research communications
of diethyl 3-(3-chlorophenyl)-2,2-dicyanocyclopropane-1,1-dicarboxylate
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
In the racemic title compound, C17H15ClN2O4, which has been synthesized and the 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.
Keywords: crystal structure; cyclopropane derivatives; MIRC; phase-transfer catalysis; crown ether.
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; 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 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. 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).
2. Structural commentary
In the molecular structure of the title compound (Fig. 1), atom C3 is a chiral centre, but the crystallizes in the centrosymmetric 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 intramolecular C3⋯O4 interaction [2.8447 (16) Å] (Fig. 2).
3. Supramolecular features
In the crystal, C3—H⋯O4i hydrogen bonds (Table 1) form inversion 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 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 which results in no residual solvent-accessible voids in the crystal.
4. Database survey
The 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-diisopropylcyclopropane (KANFOU; Zimmerman & Cassel, 1989) it is 50.8°, for diethyl 1,2-dicyano-3-phenylcyclopropane-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 C atoms enforce this 47–53° angle between the planes of the cyclopropane and benzene rings.
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-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 (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 X-ray were obtained by crystallization from ethanol.
6. Refinement
Crystal data, data collection and structure . All H atoms were located in difference electron-density maps but were included in the structure at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2Supporting information
CCDC reference: 1449224
10.1107/S2056989016001444/zs2355sup1.cif
contains datablocks I, header. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016001444/zs2355Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016001444/zs2355Isup3.cml
The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated 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
crystallizes in the centrosymmetric 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 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 which results in no residual solvent-accessible voids in the crystal.
\ The
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.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
(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 were obtained by crystallization from ethanol.The formation of C—C bonds by the Michael addition of the appropriate carboanionic reagents to α,β-unsaturated 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
crystallizes in the centrosymmetric 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 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 which results in no residual solvent-accessible voids in the crystal.
\ The
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.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
(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 were obtained by crystallization from ethanol. detailsCrystal data, data collection and structure
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 at calculated positions, with C—H = 0.95–1.00 Å, and allowed to ride, with Uiso(H) = 1.2Ueq(C).Data collection: CrystalClear (Rigaku/MSC, 2008); cell
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).Fig. 1. The molecular structure of the title compound, showing the atom numbering. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The four molecules in the unit cell of the title compound, with the intramolecular interactions shown as dashed lines. | |
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. | |
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. |
C17H15ClN2O4 | Dx = 1.383 Mg m−3 |
Mr = 346.76 | Melting point = 355–357 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9221 (6) Å | Cell parameters from 37218 reflections |
b = 9.1927 (7) Å | θ = 3.0–30.5° |
c = 20.3446 (16) Å | µ = 0.25 mm−1 |
β = 93.829 (2)° | T = 103 K |
V = 1664.9 (2) Å3 | Block, colorless |
Z = 4 | 0.50 × 0.25 × 0.25 mm |
F(000) = 720 |
RAXIS-RAPID diffractometer | 5052 independent reflections |
Radiation source: sealed tube | 4312 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 30.5°, θmin = 3.0° |
dtprofit.ref scans | h = −12→12 |
Absorption correction: empirical (using intensity measurements) (NUMABS; Higashi, 2002) | k = −13→13 |
Tmin = 0.755, Tmax = 1.000 | l = −29→29 |
57969 measured reflections |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.113 | H-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 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C17H15ClN2O4 | V = 1664.9 (2) Å3 |
Mr = 346.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9221 (6) Å | µ = 0.25 mm−1 |
b = 9.1927 (7) Å | T = 103 K |
c = 20.3446 (16) Å | 0.50 × 0.25 × 0.25 mm |
β = 93.829 (2)° |
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 = 1.000 | Rint = 0.042 |
57969 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.49 e Å−3 |
5052 reflections | Δρmin = −0.31 e Å−3 |
219 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.28965 (4) | −0.00643 (4) | 0.66880 (2) | 0.02905 (10) | |
O3 | 0.08826 (11) | 0.51460 (10) | 0.31362 (4) | 0.02054 (19) | |
O1 | 0.39223 (10) | 0.41867 (10) | 0.35507 (4) | 0.01960 (19) | |
O2 | 0.29321 (11) | 0.19550 (11) | 0.33457 (5) | 0.0237 (2) | |
O4 | 0.04757 (12) | 0.59834 (11) | 0.41513 (5) | 0.0240 (2) | |
N1 | −0.21756 (13) | 0.33382 (14) | 0.43288 (6) | 0.0254 (2) | |
N2 | 0.10162 (14) | −0.01960 (13) | 0.42424 (6) | 0.0250 (2) | |
C13 | 0.09652 (14) | 0.50931 (13) | 0.37904 (6) | 0.0167 (2) | |
C16 | −0.09432 (14) | 0.29951 (14) | 0.43266 (6) | 0.0181 (2) | |
C3 | 0.17943 (13) | 0.34622 (13) | 0.47595 (6) | 0.0156 (2) | |
H3 | 0.1350 | 0.4276 | 0.5008 | 0.019* | |
C5 | 0.24907 (14) | 0.17626 (14) | 0.56603 (6) | 0.0180 (2) | |
H5 | 0.1453 | 0.1708 | 0.5737 | 0.022* | |
C1 | 0.17187 (13) | 0.36875 (13) | 0.40292 (6) | 0.0153 (2) | |
C6 | 0.35355 (15) | 0.09894 (14) | 0.60500 (6) | 0.0203 (2) | |
C10 | 0.29152 (14) | 0.31323 (14) | 0.35989 (6) | 0.0167 (2) | |
C17 | 0.08762 (14) | 0.10373 (14) | 0.42559 (6) | 0.0188 (2) | |
C2 | 0.06331 (14) | 0.25936 (13) | 0.43230 (6) | 0.0163 (2) | |
C9 | 0.45070 (15) | 0.27250 (16) | 0.50559 (6) | 0.0224 (3) | |
H9 | 0.4847 | 0.3334 | 0.4719 | 0.027* | |
C8 | 0.55346 (15) | 0.19268 (17) | 0.54558 (7) | 0.0267 (3) | |
H8 | 0.6575 | 0.1988 | 0.5386 | 0.032* | |
C7 | 0.50616 (16) | 0.10434 (16) | 0.59547 (7) | 0.0248 (3) | |
H7 | 0.5762 | 0.0491 | 0.6224 | 0.030* | |
C11 | 0.51527 (14) | 0.38886 (15) | 0.31296 (6) | 0.0201 (2) | |
H11A | 0.4754 | 0.3568 | 0.2687 | 0.024* | |
H11B | 0.5814 | 0.3116 | 0.3325 | 0.024* | |
C14 | 0.02312 (17) | 0.64730 (16) | 0.28356 (7) | 0.0253 (3) | |
H14A | −0.0618 | 0.6804 | 0.3087 | 0.030* | |
H14B | −0.0161 | 0.6263 | 0.2379 | 0.030* | |
C12 | 0.60066 (16) | 0.52914 (16) | 0.30825 (7) | 0.0265 (3) | |
H12B | 0.5329 | 0.6052 | 0.2901 | 0.032* | |
H12C | 0.6831 | 0.5156 | 0.2793 | 0.032* | |
H12A | 0.6416 | 0.5580 | 0.3522 | 0.032* | |
C15 | 0.13952 (19) | 0.76533 (16) | 0.28303 (7) | 0.0289 (3) | |
H15C | 0.0970 | 0.8502 | 0.2593 | 0.035* | |
H15B | 0.2268 | 0.7298 | 0.2610 | 0.035* | |
H15A | 0.1707 | 0.7930 | 0.3284 | 0.035* | |
C4 | 0.29805 (14) | 0.26271 (13) | 0.51514 (6) | 0.0166 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0331 (2) | 0.02836 (18) | 0.02491 (17) | −0.00564 (13) | −0.00412 (13) | 0.01159 (12) |
O3 | 0.0264 (5) | 0.0190 (4) | 0.0161 (4) | 0.0027 (4) | −0.0001 (3) | 0.0024 (3) |
O1 | 0.0199 (4) | 0.0187 (4) | 0.0210 (4) | −0.0014 (3) | 0.0072 (3) | −0.0024 (3) |
O2 | 0.0277 (5) | 0.0187 (4) | 0.0256 (5) | −0.0004 (4) | 0.0096 (4) | −0.0045 (4) |
O4 | 0.0312 (5) | 0.0201 (5) | 0.0215 (4) | 0.0085 (4) | 0.0073 (4) | 0.0017 (4) |
N1 | 0.0210 (6) | 0.0288 (6) | 0.0263 (6) | 0.0004 (5) | 0.0012 (4) | −0.0003 (5) |
N2 | 0.0228 (6) | 0.0193 (5) | 0.0331 (6) | −0.0023 (4) | 0.0035 (5) | −0.0016 (4) |
C13 | 0.0158 (5) | 0.0169 (5) | 0.0176 (5) | −0.0002 (4) | 0.0017 (4) | 0.0017 (4) |
C16 | 0.0181 (6) | 0.0186 (6) | 0.0176 (5) | −0.0012 (4) | 0.0011 (4) | 0.0002 (4) |
C3 | 0.0174 (5) | 0.0144 (5) | 0.0153 (5) | −0.0003 (4) | 0.0031 (4) | −0.0004 (4) |
C5 | 0.0192 (6) | 0.0166 (5) | 0.0182 (5) | −0.0011 (4) | 0.0007 (4) | 0.0004 (4) |
C1 | 0.0162 (5) | 0.0144 (5) | 0.0155 (5) | 0.0005 (4) | 0.0030 (4) | 0.0002 (4) |
C6 | 0.0252 (6) | 0.0174 (6) | 0.0179 (5) | −0.0014 (5) | −0.0018 (4) | 0.0022 (4) |
C10 | 0.0189 (5) | 0.0167 (5) | 0.0145 (5) | 0.0019 (4) | 0.0029 (4) | 0.0015 (4) |
C17 | 0.0167 (6) | 0.0193 (6) | 0.0205 (5) | −0.0022 (4) | 0.0021 (4) | −0.0002 (4) |
C2 | 0.0160 (5) | 0.0154 (5) | 0.0175 (5) | −0.0004 (4) | 0.0017 (4) | 0.0002 (4) |
C9 | 0.0189 (6) | 0.0274 (7) | 0.0209 (6) | 0.0002 (5) | 0.0024 (4) | 0.0040 (5) |
C8 | 0.0173 (6) | 0.0349 (8) | 0.0279 (6) | 0.0032 (5) | 0.0009 (5) | 0.0041 (6) |
C7 | 0.0242 (7) | 0.0252 (7) | 0.0244 (6) | 0.0048 (5) | −0.0031 (5) | 0.0026 (5) |
C11 | 0.0188 (6) | 0.0230 (6) | 0.0194 (5) | 0.0012 (5) | 0.0065 (4) | 0.0002 (5) |
C14 | 0.0299 (7) | 0.0228 (6) | 0.0227 (6) | 0.0058 (5) | −0.0016 (5) | 0.0068 (5) |
C12 | 0.0241 (7) | 0.0260 (7) | 0.0302 (7) | −0.0034 (5) | 0.0083 (5) | 0.0022 (5) |
C15 | 0.0395 (8) | 0.0199 (6) | 0.0281 (7) | 0.0019 (6) | 0.0079 (6) | 0.0031 (5) |
C4 | 0.0189 (6) | 0.0154 (5) | 0.0155 (5) | 0.0008 (4) | 0.0007 (4) | −0.0003 (4) |
Cl1—C6 | 1.7455 (13) | C6—C7 | 1.389 (2) |
O1—C10 | 1.3298 (16) | C7—C8 | 1.387 (2) |
O1—C11 | 1.4628 (15) | C8—C9 | 1.393 (2) |
O2—C10 | 1.1991 (16) | C11—C12 | 1.504 (2) |
O3—C13 | 1.3290 (15) | C14—C15 | 1.503 (2) |
O3—C14 | 1.4671 (17) | C3—H3 | 1.0000 |
O4—C13 | 1.2010 (16) | C5—H5 | 0.9500 |
N1—C16 | 1.1442 (17) | C7—H7 | 0.9500 |
N2—C17 | 1.1411 (18) | C8—H8 | 0.9500 |
C1—C2 | 1.5440 (17) | C9—H9 | 0.9500 |
C1—C3 | 1.4972 (17) | C11—H11A | 0.9900 |
C1—C10 | 1.5137 (17) | C11—H11B | 0.9900 |
C1—C13 | 1.5212 (17) | C12—H12A | 0.9800 |
C2—C3 | 1.5417 (17) | C12—H12B | 0.9800 |
C2—C16 | 1.4545 (18) | C12—H12C | 0.9800 |
C2—C17 | 1.4548 (18) | C14—H14A | 0.9900 |
C3—C4 | 1.4941 (17) | C14—H14B | 0.9900 |
C4—C5 | 1.3982 (17) | C15—H15A | 0.9800 |
C4—C9 | 1.3915 (18) | C15—H15B | 0.9800 |
C5—C6 | 1.3799 (18) | C15—H15C | 0.9800 |
C10—O1—C11 | 116.35 (10) | N1—C16—C2 | 178.70 (14) |
C13—O3—C14 | 116.22 (10) | N2—C17—C2 | 175.24 (14) |
C2—C1—C3 | 60.90 (8) | C1—C3—H3 | 114.00 |
C2—C1—C10 | 119.29 (10) | C2—C3—H3 | 114.00 |
C2—C1—C13 | 113.68 (10) | C4—C3—H3 | 114.00 |
C3—C1—C10 | 122.72 (10) | C4—C5—H5 | 121.00 |
C3—C1—C13 | 115.09 (10) | C6—C5—H5 | 120.00 |
C10—C1—C13 | 114.55 (10) | C6—C7—H7 | 121.00 |
C1—C2—C3 | 58.05 (8) | C8—C7—H7 | 121.00 |
C1—C2—C16 | 117.93 (10) | C7—C8—H8 | 119.00 |
C1—C2—C17 | 120.19 (11) | C9—C8—H8 | 120.00 |
C3—C2—C16 | 118.59 (10) | C4—C9—H9 | 120.00 |
C3—C2—C17 | 117.69 (10) | C8—C9—H9 | 120.00 |
C16—C2—C17 | 113.60 (11) | O1—C11—H11A | 110.00 |
C1—C3—C2 | 61.05 (8) | O1—C11—H11B | 110.00 |
C1—C3—C4 | 125.73 (10) | C12—C11—H11A | 110.00 |
C2—C3—C4 | 117.78 (10) | C12—C11—H11B | 110.00 |
C3—C4—C5 | 116.23 (11) | H11A—C11—H11B | 109.00 |
C3—C4—C9 | 123.87 (11) | C11—C12—H12A | 109.00 |
C5—C4—C9 | 119.83 (11) | C11—C12—H12B | 109.00 |
C4—C5—C6 | 119.06 (12) | C11—C12—H12C | 109.00 |
Cl1—C6—C5 | 118.13 (10) | H12A—C12—H12B | 109.00 |
Cl1—C6—C7 | 119.71 (10) | H12A—C12—H12C | 109.00 |
C5—C6—C7 | 122.16 (12) | H12B—C12—H12C | 109.00 |
C6—C7—C8 | 118.16 (13) | O3—C14—H14A | 110.00 |
C7—C8—C9 | 121.00 (13) | O3—C14—H14B | 110.00 |
C4—C9—C8 | 119.77 (12) | C15—C14—H14A | 110.00 |
O1—C10—O2 | 126.75 (12) | C15—C14—H14B | 110.00 |
O1—C10—C1 | 107.64 (10) | H14A—C14—H14B | 108.00 |
O2—C10—C1 | 125.62 (12) | C14—C15—H15A | 109.00 |
O1—C11—C12 | 106.25 (11) | C14—C15—H15B | 109.00 |
O3—C13—O4 | 126.10 (12) | C14—C15—H15C | 109.00 |
O3—C13—C1 | 110.16 (10) | H15A—C15—H15B | 109.00 |
O4—C13—C1 | 123.68 (11) | H15A—C15—H15C | 109.00 |
O3—C14—C15 | 110.41 (12) | H15B—C15—H15C | 109.00 |
C10—O1—C11—C12 | 172.57 (10) | C3—C1—C10—O2 | 88.80 (16) |
C11—O1—C10—C1 | −177.59 (9) | C13—C1—C10—O1 | 56.21 (13) |
C11—O1—C10—O2 | 1.86 (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—O4 | 4.90 (19) | C2—C1—C10—O1 | −164.13 (10) |
C13—O3—C14—C15 | 82.31 (14) | C2—C1—C10—O2 | 16.41 (19) |
C13—C1—C2—C3 | −106.61 (11) | C17—C2—C3—C1 | 110.00 (12) |
C10—C1—C2—C17 | 7.68 (17) | C1—C2—C3—C4 | −117.58 (12) |
C2—C1—C3—C4 | 104.97 (13) | C16—C2—C3—C1 | −106.79 (12) |
C10—C1—C3—C2 | −107.93 (13) | C16—C2—C3—C4 | 135.63 (12) |
C10—C1—C3—C4 | −2.96 (18) | C17—C2—C3—C4 | −7.58 (16) |
C13—C1—C3—C2 | 104.29 (11) | C1—C3—C4—C5 | −140.24 (12) |
C13—C1—C3—C4 | −150.75 (11) | C1—C3—C4—C9 | 42.95 (19) |
C13—C1—C2—C16 | 1.30 (15) | C2—C3—C4—C9 | 115.80 (14) |
C13—C1—C2—C17 | 147.67 (11) | C2—C3—C4—C5 | −67.40 (15) |
C3—C1—C2—C16 | 107.92 (12) | C3—C4—C9—C8 | 178.59 (12) |
C3—C1—C2—C17 | −105.72 (12) | C9—C4—C5—C6 | −1.63 (19) |
C10—C1—C2—C3 | 113.39 (12) | C3—C4—C5—C6 | −178.57 (11) |
C10—C1—C2—C16 | −138.69 (12) | C5—C4—C9—C8 | 1.9 (2) |
C2—C1—C13—O3 | −108.93 (12) | C4—C5—C6—C7 | 0.2 (2) |
C2—C1—C13—O4 | 68.55 (16) | C4—C5—C6—Cl1 | 179.25 (10) |
C3—C1—C13—O3 | −176.52 (10) | Cl1—C6—C7—C8 | −178.06 (11) |
C3—C1—C13—O4 | 0.96 (18) | C5—C6—C7—C8 | 1.0 (2) |
C10—C1—C13—O3 | 33.02 (14) | C6—C7—C8—C9 | −0.8 (2) |
C10—C1—C13—O4 | −149.50 (13) | C7—C8—C9—C4 | −0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O4 | 1.00 | 2.43 | 2.8447 (16) | 104 |
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+1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) x+1, y, z. |
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+1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) x+1, y, z. |
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 | RAXIS-RAPID |
Absorption correction | Empirical (using intensity measurements) (NUMABS; Higashi, 2002) |
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), 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).
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