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 253-256
doi:10.1107/S2056989016001444

Crystal structure of di­ethyl 3-(3-chloro­phen­yl)-2,2-di­cyano­cyclo­propane-1,1-di­carboxyl­ate

CROSSMARK_Color_square_no_text.svg
Nóra Veronika May,a* Gyula Tamás Gál,a Zsolt Rapib and Péter Bakób

aInstitute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, H-1519 Budapest, POB 206, Hungary, and bDepartment of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1521 Budapest, POB 91, Hungary
*Correspondence e-mail: may.nora@ttk.mta.hu

Edited by G. Smith, Queensland University of Technology, Australia (Received 19 November 2015; accepted 22 January 2016; online 27 January 2016)

In the racemic title compound, C17H15ClN2O4, which has been synthesized and the crystal structure of the solvent-free mol­ecule determined, the angle between the planes of the benzene and cyclo­propane rings is 54.29 (10)°. The mol­ecular conformation is stabilized by two weak intra­molecular C—H⋯Ocarbox­yl inter­actions. In the crystal, C—H⋯O hydrogen bonds form centrosymmetric cyclic R22(10) dimers which are linked into chain substructures extending along c. Further C—H⋯Nnitrile hydrogen bonding, including a centrosymmetric cyclic R22(14) association, link the chain substructures, forming a two-dimensional layered structure extending across the approximate ab plane. No significant π–π or halogen–halogen inter­molecular inter­actions are present in the crystal.

CCDC reference: 1449224

1. Chemical context

The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated car­bonyl compounds is one of the most useful methods of remote functionalization in organic synthesis (Mather et al., 2006[Mather, B. D., Viswanathan, K., Miller, K. M. & Long, T. E. (2006). Prog. Polym. Sci. 31, 487-531.]; Little et al., 1995[Little, R. D., Masjedizadeh, M. R., Wallquist, O. & McLoughlin, J. I. (1995). Org. React. 47, 315-552.]). The Michael Initiated Ring Closure (MIRC) reaction represents an elegant approach which has been applied extensively for the construction of cyclo­propane derivatives (Zheng et al., 2005[Zheng, J.-C., Liao, W.-W., Tang, Y., Sun, X.-L. & Dai, L.-X. (2005). J. Am. Chem. Soc. 127, 12222-12223.]; Aggarwal & Grange, 2006[Aggarwal, V. K. & Grange, E. (2006). Chem. Eur. J. 12, 568-575.]). The cyclo­propane ring is an important building moiety for a large number of biologically active compounds and are subunits found in many natural products, so that the development of novel methods to provide new cyclo­propane derivatives is a challenge. The MIRC reaction strategy may also be utilized through a one-pot multicomponent reaction which has gained inter­est among synthetic organic chemists recently (Riches et al., 2010[Riches, S. L., Saha, C., Filgueira, N. F., Grange, E., McGarrigle, E. M. & Aggarwal, V. K. (2010). J. Am. Chem. Soc. 132, 7626-7630.]). Many phase-transfer-catalyzed methods have been developed for the Michael reaction that are simple and environmentally friendly (Shioiri, 1997[Shioiri, T. (1997). In Handbook of Phase-Transfer Catalysis, edited by Y. Sasson & R. Neumann. London: Blackie Academic & Professional.]). We have developed a new phase-transfer-catalyzed method for the MIRC reaction that is both simple and environmentally friendly. The novel title compound, C17H15ClN2O4, was prepared in good yield in such a reaction using a sugar-based crown ether as the catalyst (Bakó et al., 2015[Bakó, P., Rapi, Z., Grün, A., Nemcsók, T., Hegedűs, L. & Keglevich, G. (2015). Synlett, 26, 1847-1851.]).

[Scheme 1]

2. Structural commentary

In the mol­ecular structure of the title compound (Fig. 1[link]), atom C3 is a chiral centre, but the racemic mixture crystallizes in the centrosymmetric space group P21/c. The dihedral angle between the planes of the benzene and cyclo­propane rings is 54.29 (10)°, while the conformation is stabilized by two intra­molecular C—H⋯Ocarbox­yl inter­actions, a weak C9—H⋯O1 hydrogen bond (Table 1[link]) and a short intramolecular C3⋯O4 inter­action [2.8447 (16) Å] (Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C9—H9⋯O1 0.95 2.59 3.3529 (15) 138
C3—H3⋯O4i 1.00 2.45 3.1419 (16) 126
C15—H15C⋯O3ii 0.98 2.63 3.5656 (18) 161
C5—H5⋯N2iii 0.95 2.61 3.4621 (18) 150
C11—H11B⋯N1iv 0.99 2.63 3.3337 (17) 128
Symmetry codes: (i) -x, -y+1, -z+1; (ii) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) -x, -y, -z+1; (iv) x+1, y, z.
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom numbering. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
The four mol­ecules in the unit cell of the title compound, with the intra­molecular inter­actions shown as dashed lines.

3. Supra­molecular features

In the crystal, C3—H⋯O4i hydrogen bonds (Table 1[link]) form inversion dimers having a graph-set descriptor R22(10) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]), and are linked into chain substructures extending along c through weak C15—H⋯O3ii hydrogen bonds (Fig. 3[link]). These chain substructures are further linked through centrosymmetric cyclic R22(14) C5—H⋯N2iii and C11—H⋯N1iv hydrogen-bonding inter­actions to nitrile N-atom acceptors, forming a two-dimensional layered structure extending across the approximate ab plane (Fig. 4[link]). Although the mol­ecule contains an aromatic ring and a Cl atom, there are no significant π–π or halogen–halogen inter­actions in the crystal structure. The relatively high calculated density (1.383 Mg m−3) and the Kitaigorodskii packing index (KPI = 69.1) (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) show tight packing of the mol­ecules in the unit cell, which results in no residual solvent-accessible voids in the crystal.

[Figure 3]
Figure 3
The one-dimensional chain polymer substructures in the title compound involving centrosymmetric cyclic C3—H⋯O4i and C15–H⋯O3ii hydrogen bonds (shown as dashed lines). For symmetry codes, see Table 1[link].
[Figure 4]
Figure 4
The two-dimensional sheet-like structure in the title compound, showing the centrosymmetric C5—H⋯N2iii and C11—H⋯N1iv hydrogen-bond extensions. For symmetry codes, see Table 1[link].

4. Database survey

The crystal structure of many substituted phenyl­cyclo­propane derivatives have already been studied from which four closely related structures were chosen to compare the mol­ecular structures with the title compound. In the most relevant structures, the dihedral angle between the cyclo­propane and benzene rings was found to be very similar. For 1-cyano-3,3-dimethyl-r-2-m-nitro­phenyl-t-1-phenyl­cyclo­propane [Cam­bridge Structural Database (CSD; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) refcode GAHYOD; Tinant et al., 1988[Tinant, B., Wu, S., Declercq, J.-P., van Meerssche, M., Leroy, G. & Weiler, J. (1988). New J. Chem. 12, 53-57.]], this value is 47.6°, for 2-(2,2-di­cyano­vin­yl)-cis-1,3-diphenyl-cis-1,2-diiso­propyl­cyclopropane (KANFOU; Zimmerman & Cassel, 1989[Zimmerman, H. E. & Cassel, J. M. (1989). J. Org. Chem. 54, 3800-3816.]) it is 50.8°, for diethyl 1,2-di­cyano-3-phenylcyclo­propane-1,2-di­carboxyl­ate (PEXFAZ; Elinson et al., 1993[Elinson, M. N., Lizunova, T. L., Ugrak, B. I., Dekaprilevich, M. O., Nikishin, G. I. & Struchkov, Y. T. (1993). Tetrahedron Lett. 34, 5795-5798.]) it is 48.0° and for (E)-trimethyl 2-cyano-3-phenyl­cyclo­propane-1,1,2-tri­carboxyl­ate (YEQSOC01; Elinson et al., 2006[Elinson, M. N., Feducovich, S. K., Starikova, Z. A., Vereshchagin, A. N., Belyakov, P. A. & Nikishin, G. I. (2006). Tetrahedron, 62, 3989-3996.]) it is 49.2°. This suggests that although the benzene ring is capable of rotation about the C—C bond, the groups in close proximity on the other two cyclo­propane C atoms enforce this 47–53° angle between the planes of the cyclo­propane and benzene rings.

5. Synthesis and crystallization

The title compound was synthesized by the reaction of 2-(3-chloro­benzyl­idene)malono­nitrile with diethyl 2-bromo­mal­on­ate under phase-transfer conditions. The reaction was carried out in a solid/liquid two-phase system [Na2CO3/tetra­hydro­furan (THF)] in the presence of a gluco­pyran­oside-based crown ether as the catalyst. The compound was isolated by preparative thin-layer chromatography (TLC) (silica gel) in good yield (m.p. 355–357 K). The chemical structure of the compound was confirmed by 1H, 13C NMR and mass spectroscopies. The details of the synthesis were reported previously (Bakó et al., 2015[Bakó, P., Rapi, Z., Grün, A., Nemcsók, T., Hegedűs, L. & Keglevich, G. (2015). Synlett, 26, 1847-1851.]). Single crystals suitable for X-ray diffraction analysis were obtained by crystallization from ethanol.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were located in difference electron-density maps but were included in the structure refinement at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).

Table 2
Experimental details

Crystal data
Chemical formula C17H15ClN2O4
Mr 346.76
Crystal system, space group Monoclinic, P21/c
Temperature (K) 103
a, b, c (Å) 8.9221 (6), 9.1927 (7), 20.3446 (16)
β (°) 93.829 (2)
V (Å3) 1664.9 (2)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.25
Crystal size (mm) 0.50 × 0.25 × 0.25
 
Data collection
Diffractometer R-AXIS RAPID
Absorption correction empirical (NUMABS; Higashi, 2002[Higashi, T. (2002). NUMABS. Rigaku/MSC Inc., Tokyo, Japan.])
Tmin, Tmax 0.755, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 57969, 5052, 4312
Rint 0.042
(sin θ/λ)max (Å−1) 0.714
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.113, 1.11
No. of reflections 5052
No. of parameters 219
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.49, −0.31
Computer programs: CrystalClear (Rigaku/MSC, 2008[Rigaku/MSC (2008). CrystalClear. Rigaku/MSC Inc., Tokyo, Japan.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]).

Supporting information

CCDC reference: 1449224

Crystal structure: contains datablocks I, header. DOI: 10.1107/S2056989016001444/zs2355sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016001444/zs2355Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989016001444/zs2355Isup3.cml

checkCIF report


Chemical context top

The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated carbonyl compounds is one of the most useful methods of remote functionalization in organic synthesis (Mather et al., 2006; Little et al., 1995). The Michael Initiated Ring Closure (MIRC) reaction represents an elegant approach which has been applied extensively for the construction of cyclo­propane derivatives (Zheng et al., 2005; Aggarwal & Grange, 2006). The cyclo­propane ring is an important building moiety for a large number of biologically active compounds and are subunits found in many natural products, so that the development of novel methods to provide new cyclo­propane derivatives is a challenge. The MIRC reaction strategy may also be utilized through a one-pot multicomponent reaction which has gained inter­est among the synthetic organic chemists recently (Riches et al., 2010). Many phase-transfer catalyzed methods have been developed for the Michael reaction, that are simple and environmentally friendly (Shioiri, 1997). We have developed a new phase-transfer catalyzed method for the MIRC reaction that is both simple and environmentally friendly. This new compound, C17H15ClN2O4, was prepared in a good yield in such a reaction using a sugar-based crown ether as the catalyst (Bakó et al., 2015).

Structural commentary top

In the molecular structure of the title compound (Fig. 1), atom C3 is a chiral centre, but the racemic mixture crystallizes in the centrosymmetric space group P21/c. The dihedral angle between the planes of the benzene and cyclo­propane rings is 54.29 (10)°, while the conformation is stabilized by two intra­molecular C—H···Ocarboxyl inter­actions, a weak C9—H···O1 hydrogen bond (Table 1) and a short C3—H···O4 inter­action [2.8447 (16) Å] (Fig. 2).

Supra­molecular features top

In the crystal, C3—H···O4i hydrogen bonds (Table 1) form centrosymmetric cyclic dimers having a graph-set descriptor R22(10) (Bernstein et al., 1995), and are linked into chain substructures extending along c through weak C15—H···O3ii hydrogen bonds (Fig. 3). These chain substructures are further linked through centrosymmetric cyclic R22(14) C5—H···N2iii and C11—H···N1iv hydrogen-bonding inter­actions to nitrile N-atom acceptors, forming a two-dimensional layered structure extending across the approximate ab plane (Fig. 4). Although the molecule contains an aromatic ring and a Cl atom there are no significant π–π or halogen–halogen inter­actions in the crystal structure. The relatively high calculated density (1.383 Mg m−3) and the Kitaigorodskii packing index (KPI = 69.1) (Spek, 2009) show tight packing of the molecules in the unit cell, which results in no residual solvent-accessible voids in the crystal.

Database survey top

\ The crystal structure of many substituted phenyl­cyclo­propane derivatives have already been studied from which four closely related structures were chosen to compare the molecular structures with the title compound. In the most relevant structures, the dihedral angle between the cyclo­propane and benzene rings was found to be very similar. For 1-cyano-3,3-di­methyl-r-2-m-nitro­phenyl-t-1-\ phenyl­cyclo­propane [Cambridge Structural Database (CSD; Groom & Allen, 2014) refcode GAHYOD; Tinant et al., 1988], this value is 47.6°, for 2-(2,2-di­cyano­vinyl)-cis-1,3-di­phenyl-cis-1,2-di-\ iso­propyl­cyclo­propane (KANFOU; Zimmerman & Cassel, 1989) it is 50.8°, for di­ethyl 3-phenyl-1,2-di­cyano­cyclo­propane-1,2-di­carboxyl­ate (PEXFAZ; Elinson et al., 1993) it is 48.0° and for (E)-tri­methyl 2-cyano-3-phenyl­cyclo­propane-1,1,2-tri­carboxyl­ate (YEQSOC01; Elinson et al., 2006) it is 49.2°. This suggests that although the benzene ring is capable of rotation about the C—C bond, the groups in close proximity on the other two cyclo­propane carbon atoms enforce this 47–53° angle between the planes of the cyclo­propane and the benzene rings.

Synthesis and crystallization top

The title compound was synthesized by the reaction of 2-(3-chloro­benzyl­idene)malono­nitrile with di­ethyl 2-bromo­malonate under phase-transfer conditions. The reaction was carried out in a solid/liquid two-phase system [Na2CO3/tetra­hydro­furan (THF)] in the presence of a gluco­pyran­oside-based crown ether as the catalyst. The compound was isolated by preparative thin-layer chromatography (TLC) (silica gel) in good yield (m.p. 355–357 K). The chemical structure of the compound was confirmed by 1H, 13C NMR and mass spectroscopies. The details of the synthesis were reported previously (Bakó et al., 2015). Single crystals suitable for the X-ray diffraction analysis were obtained by crystallization from ethanol.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were located in the difference electron-density maps but were included in the structure refinement at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).

Structure description top

The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated carbonyl compounds is one of the most useful methods of remote functionalization in organic synthesis (Mather et al., 2006; Little et al., 1995). The Michael Initiated Ring Closure (MIRC) reaction represents an elegant approach which has been applied extensively for the construction of cyclo­propane derivatives (Zheng et al., 2005; Aggarwal & Grange, 2006). The cyclo­propane ring is an important building moiety for a large number of biologically active compounds and are subunits found in many natural products, so that the development of novel methods to provide new cyclo­propane derivatives is a challenge. The MIRC reaction strategy may also be utilized through a one-pot multicomponent reaction which has gained inter­est among the synthetic organic chemists recently (Riches et al., 2010). Many phase-transfer catalyzed methods have been developed for the Michael reaction, that are simple and environmentally friendly (Shioiri, 1997). We have developed a new phase-transfer catalyzed method for the MIRC reaction that is both simple and environmentally friendly. This new compound, C17H15ClN2O4, was prepared in a good yield in such a reaction using a sugar-based crown ether as the catalyst (Bakó et al., 2015).

In the molecular structure of the title compound (Fig. 1), atom C3 is a chiral centre, but the racemic mixture crystallizes in the centrosymmetric space group P21/c. The dihedral angle between the planes of the benzene and cyclo­propane rings is 54.29 (10)°, while the conformation is stabilized by two intra­molecular C—H···Ocarboxyl inter­actions, a weak C9—H···O1 hydrogen bond (Table 1) and a short C3—H···O4 inter­action [2.8447 (16) Å] (Fig. 2).

In the crystal, C3—H···O4i hydrogen bonds (Table 1) form centrosymmetric cyclic dimers having a graph-set descriptor R22(10) (Bernstein et al., 1995), and are linked into chain substructures extending along c through weak C15—H···O3ii hydrogen bonds (Fig. 3). These chain substructures are further linked through centrosymmetric cyclic R22(14) C5—H···N2iii and C11—H···N1iv hydrogen-bonding inter­actions to nitrile N-atom acceptors, forming a two-dimensional layered structure extending across the approximate ab plane (Fig. 4). Although the molecule contains an aromatic ring and a Cl atom there are no significant π–π or halogen–halogen inter­actions in the crystal structure. The relatively high calculated density (1.383 Mg m−3) and the Kitaigorodskii packing index (KPI = 69.1) (Spek, 2009) show tight packing of the molecules in the unit cell, which results in no residual solvent-accessible voids in the crystal.

\ The crystal structure of many substituted phenyl­cyclo­propane derivatives have already been studied from which four closely related structures were chosen to compare the molecular structures with the title compound. In the most relevant structures, the dihedral angle between the cyclo­propane and benzene rings was found to be very similar. For 1-cyano-3,3-di­methyl-r-2-m-nitro­phenyl-t-1-\ phenyl­cyclo­propane [Cambridge Structural Database (CSD; Groom & Allen, 2014) refcode GAHYOD; Tinant et al., 1988], this value is 47.6°, for 2-(2,2-di­cyano­vinyl)-cis-1,3-di­phenyl-cis-1,2-di-\ iso­propyl­cyclo­propane (KANFOU; Zimmerman & Cassel, 1989) it is 50.8°, for di­ethyl 3-phenyl-1,2-di­cyano­cyclo­propane-1,2-di­carboxyl­ate (PEXFAZ; Elinson et al., 1993) it is 48.0° and for (E)-tri­methyl 2-cyano-3-phenyl­cyclo­propane-1,1,2-tri­carboxyl­ate (YEQSOC01; Elinson et al., 2006) it is 49.2°. This suggests that although the benzene ring is capable of rotation about the C—C bond, the groups in close proximity on the other two cyclo­propane carbon atoms enforce this 47–53° angle between the planes of the cyclo­propane and the benzene rings.

Synthesis and crystallization top

The title compound was synthesized by the reaction of 2-(3-chloro­benzyl­idene)malono­nitrile with di­ethyl 2-bromo­malonate under phase-transfer conditions. The reaction was carried out in a solid/liquid two-phase system [Na2CO3/tetra­hydro­furan (THF)] in the presence of a gluco­pyran­oside-based crown ether as the catalyst. The compound was isolated by preparative thin-layer chromatography (TLC) (silica gel) in good yield (m.p. 355–357 K). The chemical structure of the compound was confirmed by 1H, 13C NMR and mass spectroscopies. The details of the synthesis were reported previously (Bakó et al., 2015). Single crystals suitable for the X-ray diffraction analysis were obtained by crystallization from ethanol.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were located in the difference electron-density maps but were included in the structure refinement at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom numbering. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The four molecules in the unit cell of the title compound, with the intramolecular interactions shown as dashed lines.
[Figure 3] Fig. 3. The one-dimensional chain polymer substructures in the title compound involving centrosymmetric cyclic C3—H···O4i and C15–H···O3ii hydrogen bonds (shown as dashed lines). For symmetry codes, see Table 2.
[Figure 4] Fig. 4. The two-dimensional sheet-like structure in the title compound, showing the centrosymmetric C5—H···N2iii and C11—H···N1iv hydrogen-bond extensions. For symmetry codes, see Table 2.
Diethyl 3-(3-chlorophenyl)-2,2-dicyanocyclopropane-1,1-dicarboxylate top
Crystal data top
C17H15ClN2O4Dx = 1.383 Mg m−3
Mr = 346.76Melting point = 355–357 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.9221 (6) ÅCell parameters from 37218 reflections
b = 9.1927 (7) Åθ = 3.0–30.5°
c = 20.3446 (16) ŵ = 0.25 mm−1
β = 93.829 (2)°T = 103 K
V = 1664.9 (2) Å3Block, colorless
Z = 40.50 × 0.25 × 0.25 mm
F(000) = 720
Data collection top
RAXIS-RAPID
diffractometer		5052 independent reflections
Radiation source: sealed tube4312 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 10.0000 pixels mm-1θmax = 30.5°, θmin = 3.0°
dtprofit.ref scansh = −12→12
Absorption correction: empirical (using intensity measurements)
(NUMABS; Higashi, 2002)		k = −13→13
Tmin = 0.755, Tmax = 1.000l = −29→29
57969 measured reflections
Refinement top
Refinement on F2Primary atom site location: difference Fourier map
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: difference Fourier map
wR(F2) = 0.113H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0475P)2 + 0.9362P]
where P = (Fo2 + 2Fc2)/3
5052 reflections(Δ/σ)max = 0.001
219 parametersΔρmax = 0.49 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C17H15ClN2O4V = 1664.9 (2) Å3
Mr = 346.76Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.9221 (6) ŵ = 0.25 mm−1
b = 9.1927 (7) ÅT = 103 K
c = 20.3446 (16) Å0.50 × 0.25 × 0.25 mm
β = 93.829 (2)°
Data collection top
RAXIS-RAPID
diffractometer		5052 independent reflections
Absorption correction: empirical (using intensity measurements)
(NUMABS; Higashi, 2002)		4312 reflections with I > 2σ(I)
Tmin = 0.755, Tmax = 1.000Rint = 0.042
57969 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.11Δρmax = 0.49 e Å−3
5052 reflectionsΔρmin = −0.31 e Å−3
219 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
Cl10.28965 (4)−0.00643 (4)0.66880 (2)0.02905 (10)
O30.08826 (11)0.51460 (10)0.31362 (4)0.02054 (19)
O10.39223 (10)0.41867 (10)0.35507 (4)0.01960 (19)
O20.29321 (11)0.19550 (11)0.33457 (5)0.0237 (2)
O40.04757 (12)0.59834 (11)0.41513 (5)0.0240 (2)
N1−0.21756 (13)0.33382 (14)0.43288 (6)0.0254 (2)
N20.10162 (14)−0.01960 (13)0.42424 (6)0.0250 (2)
C130.09652 (14)0.50931 (13)0.37904 (6)0.0167 (2)
C16−0.09432 (14)0.29951 (14)0.43266 (6)0.0181 (2)
C30.17943 (13)0.34622 (13)0.47595 (6)0.0156 (2)
H30.13500.42760.50080.019*
C50.24907 (14)0.17626 (14)0.56603 (6)0.0180 (2)
H50.14530.17080.57370.022*
C10.17187 (13)0.36875 (13)0.40292 (6)0.0153 (2)
C60.35355 (15)0.09894 (14)0.60500 (6)0.0203 (2)
C100.29152 (14)0.31323 (14)0.35989 (6)0.0167 (2)
C170.08762 (14)0.10373 (14)0.42559 (6)0.0188 (2)
C20.06331 (14)0.25936 (13)0.43230 (6)0.0163 (2)
C90.45070 (15)0.27250 (16)0.50559 (6)0.0224 (3)
H90.48470.33340.47190.027*
C80.55346 (15)0.19268 (17)0.54558 (7)0.0267 (3)
H80.65750.19880.53860.032*
C70.50616 (16)0.10434 (16)0.59547 (7)0.0248 (3)
H70.57620.04910.62240.030*
C110.51527 (14)0.38886 (15)0.31296 (6)0.0201 (2)
H11A0.47540.35680.26870.024*
H11B0.58140.31160.33250.024*
C140.02312 (17)0.64730 (16)0.28356 (7)0.0253 (3)
H14A−0.06180.68040.30870.030*
H14B−0.01610.62630.23790.030*
C120.60066 (16)0.52914 (16)0.30825 (7)0.0265 (3)
H12B0.53290.60520.29010.032*
H12C0.68310.51560.27930.032*
H12A0.64160.55800.35220.032*
C150.13952 (19)0.76533 (16)0.28303 (7)0.0289 (3)
H15C0.09700.85020.25930.035*
H15B0.22680.72980.26100.035*
H15A0.17070.79300.32840.035*
C40.29805 (14)0.26271 (13)0.51514 (6)0.0166 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0331 (2)0.02836 (18)0.02491 (17)−0.00564 (13)−0.00412 (13)0.01159 (12)
O30.0264 (5)0.0190 (4)0.0161 (4)0.0027 (4)−0.0001 (3)0.0024 (3)
O10.0199 (4)0.0187 (4)0.0210 (4)−0.0014 (3)0.0072 (3)−0.0024 (3)
O20.0277 (5)0.0187 (4)0.0256 (5)−0.0004 (4)0.0096 (4)−0.0045 (4)
O40.0312 (5)0.0201 (5)0.0215 (4)0.0085 (4)0.0073 (4)0.0017 (4)
N10.0210 (6)0.0288 (6)0.0263 (6)0.0004 (5)0.0012 (4)−0.0003 (5)
N20.0228 (6)0.0193 (5)0.0331 (6)−0.0023 (4)0.0035 (5)−0.0016 (4)
C130.0158 (5)0.0169 (5)0.0176 (5)−0.0002 (4)0.0017 (4)0.0017 (4)
C160.0181 (6)0.0186 (6)0.0176 (5)−0.0012 (4)0.0011 (4)0.0002 (4)
C30.0174 (5)0.0144 (5)0.0153 (5)−0.0003 (4)0.0031 (4)−0.0004 (4)
C50.0192 (6)0.0166 (5)0.0182 (5)−0.0011 (4)0.0007 (4)0.0004 (4)
C10.0162 (5)0.0144 (5)0.0155 (5)0.0005 (4)0.0030 (4)0.0002 (4)
C60.0252 (6)0.0174 (6)0.0179 (5)−0.0014 (5)−0.0018 (4)0.0022 (4)
C100.0189 (5)0.0167 (5)0.0145 (5)0.0019 (4)0.0029 (4)0.0015 (4)
C170.0167 (6)0.0193 (6)0.0205 (5)−0.0022 (4)0.0021 (4)−0.0002 (4)
C20.0160 (5)0.0154 (5)0.0175 (5)−0.0004 (4)0.0017 (4)0.0002 (4)
C90.0189 (6)0.0274 (7)0.0209 (6)0.0002 (5)0.0024 (4)0.0040 (5)
C80.0173 (6)0.0349 (8)0.0279 (6)0.0032 (5)0.0009 (5)0.0041 (6)
C70.0242 (7)0.0252 (7)0.0244 (6)0.0048 (5)−0.0031 (5)0.0026 (5)
C110.0188 (6)0.0230 (6)0.0194 (5)0.0012 (5)0.0065 (4)0.0002 (5)
C140.0299 (7)0.0228 (6)0.0227 (6)0.0058 (5)−0.0016 (5)0.0068 (5)
C120.0241 (7)0.0260 (7)0.0302 (7)−0.0034 (5)0.0083 (5)0.0022 (5)
C150.0395 (8)0.0199 (6)0.0281 (7)0.0019 (6)0.0079 (6)0.0031 (5)
C40.0189 (6)0.0154 (5)0.0155 (5)0.0008 (4)0.0007 (4)−0.0003 (4)
Geometric parameters (Å, º) top
Cl1—C61.7455 (13)C6—C71.389 (2)
O1—C101.3298 (16)C7—C81.387 (2)
O1—C111.4628 (15)C8—C91.393 (2)
O2—C101.1991 (16)C11—C121.504 (2)
O3—C131.3290 (15)C14—C151.503 (2)
O3—C141.4671 (17)C3—H31.0000
O4—C131.2010 (16)C5—H50.9500
N1—C161.1442 (17)C7—H70.9500
N2—C171.1411 (18)C8—H80.9500
C1—C21.5440 (17)C9—H90.9500
C1—C31.4972 (17)C11—H11A0.9900
C1—C101.5137 (17)C11—H11B0.9900
C1—C131.5212 (17)C12—H12A0.9800
C2—C31.5417 (17)C12—H12B0.9800
C2—C161.4545 (18)C12—H12C0.9800
C2—C171.4548 (18)C14—H14A0.9900
C3—C41.4941 (17)C14—H14B0.9900
C4—C51.3982 (17)C15—H15A0.9800
C4—C91.3915 (18)C15—H15B0.9800
C5—C61.3799 (18)C15—H15C0.9800
C10—O1—C11116.35 (10)N1—C16—C2178.70 (14)
C13—O3—C14116.22 (10)N2—C17—C2175.24 (14)
C2—C1—C360.90 (8)C1—C3—H3114.00
C2—C1—C10119.29 (10)C2—C3—H3114.00
C2—C1—C13113.68 (10)C4—C3—H3114.00
C3—C1—C10122.72 (10)C4—C5—H5121.00
C3—C1—C13115.09 (10)C6—C5—H5120.00
C10—C1—C13114.55 (10)C6—C7—H7121.00
C1—C2—C358.05 (8)C8—C7—H7121.00
C1—C2—C16117.93 (10)C7—C8—H8119.00
C1—C2—C17120.19 (11)C9—C8—H8120.00
C3—C2—C16118.59 (10)C4—C9—H9120.00
C3—C2—C17117.69 (10)C8—C9—H9120.00
C16—C2—C17113.60 (11)O1—C11—H11A110.00
C1—C3—C261.05 (8)O1—C11—H11B110.00
C1—C3—C4125.73 (10)C12—C11—H11A110.00
C2—C3—C4117.78 (10)C12—C11—H11B110.00
C3—C4—C5116.23 (11)H11A—C11—H11B109.00
C3—C4—C9123.87 (11)C11—C12—H12A109.00
C5—C4—C9119.83 (11)C11—C12—H12B109.00
C4—C5—C6119.06 (12)C11—C12—H12C109.00
Cl1—C6—C5118.13 (10)H12A—C12—H12B109.00
Cl1—C6—C7119.71 (10)H12A—C12—H12C109.00
C5—C6—C7122.16 (12)H12B—C12—H12C109.00
C6—C7—C8118.16 (13)O3—C14—H14A110.00
C7—C8—C9121.00 (13)O3—C14—H14B110.00
C4—C9—C8119.77 (12)C15—C14—H14A110.00
O1—C10—O2126.75 (12)C15—C14—H14B110.00
O1—C10—C1107.64 (10)H14A—C14—H14B108.00
O2—C10—C1125.62 (12)C14—C15—H15A109.00
O1—C11—C12106.25 (11)C14—C15—H15B109.00
O3—C13—O4126.10 (12)C14—C15—H15C109.00
O3—C13—C1110.16 (10)H15A—C15—H15B109.00
O4—C13—C1123.68 (11)H15A—C15—H15C109.00
O3—C14—C15110.41 (12)H15B—C15—H15C109.00
C10—O1—C11—C12172.57 (10)C3—C1—C10—O288.80 (16)
C11—O1—C10—C1−177.59 (9)C13—C1—C10—O156.21 (13)
C11—O1—C10—O21.86 (18)C13—C1—C10—O2−123.25 (14)
C14—O3—C13—C1−177.70 (10)C3—C1—C10—O1−91.74 (13)
C14—O3—C13—O44.90 (19)C2—C1—C10—O1−164.13 (10)
C13—O3—C14—C1582.31 (14)C2—C1—C10—O216.41 (19)
C13—C1—C2—C3−106.61 (11)C17—C2—C3—C1110.00 (12)
C10—C1—C2—C177.68 (17)C1—C2—C3—C4−117.58 (12)
C2—C1—C3—C4104.97 (13)C16—C2—C3—C1−106.79 (12)
C10—C1—C3—C2−107.93 (13)C16—C2—C3—C4135.63 (12)
C10—C1—C3—C4−2.96 (18)C17—C2—C3—C4−7.58 (16)
C13—C1—C3—C2104.29 (11)C1—C3—C4—C5−140.24 (12)
C13—C1—C3—C4−150.75 (11)C1—C3—C4—C942.95 (19)
C13—C1—C2—C161.30 (15)C2—C3—C4—C9115.80 (14)
C13—C1—C2—C17147.67 (11)C2—C3—C4—C5−67.40 (15)
C3—C1—C2—C16107.92 (12)C3—C4—C9—C8178.59 (12)
C3—C1—C2—C17−105.72 (12)C9—C4—C5—C6−1.63 (19)
C10—C1—C2—C3113.39 (12)C3—C4—C5—C6−178.57 (11)
C10—C1—C2—C16−138.69 (12)C5—C4—C9—C81.9 (2)
C2—C1—C13—O3−108.93 (12)C4—C5—C6—C70.2 (2)
C2—C1—C13—O468.55 (16)C4—C5—C6—Cl1179.25 (10)
C3—C1—C13—O3−176.52 (10)Cl1—C6—C7—C8−178.06 (11)
C3—C1—C13—O40.96 (18)C5—C6—C7—C81.0 (2)
C10—C1—C13—O333.02 (14)C6—C7—C8—C9−0.8 (2)
C10—C1—C13—O4−149.50 (13)C7—C8—C9—C4−0.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O41.002.432.8447 (16)104
C9—H9···O10.952.593.3529 (15)138
C3—H3···O4i1.002.453.1419 (16)126
C15—H15C···O3ii0.982.633.5656 (18)161
C5—H5···N2iii0.952.613.4621 (18)150
C11—H11B···N1iv0.992.633.3337 (17)128
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O10.952.593.3529 (15)138
C3—H3···O4i1.002.453.1419 (16)126
C15—H15C···O3ii0.982.633.5656 (18)161
C5—H5···N2iii0.952.613.4621 (18)150
C11—H11B···N1iv0.992.633.3337 (17)128
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC17H15ClN2O4
Mr346.76
Crystal system, space groupMonoclinic, P21/c
Temperature (K)103
a, b, c (Å)8.9221 (6), 9.1927 (7), 20.3446 (16)
β (°) 93.829 (2)
V (Å3)1664.9 (2)
Z4
Radiation typeMo Kα
µ (mm−1)0.25
Crystal size (mm)0.50 × 0.25 × 0.25
Data collection
DiffractometerRAXIS-RAPID
Absorption correctionEmpirical (using intensity measurements)
(NUMABS; Higashi, 2002)
Tmin, Tmax0.755, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		57969, 5052, 4312
Rint0.042
(sin θ/λ)max (Å−1)0.714
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.113, 1.11
No. of reflections5052
No. of parameters219
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.49, −0.31

Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2006).

 

Acknowledgements

This work was financially supported by the Hungarian Scientific Research Fund (OTKA K No. 115762 and PD No. 112166) and the New Széchenyi Development Plan (TÁMOP-4.2.1/B-09/1/KMR-2010-0002).

References

First citationAggarwal, V. K. & Grange, E. (2006). Chem. Eur. J. 12, 568–575.  CrossRef Google Scholar
 First citationBakó, P., Rapi, Z., Grün, A., Nemcsók, T., Hegedűs, L. & Keglevich, G. (2015). Synlett, 26, 1847–1851.  Google Scholar
 First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
 First citationElinson, M. N., Feducovich, S. K., Starikova, Z. A., Vereshchagin, A. N., Belyakov, P. A. & Nikishin, G. I. (2006). Tetrahedron, 62, 3989–3996.  CSD CrossRef CAS Google Scholar
 First citationElinson, M. N., Lizunova, T. L., Ugrak, B. I., Dekaprilevich, M. O., Nikishin, G. I. & Struchkov, Y. T. (1993). Tetrahedron Lett. 34, 5795–5798.  CSD CrossRef CAS Google Scholar
 First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CSD CrossRef CAS Google Scholar
 First citationHigashi, T. (2002). NUMABS. Rigaku/MSC Inc., Tokyo, Japan.  Google Scholar
 First citationLittle, R. D., Masjedizadeh, M. R., Wallquist, O. & McLoughlin, J. I. (1995). Org. React. 47, 315–552.  CAS Google Scholar
 First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationMather, B. D., Viswanathan, K., Miller, K. M. & Long, T. E. (2006). Prog. Polym. Sci. 31, 487–531.  CrossRef CAS Google Scholar
 First citationRiches, S. L., Saha, C., Filgueira, N. F., Grange, E., McGarrigle, E. M. & Aggarwal, V. K. (2010). J. Am. Chem. Soc. 132, 7626–7630.  CrossRef CAS PubMed Google Scholar
 First citationRigaku/MSC (2008). CrystalClear. Rigaku/MSC Inc., Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationShioiri, T. (1997). In Handbook of Phase-Transfer Catalysis, edited by Y. Sasson & R. Neumann. London: Blackie Academic & Professional.  Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationTinant, B., Wu, S., Declercq, J.-P., van Meerssche, M., Leroy, G. & Weiler, J. (1988). New J. Chem. 12, 53–57.  CAS Google Scholar
 First citationZheng, J.-C., Liao, W.-W., Tang, Y., Sun, X.-L. & Dai, L.-X. (2005). J. Am. Chem. Soc. 127, 12222–12223.  CSD CrossRef PubMed CAS Google Scholar
 First citationZimmerman, H. E. & Cassel, J. M. (1989). J. Org. Chem. 54, 3800–3816.  CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 253-256
doi:10.1107/S2056989016001444
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS