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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 5| May 2005| Pages o270-o275
doi:10.1107/S0108270105007547

2-(2-Acetyl­amino-5-chloro­phenyl)-2,2-di­fluoro­ethanoic acid and 2-(2-acetyl­amino-5-methyl­phenyl)-2,2-di­fluoro­ethanoic acid, and 2-(2-acetyl­amino­phenyl)-2,2-di­fluoro-N-phenyl­acetamide and 2-(2-acetyl­amino­phenyl)-N-(4-chloro­phen­yl)-2,2-di­fluoro­acetamide: examples of variation in mol­ecular packing and hydrogen-bonding motif induced by substituent change

CROSSMARK_Color_square_no_text.svg
Nubia Boechat,a Lindalva C. Maciel,a Angelo C. Pinto,b Solange M. S. V. Wardell,a Janet M. S. Skaklec and R. Alan Howiec*

aFundaçâo Oswaldo Cruz, Far-Manguinhos, Rua Sizenando Nabuco 100, Manguinhos, 21041250 Rio de Janeiro, RJ, Brazil, bInstitudo de Química, Departamento de Química Orgânica, Universidade Federal de Rio de Janeiro, Ilha do Fundão, Rio de Janeiro, CEP 21941-590, Brazil, and cDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: r.a.howie@abdn.ac.uk

(Received 24 January 2005; accepted 9 March 2005; online 2 April 2005)

Among the title compounds, viz. the acids C10H8ClF2NO3, (I)[link], and C11H11F2NO3, (II)[link], and the amides C14H14F2N2O2, (III)[link], and C14H13ClF2N2O2, (IV)[link], the change of substituent from Cl in (I)[link] to methyl in (II)[link] has a dramatic effect upon the hydrogen bonding between the mol­ecules, which occur in layers in both cases. In the structures of (III)[link] and (IV)[link], hydrogen bonds connect the mol­ecules to form chains, but the introduction of a chloro substituent in (IV)[link] has a profound effect on the orientation of the mol­ecules within the chains and the packing of the chains in the structure as a whole.

Comment

Boechat & Pinto (2000[Boechat, N. & Pinto, A. de C. (2000). US Patent No. 6 034 266.]) have investigated the syntheses and pharmaceutical potential of a series of difluorinated ethanoic acids and their amide derivatives. Such compounds were obtained by the nucleophilic cleavage, using water or amines, of 3,3-difluoroindol-2-ones prepared from appropriately substituted indoline-2,3-diones (isatins) and (diethyl­amino)sulfur trifluoride. Presented here are the crystal structures and supramolecular arrangements of the title four representative compounds, (I)[link]–(IV)[link] (see scheme).

The mol­ecules of (I)[link] to (IV)[link] are shown in Figs. 1[link]–4[link][link][link]. With the exception of the numbering of the F atoms and the cyclic order of the benzene ring defined by atoms C11–C16 in the amides (R2 as opposed to R1 for the ring defined by atoms C1–C6), all four mol­ecules are labelled in the same manner. This makes possible the gathering together of selected bond lengths and angles for all four compounds, as shown in Table 1[link]. The

[Scheme 1]
distances and angles within the benzene rings, in the ranges 1.359 (5)–1.410 (5) Å and 118.0 (2)–121.9 (4)°, respectively, are generally as expected. It is noticeable, however, that the spread of distances is greater in the R1 rings, especially in the case of (I)[link], than it is in the R2 rings of the amides. The same is true, but to a lesser degree, for the angles. Of particular inter­est in Table 1[link] are the torsion angles around the C7—C8 and C2—N1 bonds, which are very diffent for (I)[link] compared with the other compounds. Also notable in the case of (I)[link] is the large displacement [0.210 (7) Å] of atom C7 from the least-squares plane of ring R1. The next largest displacement of an atom directly attached to a benzene ring [0.115 (3) Å] is that of atom N2 relative to ring R2 of (IV)[link]. In both of these, the displaced atoms are para to a Cl ring substituent. In the amides, the dihedral angles between the rings R1 and R2, as defined above, are 75.06 (6) and 82.27 (6)° for (III)[link] and (IV)[link], respectively.

In all four structures, hydrogen bonds (Tables 2[link]–5[link][link][link]) play a major part in controlling the supramolecular assembly of the mol­ecules. In the structure of (I)[link], the O2—H2⋯O3 and N1—H1⋯O3 hydrogen bonds (Table 2[link]) have completely different roles. The O2—H2⋯O3 hydrogen bonds create dimers (Fig. 5[link]) with motif R22(18), according to the notation of Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). The N1—H1⋯O3 hydrogen bonds then create larger R64(26) rings (Fig. 6[link]). Overall, the mol­ecules are found inter­connected in layers parallel to (001) (Fig. 7[link]), in which the hexa­meric R64(26) rings provide cavities within which are found the F atoms and oxo atom O1 of the carboxyl­ate group, which play no part in hydrogen-bond formation. As shown in Fig. 7[link], the larger hexa­meric rings are connected in a herring-bone fashion to complete the layer. The layers, with Cl atoms on their surfaces, are then stacked in the a direction and are related to one another purely by cell translation. There are no inter­actions between the layers other than van der Waals contacts; this explains the occurrence of the stacking faults, which necessitated the twin refinement of this structure, as described below.

In (II)[link], O2—H2⋯O3 hydrogen bonds (Table 3[link]) connect the mol­ecules, with each mol­ecule related to its neighbour by the operation of a crystallographic twofold screw axis, forming zigzag chains propagated in the b direction. N1—H1⋯O1 hydrogen bonds connect the chains, related to one another by cell translation, in the a direction. This creates the R44(24) motif shown in Fig. 8[link]. Replication of this motif results in the formation of layers of mol­ecules parallel to (001), as shown in Fig. 9[link]. The surfaces of the layers are populated by methyl groups (atom C11 and the H atoms attached to it) and only van der Waals inter­actions occur at the layer inter­face.

N—H⋯O hydrogen bonds in (III)[link] (Table 4[link]) connect mol­ecules, related to one another by cell translation, to form chains propagated in the a direction, as shown in Fig. 10[link]. The contribution of each of the N—H⋯O hydrogen bonds to the connectivity of the chain is a four-atom repeat unit, e.g. N1, H1, O2i and C9i [symmetry code: (i) x − 1, y, z] for the first of the hydrogen bonds given in Table 4[link]. Taken together in pairs, the hydrogen bonds create rings which recur along the length of the chain. The overall connectivity can then be represented by the graph set C(4)R22(16). The distribution of the chains in the unit cell, and hence in the complete structure, where they are related to one another by crystallographic centres of symmetry, is shown in Fig. 11[link], where the chains are seen end-on. Only van der Waals inter­actions occur between neighbouring chains.

In (IV)[link], as in (III)[link], N—H⋯O hydrogen bonds (Table 5[link]) connect the mol­ecules to form chains. However, the chains (Fig. 12[link]) are now propagated in the c direction and adjacent mol­ecules are related by the operation of a crystallographic c-glide plane. Despite the mol­ecules now alternating in orientation along the length of the chain, the C(4)R22(16) graph set assigned to the situation in (III)[link] also applies to (IV)[link]. The chains in (IV)[link] are distributed in such a way as to bring about face-to-face π–π contacts between pairs of centrosymmetrically related benzene rings (R2) of the N-phenyl groups. These are shown in Fig. 13[link] distributed in an A-face-centred arrangement. For this inter­action, in which the centrosymmetric relationship (symmetry code: −x, 1 − y, 1 − z) renders the least-squares planes of the overlapping rings parallel, the distance between the ring centroids, the perpendicular distance between their least-squares planes and the lateral displacement or slippage of the rings are 3.803, 3.473 and 1.550 Å, respectively. The combination of the hydrogen bonding within the chains and pairwise overlap of the phenyl groups inter­connects the mol­ecules to form layers parallel to (100). The Cl atoms are confined to a region at the centre of the layer, while the layer surfaces are occupied by the methyl groups (atom C10 and the attached H atoms) of the acetamide group and by the atoms of the C3—C4 edge of the ring defined by atoms C1–C6 (R1).

The difference in structure between acids (I)[link] and (II)[link] must be due to the difference in the substituents at the 5-position of the benzene ring, viz. Cl for (I)[link] and Me for (II)[link]. The essential difference between the two structures, i.e. the non-participation in hydrogen bonding of atom O1 in (I)[link], suggests that electronic effects arising from the electronegativity and the position of Cl on the ring have brought this about. The structural differences between acids (I)[link] and (II)[link], on the one hand, and amides (III)[link] and (IV)[link] on the other, where, for the amides, utilization of all available hydrogen-bond donors and acceptors only creates chains of mol­ecules rather than layers or sheets, is considered to be due to the need to accommodate the steric requirements of the N-phenyl groups of the amides. The difference between the structures of amides (III)[link] and (IV)[link], specifically in the manner in which the hydrogen-bonded chains of mol­ecules are associated in pairs, is attributed to the presence of the Cl substituent in (IV)[link], but is perceived as steric rather than electronic in origin.

[Figure 1]
Figure 1
A view of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
A view of (II)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3]
Figure 3
A view of (III)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4]
Figure 4
A view of (IV)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 5]
Figure 5
The centrosymmetric R22(18) motif in (I)[link]. Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]
[Figure 6]
Figure 6
The hexa­molecular R64(26) motif in (I)[link]. For clarity, bonds to atoms C3–C6 are shown as thin lines. Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled, primarily to provide a key for the coding of the ellipsoids, which is the same for all of Figs. 6[link]–9[link][link][link], 11[link] and 13[link]. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (iii) 1 − x, [{1\over 2}] + y, [{3\over 2}] − z; (iv) 1 − x, 1 − y, 2 − z; (v) x, y, 1 + z; (vi) x, [{1\over 2}] − y, [{1\over 2}] + z.]
[Figure 7]
Figure 7
A more extensive view of the hydrogen-bonding within a layer of mol­ecules of (I)[link]. The representation is the same as in Fig. 6[link], except that the displacement ellipsoids are now at the 20% probability level, symmetry codes and atom labels have been omitted and the outline of the unit cell is shown.
[Figure 8]
Figure 8
The R44(24) motif in (II)[link]. For clarity, bonds to atoms C3–C6 and C11 are shown as thin lines. Ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Coding is indicated by the labelling of selected atoms. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) x − 1, y, z; (ii) 1 − x, [{1\over 2}] + y, 1 − z; (iii) x, [{1\over 2}] + y, 1 − z.]
[Figure 9]
Figure 9
A more extensive view of the hydrogen bonding within a layer of mol­ecules of (II)[link]. The representation is the same as in Fig. 8[link], except that the outline of the unit cell is shown, while atom labels and symmetry codes have been omitted.
[Figure 10]
Figure 10
A hydrogen-bonded chain in (III)[link]. Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) x − 1, y, z; (ii) x + 1, y, z.]
[Figure 11]
Figure 11
The packing of the hydrogen-bonded chains of mol­ecules in (III)[link]. Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds are shown as small spheres of arbitrary radii. The coding of the atoms is the same as in Figs. 6[link]–9[link][link][link].
[Figure 12]
Figure 12
A hydrogen-bonded chain in (IV)[link]. Displacement ellipsoids are drawn at the 30% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) x, [{3\over 2}] − y, [{1\over 2}] + z; (ii) x, [{3\over 2}] − y, z − [{1\over 2}].]
[Figure 13]
Figure 13
Inter­molecular contacts within a layer of mol­ecules of (IV)[link]. Displacement ellipsoids are drawn at the 20% probability level. For convenience, the origin of the cell has been shifted to (−[{1\over 2}], 0, 0). Dashed lines indicate the join of the centroids of overlapping benzene rings (see Comment) as well as hydrogen bonds. For clarity, bonds to atoms C3–C6 and C11–C16 are shown as thin lines. Coding is the same as for Figs. 6[link]–9[link][link][link] and 11[link].

Experimental

Compounds (I)–(IV) were prepared by general procedures (Boechat & Pinto, 2000[Boechat, N. & Pinto, A. de C. (2000). US Patent No. 6 034 266.]). Compound (I)[link] (m.p. 438–440 K) was recrystallized from dichloro­ethane, (II)[link] (m.p. 437–440 K) from MeOH, and both (III)[link] (m.p. 441–443 K) and (IV)[link] (m.p. 445–446 K) from EtOH.

Compound (I)[link]

Crystal data

  • C10H8ClF2NO3

  • Mr = 263.62

  • Monoclinic, P 21 /c

  • a = 11.5493 (6) Å

  • b = 11.6207 (6) Å

  • c = 8.5251 (4) Å

  • β = 107.334 (2)°

  • V = 1092.20 (10) Å3

  • Z = 4

  • Dx = 1.603 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2529 reflections

  • θ = 2.9–27.5°

  • μ = 0.37 mm−1

  • T = 120 (2) K

  • Plate, colourless

  • 0.60 × 0.25 × 0.05 mm
Data collection

  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • 13 369 measured reflections

  • 13 369 independent reflections

  • 6202 reflections with I > 2σ(I)

  • Rint = 0.000

  • θmax = 27.5°

  • h = −14 → 14

  • k = −15 → 15

  • l = −10 → 10
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.121

  • wR(F2) = 0.330

  • S = 1.57

  • 13 369 reflections

  • 160 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 1.28 e Å−3

  • Δρmin = −0.72 e Å−3

Table 1
Selected geometric parameters (Å, °) for compounds (I)[link]–(IV)[link]

  (I[link])† (II[link])‡ (III[link])§ (IV[link])§
C2—N1 1.433 (5) 1.435 (3)  1.426 (3)  1.419 (2) 
C5—X 1.753 (4) 1.507 (3)     
C8—O1 1.202 (5) 1.213 (3)  1.229 (2)  1.2158 (19)
C8—O2 1.330 (4) 1.298 (3)  1.340 (3)  1.333 (2) 
C9—N1 1.333 (5) 1.346 (3)  1.366 (3)  1.352 (2) 
C9—O3 1.250 (4) 1.242 (3)  1.228 (2)  1.222 (2) 
C9—C10 1.512 (5) 1.495 (3)  1.492 (3)  1.490 (3) 
C11—N2     1.418 (3)  1.420 (2) 
C14—Cl1       1.7424 (19)
         
C1—C7—C8 119.5 (4) 112.92 (18) 116.77 (18) 115.46 (14)
O1—C8—O2 127.1 (4) 126.2 (2) 125.5 (2) 126.13 (16)
O1—C8—C7 123.1 (4) 118.7 (2) 118.69 (19) 117.85 (15)
O2—C8—C7 109.7 (4) 115.0 (2) 115.77 (18) 115.85 (14)
C8—N2—C11     125.84 (18) 127.67 (14)
C9—N1—C2 120.9 (4) 121.82 (19) 122.86 (17) 123.54 (16)
O3—C9—N1 121.2 (4) 120.6 (2) 122.2 (2) 122.77 (19)
O3—C9—C10 121.8 (4) 121.67 (19) 122.7 (2) 122.22 (19)
N1—C9—C10 116.9 (4) 117.7 (2) 115.10 (19) 115.01 (18)
         
C1—C7—C8—O1 −113.6 (5) −44.0 (3) −49.4 (3) −33.8 (2)
C1—C7—C8—O2 68.2 (5) 136.4 (2) 131.7 (2) 150.49 (15)
C3—C2—N1—C9 103.1 (5) −64.3 (3) −59.0 (3) −51.4 (3)
C1—C2—N1—C9 −76.7 (5) 112.8 (2) 120.4 (2) 128.08 (19)
†X = Cl1.
‡X = methyl C11.
§For O2 read N2 and for O3 read O2.

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

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2⋯O3i 0.84 1.73 2.570 (4) 176
N1—H1⋯O3ii 0.88 (4) 2.23 (4) 3.014 (4) 148 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Compound (II)[link]

Crystal data

  • C11H11F2NO3

  • Mr = 243.21

  • Monoclinic, P 21

  • a = 4.9174 (3) Å

  • b = 8.3976 (3) Å

  • c = 13.5487 (7) Å

  • β = 91.208 (2)°

  • V = 559.36 (5) Å3

  • Z = 2

  • Dx = 1.444 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1294 reflections

  • θ = 2.9–27.5°

  • μ = 0.13 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.30 × 0.08 × 0.03 mm
Data collection

  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.])Tmin = 0.813, Tmax = 1.000

  • 5630 measured reflections

  • 1373 independent reflections

  • 1240 reflections with I > 2σ(I)

  • Rint = 0.032

  • θmax = 27.5°

  • h = −6 → 6

  • k = −10 → 10

  • l = −17 → 17
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.086

  • S = 1.08

  • 1373 reflections

  • 160 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0465P)2 + 0.1105P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.23 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O1i 0.94 (3) 1.97 (3) 2.884 (3) 165 (2)
O2—H2⋯O3ii 0.84 1.67 2.502 (2) 169
Symmetry codes: (i) x-1, y, z; (ii) [-x+1, y+{\script{1\over 2}}, -z+1].

Compound (III)[link]

Crystal data

  • C16H14F2N2O2

  • Mr = 304.29

  • Triclinic, [P \overline 1]

  • a = 5.0075 (3) Å

  • b = 11.5863 (11) Å

  • c = 12.2219 (11) Å

  • α = 87.304 (4)°

  • β = 89.327 (5)°

  • γ = 78.588 (5)°

  • V = 694.30 (10) Å3

  • Z = 2

  • Dx = 1.456 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 6753 reflections

  • θ = 2.9–27.5°

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Lath, colourless

  • 0.20 × 0.13 × 0.08 mm
Data collection

  • Enraf–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-37.], 1997[Blessing, R. H. (1997). J. Appl. Cryst. 30, 421-426.])Tmin = 0.924, Tmax = 1.000

  • 5877 measured reflections

  • 3177 independent reflections

  • 1631 reflections with I > 2σ(I)

  • Rint = 0.071

  • θmax = 27.6°

  • h = −6 → 6

  • k = −15 → 14

  • l = −15 → 15
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.118

  • S = 0.94

  • 3177 reflections

  • 206 parameters

  • H atoms treated by independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.28 e Å−3

Table 4
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O2i 0.89 (2) 2.24 (2) 3.114 (2) 166 (2)
N2—H2⋯O1i 0.87 (2) 2.06 (2) 2.875 (2) 156 (2)
Symmetry code: (i) x-1, y, z.

Compound (IV)[link]

Crystal data

  • C16H13ClF2N2O2

  • Mr = 338.73

  • Monoclinic, P 21 /c

  • a = 16.5777 (10) Å

  • b = 9.8176 (6) Å

  • c = 9.6962 (6) Å

  • β = 96.0100 (10)°

  • V = 1569.41 (17) Å3

  • Z = 4

  • Dx = 1.434 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3620 reflections

  • θ = 2.4–31.2°

  • μ = 0.28 mm−1

  • T = 291 (2) K

  • Block, colourless

  • 0.48 × 0.23 × 0.17 mm
Data collection

  • Bruker SMART 1000 CCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2000[Sheldrick, G. M. (2000). SADABS. Version 2.03. Bruker AXS Inc., Madison, Wisconsin, USA.])Tmin = 0.841, Tmax = 1.000

  • 15 368 measured reflections

  • 5629 independent reflections

  • 2824 reflections with I > 2σ(I)

  • Rint = 0.045

  • θmax = 32.6°

  • h = −20 → 25

  • k = −14 → 14

  • l = −14 → 11
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 0.132

  • S = 1.00

  • 5629 reflections

  • 215 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0478P)2 + 0.3392P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.24 e Å−3

Table 5
Hydrogen-bond geometry (Å, °) for (IV)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O2i 0.83 (2) 2.19 (2) 3.002 (2) 169 (2)
N2—H2⋯O1i 0.84 (1) 2.07 (2) 2.8524 (18) 155 (2)
Symmetry code: (i) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].

The sample crystal of (I)[link] was twinned, with major and minor twin components present, as indicated by the refinement, to the extent of 61.0 (1) and 39.0 (1)%, respectively. As a consequence, twin refinement by means of the SHELXL97 HKLF 5 instruction (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]), which precludes merging of the data as part of the refinement process, was employed, along with intensity data containing a mixture of completely overlapping, partially overlapping and completely non-overlapping reflections identified as follows. For the cell corresponding to the space group P21/a in use when the intensity data were collected, the COMPARECELL function of DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) identified the presence of two reciprocal lattices relating to major and minor twin components, the reflections of which were assigned batch numbers 1 and 2, respectively. The two reciprocal lattices are related by rotation through 180° about a*. The relationship between the Miller indices [H(1), K(1), L(1) for the major component and H(2), K(2), L(2) for the minor component], which is used to determine the presence or absence of points of coincidence of the two reciprocal lattices and therefore of overlap of reflections, is defined as H(1) = H(2), K(1) = –K(2), L(1) = −[0.8 × H(2) + L(2)]. The criterion for overlap is the remainder, M, left after dividing H(2) by 5; M = 0 implies complete overlap, and M = 1 or 4 implies partial but significant overlap [the calculated value of L(1) will be non-integer by no more than ± [{1\over 5}]]. In both of these cases, the measured intensity is shared between the code 2 reflection and the code 1 reflection with which it is paired. M = 2 or 3 indicates the total absence of overlap. The .hkl file used in the refinement contains, therefore, three groups of reflections, namely individual code 1 reflections associated exclusively with the major twin component, reflections in overlapping pairs with code −2 for the first and code 1 for the second, the intensity of which is to be shared between the two twin components and, finally, individual code 2 reflections associated exclusively with the minor twin component. The indices of the reflections in all of these groups were adjusted in the usual manner for the solution and refinement of the structure in the standard setting of the space group P21/c. The nature of the intensity data also precludes merging and multi-scan absorption correction as part of the data reduction process, and also creates difficulties in scaling the data. These difficulties combine to limit the refinement, yielding an R factor, in this case 0.121, rather higher than would be anticipated for a refinement of the usual kind. Also, on completion, this refinement revealed residual electron-density features of a peak of 1.28 e Å−3 0.10 Å from atom Cl1 and a hole of −0.72 e Å−3 1.47 Å from atom H10C.

In the absence of any element of atomic number higher than F, the refinement of the structure of (II)[link] in the non-centrosymmetic space group P21 was carried out on merged intensity data. The Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter is therefore indeterminate, so the absolute structure could not be determined.

In all four refinements, aryl and methyl H atoms were placed in calculated positions, with C—H distances of 0.95 and 0.98 Å, respectively, for (I)[link]–(III)[link], and 0.93 and 0.96 Å, respectively, for (IV)[link], and refined with a riding model, with Uiso(H) = 1.2Ueq(C) for aryl H atoms and 1.5Ueq(C) for methyl H atoms. The orientations of the methyl groups were also refined. The positions of the amide H atoms of (I)[link], (II)[link] and (IV)[link], and of the hydroxyl H atoms of (I)[link] and (II)[link], were obtained from difference maps. The amide H atoms of (III)[link] were initially placed in the manner of aryl H atoms. The coordinates of all amide H atoms of all four compounds were refined, with Uiso(H) = 1.2Ueq(N), and for (III)[link] and (IV)[link] with N—H distances restrained to 0.88 and 0.86 Å, respectively. The hydroxyl groups of (I)[link] and (II)[link] were idealized with O—H distances of 0.84 Å and refined as rigid bodies, with Uiso(H) = 1.2Ueq(O).

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]) for (I)[link], (II)[link] and (III)[link]; SMART (Bruker, 1998[Bruker (1998). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, USA.]) for (IV)[link]. Cell refinement: DENZO (Otwin­owski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT for (I)[link], (II)[link] and (III)[link]; SAINT (Bruker, 2000[Bruker (2000). SAINT. Version 6.02a. Bruker AXS Inc., Madison, Wisconsin, USA.]) for (IV)[link]. Data reduction: DENZO and COLLECT for (I)[link], (II)[link] and (III)[link]; SAINT for (IV)[link]. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); programs(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]).

Supporting information

Crystal structure: contains datablocks global, I, II, III, IV. DOI: 10.1107/S0108270105007547/gd1371sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105007547/gd1371Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105007547/gd1371IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105007547/gd1371IIIsup4.hkl

Structure factors: contains datablock IV. DOI: 10.1107/S0108270105007547/gd1371IVsup5.hkl


Comment top

Boechat & Pinto (2000) have investigated the syntheses and pharmaceutical potential of a series of difluorinated ethanoic acids and their amide derivatives. Such compounds were obtained by the nucleophilic cleavage, using water or amines, of 3,3-difluoro-2-oxoindoles prepared from appropriately substituted 2,3-indolinediones (isatins) and (diethylamino)sulfur trifluoride. Presented here are the crystal structures and supramolecular arrangements of the title four representative compounds, (I)–(IV).

The molecules of (I) to (IV) are shown in Figs. 1–4. With the exception of the numbering of the F atoms and the cyclic order of the benzene ring defined by C11–C16 in the amides (R2 as opposed to R1 for the ring defined by C1–C6), all four molecules are labelled in the same manner. This makes possible the gathering together of selected bond lengths and angles for all four compounds, as shown in Table 1. The distances and angles within the benzene rings, in the ranges 1.359 (5)–1.410 (5) Å and 118.0 (2)–121.9 (4) °, respectively, are generally as expected. It is noticeable, however, that the spread of distances is greater in the R1 rings, especially in the case of (I), than it is in the R2 rings of the amides. The same is true, but to a lesser degree, for the angles. Of particular interest in Table 1 are the torsion angles around the C7—C8 and C2—N1 bonds, which are very diffent for (I) compared with the other compounds. Also notable in the case of (I) is the large displacement [0.210 (7) Å] of atom C7 from the least-squares plane of ring R1. The next largest displacement of an atom directly attached to a benzene ring [0.115 (3) Å] is that of atom N2 relative to ring R2 of (IV). In both of these, the displaced atoms are para to a Cl ring substituent. In the amides, the dihedral angles between the rings R1 and R2, as defined above, are 75.06 (6) and 82.27 (6) ° for (III) and (IV), respectively.

In all four structures, hydrogen bonds (Tables 2–5) play a major part in controlling the supramolecular assembly of the molecules. In the structure of (I), the O2—H2···O3 and N1—H1···O3 hydrogen bonds (Table 2) have completely different roles. The O2—H2···O3 hydrogen bonds create dimers (Fig. 5) with motif R22(18), in the notation of Bernstein et al. (1995). The N1—H1···O3 hydrogen bonds then create larger R64(26) rings (Fig. 6). Overall, the molecules are found interconnected in layers parallel to (001) (Fig. 7), in which the hexameric R64(26) rings provide cavities within which are found the F atoms and oxo atom O1 of the carboxylate group, which play no part in hydrogen-bond formation. As shown in Fig. 7, the larger hexameric rings are connected herring-bone fashion to complete the layer. The layers, with Cl atoms on their surfaces, are then stacked in the direction of a and are related to one another purely by cell translation. There is no interaction between the layers other than van der Waals contacts, hence the occurrence of the stacking faults which necessitated twin refinement of this structure, as described below.

In (II), the O2—H2···O3 hydrogen bonds (Table 3) connect the molecules, with each molecule related to its neighbour by the operation of a crystallographic twofold screw axis, to form zigzag chains propagated in the direction of b. The N1—H1···O1 hydrogen bonds connect the chains, related to one another by cell translation, in the direction of a. This creates the R44(24) motif shown in Fig. 8. Replication of this motif results in the formation of layers of molecules parallel to (001), as shown in Fig. 9. The surfaces of the layers are populated by methyl groups (atom C11 and the H atoms attached to it) and only van der Waals interactions occur at the layer interface.

The N—H···O hydrogen-bonds in (III) (Table 4) connect molecules, related to one another by cell translation, to form chains propagated in the direction of a, as shown in Fig. 10. The contribution of each of the N—H···O hydrogen bonds to the connectivity of the chain is a four-atom repeat unit, e.g. N1, H1, O2i and C9i [symmetry code: (i) x − 1, y, z] for the first of the hydrogen bonds given in Table 4. Taken together in pairs, the hydrogen bonds create rings which recur along the length of the chain. The overall connectivity can then be represented by the graph set C(4)R22(16). The distribution of the chains in the unit cell, and hence in the complete structure, where they are related to one another by crystallographic centres of symmetry, is shown in Fig. 11, where the chains are seen end on. Only van der Waals interactions occur between neighbouring chains.

In (IV), as in (III), N—H···O hydrogen bonds (Table 5) connect the molecules to form chains. However, the chains (Fig. 12) are now propagated in the direction of c and adjacent molecules are related by the operation of a crystallographic c-glide plane. Despite the molecules now alternating in orientation along the length of the chain, the C(4)R22(16) graph set assigned to the situation in (III) also applies to (IV). The chains in (IV) are distributed in such a way as to bring about face-to-face π–π contacts between pairs of centrosymmetrically related benzene rings (R2) of the N-phenyl groups. These are shown in Fig. 13 distributed in an A-face-centred arrangement. For this interaction, in which the centrosymmetric relationship (symmetry code: −x, 1 − y, 1 − z) renders the least-squares planes of the overlapping rings parallel, the distance between the ring centroids, the perpendicular distance between their least-squares planes and the lateral displacement or slippage of the rings are 3.803, 3.473 and 1.550 Å, respectively. The combination of the hydrogen bonding within the chains and pairwise overlap of the phenyl groups interconnects the molecules to form layers parallel to (100). The Cl atoms are confined to a region at the centre of the layer, while the layer surfaces are occupied by the methyl groups (atom C10 and the attached H atoms) of the acetamide group and by the atoms of the C3—C4 edge of the ring defined by C1–C6 (R1).

The difference in structure between the two acids, (I) and (II), must be due to the difference in the substituents at the 5-position of the benzene ring, Cl for (I) and Me for (II). The essential difference between the two structures, the non-participation in hydrogen bonding of atom O1 in (I), suggests that electronic effects arising from the electronegativity and the position of Cl on the ring have brought this about. The structural differences between acids (I) and (II), on the one hand, and amides (III) and (IV) on the other, where, for the amides, utilization of all available hydrogen-bond donors and acceptors only creates chains of molecules rather than layers or sheets, is considered to be due to the need to accommodate the steric requirements of the N-phenyl groups of the amides. The difference between the structures of the two amides, (III) and (IV), specifically in the manner in which the hydrogen-bonded chains of molecules are associated in pairs, is attributed to the presence of the Cl substituent in (IV), but is perceived as steric rather than electronic in origin.

Experimental top

Compounds (I)–(IV) were prepared by general procedures (Boechat & Pinto, 2000). Compound (I) (m.p. 438–440 K) was recrystallized from dichloroethane, (II) (m.p. 437–440 K) from MeOH, and (III) (m.p. 441–443 K) and (IV) (m.p. 445–446 K) both from EtOH.

Refinement top

The sample crystal of (I) was twinned, with major and minor twin components present, as indicated by the refinement, to the extent of 61.0 (1) and 39.0 (1)%, respectively. As a consequence, twin refinement by means of the SHELXL97 HKLF 5 instruction (Sheldrick, 1997), which precludes merging of the data as part of the refinement process, was employed, along with intensity data containing a mixture of completely overlapping, partially overlapping and completely non-overlapping reflections identified as follows. For the cell corresponding to the space group P21/a in use when the intensity data were collected, the COMPARECELL function of DENZO (Otwinowski & Minor, 1997) identified the presence of two reciprocal lattices relating to major and minor twin components, the reflections of which were assigned batch numbers 1 and 2, respectively. The two reciprocal lattices are related by rotation through 180° about a*. The relationship between the Miller indices [H(1), K(1), L(1) for the major component and H(2), K(2), L(2) for the minor component], which is used to determine the presence or absence of points of coincidence of the two reciprocal lattices and therefore of overlap of reflections, is defined as H(1) = H(2), K(1) = –K(2), L(1) = -[0.8 × H(2) + L(2)]. The criterion for overlap is the remainder, M, left after dividing H(2) by 5. M = 0 implies complete overlap, and M = 1 or 4 implies partial but significant overlap [the calculated value of L(1) will be non-integer by no more than ± 1/5]. In both of these cases, the measured intensity is shared between the code 2 reflection and the code 1 reflection with which it is paired. M = 2 or 3 indicates the total absence of overlap. The. hkl file used in the refinement contains, therefore, three groups of reflections, namely individual code 1 reflections associated exclusively with the major twin component, reflections in overlapping pairs with code −2 for the first and code 1 for the second, the intensity of which is to be shared between the two twin components and, finally, individual code 2 reflections associated exclusively with the minor twin component. The indices of the reflections in all of these groups were adjusted in the usual manner for the solution and refinement of the structure in the standard setting of the space group P21/c. The nature of the intensity data also precludes merging and multi-scan absorption correction as part of the data reduction process, and also creates difficulties in scaling the data. These difficulties combine to limit the refinement, to yield an R factor, in this case 0.121, rather higher than would be anticipated for a refinement of the usual kind. Also, on completion, this refinement revealed residual electron-density features of a peak of 1.28 e Å−3 0.10 Å from atom Cl1 and a hole of −0.72 e Å−3 1.47 Å from atom H10C.

In the absence of any element of atomic number higher than F, the refinement of the structure of (II) in the non-centrosymmetic space group P21 was carried out on merged intensity data. The Flack parameter (Flack, 1983) is therefore indeterminate, so the absolute structure could not be determined.

In all four refinements, aryl and methyl H atoms were placed in calculated positions, with C—H distances of 0.95 and 0.98 Å, respectively, for (I)–(III), and 0.93 and 0.96 Å, respectively, for (IV), and refined with a riding model, with Uiso(H) = 1.2Ueq(C) for aryl H atoms and 1.5Ueq(C) for methyl H atoms. The orientations of the methyl groups were also refined. The positions of the amide H atoms of (I), (II) and (IV), and of the hydroxyl H atoms of (I) and (II), were obtained from difference maps. The amide H atoms of (III) were initially placed in the manner of aryl H atoms. The coordinates of all amide H atoms of Text missing? were refined, with Uiso(H) = 1.2Ueq(N), and for (III) and (IV) with N—H distances restrained to 0.88 and 0.86 Å, respectively. The hydroxyl groups of (I) and (II) were idealized with O—H distances of 0.84 Å and refined as rigid bodies, with Uiso(H) = 1.2Ueq(O).

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I), (II), (III); SMART (Bruker, 1998) for (IV). Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT for (I), (II), (III); SAINT (Bruker, 2000) for (IV). Data reduction: DENZO and COLLECT for (I), (II), (III); SAINT for (IV). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. A view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. A view of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 5] Fig. 5. The centrosymmetric R22(18) motif in (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]
[Figure 6] Fig. 6. The hexamolecular R64(26) motif in (I). For clarity, bonds to C3–C6 are shown as thin lines. Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled, primarily to provide a key for the coding of the ellipsoids, which is the same for all of Figs. 6–9, 11 and 13. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (iii) 1 − x, 1/2 + y, 3/2 − z; (iv) 1 − x, 1 − y, 2 − z, (v) x, y, 1 + z; (vi) x, 1/2 − y, 1/2 + z.]
[Figure 7] Fig. 7. A more extensive view of the hydrogen-bonding within a layer of molecules of (I). The representation is the same as in Fig. 6, except that the displacement ellipsoids are now at the 20% probability level, symmetry codes and atom labels are absent, and the outline of the unit cell is shown.
[Figure 8] Fig. 8. The R44(24) motif in (II). For clarity bonds, to atoms C3–C6 and C11 are shown as thin lines. Ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Coding is indicated by the labelling of selected atoms. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) x − 1, y, z; (ii) 1 − x, 1/2 + y, 1 − z; (iii) x, 1/2 + y, 1 − z.]
[Figure 9] Fig. 9. A more extensive view of the hydrogen-bonding within a layer of molecules of (II). The representation is the same as in Fig. 8, except that the outline of the unit cell is shown, while atom labels and symmetry codes are absent.
[Figure 10] Fig. 10. A hydrogen-bonded chain in (III). Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) x − 1, y, z; (ii) x + 1, y, z.]
[Figure 11] Fig. 11. The packing of the hydrogen-bonded chains of molecules in (III). Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds are shown as small spheres of arbitrary radii. The coding of the atoms is the same as in Figs. 6–9.
[Figure 12] Fig. 12. A hydrogen-bonded chain in (IV). Displacement ellipsoids are drawn at the 30% probability level and H atoms involved in hydrogen bonds (dashed lines) are shown as small spheres of arbitrary radii. Selected atoms are labelled. For the sake of clarity, the unit-cell outline has been omitted. [Symmetry codes: (i) x, 3/2 − y, 1/2 + z; (ii) x, 3/2 − y, z − 1/2.]
[Figure 13] Fig. 13. Intermolecular contacts within a layer of molecules of (IV). Displacement ellipsoids are drawn at the 20% probability level. For convenience, the origin of the cell has been shifted to (−1/2,0,0). Dashed lines indicate the join of the centroids of overlapping benzene rings (see text) as well as hydrogen bonds. For clarity, bonds to atoms C3–C6 and C11–C16 are shown as thin lines. Coding is the same as for Figs. 6–9 and 11.
(I) 2-(2-Acetylamino-5-chlorophenyl)-2,2-difluoroethanoic acid top
Crystal data top
C10H8ClF2NO3F(000) = 536
Mr = 263.62Dx = 1.603 Mg m−3
Monoclinic, P21/cMelting point = 438–440 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 11.5493 (6) ÅCell parameters from 2529 reflections
b = 11.6207 (6) Åθ = 2.9–27.5°
c = 8.5251 (4) ŵ = 0.37 mm−1
β = 107.334 (2)°T = 120 K
V = 1092.20 (10) Å3Plate, colourless
Z = 40.60 × 0.25 × 0.05 mm
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer		6202 reflections with I > 2σ(I)
Radiation source: Bruker-Nonius FR591 rotating anodeRint = 0.000
Graphite monochromatorθmax = 27.5°, θmin = 4.8°
Detector resolution: 9.091 pixels mm-1h = −14→14
ϕ and ω scansk = −15→15
13369 measured reflectionsl = −10→10
13369 independent reflections
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)] = 0.121Hydrogen site location: geom and difmap
wR(F2) = 0.330H atoms treated by a mixture of independent and constrained refinement
S = 1.57 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
13369 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 1.28 e Å−3
0 restraintsΔρmin = −0.72 e Å−3
Crystal data top
C10H8ClF2NO3V = 1092.20 (10) Å3
Mr = 263.62Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.5493 (6) ŵ = 0.37 mm−1
b = 11.6207 (6) ÅT = 120 K
c = 8.5251 (4) Å0.60 × 0.25 × 0.05 mm
β = 107.334 (2)°
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer		6202 reflections with I > 2σ(I)
13369 measured reflectionsRint = 0.000
13369 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.1210 restraints
wR(F2) = 0.330H atoms treated by a mixture of independent and constrained refinement
S = 1.57Δρmax = 1.28 e Å−3
13369 reflectionsΔρmin = −0.72 e Å−3
160 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.5502 (0.0132) x + 0.7940 (0.0186) y − 7.3228 (0.0074) z = 4.0352 (0.0144)

* 0.0137 (0.0030) C1 * −0.0129 (0.0028) C2 * 0.0005 (0.0029) C3 * 0.0116 (0.0033) C4 * −0.0109 (0.0031) C5 * −0.0020 (0.0029) C6 − 0.0282 (0.0057) Cl1 0.2098 (0.0066) C7 − 0.9091 (0.0079) C8 − 1.1917 (0.0077) C9 − 1.1537 (0.0099) C10 1.3371 (0.0059) F1 0.4927 (0.0063) F2 − 0.0581 (0.0063) N1 − 0.8086 (0.0082) O1 − 1.9463 (0.0070) O2 − 2.2290 (0.0058) O3

Rms deviation of fitted atoms = 0.0101

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.

This is the refinement with the large. hkl file for which there has been neither correction for absorption nor, because of HKL 5 twin refinement, merge of symmetry related reflections.

Coordinates of H atom of NH obtained from difference map and refined in the usual manner with Uiso(H) = 1.2 Ueq(N). AFIX 87 for H of OH and AFIX 43 or AFIX 137, as appropriate, for H atoms attached to C atoms.

Residual electron density peak of 1.28 e/Ang**3 0.10 A ng. from Cl1 and residual electron density hole of −0.72 e/Ang**3 1.47 A ng. from H10C.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl11.05440 (11)0.17531 (11)0.70294 (14)0.0452 (4)
C10.7870 (4)0.3601 (4)0.4051 (5)0.0192 (11)
C20.7120 (4)0.2735 (4)0.3117 (5)0.0193 (11)
C30.7452 (4)0.1612 (4)0.3365 (5)0.0257 (11)
H30.69490.10350.27130.031*
C40.8515 (4)0.1290 (4)0.4556 (6)0.0330 (13)
H40.87490.05050.47130.040*
C50.9213 (4)0.2132 (4)0.5493 (5)0.0317 (13)
C60.8909 (4)0.3291 (4)0.5251 (5)0.0251 (11)
H60.94150.38620.59100.030*
C70.7621 (4)0.4866 (4)0.3629 (5)0.0215 (11)
F10.7533 (2)0.50308 (19)0.2005 (3)0.0304 (7)
F20.8608 (2)0.54914 (19)0.4463 (3)0.0336 (7)
C80.6517 (4)0.5441 (4)0.3930 (6)0.0213 (11)
O10.5668 (3)0.5789 (2)0.2840 (3)0.0293 (8)
O20.6673 (3)0.5516 (2)0.5537 (3)0.0254 (8)
H20.60900.58780.57000.031*
N10.6000 (3)0.3016 (3)0.1902 (4)0.0209 (9)
H10.592 (3)0.281 (3)0.088 (4)0.025*
C90.5021 (4)0.3301 (3)0.2337 (5)0.0188 (10)
O30.5064 (2)0.3392 (2)0.3814 (3)0.0191 (7)
C100.3867 (4)0.3528 (4)0.0963 (5)0.0290 (12)
H10A0.31880.31350.12010.043*
H10B0.39570.3238−0.00740.043*
H10C0.37090.43580.08710.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0282 (8)0.0615 (10)0.0437 (9)0.0163 (7)0.0072 (7)0.0181 (7)
C10.013 (2)0.022 (3)0.028 (3)0.001 (2)0.015 (2)0.002 (2)
C20.017 (2)0.029 (3)0.017 (3)0.004 (2)0.013 (2)−0.002 (2)
C30.029 (3)0.021 (3)0.032 (3)−0.007 (2)0.018 (3)−0.006 (2)
C40.032 (3)0.034 (3)0.037 (3)0.008 (3)0.017 (3)0.006 (3)
C50.024 (3)0.046 (3)0.033 (3)0.010 (2)0.020 (3)0.011 (3)
C60.016 (3)0.038 (3)0.025 (3)−0.001 (2)0.011 (2)−0.001 (2)
C70.016 (3)0.027 (3)0.023 (3)−0.005 (2)0.007 (2)−0.001 (2)
F10.0365 (17)0.0349 (17)0.0269 (16)0.0015 (13)0.0202 (14)0.0004 (12)
F20.0181 (15)0.0350 (17)0.0479 (18)−0.0064 (12)0.0103 (13)−0.0059 (14)
C80.023 (3)0.019 (3)0.026 (3)−0.009 (2)0.012 (2)−0.001 (2)
O10.0206 (19)0.034 (2)0.029 (2)0.0057 (15)0.0001 (16)0.0002 (15)
O20.0205 (19)0.036 (2)0.0203 (19)0.0103 (15)0.0062 (16)−0.0004 (16)
N10.021 (2)0.030 (2)0.013 (2)0.0001 (18)0.007 (2)−0.0043 (18)
C90.019 (3)0.016 (2)0.022 (3)−0.006 (2)0.007 (2)−0.003 (2)
O30.0184 (17)0.0284 (18)0.0111 (16)0.0021 (14)0.0054 (14)−0.0027 (15)
C100.025 (3)0.034 (3)0.025 (3)0.002 (2)0.003 (2)−0.005 (2)
Geometric parameters (Å, º) top
Cl1—C51.753 (4)C7—F11.371 (4)
C1—C61.373 (5)C7—C81.528 (6)
C1—C21.410 (5)C8—O11.202 (5)
C1—C71.520 (5)C8—O21.330 (4)
C2—C31.359 (5)O2—H20.8400
C2—N11.433 (5)N1—C91.333 (5)
C3—C41.391 (5)N1—H10.88 (4)
C3—H30.9500C9—O31.250 (4)
C4—C51.364 (6)C9—C101.512 (5)
C4—H40.9500C10—H10A0.9800
C5—C61.391 (6)C10—H10B0.9800
C6—H60.9500C10—H10C0.9800
C7—F21.360 (4)
C6—C1—C2119.2 (4)F1—C7—C1109.0 (3)
C6—C1—C7119.4 (4)F2—C7—C8106.8 (3)
C2—C1—C7121.1 (4)F1—C7—C8107.1 (3)
C3—C2—C1120.0 (4)C1—C7—C8119.5 (4)
C3—C2—N1119.0 (4)O1—C8—O2127.1 (4)
C1—C2—N1121.0 (4)O1—C8—C7123.1 (4)
C2—C3—C4121.2 (4)O2—C8—C7109.7 (4)
C2—C3—H3119.4C8—O2—H2109.5
C4—C3—H3119.4C9—N1—C2120.9 (4)
C5—C4—C3118.3 (4)C9—N1—H1119 (3)
C5—C4—H4120.9C2—N1—H1117 (3)
C3—C4—H4120.9O3—C9—N1121.2 (4)
C4—C5—C6121.9 (4)O3—C9—C10121.8 (4)
C4—C5—Cl1119.4 (4)N1—C9—C10116.9 (4)
C6—C5—Cl1118.7 (4)C9—C10—H10A109.5
C1—C6—C5119.3 (4)C9—C10—H10B109.5
C1—C6—H6120.3H10A—C10—H10B109.5
C5—C6—H6120.3C9—C10—H10C109.5
F2—C7—F1104.6 (3)H10A—C10—H10C109.5
F2—C7—C1108.9 (3)H10B—C10—H10C109.5
C6—C1—C2—C3−2.6 (6)C6—C1—C7—F1120.2 (4)
C7—C1—C2—C3170.7 (4)C2—C1—C7—F1−53.1 (5)
C6—C1—C2—N1177.2 (4)C6—C1—C7—C8−116.3 (5)
C7—C1—C2—N1−9.5 (6)C2—C1—C7—C870.4 (5)
C1—C2—C3—C41.4 (6)F2—C7—C8—O1122.4 (4)
N1—C2—C3—C4−178.4 (4)F1—C7—C8—O110.8 (6)
C2—C3—C4—C50.9 (7)C1—C7—C8—O1−113.6 (5)
C3—C4—C5—C6−2.1 (7)F2—C7—C8—O2−55.8 (4)
C3—C4—C5—Cl1178.9 (3)F1—C7—C8—O2−167.4 (3)
C2—C1—C6—C51.5 (6)C1—C7—C8—O268.2 (5)
C7—C1—C6—C5−171.9 (4)C3—C2—N1—C9103.1 (5)
C4—C5—C6—C10.8 (6)C1—C2—N1—C9−76.7 (5)
Cl1—C5—C6—C1179.9 (3)C2—N1—C9—O33.9 (6)
C6—C1—C7—F26.8 (5)C2—N1—C9—C10−177.1 (3)
C2—C1—C7—F2−166.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.841.732.570 (4)176
N1—H1···O3ii0.88 (4)2.23 (4)3.014 (4)148 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z−1/2.
(II) 2-(2-acetylamino-5-methylphenyl)-2,2-difluoroethanoic acid top
Crystal data top
C11H11F2NO3F(000) = 252
Mr = 243.21Dx = 1.444 Mg m−3
Monoclinic, P21Melting point = 437–440 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 4.9174 (3) ÅCell parameters from 1294 reflections
b = 8.3976 (3) Åθ = 2.9–27.5°
c = 13.5487 (7) ŵ = 0.13 mm−1
β = 91.208 (2)°T = 120 K
V = 559.36 (5) Å3Block, colourless
Z = 20.30 × 0.08 × 0.03 mm
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer		1373 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1240 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scansh = −6→6
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −10→10
Tmin = 0.813, Tmax = 1.000l = −17→17
5630 measured reflections
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)] = 0.036Hydrogen site location: geom and difmap
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0465P)2 + 0.1105P]
where P = (Fo2 + 2Fc2)/3
1373 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.18 e Å−3
1 restraintΔρmin = −0.23 e Å−3
Crystal data top
C11H11F2NO3V = 559.36 (5) Å3
Mr = 243.21Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.9174 (3) ŵ = 0.13 mm−1
b = 8.3976 (3) ÅT = 120 K
c = 13.5487 (7) Å0.30 × 0.08 × 0.03 mm
β = 91.208 (2)°
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer		1373 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1240 reflections with I > 2σ(I)
Tmin = 0.813, Tmax = 1.000Rint = 0.032
5630 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0361 restraint
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.18 e Å−3
1373 reflectionsΔρmin = −0.23 e Å−3
160 parameters
Special details top

Experimental. Unit cell determined with DIRAX (Duisenberg, 1992; Duisenberg et al., 2000) but refined with the DENZO/COLLECT HKL package.

Refs as: Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96. Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000). J. Appl. Cryst. 33, 893–898.

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 3.9217 (0.0029) x − 0.6847 (0.0089) y + 8.3250 (0.0102) z = 4.1515 (0.0112)

* 0.0015 (0.0016) C1 * −0.0073 (0.0016) C2 * 0.0059 (0.0018) C3 * 0.0013 (0.0019) C4 * −0.0069 (0.0019) C5 * 0.0056 (0.0018) C6 − 0.0487 (0.0039) C7 − 1.2674 (0.0043) C8 − 1.1756 (0.0041) C9 − 1.1838 (0.0053) C10 − 0.0586 (0.0043) C11 − 0.0928 (0.0035) N1 − 2.3503 (0.0035) O1 − 1.0174 (0.0051) O2 − 2.1404 (0.0033) O3 − 0.1194 (0.0041) F1 1.1060 (0.0038) F2

Rms deviation of fitted atoms = 0.0053

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.

In the absence of any atom of atomic number greater than that of F the intensity data were merged and the absolute structure is therefore indeterminate and the Flack asymmetry parameter (Flack, 1983) meaningless.

Positions of NH and OH H atoms from difference map. H atom of NH refined isotropically. OH idealized (AFIX 87) with O—H 0.84 A. For both of these Uiso(H) = 1.2Ueq(X), X = N or O as appropriate. Methyl and aryl H in calulated positions with C—H 0.98 and 0.95 A, respectively, and refined with a riding model with Uiso(H) 1.5Ueq(C) or 1.2Ueq(C), respectively. Rotational orientation of methyl groups refined.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2079 (4)0.7209 (2)0.64474 (13)0.0177 (4)
H10.057 (6)0.785 (4)0.6580 (19)0.021*
F10.6191 (3)0.99701 (17)0.85799 (10)0.0247 (3)
F20.2010 (3)0.96433 (18)0.80550 (9)0.0240 (3)
O10.7595 (3)0.9417 (2)0.65157 (12)0.0233 (4)
O20.3876 (3)1.0957 (2)0.64915 (12)0.0217 (4)
H20.43991.12050.59260.026*
O30.4948 (3)0.6412 (2)0.52737 (11)0.0221 (4)
C10.4956 (5)0.7441 (3)0.79353 (16)0.0181 (5)
C20.3650 (5)0.6482 (3)0.72304 (16)0.0186 (5)
C30.3980 (5)0.4854 (3)0.72678 (17)0.0242 (5)
H30.30640.41960.67970.029*
C40.5642 (6)0.4172 (3)0.79890 (18)0.0271 (6)
H40.58620.30490.80030.033*
C50.6997 (5)0.5104 (3)0.86941 (17)0.0246 (6)
C60.6606 (5)0.6744 (3)0.86602 (17)0.0225 (5)
H60.74840.73990.91410.027*
C70.4635 (5)0.9216 (3)0.78698 (16)0.0179 (5)
C80.5505 (5)0.9895 (3)0.68712 (16)0.0177 (5)
C90.2843 (5)0.7131 (3)0.55001 (16)0.0176 (5)
C100.1112 (5)0.7969 (3)0.47439 (17)0.0209 (5)
H10A−0.05410.83670.50520.031*
H10B0.06130.72260.42130.031*
H10C0.21270.88660.44710.031*
C110.8875 (6)0.4355 (4)0.9455 (2)0.0363 (7)
H11A0.90440.50581.00300.054*
H11B1.06700.41940.91710.054*
H11C0.81310.33260.96590.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0166 (9)0.0208 (9)0.0156 (9)0.0029 (8)−0.0020 (7)0.0000 (8)
F10.0316 (8)0.0225 (7)0.0197 (6)−0.0018 (6)−0.0055 (6)−0.0047 (6)
F20.0225 (7)0.0267 (8)0.0231 (6)0.0052 (6)0.0063 (5)0.0002 (6)
O10.0192 (9)0.0255 (9)0.0253 (8)0.0032 (7)0.0034 (6)0.0026 (7)
O20.0222 (9)0.0235 (9)0.0196 (8)0.0047 (7)0.0017 (7)0.0043 (7)
O30.0194 (9)0.0261 (9)0.0208 (8)0.0052 (7)−0.0009 (7)−0.0041 (7)
C10.0183 (11)0.0190 (12)0.0171 (11)0.0006 (9)0.0021 (9)0.0006 (9)
C20.0181 (12)0.0218 (12)0.0159 (11)0.0017 (9)0.0004 (8)0.0020 (9)
C30.0297 (13)0.0212 (12)0.0215 (11)0.0001 (10)−0.0016 (9)−0.0034 (10)
C40.0379 (16)0.0180 (12)0.0253 (13)0.0032 (11)−0.0001 (11)0.0015 (10)
C50.0287 (14)0.0244 (13)0.0205 (11)0.0058 (10)−0.0012 (10)0.0047 (10)
C60.0240 (12)0.0253 (13)0.0179 (11)0.0008 (10)−0.0033 (9)0.0001 (9)
C70.0169 (11)0.0200 (12)0.0170 (10)−0.0003 (9)0.0005 (9)−0.0027 (9)
C80.0195 (11)0.0154 (11)0.0180 (10)0.0007 (9)−0.0027 (8)−0.0027 (9)
C90.0180 (11)0.0160 (10)0.0188 (10)−0.0030 (9)−0.0008 (8)−0.0008 (9)
C100.0191 (12)0.0249 (13)0.0186 (11)0.0017 (9)−0.0019 (9)0.0015 (9)
C110.0467 (18)0.0341 (16)0.0278 (13)0.0115 (14)−0.0074 (12)0.0073 (12)
Geometric parameters (Å, º) top
N1—C91.346 (3)C3—H30.9500
N1—C21.435 (3)C4—C51.393 (4)
N1—H10.94 (3)C4—H40.9500
F1—C71.372 (3)C5—C61.391 (4)
F2—C71.369 (3)C5—C111.507 (3)
O1—C81.213 (3)C6—H60.9500
O2—C81.298 (3)C7—C81.537 (3)
O2—H20.8400C9—C101.495 (3)
O3—C91.242 (3)C10—H10A0.9800
C1—C61.390 (3)C10—H10B0.9800
C1—C21.395 (3)C10—H10C0.9800
C1—C71.501 (3)C11—H11A0.9800
C2—C31.378 (4)C11—H11B0.9800
C3—C41.384 (4)C11—H11C0.9800
C9—N1—C2121.82 (19)F2—C7—C1110.36 (19)
C9—N1—H1116.6 (16)F1—C7—C1111.15 (19)
C2—N1—H1121.3 (16)F2—C7—C8110.19 (18)
C8—O2—H2109.5F1—C7—C8106.54 (18)
C6—C1—C2119.6 (2)C1—C7—C8112.92 (19)
C6—C1—C7121.3 (2)O1—C8—O2126.2 (2)
C2—C1—C7119.1 (2)O1—C8—C7118.7 (2)
C3—C2—C1119.7 (2)O2—C8—C7115.0 (2)
C3—C2—N1120.7 (2)O3—C9—N1120.6 (2)
C1—C2—N1119.6 (2)O3—C9—C10121.67 (19)
C2—C3—C4120.2 (2)N1—C9—C10117.7 (2)
C2—C3—H3119.9C9—C10—H10A109.5
C4—C3—H3119.9C9—C10—H10B109.5
C3—C4—C5121.2 (2)H10A—C10—H10B109.5
C3—C4—H4119.4C9—C10—H10C109.5
C5—C4—H4119.4H10A—C10—H10C109.5
C6—C5—C4118.0 (2)H10B—C10—H10C109.5
C6—C5—C11121.2 (2)C5—C11—H11A109.5
C4—C5—C11120.8 (2)C5—C11—H11B109.5
C1—C6—C5121.2 (2)H11A—C11—H11B109.5
C1—C6—H6119.4C5—C11—H11C109.5
C5—C6—H6119.4H11A—C11—H11C109.5
F2—C7—F1105.35 (17)H11B—C11—H11C109.5
C6—C1—C2—C30.9 (3)C6—C1—C7—F2−115.1 (2)
C7—C1—C2—C3178.4 (2)C2—C1—C7—F267.4 (3)
C6—C1—C2—N1−176.3 (2)C6—C1—C7—F11.5 (3)
C7—C1—C2—N11.3 (3)C2—C1—C7—F1−176.09 (18)
C9—N1—C2—C3−64.3 (3)C6—C1—C7—C8121.1 (2)
C9—N1—C2—C1112.8 (2)C2—C1—C7—C8−56.4 (3)
C1—C2—C3—C4−1.3 (4)F2—C7—C8—O1−167.90 (19)
N1—C2—C3—C4175.8 (2)F1—C7—C8—O178.3 (3)
C2—C3—C4—C50.5 (4)C1—C7—C8—O1−44.0 (3)
C3—C4—C5—C60.7 (4)F2—C7—C8—O212.5 (3)
C3—C4—C5—C11−177.9 (2)F1—C7—C8—O2−101.3 (2)
C2—C1—C6—C50.4 (4)C1—C7—C8—O2136.4 (2)
C7—C1—C6—C5−177.2 (2)C2—N1—C9—O30.3 (3)
C4—C5—C6—C1−1.2 (4)C2—N1—C9—C10−178.1 (2)
C11—C5—C6—C1177.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.94 (3)1.97 (3)2.884 (3)165 (2)
O2—H2···O3ii0.841.672.502 (2)169
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1.
(III) 2-(2-acetylaminophenyl)-2,2-difluoro-N-phenylacetamide top
Crystal data top
C16H14F2N2O2Z = 2
Mr = 304.29F(000) = 316
Triclinic, P1Dx = 1.456 Mg m−3
Hall symbol: -P 1Melting point = 441–443 K
a = 5.0075 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.5863 (11) ÅCell parameters from 6753 reflections
c = 12.2219 (11) Åθ = 2.9–27.5°
α = 87.304 (4)°µ = 0.12 mm−1
β = 89.327 (5)°T = 120 K
γ = 78.588 (5)°Lath, colourless
V = 694.30 (10) Å30.20 × 0.13 × 0.08 mm
Data collection top
Enraf-Nonius KappaCCD area-detector
diffractometer		3177 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode1631 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.3°
ϕ and ω scansh = −6→6
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)		k = −15→14
Tmin = 0.924, Tmax = 1.000l = −15→15
5877 measured reflections
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 0.94 w = 1/[σ2(Fo2) + (0.0443P)2]
where P = (Fo2 + 2Fc2)/3
3177 reflections(Δ/σ)max < 0.001
206 parametersΔρmax = 0.26 e Å−3
2 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C16H14F2N2O2γ = 78.588 (5)°
Mr = 304.29V = 694.30 (10) Å3
Triclinic, P1Z = 2
a = 5.0075 (3) ÅMo Kα radiation
b = 11.5863 (11) ŵ = 0.12 mm−1
c = 12.2219 (11) ÅT = 120 K
α = 87.304 (4)°0.20 × 0.13 × 0.08 mm
β = 89.327 (5)°
Data collection top
Enraf-Nonius KappaCCD area-detector
diffractometer		3177 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)		1631 reflections with I > 2σ(I)
Tmin = 0.924, Tmax = 1.000Rint = 0.071
5877 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0532 restraints
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.26 e Å−3
3177 reflectionsΔρmin = −0.28 e Å−3
206 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 4.1370 (0.0024) x − 5.0600 (0.0084) y + 5.7038 (0.0090) z = 0.2582 (0.0116)

* −0.0124 (0.0014) C1 * 0.0095 (0.0014) C2 * 0.0005 (0.0014) C3 * −0.0077 (0.0015) C4 * 0.0047 (0.0015) C5 * 0.0054 (0.0014) C6 0.0278 (0.0029) N1 − 0.9456 (0.0038) C9 − 1.9035 (0.0031) O2 − 0.7682 (0.0046) C10 − 0.0287 (0.0033) C7 1.2399 (0.0032) F1 − 0.3792 (0.0034) F2 − 1.0006 (0.0038) C8 − 2.1717 (0.0033) O1 − 0.4836 (0.0046) N2 − 1.1904 (0.0055) C11 − 0.4914 (0.0062) C12 − 2.5249 (0.0056) C16

Rms deviation of fitted atoms = 0.0077

3.1961 (0.0037) x − 7.1776 (0.0087) y + 1.1006 (0.0115) z = 0.1688 (0.0074)

Angle to previous plane (with approximate e.s.d.) = 75.06 (0.06)

* 0.0053 (0.0015) C11 * −0.0035 (0.0016) C12 * −0.0011 (0.0016) C13 * 0.0039 (0.0016) C14 * −0.0020 (0.0016) C15 * −0.0026 (0.0015) C16 − 0.0333 (0.0033) N2 0.5170 (0.0041) C8 1.1340 (0.0039) O1 0.3181 (0.0053) C7 − 0.2937 (0.0052) F1 − 0.6173 (0.0055) F2 1.5325 (0.0061) C1 2.7248 (0.0057) C2 1.4815 (0.0072) C6

Rms deviation of fitted atoms = 0.0034

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.

Methyl and aryl H in calculated positions with C—H 0.98 and 0.95 A, respectively, and refined with a riding model with Uiso(H) 1.5Ueq(C) for methyl H and 1.2Ueq(C) for aryl H. Rotational position of methyl group refined.

H of NH initially placed in calculated positions then refined with the N—H distance restrained to 0.88 (2) A and with Uiso(H) = 1.2Ueq(N).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8719 (4)0.2949 (2)0.93715 (18)0.0205 (5)
C20.9868 (4)0.1773 (2)0.91997 (18)0.0221 (6)
C31.1706 (4)0.1134 (2)0.99494 (19)0.0268 (6)
H31.25090.03370.98240.032*
C41.2377 (4)0.1651 (2)1.08811 (19)0.0294 (6)
H41.36490.12141.13910.035*
C51.1180 (4)0.2811 (2)1.10632 (19)0.0284 (6)
H51.16120.31661.17060.034*
C60.9364 (4)0.3452 (2)1.03162 (19)0.0254 (6)
H60.85470.42451.04500.030*
C70.6777 (4)0.3652 (2)0.85571 (19)0.0239 (6)
F10.4237 (2)0.33966 (12)0.87128 (10)0.0339 (4)
F20.6438 (2)0.48327 (12)0.87449 (11)0.0365 (4)
C80.7583 (4)0.3548 (2)0.73459 (18)0.0224 (6)
O10.9882 (3)0.36692 (14)0.70680 (12)0.0306 (4)
N20.5648 (3)0.33492 (16)0.66723 (15)0.0229 (5)
H20.407 (3)0.3278 (19)0.6934 (17)0.028*
C110.5910 (4)0.3236 (2)0.55235 (19)0.0227 (5)
C120.4431 (4)0.2515 (2)0.5036 (2)0.0284 (6)
H120.33190.20980.54720.034*
C130.4564 (4)0.2399 (2)0.3916 (2)0.0338 (6)
H130.35490.18990.35840.041*
C140.6159 (4)0.3004 (2)0.3276 (2)0.0305 (6)
H140.62580.29200.25060.037*
C150.7612 (4)0.3734 (2)0.3764 (2)0.0317 (6)
H150.87040.41590.33260.038*
C160.7495 (4)0.3854 (2)0.48812 (19)0.0283 (6)
H160.85000.43600.52100.034*
N10.9183 (3)0.12263 (16)0.82493 (15)0.0244 (5)
H10.745 (3)0.1188 (19)0.8147 (17)0.029*
C91.1074 (4)0.0754 (2)0.74964 (19)0.0249 (6)
O21.3506 (3)0.07682 (14)0.75924 (13)0.0321 (4)
C100.9962 (4)0.0241 (2)0.6546 (2)0.0340 (6)
H10A1.02680.06890.58710.051*
H10B0.80040.02810.66500.051*
H10C1.0885−0.05830.64910.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0138 (11)0.0267 (15)0.0220 (14)−0.0070 (10)0.0009 (9)0.0007 (11)
C20.0181 (11)0.0280 (16)0.0214 (14)−0.0083 (10)0.0018 (10)0.0014 (11)
C30.0242 (12)0.0245 (15)0.0313 (16)−0.0043 (11)−0.0012 (11)0.0012 (12)
C40.0247 (13)0.0351 (17)0.0278 (16)−0.0059 (11)−0.0033 (11)0.0045 (12)
C50.0249 (12)0.0422 (18)0.0204 (14)−0.0123 (12)−0.0008 (10)−0.0010 (12)
C60.0204 (12)0.0290 (16)0.0265 (15)−0.0043 (10)0.0036 (10)−0.0005 (12)
C70.0180 (12)0.0245 (16)0.0303 (15)−0.0060 (10)0.0013 (10)−0.0042 (12)
F10.0164 (7)0.0565 (10)0.0299 (8)−0.0100 (6)0.0032 (5)−0.0008 (7)
F20.0415 (8)0.0289 (9)0.0362 (9)0.0010 (6)−0.0075 (6)−0.0042 (7)
C80.0177 (12)0.0237 (15)0.0258 (14)−0.0049 (10)−0.0010 (10)0.0015 (11)
O10.0179 (8)0.0460 (12)0.0291 (10)−0.0101 (7)0.0008 (7)0.0038 (8)
N20.0165 (10)0.0327 (13)0.0210 (12)−0.0087 (9)0.0012 (8)0.0012 (9)
C110.0146 (11)0.0270 (15)0.0253 (14)−0.0015 (10)−0.0005 (10)−0.0008 (11)
C120.0234 (12)0.0357 (17)0.0274 (16)−0.0094 (11)0.0003 (10)−0.0006 (12)
C130.0305 (14)0.0434 (18)0.0297 (16)−0.0115 (12)−0.0011 (11)−0.0056 (13)
C140.0250 (13)0.0430 (17)0.0213 (14)−0.0021 (12)−0.0009 (10)0.0001 (12)
C150.0267 (13)0.0402 (17)0.0280 (16)−0.0073 (12)0.0025 (11)0.0040 (13)
C160.0223 (12)0.0328 (16)0.0309 (16)−0.0085 (11)−0.0015 (11)0.0003 (12)
N10.0173 (10)0.0274 (13)0.0299 (13)−0.0077 (9)−0.0002 (9)−0.0033 (10)
C90.0224 (13)0.0258 (15)0.0275 (15)−0.0070 (10)0.0026 (10)−0.0010 (11)
O20.0212 (9)0.0405 (12)0.0351 (11)−0.0065 (7)0.0018 (7)−0.0042 (8)
C100.0308 (14)0.0369 (17)0.0357 (17)−0.0084 (12)0.0009 (11)−0.0086 (13)
Geometric parameters (Å, º) top
C1—C61.387 (3)C11—C121.380 (3)
C1—C21.395 (3)C11—C161.384 (3)
C1—C71.494 (3)C12—C131.382 (3)
C2—C31.386 (3)C12—H120.9500
C2—N11.426 (3)C13—C141.377 (3)
C3—C41.386 (3)C13—H130.9500
C3—H30.9500C14—C151.379 (3)
C4—C51.386 (3)C14—H140.9500
C4—H40.9500C15—C161.378 (3)
C5—C61.379 (3)C15—H150.9500
C5—H50.9500C16—H160.9500
C6—H60.9500N1—C91.366 (3)
C7—F11.371 (2)N1—H10.890 (15)
C7—F21.375 (2)C9—O21.228 (2)
C7—C81.534 (3)C9—C101.492 (3)
C8—O11.229 (2)C10—H10A0.9800
C8—N21.340 (3)C10—H10B0.9800
N2—C111.418 (3)C10—H10C0.9800
N2—H20.865 (15)
C6—C1—C2119.2 (2)C12—C11—C16119.6 (2)
C6—C1—C7120.4 (2)C12—C11—N2117.9 (2)
C2—C1—C7120.3 (2)C16—C11—N2122.5 (2)
C3—C2—C1120.0 (2)C11—C12—C13120.1 (2)
C3—C2—N1119.7 (2)C11—C12—H12120.0
C1—C2—N1120.3 (2)C13—C12—H12120.0
C2—C3—C4120.3 (2)C14—C13—C12120.4 (2)
C2—C3—H3119.8C14—C13—H13119.8
C4—C3—H3119.8C12—C13—H13119.8
C5—C4—C3119.5 (2)C13—C14—C15119.3 (2)
C5—C4—H4120.2C13—C14—H14120.3
C3—C4—H4120.2C15—C14—H14120.3
C6—C5—C4120.3 (2)C16—C15—C14120.7 (2)
C6—C5—H5119.8C16—C15—H15119.7
C4—C5—H5119.8C14—C15—H15119.7
C5—C6—C1120.6 (2)C15—C16—C11119.9 (2)
C5—C6—H6119.7C15—C16—H16120.0
C1—C6—H6119.7C11—C16—H16120.0
F1—C7—F2104.57 (16)C9—N1—C2122.86 (17)
F1—C7—C1109.79 (18)C9—N1—H1118.8 (14)
F2—C7—C1110.02 (18)C2—N1—H1118.4 (14)
F1—C7—C8109.75 (18)O2—C9—N1122.2 (2)
F2—C7—C8105.17 (18)O2—C9—C10122.7 (2)
C1—C7—C8116.77 (18)N1—C9—C10115.10 (19)
O1—C8—N2125.5 (2)C9—C10—H10A109.5
O1—C8—C7118.69 (19)C9—C10—H10B109.5
N2—C8—C7115.77 (18)H10A—C10—H10B109.5
C8—N2—C11125.84 (18)C9—C10—H10C109.5
C8—N2—H2119.8 (14)H10A—C10—H10C109.5
C11—N2—H2114.4 (14)H10B—C10—H10C109.5
C1—C2—N1—C9120.4 (2)C6—C1—C7—C8135.7 (2)
C3—C2—N1—C9−59.0 (3)C1—C7—C8—O1−49.4 (3)
C2—N1—C9—O20.2 (3)C1—C7—C8—N2131.7 (2)
C2—N1—C9—C10−178.9 (2)F1—C7—C8—O1−175.18 (19)
C7—C1—C2—N1−0.5 (3)F1—C7—C8—N26.0 (3)
C7—C1—C2—C3178.86 (19)F2—C7—C8—O172.8 (2)
C7—C1—C6—C5−179.2 (2)F2—C7—C8—N2−106.0 (2)
C2—C1—C7—F180.3 (2)C7—C8—N2—C11179.2 (2)
C2—C1—C7—F2−165.17 (17)O1—C8—N2—C110.5 (4)
C2—C1—C7—C8−45.4 (3)C8—N2—C11—C12149.5 (2)
C6—C1—C7—F1−98.6 (2)C8—N2—C11—C16−33.2 (3)
C6—C1—C7—F216.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.89 (2)2.24 (2)3.114 (2)166 (2)
N2—H2···O1i0.87 (2)2.06 (2)2.875 (2)156 (2)
Symmetry code: (i) x−1, y, z.
(IV) 2-(2-acetylaminophenyl)-N-(4-chlorophenyl)-2,2-difluoroacetamide top
Crystal data top
C16H13ClF2N2O2F(000) = 696
Mr = 338.73Dx = 1.434 Mg m−3
Monoclinic, P21/cMelting point = 445–446 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 16.5777 (10) ÅCell parameters from 3620 reflections
b = 9.8176 (6) Åθ = 2.4–31.2°
c = 9.6962 (6) ŵ = 0.28 mm−1
β = 96.010 (1)°T = 291 K
V = 1569.41 (17) Å3Block, colourless
Z = 40.48 × 0.23 × 0.17 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		5629 independent reflections
Radiation source: fine-focus sealed tube2824 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
ϕ and ω scansθmax = 32.6°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −20→25
Tmin = 0.841, Tmax = 1.000k = −14→14
15368 measured reflectionsl = −14→11
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)] = 0.055Hydrogen site location: geom and difmap
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0478P)2 + 0.3392P]
where P = (Fo2 + 2Fc2)/3
5629 reflections(Δ/σ)max < 0.001
215 parametersΔρmax = 0.26 e Å−3
2 restraintsΔρmin = −0.24 e Å−3
Crystal data top
C16H13ClF2N2O2V = 1569.41 (17) Å3
Mr = 338.73Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.5777 (10) ŵ = 0.28 mm−1
b = 9.8176 (6) ÅT = 291 K
c = 9.6962 (6) Å0.48 × 0.23 × 0.17 mm
β = 96.010 (1)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		5629 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		2824 reflections with I > 2σ(I)
Tmin = 0.841, Tmax = 1.000Rint = 0.045
15368 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0552 restraints
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.26 e Å−3
5629 reflectionsΔρmin = −0.24 e Å−3
215 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.5205 (0.0144) x + 3.0881 (0.0086) y + 7.9313 (0.0053) z = 8.8627 (0.0082)

* −0.0025 (0.0014) C1 * −0.0034 (0.0014) C2 * 0.0051 (0.0016) C3 * −0.0007 (0.0018) C4 * −0.0053 (0.0018) C5 * 0.0069 (0.0016) C6 − 0.0171 (0.0031) C7 − 1.2188 (0.0036) C8 − 0.9173 (0.0037) C9 − 0.7914 (0.0052) C10 − 1.9542 (0.0055) C11 1.1575 (0.0032) F1 − 0.0459 (0.0036) F2 − 0.0247 (0.0029) N1 − 0.9939 (0.0046) N2 − 2.2899 (0.0030) O1 − 1.7675 (0.0034) O2

Rms deviation of fitted atoms = 0.0045

− 13.7420 (0.0071) x + 3.9787 (0.0067) y + 4.5590 (0.0070) z = 2.5327 (0.0048)

Angle to previous plane (with approximate e.s.d.) = 82.27 (0.06)

* 0.0064 (0.0013) C11 * −0.0005 (0.0013) C12 * −0.0060 (0.0014) C13 * 0.0064 (0.0013) C14 * −0.0003 (0.0014) C15 * −0.0061 (0.0014) C16 − 0.2562 (0.0050) C1 0.4591 (0.0042) C7 − 0.0096 (0.0034) C8 − 3.4710 (0.0041) C9 − 4.0774 (0.0040) C10 0.3893 (0.0043) F1 1.7908 (0.0040) F2 − 2.3774 (0.0044) N1 0.1147 (0.0027) N2 − 0.3773 (0.0034) O1 − 3.9308 (0.0042) O2 0.0421 (0.0025) Cl1

Rms deviation of fitted atoms = 0.0051

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.

Methyl and aryl H atoms in calculated positions with C—H 0.96 and 0.93 A, respectively, and refined with a riding model with Uiso(H) 1.5 (methyl) or 1.2Ueq(C) for aryl H. Rotaational positiion of methyl group also refined. Positions for H atoms of NH found in difference map and refined with N—H restrained to 0.86 A and Uiso(H) = 1.2Ueq(N).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.01170 (3)0.18823 (6)0.43578 (7)0.06432 (18)
F10.27633 (7)0.90550 (12)0.68363 (10)0.0543 (3)
F20.16899 (7)1.00342 (12)0.58202 (13)0.0602 (3)
O10.19474 (9)0.80925 (14)0.35353 (12)0.0554 (4)
O20.41213 (10)0.78588 (16)0.24977 (14)0.0643 (4)
N10.38773 (9)0.84251 (16)0.46752 (15)0.0408 (4)
H10.3883 (12)0.811 (2)0.5468 (17)0.049*
N20.19526 (9)0.69866 (15)0.55955 (14)0.0376 (3)
H20.2098 (11)0.7069 (19)0.6452 (16)0.045*
C10.29047 (11)1.02738 (18)0.47829 (17)0.0386 (4)
C20.36331 (11)0.97876 (18)0.43722 (17)0.0396 (4)
C30.41103 (14)1.0641 (2)0.3658 (2)0.0573 (5)
H30.45991.03250.33910.069*
C40.38634 (17)1.1956 (2)0.3342 (3)0.0732 (7)
H40.41851.25210.28570.088*
C50.31449 (17)1.2435 (2)0.3740 (3)0.0729 (7)
H50.29791.33200.35180.088*
C60.26699 (14)1.1605 (2)0.4470 (2)0.0560 (5)
H60.21891.19390.47530.067*
C70.23760 (11)0.93618 (18)0.55542 (17)0.0386 (4)
C80.20835 (10)0.80480 (18)0.47912 (17)0.0355 (4)
C90.40981 (12)0.7543 (2)0.37116 (19)0.0457 (4)
C100.43105 (18)0.6149 (2)0.4238 (3)0.0771 (8)
H10A0.41850.54980.35090.116*
H10B0.40040.59410.49990.116*
H10C0.48790.61090.45470.116*
C110.15436 (10)0.57536 (17)0.52011 (16)0.0345 (4)
C120.10771 (11)0.5570 (2)0.39396 (18)0.0433 (4)
H120.10530.62520.32700.052*
C130.06489 (12)0.4374 (2)0.36806 (19)0.0470 (5)
H130.03400.42490.28330.056*
C140.06770 (11)0.33733 (19)0.4666 (2)0.0428 (4)
C150.11439 (12)0.35314 (19)0.5921 (2)0.0475 (5)
H150.11660.28450.65850.057*
C160.15764 (12)0.47168 (19)0.61774 (18)0.0449 (4)
H160.18960.48250.70180.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0623 (3)0.0490 (3)0.0808 (4)−0.0102 (3)0.0035 (3)−0.0125 (3)
F10.0736 (8)0.0603 (7)0.0281 (5)−0.0124 (6)0.0009 (5)−0.0029 (5)
F20.0574 (7)0.0554 (7)0.0728 (8)0.0102 (6)0.0308 (6)−0.0063 (6)
O10.0851 (10)0.0576 (8)0.0234 (6)−0.0158 (8)0.0054 (6)0.0030 (6)
O20.0920 (11)0.0663 (10)0.0364 (8)0.0065 (9)0.0150 (7)−0.0040 (7)
N10.0464 (9)0.0459 (9)0.0309 (7)0.0062 (7)0.0070 (6)0.0019 (6)
N20.0476 (8)0.0425 (8)0.0223 (6)−0.0033 (7)0.0021 (6)0.0006 (6)
C10.0451 (10)0.0373 (9)0.0340 (8)−0.0026 (8)0.0071 (7)−0.0035 (7)
C20.0447 (10)0.0400 (9)0.0342 (9)−0.0029 (8)0.0053 (7)−0.0014 (7)
C30.0574 (13)0.0570 (13)0.0606 (13)−0.0103 (10)0.0204 (10)0.0010 (10)
C40.0873 (18)0.0523 (14)0.0842 (18)−0.0188 (13)0.0288 (14)0.0113 (13)
C50.0954 (19)0.0383 (12)0.0869 (18)−0.0020 (13)0.0179 (15)0.0099 (12)
C60.0653 (13)0.0405 (11)0.0639 (13)0.0057 (10)0.0146 (11)−0.0017 (10)
C70.0445 (10)0.0425 (10)0.0297 (8)0.0056 (8)0.0082 (7)−0.0018 (7)
C80.0379 (8)0.0410 (9)0.0282 (8)0.0008 (8)0.0064 (6)0.0002 (7)
C90.0486 (10)0.0514 (11)0.0374 (10)0.0086 (9)0.0053 (8)−0.0042 (9)
C100.110 (2)0.0626 (15)0.0578 (14)0.0375 (15)0.0055 (14)−0.0013 (12)
C110.0371 (9)0.0400 (9)0.0274 (8)0.0015 (7)0.0077 (6)−0.0023 (7)
C120.0491 (11)0.0496 (11)0.0309 (9)−0.0006 (9)0.0022 (8)0.0017 (8)
C130.0466 (11)0.0553 (12)0.0377 (9)0.0001 (9)−0.0010 (8)−0.0086 (9)
C140.0399 (9)0.0400 (10)0.0494 (11)0.0008 (8)0.0098 (8)−0.0105 (8)
C150.0638 (12)0.0390 (10)0.0406 (10)0.0002 (9)0.0092 (9)0.0004 (8)
C160.0611 (12)0.0427 (10)0.0300 (8)0.0009 (9)−0.0001 (8)−0.0007 (8)
Geometric parameters (Å, º) top
Cl1—C141.7424 (19)C5—C61.379 (3)
F1—C71.3716 (19)C5—H50.9300
F2—C71.363 (2)C6—H60.9300
O1—C81.2158 (19)C7—C81.540 (2)
O2—C91.222 (2)C9—C101.490 (3)
N1—C91.352 (2)C10—H10A0.9600
N1—C21.419 (2)C10—H10B0.9600
N1—H10.827 (15)C10—H10C0.9600
N2—C81.333 (2)C11—C161.387 (2)
N2—C111.420 (2)C11—C121.389 (2)
N2—H20.844 (14)C12—C131.381 (3)
C1—C61.388 (3)C12—H120.9300
C1—C21.395 (3)C13—C141.368 (3)
C1—C71.505 (3)C13—H130.9300
C2—C31.386 (3)C14—C151.381 (3)
C3—C41.379 (3)C15—C161.376 (3)
C3—H30.9300C15—H150.9300
C4—C51.373 (4)C16—H160.9300
C4—H40.9300
C9—N1—C2123.54 (16)O1—C8—N2126.13 (16)
C9—N1—H1115.4 (14)O1—C8—C7117.85 (15)
C2—N1—H1121.0 (14)N2—C8—C7115.85 (14)
C8—N2—C11127.67 (14)O2—C9—N1122.77 (19)
C8—N2—H2117.0 (13)O2—C9—C10122.22 (19)
C11—N2—H2115.2 (13)N1—C9—C10115.01 (18)
C6—C1—C2119.41 (18)C9—C10—H10A109.5
C6—C1—C7120.28 (17)C9—C10—H10B109.5
C2—C1—C7120.31 (16)H10A—C10—H10B109.5
C3—C2—C1119.48 (18)C9—C10—H10C109.5
C3—C2—N1120.51 (18)H10A—C10—H10C109.5
C1—C2—N1120.01 (16)H10B—C10—H10C109.5
C4—C3—C2120.3 (2)C16—C11—C12118.98 (16)
C4—C3—H3119.8C16—C11—N2117.27 (14)
C2—C3—H3119.8C12—C11—N2123.62 (15)
C5—C4—C3120.3 (2)C13—C12—C11119.89 (17)
C5—C4—H4119.9C13—C12—H12120.1
C3—C4—H4119.9C11—C12—H12120.1
C4—C5—C6120.0 (2)C14—C13—C12120.29 (17)
C4—C5—H5120.0C14—C13—H13119.9
C6—C5—H5120.0C12—C13—H13119.9
C5—C6—C1120.4 (2)C13—C14—C15120.64 (17)
C5—C6—H6119.8C13—C14—Cl1120.33 (15)
C1—C6—H6119.8C15—C14—Cl1119.02 (15)
F2—C7—F1104.81 (13)C16—C15—C14119.20 (18)
F2—C7—C1110.29 (14)C16—C15—H15120.4
F1—C7—C1109.83 (15)C14—C15—H15120.4
F2—C7—C8105.64 (14)C15—C16—C11120.99 (17)
F1—C7—C8110.21 (14)C15—C16—H16119.5
C1—C7—C8115.46 (14)C11—C16—H16119.5
C1—C2—N1—C9128.08 (19)C6—C1—C7—C8120.84 (19)
C3—C2—N1—C9−51.4 (3)C1—C7—C8—O1−33.8 (2)
C2—N1—C9—O21.6 (3)C1—C7—C8—N2150.49 (15)
C2—N1—C9—C10−178.31 (19)F1—C7—C8—O1−158.97 (16)
C7—C1—C2—N10.3 (2)F1—C7—C8—N225.3 (2)
C7—C1—C2—C3179.76 (17)F2—C7—C8—O188.33 (19)
C7—C1—C6—C5−178.8 (2)F2—C7—C8—N2−87.36 (17)
C2—C1—C7—F166.4 (2)C7—C8—N2—C11167.09 (16)
C2—C1—C7—F2−178.55 (15)O1—C8—N2—C11−8.2 (3)
C2—C1—C7—C8−58.9 (2)C8—N2—C11—C12−12.8 (3)
C6—C1—C7—F1−113.81 (19)C8—N2—C11—C16171.47 (17)
C6—C1—C7—F21.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.83 (2)2.19 (2)3.002 (2)169 (2)
N2—H2···O1i0.84 (1)2.07 (2)2.8524 (18)155 (2)
Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC10H8ClF2NO3C11H11F2NO3C16H14F2N2O2C16H13ClF2N2O2
Mr263.62243.21304.29338.73
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21Triclinic, P1Monoclinic, P21/c
Temperature (K)120120120291
a, b, c (Å)11.5493 (6), 11.6207 (6), 8.5251 (4)4.9174 (3), 8.3976 (3), 13.5487 (7)5.0075 (3), 11.5863 (11), 12.2219 (11)16.5777 (10), 9.8176 (6), 9.6962 (6)
α, β, γ (°)90, 107.334 (2), 9090, 91.208 (2), 9087.304 (4), 89.327 (5), 78.588 (5)90, 96.010 (1), 90
V (Å3)1092.20 (10)559.36 (5)694.30 (10)1569.41 (17)
Z4224
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm−1)0.370.130.120.28
Crystal size (mm)0.60 × 0.25 × 0.050.30 × 0.08 × 0.030.20 × 0.13 × 0.080.48 × 0.23 × 0.17
Data collection
DiffractometerBruker-Nonius KappaCCD area-detector
diffractometer		Bruker-Nonius KappaCCD area-detector
diffractometer		Enraf-Nonius KappaCCD area-detector
diffractometer		Bruker SMART 1000 CCD area-detector
diffractometer
Absorption correction–Multi-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SORTAV; Blessing, 1995, 1997)		Multi-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax–0.813, 1.0000.924, 1.0000.841, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		13369, 13369, 6202 5630, 1373, 1240 5877, 3177, 1631 15368, 5629, 2824
Rint0.0000.0320.0710.045
(sin θ/λ)max (Å−1)0.6500.6510.6520.757
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.121, 0.330, 1.57 0.036, 0.086, 1.08 0.053, 0.118, 0.94 0.055, 0.132, 1.00
No. of reflections13369137331775629
No. of parameters160160206215
No. of restraints0122
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 refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)1.28, −0.720.18, −0.230.26, −0.280.26, −0.24

Computer programs: COLLECT (Nonius, 1998), SMART (Bruker, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT, SAINT (Bruker, 2000), DENZO and COLLECT, SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.841.732.570 (4)176
N1—H1···O3ii0.88 (4)2.23 (4)3.014 (4)148 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.94 (3)1.97 (3)2.884 (3)165 (2)
O2—H2···O3ii0.841.672.502 (2)169
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.890 (15)2.243 (16)3.114 (2)166.1 (19)
N2—H2···O1i0.865 (15)2.063 (16)2.875 (2)156 (2)
Symmetry code: (i) x−1, y, z.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.827 (15)2.186 (15)3.002 (2)169.2 (19)
N2—H2···O1i0.844 (14)2.067 (16)2.8524 (18)154.5 (18)
Symmetry code: (i) x, −y+3/2, z+1/2.
Table 1. Selected geometric parameters (Å, °) for compounds I-IV top
IaIIbIIIcIVc
C2—N11.433 (5)1.435 (3)1.426 (3)1.419 (2)
C5—X1.753 (4)1.507 (3)
C8—O11.202 (5)1.213 (3)1.229 (2)1.2158 (19)
C8—O21.330 (4)1.298 (3)1.340 (3)1.333 (2)
C9—N11.333 (5)1.346 (3)1.366 (3)1.352 (2)
C9—O31.250 (4)1.242 (3)1.228 (2)1.222 (2)
C9—C101.512 (5)1.495 (3)1.492 (3)1.490 (3)
C11—N21.418 (3)1.420 (2)
C14—Cl11.7424 (19)
C1—C7—C8119.5 (4)112.92 (18)116.77 (18)115.46 (14)
O1—C8—O2127.1 (4)126.2 (2)125.5 (2)126.13 (16)
O1—C8—C7123.1 (4)118.7 (2)118.69 (19)117.85 (15)
O2—C8—C7109.7 (4)115.0 (2)115.77 (18)115.85 (14)
C8—N2—C11125.84 (18)127.67 (14)
C9—N1—C2120.9 (4)121.82 (19)122.86 (17)123.54 (16)
O3—C9—N1121.2 (4)120.6 (2)122.2 (2)122.77 (19)
O3—C9—C10121.8 (4)121.67 (19)122.7 (2)122.22 (19)
N1—C9—C10116.9 (4)117.7 (2)115.10 (19)115.01 (18)
C1-C7-C8-O1-113.6 (5)-44.0 (3)-49.4 (3)-33.8 (2)
C1-C7-C8-O268.2 (5)136.4 (2)131.7 (2)150.49 (15)
C3-C2-N1-C9103.1 (5)-64.3 (3)-59.0 (3)-51.4 (3)
C1-C2-N1-C9-76.7 (5)112.8 (2)120.4 (2)128.08 (19)
a X = Cl1. b X = methyl C11. c for O2 read N2 and for O3 read O2.
 

Acknowledgements

The use of the EPSRC X-ray crystallographic service at Southampton and the valuable assistance of the staff there, particularly in indexing the intensity data from the twinned crystal of (I)[link], are gratefully acknowledged.

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 5| May 2005| Pages o270-o275
doi:10.1107/S0108270105007547
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