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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 74| Part 12| December 2018| Pages 1741-1745
https://doi.org/10.1107/S2056989018015451

Two polymorphic forms of the oxathiin systemic fungicide active carboxine

CROSSMARK_Color_square_no_text.svg
Christopher S. Frampton,a* Eleanor S. Framptonb and Paul A. Thomsonc

aExperimental Techniques Centre, Brunel University London, Kingston Lane, Uxbridge UB8 3PH, England, bUniversity of Nottingham, University Park, Clifton Blvd, Nottingham NG7 2RD, England, and cVive Crop Protection, 6275 Northam Drive, Unit 1, Mississauga, ON L4V 1Y8, Canada
*Correspondence e-mail: chris.frampton@brunel.ac.uk

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 29 October 2018; accepted 1 November 2018; online 9 November 2018)

Two polymorphic crystal forms of the title compound, C12H13NO2S (systematic name: 6-methyl-N-phenyl-2,3-di­hydro-1,4-oxathiine-5-carboxamide), were isolated from a truncated, (12 solvent), polymorph screen on pure lyophillized material. Crystals of form 1 were obtained from all solvents included in the screen with the exception of methanol. As isolated from aceto­nitrile the crystals are triclinic, space group P[\overline{1}] with Z′ = 2. Crystals of form 2, which were isolated from methanol only are monoclinic, space group I2/a with Z′ = 1. The crystal packing in both structures is dominated by the formation of infinite –NH⋯O hydrogen-bonded chains through the carboxamide core.

CCDC references: 1876595; 1876594

Similar articles

1. Chemical context

6-Methyl-N-phenyl-2,3-di­hydro-1,4-oxathiine-5-carboxamide, (Carboxine or Carboxin) 1, is a systemic fungicide from the oxathiin class of agents. This class of agents was discovered in 1964 (von Schmeling & Kulka, 1966[Schmeling, B. von & Kulka, M. (1966). Science, 152, 659-660.]) and was notable in that they were among the first fungicides that were known to exhibit translocation i.e. the ability to move from the leaves to other tissues in the plant. This unique property has made them particularly effective for protection against rusts and smuts. In particular 1, which is marketed under the trade name VITAVAX®, has itself demonstrated high specificity against the fungal class Basideomycetes, Deuteromycetes and Phycomycetes (Edgington et al., 1966[Edgington, L. V., Walton, G. S. & Miller, P. M. (1966). Science, 153, 307-308.]; Edgington & Barron, 1967[Edgington, L. V. & Barron, G. L. (1967). Phytopathology, 57, 1256-1257.]; Snel et al., 1970[Snel, M., von Schmeling, B. & Edgington, L. V. (1970). Phytopathology, 60, 1164-1169.]). There is currently no report of any crystal structure of this important fungicide in the literature although the material has been reported to be dimorphic based upon the observation of two distinct melting points, 91.5–92.5 °C and 98–100 °C (Worthing, 1979[Worthing, C. R. (1979). The Pesticide Manual: A World Compendium, 6th ed. The British Crop Protection Council, Croydon, England.]). As part of an ongoing program into the preparation of co-crystal forms of agrichemical active materials to enhance or adapt their physicochemical properties (Eberlin & Frampton, 2017[Eberlin, A. R. & Frampton, C. S. (2017). Acta Cryst. E73, 886-889.]), it was pertinent to investigate the possible crystal structures of this active material. Given that there is just one hydrogen-bond donor and three possible acceptor groups it was deemed necessary to probe the nature of the hydrogen-bonding inter­actions present in the two distinct forms, thus directing the choice of prospective coformers for a screen. In this paper we report the single crystal X-ray structures of the two reported dimorphic forms of Carboxine 1 at 100 K.

[Scheme 1]

2. Structural commentary

Colourless block-shaped crystals of form 1 were obtained from aceto­nitrile. The crystal structure of form 1 of Carboxine is triclinic, Space group P[\overline{1}], with two independent mol­ecules in the asymmetric unit, (Z '= 2). For clarity, each independent mol­ecule is labelled with suffix A or B. Figs. 1[link] and 2[link] show displacement ellipsoid plots for the two mol­ecules, A and B. Hydrogen-bond distances and angles are given in Table 1[link]. The mol­ecule contains two rotational degrees of freedom such that the phenyl and oxathiin rings can rotate with respect to the central carboxamide core. The phenyl ring defined by atoms C1–C6 and the carboxamide core defined by atoms C6, N1, C7, O1 and C8 are almost planar. A calculated least-squares plane through the six atoms of the phenyl ring and through the five atoms of the carboxamide core gave r.m.s. deviations from planarity and a calculated dihedral angle between them as follows; Mol­ecule A, 0.0016 Å, 0.0278 Å, 24.80 (6)°, respect­ively; mol­ecule B, 0.0020 Å, 0.0040 Å, 43.06 (5)°, respectively. It is inter­esting to note that the carboxamide core for Mol­ecule A is significantly less planar than that of Mol­ecule B with atom N1A displaced from the mean plane by −0.0481 (6) Å. The orientation of the oxathiin moiety with respect to the carboxamide core also differs for each mol­ecule in the asymmetric unit with the torsion angle O1—C7—C8—S1 having values of 33.1 (2)° and 143.4 (1)° for mol­ecules A and B, respectively. Fig. 3[link] shows an overlay of the two mol­ecules in the asymmetric unit (Mol­ecule A in violet and Mol­ecule B in green), showing the differences in their conformations; the overlay was constructed based on the six atoms of the phenyl ring only (r.m.s. deviation = 0.0034 Å) using the Structure Overlay routine in Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]). A DSC of the material from this crystallization experiment gave a single sharp melting endotherm, (onset 97.4 °C, peak 98.2 °C).

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

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1A—H1C⋯O1Ai 0.860 (18) 2.179 (18) 2.9571 (14) 150.4 (15)
N1B—H1D⋯O1Bi 0.84 (2) 2.21 (2) 2.9784 (14) 151.4 (17)
Symmetry code: (i) x+1, y, z.
[Figure 1]
Figure 1
View of mol­ecule A of the asymmetric unit of form 1 with the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
View of mol­ecule B of the asymmetric unit of form 1 with the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3]
Figure 3
View of the structure overlay of mol­ecule A (violet) and mol­ecule B (green) from the form 1 structure.

Colourless lath-shaped crystals of form 2 were obtained by slow evaporation from methanol. The crystal structure of form 2 is monoclinic, space group I2/a with a single mol­ecule in the asymmetric unit, (Z '= 1). Fig. 4[link] shows a displacement ellipsoid plot and the hydrogen-bond distance and angle is given in Table 2[link]. Calculated least-squares planes through the phenyl ring and carboxamide core as described above for the form 1 structure show that these two groups are closer to being coplanar than in the form 1 structure, with r.m.s. deviations from planarity and a calculated dihedral angle between the planes being 0.0064 Å, 0.0154 Å and 9.59 (6)°, respectively. The O1—C7—C8—S1 torsion angle for the form 2 structure is 47.3 (2)°.

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

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯O1i 0.87 (2) 2.00 (2) 2.8683 (18) 178.1 (18)
Symmetry code: (i) [x+{\script{1\over 2}}, -y+1, z].
[Figure 4]
Figure 4
View of mol­ecule 1 of the asymmetric unit of form 2 with the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

A DSC of the form 2 material is shown in Fig. 5[link]. It shows a sharp melting endotherm, (onset 90.1 °C, peak 91.1 °C), followed by an exothermic recrystallization event, (onset 92.1 °C, peak 92.5 °C) to form 1, which subsequently gives a sharp melting endotherm (onset 97.5 °C, peak 98.4 °C). From this we deduce that form 1 is the most thermodynamically stable of the two forms, which is also supported by the higher density of form 1 over form 2, 1.431 g cm−3 versus 1.316 g cm−3, respectively. We also note that if crystals of form 2 are left in the methanol mother liquor for a period of time they will spontaneously convert to the form 1 polymorph.

[Figure 5]
Figure 5
Differential scanning calorimetry thermogram of form 2.

3. Supra­molecular features

The packing of mol­ecules in the crystal structure of form 1 is governed by the formation of two infinite hydrogen-bonded chains, which run parallel to the crystallographic a axis, Fig. 6[link]. These two chains are formed from discrete Mol­ecule A and Mol­ecule B moieties respectively. The hydrogen-bonding inter­actions are through the amide –NH to carbonyl O for both chains with D⋯A distances of 2.957 (1) and 2.978 (1) Å for the A and B chains, respectively. The N—H⋯O hydrogen bond angles for both chains are significantly reduced from 180° to ∼150 (2)° in both chains. The crystal packing found in form 2 is also governed by the formation of an infinite amide –NH to carbonyl O hydrogen-bonded chain, which again runs parallel to the crystallographic a axis of the unit cell, Fig. 7[link]. The D⋯A distance for this chain is significantly shorter than that found in the form 1 structure at 2.868 (2) Å and the N—H⋯O hydrogen bond angle for this chain is ∼178 (2)°, which is closer to the expected linear value.

[Figure 6]
Figure 6
View of the crystal packing of form 1 as viewed approximately down the a axis. The N—H⋯O hydrogen bonds are shown as dotted lines (see Table 1[link] and text).
[Figure 7]
Figure 7
View of the crystal packing of form 2 as viewed down the b axis. The N—H⋯O hydrogen bonds are shown as dotted lines (see Table 2[link] and text).

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.39 update August 2018; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) for the oxathiin moiety yielded just five hits, all of which were genuine examples or analogues of the material under investigation. The closest example to the title compound is the direct dioxide, (–SO2), analogue KABFEA (Brown & Baughman, 2010[Brown, J. E. & Baughman, R. G. (2010). Acta Cryst. E66, o2654.]). A further close example is one where the phenyl group has been substituted at the 4- and 5-positions with a chloro and isopropyl benzoate group, respectively, SOHZUK (Silverton et al., 1991[Silverton, J. V., Quinn, F. R. & Haugwitz, R. D. (1991). Acta Cryst. C47, 1911-1913.]). Structure ZANDUQ (Kulkarni, 2017[Kulkarni, M. V. (2017). CSD Private Communication.]) is a chromene-substituted oxathiin and structure XEQPEO (Caputo et al., 1999[Caputo, R., Giordano, F., Guaragna, A., Palumbo, G. & Pedatella, S. (1999). Tetrahedron Asymmetry, 10, 3463-3466.]) is an example of a chiral sulfoxide oxathiin with a single phenyl substituent. The remaining example, TUHDUV is a fused oxathiin (Moge et al., 1996[Moge, M., Hellberg, J., Törnroos, K. W. & von Schütz, J.-U. (1996). Adv. Mater. 8, 807-808.]) synthesized in order to incorporate an oxygen atom into tetra­thia­fulvalene.

5. Synthesis and crystallization

Crystals of form 1 and form 2 of Carboxine were isolated from a truncated polymorph screen based on the recrystallization of lyophillized amorphous material from twelve different solvent or solvent water mixtures. Carboxine (Sigma Aldrich, 99.9%, Lot # SZBC023XV), was analyzed by X-ray powder diffraction and DSC as received prior to commencing the polymorph screen. The data demonstrated the starting material to be highly crystalline with a single sharp melting endotherm, (onset 97.4 °C, peak 98.2 °C). This material was assigned as form 1. The polymorph screen consisted of approximately 50 mg of lyophillized Carboxine being dispensed per vial along with approximately 40 volumes of the appropriate solvent or solvent/water mixture (ca 2 ml) at room temperature. For the vials that gave clear solutions, these were filtered through a 4 µm filter to remove any potential seeds that may have remained in the solution. Samples that did not dissolve were kept as a slurry. The vials were placed in a platform shaker incubator (Heidolph Titramax/Inkubator 1000) and subjected to a series of heat–cool cycles under shaking from room temperature (RT) to 50 °C (8 h cycles; heating to 50 °C for 4 h and then cooling to RT for a further 4 h) for a maximum of 48 h. The resulting solutions were then allowed to evaporate slowly. Samples that crystallized by saturation crystallization were filtered and the resultant filtrate was then allowed to evaporate to dryness. Samples that did not crystallize were allowed to evaporate to dryness. All solid materials obtained from the screen were analyzed by X-ray powder diffraction. Of the twelve vials in the polymorph screen, eleven demonstrated an X-ray powder diffraction pattern that was identical to that of the starting material (form 1) whereas the material from the twelfth vial gave a pattern that was completely different. Suitable single-crystal samples were selected, form 1 from vial 9, (aceto­nitrile) and form 2 from vial 8 (methanol). A DSC of the form 2 crystalline material was also measured. It should be noted that in the course of this study, it was discovered that if the crystals of form 2 were allowed to remain in the methanol mother liquor, they will over a period of time convert to yield the form 1 structure. A list of solvents and the results of the truncated polymorph screen are given in the supporting information.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. N-bound H atoms were freely refined. C-bound H atoms were positioned geometrically (C—H = 0.95 0.99 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C).

Table 3
Experimental details

  form 1 form 2
Crystal data
Chemical formula C12H13NO2S C12H13NO2S
Mr 235.29 235.29
Crystal system, space group Triclinic, P[\overline{1}] Monoclinic, I2/a
Temperature (K) 100 100
a, b, c (Å) 5.1669 (2), 14.0781 (5), 15.5152 (5) 9.6424 (2), 11.4059 (3), 21.6672 (5)
α, β, γ (°) 82.596 (3), 80.552 (3), 80.463 (3) 90, 94.711 (2), 90
V (Å3) 1091.87 (7) 2374.92 (9)
Z 4 8
Radiation type Cu Kα Cu Kα
μ (mm−1) 2.51 2.30
Crystal size (mm) 0.56 × 0.20 × 0.14 0.31 × 0.07 × 0.06
 
Data collection
Diffractometer Rigaku SuperNova, Dualflex, AtlasS2 Rigaku SuperNova, Dualflex, AtlasS2
Absorption correction Analytical (CrysAlis PRO; Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Rigaku Corporation, Yarnton, England.]) Analytical (CrysAlis PRO; Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Rigaku Corporation, Yarnton, England.])
Tmin, Tmax 0.420, 0.717 0.664, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections 8710, 4481, 4393 4644, 2415, 2244
Rint 0.016 0.016
(sin θ/λ)max (Å−1) 0.625 0.625
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.080, 1.03 0.040, 0.116, 1.03
No. of reflections 4481 2415
No. of parameters 299 150
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.32, −0.35 0.51, −0.45
Computer programs: CrysAlis PRO (Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Rigaku Corporation, Yarnton, England.]), SHELXD2014/6 (Schneider & Sheldrick, 2002[Schneider, T. R. & Sheldrick, G. M. (2002). Acta Cryst. D58, 1772-1779.]), SHELXL2014/6 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Supporting information

CCDC references: 1876595; 1876594

Crystal structure: contains datablocks b17006r, b17007r. DOI: https://doi.org/10.1107/S2056989018015451/hb7783sup1.cif

Structure factors: contains datablock b17006r. DOI: https://doi.org/10.1107/S2056989018015451/hb7783b17006rsup2.hkl

Structure factors: contains datablock b17007r. DOI: https://doi.org/10.1107/S2056989018015451/hb7783b17007rsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018015451/hb7783b17006rsup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989018015451/hb7783b17007rsup5.cml

Table of solvents used in the truncated polymorph screen. DOI: https://doi.org/10.1107/S2056989018015451/hb7783sup6.docx

checkCIF report


Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXD2014/6 (Schneider & Sheldrick, 2002); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015). Molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008) for b17006r; SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008) for b17007r. Software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008) for b17006r; SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008) for b17007r.

6-Methyl-N-phenyl-2,3-dihydro-1,4-oxathiine-5-carboxamide (b17006r) top
Crystal data top
C12H13NO2SF(000) = 496
Mr = 235.29Dx = 1.431 Mg m−3
Triclinic, P1Melting point: 371.22 K
a = 5.1669 (2) ÅCu Kα radiation, λ = 1.54178 Å
b = 14.0781 (5) ÅCell parameters from 7281 reflections
c = 15.5152 (5) Åθ = 3.2–76.4°
α = 82.596 (3)°µ = 2.51 mm−1
β = 80.552 (3)°T = 100 K
γ = 80.463 (3)°Block, colourless
V = 1091.87 (7) Å30.56 × 0.20 × 0.14 mm
Z = 4
Data collection top
Rigaku SuperNova, Dualflex, AtlasS2
diffractometer		4481 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source4393 reflections with I > 2σ(I)
Detector resolution: 5.2921 pixels mm-1Rint = 0.016
ω scansθmax = 74.5°, θmin = 2.9°
Absorption correction: analytical
(CrysAlis PRO; Rigaku OD, 2015)		h = −5→6
Tmin = 0.420, Tmax = 0.717k = −17→17
8710 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.080 w = 1/[σ2(Fo2) + (0.0425P)2 + 0.650P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
4481 reflectionsΔρmax = 0.32 e Å−3
299 parametersΔρmin = −0.35 e Å−3
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1A0.24969 (6)0.59541 (2)0.62071 (2)0.01479 (9)
O1A0.07910 (18)0.74358 (7)0.74003 (7)0.0169 (2)
O2A0.70130 (18)0.45917 (7)0.71133 (6)0.01512 (19)
N1A0.4950 (2)0.75662 (8)0.76391 (7)0.0127 (2)
H1C0.659 (4)0.7308 (12)0.7563 (11)0.013 (4)*
C1A0.2283 (3)0.91659 (9)0.78592 (8)0.0135 (2)
H1A0.11070.90680.74790.016*
C2A0.1908 (3)1.00263 (10)0.82504 (9)0.0155 (3)
H2A0.04651.05140.81350.019*
C3A0.3614 (3)1.01785 (10)0.88044 (9)0.0163 (3)
H3A0.33481.07680.90650.020*
C4A0.5717 (3)0.94615 (10)0.89754 (9)0.0161 (3)
H4A0.68900.95620.93560.019*
C5A0.6115 (3)0.85993 (10)0.85930 (8)0.0140 (3)
H5A0.75520.81110.87130.017*
C6A0.4398 (2)0.84526 (9)0.80313 (8)0.0121 (2)
C7A0.3145 (3)0.70923 (9)0.73973 (8)0.0124 (2)
C8A0.4183 (2)0.61317 (9)0.70683 (8)0.0123 (2)
C9A0.3579 (3)0.46729 (9)0.61878 (9)0.0159 (3)
H9A0.25440.43150.66800.019*
H9B0.32630.44690.56310.019*
C10A0.6506 (3)0.44334 (10)0.62671 (9)0.0176 (3)
H10A0.71330.37470.61680.021*
H10B0.75150.48410.58080.021*
C11A0.6002 (2)0.54610 (9)0.74270 (8)0.0127 (2)
C12A0.7129 (3)0.54989 (10)0.82493 (9)0.0165 (3)
H12A0.72040.48640.85950.025*
H12B0.59990.59870.85960.025*
H12C0.89220.56710.80960.025*
S1B0.82208 (6)0.75132 (2)0.43964 (2)0.01312 (9)
O1B0.39731 (18)0.78370 (7)0.25355 (6)0.0160 (2)
O2B0.35235 (18)0.91997 (7)0.48272 (6)0.01362 (19)
N1B0.8469 (2)0.75216 (8)0.24445 (7)0.0120 (2)
H1D0.975 (4)0.7656 (13)0.2653 (12)0.022 (5)*
C1B0.7445 (3)0.65546 (9)0.13678 (9)0.0141 (3)
H1B0.59990.63540.17730.017*
C2B0.8057 (3)0.62198 (10)0.05419 (9)0.0168 (3)
H2B0.70290.57850.03870.020*
C3B1.0153 (3)0.65141 (11)−0.00591 (9)0.0180 (3)
H3B1.05550.6284−0.06220.022*
C4B1.1653 (3)0.71480 (11)0.01725 (9)0.0185 (3)
H4B1.30850.7354−0.02360.022*
C5B1.1079 (3)0.74833 (10)0.09968 (9)0.0152 (3)
H5B1.21210.79130.11520.018*
C6B0.8970 (2)0.71870 (9)0.15961 (8)0.0122 (2)
C7B0.5989 (3)0.78364 (9)0.28597 (8)0.0119 (2)
C8B0.5859 (2)0.81617 (9)0.37465 (8)0.0116 (2)
C9B0.7615 (3)0.82802 (10)0.52748 (8)0.0143 (3)
H9C0.83720.79280.57920.017*
H9D0.84850.88640.50860.017*
C10B0.4647 (3)0.85779 (10)0.55196 (8)0.0145 (3)
H10C0.37690.79910.56520.017*
H10D0.43130.89170.60560.017*
C11B0.3986 (2)0.88970 (9)0.40068 (8)0.0118 (2)
C12B0.2180 (3)0.95418 (10)0.34453 (9)0.0143 (3)
H12D0.04590.93100.35340.021*
H12E0.29650.95340.28260.021*
H12F0.19321.02050.36070.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.01540 (16)0.01280 (15)0.01776 (16)−0.00099 (12)−0.00729 (12)−0.00270 (11)
O1A0.0094 (4)0.0170 (5)0.0254 (5)−0.0008 (4)−0.0028 (4)−0.0070 (4)
O2A0.0142 (4)0.0125 (4)0.0186 (5)0.0010 (3)−0.0046 (4)−0.0025 (4)
N1A0.0086 (5)0.0125 (5)0.0170 (5)0.0003 (4)−0.0024 (4)−0.0035 (4)
C1A0.0126 (6)0.0142 (6)0.0140 (6)−0.0028 (5)−0.0025 (5)−0.0012 (5)
C2A0.0145 (6)0.0144 (6)0.0166 (6)−0.0011 (5)−0.0009 (5)−0.0013 (5)
C3A0.0190 (7)0.0157 (6)0.0146 (6)−0.0041 (5)0.0006 (5)−0.0047 (5)
C4A0.0161 (6)0.0214 (7)0.0121 (6)−0.0057 (5)−0.0021 (5)−0.0033 (5)
C5A0.0114 (6)0.0176 (6)0.0126 (6)−0.0020 (5)−0.0009 (5)−0.0010 (5)
C6A0.0118 (6)0.0125 (6)0.0120 (6)−0.0033 (5)0.0002 (5)−0.0010 (5)
C7A0.0116 (6)0.0134 (6)0.0120 (6)−0.0022 (5)−0.0010 (5)−0.0007 (5)
C8A0.0102 (6)0.0133 (6)0.0138 (6)−0.0027 (5)−0.0015 (5)−0.0020 (5)
C9A0.0181 (7)0.0128 (6)0.0179 (6)−0.0022 (5)−0.0037 (5)−0.0041 (5)
C10A0.0176 (7)0.0181 (6)0.0171 (6)−0.0002 (5)−0.0016 (5)−0.0060 (5)
C11A0.0104 (6)0.0126 (6)0.0150 (6)−0.0026 (5)−0.0006 (5)−0.0016 (5)
C12A0.0168 (6)0.0167 (6)0.0166 (6)−0.0017 (5)−0.0065 (5)0.0003 (5)
S1B0.01241 (15)0.01383 (15)0.01324 (15)0.00139 (11)−0.00400 (11)−0.00350 (11)
O1B0.0107 (4)0.0232 (5)0.0160 (4)−0.0026 (4)−0.0030 (4)−0.0075 (4)
O2B0.0139 (4)0.0158 (4)0.0110 (4)0.0011 (4)−0.0027 (3)−0.0039 (3)
N1B0.0095 (5)0.0157 (5)0.0119 (5)−0.0017 (4)−0.0026 (4)−0.0043 (4)
C1B0.0128 (6)0.0150 (6)0.0145 (6)−0.0012 (5)−0.0014 (5)−0.0030 (5)
C2B0.0157 (6)0.0181 (6)0.0180 (6)−0.0006 (5)−0.0057 (5)−0.0059 (5)
C3B0.0173 (7)0.0236 (7)0.0125 (6)0.0023 (5)−0.0033 (5)−0.0056 (5)
C4B0.0144 (6)0.0255 (7)0.0144 (6)−0.0024 (5)−0.0002 (5)−0.0006 (5)
C5B0.0122 (6)0.0181 (6)0.0159 (6)−0.0025 (5)−0.0037 (5)−0.0014 (5)
C6B0.0117 (6)0.0123 (6)0.0121 (6)0.0016 (5)−0.0032 (5)−0.0019 (5)
C7B0.0118 (6)0.0111 (6)0.0130 (6)−0.0025 (4)−0.0014 (5)−0.0016 (4)
C8B0.0102 (6)0.0138 (6)0.0115 (6)−0.0032 (5)−0.0021 (4)−0.0017 (5)
C9B0.0140 (6)0.0183 (6)0.0115 (6)−0.0014 (5)−0.0037 (5)−0.0043 (5)
C10B0.0146 (6)0.0185 (6)0.0102 (6)−0.0012 (5)−0.0029 (5)−0.0013 (5)
C11B0.0109 (6)0.0141 (6)0.0114 (6)−0.0041 (5)−0.0020 (5)−0.0023 (5)
C12B0.0137 (6)0.0155 (6)0.0137 (6)−0.0001 (5)−0.0036 (5)−0.0023 (5)
Geometric parameters (Å, º) top
S1A—C8A1.7741 (13)S1B—C8B1.7712 (13)
S1A—C9A1.8003 (13)S1B—C9B1.8024 (13)
O1A—C7A1.2317 (16)O1B—C7B1.2287 (16)
O2A—C11A1.3658 (16)O2B—C11B1.3657 (15)
O2A—C10A1.4316 (16)O2B—C10B1.4323 (15)
N1A—C7A1.3571 (17)N1B—C7B1.3666 (17)
N1A—C6A1.4247 (16)N1B—C6B1.4244 (16)
N1A—H1C0.860 (18)N1B—H1D0.84 (2)
C1A—C6A1.3917 (18)C1B—C2B1.3919 (18)
C1A—C2A1.3951 (18)C1B—C6B1.3945 (18)
C1A—H1A0.9500C1B—H1B0.9500
C2A—C3A1.3858 (19)C2B—C3B1.390 (2)
C2A—H2A0.9500C2B—H2B0.9500
C3A—C4A1.390 (2)C3B—C4B1.389 (2)
C3A—H3A0.9500C3B—H3B0.9500
C4A—C5A1.3895 (19)C4B—C5B1.3896 (19)
C4A—H4A0.9500C4B—H4B0.9500
C5A—C6A1.3965 (18)C5B—C6B1.3943 (18)
C5A—H5A0.9500C5B—H5B0.9500
C7A—C8A1.4915 (17)C7B—C8B1.4930 (17)
C8A—C11A1.3517 (18)C8B—C11B1.3486 (18)
C9A—C10A1.5159 (19)C9B—C10B1.5190 (18)
C9A—H9A0.9900C9B—H9C0.9900
C9A—H9B0.9900C9B—H9D0.9900
C10A—H10A0.9900C10B—H10C0.9900
C10A—H10B0.9900C10B—H10D0.9900
C11A—C12A1.4971 (18)C11B—C12B1.4953 (17)
C12A—H12A0.9800C12B—H12D0.9800
C12A—H12B0.9800C12B—H12E0.9800
C12A—H12C0.9800C12B—H12F0.9800
C8A—S1A—C9A97.81 (6)C8B—S1B—C9B98.52 (6)
C11A—O2A—C10A118.67 (10)C11B—O2B—C10B118.26 (10)
C7A—N1A—C6A126.29 (11)C7B—N1B—C6B123.68 (11)
C7A—N1A—H1C117.9 (11)C7B—N1B—H1D116.5 (13)
C6A—N1A—H1C115.8 (11)C6B—N1B—H1D118.2 (13)
C6A—C1A—C2A119.32 (12)C2B—C1B—C6B119.48 (12)
C6A—C1A—H1A120.3C2B—C1B—H1B120.3
C2A—C1A—H1A120.3C6B—C1B—H1B120.3
C3A—C2A—C1A120.87 (13)C3B—C2B—C1B120.82 (13)
C3A—C2A—H2A119.6C3B—C2B—H2B119.6
C1A—C2A—H2A119.6C1B—C2B—H2B119.6
C2A—C3A—C4A119.48 (12)C4B—C3B—C2B119.30 (12)
C2A—C3A—H3A120.3C4B—C3B—H3B120.4
C4A—C3A—H3A120.3C2B—C3B—H3B120.4
C5A—C4A—C3A120.38 (12)C3B—C4B—C5B120.57 (13)
C5A—C4A—H4A119.8C3B—C4B—H4B119.7
C3A—C4A—H4A119.8C5B—C4B—H4B119.7
C4A—C5A—C6A119.86 (12)C4B—C5B—C6B119.85 (12)
C4A—C5A—H5A120.1C4B—C5B—H5B120.1
C6A—C5A—H5A120.1C6B—C5B—H5B120.1
C1A—C6A—C5A120.08 (12)C5B—C6B—C1B119.98 (12)
C1A—C6A—N1A122.60 (12)C5B—C6B—N1B118.67 (12)
C5A—C6A—N1A117.30 (12)C1B—C6B—N1B121.32 (12)
O1A—C7A—N1A123.41 (12)O1B—C7B—N1B122.47 (12)
O1A—C7A—C8A120.18 (12)O1B—C7B—C8B121.54 (11)
N1A—C7A—C8A116.32 (11)N1B—C7B—C8B115.97 (11)
C11A—C8A—C7A124.36 (12)C11B—C8B—C7B119.59 (11)
C11A—C8A—S1A124.84 (10)C11B—C8B—S1B124.58 (10)
C7A—C8A—S1A110.59 (9)C7B—C8B—S1B115.82 (9)
C10A—C9A—S1A110.23 (9)C10B—C9B—S1B109.60 (9)
C10A—C9A—H9A109.6C10B—C9B—H9C109.8
S1A—C9A—H9A109.6S1B—C9B—H9C109.8
C10A—C9A—H9B109.6C10B—C9B—H9D109.8
S1A—C9A—H9B109.6S1B—C9B—H9D109.8
H9A—C9A—H9B108.1H9C—C9B—H9D108.2
O2A—C10A—C9A111.67 (11)O2B—C10B—C9B111.73 (10)
O2A—C10A—H10A109.3O2B—C10B—H10C109.3
C9A—C10A—H10A109.3C9B—C10B—H10C109.3
O2A—C10A—H10B109.3O2B—C10B—H10D109.3
C9A—C10A—H10B109.3C9B—C10B—H10D109.3
H10A—C10A—H10B107.9H10C—C10B—H10D107.9
C8A—C11A—O2A124.57 (12)C8B—C11B—O2B124.79 (12)
C8A—C11A—C12A127.17 (12)C8B—C11B—C12B126.26 (12)
O2A—C11A—C12A108.16 (11)O2B—C11B—C12B108.88 (11)
C11A—C12A—H12A109.5C11B—C12B—H12D109.5
C11A—C12A—H12B109.5C11B—C12B—H12E109.5
H12A—C12A—H12B109.5H12D—C12B—H12E109.5
C11A—C12A—H12C109.5C11B—C12B—H12F109.5
H12A—C12A—H12C109.5H12D—C12B—H12F109.5
H12B—C12A—H12C109.5H12E—C12B—H12F109.5
C6A—C1A—C2A—C3A0.1 (2)C6B—C1B—C2B—C3B−0.5 (2)
C1A—C2A—C3A—C4A−0.3 (2)C1B—C2B—C3B—C4B0.2 (2)
C2A—C3A—C4A—C5A0.2 (2)C2B—C3B—C4B—C5B0.2 (2)
C3A—C4A—C5A—C6A0.2 (2)C3B—C4B—C5B—C6B−0.4 (2)
C2A—C1A—C6A—C5A0.25 (19)C4B—C5B—C6B—C1B0.1 (2)
C2A—C1A—C6A—N1A−178.34 (12)C4B—C5B—C6B—N1B178.37 (12)
C4A—C5A—C6A—C1A−0.42 (19)C2B—C1B—C6B—C5B0.37 (19)
C4A—C5A—C6A—N1A178.24 (11)C2B—C1B—C6B—N1B−177.87 (12)
C7A—N1A—C6A—C1A−30.94 (19)C7B—N1B—C6B—C5B137.13 (13)
C7A—N1A—C6A—C5A150.44 (13)C7B—N1B—C6B—C1B−44.61 (18)
C6A—N1A—C7A—O1A8.5 (2)C6B—N1B—C7B—O1B1.5 (2)
C6A—N1A—C7A—C8A−175.00 (11)C6B—N1B—C7B—C8B−179.89 (11)
O1A—C7A—C8A—C11A−141.95 (14)O1B—C7B—C8B—C11B−35.57 (18)
N1A—C7A—C8A—C11A41.41 (18)N1B—C7B—C8B—C11B145.77 (12)
O1A—C7A—C8A—S1A33.06 (15)O1B—C7B—C8B—S1B143.35 (11)
N1A—C7A—C8A—S1A−143.58 (10)N1B—C7B—C8B—S1B−35.30 (14)
C9A—S1A—C8A—C11A9.14 (13)C9B—S1B—C8B—C11B−9.94 (13)
C9A—S1A—C8A—C7A−165.85 (9)C9B—S1B—C8B—C7B171.20 (9)
C8A—S1A—C9A—C10A−42.83 (11)C8B—S1B—C9B—C10B42.24 (10)
C11A—O2A—C10A—C9A−50.88 (15)C11B—O2B—C10B—C9B53.01 (15)
S1A—C9A—C10A—O2A67.27 (13)S1B—C9B—C10B—O2B−67.15 (12)
C7A—C8A—C11A—O2A−178.09 (11)C7B—C8B—C11B—O2B173.91 (11)
S1A—C8A—C11A—O2A7.60 (19)S1B—C8B—C11B—O2B−4.91 (19)
C7A—C8A—C11A—C12A6.0 (2)C7B—C8B—C11B—C12B−9.3 (2)
S1A—C8A—C11A—C12A−168.29 (10)S1B—C8B—C11B—C12B171.87 (10)
C10A—O2A—C11A—C8A11.62 (18)C10B—O2B—C11B—C8B−14.86 (18)
C10A—O2A—C11A—C12A−171.82 (11)C10B—O2B—C11B—C12B167.87 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1C···O1Ai0.860 (18)2.179 (18)2.9571 (14)150.4 (15)
N1B—H1D···O1Bi0.84 (2)2.21 (2)2.9784 (14)151.4 (17)
Symmetry code: (i) x+1, y, z.
6-methyl-N-phenyl-2,3-dihydro-1,4-oxathiine-5-carboxamide (b17007r) top
Crystal data top
C12H13NO2SDx = 1.316 Mg m−3
Mr = 235.29Melting point: 364.13 K
Monoclinic, I2/aCu Kα radiation, λ = 1.54178 Å
a = 9.6424 (2) ÅCell parameters from 2580 reflections
b = 11.4059 (3) Åθ = 4.1–75.8°
c = 21.6672 (5) ŵ = 2.30 mm−1
β = 94.711 (2)°T = 100 K
V = 2374.92 (9) Å3Plate, colourless
Z = 80.31 × 0.07 × 0.06 mm
F(000) = 992
Data collection top
Rigaku SuperNova, Dualflex, AtlasS2
diffractometer		2415 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source2244 reflections with I > 2σ(I)
Detector resolution: 5.2921 pixels mm-1Rint = 0.016
ω scansθmax = 74.5°, θmin = 4.1°
Absorption correction: analytical
(CrysAlis PRO; Rigaku OD, 2015)		h = −8→11
Tmin = 0.664, Tmax = 0.880k = −14→12
4644 measured reflectionsl = −26→27
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.070P)2 + 2.2P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2415 reflectionsΔρmax = 0.51 e Å−3
150 parametersΔρmin = −0.44 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.41282 (5)0.67311 (4)0.72445 (2)0.03174 (16)
O10.32397 (12)0.46505 (10)0.64353 (6)0.0322 (3)
O20.58438 (12)0.80835 (10)0.62859 (5)0.0252 (3)
N10.55181 (13)0.43217 (11)0.62844 (6)0.0208 (3)
H1A0.635 (2)0.4633 (18)0.6321 (9)0.023 (5)*
C10.43269 (18)0.23962 (14)0.61678 (8)0.0269 (3)
H10.35120.26940.63300.032*
C20.4391 (2)0.12309 (15)0.59833 (9)0.0333 (4)
H20.36040.07390.60120.040*
C30.5581 (2)0.07730 (15)0.57582 (8)0.0338 (4)
H30.5612−0.00250.56350.041*
C40.6725 (2)0.14945 (16)0.57147 (8)0.0318 (4)
H40.75510.11850.55680.038*
C50.66723 (17)0.26668 (15)0.58839 (8)0.0260 (3)
H50.74550.31590.58450.031*
C60.54737 (16)0.31217 (13)0.61114 (7)0.0213 (3)
C70.44398 (16)0.50099 (14)0.64111 (7)0.0218 (3)
C80.48110 (15)0.62578 (13)0.65536 (7)0.0207 (3)
C90.4412 (2)0.82819 (14)0.71537 (9)0.0315 (4)
H9A0.36700.86130.68620.038*
H9B0.43720.86800.75580.038*
C100.58140 (19)0.84960 (15)0.69104 (8)0.0297 (4)
H10A0.60220.93460.69250.036*
H10B0.65430.80890.71790.036*
C110.54640 (16)0.69442 (13)0.61652 (7)0.0206 (3)
C120.57867 (18)0.66346 (14)0.55218 (8)0.0262 (3)
H12A0.54240.72460.52340.039*
H12B0.53510.58830.54030.039*
H12C0.67970.65720.55060.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0473 (3)0.0234 (2)0.0265 (2)−0.00202 (16)0.01526 (18)−0.00236 (14)
O10.0212 (6)0.0206 (6)0.0553 (8)−0.0003 (4)0.0062 (5)−0.0025 (5)
O20.0341 (6)0.0158 (5)0.0265 (6)−0.0016 (4)0.0064 (5)−0.0005 (4)
N10.0207 (6)0.0159 (6)0.0258 (7)−0.0012 (5)0.0031 (5)−0.0007 (5)
C10.0309 (8)0.0199 (8)0.0298 (8)−0.0033 (6)0.0027 (6)0.0014 (6)
C20.0454 (10)0.0196 (8)0.0342 (9)−0.0061 (7)−0.0011 (7)0.0012 (7)
C30.0531 (11)0.0164 (7)0.0306 (9)0.0043 (7)−0.0045 (7)−0.0010 (6)
C40.0414 (9)0.0243 (8)0.0290 (8)0.0106 (7)−0.0009 (7)−0.0035 (7)
C50.0279 (8)0.0224 (8)0.0272 (8)0.0033 (6)−0.0005 (6)−0.0011 (6)
C60.0267 (8)0.0160 (7)0.0207 (7)0.0013 (6)−0.0004 (6)0.0011 (5)
C70.0228 (7)0.0191 (7)0.0235 (7)0.0002 (5)0.0019 (6)0.0011 (6)
C80.0225 (7)0.0177 (7)0.0220 (7)0.0013 (5)0.0026 (5)−0.0016 (5)
C90.0484 (10)0.0199 (8)0.0272 (9)0.0019 (7)0.0089 (7)−0.0062 (6)
C100.0407 (9)0.0208 (7)0.0269 (8)−0.0021 (7)−0.0011 (7)−0.0040 (6)
C110.0223 (7)0.0167 (7)0.0230 (7)0.0023 (5)0.0023 (5)−0.0008 (6)
C120.0337 (8)0.0232 (8)0.0222 (8)0.0023 (6)0.0055 (6)0.0011 (6)
Geometric parameters (Å, º) top
S1—C81.7684 (15)C4—C51.388 (2)
S1—C91.8031 (17)C4—H40.9500
O1—C71.2328 (19)C5—C61.393 (2)
O2—C111.3694 (19)C5—H50.9500
O2—C101.435 (2)C7—C81.494 (2)
N1—C71.349 (2)C8—C111.343 (2)
N1—C61.4188 (19)C9—C101.511 (3)
N1—H1A0.87 (2)C9—H9A0.9900
C1—C21.391 (2)C9—H9B0.9900
C1—C61.395 (2)C10—H10A0.9900
C1—H10.9500C10—H10B0.9900
C2—C31.385 (3)C11—C121.496 (2)
C2—H20.9500C12—H12A0.9800
C3—C41.385 (3)C12—H12B0.9800
C3—H30.9500C12—H12C0.9800
C8—S1—C997.85 (8)N1—C7—C8114.90 (13)
C11—O2—C10117.73 (13)C11—C8—C7122.85 (14)
C7—N1—C6127.45 (13)C11—C8—S1125.35 (12)
C7—N1—H1A117.4 (13)C7—C8—S1111.49 (11)
C6—N1—H1A115.1 (13)C10—C9—S1110.17 (12)
C2—C1—C6119.17 (16)C10—C9—H9A109.6
C2—C1—H1120.4S1—C9—H9A109.6
C6—C1—H1120.4C10—C9—H9B109.6
C3—C2—C1121.30 (17)S1—C9—H9B109.6
C3—C2—H2119.3H9A—C9—H9B108.1
C1—C2—H2119.3O2—C10—C9111.33 (14)
C2—C3—C4119.13 (16)O2—C10—H10A109.4
C2—C3—H3120.4C9—C10—H10A109.4
C4—C3—H3120.4O2—C10—H10B109.4
C3—C4—C5120.52 (17)C9—C10—H10B109.4
C3—C4—H4119.7H10A—C10—H10B108.0
C5—C4—H4119.7C8—C11—O2124.41 (14)
C4—C5—C6120.08 (16)C8—C11—C12126.19 (14)
C4—C5—H5120.0O2—C11—C12109.22 (13)
C6—C5—H5120.0C11—C12—H12A109.5
C5—C6—C1119.78 (15)C11—C12—H12B109.5
C5—C6—N1116.41 (14)H12A—C12—H12B109.5
C1—C6—N1123.80 (14)C11—C12—H12C109.5
O1—C7—N1123.86 (15)H12A—C12—H12C109.5
O1—C7—C8121.19 (14)H12B—C12—H12C109.5
C6—C1—C2—C31.4 (3)O1—C7—C8—S147.26 (19)
C1—C2—C3—C4−0.2 (3)N1—C7—C8—S1−130.00 (12)
C2—C3—C4—C5−1.2 (3)C9—S1—C8—C116.79 (16)
C3—C4—C5—C61.3 (3)C9—S1—C8—C7−166.98 (12)
C4—C5—C6—C1−0.1 (2)C8—S1—C9—C10−41.24 (14)
C4—C5—C6—N1178.84 (14)C11—O2—C10—C9−53.62 (19)
C2—C1—C6—C5−1.3 (2)S1—C9—C10—O267.88 (16)
C2—C1—C6—N1179.90 (15)C7—C8—C11—O2−178.68 (14)
C7—N1—C6—C5167.39 (15)S1—C8—C11—O28.2 (2)
C7—N1—C6—C1−13.7 (3)C7—C8—C11—C126.6 (2)
C6—N1—C7—O15.4 (3)S1—C8—C11—C12−166.46 (12)
C6—N1—C7—C8−177.45 (14)C10—O2—C11—C813.7 (2)
O1—C7—C8—C11−126.69 (18)C10—O2—C11—C12−170.79 (13)
N1—C7—C8—C1156.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.87 (2)2.00 (2)2.8683 (18)178.1 (18)
Symmetry code: (i) x+1/2, −y+1, z.
 

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ISSN: 2056-9890
Volume 74| Part 12| December 2018| Pages 1741-1745
https://doi.org/10.1107/S2056989018015451
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