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Among the three compounds reported here, namely N-(4-fluoro­phenyl)-β-D-mannopyran­osyl­amine, (I), N-(3-fluoro­phenyl)-β-D-mannopyran­osyl­amine, (II), and N-(2-fluoro­phenyl)-β-D-mannopyran­osyl­amine, (III), all with chemical formula C12H16FNO5, (I) and (II) are isostructural, whereas (III) assumes the same packing arrangement as the unfluorin­ated analogue N-phenyl-β-D-mannopyran­osyl­amine, (IV), which has been reported previously. Similarities with respect to the inter­molecular hydrogen-bonding patterns exist across the series (I)–(III). A packing motif that distinguishes the shared packing arrangement of (I) and (II) from that of (III) is a C—F...H—C chain of graph set C(4) that is preserved in the formal exchange of F and H atoms at the 4- and 3-positions on the aromatic ring of (I) and (II), but is replaced by a different chain of graph set C(5) when the F atom is located at the 2-position of the aromatic ring in (III). The steric role of the F atom in (I)–(III) is ambiguous but is examined here in detail.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110043556/gz3186sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110043556/gz3186Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110043556/gz3186IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110043556/gz3186IIIsup4.hkl
Contains datablock III

CCDC references: 810005; 810006; 810007

Comment top

The role played by covalently bonded fluorine in the solid-state packing of organic molecules is a topic of continuing active interest and is of direct relevance to the field of crystal engineering (Chopra & Guru Row, 2008; Zhu et al., 2007; Reichenbächer et al., 2005; Choudhury & Guru Row, 2004; Choudhury et al., 2004, Brammer et al., 2001), although whether solid-state interactions involving fluorine can actually be useful in the design and preparation of desired molecular packing motifs has been questioned in the literature. Previous studies have shown that the F atom of the C—F moiety is an exceptionally weak hydrogen-bond acceptor and that such interactions are significant only in particular cases, such as in those crystal structures from which stronger hydrogen-bonding groups are absent (Dunitz, 2004; Thalladi et al., 1998; Dunitz & Taylor, 1997; Howard et al., 1996). Solid-state halogen···halogen contacts between F atoms have been reported to be the consequence of molecular packing, rather than of attractive interactions that help determine that packing (Desiraju & Parthasarathy, 1989). Nevertheless, interactions of covalently bonded F atoms with neighbouring H atoms, as well as with nearby π systems and with other halogen atoms, continue to be cited in the literature as factors that influence the packing of a variety of fluorine-bearing molecules, even in the presence of certain relatively strong hydrogen-bonding donors and acceptors (In et al., 2003; Vangala et al., 2002; Prasanna & Guru Row, 2000; Nangia, 2000).

Given this rather contradictory situation and the subtle nature of solid-state interactions involving C—F, we have been particularly interested in fluorine-substituted monosaccharide derivatives, which we have prepared and examined as part of our continuing study of the structures of the compounds formed upon reaction of monosaccharides with nitrogenous bases. We describe here the molecular and crystal structures of three fluorine-substituted glycosylamine derivatives of D-mannose, N-(4-fluorophenyl)-β-D-mannopyranosylamine, (I), N-(3-fluorophenyl)-β-D-mannopyranosylamine, (II), and N-(2-fluorophenyl)-β-D-mannopyranosylamine, (III).

In general, the reaction of a monosaccharide with a nitrogenous base can yield as the crystalline product an open-chain Schiff base, as well as (or instead of) a cyclic glycosylamine. For example, we found in a previous study that D-mannose reacts with hydroxylamine to yield an open-chain oxime as the crystalline product (Ojala et al., 2000). On the other hand, in related work we obtained glycosylamines, including the phenyl-substituted derivative, (IV), rather than Schiff bases, from the reaction of D-mannose with aniline and its derivatives (Ojala et al., 2000; Ojala, Ostman, Hanson & Ojala, 2001; Ojala, Ostman, Ojala & Hanson, 2001). We have now obtained the fluoro-substituted glycosylamines (I)–(III) by reaction of D-mannose with the corresponding fluoroanilines. In our previous studies we found isostructuralism among certain glycosylamines, indicating that the solid-state hydrogen-bonding networks linking the monosaccharide moieties are sufficiently strong and extensive that even fairly drastic changes in the size, shape and even position of substitutents on the aryl ring may have little effect on them. For example, the N-4-bromophenyl, N-4-chlorophenyl, N-4-methylphenyl and N-3-chlorophenyl glycosylamines formed upon reaction between D-mannose and 4-bromoaniline, 4-chloroaniline, 4-methylaniline and 3-chloroaniline, respectively, assume the same molecular packing arrangement. We thus consider it noteworthy that the crystal structures of (I), (II) and (III) are not all identical, given the rigidity expected of their hydrogen-bonding networks. If only the general size similarity between the F atom and the H atom were relevant to the packing, (I), (II) and (III) might all have been found to be isostructural with unfluorinated (IV). Although (I) and (II) are in fact isostructural with each other, they are not isostructural with (IV); only (III) is.

At the molecular level, little difference exists between (I), (II) and (III), except for the position of the F atom. The conformations of the three isomers are closely similar, as shown in Figs. 1–3 and by the corresponding torsion angles in Tables 1, 3 and 5. Similarities exist at the level of molecular packing as well. Details of the intermolecular hydrogen-bonding contacts are given in Tables 2, 4 and 6. A view of the hydrogen-bonding array in the molecular packing of (I) is shown in Fig. 4; the hydrogen-bonding in (II) and (III) with respect to the monosaccharide moieties is similar. In all three structures, neighbouring molecules are connected by an R22(10) hydrogen-bonding motif (Etter, 1990) between molecules related by translation along [100]. Neighbouring molecules are also connected by an R22(11) interaction (in which the N—H group participates as a hydrogen-bond donor) between molecules related by translation along [010]. Each molecule also participates, with two additional neighbouring molecules, both related to the first by twofold screw-axial symmetry, in a 12-membered hydrogen-bonded ring interaction that builds up the structure along [001] and defines hydrophilic hydrogen-bonded regions extending parallel to (001) in all three structures (Figs. 5 and 6). With similar hydrogen-bonding contacts linking the monosaccharide moieties in all three structures, the differentiating factor that sets the overall crystal structure of (III) apart from that assumed by both (I) and (II) must lie elsewhere than in the conventional hydrogen-bonding system.

That differentiating factor appears to be differences in packing motifs involving C—F···H—C interactions. In all three structures these interactions occur in the hydrophobic regions defined by the aryl groups, regions that lie between the hydrophilic regions defined by the hydrogen-bonded monosaccharide moieties (Figs. 5 and 6). In terms of graph-set notation, these C—F···H—C interactions define a C(4) chain motif in both (I) and (II), but a C(5) chain motif in (III). A view of the C(4) motif in (I) is shown in Fig. 7; exchanging the F and H atoms in the contact shown in Fig. 7 produces the corresponding C(4) chain motif in (II). In (I) the motif is defined by the C10—F1···H9—C9 interaction and in (II) the motif is defined by the C9—F1···H10—C10 interaction (see Table 7 for distances and angles). The only significant difference between (I) and (II) is the exchange of the F and H atoms at the 3- and 4-positions, an exchange that leaves the C(4) chain motif intact and does not yield a new crystal structure. When the F atom is located in the 2-position, this motif is replaced by the C(5) motif defined by the C8—F1···H12—C12 interaction (Fig. 8; see Table 7 for distances and angles) and (III) assumes a different packing arrangement, the higher-symmetry P212121 structure, rather than the lower-symmetry P21 structure assumed by (I) and (II). Although a C—F···H—C contact is maintained in (III), the fact that unfluorinated (IV) assumes the same packing arrangement as (III) makes it unlikely (or at least unnecessary) that the F atom in (III) is doing anything special in terms of hydrogen-bonding; the structural similarity between (III) and (IV) is consistent with the steric similarity between F and H atoms.

Behaviour parallel to that of the series (I)–(III) is shown by the 4-chlorophenyl-, 3-chlorophenyl- and 2-chlorophenylmannopyranosylamine analogues reported previously (Ojala et al., 2000; Ojala, Ostman, Hanson & Ojala 2001) and listed in the Cambridge Structural Database (Allen, 2002) as QEDXEC, YIJJOQ and YIJDUQ, respectively. QEDXEC and YIJJOQ are isostructural with each other and with (I) and (II), and exhibit a chain motif defined by a C—Cl···H—C interaction, analogous to the C—F···H—C chain motif exhibited by (I) and (II). YIJDUQ, in contrast, assumes a packing arrangement different from those assumed by (I)–(III). In the 3- and 4-chlorinated structures, the halogen-for-hydrogen exchange between the 3- and 4-positions on the aromatic ring involves a more drastic change in space-filling requirements than in the corresponding fluorinated structures. Weak hydrogen-bonding character in the C—Cl···H—C interactions might help stabilize this motif in the face of that change. With (I) and (II) assuming the same packing arrangement as their chlorinated analogues, some attractive character in the C—F···H—C interactions in (I) and (II) may exist as well. In both the fluorinated and chlorinated series, the C(4) chain motif is disrupted when the halogen atom is located in the 2-position on the aromatic ring. At this position, fluorine thus behaves more like an H atom than a halogen atom. When located on the 3- or 4-positions on the aromatic ring, fluorine engages in the C—F···H—C motif analogous to the C—Cl···H—C motif and behaves more like a halogen atom than an H atom.

Previous structural studies in which all three compounds in a 2-fluorophenyl/3-fluorophenyl/4-fluorophenyl series have been published together have yielded mixed results in terms of whether changing the fluorine position changes the packing arrangement (at least to the degree of changing the space-group symmetry). In some cases all three compounds are isostructural (Donnelly et al., 2008); in others, all three compounds assume unique packing arrangements, which appears to us to be the more common situation (Langley et al., 1996; Klösener et al., 2008; Wardell et al.,2007; Chisholm et al., 2002; Taira et al., 1988; Larsen & Marthi, 1994). Our present series of fluorophenyl mannoglycosylamines represents the unusual situation in which a packing arrangement in the series is shared by more than one fluorine positional isomer. This situation may represent a compromise between a tendency toward isostructuralism arising from the rigidity of the hydrogen-bond network and a tendency toward non-isostructuralism arising from the disruption of the less rigid non-hydrogen-bonded part of the structure caused by the repositioning of the F atom from isomer to isomer. The loss of isostructuralism with the alteration of the C—F···H—C chain motif in (I)–(III) may be evidence for the structural significance of these contacts in this and other particular cases in which strong hydrogen-bond acceptors and donors are present but interact strongly only among themselves, leaving open the possibility that secondary interactions, even those as exceedingly weak as C—F···H—C interactions, might influence the overall packing arrangement, with the F atom acting as more than a simple size-and-shape mimic for the H atom.

Experimental top

Compounds (I)–(III) were prepared by combining D-mannose (0.5 g) with equimolar amounts of 4-fluoroaniline, 3-fluoroaniline and 2-fluoroaniline, respectively, in ethanol, heating the solution to boiling for approximately 10 min and then allowing the solutions to cool and the products to crystallize. The synthesis of a series of N-arylglycosylamines from fluorinated anilines by a similar method has been reported elsewhere (Qian et al., 2001), but none of the compounds we describe here was included in that study. Compound (I) was obtained as colourless plates, m.p. 449–456 K, compound (II) as colourless plates, m.p. 463–465 K, and compound (III) as colourless plates, m.p. 466–474 K. The synthesis and crystal structure of (IV) have been described previously (Ojala et al., 2000; Metlitskikh et al., 2005).

Refinement top

Given the absence from all three structures of significant anomalous scattering effects, equivalent reflections, including Friedel pairs, were merged. H atoms located on C atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aryl H atoms, C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C) for methine H atoms, and C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms. H atoms located on O atoms were refined isotropically using a rotating-group model, with O—H constrained to 0.84 Å. H atoms located on N atoms were refined isotropically without constraints. Absolute configurations were assigned on the basis of the synthesis of each compound from D-mannose.

Computing details top

For all compounds, data collection: SMART (Bruker, 2001); 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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellispoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellispoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. The molecular structure of (III), showing the atom-numbering scheme. Displacement ellispoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. A view of part of the molecular packing arrangement in (I), showing the R22(10) and R22(11) hydrogen-bonding contacts. For clarity, only those H atoms involved in the hydrogen-bonding scheme are shown. At the centre of the figure is the molecule at (x, y, z); surrounding it are molecules at (x, 1 + y, z) at top right; (1 + x, y, z) at bottom right; (x, -1 + y, z) at bottom left; and (-1 + x, y, z) at top left.
[Figure 5] Fig. 5. A view of the molecular packing arrangement in (I), along the b axis; the packing in (II) is identical. Hydrogen-bonded layers defined by the monosaccharide moieties alternate with non-hydrogen-bonded regions defined by the aryl groups along [001]. For clarity, only those H atoms involved in the hydrogen-bonding scheme are shown.
[Figure 6] Fig. 6. A view of the molecular packing arrangement in (III), along the b axis. As in (I) and (II), hydrogen-bonded layers defined by the monosaccharide moieties alternate with non-hydrogen-bonded regions defined by the aryl groups along [001]. For clarity, only those H atoms involved in the hydrogen-bonding scheme are shown.
[Figure 7] Fig. 7. A view of the C—F···H—C C(4) chain motif in (I). Dashed lines represent approaches equal to or shorter than the van der Waals contact distance. Only the H atom participating in the contact with the F atom is shown. Exchanging the positions of the F and H atoms on each molecule gives the corresponding C(4) motif in (II).
[Figure 8] Fig. 8. A view of the C—F···H—C C(5) chain motif in (III). Dashed lines represent approaches equal to or shorter than the van der Waals contact distance. Only the H atom participating in the contact with the F atom is shown.
(I) N-(4-fluorophenyl)-β-D-mannopyranosylamine top
Crystal data top
C12H16FNO5F(000) = 288
Mr = 273.26Dx = 1.473 Mg m3
Monoclinic, P21Melting point = 449–456 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 6.4612 (12) ÅCell parameters from 2130 reflections
b = 6.7246 (13) Åθ = 2.9–27.5°
c = 14.501 (3) ŵ = 0.12 mm1
β = 102.151 (3)°T = 173 K
V = 615.9 (2) Å3Plate, colourless
Z = 20.52 × 0.50 × 0.05 mm
Data collection top
Siemens SMART Platform CCD area-detector
diffractometer
1528 independent reflections
Radiation source: fine-focus sealed tube1393 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω scans per ϕθmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
h = 88
Tmin = 0.937, Tmax = 0.993k = 08
7296 measured reflectionsl = 018
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0367P)2 + 0.1325P]
where P = (Fo2 + 2Fc2)/3
1528 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.23 e Å3
1 restraintΔρmin = 0.18 e Å3
Crystal data top
C12H16FNO5V = 615.9 (2) Å3
Mr = 273.26Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.4612 (12) ŵ = 0.12 mm1
b = 6.7246 (13) ÅT = 173 K
c = 14.501 (3) Å0.52 × 0.50 × 0.05 mm
β = 102.151 (3)°
Data collection top
Siemens SMART Platform CCD area-detector
diffractometer
1528 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
1393 reflections with I > 2σ(I)
Tmin = 0.937, Tmax = 0.993Rint = 0.029
7296 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.23 e Å3
1528 reflectionsΔρmin = 0.18 e Å3
181 parameters
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.

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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7356 (3)0.8305 (3)0.74293 (14)0.0219 (4)
H10.79760.90980.80050.026*
C20.9134 (3)0.7583 (3)0.69619 (13)0.0207 (4)
H21.01940.68230.74330.025*
C31.0236 (3)0.9322 (3)0.65893 (14)0.0203 (4)
H31.10301.01130.71340.024*
C40.8641 (3)1.0665 (3)0.59611 (14)0.0186 (4)
H40.80060.99500.53640.022*
C50.6886 (3)1.1274 (3)0.64718 (13)0.0187 (4)
H50.75161.20920.70370.022*
C60.5173 (3)1.2460 (3)0.58380 (14)0.0219 (4)
H6A0.58241.34600.54860.026*
H6B0.42871.15630.53750.026*
C70.4818 (3)0.6829 (3)0.82922 (14)0.0257 (4)
C80.3758 (3)0.5102 (4)0.84729 (15)0.0317 (5)
H80.39780.38940.81680.038*
C90.2393 (4)0.5138 (4)0.90910 (18)0.0392 (6)
H90.16770.39670.92160.047*
C100.2098 (4)0.6899 (5)0.95183 (17)0.0428 (7)
C110.3075 (4)0.8619 (5)0.93554 (17)0.0410 (6)
H110.28340.98160.96650.049*
C120.4440 (3)0.8589 (4)0.87245 (15)0.0321 (5)
H120.51100.97810.85920.039*
F10.0800 (2)0.6902 (3)1.01517 (12)0.0678 (6)
H1N0.586 (4)0.581 (4)0.7261 (16)0.025 (6)*
N10.6244 (3)0.6657 (3)0.76885 (13)0.0248 (4)
O20.8215 (2)0.6300 (2)0.62071 (10)0.0257 (3)
H2O0.89790.52870.62150.039*
O31.16922 (19)0.8561 (2)0.60617 (9)0.0249 (3)
H3O1.29320.88690.63320.037*
O40.9709 (2)1.2419 (2)0.57470 (10)0.0228 (3)
H4O0.93431.26670.51680.034*
O50.59062 (19)0.9545 (2)0.67698 (9)0.0204 (3)
O60.3889 (2)1.3433 (3)0.63840 (11)0.0318 (4)
H6O0.26221.30880.61940.038 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0205 (9)0.0225 (10)0.0224 (9)0.0003 (8)0.0040 (7)0.0031 (8)
C20.0183 (8)0.0199 (9)0.0237 (9)0.0011 (8)0.0035 (7)0.0017 (8)
C30.0148 (8)0.0224 (10)0.0240 (9)0.0006 (8)0.0045 (7)0.0020 (8)
C40.0152 (8)0.0192 (9)0.0219 (9)0.0017 (7)0.0054 (7)0.0002 (8)
C50.0156 (8)0.0182 (9)0.0232 (9)0.0030 (8)0.0064 (7)0.0017 (8)
C60.0181 (8)0.0183 (9)0.0301 (10)0.0010 (8)0.0066 (7)0.0008 (8)
C70.0214 (9)0.0321 (11)0.0234 (9)0.0025 (9)0.0044 (8)0.0070 (8)
C80.0316 (11)0.0332 (12)0.0320 (11)0.0021 (10)0.0103 (9)0.0087 (10)
C90.0329 (12)0.0471 (15)0.0412 (13)0.0021 (11)0.0163 (10)0.0166 (12)
C100.0341 (12)0.0646 (18)0.0345 (12)0.0082 (13)0.0181 (10)0.0087 (13)
C110.0374 (12)0.0514 (16)0.0359 (13)0.0075 (13)0.0116 (10)0.0058 (13)
C120.0295 (10)0.0376 (12)0.0299 (11)0.0008 (10)0.0076 (9)0.0007 (10)
F10.0643 (11)0.0864 (15)0.0693 (11)0.0077 (11)0.0516 (10)0.0063 (11)
N10.0269 (8)0.0237 (9)0.0257 (9)0.0023 (7)0.0101 (7)0.0018 (8)
O20.0246 (7)0.0191 (7)0.0339 (8)0.0010 (6)0.0073 (6)0.0038 (6)
O30.0141 (6)0.0314 (8)0.0303 (7)0.0011 (6)0.0072 (5)0.0048 (7)
O40.0189 (6)0.0230 (7)0.0273 (7)0.0041 (6)0.0067 (5)0.0031 (6)
O50.0156 (6)0.0193 (7)0.0264 (7)0.0005 (5)0.0050 (5)0.0027 (6)
O60.0176 (6)0.0307 (8)0.0474 (9)0.0027 (7)0.0075 (6)0.0110 (8)
Geometric parameters (Å, º) top
C1—N11.414 (3)C6—H6B0.990
C1—O51.453 (2)C7—C121.385 (3)
C1—C21.530 (3)C7—C81.401 (3)
C1—H11.000C7—N11.403 (2)
C2—O21.422 (2)C8—C91.384 (3)
C2—C31.526 (3)C8—H80.950
C2—H21.000C9—C101.368 (4)
C3—O31.427 (2)C9—H90.950
C3—C41.521 (3)C10—C111.361 (4)
C3—H31.000C10—F11.368 (2)
C4—O41.434 (2)C11—C121.398 (3)
C4—C51.535 (2)C11—H110.950
C4—H41.000C12—H120.950
C5—O51.434 (2)N1—H1N0.84 (3)
C5—C61.509 (3)O2—H2O0.840
C5—H51.000O3—H3O0.840
C6—O61.421 (2)O4—H4O0.840
C6—H6A0.990O6—H6O0.840
N1—C1—O5109.34 (15)O6—C6—H6A109.6
N1—C1—C2109.89 (17)C5—C6—H6A109.6
O5—C1—C2109.30 (14)O6—C6—H6B109.6
N1—C1—H1109.4C5—C6—H6B109.6
O5—C1—H1109.4H6A—C6—H6B108.2
C2—C1—H1109.4C12—C7—C8118.93 (19)
O2—C2—C3110.06 (15)C12—C7—N1123.7 (2)
O2—C2—C1107.61 (14)C8—C7—N1117.4 (2)
C3—C2—C1111.32 (17)C9—C8—C7120.7 (2)
O2—C2—H2109.3C9—C8—H8119.7
C3—C2—H2109.3C7—C8—H8119.7
C1—C2—H2109.3C10—C9—C8118.5 (2)
O3—C3—C4109.40 (15)C10—C9—H9120.8
O3—C3—C2108.93 (17)C8—C9—H9120.8
C4—C3—C2111.05 (14)C11—C10—F1119.2 (3)
O3—C3—H3109.1C11—C10—C9122.9 (2)
C4—C3—H3109.1F1—C10—C9118.0 (3)
C2—C3—H3109.1C10—C11—C12118.7 (3)
O4—C4—C3108.78 (14)C10—C11—H11120.6
O4—C4—C5108.83 (15)C12—C11—H11120.6
C3—C4—C5110.24 (15)C7—C12—C11120.3 (3)
O4—C4—H4109.7C7—C12—H12119.9
C3—C4—H4109.7C11—C12—H12119.9
C5—C4—H4109.7C7—N1—C1122.61 (19)
O5—C5—C6107.36 (14)C7—N1—H1N112.8 (16)
O5—C5—C4110.29 (15)C1—N1—H1N115.0 (16)
C6—C5—C4111.65 (15)C2—O2—H2O109.5
O5—C5—H5109.2C3—O3—H3O109.5
C6—C5—H5109.2C4—O4—H4O109.5
C4—C5—H5109.2C5—O5—C1113.54 (13)
O6—C6—C5110.08 (16)C6—O6—H6O109.5
N1—C1—C2—O254.0 (2)C3—C4—C5—C6175.02 (16)
O5—C1—C2—O266.03 (19)O5—C5—C6—O674.23 (19)
N1—C1—C2—C3174.64 (16)C4—C5—C6—O6164.77 (15)
O5—C1—C2—C354.6 (2)N1—C7—C8—C9177.4 (2)
O2—C2—C3—O353.69 (18)C8—C9—C10—F1177.9 (2)
C1—C2—C3—O3172.92 (14)F1—C10—C11—C12178.4 (2)
O2—C2—C3—C466.85 (19)N1—C7—C12—C11176.72 (19)
C1—C2—C3—C452.4 (2)C12—C7—N1—C13.2 (3)
O3—C3—C4—O468.34 (19)C8—C7—N1—C1177.94 (18)
C2—C3—C4—O4171.39 (16)O5—C1—N1—C773.0 (2)
O3—C3—C4—C5172.40 (15)C2—C1—N1—C7167.00 (17)
C2—C3—C4—C552.1 (2)C6—C5—O5—C1176.91 (15)
O4—C4—C5—O5174.96 (14)C4—C5—O5—C161.24 (18)
C3—C4—C5—O555.74 (19)N1—C1—O5—C5179.37 (16)
O4—C4—C5—C665.76 (19)C2—C1—O5—C560.30 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O6i0.84 (3)2.26 (3)3.063 (3)160 (2)
O2—H2O···O4i0.842.132.908 (2)154
O3—H3O···O5ii0.841.952.7800 (18)171
O4—H4O···O3iii0.841.872.700 (2)171
O6—H6O···O4iv0.841.912.7504 (19)178
Symmetry codes: (i) x, y1, z; (ii) x+1, y, z; (iii) x+2, y+1/2, z+1; (iv) x1, y, z.
(II) N-(3-fluorophenyl)-β-D-mannopyranosylamine top
Crystal data top
C12H16FNO5F(000) = 288
Mr = 273.26Dx = 1.475 Mg m3
Monoclinic, P21Melting point = 463–465 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 6.4579 (8) ÅCell parameters from 2073 reflections
b = 6.7248 (9) Åθ = 2.9–27.1°
c = 14.5052 (19) ŵ = 0.12 mm1
β = 102.364 (2)°T = 173 K
V = 615.32 (14) Å3Plate, colourless
Z = 20.50 × 0.48 × 0.05 mm
Data collection top
Bruker SMART Platform CCD area-detector
diffractometer
1460 independent reflections
Radiation source: fine-focus sealed tube1261 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω scans per ϕθmax = 27.1°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
h = 88
Tmin = 0.941, Tmax = 0.995k = 08
4666 measured reflectionsl = 018
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0543P)2 + 0.1551P]
where P = (Fo2 + 2Fc2)/3
1460 reflections(Δ/σ)max < 0.001
180 parametersΔρmax = 0.24 e Å3
1 restraintΔρmin = 0.22 e Å3
Crystal data top
C12H16FNO5V = 615.32 (14) Å3
Mr = 273.26Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.4579 (8) ŵ = 0.12 mm1
b = 6.7248 (9) ÅT = 173 K
c = 14.5052 (19) Å0.50 × 0.48 × 0.05 mm
β = 102.364 (2)°
Data collection top
Bruker SMART Platform CCD area-detector
diffractometer
1460 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
1261 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.995Rint = 0.029
4666 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0371 restraint
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.24 e Å3
1460 reflectionsΔρmin = 0.22 e Å3
180 parameters
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.

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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7377 (4)0.8308 (4)0.74299 (18)0.0216 (5)
H10.80060.91020.80040.026*
C20.9147 (4)0.7584 (4)0.69614 (18)0.0213 (5)
H21.02130.68240.74320.026*
C31.0242 (3)0.9325 (4)0.65902 (18)0.0197 (5)
H31.10391.01160.71360.024*
C40.8644 (4)1.0663 (3)0.59611 (19)0.0180 (5)
H40.80060.99460.53640.022*
C50.6893 (3)1.1269 (4)0.64702 (18)0.0183 (5)
H50.75271.20910.70350.022*
C60.5179 (3)1.2455 (4)0.58351 (17)0.0212 (5)
H6A0.58301.34500.54820.025*
H6B0.42861.15580.53730.025*
C70.4837 (4)0.6831 (4)0.82919 (19)0.0260 (6)
C80.3749 (4)0.5090 (5)0.8449 (2)0.0313 (6)
H80.39670.38710.81530.038*
C90.2364 (5)0.5213 (6)0.9045 (2)0.0409 (8)
C100.1981 (5)0.6899 (6)0.9499 (2)0.0456 (9)
H100.10050.69100.99050.055*
C110.3065 (5)0.8588 (6)0.9346 (2)0.0421 (8)
H110.28460.97850.96600.051*
C120.4481 (4)0.8579 (6)0.8740 (2)0.0330 (6)
H120.51950.97660.86360.040*
F10.1293 (3)0.3510 (4)0.91659 (18)0.0679 (7)
N10.6260 (4)0.6660 (4)0.76938 (18)0.0251 (5)
H1N0.593 (6)0.593 (7)0.724 (3)0.053 (12)*
O20.8218 (3)0.6300 (3)0.62100 (14)0.0259 (4)
H2O0.90440.53480.61810.031*
O31.1701 (2)0.8559 (3)0.60615 (13)0.0253 (4)
H3O1.29440.88580.63340.030*
O40.9709 (2)1.2417 (3)0.57459 (13)0.0229 (4)
H4O0.93241.26730.51680.028*
O50.5920 (2)0.9545 (3)0.67733 (13)0.0203 (4)
O60.3898 (2)1.3437 (3)0.63823 (14)0.0307 (5)
H6O0.26291.30890.61950.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0193 (11)0.0208 (13)0.0246 (13)0.0002 (10)0.0047 (9)0.0026 (11)
C20.0182 (10)0.0178 (12)0.0280 (13)0.0007 (10)0.0056 (9)0.0023 (11)
C30.0120 (10)0.0217 (13)0.0265 (13)0.0010 (10)0.0067 (9)0.0017 (11)
C40.0154 (11)0.0143 (12)0.0258 (13)0.0025 (9)0.0080 (10)0.0004 (10)
C50.0146 (10)0.0172 (12)0.0246 (12)0.0016 (10)0.0074 (9)0.0004 (10)
C60.0180 (10)0.0154 (12)0.0310 (13)0.0010 (10)0.0071 (10)0.0002 (11)
C70.0221 (11)0.0297 (15)0.0268 (13)0.0046 (11)0.0063 (10)0.0077 (11)
C80.0293 (13)0.0282 (15)0.0393 (16)0.0034 (12)0.0136 (12)0.0106 (13)
C90.0328 (15)0.047 (2)0.0485 (19)0.0034 (15)0.0204 (14)0.0214 (16)
C100.0385 (16)0.067 (3)0.0375 (17)0.0171 (17)0.0220 (14)0.0149 (17)
C110.0416 (16)0.055 (2)0.0318 (16)0.0150 (17)0.0123 (13)0.0034 (16)
C120.0309 (13)0.0370 (16)0.0317 (15)0.0051 (13)0.0079 (11)0.0013 (13)
F10.0608 (13)0.0610 (14)0.0975 (18)0.0002 (13)0.0522 (13)0.0314 (14)
N10.0255 (11)0.0222 (12)0.0314 (13)0.0009 (9)0.0147 (10)0.0014 (10)
O20.0224 (9)0.0173 (9)0.0390 (11)0.0010 (8)0.0091 (8)0.0045 (8)
O30.0126 (7)0.0286 (10)0.0362 (11)0.0010 (8)0.0085 (7)0.0050 (9)
O40.0188 (8)0.0200 (9)0.0314 (9)0.0048 (7)0.0088 (7)0.0031 (8)
O50.0147 (7)0.0165 (9)0.0309 (10)0.0013 (7)0.0072 (7)0.0028 (8)
O60.0148 (8)0.0280 (10)0.0506 (13)0.0032 (8)0.0096 (8)0.0095 (10)
Geometric parameters (Å, º) top
C1—N11.419 (3)C6—H6B0.990
C1—O51.449 (3)C7—C121.386 (4)
C1—C21.529 (3)C7—N11.397 (3)
C1—H11.000C7—C81.409 (4)
C2—O21.419 (3)C8—C91.373 (4)
C2—C31.525 (4)C8—H80.950
C2—H21.000C9—C101.360 (5)
C3—O31.432 (3)C9—F11.368 (4)
C3—C41.518 (3)C10—C111.376 (5)
C3—H31.000C10—H100.950
C4—O41.433 (3)C11—C121.398 (4)
C4—C51.533 (3)C11—H110.950
C4—H41.000C12—H120.950
C5—O51.432 (3)N1—H1N0.81 (4)
C5—C61.508 (3)O2—H2O0.840
C5—H51.000O3—H3O0.840
C6—O61.425 (3)O4—H4O0.840
C6—H6A0.990O6—H6O0.840
N1—C1—O5109.25 (19)O6—C6—H6A109.7
N1—C1—C2110.0 (2)C5—C6—H6A109.7
O5—C1—C2109.43 (19)O6—C6—H6B109.7
N1—C1—H1109.4C5—C6—H6B109.7
O5—C1—H1109.4H6A—C6—H6B108.2
C2—C1—H1109.4C12—C7—N1123.9 (3)
O2—C2—C3110.35 (19)C12—C7—C8119.3 (2)
O2—C2—C1107.59 (18)N1—C7—C8116.7 (3)
C3—C2—C1111.1 (2)C9—C8—C7117.8 (3)
O2—C2—H2109.3C9—C8—H8121.1
C3—C2—H2109.3C7—C8—H8121.1
C1—C2—H2109.3C10—C9—F1119.1 (3)
O3—C3—C4109.37 (19)C10—C9—C8124.4 (3)
O3—C3—C2108.7 (2)F1—C9—C8116.5 (3)
C4—C3—C2111.15 (18)C9—C10—C11117.3 (3)
O3—C3—H3109.2C9—C10—H10121.4
C4—C3—H3109.2C11—C10—H10121.4
C2—C3—H3109.2C10—C11—C12121.4 (4)
O4—C4—C3108.84 (19)C10—C11—H11119.3
O4—C4—C5108.94 (19)C12—C11—H11119.3
C3—C4—C5110.16 (19)C7—C12—C11119.7 (3)
O4—C4—H4109.6C7—C12—H12120.2
C3—C4—H4109.6C11—C12—H12120.2
C5—C4—H4109.6C7—N1—C1122.9 (3)
O5—C5—C6107.64 (18)C7—N1—H1N117 (3)
O5—C5—C4110.51 (19)C1—N1—H1N108 (3)
C6—C5—C4111.5 (2)C2—O2—H2O109.5
O5—C5—H5109.0C3—O3—H3O109.5
C6—C5—H5109.0C4—O4—H4O109.5
C4—C5—H5109.0C5—O5—C1113.63 (17)
O6—C6—C5110.0 (2)C6—O6—H6O109.5
N1—C1—C2—O253.9 (3)C12—C7—C8—C90.2 (4)
O5—C1—C2—O266.1 (2)N1—C7—C8—C9179.1 (3)
N1—C1—C2—C3174.8 (2)C7—C8—C9—C100.5 (5)
O5—C1—C2—C354.8 (3)C7—C8—C9—F1178.5 (3)
O2—C2—C3—O353.9 (2)F1—C9—C10—C11179.0 (3)
C1—C2—C3—O3173.09 (18)C8—C9—C10—C110.0 (5)
O2—C2—C3—C466.6 (3)C9—C10—C11—C120.8 (5)
C1—C2—C3—C452.6 (3)N1—C7—C12—C11178.3 (2)
O3—C3—C4—O468.4 (3)C8—C7—C12—C110.6 (4)
C2—C3—C4—O4171.6 (2)C10—C11—C12—C71.1 (4)
O3—C3—C4—C5172.27 (19)C12—C7—N1—C14.8 (4)
C2—C3—C4—C552.2 (3)C8—C7—N1—C1176.4 (2)
O4—C4—C5—O5174.73 (19)O5—C1—N1—C772.4 (3)
C3—C4—C5—O555.4 (2)C2—C1—N1—C7167.4 (2)
O4—C4—C5—C665.6 (3)C6—C5—O5—C1177.2 (2)
C3—C4—C5—C6175.1 (2)C4—C5—O5—C160.8 (2)
O5—C5—C6—O674.2 (2)N1—C1—O5—C5179.4 (2)
C4—C5—C6—O6164.46 (19)C2—C1—O5—C560.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6O···O4i0.841.912.752 (2)177
O4—H4O···O3ii0.841.862.696 (3)172
O3—H3O···O5iii0.841.952.780 (2)171
O2—H2O···O4iv0.842.142.911 (3)152
N1—H1N···O6iv0.81 (4)2.32 (5)3.066 (3)153 (4)
Symmetry codes: (i) x1, y, z; (ii) x+2, y+1/2, z+1; (iii) x+1, y, z; (iv) x, y1, z.
(III) N-(2-fluorophenyl)-β-D-mannopyranosylamine top
Crystal data top
C12H16FNO5Dx = 1.474 Mg m3
Mr = 273.26Melting point = 466–474 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3654 reflections
a = 6.4133 (6) Åθ = 2.8–27.4°
b = 6.6924 (6) ŵ = 0.12 mm1
c = 28.699 (3) ÅT = 173 K
V = 1231.76 (19) Å3Plate, colourless
Z = 40.48 × 0.20 × 0.05 mm
F(000) = 576
Data collection top
Siemens SMART Platform CCD area-detector
diffractometer
1672 independent reflections
Radiation source: fine-focus sealed tube1489 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω scans per ϕθmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
h = 08
Tmin = 0.970, Tmax = 0.993k = 08
14484 measured reflectionsl = 036
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0342P)2 + 0.3274P]
where P = (Fo2 + 2Fc2)/3
1672 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C12H16FNO5V = 1231.76 (19) Å3
Mr = 273.26Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.4133 (6) ŵ = 0.12 mm1
b = 6.6924 (6) ÅT = 173 K
c = 28.699 (3) Å0.48 × 0.20 × 0.05 mm
Data collection top
Siemens SMART Platform CCD area-detector
diffractometer
1672 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
1489 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.993Rint = 0.037
14484 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.17 e Å3
1672 reflectionsΔρmin = 0.22 e Å3
181 parameters
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.

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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8862 (3)0.0361 (3)0.12885 (6)0.0199 (4)
H10.84620.12120.10160.024*
C20.6886 (3)0.0450 (3)0.15143 (6)0.0207 (4)
H20.60610.12020.12760.025*
C30.5560 (3)0.1250 (3)0.17072 (6)0.0201 (4)
H30.49840.20480.14420.024*
C40.6829 (3)0.2616 (3)0.20215 (6)0.0181 (4)
H40.71930.18960.23160.022*
C50.8827 (3)0.3296 (3)0.17759 (6)0.0174 (4)
H50.84500.41330.15000.021*
C61.0208 (3)0.4488 (3)0.20956 (6)0.0201 (4)
H6A0.93380.53920.22870.024*
H6B1.09540.35690.23080.024*
C71.1807 (3)0.0810 (3)0.08249 (6)0.0223 (4)
C81.3077 (3)0.2361 (3)0.06713 (7)0.0244 (4)
C91.4679 (3)0.2130 (3)0.03605 (7)0.0302 (5)
H91.55040.32410.02690.036*
C101.5072 (4)0.0237 (3)0.01819 (8)0.0360 (5)
H101.61630.00390.00370.043*
C111.3865 (4)0.1346 (3)0.03253 (8)0.0363 (5)
H111.41400.26430.02060.044*
C121.2249 (3)0.1081 (3)0.06430 (7)0.0288 (4)
H121.14360.21970.07370.035*
F11.2704 (2)0.42158 (17)0.08474 (4)0.0362 (3)
H1N1.037 (4)0.215 (4)0.1327 (8)0.035 (7)*
N11.0170 (3)0.1202 (2)0.11302 (5)0.0226 (3)
O20.7499 (2)0.17821 (19)0.18749 (5)0.0262 (3)
H2O0.65900.26760.19060.039*
O30.3870 (2)0.0404 (2)0.19669 (4)0.0254 (3)
H3O0.27360.06960.18370.038*
O40.5592 (2)0.4342 (2)0.21284 (5)0.0239 (3)
H4O0.57000.46080.24130.052 (8)*
O50.99921 (19)0.15829 (19)0.16213 (4)0.0194 (3)
O61.1683 (2)0.5633 (2)0.18410 (5)0.0274 (3)
H6O1.28920.52250.19010.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0191 (8)0.0205 (9)0.0201 (8)0.0000 (8)0.0008 (7)0.0020 (7)
C20.0192 (8)0.0200 (9)0.0228 (8)0.0009 (8)0.0030 (7)0.0018 (7)
C30.0149 (8)0.0237 (9)0.0216 (9)0.0009 (8)0.0003 (7)0.0023 (8)
C40.0156 (8)0.0186 (8)0.0202 (8)0.0033 (7)0.0004 (7)0.0002 (7)
C50.0151 (8)0.0167 (8)0.0203 (8)0.0021 (7)0.0007 (7)0.0006 (7)
C60.0183 (8)0.0195 (9)0.0224 (8)0.0005 (8)0.0005 (7)0.0008 (8)
C70.0217 (8)0.0259 (10)0.0195 (8)0.0023 (8)0.0000 (7)0.0044 (8)
C80.0289 (10)0.0215 (9)0.0226 (9)0.0005 (8)0.0013 (8)0.0038 (8)
C90.0289 (11)0.0310 (11)0.0308 (10)0.0058 (10)0.0057 (9)0.0088 (9)
C100.0337 (11)0.0371 (12)0.0371 (11)0.0019 (11)0.0156 (10)0.0029 (10)
C110.0406 (12)0.0277 (11)0.0407 (12)0.0022 (10)0.0133 (11)0.0022 (10)
C120.0311 (11)0.0241 (10)0.0313 (10)0.0033 (9)0.0066 (9)0.0015 (8)
F10.0478 (8)0.0227 (6)0.0382 (6)0.0044 (6)0.0118 (6)0.0001 (5)
N10.0254 (8)0.0204 (8)0.0221 (8)0.0031 (7)0.0039 (7)0.0007 (7)
O20.0237 (7)0.0209 (6)0.0340 (7)0.0019 (6)0.0005 (6)0.0058 (6)
O30.0144 (6)0.0332 (8)0.0286 (7)0.0028 (6)0.0002 (5)0.0058 (6)
O40.0196 (6)0.0253 (7)0.0269 (7)0.0062 (6)0.0019 (6)0.0036 (6)
O50.0160 (6)0.0190 (6)0.0233 (6)0.0020 (6)0.0017 (5)0.0040 (5)
O60.0174 (6)0.0286 (7)0.0361 (7)0.0048 (6)0.0011 (6)0.0079 (6)
Geometric parameters (Å, º) top
C1—N11.415 (2)C6—H6B0.990
C1—O51.451 (2)C7—C81.391 (3)
C1—C21.524 (2)C7—N11.393 (2)
C1—H11.000C7—C121.398 (3)
C2—O21.421 (2)C8—F11.361 (2)
C2—C31.525 (3)C8—C91.369 (3)
C2—H21.000C9—C101.389 (3)
C3—O31.432 (2)C9—H90.950
C3—C41.520 (2)C10—C111.375 (3)
C3—H31.000C10—H100.950
C4—O41.435 (2)C11—C121.392 (3)
C4—C51.532 (2)C11—H110.950
C4—H41.000C12—H120.950
C5—O51.438 (2)N1—H1N0.86 (2)
C5—C61.504 (2)O2—H2O0.840
C5—H51.000O3—H3O0.840
C6—O61.420 (2)O4—H4O0.840
C6—H6A0.990O6—H6O0.840
N1—C1—O5109.38 (14)O6—C6—H6A109.4
N1—C1—C2111.46 (16)C5—C6—H6A109.4
O5—C1—C2109.64 (14)O6—C6—H6B109.4
N1—C1—H1108.8C5—C6—H6B109.4
O5—C1—H1108.8H6A—C6—H6B108.0
C2—C1—H1108.8C8—C7—N1120.02 (17)
O2—C2—C1107.66 (14)C8—C7—C12116.03 (17)
O2—C2—C3110.98 (14)N1—C7—C12123.92 (18)
C1—C2—C3110.65 (15)F1—C8—C9118.50 (17)
O2—C2—H2109.2F1—C8—C7117.37 (17)
C1—C2—H2109.2C9—C8—C7124.12 (18)
C3—C2—H2109.2C8—C9—C10118.66 (19)
O3—C3—C4109.51 (14)C8—C9—H9120.7
O3—C3—C2108.43 (15)C10—C9—H9120.7
C4—C3—C2111.42 (14)C11—C10—C9119.35 (19)
O3—C3—H3109.1C11—C10—H10120.3
C4—C3—H3109.1C9—C10—H10120.3
C2—C3—H3109.1C10—C11—C12121.1 (2)
O4—C4—C3108.37 (14)C10—C11—H11119.4
O4—C4—C5108.76 (14)C12—C11—H11119.4
C3—C4—C5110.71 (14)C11—C12—C7120.73 (19)
O4—C4—H4109.7C11—C12—H12119.6
C3—C4—H4109.7C7—C12—H12119.6
C5—C4—H4109.7C7—N1—C1120.64 (16)
O5—C5—C6107.75 (14)C7—N1—H1N115.9 (17)
O5—C5—C4109.86 (14)C1—N1—H1N115.3 (16)
C6—C5—C4111.70 (14)C2—O2—H2O109.5
O5—C5—H5109.2C3—O3—H3O109.5
C6—C5—H5109.2C4—O4—H4O109.5
C4—C5—H5109.2C5—O5—C1113.12 (13)
O6—C6—C5111.38 (14)C6—O6—H6O109.5
N1—C1—C2—O255.32 (19)O5—C5—C6—O677.93 (17)
O5—C1—C2—O265.94 (18)C4—C5—C6—O6161.32 (14)
N1—C1—C2—C3176.75 (15)N1—C7—C8—F12.9 (3)
O5—C1—C2—C355.49 (18)C12—C7—C8—F1179.12 (17)
O2—C2—C3—O353.16 (18)N1—C7—C8—C9177.84 (18)
C1—C2—C3—O3172.61 (13)F1—C8—C9—C10179.7 (2)
O2—C2—C3—C467.42 (19)N1—C7—C12—C11177.54 (19)
C1—C2—C3—C452.03 (19)C8—C7—N1—C1179.87 (17)
O3—C3—C4—O469.28 (18)C12—C7—N1—C12.0 (3)
C2—C3—C4—O4170.76 (14)O5—C1—N1—C773.0 (2)
O3—C3—C4—C5171.52 (13)C2—C1—N1—C7165.61 (15)
C2—C3—C4—C551.57 (19)C6—C5—O5—C1176.83 (14)
O4—C4—C5—O5174.00 (13)C4—C5—O5—C161.27 (17)
C3—C4—C5—O555.04 (18)N1—C1—O5—C5175.84 (14)
O4—C4—C5—C666.49 (17)C2—C1—O5—C561.66 (18)
C3—C4—C5—C6174.55 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O6i0.86 (2)2.25 (2)3.097 (2)167 (2)
O2—H2O···O4i0.842.192.9584 (19)152
O3—H3O···O5ii0.841.962.7914 (17)172
O4—H4O···O3iii0.841.882.7139 (19)174
O6—H6O···O4iv0.841.942.7774 (19)172
Symmetry codes: (i) x, y1, z; (ii) x1, y, z; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC12H16FNO5C12H16FNO5C12H16FNO5
Mr273.26273.26273.26
Crystal system, space groupMonoclinic, P21Monoclinic, P21Orthorhombic, P212121
Temperature (K)173173173
a, b, c (Å)6.4612 (12), 6.7246 (13), 14.501 (3)6.4579 (8), 6.7248 (9), 14.5052 (19)6.4133 (6), 6.6924 (6), 28.699 (3)
α, β, γ (°)90, 102.151 (3), 9090, 102.364 (2), 9090, 90, 90
V3)615.9 (2)615.32 (14)1231.76 (19)
Z224
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.120.120.12
Crystal size (mm)0.52 × 0.50 × 0.050.50 × 0.48 × 0.050.48 × 0.20 × 0.05
Data collection
DiffractometerSiemens SMART Platform CCD area-detector
diffractometer
Bruker SMART Platform CCD area-detector
diffractometer
Siemens SMART Platform CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Blessing, 1995)
Multi-scan
(SADABS; Blessing, 1995)
Multi-scan
(SADABS; Blessing, 1995)
Tmin, Tmax0.937, 0.9930.941, 0.9950.970, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
7296, 1528, 1393 4666, 1460, 1261 14484, 1672, 1489
Rint0.0290.0290.037
(sin θ/λ)max1)0.6500.6410.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.075, 1.06 0.037, 0.097, 1.07 0.031, 0.072, 1.04
No. of reflections152814601672
No. of parameters181180181
No. of restraints110
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.180.24, 0.220.17, 0.22

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected torsion angles (º) for (I) top
O5—C5—C6—O674.23 (19)O5—C1—N1—C773.0 (2)
C4—C5—C6—O6164.77 (15)C2—C1—N1—C7167.00 (17)
C8—C7—N1—C1177.94 (18)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O6i0.84 (3)2.26 (3)3.063 (3)160 (2)
O2—H2O···O4i0.842.132.908 (2)154.1
O3—H3O···O5ii0.841.952.7800 (18)171.3
O4—H4O···O3iii0.841.872.700 (2)171.0
O6—H6O···O4iv0.841.912.7504 (19)177.5
Symmetry codes: (i) x, y1, z; (ii) x+1, y, z; (iii) x+2, y+1/2, z+1; (iv) x1, y, z.
Selected torsion angles (º) for (II) top
O5—C5—C6—O674.2 (2)O5—C1—N1—C772.4 (3)
C4—C5—C6—O6164.46 (19)C2—C1—N1—C7167.4 (2)
C8—C7—N1—C1176.4 (2)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O6—H6O···O4i0.841.912.752 (2)177.4
O4—H4O···O3ii0.841.862.696 (3)172.0
O3—H3O···O5iii0.841.952.780 (2)171.1
O2—H2O···O4iv0.842.142.911 (3)152.3
N1—H1N···O6iv0.81 (4)2.32 (5)3.066 (3)153 (4)
Symmetry codes: (i) x1, y, z; (ii) x+2, y+1/2, z+1; (iii) x+1, y, z; (iv) x, y1, z.
Selected torsion angles (º) for (III) top
O5—C5—C6—O677.93 (17)O5—C1—N1—C773.0 (2)
C4—C5—C6—O6161.32 (14)C2—C1—N1—C7165.61 (15)
C8—C7—N1—C1179.87 (17)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O6i0.86 (2)2.25 (2)3.097 (2)167 (2)
O2—H2O···O4i0.842.192.9584 (19)152.0
O3—H3O···O5ii0.841.962.7914 (17)171.5
O4—H4O···O3iii0.841.882.7139 (19)174.2
O6—H6O···O4iv0.841.942.7774 (19)172.2
Symmetry codes: (i) x, y1, z; (ii) x1, y, z; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y, z.
Fluorine contact geometries (Å, °) in (I)–(III) top
C—F···H—CF···HH···CC—F···HF···H—C
(I)C10—F1···H9—C9i2.440.95143158
(II)C9—F1···H10—C10ii2.460.95145154
(III)C8—F1···H12—C12iii2.550.95150127
Symmetry codes: (i) -x, 1/2 + y, 2 - z; (ii) -x, -1/2 + y, 2 - z; (iii) x, -1 + y, z.
 

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