research communications
S,2S,5R)-5-acetylamino-4-oxo-2,3-diphenyl-1,3-thiazinan-1-ium-1-olate
of (1aDepartment of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, PA 16802, USA, and bPennsylvania State University, Schuylkill Campus, 200 University Drive, Schuylkill Haven, PA 17972, USA
*Correspondence e-mail: ljs43@psu.edu
The 18H18N2O3S, comprises two independent molecules (A and B) having almost identical conformations. When overlayed, the alignment–r.m.s. deviation value is 0.30 Å. The six-membered heterocycle has a twisted half-chair conformation in both molecules. The O atom on the S atom of the ring is pseudo-axial on the thiazine ring and trans to both a phenyl group substituent and the acetamide group in each case. The two benzene rings in each molecule are almost orthogonal to each other, with interplanar dihedral angles of 83.79 (17) and 86.95 (16)°. The acetamide group is pseudo-equatorial and a phenyl ring is pseudo-axial on the thiazine ring. Both molecules show a weak intramolecular C—H⋯O interaction between H-atom donors of one of the phenyl rings and the acetamide group. In the crystal, an intermolecular N—H⋯O(thiazine) hydrogen bond links B molecules along the 21 (b) screw axis and, in addition, an N—H⋯O(acetamide) hydrogen bond links A and B molecules across a. A two-dimensional layered structure lying parallel to (001) is generated, also involving weak intermolecular C—H⋯O interactions.
of the enantiomerically pure title compound, CKeywords: 1,3-thiazin-4-one; twisted half-chair pucker; N—H⋯O and C—H⋯O interactions; crystal structure.
CCDC reference: 1571357
1. Chemical context
The 1,3-thiazin-4-ones are a group of six-membered heterocycles with a wide range of biological activity (Ryabukhin et al., 1996). Surrey's research (Surrey et al., 1958; Surrey, 1963a,b) resulted in the discovery of two drugs, the anti-anxiety and muscle relaxant chlormezanone [2-(4-chlorophenyl)-3-methyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one 1,1-dioxide] (O'Neil, 2006; Tanaka & Horayama, 2005) and muscle relaxant dichloromezanone [2-(3,4-dichlorophenyl)-3-methyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one 1,1-dioxide] (Elks & Ganellin, 1990). These showed greater activity than the from which they were synthesized (Surrey et al., 1958). Surrey also prepared a variety of other and of 3-alkyl-2-aryl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-ones (Surrey, 1963a,b). We have reported previously the of the first N-aryl sulfoxide in this family, racemic 2,3-diphenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one 1-oxide (Yennawar et al., 2016).
A sulfoxide typically has an S—O bond that is between a double bond and a single bond, with one of the lone pairs that was on the sulfide coordinating to the O atom, while O atom contributes electrons from a lone pair to a d orbital of the S atom. The geometry of a sulfoxide is pyramidal, with a high energy barrier for inversion, making it possible to isolate stable enantiomers (Bentley, 2005). Herein, we report the of the sulfoxide of N-[(2S,5R)-4-oxo-2,3-diphenyl-1,3-thiazinan-5-yl]acetamide (Yennawar, Singh & Silverberg, 2015), C18H18N2O3S, prepared using the method we have reported previously for the oxidation of other 2,3-diphenyl-1,3-thiazin-4-ones (Yennawar et al., 2016; Yennawar, Noble et al., 2017) and 1,3-thiazolidinones (Yennawar, Hullihen et al., 2015; Cannon et al., 2015). The oxidation of the confirmed enantiopure sulfide N-[(2S,5R)-4-oxo-2,3-diphenyl-1,3-thiazinan-5-yl]acetamide 0.375-hydrate (Yennawar, Singh & Silverberg, 2015), derived from N-acetyl-L-cysteine, yielded a single stereoisomer as the only product.
2. Structural commentary
The A and B) in the (Fig. 1), which have almost identical conformational features, having an alignment–r.m.s. deviation value of 0.3 Å. Both have the thiazine rings in a twisted half-chair configuration, with puckering amplitudes = 0.6753 (19)/0.653 (2) Å and θ = 131.05 (17)/135.66 (18)° in molecules A/B, respectively (Cremer & Pople, 1975). The O atom on the S atom of the ring is pseudo-axial on the thiazine ring and trans to both the 2-phenyl group and the acetamide group in each case. The two phenyl rings in each molecule are almost orthogonal to one another, with dihedral angles of 83.79 (17) and 86.95 (16)° in molecules A and B, respectively. The acetamide group is pseudo-equatorial and the 2-phenyl group is pseudo-axial on the thiazine ring. A weak intramolecular C—H⋯O hydrogen bond between the 2-phenyl ring and the O atom of the acetamide group is seen in both molecules (C10A—H⋯O3A and C10B—H⋯O3B), as detailed in Table 1.
of the title compound has two independent homochiral molecules (We reported previously the N-[(2S,5R)-4-oxo-2,3-diphenyl-1,3-thiazinan-5-yl]acetamide 0.375-hydrate (Yennawar, Singh & Silverberg, 2015), which also had two independent homochiral molecules in the However, they were not identical: in one molecule, the thiazine ring was in a half-chair conformation in which the 2-phenyl ring was nearly pseudo-axial and the acetamide group was nearly pseudo-equatorial. The other molecule had the thiazine ring in a boat conformation in which both substituents were pseudo-equatorial.
of the starting sulfide,3. Supramolecular features
In the crystal, the B molecule and its 21-related symmetry neighbours form a continuous hydrogen-bonded chain along the b-cell direction through N—H⋯O interactions involving the acetamide N atom and the thiazin-1-ium-1-olate O atoms [N2B—H⋯O1Bii; symmetry code: (ii) −x, y + , −z; Table 1] (Fig. 2). Molecules A and B interact, wherein the O atom in the 4-position of molecule B accepts a proton from the acetamide N atom of molecule A [N2A—H⋯O1Bi; symmetry code: (i) x + 1, y, z]. The sulfoxide O atom of molecule A does not participate in any hydrogen bonding. A two-dimensional sheet structure lying parallel to (001) is generated. No benzene ring in either of the molecules participates in face-to-face π–π stacking interactions.
4. Database survey
Crystal structures of a number of 1,3-thiazolidin-4-one 1-oxides have been reported (Wang et al., 2010; Johnson et al., 1983; Chen et al., 2011; Colombo et al., 2008; Yennawar, Hullihen et al., 2015) and the structure of chlormezanone [2-(4-chlorophenyl)-3-methyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one 1,1-dioxide] has also been reported (Tanaka & Horayama, 2005). We have reported previously the of 2,3-diphenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one 1-oxide (Yennawar et al., 2016). We have also reported recently the crystal structures of 2,3-diphenyl-2,3-dihydro-4H-1,3-benzothiazin-4-one 1-oxide (Yennawar, Fox et al., 2017) and 2,3-diphenyl-2,3-dihydro-4H-pyrido[3,2-e][1,3]thiazin-4-one 1-oxide (Yennawar, Noble et al., 2017).
5. Synthesis and crystallization
A 5 ml round-bottomed flask was charged with 53.9 mg of N-[(2S,5R)-4-oxo-2,3-diphenyl-1,3-thiazinan-5-yl]acetamide 0.375-hydrate, whose configuration was established previously (Yennawar, Singh & Silverberg, 2015), and 1.4 ml of methanol and stirred. A solution of 79.5 mg of Oxone® and 1 ml of distilled water was added dropwise and the mixture was stirred until the reaction was complete, as determined by (TLC). The solids were dissolved by the addition of 5 ml of distilled water. The solution was extracted with 10 ml of dichloromethane. The organic layer was washed with 5 ml of distilled water and then with 5 ml of saturated sodium chloride. The solution was dried over Na2SO4 and concentrated under vacuum giving a crude solid. This was chromatographed on flash silica gel, eluting with a gradient of 0–60% acetone in ethyl acetate, giving 55.8 mg of product [98.6% yield; m.p. 449–452 K; RF = 0.20 (30% acetone/70% ethyl acetate)]. Crystals suitable for X-ray crystallography were grown by slow evaporation from propan-2-ol.
6. Refinement
Crystal data, data collection and structure . The H atoms, excepting those on N atoms, were placed geometrically and allowed to ride on their parent C atoms during with C—H distances of 0.93 (aromatic), 0.96 (methyl), 0.97 or (methylene) and 0.98 Å (methyl), and with Uiso(H) = 1.2Ueq(aromatic or methylene C) or 1.5Ueq(methyl C). H atoms on N atoms were located in a difference Fourier map and were refined isotropically. The for the chiral centres in the molecule was determined as (1S,2S,5R) (for the arbitrarily numbered atoms C1A/B,C3A/B), with a Flack parameter (Flack, 1983) of 0.07 (6) for 4160 Friedel pairs.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1571357
https://doi.org/10.1107/S2056989017012488/zs2387sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017012488/zs2387Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017012488/zs2387Isup3.mol
Analysis of short ring interactions. DOI: https://doi.org/10.1107/S2056989017012488/zs2387sup4.pdf
Data collection: SMART (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C18H18N2O3S | Dx = 1.329 Mg m−3 |
Mr = 342.40 | Melting point = 449–452 K |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.872 (6) Å | Cell parameters from 7433 reflections |
b = 10.139 (5) Å | θ = 2.5–28.2° |
c = 13.460 (6) Å | µ = 0.21 mm−1 |
β = 103.104 (9)° | T = 298 K |
V = 1710.8 (14) Å3 | Block, colorless |
Z = 4 | 0.23 × 0.20 × 0.19 mm |
F(000) = 720 |
Bruker SCD area detector diffractometer | 8079 independent reflections |
Radiation source: fine-focus sealed tube | 6949 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 28.2°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −16→17 |
Tmin = 0.309, Tmax = 0.900 | k = −13→13 |
15296 measured reflections | l = −17→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0745P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
8079 reflections | Δρmax = 0.37 e Å−3 |
443 parameters | Δρmin = −0.27 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 4160 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (6) |
Experimental. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different φ and/or 2θ angles and each scan (10 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 5.82 cm. |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
C1A | 0.79355 (19) | 0.2939 (3) | 0.48969 (16) | 0.0397 (5) | |
H1A | 0.7893 | 0.2095 | 0.5241 | 0.048* | |
C2A | 0.86711 (19) | 0.3246 (3) | 0.33058 (17) | 0.0393 (5) | |
C3A | 0.93950 (18) | 0.4386 (2) | 0.37719 (15) | 0.0344 (5) | |
H3A | 1.0109 | 0.4009 | 0.4010 | 0.041* | |
C4A | 0.91189 (19) | 0.5047 (2) | 0.46957 (15) | 0.0356 (5) | |
H4AA | 0.8426 | 0.5468 | 0.4499 | 0.043* | |
H4AB | 0.9645 | 0.5718 | 0.4964 | 0.043* | |
C5A | 0.69426 (19) | 0.3706 (3) | 0.49564 (17) | 0.0431 (5) | |
C6A | 0.6572 (2) | 0.3596 (4) | 0.5857 (2) | 0.0598 (8) | |
H6A | 0.6895 | 0.3011 | 0.6365 | 0.072* | |
C7A | 0.5723 (3) | 0.4365 (5) | 0.5981 (2) | 0.0759 (11) | |
H7A | 0.5479 | 0.4297 | 0.6579 | 0.091* | |
C8A | 0.5243 (3) | 0.5217 (5) | 0.5243 (3) | 0.0763 (10) | |
H8A | 0.4674 | 0.5728 | 0.5340 | 0.092* | |
C9A | 0.5592 (2) | 0.5335 (4) | 0.4343 (2) | 0.0636 (8) | |
H9A | 0.5262 | 0.5926 | 0.3841 | 0.076* | |
C10A | 0.6433 (2) | 0.4567 (3) | 0.4200 (2) | 0.0497 (6) | |
H10A | 0.6658 | 0.4627 | 0.3592 | 0.060* | |
C11A | 0.7454 (2) | 0.1476 (2) | 0.34101 (17) | 0.0398 (5) | |
C16A | 0.7794 (2) | 0.0238 (3) | 0.3750 (2) | 0.0563 (7) | |
H16A | 0.8400 | 0.0136 | 0.4273 | 0.068* | |
C15A | 0.7227 (3) | −0.0862 (3) | 0.3309 (3) | 0.0719 (10) | |
H15A | 0.7447 | −0.1701 | 0.3546 | 0.086* | |
C14A | 0.6350 (3) | −0.0716 (4) | 0.2531 (3) | 0.0709 (10) | |
H14A | 0.5983 | −0.1455 | 0.2228 | 0.085* | |
C13A | 0.6014 (3) | 0.0507 (4) | 0.2197 (3) | 0.0734 (10) | |
H13A | 0.5411 | 0.0602 | 0.1671 | 0.088* | |
C12A | 0.6561 (2) | 0.1616 (4) | 0.2634 (2) | 0.0588 (7) | |
H12A | 0.6325 | 0.2453 | 0.2403 | 0.071* | |
C17A | 0.8618 (2) | 0.5983 (3) | 0.2465 (2) | 0.0487 (6) | |
C18A | 0.8817 (3) | 0.7020 (4) | 0.1734 (3) | 0.0784 (11) | |
H18A | 0.9497 | 0.7427 | 0.1999 | 0.118* | |
H18B | 0.8266 | 0.7676 | 0.1648 | 0.118* | |
H18C | 0.8814 | 0.6621 | 0.1087 | 0.118* | |
N1A | 0.80481 (17) | 0.26229 (19) | 0.38641 (14) | 0.0384 (4) | |
N2A | 0.94797 (16) | 0.5352 (2) | 0.29910 (14) | 0.0392 (4) | |
H2A | 1.014 (2) | 0.561 (3) | 0.2912 (19) | 0.036 (7)* | |
O1A | 1.00529 (16) | 0.2968 (2) | 0.56800 (15) | 0.0581 (5) | |
O2A | 0.87065 (18) | 0.2840 (2) | 0.24629 (13) | 0.0615 (6) | |
O3A | 0.77158 (16) | 0.5727 (3) | 0.25622 (17) | 0.0702 (7) | |
S1A | 0.91010 (5) | 0.38151 (6) | 0.56562 (4) | 0.04051 (15) | |
C1B | 0.22990 (19) | 0.4488 (2) | 0.06076 (17) | 0.0389 (5) | |
H1B | 0.2075 | 0.3562 | 0.0584 | 0.047* | |
C2B | 0.16558 (17) | 0.6316 (2) | 0.16162 (17) | 0.0357 (5) | |
C3B | 0.13964 (19) | 0.7241 (3) | 0.06778 (18) | 0.0410 (5) | |
H3B | 0.0625 | 0.7164 | 0.0407 | 0.049* | |
C4B | 0.1904 (2) | 0.6890 (3) | −0.02038 (17) | 0.0418 (5) | |
H4BA | 0.2672 | 0.6983 | 0.0009 | 0.050* | |
H4BB | 0.1649 | 0.7488 | −0.0769 | 0.050* | |
C5B | 0.34898 (18) | 0.4469 (3) | 0.06755 (16) | 0.0377 (5) | |
C6B | 0.3913 (2) | 0.3500 (3) | 0.0150 (2) | 0.0528 (7) | |
H6B | 0.3468 | 0.2870 | −0.0229 | 0.063* | |
C7B | 0.4994 (3) | 0.3473 (3) | 0.0189 (2) | 0.0615 (8) | |
H7B | 0.5269 | 0.2836 | −0.0177 | 0.074* | |
C8B | 0.5669 (2) | 0.4381 (4) | 0.0764 (2) | 0.0578 (7) | |
H8B | 0.6397 | 0.4350 | 0.0791 | 0.069* | |
C9B | 0.5264 (2) | 0.5332 (3) | 0.1298 (2) | 0.0499 (6) | |
H9B | 0.5721 | 0.5941 | 0.1692 | 0.060* | |
C10B | 0.4174 (2) | 0.5390 (3) | 0.12537 (18) | 0.0424 (5) | |
H10B | 0.3903 | 0.6043 | 0.1609 | 0.051* | |
C11B | 0.2058 (2) | 0.4150 (2) | 0.23392 (18) | 0.0419 (5) | |
C12B | 0.2934 (3) | 0.4162 (4) | 0.3126 (2) | 0.0722 (10) | |
H12B | 0.3466 | 0.4787 | 0.3143 | 0.087* | |
C13B | 0.3032 (4) | 0.3236 (5) | 0.3903 (3) | 0.0893 (13) | |
H13B | 0.3635 | 0.3232 | 0.4436 | 0.107* | |
C14B | 0.2239 (3) | 0.2330 (4) | 0.3880 (3) | 0.0775 (11) | |
H14B | 0.2307 | 0.1705 | 0.4397 | 0.093* | |
C15B | 0.1358 (3) | 0.2339 (3) | 0.3110 (3) | 0.0669 (9) | |
H15B | 0.0818 | 0.1729 | 0.3107 | 0.080* | |
C16B | 0.1249 (2) | 0.3260 (3) | 0.2317 (2) | 0.0505 (6) | |
H16B | 0.0644 | 0.3268 | 0.1787 | 0.061* | |
C17B | 0.2575 (2) | 0.9072 (3) | 0.13509 (19) | 0.0458 (6) | |
C18B | 0.2671 (4) | 1.0542 (3) | 0.1506 (3) | 0.0763 (10) | |
H18D | 0.3007 | 1.0727 | 0.2204 | 0.114* | |
H18E | 0.1974 | 1.0932 | 0.1342 | 0.114* | |
H18F | 0.3095 | 1.0903 | 0.1069 | 0.114* | |
N1B | 0.19754 (16) | 0.5070 (2) | 0.14898 (14) | 0.0381 (4) | |
N2B | 0.15836 (19) | 0.8610 (2) | 0.09612 (17) | 0.0469 (5) | |
H2B | 0.110 (2) | 0.910 (3) | 0.089 (2) | 0.042 (8)* | |
O1B | 0.04145 (15) | 0.5076 (3) | −0.06247 (17) | 0.0666 (6) | |
O2B | 0.14719 (15) | 0.66808 (19) | 0.24289 (14) | 0.0484 (4) | |
O3B | 0.33503 (15) | 0.83467 (19) | 0.15418 (15) | 0.0530 (5) | |
S1B | 0.15756 (5) | 0.52300 (7) | −0.06050 (4) | 0.04663 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0472 (13) | 0.0435 (13) | 0.0292 (10) | −0.0069 (11) | 0.0101 (9) | −0.0013 (9) |
C2A | 0.0442 (12) | 0.0432 (13) | 0.0316 (10) | −0.0011 (10) | 0.0108 (9) | −0.0049 (9) |
C3A | 0.0338 (11) | 0.0389 (12) | 0.0300 (10) | −0.0003 (9) | 0.0065 (8) | −0.0027 (9) |
C4A | 0.0397 (11) | 0.0343 (12) | 0.0319 (9) | 0.0014 (9) | 0.0062 (9) | −0.0056 (8) |
C5A | 0.0441 (12) | 0.0518 (14) | 0.0355 (11) | −0.0110 (12) | 0.0135 (10) | −0.0064 (11) |
C6A | 0.0595 (16) | 0.083 (2) | 0.0409 (13) | −0.0101 (16) | 0.0195 (12) | −0.0040 (14) |
C7A | 0.0571 (18) | 0.125 (3) | 0.0529 (16) | −0.0064 (19) | 0.0280 (15) | −0.0207 (19) |
C8A | 0.0464 (17) | 0.110 (3) | 0.073 (2) | 0.0079 (19) | 0.0156 (15) | −0.025 (2) |
C9A | 0.0417 (14) | 0.084 (2) | 0.0621 (16) | 0.0076 (16) | 0.0050 (12) | −0.0074 (17) |
C10A | 0.0429 (13) | 0.0638 (18) | 0.0428 (12) | −0.0026 (13) | 0.0106 (10) | −0.0038 (12) |
C11A | 0.0426 (13) | 0.0425 (13) | 0.0367 (11) | −0.0081 (11) | 0.0137 (9) | −0.0063 (10) |
C16A | 0.0598 (17) | 0.0445 (15) | 0.0607 (16) | −0.0018 (14) | 0.0055 (13) | −0.0077 (13) |
C15A | 0.100 (3) | 0.0442 (18) | 0.076 (2) | −0.0166 (17) | 0.029 (2) | −0.0106 (14) |
C14A | 0.084 (2) | 0.070 (2) | 0.0665 (19) | −0.0399 (19) | 0.0320 (19) | −0.0292 (17) |
C13A | 0.062 (2) | 0.094 (3) | 0.0601 (18) | −0.0213 (19) | 0.0051 (15) | −0.0221 (18) |
C12A | 0.0604 (18) | 0.0622 (19) | 0.0468 (14) | −0.0062 (14) | −0.0028 (13) | −0.0074 (13) |
C17A | 0.0390 (13) | 0.0625 (18) | 0.0442 (13) | −0.0003 (12) | 0.0085 (11) | 0.0123 (12) |
C18A | 0.0573 (18) | 0.097 (3) | 0.081 (2) | 0.0043 (19) | 0.0149 (17) | 0.050 (2) |
N1A | 0.0482 (11) | 0.0372 (11) | 0.0311 (9) | −0.0086 (9) | 0.0115 (8) | −0.0076 (7) |
N2A | 0.0349 (10) | 0.0446 (12) | 0.0388 (9) | −0.0033 (9) | 0.0102 (8) | 0.0027 (9) |
O1A | 0.0572 (11) | 0.0548 (12) | 0.0561 (11) | 0.0131 (10) | −0.0005 (9) | 0.0087 (9) |
O2A | 0.0785 (14) | 0.0743 (14) | 0.0388 (9) | −0.0276 (12) | 0.0280 (10) | −0.0233 (9) |
O3A | 0.0353 (10) | 0.103 (2) | 0.0692 (13) | −0.0017 (10) | 0.0059 (9) | 0.0341 (13) |
S1A | 0.0493 (3) | 0.0405 (3) | 0.0289 (2) | 0.0010 (3) | 0.0029 (2) | −0.0018 (2) |
C1B | 0.0428 (12) | 0.0363 (12) | 0.0386 (11) | −0.0073 (10) | 0.0114 (10) | −0.0046 (9) |
C2B | 0.0284 (10) | 0.0408 (12) | 0.0396 (11) | −0.0031 (9) | 0.0111 (9) | 0.0040 (9) |
C3B | 0.0320 (11) | 0.0487 (14) | 0.0423 (12) | 0.0031 (10) | 0.0083 (9) | 0.0088 (10) |
C4B | 0.0400 (12) | 0.0535 (15) | 0.0296 (10) | −0.0044 (11) | 0.0030 (9) | 0.0073 (10) |
C5B | 0.0390 (12) | 0.0417 (13) | 0.0334 (10) | 0.0012 (10) | 0.0099 (9) | 0.0018 (9) |
C6B | 0.0530 (15) | 0.0572 (18) | 0.0474 (14) | 0.0036 (13) | 0.0099 (11) | −0.0136 (12) |
C7B | 0.0560 (16) | 0.070 (2) | 0.0626 (17) | 0.0151 (15) | 0.0223 (14) | −0.0136 (15) |
C8B | 0.0397 (14) | 0.074 (2) | 0.0604 (16) | 0.0124 (14) | 0.0134 (12) | 0.0068 (15) |
C9B | 0.0410 (13) | 0.0488 (15) | 0.0568 (14) | −0.0004 (12) | 0.0047 (11) | 0.0037 (13) |
C10B | 0.0423 (12) | 0.0381 (13) | 0.0465 (12) | 0.0000 (10) | 0.0093 (10) | −0.0022 (10) |
C11B | 0.0459 (13) | 0.0422 (14) | 0.0414 (12) | 0.0020 (10) | 0.0178 (10) | 0.0077 (9) |
C12B | 0.070 (2) | 0.082 (3) | 0.0588 (17) | −0.0207 (17) | 0.0013 (15) | 0.0301 (17) |
C13B | 0.096 (3) | 0.104 (3) | 0.061 (2) | −0.010 (2) | 0.0021 (19) | 0.040 (2) |
C14B | 0.090 (3) | 0.075 (2) | 0.075 (2) | 0.011 (2) | 0.034 (2) | 0.0384 (19) |
C15B | 0.067 (2) | 0.0498 (18) | 0.097 (2) | 0.0029 (15) | 0.046 (2) | 0.0232 (17) |
C16B | 0.0485 (14) | 0.0436 (15) | 0.0639 (17) | 0.0020 (12) | 0.0224 (13) | 0.0070 (12) |
C17B | 0.0572 (16) | 0.0417 (15) | 0.0410 (12) | 0.0062 (12) | 0.0160 (11) | 0.0010 (10) |
C18B | 0.098 (3) | 0.0469 (19) | 0.084 (2) | 0.0031 (17) | 0.021 (2) | −0.0066 (16) |
N1B | 0.0428 (10) | 0.0384 (11) | 0.0360 (9) | −0.0021 (8) | 0.0148 (8) | 0.0055 (8) |
N2B | 0.0459 (12) | 0.0432 (13) | 0.0541 (12) | 0.0160 (11) | 0.0163 (10) | 0.0089 (10) |
O1B | 0.0388 (10) | 0.0814 (16) | 0.0722 (13) | −0.0158 (11) | −0.0029 (9) | −0.0075 (12) |
O2B | 0.0558 (11) | 0.0522 (11) | 0.0435 (9) | 0.0023 (8) | 0.0246 (8) | 0.0015 (8) |
O3B | 0.0478 (10) | 0.0490 (11) | 0.0607 (11) | 0.0041 (8) | 0.0093 (9) | −0.0076 (8) |
S1B | 0.0416 (3) | 0.0590 (4) | 0.0362 (3) | −0.0103 (3) | 0.0023 (2) | −0.0070 (3) |
C1A—H1A | 0.9800 | C1B—H1B | 0.9800 |
C1A—C5A | 1.514 (4) | C1B—C5B | 1.515 (3) |
C1A—N1A | 1.465 (3) | C1B—N1B | 1.468 (3) |
C1A—S1A | 1.841 (3) | C1B—S1B | 1.846 (3) |
C2A—C3A | 1.527 (3) | C2B—C3B | 1.547 (3) |
C2A—N1A | 1.371 (3) | C2B—N1B | 1.351 (3) |
C2A—O2A | 1.217 (3) | C2B—O2B | 1.227 (3) |
C3A—H3A | 0.9800 | C3B—H3B | 0.9800 |
C3A—C4A | 1.524 (3) | C3B—C4B | 1.521 (3) |
C3A—N2A | 1.459 (3) | C3B—N2B | 1.445 (4) |
C4A—H4AA | 0.9700 | C4B—H4BA | 0.9700 |
C4A—H4AB | 0.9700 | C4B—H4BB | 0.9700 |
C4A—S1A | 1.801 (2) | C4B—S1B | 1.788 (3) |
C5A—C6A | 1.404 (3) | C5B—C6B | 1.392 (4) |
C5A—C10A | 1.388 (4) | C5B—C10B | 1.394 (4) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C6A—C7A | 1.383 (5) | C6B—C7B | 1.380 (4) |
C7A—H7A | 0.9300 | C7B—H7B | 0.9300 |
C7A—C8A | 1.355 (6) | C7B—C8B | 1.377 (5) |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C8A—C9A | 1.389 (5) | C8B—C9B | 1.374 (4) |
C9A—H9A | 0.9300 | C9B—H9B | 0.9300 |
C9A—C10A | 1.382 (4) | C9B—C10B | 1.392 (4) |
C10A—H10A | 0.9300 | C10B—H10B | 0.9300 |
C11A—C16A | 1.372 (4) | C11B—C12B | 1.361 (4) |
C11A—C12A | 1.375 (4) | C11B—C16B | 1.372 (4) |
C11A—N1A | 1.449 (3) | C11B—N1B | 1.460 (3) |
C16A—H16A | 0.9300 | C12B—H12B | 0.9300 |
C16A—C15A | 1.390 (5) | C12B—C13B | 1.389 (5) |
C15A—H15A | 0.9300 | C13B—H13B | 0.9300 |
C15A—C14A | 1.362 (6) | C13B—C14B | 1.369 (6) |
C14A—H14A | 0.9300 | C14B—H14B | 0.9300 |
C14A—C13A | 1.356 (6) | C14B—C15B | 1.353 (5) |
C13A—H13A | 0.9300 | C15B—H15B | 0.9300 |
C13A—C12A | 1.385 (5) | C15B—C16B | 1.401 (4) |
C12A—H12A | 0.9300 | C16B—H16B | 0.9300 |
C17A—C18A | 1.502 (4) | C17B—C18B | 1.505 (4) |
C17A—N2A | 1.336 (3) | C17B—N2B | 1.350 (4) |
C17A—O3A | 1.226 (3) | C17B—O3B | 1.219 (3) |
C18A—H18A | 0.9600 | C18B—H18D | 0.9600 |
C18A—H18B | 0.9600 | C18B—H18E | 0.9600 |
C18A—H18C | 0.9600 | C18B—H18F | 0.9600 |
N2A—H2A | 0.91 (3) | N2B—H2B | 0.79 (3) |
O1A—S1A | 1.491 (2) | O1B—S1B | 1.497 (2) |
C5A—C1A—H1A | 106.6 | C5B—C1B—H1B | 106.0 |
C5A—C1A—S1A | 108.30 (17) | C5B—C1B—S1B | 111.05 (15) |
N1A—C1A—H1A | 106.6 | N1B—C1B—H1B | 106.0 |
N1A—C1A—C5A | 115.4 (2) | N1B—C1B—C5B | 115.16 (19) |
N1A—C1A—S1A | 112.87 (15) | N1B—C1B—S1B | 111.87 (17) |
S1A—C1A—H1A | 106.6 | S1B—C1B—H1B | 106.0 |
N1A—C2A—C3A | 120.12 (19) | N1B—C2B—C3B | 118.6 (2) |
O2A—C2A—C3A | 119.4 (2) | O2B—C2B—C3B | 119.7 (2) |
O2A—C2A—N1A | 120.3 (2) | O2B—C2B—N1B | 121.3 (2) |
C2A—C3A—H3A | 106.2 | C2B—C3B—H3B | 105.6 |
C4A—C3A—C2A | 115.76 (18) | C4B—C3B—C2B | 116.3 (2) |
C4A—C3A—H3A | 106.2 | C4B—C3B—H3B | 105.6 |
N2A—C3A—C2A | 110.52 (18) | N2B—C3B—C2B | 112.0 (2) |
N2A—C3A—H3A | 106.2 | N2B—C3B—H3B | 105.6 |
N2A—C3A—C4A | 111.2 (2) | N2B—C3B—C4B | 110.8 (2) |
C3A—C4A—H4AA | 109.9 | C3B—C4B—H4BA | 109.7 |
C3A—C4A—H4AB | 109.9 | C3B—C4B—H4BB | 109.7 |
C3A—C4A—S1A | 108.90 (16) | C3B—C4B—S1B | 109.99 (17) |
H4AA—C4A—H4AB | 108.3 | H4BA—C4B—H4BB | 108.2 |
S1A—C4A—H4AA | 109.9 | S1B—C4B—H4BA | 109.7 |
S1A—C4A—H4AB | 109.9 | S1B—C4B—H4BB | 109.7 |
C6A—C5A—C1A | 117.5 (3) | C6B—C5B—C1B | 119.1 (2) |
C10A—C5A—C1A | 123.3 (2) | C6B—C5B—C10B | 119.1 (2) |
C10A—C5A—C6A | 119.1 (3) | C10B—C5B—C1B | 121.8 (2) |
C5A—C6A—H6A | 120.2 | C5B—C6B—H6B | 119.9 |
C7A—C6A—C5A | 119.5 (3) | C7B—C6B—C5B | 120.1 (3) |
C7A—C6A—H6A | 120.2 | C7B—C6B—H6B | 119.9 |
C6A—C7A—H7A | 119.6 | C6B—C7B—H7B | 119.6 |
C8A—C7A—C6A | 120.8 (3) | C8B—C7B—C6B | 120.7 (3) |
C8A—C7A—H7A | 119.6 | C8B—C7B—H7B | 119.6 |
C7A—C8A—H8A | 119.6 | C7B—C8B—H8B | 120.1 |
C7A—C8A—C9A | 120.7 (3) | C9B—C8B—C7B | 119.8 (3) |
C9A—C8A—H8A | 119.6 | C9B—C8B—H8B | 120.1 |
C8A—C9A—H9A | 120.3 | C8B—C9B—H9B | 119.8 |
C10A—C9A—C8A | 119.4 (3) | C8B—C9B—C10B | 120.4 (3) |
C10A—C9A—H9A | 120.3 | C10B—C9B—H9B | 119.8 |
C5A—C10A—H10A | 119.8 | C5B—C10B—H10B | 120.0 |
C9A—C10A—C5A | 120.5 (3) | C9B—C10B—C5B | 119.9 (2) |
C9A—C10A—H10A | 119.8 | C9B—C10B—H10B | 120.0 |
C16A—C11A—C12A | 119.8 (3) | C12B—C11B—C16B | 120.9 (3) |
C16A—C11A—N1A | 119.7 (2) | C12B—C11B—N1B | 120.3 (2) |
C12A—C11A—N1A | 120.5 (3) | C16B—C11B—N1B | 118.8 (2) |
C11A—C16A—H16A | 120.2 | C11B—C12B—H12B | 120.1 |
C11A—C16A—C15A | 119.6 (3) | C11B—C12B—C13B | 119.9 (3) |
C15A—C16A—H16A | 120.2 | C13B—C12B—H12B | 120.1 |
C16A—C15A—H15A | 119.9 | C12B—C13B—H13B | 120.1 |
C14A—C15A—C16A | 120.3 (3) | C14B—C13B—C12B | 119.8 (4) |
C14A—C15A—H15A | 119.9 | C14B—C13B—H13B | 120.1 |
C15A—C14A—H14A | 120.0 | C13B—C14B—H14B | 119.9 |
C13A—C14A—C15A | 120.0 (3) | C15B—C14B—C13B | 120.3 (3) |
C13A—C14A—H14A | 120.0 | C15B—C14B—H14B | 119.9 |
C14A—C13A—H13A | 119.7 | C14B—C15B—H15B | 119.7 |
C14A—C13A—C12A | 120.6 (3) | C14B—C15B—C16B | 120.7 (3) |
C12A—C13A—H13A | 119.7 | C16B—C15B—H15B | 119.7 |
C11A—C12A—C13A | 119.7 (3) | C11B—C16B—C15B | 118.5 (3) |
C11A—C12A—H12A | 120.2 | C11B—C16B—H16B | 120.7 |
C13A—C12A—H12A | 120.2 | C15B—C16B—H16B | 120.7 |
N2A—C17A—C18A | 116.0 (2) | N2B—C17B—C18B | 116.0 (3) |
O3A—C17A—C18A | 121.6 (3) | O3B—C17B—C18B | 122.0 (3) |
O3A—C17A—N2A | 122.4 (2) | O3B—C17B—N2B | 121.9 (2) |
C17A—C18A—H18A | 109.5 | C17B—C18B—H18D | 109.5 |
C17A—C18A—H18B | 109.5 | C17B—C18B—H18E | 109.5 |
C17A—C18A—H18C | 109.5 | C17B—C18B—H18F | 109.5 |
H18A—C18A—H18B | 109.5 | H18D—C18B—H18E | 109.5 |
H18A—C18A—H18C | 109.5 | H18D—C18B—H18F | 109.5 |
H18B—C18A—H18C | 109.5 | H18E—C18B—H18F | 109.5 |
C2A—N1A—C1A | 127.96 (19) | C2B—N1B—C1B | 128.89 (19) |
C2A—N1A—C11A | 117.19 (18) | C2B—N1B—C11B | 117.93 (19) |
C11A—N1A—C1A | 114.79 (18) | C11B—N1B—C1B | 113.1 (2) |
C3A—N2A—H2A | 120.0 (16) | C3B—N2B—H2B | 120 (2) |
C17A—N2A—C3A | 121.0 (2) | C17B—N2B—C3B | 121.5 (2) |
C17A—N2A—H2A | 118.6 (16) | C17B—N2B—H2B | 119 (2) |
C4A—S1A—C1A | 94.46 (11) | C4B—S1B—C1B | 94.54 (11) |
O1A—S1A—C1A | 107.22 (13) | O1B—S1B—C1B | 105.93 (12) |
O1A—S1A—C4A | 105.71 (11) | O1B—S1B—C4B | 105.70 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2A···O2Bi | 0.91 (3) | 2.25 (3) | 3.137 (3) | 164 (2) |
N2B—H2B···O1Bii | 0.79 (3) | 2.14 (3) | 2.916 (3) | 168 (3) |
C10A—H10A···O3A | 0.93 | 2.42 | 3.259 (3) | 149 |
C10B—H10B···O3B | 0.93 | 2.44 | 3.232 (4) | 143 |
C4B—H4BB···O2Aiii | 0.97 | 2.25 | 3.116 (3) | 148 |
Symmetry codes: (i) x+1, y, z; (ii) −x, y+1/2, −z; (iii) −x+1, y+1/2, −z. |
Funding information
Funding for this research was provided by: National Science Foundation (grant No. CHEM-0131112 for the X-ray diffractometer); Penn State Schuylkill.
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