830 (5) ŵ = 0.37 mm−1
β = 94.521 (2)°T = 293 K
V = 1934.17 (11) Å3Block, yellow
Z = 40.28 × 0.22 × 0.19 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		3481 independent reflections
Radiation source: fine-focus sealed tube2382 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω and φ scansθmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −11→10
Tmin = 0.942, Tmax = 0.961k = −14→17
12108 measured reflectionsl = −12→17
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.143 w = 1/[σ2(Fo2) + (0.0555P)2 + 1.4111P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3481 reflectionsΔρmax = 0.56 e Å−3
245 parametersΔρmin = −0.31 e Å−3
Crystal data top
C19H15Cl2NO5V = 1934.17 (11) Å3
Mr = 408.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.2372 (3) ŵ = 0.37 mm−1
b = 14.5027 (5) ÅT = 293 K
c = 14.4830 (5) Å0.28 × 0.22 × 0.19 mm
β = 94.521 (2)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer		3481 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		2382 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.961Rint = 0.029
12108 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.04Δρmax = 0.56 e Å−3
3481 reflectionsΔρmin = −0.31 e Å−3
245 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.17238 (14)0.12004 (8)1.07720 (8)0.0933 (4)
Cl20.41061 (13)0.09022 (7)0.31090 (6)0.0812 (4)
O10.9540 (3)0.1694 (2)0.8133 (2)0.0860 (9)
O20.9968 (3)0.1892 (2)0.6721 (2)0.0870 (9)
O30.46144 (19)0.15787 (14)0.71181 (12)0.0405 (5)
O40.4419 (3)0.35608 (16)0.93013 (16)0.0679 (7)
O50.4219 (3)0.35463 (15)0.77613 (15)0.0611 (6)
N10.9138 (3)0.17359 (19)0.7312 (2)0.0577 (7)
C10.7610 (3)0.1607 (2)0.7049 (2)0.0490 (8)
H10.69420.15980.74970.059*
C20.7171 (3)0.1501 (2)0.6157 (2)0.0457 (7)
H20.79040.15160.57530.055*
C30.5725 (3)0.13660 (19)0.5727 (2)0.0403 (7)
C40.5582 (4)0.1206 (2)0.4764 (2)0.0497 (8)
H40.64070.11860.44370.060*
C50.4247 (4)0.1082 (2)0.4307 (2)0.0500 (8)
C60.3012 (4)0.1102 (2)0.4768 (2)0.0516 (8)
H60.21110.10070.44490.062*
C70.3112 (3)0.1264 (2)0.5709 (2)0.0439 (7)
H70.22710.12820.60220.053*
C80.4440 (3)0.13990 (18)0.61909 (18)0.0356 (7)
C90.3311 (3)0.1789 (2)0.75710 (19)0.0405 (7)
H9A0.27330.12360.76220.049*
H9B0.27320.22410.72120.049*
C100.3751 (3)0.2162 (2)0.85085 (19)0.0383 (7)
C110.4169 (3)0.3154 (2)0.8587 (2)0.0446 (7)
C120.4565 (5)0.4514 (2)0.7742 (3)0.0754 (11)
H12A0.39270.48470.81140.113*
H12B0.44480.47340.71160.113*
H12C0.55530.46050.79850.113*
C130.3713 (3)0.1683 (2)0.9294 (2)0.0427 (7)
H130.39370.20040.98420.051*
C140.3356 (3)0.0703 (2)0.93813 (19)0.0450 (7)
C150.3945 (4)0.0031 (2)0.8832 (2)0.0538 (8)
H150.45630.02070.83860.065*
C160.3629 (4)−0.0887 (2)0.8939 (3)0.0682 (11)
H160.4031−0.13260.85670.082*
C170.2720 (5)−0.1158 (3)0.9593 (3)0.0780 (12)
H170.2501−0.17790.96610.094*
C180.2140 (5)−0.0517 (3)1.0146 (3)0.0744 (11)
H180.1525−0.07021.05890.089*
C190.2458 (4)0.0402 (2)1.0050 (2)0.0570 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1329 (10)0.0784 (7)0.0764 (7)−0.0237 (7)0.0577 (7)−0.0153 (5)
Cl20.1300 (9)0.0795 (7)0.0346 (5)−0.0058 (6)0.0091 (5)−0.0058 (4)
O10.0641 (17)0.111 (2)0.080 (2)−0.0158 (16)−0.0138 (15)0.0255 (17)
O20.0459 (14)0.121 (2)0.097 (2)−0.0142 (15)0.0225 (14)−0.0075 (18)
O30.0360 (11)0.0520 (12)0.0340 (10)0.0031 (9)0.0067 (8)−0.0017 (9)
O40.0971 (19)0.0564 (15)0.0523 (14)−0.0270 (14)0.0186 (13)−0.0149 (12)
O50.0910 (18)0.0397 (13)0.0527 (14)−0.0054 (12)0.0057 (12)0.0067 (11)
N10.0494 (17)0.0518 (18)0.072 (2)−0.0018 (14)0.0060 (16)0.0078 (15)
C10.0341 (17)0.052 (2)0.062 (2)−0.0015 (14)0.0099 (14)0.0064 (16)
C20.0455 (18)0.0397 (17)0.0544 (19)0.0011 (14)0.0196 (15)0.0049 (15)
C30.0478 (18)0.0326 (16)0.0416 (16)−0.0009 (13)0.0106 (13)0.0023 (13)
C40.066 (2)0.0406 (18)0.0448 (18)−0.0007 (16)0.0217 (16)0.0034 (14)
C50.074 (2)0.0439 (18)0.0320 (16)0.0014 (17)0.0050 (16)−0.0006 (14)
C60.060 (2)0.050 (2)0.0435 (18)0.0034 (16)−0.0073 (15)−0.0039 (15)
C70.0419 (17)0.0498 (19)0.0401 (16)0.0021 (14)0.0038 (13)−0.0024 (14)
C80.0437 (17)0.0301 (15)0.0338 (15)0.0027 (13)0.0071 (12)0.0016 (12)
C90.0373 (16)0.0442 (17)0.0408 (16)0.0020 (13)0.0078 (12)0.0006 (13)
C100.0316 (15)0.0443 (18)0.0398 (16)−0.0006 (13)0.0068 (12)−0.0044 (13)
C110.0441 (18)0.0423 (18)0.0490 (19)−0.0011 (14)0.0135 (14)−0.0017 (15)
C120.097 (3)0.044 (2)0.086 (3)−0.006 (2)0.010 (2)0.014 (2)
C130.0477 (18)0.0420 (18)0.0390 (16)−0.0032 (14)0.0070 (13)−0.0064 (14)
C140.0535 (19)0.0444 (18)0.0364 (16)−0.0044 (15)−0.0019 (14)−0.0008 (14)
C150.066 (2)0.047 (2)0.0475 (18)0.0009 (17)0.0032 (16)−0.0035 (16)
C160.091 (3)0.046 (2)0.066 (2)0.004 (2)−0.005 (2)−0.0083 (18)
C170.113 (4)0.039 (2)0.079 (3)−0.018 (2)−0.009 (3)0.007 (2)
C180.102 (3)0.061 (3)0.061 (2)−0.030 (2)0.011 (2)0.007 (2)
C190.075 (2)0.054 (2)0.0432 (18)−0.0142 (18)0.0092 (16)−0.0003 (16)
Geometric parameters (Å, º) top
Cl1—C191.734 (4)C7—H70.9300
Cl2—C51.749 (3)C9—C101.488 (4)
O1—N11.220 (4)C9—H9A0.9700
O2—N11.215 (4)C9—H9B0.9700
O3—C81.365 (3)C10—C131.336 (4)
O3—C91.448 (3)C10—C111.491 (4)
O4—C111.198 (4)C12—H12A0.9600
O5—C111.328 (4)C12—H12B0.9600
O5—C121.440 (4)C12—H12C0.9600
N1—C11.444 (4)C13—C141.467 (4)
C1—C21.332 (4)C13—H130.9300
C1—H10.9300C14—C191.393 (4)
C2—C31.442 (4)C14—C151.396 (4)
C2—H20.9300C15—C161.374 (5)
C3—C41.409 (4)C15—H150.9300
C3—C81.410 (4)C16—C171.372 (6)
C4—C51.365 (5)C16—H160.9300
C4—H40.9300C17—C181.364 (6)
C5—C61.367 (5)C17—H170.9300
C6—C71.379 (4)C18—C191.374 (5)
C6—H60.9300C18—H180.9300
C7—C81.378 (4)
C8—O3—C9116.6 (2)H9A—C9—H9B108.4
C11—O5—C12117.3 (3)C13—C10—C9124.4 (3)
O2—N1—O1122.4 (3)C13—C10—C11117.5 (3)
O2—N1—C1119.8 (3)C9—C10—C11118.0 (2)
O1—N1—C1117.8 (3)O4—C11—O5123.3 (3)
C2—C1—N1119.1 (3)O4—C11—C10124.9 (3)
C2—C1—H1120.4O5—C11—C10111.8 (3)
N1—C1—H1120.4O5—C12—H12A109.5
C1—C2—C3129.5 (3)O5—C12—H12B109.5
C1—C2—H2115.3H12A—C12—H12B109.5
C3—C2—H2115.3O5—C12—H12C109.5
C4—C3—C8117.4 (3)H12A—C12—H12C109.5
C4—C3—C2117.5 (3)H12B—C12—H12C109.5
C8—C3—C2125.1 (3)C10—C13—C14126.8 (3)
C5—C4—C3120.8 (3)C10—C13—H13116.6
C5—C4—H4119.6C14—C13—H13116.6
C3—C4—H4119.6C19—C14—C15117.3 (3)
C4—C5—C6121.1 (3)C19—C14—C13120.9 (3)
C4—C5—Cl2119.7 (3)C15—C14—C13121.8 (3)
C6—C5—Cl2119.2 (3)C16—C15—C14121.1 (3)
C5—C6—C7119.5 (3)C16—C15—H15119.5
C5—C6—H6120.2C14—C15—H15119.5
C7—C6—H6120.2C17—C16—C15120.2 (4)
C8—C7—C6120.9 (3)C17—C16—H16119.9
C8—C7—H7119.6C15—C16—H16119.9
C6—C7—H7119.6C18—C17—C16120.0 (3)
O3—C8—C7123.9 (2)C18—C17—H17120.0
O3—C8—C3115.9 (2)C16—C17—H17120.0
C7—C8—C3120.2 (3)C17—C18—C19120.3 (4)
O3—C9—C10108.2 (2)C17—C18—H18119.8
O3—C9—H9A110.1C19—C18—H18119.8
C10—C9—H9A110.1C18—C19—C14121.1 (3)
O3—C9—H9B110.1C18—C19—Cl1119.3 (3)
C10—C9—H9B110.1C14—C19—Cl1119.5 (3)
O2—N1—C1—C211.6 (5)O3—C9—C10—C1181.2 (3)
O1—N1—C1—C2−169.3 (3)C12—O5—C11—O4−1.3 (5)
N1—C1—C2—C3−179.8 (3)C12—O5—C11—C10178.1 (3)
C1—C2—C3—C4−175.6 (3)C13—C10—C11—O4−2.9 (5)
C1—C2—C3—C85.8 (5)C9—C10—C11—O4173.0 (3)
C8—C3—C4—C5−0.5 (4)C13—C10—C11—O5177.7 (3)
C2—C3—C4—C5−179.3 (3)C9—C10—C11—O5−6.3 (4)
C3—C4—C5—C6−0.4 (5)C9—C10—C13—C145.3 (5)
C3—C4—C5—Cl2179.1 (2)C11—C10—C13—C14−179.0 (3)
C4—C5—C6—C71.0 (5)C10—C13—C14—C19−137.2 (3)
Cl2—C5—C6—C7−178.5 (2)C10—C13—C14—C1545.7 (4)
C5—C6—C7—C8−0.5 (5)C19—C14—C15—C161.1 (5)
C9—O3—C8—C7−10.8 (4)C13—C14—C15—C16178.3 (3)
C9—O3—C8—C3168.6 (2)C14—C15—C16—C170.0 (5)
C6—C7—C8—O3178.8 (3)C15—C16—C17—C18−0.6 (6)
C6—C7—C8—C3−0.5 (4)C16—C17—C18—C190.0 (6)
C4—C3—C8—O3−178.3 (2)C17—C18—C19—C141.1 (6)
C2—C3—C8—O30.3 (4)C17—C18—C19—Cl1−179.1 (3)
C4—C3—C8—C71.0 (4)C15—C14—C19—C18−1.7 (5)
C2—C3—C8—C7179.7 (3)C13—C14—C19—C18−178.9 (3)
C8—O3—C9—C10−167.7 (2)C15—C14—C19—Cl1178.6 (2)
O3—C9—C10—C13−103.1 (3)C13—C14—C19—Cl11.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O4i0.932.563.371 (4)146
C7—H7···O2ii0.932.583.476 (4)161
C18—H18···O1iii0.932.603.485 (5)160
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, º) for (I) top
Cg2 is the centroid of the C14–C19 ring.
D—H···AD—HH···AD···AD—H···A
C12—H12A···O1i0.962.453.406 (2)172
C2—H2···Cl1ii0.932.853.7515 (16)165
C13—H13···Cg2iii0.932.913.5828 (16)130
Symmetry codes: (i) −x+5/2, y−1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+2, −y+1, −z−3.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O4i0.932.563.371 (4)146
C7—H7···O2ii0.932.583.476 (4)161
C18—H18···O1iii0.932.603.485 (5)160
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) −x+1, −y, −z+2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H16ClNO5C19H15Cl2NO5
Mr373.78408.22
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)293293
a, b, c (Å)9.0152 (3), 13.6579 (4), 14.6366 (4)9.2372 (3), 14.5027 (5), 14.4830 (5)
β (°) 102.176 (1) 94.521 (2)
V (Å3)1761.64 (9)1934.17 (11)
Z44
Radiation typeMo KαMo Kα
µ (mm−1)0.250.37
Crystal size (mm)0.27 × 0.24 × 0.180.28 × 0.22 × 0.19
Data collection
DiffractometerBruker Kappa APEXII CCDBruker Kappa APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)		Multi-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.935, 0.9350.942, 0.961
No. of measured, independent and
observed [I > 2σ(I)] reflections		15968, 4365, 3186 12108, 3481, 2382
Rint0.0190.029
(sin θ/λ)max (Å−1)0.6670.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.109, 1.04 0.055, 0.143, 1.04
No. of reflections43653481
No. of parameters236245
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.23, −0.230.56, −0.31

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

 

Acknowledgements

The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.

References

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ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 261-265
doi:10.1107/S2056989016001493
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