research communications
E)-3-[(2S,4S,5R)-2-amino-5-hydroxymethyl-2-trichloromethyl-1,3-dioxolan-4-yl]-2-methylprop-2-enoate
of (+)-methyl (aSchool of Medicine, Keio University, Hiyoshi 4-1-1, Kohoku-ku, Yokohama 223-8521, Japan, and bDepartment of Applied Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
*Correspondence e-mail: oec@keio.jp
In the title compound, C10H14Cl3NO5, the five-membered dioxolane ring adopts an The C atom at the flap, which is bonded to the hydroxymethyl substituent, deviates from the mean plane of other ring atoms by 0.357 (5) Å. There are two intramolecular hydrogen bonds (O—H⋯N and N—H⋯O) between the hydroxy and amino groups, so that O- and N-bound H atoms involved in these hydrogen bonds are each disordered with equal occupancies of 0.50. The methyl 2-methylprop-2-enoate substituent also shows a disordered structure over two sets of sites with refined occupancies of 0.482 (5) and 0.518 (5). In the crystal, molecules are connected into a dimer by an O—H⋯O hydrogen bond. The dimers are further linked by N—H⋯O, C—H⋯N and C—H⋯O interactions, extending a sheet structure parallel to (-101).
Keywords: crystal structure; orthoamide; dioxolane; hydrogen bonding; hydroxy group; amino group; disorder.
CCDC reference: 1452471
1. Chemical context
The 3,3-sigmatropic rearrangement of an allylic trichloroacetimidate (Overman rearrangement; Overman, 1974, 1976) is one of the most important reactions in organic chemistry. It has been utilized as a quite powerful tool to introduce the nitrogen because this imidate is easily available from an allylic alcohol with trichloroacetonitrile (Cl3CC≡N). In the case of a diol, a cyclic orthoamide (2-amino-2-trichloromethyl-1,3-dioxolane) may be afforded by controlling the reaction conditions though bis-imidates are usually produced. We have explored the rearrangement of the cyclic orthoamide prepared from a contiguous diol or triol, and have developed a novel strategy for the total synthesis of certain natural products (Nakayama et al., 2013). As part of our ongoing studies in this area, we now describe the synthesis and structure of the title compound.
2. Structural commentary
The molecular structure of the title compound is shown in Fig. 1. The dioxolane ring (C5/O7/C8/C9/O10) adopts an envelope form with puckering parameters of Q(2) = 0.223 (3) Å and φ(2) = 111.7 (8)°. Atom C9 deviates from the mean plane of the other four atoms by 0.357 (5) Å. The hydroxy H atom has two possible positions and the amino H atoms have three possible positions, generating two types of intramolecular hydrogen bonds with an S(7) graph-set motif between the hydroxy and amino groups, N6—H6A⋯O12 and O12—H12B⋯N6 (Table 1 and Fig. 2). The occupation factor of atoms H12A, H12B and H6A is 0.5, while that of atoms H6B and H6C is 0.75. The unsaturated ester substituent (C15/C14/C16/O17/O18/C19) is disordered over two orientations with refined occupancies of 0.482 (5) and 0.518 (5).
3. Supramolecular features
The crystal packing is stabilized by O—H⋯O hydrogen bonding (O12—H12A⋯O12i; Table 1), connecting molecules related by a twofold rotation axis into a dimer. As the result of this intermolecular linkage, the intramolecular hydrogen-bonding pattern is restricted, as shown in Fig. 3. The dimers are further linked by weak N—H⋯O, C—H⋯N and C—H⋯O interactions (N6—H6C⋯O17Bii and N6—H6B⋯O17Aiv, C19A—H19C⋯N6iii and C19B—H19E⋯O12v; Table 1, Figs. 4 and 5) to form a sheet structure parallel to (01).
4. Database survey
In the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014), eight structures possessing a 1,3-dioxolane core with 4-(prop-2-enoate-3-yl) and 5-hydroxymethyl substituents, (a), are registered (Fig. 6). These include its 2,2-dimethyl, (b), 2-oxo, (c) and 2-alkoxy-2-alkyl (orthoester) derivative, (d), but its 2-amino-2-trichloromethyl derivative, (e), which is related to the title compound, (h), has not been reported.
On the other hand, a search in CSD for a 2,2,2-trichloroethan-1-amine skeleton, (f), gave 12 entries. These include two structures (LIBHIO: Rondot et al., 2007; WEKWOY: Haeckel et al., 1994) with a 2-amino-2-trichloromethyl-1,3-dioxolane or -1,3-dioxane core, (g). N-bound hydrogen atoms in the structure of LIBHIO were refined as having an sp3 configuration and tilted towards chlorine atoms, whereas those in other 11 structures were refined assuming an sp2 configuration of the N atom.
5. Synthesis and crystallization
The title compound was derived from D-erythrose, which was prepared according to the reported procedure (Storz et al., 1999) from D-glucose (Yasushima et al., 2016). Purification was carried out by silica gel and colourless crystals were obtained from a toluene solution by slow evaporation at ambient temperature. M.p. 365–366 K. [α]20D + 33.8 (c 0.32, CHCl3).
6. Refinement
Crystal data, data collection and structure . The unsaturated ester group is disordered; the atoms C15/C16/O17/O18/C19 were split into two sets of positions A and B with their geometries restrained, and the refined occupancies being 0.482 (5) and 0.518 (5), respectively.
details are summarized in Table 2
|
C-bound H atoms were positioned geometrically with C—H = 0.95–1.00 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The O-bound hydrogen atom has two possible positions. They were refined isotropically with Uiso(H) = 1.5Ueq(O) and the O—H distances restrained. The N-bound hydrogen atoms have three possible positions. They were refined isotropically with Uiso(H) = 1.2Ueq(N) and the N—H and H⋯H distances restrained. The site-occupation factors of the disordered H atoms of the hydroxy group (H12A and H12B) and one of the amino group (H6A) were uniquely assigned to 0.5 each based on the two possible patterns of the hydrogen-bonding linkages related by the twofold axis. The occupation factors of the other N-bound H6B and H6C atoms were assumed to be 0.75 each from a difference map.
Supporting information
CCDC reference: 1452471
10.1107/S2056989016002474/is5442sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002474/is5442Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016002474/is5442Isup3.cml
The 3,3-sigmatropic rearrangement of an allylic trichloroacetimidate (Overman rearrangement; Overman, 1974, 1976) is one of the most important reactions in organic chemistry. It has been utilized as a quite powerful tool to introduce the nitrogen ≡N). In the case of a diol, a cyclic orthoamide (2-amino-2-trichloromethyl-1,3-dioxolane) may be afforded by controlling the reaction conditions though bis-imidates are usually produced. We have explored the rearrangement of the cyclic orthoamide prepared from a contiguous diol or triol, and have developed a novel strategy for the total synthesis of certain natural products (Nakayama et al., 2013).
because this imidate is easily available from an allylic alcohol with trichloroacetonitrile (Cl3CCThe molecular structure of the title compound is shown in Fig. 1. The dioxolane ring (C5/O7/C8/C9/O10) adopts an envelope form with puckering parameters of Q(2) = 0.223 (3) Å and φ(2) = 111.7 (8)°. Atom C9 deviates from the mean plane of the other four atoms by 0.357 (5) Å. The hydroxy H atom has two possible positions and the amino H atoms have three possible positions, generating two types of intramolecular hydrogen bonds with an S(7) graph-set motif between the hydroxy and amino groups, N6—H6A···O12 and O12—H12B···N6 (Table 1and Fig. 2). The occupation factor of atoms H12A, H12B and H6A is 0.5, while that of atoms H6B and H6C is 0.75. The unsaturated ester substituent (C15/C14/C16/O17/O18/C19) is disordered over two orientations with refined occupancies of 0.482 (5) and 0.518 (5).
The crystal packing is stabilized by O—H···O hydrogen bonding (O12—H12A···O12i; Table 1), connecting molecules related by a twofold rotation axis into a dimer. As the result of this intermolecular linkage, the intramolecular hydrogen-bonding pattern is restricted, as shown in Fig. 3. The dimers are further linked by weak N—H···O, C—H···N and C—H···O interactions (N6—H6C···O17Bii and N6—H6B···O17Aiv, C19A—H19C···N6iii and C19B—H19E···O12v; Table 1, Figs. 4 and 5) to form a sheet structure parallel to (101).
In the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014), eight structures possessing a 1,3-dioxolane core with 4-(prop-2-enoate-3-yl) and 5-hydroxymethyl substituents, (a), are registered (Fig. 6). These include its 2,2-dimethyl, (b), 2-oxo, (c) and 2-alkoxy-2-alkyl (orthoester) derivative, (d), but its 2-amino-2-trichloromethyl derivative, (e), which is related to the title compound, (h), has not been reported.
On the other hand, a search in CSD for a 2,2,2-trichloroethan-1-amine skeleton, (f), gave 12 entries. These include two structures (LIBHIO: Rondot et al., 2007; WEKWOY: Haeckel et al., 1994) with a 2-amino-2-trichloromethyl-1,3-dioxolane or -1,3-dioxane core, (g). N-bound hydrogen atoms in the structure of LIBHIO were refined as having an sp3 configuration and tilted towards chlorine atoms, whereas those in other 11 structures were refined assuming an sp2 configuration of the N atom.
The title compound was derived from D-erythrose, which was prepared according to the reported procedure (Storz et al., 1999) from D-glucose (Yasushima et al., 2016). Purification was carried out by silica gel α]20D + 33.8 (c 0.32, CHCl3).
and colourless crystals were obtained from a toluene solution by slow evaporation at ambient temperature. M.p. 365–366 K. [Crystal data, data collection and structure
details are summarized in Table 2. The unsaturated ester group is disordered; the atoms C15/C16/O17/O18/C19 were split into two sets of positions A and B with their geometries restrained, and the refined occupancies being 0.482 (5) and 0.518 (5), respectively.C-bound H atoms were positioned geometrically with C—H = 0.95–1.00 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The O-bound hydrogen atom has two possible positions. They were refined isotropically with Uiso(H) = 1.5Ueq(O) and the O—H distances restrained. The N-bound hydrogen atoms have three possible positions. They were refined isotropically with Uiso(H) = 1.2Ueq(N) and the N—H and H···H distances restrained. The site-occupation factors of the disordered H atoms of the hydroxy group (H12A and H12B) and one of the amino group (H6A) were uniquely assigned to 0.5 each based on the two possible patterns of the hydrogen-bonding linkages related by the twofold axis. The occupation factors of the other N-bound H6B and H6C atoms were assumed to be 0.75 each from a difference map.
The 3,3-sigmatropic rearrangement of an allylic trichloroacetimidate (Overman rearrangement; Overman, 1974, 1976) is one of the most important reactions in organic chemistry. It has been utilized as a quite powerful tool to introduce the nitrogen ≡N). In the case of a diol, a cyclic orthoamide (2-amino-2-trichloromethyl-1,3-dioxolane) may be afforded by controlling the reaction conditions though bis-imidates are usually produced. We have explored the rearrangement of the cyclic orthoamide prepared from a contiguous diol or triol, and have developed a novel strategy for the total synthesis of certain natural products (Nakayama et al., 2013).
because this imidate is easily available from an allylic alcohol with trichloroacetonitrile (Cl3CCThe molecular structure of the title compound is shown in Fig. 1. The dioxolane ring (C5/O7/C8/C9/O10) adopts an envelope form with puckering parameters of Q(2) = 0.223 (3) Å and φ(2) = 111.7 (8)°. Atom C9 deviates from the mean plane of the other four atoms by 0.357 (5) Å. The hydroxy H atom has two possible positions and the amino H atoms have three possible positions, generating two types of intramolecular hydrogen bonds with an S(7) graph-set motif between the hydroxy and amino groups, N6—H6A···O12 and O12—H12B···N6 (Table 1and Fig. 2). The occupation factor of atoms H12A, H12B and H6A is 0.5, while that of atoms H6B and H6C is 0.75. The unsaturated ester substituent (C15/C14/C16/O17/O18/C19) is disordered over two orientations with refined occupancies of 0.482 (5) and 0.518 (5).
The crystal packing is stabilized by O—H···O hydrogen bonding (O12—H12A···O12i; Table 1), connecting molecules related by a twofold rotation axis into a dimer. As the result of this intermolecular linkage, the intramolecular hydrogen-bonding pattern is restricted, as shown in Fig. 3. The dimers are further linked by weak N—H···O, C—H···N and C—H···O interactions (N6—H6C···O17Bii and N6—H6B···O17Aiv, C19A—H19C···N6iii and C19B—H19E···O12v; Table 1, Figs. 4 and 5) to form a sheet structure parallel to (101).
In the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014), eight structures possessing a 1,3-dioxolane core with 4-(prop-2-enoate-3-yl) and 5-hydroxymethyl substituents, (a), are registered (Fig. 6). These include its 2,2-dimethyl, (b), 2-oxo, (c) and 2-alkoxy-2-alkyl (orthoester) derivative, (d), but its 2-amino-2-trichloromethyl derivative, (e), which is related to the title compound, (h), has not been reported.
On the other hand, a search in CSD for a 2,2,2-trichloroethan-1-amine skeleton, (f), gave 12 entries. These include two structures (LIBHIO: Rondot et al., 2007; WEKWOY: Haeckel et al., 1994) with a 2-amino-2-trichloromethyl-1,3-dioxolane or -1,3-dioxane core, (g). N-bound hydrogen atoms in the structure of LIBHIO were refined as having an sp3 configuration and tilted towards chlorine atoms, whereas those in other 11 structures were refined assuming an sp2 configuration of the N atom.
The title compound was derived from D-erythrose, which was prepared according to the reported procedure (Storz et al., 1999) from D-glucose (Yasushima et al., 2016). Purification was carried out by silica gel α]20D + 33.8 (c 0.32, CHCl3).
and colourless crystals were obtained from a toluene solution by slow evaporation at ambient temperature. M.p. 365–366 K. [ detailsCrystal data, data collection and structure
details are summarized in Table 2. The unsaturated ester group is disordered; the atoms C15/C16/O17/O18/C19 were split into two sets of positions A and B with their geometries restrained, and the refined occupancies being 0.482 (5) and 0.518 (5), respectively.C-bound H atoms were positioned geometrically with C—H = 0.95–1.00 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The O-bound hydrogen atom has two possible positions. They were refined isotropically with Uiso(H) = 1.5Ueq(O) and the O—H distances restrained. The N-bound hydrogen atoms have three possible positions. They were refined isotropically with Uiso(H) = 1.2Ueq(N) and the N—H and H···H distances restrained. The site-occupation factors of the disordered H atoms of the hydroxy group (H12A and H12B) and one of the amino group (H6A) were uniquely assigned to 0.5 each based on the two possible patterns of the hydrogen-bonding linkages related by the twofold axis. The occupation factors of the other N-bound H6B and H6C atoms were assumed to be 0.75 each from a difference map.
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2013 (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: publCIF (Westrip, 2010) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability levels. Only H atoms connected to O, N and chiral C atoms are shown for clarity. Other possible positions of disordered atoms have been omitted. | |
Fig. 2. Three possible combinations of the hydroxy and amino H atoms, the probabilities being (a) 25%, (a') 25% and (b) 50%. Purple dotted lines indicate the intramolecular N—H···O and O—H···N hydrogen bonds. Other H atoms have been omitted for clarity. | |
Fig. 3. A pair of molecules showing a correlation between the intra- and intermolecular hydrogen bonds. A yellow dashed line indicates the intermolecular O—H···O hydrogen bond. Purple dotted lines indicate the intramolecular N—H···O and O—H···N hydrogen bonds. Only the H atoms of the hydroxy and amino groups are shown for clarity. The other possible position of N-bound H atoms due to the disorder are omitted. [Symmetry code: (i) -x + 1, y, -z + 1.] | |
Fig. 4. A packing diagram viewed down to the b axis. Yellow lines indicate the intermolecular O—H···O hydrogen bonds, generating the dimers. Black dashed lines indicate the intermolecular N—H···O, C—H···N and C—H···O interactions. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry codes: (i) -x + 1, y, -z + 1; (ii) x - 1/2, y - 1/2, z - 1/2; (iii) x + 1/2, y + 1/2, z + 1/2; (vi) -x + 3/2, y + 1/2, -z + 3/2; (vii) -x + 1/2, y + 1/2, -z + 1/2.] | |
Fig. 5. A partial packing diagram viewed along [101], showing hydrogen bonding in the sheet structure. Overlapped molecules indicate the dimer. Black dashed lines indicate the intermolecular N—H···O, C—H···N and C—H···O interactions. Only H atoms involved in hydrogen bonds are shown for clarity. | |
Fig. 6. The core structures for database survey; (a) 5-hydroxymethyl-4-(prop-2-enoate-3-yl) substituted 1,3-dioxolane, and its (b) 2,2-dimethyl, (c) 2-oxo, (d) 2-alkoxy-2-alkyl and (e) 2-amino-2-trichloromethyl derivatives, (f) 2,2,2-trichloroethan-1-amine, and its derivatives (g) 2-amino-2-trichloromethyl-1,3-dioxolane (n = 1) or -1,3-dioxane (n = 2); and (h) the structure of the title compound. |
C10H14Cl3NO5 | Dx = 1.607 Mg m−3 |
Mr = 334.57 | Melting point = 366–365 K |
Monoclinic, I2 | Mo Kα radiation, λ = 0.71073 Å |
a = 14.8821 (9) Å | Cell parameters from 6489 reflections |
b = 5.5847 (3) Å | θ = 2.5–24.9° |
c = 17.2971 (14) Å | µ = 0.68 mm−1 |
β = 105.847 (2)° | T = 90 K |
V = 1382.96 (16) Å3 | Prism, colourless |
Z = 4 | 0.26 × 0.22 × 0.16 mm |
F(000) = 688 |
Bruker D8 Venture diffractometer | 2420 independent reflections |
Radiation source: fine-focus sealed tube | 2272 reflections with I > 2σ(I) |
Multilayered confocal mirror monochromator | Rint = 0.030 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
φ and ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −6→6 |
Tmin = 0.84, Tmax = 0.90 | l = −20→20 |
11488 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.0137P)2 + 1.951P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2420 reflections | Δρmax = 0.29 e Å−3 |
207 parameters | Δρmin = −0.21 e Å−3 |
36 restraints | Absolute structure: Flack x determined using 959 quotients [(I+)–(I–)]/[(I+)+(I–)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (2) |
C10H14Cl3NO5 | V = 1382.96 (16) Å3 |
Mr = 334.57 | Z = 4 |
Monoclinic, I2 | Mo Kα radiation |
a = 14.8821 (9) Å | µ = 0.68 mm−1 |
b = 5.5847 (3) Å | T = 90 K |
c = 17.2971 (14) Å | 0.26 × 0.22 × 0.16 mm |
β = 105.847 (2)° |
Bruker D8 Venture diffractometer | 2420 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 2272 reflections with I > 2σ(I) |
Tmin = 0.84, Tmax = 0.90 | Rint = 0.030 |
11488 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.052 | Δρmax = 0.29 e Å−3 |
S = 1.03 | Δρmin = −0.21 e Å−3 |
2420 reflections | Absolute structure: Flack x determined using 959 quotients [(I+)–(I–)]/[(I+)+(I–)] (Parsons et al., 2013) |
207 parameters | Absolute structure parameter: −0.02 (2) |
36 restraints |
Experimental. M.p. 365–366 K (not corrected); [α]20D + 33.8 (c 0.32, CHCl3); IR (KBr): 3450, 3393, 3371, 3295, 3020, 2947, 2921, 2873, 1715, 1656, 1613, 1579, 1438, 1376, 1336, 1313, 1251, 1220, 1121, 1098, 1080, 1037, 1003, 977, 933, 909, 826, 803, 740, 585 cm-1; 1H NMR (500 MHz, CDCl3): δ (p.p.m.) 7.12 (dq, J = 7.5, 1.4 Hz, 1H; H13), 5.49 (t, J = 7.5 Hz, 1H; H8), 4.74 (dt, J = 7.5, 2.3 Hz, 1H; H9), 4.63 (bs, 1H; H12), 3.90 (dd, J = 12.9, 2.3 Hz, 1H; H11A), 3.77 (s, 3H; H19A–F), 3.57 (bd, J = 12.9 Hz, 1H; H11B), 3.06 (bs, 2H; H6), 1.90 (d, J = 1.4 Hz, 3H; H15A–F); 13C NMR (125 MHz, CDCl3): δ (p.p.m.) 167.6 (C), 135.6 (CH), 131.7 (C), 115.3 (C), 103.8 (C), 83.6 (CH), 79.8 (CH), 62.1 (CH2), 52.4 (CH3), 13.5 (CH3); |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. Problematic three reflections (1 –5 10, –13 0 15 and –12 0 16) with |Iobs–Icalc|/σW(I) greater than 10 have been omitted in the final refinement. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.49607 (5) | 0.41064 (14) | 0.10141 (4) | 0.02169 (18) | |
Cl2 | 0.69020 (5) | 0.44496 (13) | 0.18886 (5) | 0.02292 (19) | |
Cl3 | 0.57725 (5) | 0.87077 (13) | 0.15202 (5) | 0.0279 (2) | |
C4 | 0.5774 (2) | 0.5655 (5) | 0.17849 (19) | 0.0165 (7) | |
C5 | 0.5517 (2) | 0.5446 (6) | 0.25983 (19) | 0.0192 (7) | |
N6 | 0.4607 (2) | 0.6381 (8) | 0.25371 (19) | 0.0432 (10) | |
H6A | 0.453 (6) | 0.657 (12) | 0.301 (2) | 0.052* | 0.5 |
H6B | 0.453 (4) | 0.781 (5) | 0.236 (3) | 0.052* | 0.75 |
H6C | 0.433 (2) | 0.523 (6) | 0.230 (3) | 0.052* | 0.75 |
O7 | 0.61956 (15) | 0.6675 (4) | 0.31855 (13) | 0.0202 (5) | |
C8 | 0.6707 (2) | 0.5008 (6) | 0.37781 (19) | 0.0190 (7) | |
H8 | 0.7322 | 0.4656 | 0.3673 | 0.023* | |
C9 | 0.6103 (2) | 0.2743 (6) | 0.36247 (19) | 0.0206 (7) | |
H9 | 0.6519 | 0.1318 | 0.3659 | 0.025* | |
O10 | 0.55577 (18) | 0.3032 (4) | 0.28050 (13) | 0.0267 (6) | |
C11 | 0.5478 (2) | 0.2341 (6) | 0.4164 (2) | 0.0227 (7) | |
H11A | 0.5078 | 0.0928 | 0.3971 | 0.027* | |
H11B | 0.5867 | 0.1992 | 0.4715 | 0.027* | |
O12 | 0.49006 (15) | 0.4361 (5) | 0.41859 (12) | 0.0263 (5) | |
H12A | 0.496 (4) | 0.488 (9) | 0.4653 (18) | 0.039* | 0.5 |
H12B | 0.465 (5) | 0.491 (14) | 0.374 (2) | 0.039* | 0.5 |
C13 | 0.6872 (2) | 0.6143 (6) | 0.45876 (19) | 0.0230 (7) | |
H13 | 0.647 | 0.7423 | 0.4636 | 0.028* | |
C14 | 0.7528 (2) | 0.5524 (7) | 0.5242 (2) | 0.0294 (9) | |
C15A | 0.818 (3) | 0.343 (6) | 0.5238 (16) | 0.044 (3) | 0.482 (5) |
H15A | 0.8202 | 0.311 | 0.4686 | 0.066* | 0.482 (5) |
H15B | 0.7958 | 0.2007 | 0.5458 | 0.066* | 0.482 (5) |
H15C | 0.8813 | 0.3833 | 0.5568 | 0.066* | 0.482 (5) |
C16A | 0.767 (4) | 0.651 (8) | 0.6034 (12) | 0.033 (4) | 0.482 (5) |
O17A | 0.8138 (4) | 0.5539 (12) | 0.6617 (3) | 0.0250 (10) | 0.482 (5) |
O18A | 0.7178 (8) | 0.851 (4) | 0.5940 (10) | 0.028 (2) | 0.482 (5) |
C19A | 0.7246 (9) | 0.960 (3) | 0.6710 (10) | 0.032 (2) | 0.482 (5) |
H19A | 0.6983 | 0.8512 | 0.7037 | 0.047* | 0.482 (5) |
H19B | 0.6899 | 1.1108 | 0.6631 | 0.047* | 0.482 (5) |
H19C | 0.7904 | 0.9908 | 0.6985 | 0.047* | 0.482 (5) |
C15B | 0.825 (2) | 0.365 (6) | 0.5320 (16) | 0.044 (3) | 0.518 (5) |
H15D | 0.8045 | 0.2507 | 0.4876 | 0.066* | 0.518 (5) |
H15E | 0.8331 | 0.2813 | 0.5832 | 0.066* | 0.518 (5) |
H15F | 0.8837 | 0.439 | 0.5302 | 0.066* | 0.518 (5) |
C16B | 0.757 (3) | 0.706 (7) | 0.5989 (12) | 0.033 (4) | 0.518 (5) |
O17B | 0.8182 (4) | 0.6902 (11) | 0.6645 (3) | 0.0250 (10) | 0.518 (5) |
O18B | 0.6889 (7) | 0.875 (3) | 0.5956 (10) | 0.028 (2) | 0.518 (5) |
C19B | 0.6959 (9) | 1.028 (2) | 0.6652 (9) | 0.032 (2) | 0.518 (5) |
H19D | 0.6942 | 0.9286 | 0.7115 | 0.047* | 0.518 (5) |
H19E | 0.6433 | 1.1402 | 0.6535 | 0.047* | 0.518 (5) |
H19F | 0.7547 | 1.1171 | 0.6773 | 0.047* | 0.518 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0302 (4) | 0.0189 (4) | 0.0146 (3) | −0.0018 (4) | 0.0037 (3) | −0.0028 (3) |
Cl2 | 0.0207 (4) | 0.0251 (5) | 0.0273 (4) | 0.0083 (3) | 0.0141 (3) | 0.0056 (4) |
Cl3 | 0.0237 (4) | 0.0137 (4) | 0.0420 (5) | 0.0004 (3) | 0.0018 (4) | 0.0047 (4) |
C4 | 0.0155 (16) | 0.0148 (16) | 0.0214 (16) | 0.0008 (12) | 0.0086 (13) | −0.0014 (13) |
C5 | 0.0131 (17) | 0.0287 (18) | 0.0165 (17) | −0.0020 (13) | 0.0051 (13) | −0.0073 (14) |
N6 | 0.0131 (15) | 0.089 (3) | 0.0263 (18) | 0.0115 (18) | 0.0024 (13) | −0.0247 (19) |
O7 | 0.0208 (12) | 0.0169 (12) | 0.0172 (11) | 0.0036 (9) | −0.0047 (9) | −0.0012 (9) |
C8 | 0.0137 (15) | 0.0210 (18) | 0.0223 (17) | 0.0045 (13) | 0.0048 (13) | 0.0037 (13) |
C9 | 0.0240 (18) | 0.0197 (17) | 0.0206 (16) | 0.0036 (14) | 0.0104 (14) | 0.0002 (14) |
O10 | 0.0369 (15) | 0.0285 (14) | 0.0170 (12) | −0.0178 (11) | 0.0112 (11) | −0.0035 (10) |
C11 | 0.0295 (19) | 0.0227 (19) | 0.0208 (17) | −0.0012 (15) | 0.0150 (15) | −0.0007 (14) |
O12 | 0.0254 (12) | 0.0362 (15) | 0.0209 (11) | 0.0051 (12) | 0.0123 (10) | −0.0023 (12) |
C13 | 0.0171 (16) | 0.0258 (19) | 0.0244 (18) | −0.0025 (14) | 0.0027 (14) | 0.0030 (15) |
C14 | 0.0161 (18) | 0.042 (2) | 0.0273 (19) | −0.0112 (15) | 0.0012 (15) | 0.0131 (17) |
C15A | 0.021 (4) | 0.066 (5) | 0.039 (4) | 0.007 (4) | 0.000 (4) | 0.030 (4) |
C16A | 0.014 (8) | 0.065 (16) | 0.018 (3) | −0.015 (6) | 0.000 (2) | 0.014 (5) |
O17A | 0.0230 (16) | 0.033 (3) | 0.0179 (15) | −0.003 (3) | 0.0029 (13) | 0.002 (3) |
O18A | 0.022 (6) | 0.039 (4) | 0.0231 (14) | −0.011 (5) | 0.006 (4) | −0.0089 (19) |
C19A | 0.031 (7) | 0.034 (7) | 0.031 (3) | −0.005 (4) | 0.012 (5) | −0.017 (4) |
C15B | 0.021 (4) | 0.066 (5) | 0.039 (4) | 0.007 (4) | 0.000 (4) | 0.030 (4) |
C16B | 0.014 (8) | 0.065 (16) | 0.018 (3) | −0.015 (6) | 0.000 (2) | 0.014 (5) |
O17B | 0.0230 (16) | 0.033 (3) | 0.0179 (15) | −0.003 (3) | 0.0029 (13) | 0.002 (3) |
O18B | 0.022 (6) | 0.039 (4) | 0.0231 (14) | −0.011 (5) | 0.006 (4) | −0.0089 (19) |
C19B | 0.031 (7) | 0.034 (7) | 0.031 (3) | −0.005 (4) | 0.012 (5) | −0.017 (4) |
Cl1—C4 | 1.763 (3) | C13—H13 | 0.95 |
Cl2—C4 | 1.772 (3) | C14—C16A | 1.439 (17) |
Cl3—C4 | 1.765 (3) | C14—C15B | 1.475 (17) |
C4—C5 | 1.560 (4) | C14—C15A | 1.524 (18) |
C5—O10 | 1.392 (4) | C14—C16B | 1.538 (16) |
C5—O7 | 1.401 (4) | C15A—H15A | 0.98 |
C5—N6 | 1.428 (5) | C15A—H15B | 0.98 |
N6—H6A | 0.87 (3) | C15A—H15C | 0.98 |
N6—H6B | 0.85 (2) | C16A—O17A | 1.19 (2) |
N6—H6C | 0.81 (2) | C16A—O18A | 1.318 (19) |
O7—C8 | 1.439 (4) | O18A—C19A | 1.442 (17) |
C8—C13 | 1.495 (4) | C19A—H19A | 0.98 |
C8—C9 | 1.532 (4) | C19A—H19B | 0.98 |
C8—H8 | 1.0 | C19A—H19C | 0.98 |
C9—O10 | 1.437 (4) | C15B—H15D | 0.98 |
C9—C11 | 1.502 (5) | C15B—H15E | 0.98 |
C9—H9 | 1.0 | C15B—H15F | 0.98 |
C11—O12 | 1.425 (4) | C16B—O17B | 1.252 (19) |
C11—H11A | 0.99 | C16B—O18B | 1.370 (18) |
C11—H11B | 0.99 | O18B—C19B | 1.455 (16) |
O12—H12A | 0.84 (3) | C19B—H19D | 0.98 |
O12—H12B | 0.82 (3) | C19B—H19E | 0.98 |
C13—C14 | 1.323 (5) | C19B—H19F | 0.98 |
C5—C4—Cl1 | 111.0 (2) | C14—C13—C8 | 125.8 (3) |
C5—C4—Cl3 | 108.9 (2) | C14—C13—H13 | 117.1 |
Cl1—C4—Cl3 | 109.02 (17) | C8—C13—H13 | 117.1 |
C5—C4—Cl2 | 109.8 (2) | C13—C14—C16A | 126.6 (9) |
Cl1—C4—Cl2 | 109.01 (16) | C13—C14—C15B | 127.6 (11) |
Cl3—C4—Cl2 | 109.09 (16) | C13—C14—C15A | 121.4 (11) |
O10—C5—O7 | 108.4 (3) | C16A—C14—C15A | 111.8 (12) |
O10—C5—N6 | 110.3 (3) | C13—C14—C16B | 115.0 (7) |
O7—C5—N6 | 110.8 (3) | C15B—C14—C16B | 117.3 (13) |
O10—C5—C4 | 107.5 (3) | C14—C15A—H15A | 109.5 |
O7—C5—C4 | 108.2 (3) | C14—C15A—H15B | 109.5 |
N6—C5—C4 | 111.5 (3) | H15A—C15A—H15B | 109.5 |
C5—N6—H6A | 110 (5) | C14—C15A—H15C | 109.5 |
C5—N6—H6B | 113 (4) | H15A—C15A—H15C | 109.5 |
H6A—N6—H6B | 101 (5) | H15B—C15A—H15C | 109.5 |
C5—N6—H6C | 95 (2) | O17A—C16A—O18A | 132.0 (16) |
H6A—N6—H6C | 113 (5) | O17A—C16A—C14 | 122.1 (15) |
H6B—N6—H6C | 124 (5) | O18A—C16A—C14 | 106.0 (14) |
C5—O7—C8 | 109.6 (2) | C16A—O18A—C19A | 110.2 (15) |
O7—C8—C13 | 108.2 (2) | O18A—C19A—H19A | 109.5 |
O7—C8—C9 | 103.9 (2) | O18A—C19A—H19B | 109.5 |
C13—C8—C9 | 116.8 (3) | H19A—C19A—H19B | 109.5 |
O7—C8—H8 | 109.2 | O18A—C19A—H19C | 109.5 |
C13—C8—H8 | 109.2 | H19A—C19A—H19C | 109.5 |
C9—C8—H8 | 109.2 | H19B—C19A—H19C | 109.5 |
O10—C9—C11 | 110.5 (3) | C14—C15B—H15D | 109.5 |
O10—C9—C8 | 103.0 (2) | C14—C15B—H15E | 109.5 |
C11—C9—C8 | 116.7 (3) | H15D—C15B—H15E | 109.5 |
O10—C9—H9 | 108.8 | C14—C15B—H15F | 109.5 |
C11—C9—H9 | 108.8 | H15D—C15B—H15F | 109.5 |
C8—C9—H9 | 108.8 | H15E—C15B—H15F | 109.5 |
C5—O10—C9 | 109.6 (2) | O17B—C16B—O18B | 115.7 (13) |
O12—C11—C9 | 112.2 (3) | O17B—C16B—C14 | 124.9 (15) |
O12—C11—H11A | 109.2 | O18B—C16B—C14 | 119.4 (15) |
C9—C11—H11A | 109.2 | C16B—O18B—C19B | 119.0 (13) |
O12—C11—H11B | 109.2 | O18B—C19B—H19D | 109.5 |
C9—C11—H11B | 109.2 | O18B—C19B—H19E | 109.5 |
H11A—C11—H11B | 107.9 | H19D—C19B—H19E | 109.5 |
C11—O12—H12A | 113 (2) | O18B—C19B—H19F | 109.5 |
C11—O12—H12B | 113 (6) | H19D—C19B—H19F | 109.5 |
H12A—O12—H12B | 133 (6) | H19E—C19B—H19F | 109.5 |
Cl1—C4—C5—O10 | 62.2 (3) | C8—C9—O10—C5 | −22.5 (3) |
Cl3—C4—C5—O10 | −177.8 (2) | O10—C9—C11—O12 | −64.2 (3) |
Cl2—C4—C5—O10 | −58.5 (3) | C8—C9—C11—O12 | 52.9 (4) |
Cl1—C4—C5—O7 | 179.0 (2) | O7—C8—C13—C14 | −158.9 (3) |
Cl3—C4—C5—O7 | −61.0 (3) | C9—C8—C13—C14 | 84.4 (4) |
Cl2—C4—C5—O7 | 58.4 (3) | C8—C13—C14—C16A | −177 (4) |
Cl1—C4—C5—N6 | −58.9 (4) | C8—C13—C14—C15B | 2 (2) |
Cl3—C4—C5—N6 | 61.2 (3) | C8—C13—C14—C15A | −2 (2) |
Cl2—C4—C5—N6 | −179.5 (3) | C8—C13—C14—C16B | 178 (3) |
O10—C5—O7—C8 | 1.5 (4) | C13—C14—C16A—O17A | 164 (4) |
N6—C5—O7—C8 | 122.7 (3) | C15A—C14—C16A—O17A | −11 (7) |
C4—C5—O7—C8 | −114.7 (3) | C13—C14—C16A—O18A | −15 (6) |
C5—O7—C8—C13 | −139.8 (3) | C15A—C14—C16A—O18A | 170 (4) |
C5—O7—C8—C9 | −15.0 (3) | O17A—C16A—O18A—C19A | −1 (8) |
O7—C8—C9—O10 | 22.3 (3) | C14—C16A—O18A—C19A | 178 (3) |
C13—C8—C9—O10 | 141.3 (3) | C13—C14—C16B—O17B | −174 (4) |
O7—C8—C9—C11 | −98.9 (3) | C15B—C14—C16B—O17B | 3 (7) |
C13—C8—C9—C11 | 20.1 (4) | C13—C14—C16B—O18B | 6 (6) |
O7—C5—O10—C9 | 14.0 (4) | C15B—C14—C16B—O18B | −177 (4) |
N6—C5—O10—C9 | −107.5 (3) | O17B—C16B—O18B—C19B | 3 (6) |
C4—C5—O10—C9 | 130.7 (2) | C14—C16B—O18B—C19B | −177 (3) |
C11—C9—O10—C5 | 102.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12B···N6 | 0.82 (3) | 2.22 (4) | 2.986 (4) | 155 (7) |
N6—H6A···O12 | 0.87 (3) | 2.31 (5) | 2.986 (4) | 135 (6) |
O12—H12A···O12i | 0.84 (3) | 1.98 (4) | 2.750 (4) | 151 (5) |
N6—H6C···O17Bii | 0.81 (2) | 2.57 (2) | 3.369 (7) | 169 (3) |
C19A—H19C···N6iii | 0.98 | 2.59 | 3.555 (15) | 167 |
N6—H6B···O17Aiv | 0.85 (2) | 2.61 (5) | 3.286 (7) | 137 (5) |
C19B—H19E···O12v | 0.98 | 2.62 | 3.573 (11) | 164 |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x−1/2, y−1/2, z−1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x−1/2, y+1/2, z−1/2; (v) −x+1, y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12B···N6 | 0.82 (3) | 2.22 (4) | 2.986 (4) | 155 (7) |
N6—H6A···O12 | 0.87 (3) | 2.31 (5) | 2.986 (4) | 135 (6) |
O12—H12A···O12i | 0.84 (3) | 1.98 (4) | 2.750 (4) | 151 (5) |
N6—H6C···O17Bii | 0.81 (2) | 2.57 (2) | 3.369 (7) | 169 (3) |
C19A—H19C···N6iii | 0.98 | 2.59 | 3.555 (15) | 167 |
N6—H6B···O17Aiv | 0.85 (2) | 2.61 (5) | 3.286 (7) | 137 (5) |
C19B—H19E···O12v | 0.98 | 2.62 | 3.573 (11) | 164 |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x−1/2, y−1/2, z−1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x−1/2, y+1/2, z−1/2; (v) −x+1, y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H14Cl3NO5 |
Mr | 334.57 |
Crystal system, space group | Monoclinic, I2 |
Temperature (K) | 90 |
a, b, c (Å) | 14.8821 (9), 5.5847 (3), 17.2971 (14) |
β (°) | 105.847 (2) |
V (Å3) | 1382.96 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.26 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Bruker D8 Venture |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.84, 0.90 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11488, 2420, 2272 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.052, 1.03 |
No. of reflections | 2420 |
No. of parameters | 207 |
No. of restraints | 36 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.21 |
Absolute structure | Flack x determined using 959 quotients [(I+)–(I–)]/[(I+)+(I–)] (Parsons et al., 2013) |
Absolute structure parameter | −0.02 (2) |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010) and PLATON (Spek, 2009).
Acknowledgements
This research was partially supported by the Keio Gijuku Fukuzawa Memorial Fund for the Advancement of Education and Research. We also thank Professor S. Ohba (Keio University, Japan) for his valuable advice.
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