organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 2| February 2014| Pages o134-o135

1,3,4-Tri-O-acetyl-2-N-(tri­fluoro­acetyl)-β-L-fucose

aDepartment of Chemistry, Youngstown State University, 1 University Plaza, Youngstown, OH 44555-3663, USA
*Correspondence e-mail: pnorris@ysu.edu

(Received 6 December 2013; accepted 30 December 2013; online 15 January 2014)

The title compound, C14H18F3NO8, was produced through conjugation of 1,3,4-tri-O-acetyl-2-azidode­oxy-α,β-L-fucose with tri­fluoro­acetyl chloride in the presence of bis­(di­phenyl­phosphino)ethane in tetra­hydro­furan at room temperature. The X-ray crystal structure reveals that the β-anomer of the product mixture crystallizes from ethyl acetate/hexa­nes. The compound exists in a typical chair conformation with the maximum possible number of substituents, four out of five, located in the sterically preferred equatorial positions. The major directional force facilitating packing of the mol­ecules are N—H⋯O hydrogen bonds involving the amide moieties of neighboring mol­ecules, which connect mol­ecules stacked along the a-axis direction into infinite strands with a C11(4) graph-set motif. Formation of the strands is assisted by a number of weaker C—H⋯O inter­actions involving the methine and methyl H atoms. These strands are connected through further C—H⋯O and C—H⋯F inter­actions into a three dimensional network

Related literature

Information related to the synthesis of N-acetyl-L-fucosa­mine analogues may be found in Alhassan et al. (2012[Alhassan, A.-B., McCutcheon, D. C., Zeller, M. & Norris, P. (2012). J. Carbohydr. Chem. 31, 371-383.]). Rao et al. (1998[Rao, V. S. R., Qasba, P. K., Chandrasekaran, R. & Balaji, P. V. (1998). Conformation of Carbohydrates. Amsterdam: Harwood Academic Publishers.]) describe conformations of carbohydrate mol­ecules.

[Scheme 1]

Experimental

Crystal data
  • C14H18F3NO8

  • Mr = 385.29

  • Orthorhombic, P 21 21 21

  • a = 5.1818 (10) Å

  • b = 16.968 (3) Å

  • c = 19.484 (4) Å

  • V = 1713.1 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.14 mm−1

  • T = 100 K

  • 0.48 × 0.31 × 0.30 mm

Data collection
  • Bruker AXS Smart Apex CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007[Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany.]) Tmin = 0.839, Tmax = 0.958

  • 11394 measured reflections

  • 4232 independent reflections

  • 3869 reflections with I > 2σ(I)

  • Rint = 0.029

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.088

  • S = 1.06

  • 4232 reflections

  • 239 parameters

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.17 e Å−3

  • Absolute structure: Flack parameter determined using 1493 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])

  • Absolute structure parameter: 0.4 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯O6i 0.88 2.14 2.959 (2) 155
C3—H3⋯O6i 1.00 2.45 3.308 (3) 144
C6—H6B⋯F3ii 0.98 2.63 3.487 (3) 147
C8—H8A⋯O5iii 0.98 2.48 3.445 (3) 169
C8—H8B⋯O5iv 0.98 2.41 3.206 (3) 137
C8—H8C⋯O8v 0.98 2.64 3.443 (3) 139
C14—H14A⋯O8iv 0.98 2.38 3.292 (3) 155
Symmetry codes: (i) x-1, y, z; (ii) [-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (iv) x+1, y, z; (v) [-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}].

Data collection: SMART (Bruker, 2002[Bruker (2002). SMART. Bruker AXS Inc, Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2003[Bruker (2003). SAINT-Plus. Bruker AXS Inc, Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and SHELXLE (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]); molecular graphics: 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.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The title compound, 1,3,4-tri-O-acetyl-2-N-(trifluoro)acetyl-β-L-fucose, was synthesized during a project focused on the production of glycomimetic analogs of the bacterial aminosugar, N-acetyl-L-fucosamine (Alhassan et al., 2012). Beginning with an anomeric mixture of 1,3,4-tri-O-acetyl-2-azidodeoxy-α,β-L-fucoses, treatment with trifluoroacetyl chloride in the presence of bis(diphenylphosphino)ethane in THF at room temperature afforded a mixture of 1,3,4-tri-O-acetyl-2-N-(trifluoro)acetyl-α,β-L-fucoses as a colorless syrup. The mixture of anomers was purified by column chromatography, and one of the two anomers was selectively isolated by vapor diffusion crystallization using ethyl acetate and hexanes, with the other anomer remaining in solution. The crystals (m.p. 157–159 °C) were initially identified as the β-anomer by 1H NMR spectroscopy. Single-crystal diffraction was then employed in order to unambiguously confirm the configuration of the anomer isolated by crystallization.

Figure 1 shows a depiction of one molecule of 1,3,4-tri-O-acetyl-2-N-(trifluoro)acetyl-β-L-fucose as present in the solid state. From the crystal structure, it was confirmed that the isolated and crystallized fraction is indeed the β anomer, as had been already suspected based on 1H NMR shifts and coupling constants. The molecule crystallizes in a chair conformation as typical for pyranose sugar derivatives (Rao et al., 1998) with the choice of the chair conformation – from the two that are possible – being apparently the result of sterical interactions. The maximum possible number of substituents, four out of five, are located in the sterically preferred equatorial positions. Only the O-acetyl group at carbon atom C4 is, out of necessity to be able to maintain the overall chair conformation, forced into an axial position. This conformation is in agreement with the observed solution conformation as determined from the 1H NMR coupling constants (see experimental section). The acetyl and amide groups are, as expected, nearly perfectly planar – the r.m.s. deviation from planarity for the five atoms of the amide group is only 0.0052. Those for the four atoms of each acetate group at C1, C3 and C4 are 0.0196, 0.0087 and 0.0475, respectively – and they are tilted to variable degrees against the average plane of the pyranose moiety (48.17 (9)° at C1, 57.98 (9)° at C3, 79.04 (7)° at C4, and 71.97 (8)° for the amide group).

This conformation allows for dense packing of the molecules in the solid state, with no significant distortions of the molecules or voids present in the solid state. The major directional force facilitating packing of the molecules are N—H···O hydrogen bonds involving the amide moieties of neighboring molecules. Through these interactions, molecules stacked along the direction of the a-axis (created through translation from each other) are connected into infinite strands, with a C11(4) graph set motif for the N—H···O hydrogen bonds. Formation of the strands is assisted by a number of weaker but nevertheless still attractive C—H···O interactions involving the methine and methyl hydrogen atoms, with three of these interactions featuring H···O separations of 2.5 Å or less (2.38, 2.41 and 2.45 Å, involving H14A, H8B and H3, respectively. See Table 1 for details and symmetry operators). These strands, Figure 2, are in turn connected with each other through further C—H···O and C—H···F interactions into a three dimensional network, Figure 3 and Table 1. The stabilizing and directional effect of the C—H···F interactions might also have contributed to the ordered nature of the trifluoro methyl group. No signs of rotational disorder, as often observed for CF3 groups, is evident for this structure.

Related literature top

Information related to the synthesis of N-acetyl-L-fucosamine analogues may be found in Alhassan et al. (2012). Rao et al. (1998) describe conformations of carbohydrate molecules.

Experimental top

The title compound was synthesized from 1,3,4-tri-O-acetyl-2-azidodeoxy-α,β-L-fucoses (anomeric α/β ratio of 3:2 by NMR) by Staudinger-type synthesis with trifluoroacetyl chloride in the presence of bis(diphenylphosphino)ethane following a previously reported procedure (Alhassan et al., 2012). Column chromatography (silica gel, 2:1 hexanes-EtOAc) yielded a 3:2 anomeric α/β mixture (by NMR) of the title compound as a colorless syrup in an overall yield of 37%. The β-anomer was selectively isolated as a crystalline solid by vapor diffusion from ethyl acetate and hexanes, m.p. 157–159 °C.

1H NMR (400 MHz, CDC13): 1.25 (d, 3H, H-6, J = 6.40 Hz); 2.02 (s, 3H, COCH3); 2.12 (s, 3H, COCH3); 2.21 (s, 3H, COCH3); 3.94 (dq, 1H, H-5, J = 0.96, 6.44 Hz); 4.47 (ddd, 1H, H-2, J = 9.28, 9.28, 11.12 Hz); 5.14 (dd, 1H, H-3, J = 3.28, 11.28 Hz); 5.25 (dd, 1H, H-4, J = 0.78, 3.30 Hz); 5.74 (d, 1H, H-1, J = 8.76 Hz); 6.56 (d, 1H, N—H, J = 9.44 Hz).

13C NMR (100 MHz, CDC13): 16.03 (C-6); 20.45 (COCH3); 20.63 (COCH3); 20.68 (COCH3); 50.48 (C-2); 69.18 (C-4); 70.28 (C-3); 70.75 (C-5); 92.40 (C-1); 157.44 (COCF3); 157.81 (COCF3); 169.64 (COCH3); 170.43 (COCH3); 170.90 (COCH3).

MS: m/z calculated: 385.1 m/z found (ESI): 408.2 (+Na+).

Refinement top

H atoms attached to carbon and nitrogen atoms were positioned geometrically and constrained to ride on their parent atoms, with carbon hydrogen bond distances of 1.00 and 0.98 Å for C—H and CH3 and 0.88 Å for N—H moieties, respectively. Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Uiso(H) values were set to a multiple of Ueq(C/N) with 1.5 for CH3 and 1.2 for C—H and N—H units, respectively. Reflection 0 1 1 was affected by the beam stop and was omitted from the refinement.

Structure description top

The title compound, 1,3,4-tri-O-acetyl-2-N-(trifluoro)acetyl-β-L-fucose, was synthesized during a project focused on the production of glycomimetic analogs of the bacterial aminosugar, N-acetyl-L-fucosamine (Alhassan et al., 2012). Beginning with an anomeric mixture of 1,3,4-tri-O-acetyl-2-azidodeoxy-α,β-L-fucoses, treatment with trifluoroacetyl chloride in the presence of bis(diphenylphosphino)ethane in THF at room temperature afforded a mixture of 1,3,4-tri-O-acetyl-2-N-(trifluoro)acetyl-α,β-L-fucoses as a colorless syrup. The mixture of anomers was purified by column chromatography, and one of the two anomers was selectively isolated by vapor diffusion crystallization using ethyl acetate and hexanes, with the other anomer remaining in solution. The crystals (m.p. 157–159 °C) were initially identified as the β-anomer by 1H NMR spectroscopy. Single-crystal diffraction was then employed in order to unambiguously confirm the configuration of the anomer isolated by crystallization.

Figure 1 shows a depiction of one molecule of 1,3,4-tri-O-acetyl-2-N-(trifluoro)acetyl-β-L-fucose as present in the solid state. From the crystal structure, it was confirmed that the isolated and crystallized fraction is indeed the β anomer, as had been already suspected based on 1H NMR shifts and coupling constants. The molecule crystallizes in a chair conformation as typical for pyranose sugar derivatives (Rao et al., 1998) with the choice of the chair conformation – from the two that are possible – being apparently the result of sterical interactions. The maximum possible number of substituents, four out of five, are located in the sterically preferred equatorial positions. Only the O-acetyl group at carbon atom C4 is, out of necessity to be able to maintain the overall chair conformation, forced into an axial position. This conformation is in agreement with the observed solution conformation as determined from the 1H NMR coupling constants (see experimental section). The acetyl and amide groups are, as expected, nearly perfectly planar – the r.m.s. deviation from planarity for the five atoms of the amide group is only 0.0052. Those for the four atoms of each acetate group at C1, C3 and C4 are 0.0196, 0.0087 and 0.0475, respectively – and they are tilted to variable degrees against the average plane of the pyranose moiety (48.17 (9)° at C1, 57.98 (9)° at C3, 79.04 (7)° at C4, and 71.97 (8)° for the amide group).

This conformation allows for dense packing of the molecules in the solid state, with no significant distortions of the molecules or voids present in the solid state. The major directional force facilitating packing of the molecules are N—H···O hydrogen bonds involving the amide moieties of neighboring molecules. Through these interactions, molecules stacked along the direction of the a-axis (created through translation from each other) are connected into infinite strands, with a C11(4) graph set motif for the N—H···O hydrogen bonds. Formation of the strands is assisted by a number of weaker but nevertheless still attractive C—H···O interactions involving the methine and methyl hydrogen atoms, with three of these interactions featuring H···O separations of 2.5 Å or less (2.38, 2.41 and 2.45 Å, involving H14A, H8B and H3, respectively. See Table 1 for details and symmetry operators). These strands, Figure 2, are in turn connected with each other through further C—H···O and C—H···F interactions into a three dimensional network, Figure 3 and Table 1. The stabilizing and directional effect of the C—H···F interactions might also have contributed to the ordered nature of the trifluoro methyl group. No signs of rotational disorder, as often observed for CF3 groups, is evident for this structure.

Information related to the synthesis of N-acetyl-L-fucosamine analogues may be found in Alhassan et al. (2012). Rao et al. (1998) describe conformations of carbohydrate molecules.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) and SHELXLE (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : Thermal ellipsoid plot, with atom labels for non-hydrogen atoms and 50 percent probability ellipsoids.
[Figure 2] Fig. 2. : Major packing interactions, viewed roughly perpendicular to the a axis direction showing the strands parallel to [1 0 0]. Blue dotted lines denote N—H···O hydrogen bonds and assisting C—H···O interactions. Symmetry codes: (i) x - 1, y, z; (iv) x + 1, y, z.
[Figure 3] Fig. 3. : View along the a axis direction, showing C—H···O and C—H···F interactions connecting parallel strands with each other. For atoms involved and symmetry operators, see Table 1.
1,3,4-Tri-O-acetyl-2-N-(trifluoroacetyl)-β-L-fucose top
Crystal data top
C14H18F3NO8Dx = 1.494 Mg m3
Mr = 385.29Melting point = 430.5–432.5 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6913 reflections
a = 5.1818 (10) Åθ = 2.4–30.5°
b = 16.968 (3) ŵ = 0.14 mm1
c = 19.484 (4) ÅT = 100 K
V = 1713.1 (6) Å3Block, colourless
Z = 40.48 × 0.31 × 0.30 mm
F(000) = 800
Data collection top
Bruker AXS Smart Apex CCD
diffractometer
4232 independent reflections
Radiation source: fine-focus sealed tube3869 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 66
Tmin = 0.839, Tmax = 0.958k = 2221
11394 measured reflectionsl = 2225
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0424P)2 + 0.1715P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
4232 reflectionsΔρmax = 0.30 e Å3
239 parametersΔρmin = 0.17 e Å3
0 restraintsAbsolute structure: Flack parameter determined using 1493 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.4 (3)
Crystal data top
C14H18F3NO8V = 1713.1 (6) Å3
Mr = 385.29Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.1818 (10) ŵ = 0.14 mm1
b = 16.968 (3) ÅT = 100 K
c = 19.484 (4) Å0.48 × 0.31 × 0.30 mm
Data collection top
Bruker AXS Smart Apex CCD
diffractometer
4232 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
3869 reflections with I > 2σ(I)
Tmin = 0.839, Tmax = 0.958Rint = 0.029
11394 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.088Δρmax = 0.30 e Å3
S = 1.06Δρmin = 0.17 e Å3
4232 reflectionsAbsolute structure: Flack parameter determined using 1493 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
239 parametersAbsolute structure parameter: 0.4 (3)
0 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3282 (4)0.43097 (12)0.65855 (10)0.0225 (4)
H10.15660.43270.63510.027*
C20.3854 (4)0.50942 (11)0.69399 (10)0.0190 (4)
H20.56260.50770.71430.023*
C30.1889 (4)0.52308 (11)0.75081 (10)0.0209 (4)
H30.01740.53510.72970.025*
C40.1619 (4)0.45132 (12)0.79776 (11)0.0239 (4)
H40.00890.45850.82840.029*
C50.1274 (5)0.37669 (12)0.75536 (11)0.0284 (5)
H50.03920.38010.72960.034*
C60.1278 (6)0.30211 (14)0.79839 (12)0.0417 (7)
H6A0.10260.25630.76850.063*
H6B0.01240.30460.83210.063*
H6C0.29340.29730.82230.063*
C70.4717 (4)0.36394 (12)0.55954 (11)0.0255 (5)
C80.6856 (5)0.35718 (14)0.50908 (11)0.0306 (5)
H8A0.71020.30170.49680.046*
H8B0.84480.37790.52940.046*
H8C0.64270.38750.46780.046*
C90.5799 (4)0.60760 (12)0.61779 (10)0.0201 (4)
C100.5121 (4)0.67368 (12)0.56627 (11)0.0231 (4)
C110.0942 (5)0.63360 (13)0.82140 (11)0.0274 (5)
C120.2160 (6)0.70111 (14)0.85856 (13)0.0361 (6)
H12A0.08260.73920.87160.054*
H12B0.34240.72680.82850.054*
H12C0.30290.68160.89990.054*
C130.3851 (4)0.47114 (12)0.90408 (11)0.0247 (4)
C140.6170 (4)0.44563 (14)0.94350 (11)0.0306 (5)
H14A0.76710.47640.92870.046*
H14B0.64920.38950.93510.046*
H14C0.58730.45420.99260.046*
F10.4052 (3)0.64366 (8)0.50988 (6)0.0343 (3)
F20.7207 (3)0.71321 (8)0.54797 (7)0.0374 (3)
F30.3429 (3)0.72485 (8)0.59280 (7)0.0373 (4)
N10.3700 (3)0.57409 (10)0.64480 (8)0.0203 (4)
H1A0.21700.59160.63250.024*
O10.3363 (3)0.36940 (8)0.70706 (7)0.0269 (3)
O20.5281 (3)0.41733 (8)0.61054 (7)0.0236 (3)
O30.2779 (3)0.59116 (8)0.78734 (7)0.0230 (3)
O40.3917 (3)0.44154 (8)0.83929 (7)0.0241 (3)
O50.2690 (3)0.32900 (9)0.55792 (9)0.0338 (4)
O60.8048 (3)0.59089 (9)0.62873 (8)0.0272 (3)
O70.1313 (3)0.61666 (11)0.82064 (9)0.0382 (4)
O80.2109 (3)0.51128 (9)0.92552 (8)0.0292 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0229 (11)0.0235 (9)0.0210 (10)0.0005 (8)0.0013 (8)0.0021 (8)
C20.0170 (9)0.0221 (9)0.0181 (9)0.0001 (8)0.0011 (8)0.0034 (7)
C30.0173 (9)0.0235 (9)0.0220 (10)0.0017 (8)0.0006 (8)0.0003 (8)
C40.0200 (10)0.0290 (10)0.0228 (10)0.0037 (9)0.0008 (8)0.0028 (8)
C50.0312 (12)0.0276 (10)0.0265 (11)0.0090 (9)0.0003 (10)0.0044 (8)
C60.0604 (18)0.0305 (12)0.0342 (13)0.0151 (13)0.0019 (13)0.0073 (10)
C70.0296 (12)0.0216 (10)0.0251 (11)0.0053 (9)0.0062 (9)0.0005 (8)
C80.0313 (12)0.0330 (11)0.0275 (11)0.0063 (10)0.0004 (10)0.0045 (9)
C90.0193 (10)0.0229 (9)0.0181 (9)0.0008 (8)0.0011 (8)0.0001 (7)
C100.0237 (10)0.0225 (10)0.0233 (10)0.0010 (8)0.0014 (8)0.0006 (8)
C110.0282 (12)0.0292 (11)0.0247 (11)0.0061 (9)0.0019 (9)0.0026 (8)
C120.0418 (15)0.0329 (12)0.0335 (12)0.0019 (11)0.0022 (11)0.0054 (10)
C130.0235 (11)0.0270 (10)0.0237 (10)0.0045 (9)0.0001 (9)0.0037 (8)
C140.0259 (11)0.0385 (12)0.0275 (11)0.0003 (10)0.0032 (10)0.0007 (9)
F10.0460 (9)0.0312 (6)0.0258 (7)0.0004 (6)0.0113 (6)0.0026 (5)
F20.0354 (8)0.0380 (8)0.0389 (8)0.0104 (6)0.0042 (7)0.0133 (6)
F30.0483 (9)0.0295 (6)0.0342 (7)0.0157 (7)0.0119 (7)0.0063 (5)
N10.0159 (8)0.0237 (8)0.0214 (8)0.0009 (7)0.0009 (7)0.0041 (6)
O10.0334 (9)0.0230 (7)0.0243 (7)0.0011 (7)0.0003 (7)0.0038 (6)
O20.0216 (7)0.0260 (7)0.0233 (7)0.0006 (6)0.0002 (6)0.0022 (6)
O30.0210 (7)0.0241 (7)0.0240 (7)0.0021 (6)0.0018 (6)0.0021 (6)
O40.0231 (8)0.0286 (7)0.0206 (7)0.0004 (6)0.0021 (6)0.0029 (6)
O50.0306 (9)0.0324 (9)0.0385 (9)0.0035 (7)0.0044 (7)0.0076 (7)
O60.0177 (7)0.0354 (8)0.0286 (8)0.0002 (6)0.0004 (6)0.0061 (6)
O70.0234 (9)0.0477 (10)0.0435 (10)0.0088 (8)0.0017 (8)0.0075 (8)
O80.0268 (8)0.0343 (8)0.0265 (8)0.0018 (7)0.0003 (7)0.0004 (6)
Geometric parameters (Å, º) top
C1—O11.410 (2)C8—H8A0.9800
C1—O21.415 (3)C8—H8B0.9800
C1—C21.528 (3)C8—H8C0.9800
C1—H11.0000C9—O61.218 (3)
C2—N11.459 (2)C9—N11.335 (3)
C2—C31.522 (3)C9—C101.545 (3)
C2—H21.0000C10—F21.321 (2)
C3—O31.433 (2)C10—F11.332 (2)
C3—C41.529 (3)C10—F31.338 (2)
C3—H31.0000C11—O71.203 (3)
C4—O41.449 (3)C11—O31.366 (3)
C4—C51.523 (3)C11—C121.495 (3)
C4—H41.0000C12—H12A0.9800
C5—O11.440 (3)C12—H12B0.9800
C5—C61.518 (3)C12—H12C0.9800
C5—H51.0000C13—O81.205 (3)
C6—H6A0.9800C13—O41.359 (3)
C6—H6B0.9800C13—C141.490 (3)
C6—H6C0.9800C14—H14A0.9800
C7—O51.207 (3)C14—H14B0.9800
C7—O21.376 (3)C14—H14C0.9800
C7—C81.486 (3)N1—H1A0.8800
O1—C1—O2107.48 (16)C7—C8—H8B109.5
O1—C1—C2109.69 (16)H8A—C8—H8B109.5
O2—C1—C2107.42 (17)C7—C8—H8C109.5
O1—C1—H1110.7H8A—C8—H8C109.5
O2—C1—H1110.7H8B—C8—H8C109.5
C2—C1—H1110.7O6—C9—N1127.7 (2)
N1—C2—C3109.07 (16)O6—C9—C10120.00 (18)
N1—C2—C1110.34 (15)N1—C9—C10112.33 (17)
C3—C2—C1109.37 (16)F2—C10—F1108.16 (17)
N1—C2—H2109.3F2—C10—F3108.13 (16)
C3—C2—H2109.3F1—C10—F3107.12 (18)
C1—C2—H2109.3F2—C10—C9110.97 (18)
O3—C3—C2105.59 (16)F1—C10—C9110.66 (16)
O3—C3—C4111.98 (16)F3—C10—C9111.64 (17)
C2—C3—C4112.03 (17)O7—C11—O3123.0 (2)
O3—C3—H3109.0O7—C11—C12126.8 (2)
C2—C3—H3109.0O3—C11—C12110.2 (2)
C4—C3—H3109.0C11—C12—H12A109.5
O4—C4—C5107.73 (17)C11—C12—H12B109.5
O4—C4—C3110.49 (17)H12A—C12—H12B109.5
C5—C4—C3110.39 (16)C11—C12—H12C109.5
O4—C4—H4109.4H12A—C12—H12C109.5
C5—C4—H4109.4H12B—C12—H12C109.5
C3—C4—H4109.4O8—C13—O4123.3 (2)
O1—C5—C6106.8 (2)O8—C13—C14126.1 (2)
O1—C5—C4109.73 (17)O4—C13—C14110.56 (19)
C6—C5—C4113.17 (18)C13—C14—H14A109.5
O1—C5—H5109.0C13—C14—H14B109.5
C6—C5—H5109.0H14A—C14—H14B109.5
C4—C5—H5109.0C13—C14—H14C109.5
C5—C6—H6A109.5H14A—C14—H14C109.5
C5—C6—H6B109.5H14B—C14—H14C109.5
H6A—C6—H6B109.5C9—N1—C2122.31 (17)
C5—C6—H6C109.5C9—N1—H1A118.8
H6A—C6—H6C109.5C2—N1—H1A118.8
H6B—C6—H6C109.5C1—O1—C5110.62 (16)
O5—C7—O2121.8 (2)C7—O2—C1115.46 (16)
O5—C7—C8126.4 (2)C11—O3—C3116.22 (17)
O2—C7—C8111.75 (19)C13—O4—C4117.13 (17)
C7—C8—H8A109.5
O1—C1—C2—N1178.28 (17)N1—C9—C10—F350.2 (2)
O2—C1—C2—N165.2 (2)O6—C9—N1—C20.2 (3)
O1—C1—C2—C358.3 (2)C10—C9—N1—C2179.05 (16)
O2—C1—C2—C3174.82 (16)C3—C2—N1—C9137.83 (19)
N1—C2—C3—O367.37 (19)C1—C2—N1—C9102.0 (2)
C1—C2—C3—O3171.87 (15)O2—C1—O1—C5176.42 (15)
N1—C2—C3—C4170.49 (16)C2—C1—O1—C567.1 (2)
C1—C2—C3—C449.7 (2)C6—C5—O1—C1171.70 (18)
O3—C3—C4—O448.1 (2)C4—C5—O1—C165.3 (2)
C2—C3—C4—O470.4 (2)O5—C7—O2—C12.9 (3)
O3—C3—C4—C5167.13 (18)C8—C7—O2—C1176.33 (17)
C2—C3—C4—C548.7 (2)O1—C1—O2—C781.6 (2)
O4—C4—C5—O165.9 (2)C2—C1—O2—C7160.48 (16)
C3—C4—C5—O154.8 (2)O7—C11—O3—C31.2 (3)
O4—C4—C5—C653.2 (3)C12—C11—O3—C3178.36 (17)
C3—C4—C5—C6173.9 (2)C2—C3—O3—C11154.73 (16)
O6—C9—C10—F210.1 (3)C4—C3—O3—C1183.1 (2)
N1—C9—C10—F2170.94 (18)O8—C13—O4—C47.8 (3)
O6—C9—C10—F1110.0 (2)C14—C13—O4—C4171.13 (17)
N1—C9—C10—F169.0 (2)C5—C4—O4—C13142.17 (18)
O6—C9—C10—F3130.8 (2)C3—C4—O4—C1397.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O6i0.882.142.959 (2)155
C3—H3···O6i1.002.453.308 (3)144
C6—H6B···F3ii0.982.633.487 (3)147
C8—H8A···O5iii0.982.483.445 (3)169
C8—H8B···O5iv0.982.413.206 (3)137
C8—H8C···O8v0.982.643.443 (3)139
C14—H14A···O8iv0.982.383.292 (3)155
Symmetry codes: (i) x1, y, z; (ii) x, y1/2, z+3/2; (iii) x+1/2, y+1/2, z+1; (iv) x+1, y, z; (v) x+1/2, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O6i0.882.1372.959 (2)155.2
C3—H3···O6i1.002.4453.308 (3)144.1
C6—H6B···F3ii0.982.6283.487 (3)146.5
C8—H8A···O5iii0.982.4793.445 (3)168.7
C8—H8B···O5iv0.982.4143.206 (3)137.4
C8—H8C···O8v0.982.6433.443 (3)138.9
C14—H14A···O8iv0.982.3753.292 (3)155.3
Symmetry codes: (i) x1, y, z; (ii) x, y1/2, z+3/2; (iii) x+1/2, y+1/2, z+1; (iv) x+1, y, z; (v) x+1/2, y+1, z1/2.
 

Acknowledgements

DCM and PN thank the School of Graduate Studies and Research at Youngstown State University for financial support. The diffractometer was funded by NSF grant No. 0087210, by Ohio Board of Regents grant No. CAP-491 and by YSU.

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Volume 70| Part 2| February 2014| Pages o134-o135
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