3,3-Difluoro-5-nitro-1H-indol-2(3H)-one: sheets of R22(8) and R46(34) rings built from three-centre N—H⋯(O)2 hydrogen bonds

Glidewell, C.; Low, J.N.; Wardell, J.L.

doi:10.1107/S0108270104031026

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 1| January 2005| Pages o57-o59

doi:10.1107/S0108270104031026

3,3-Difluoro-5-nitro-1H-indol-2(3H)-one: sheets of R₂²(8) and R₄⁶(34) rings built from three-centre N—H⋯(O)₂ hydrogen bonds

Christopher Glidewell,^a ^* John N. Low ^b and James L. Wardell ^c

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 25 November 2004; accepted 26 November 2004; online 18 December 2004)

The title compound, C₈H₄F₂N₂O₃, crystallizes with Z′ = 2 in the space group P2₁/c. The molecules are linked into sheets of $[R_{2}^{2}]$ (8) and $[R_{4}^{6}]$ (34) rings by two independent asymmetric three-centre N—H⋯(O)₂ hydrogen bonds [H⋯O = 2.15/2.57 Å in one system and 2.23/2.46 Å in the other; N⋯O = 2.8959 (17)/3.2972 (16) and 2.9561 (16)/3.1774 (15) Å; N—H⋯O = 142/140 and 140/139°; O⋯H⋯O = 77 and 79°].

Comment

Indoline-2,3-diones (isatins) are very versatile synthetic substrates, useful both in the synthesis of heterocyclic compounds and as raw materials for drugs (da Silva et al., 2001 ). 3,3-Difluorooxindolones, prepared from indoline-2,3-diones by reaction with (diethylamino)sulfur trifluoride (Torres et al., 1999 ), have been shown to be particularly valuable precursors of pharmaceutically active materials (Boechat & Pinto, 2000 ). We report here the molecular and supramolecular structure of the title compound, (I), a typical simply substituted 3,3-difluorooxindolone.

Compound (I) (Fig. 1) crystallizes in space group P2₁/c with Z′ = 2. The bond distances and angles within the two independent molecules are very similar (Table 1), but there are a number of unusual values consistently observed for the two molecules. The distances Cn2—Cn3 (n = 1 or 2) are long for their type, where the mean value (Allen et al., 1987 ) is 1.511 Å and the upper-quartile value 1.521 Å. In addition, there are indications of weak bond fixation within the aryl rings. Likewise, the interbond angles at both Cn2 and Cn3 show some unexpected values. In particular, the opposed pair of angles Fn31—Cn3—Fn32 and Cn2—Cn3—Cn3A (n = 1 or 2) are all significantly less than the idealized tetrahedral values; normally, the distortions in opposed pairs of angles are such that one angle is significantly larger and one is significantly smaller than the idealized value. While the bicyclic skeletons are essentially planar, the nitro groups are both twisted away from these planes. The nitro groups containing atoms N15 and N25 make dihedral angles with the adjacent rings of 13.2 (2) and 15.6 (2)°, respectively. The sense of these rotations, as shown by the key torsion angles (Table 1), indicates approximate twofold rotational symmetry for the selected asymmetric unit.

The two independent molecules of (I) are linked by paired N—H⋯O hydrogen bonds with carbonyl acceptors (Table 2), the dimensions of which differ sufficiently to preclude the possibility of any additional symmetry. These two interactions are each, in fact, one component of a planar but asymmetric three-centre N—H⋯(O)₂ system, in each of which the second acceptor is a nitro O atom, and these longer, and weaker, components link the bimolecular aggregates (Fig. 1) into continuous sheets.

Atom N11 in the type 1 molecule (n = 1) at (x, y, z) acts as hydrogen-bond donor to nitro atom O252 in the type 2 molecule (n = 2) at (1 − x, y − $[{1\over 2}]$ , $[{1\over 2}]$ − z), so forming a C ₁²(9)[ $[R_{2}^{2}]$ (8)] chain of rings (Bernstein et al., 1995 ) running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{1\over 2}]$ , y, $[{1\over 4}]$ ) (Fig. 2). Similarly, atom N21 at (x, y, z) acts as hydrogen-bond donor to O152 at (−x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z), so producing a second C ₁²(9)[ $[R_{2}^{2}]$ (8)] chain of rings, this time along (0, y, $[{3\over 4}]$ ) (Fig. 3). The combination of these two chain motifs generates a (101) sheet containing $[R_{2}^{2}]$ (8) and $[R_{4}^{6}]$ (34) rings (Fig. 4), in which each bimolecular aggregate is linked to four others. Hence, if these aggregates are regarded as the nodes of the resulting net, this is of the (4,4)-type (Batten & Robson, 1998 ). Two (101) sheets, related to one another by inversion, pass through each unit cell.

There are neither C—H⋯π(arene) hydrogen bonds nor aromatic π–π stacking interactions between the components of adjacent sheets. The only significant C—H⋯O hydrogen bonds (Table 2) all lie within a single (101) sheet. There are some short F⋯N contacts involving nitro N atoms between molecules in adjacent sheets, namely C15—N15⋯F232ⁱ, with N15⋯F232ⁱ = 2.915 (2) Å and C15—N15⋯F232ⁱ = 109.6 (2)° [symmetry code: (i) −x, 1 − y, 1 − z], and C25—H25⋯F232ⁱⁱ, with N25⋯F231ⁱⁱ = 2.947 (2) Å and C25—N25⋯F231ⁱⁱ = 91.2 (2)° [symmetry code: (ii) x, $[{3\over 2}]$ − y, z − $[{1\over 2}]$ ], but the status of such dipolar contacts, in terms of their possible structural significance, has not yet been established.

Figure 1
The two independent molecules in compound (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2
A stereoview of part of the crystal structure of (I

), showing the formation of a chain of rings along ( $[{1\over 2}]$ , y, $[{1\over 4}]$ ). For the sake of clarity, H atoms bonded to C atoms have been omitted.

Figure 3
A stereoview of part of the crystal structure of (I

), showing the formation of a chain of rings along (0, y, $[{3\over 4}]$ ). For the sake of clarity, H atoms bonded to C atoms have been omitted.

Figure 4
A stereoview of part of the crystal structure of (I

), showing the formation of a (101) sheet of $[R_{2}^{2}]$ (8) and $[R_{4}^{6}]$ (34) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Experimental

The title compound was obtained according to the procedure published by Torres et al. (1999) [m.p. 459–460 K; literature m.p. 461–462 K (Torres et al., 1999)]. Crystals of (I) suitable for single-crystal X-ray diffraction were obtained by slow evaporation of a solution in acetonitrile.

Crystal data

C₈H₄F₂N₂O₃
M_r = 214.13
Monoclinic, P2₁/c
a = 11.0529 (4) Å
b = 15.4381 (6) Å
c = 9.2768 (4) Å
β = 90.951 (2)°
V = 1582.74 (11) Å³
Z = 8
D_x = 1.797 Mg m⁻³
Mo Kα radiation
Cell parameters from 3611 reflections
θ = 3.1–27.5°
μ = 0.17 mm⁻¹
T = 120 (2) K
Block, yellow
0.04 × 0.04 × 0.03 mm

Data collection

Bruker-Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan, (SADABS; Sheldrick, 2003 ) T_min = 0.980, T_max = 0.995
18 600 measured reflections
3611 independent reflections
2980 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 27.5°
h = −11 → 14
k = −19 → 20
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.04
3611 reflections
271 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0405P)² + 0.7598P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

N11—C12	1.3668 (19)
C12—C13	1.5576 (19)
C13—C13A	1.4886 (19)
C13A—C14	1.3744 (19)
C14—C15	1.3907 (19)
C15—C16	1.3868 (19)
C16—C17	1.3980 (19)
C17—C17A	1.387 (2)
C17A—N11	1.4064 (17)
C13A—C17A	1.4031 (19)
C12—O12	1.2070 (17)
C13—F131	1.3728 (16)
C13—F132	1.3534 (16)
C15—N15	1.4644 (17)
N15—O151	1.2294 (15)
N15—O152	1.2361 (15)
N21—C22	1.3602 (18)
C22—C23	1.5562 (19)
C23—C23A	1.4863 (19)
C23A—C24	1.3761 (19)
C24—C25	1.3925 (19)
C25—C26	1.3899 (19)
C26—C27	1.3963 (19)
C27—C27A	1.388 (2)
C27A—N21	1.4109 (17)
C23A—C27A	1.3999 (19)
C22—O22	1.2085 (18)
C23—F231	1.3641 (16)
C23—F232	1.3620 (16)
C25—N25	1.4662 (17)
N25—O251	1.2327 (15)
N25—O252	1.2301 (15)

N11—C12—C13	106.05 (11)
N11—C12—O12	129.45 (13)
O12—C12—C13	124.51 (13)
F131—C13—F132	105.94 (11)
C12—C13—C13A	103.80 (11)
N21—C22—C23	106.46 (11)
N21—C22—O22	129.78 (13)
O22—C22—C23	123.75 (13)
F231—C23—F232	106.00 (11)
C22—C23—C23A	103.84 (11)

C14—C15—N15—O151	13.26 (19)
C24—C25—N25—O251	15.37 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O22	0.88	2.15	2.8959 (17)	142
N11—H11⋯O252ⁱ	0.88	2.57	3.2972 (16)	140
N21—H21⋯O12	0.88	2.23	2.9561 (16)	140
N21—H21⋯O152ⁱⁱ	0.88	2.46	3.1774 (15)	139
C14—H14⋯O251ⁱⁱⁱ	0.95	2.52	3.3102 (18)	140
C17—H17⋯O252ⁱ	0.95	2.59	3.3708 (18)	140
C24—H24⋯O151^iv	0.95	2.46	3.2766 (18)	144
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x-1, y, z+1; (iv) x+1, y, z-1.

The space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 Å and N—H distances of 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N).

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270104031026/sk1799sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104031026/sk1799Isup2.hkl

Comment top

2,3-Indolinediones (isatins) are very versatile synthetic substrates, useful both in the synthesis of heterocyclic compounds, and as raw materials for drugs (da Silva et al., 2001). 3,3-Difluoro-2-oxindoles, prepared from 2,3-indolinediones by reaction with (diethylamino)sulfur trifluoride (Torres et al., 1999) have been shown to be particularly valuable precursors of pharmaceutically active materials (Boechat & Pinto, 2000). Here we report the molecular and supramolecular structure of the title compound, (I), a typical simply substituted 3,3-difluoro-2-oxindole.

Compound (I) (Fig. 1) crystallizes in space group P2₁/c with Z' = 2. The bond distances and angles within the two independent molecules are very similar (Table 1), but there are a number of unusual values consistently observed for the two molecules. The distances Cn2—Cn3 (n = 1 or 2) are long for their type, where the mean value (Allen et al., 1987) is 1.511 Å and the upper-quartile value 1.521 Å. In addition, there are indications of weak bond fixation within the aryl rings. Likewise, the interbond angles at both Cn2 and Cn3 show some unexpected values. In particular, the opposed pair of angles Fn31—Cn3—Fn32 and Cn2—Cn3—Cn3A (n = 1 or 2) are all significantly less than the idealized tetrahedral values; normally, the distortions in opposed pairs of angles are such that one angle is significantly larger and one is significantly smaller than the idealized value. While the bicyclic skeletons are essentially planar, the nitro groups are both twisted away from these planes. The nitro groups containing atoms N15 and N25 make dihedral angles with the adjacent rings of 13.2 (2)° and 15.6 (2)°, respectively. The sense of these rotations, as shown by the key torsion angles (Table 1), indicates approximate twofold rotational symmetry for the selected asymmetric unit.

The two independent molecules of (I) are linked by paired N—H···O hydrogen bonds with carbonyl acceptors (Table 2), the dimensions of which differ sufficiently to preclude the possibility of any additional symmetry. These two interactions are each, in fact, one component of a planar but asymmetric three-centre N—H···(O)₂ system, in each of which the second acceptor is a nitro O atom, and these longer, and weaker, components link the bimolecular aggregates (Fig. 1) into continuous sheets.

Atom N11 in the type 1 molecule (n = 1) at (x, y, z) acts as hydrogen-bond donor to nitro atom O252 in the type 2 molecule (n = 2) at (1 − x, y − 1/2, 1/2 − z), so forming a C₁²(9)[R₂²(8)] chain of rings (Bernstein et al., 1995) running parallel to the [010] direction, and generated by the 2₁ screw axis along (1/2, y, 1/4) (Fig. 2). Similarly, atom N21 at (x, y, z) acts as hydrogen-bond donor to O152 at (−x, 1/2 + y, 3/2 − z), so producing a second C₁²(9)[R₂²(8)] chain of rings, this time along (0, y, 3/4) (Fig. 3). The combination of these two chain motifs generates a (101) sheet containing R₂²(8) and R₄⁶(34) rings (Fig. 4), in which each bimolecular aggregate is linked to four others. Hence, if these aggregates are regarded as the nodes of the resulting net, this is of the (4,4) type (Batten & Robson, 1998). Two (101) sheets, related to one another by inversion, pass through each unit cell.

There are neither C—H···π(arene) hydrogen bonds nor aromatic π–π stacking interactions between the components of adjacent sheets. The only significant C—H···O hydrogen bonds (Table 2) all lie within a single (101) sheet. There are some short F···N contacts involving nitro N atoms between molecules in adjacent sheets, namely C15—N15···F232ⁱ, with N15···F232ⁱ 2.915 (2) Å and C15—N15···F232ⁱ 109.6 (2)° [symmetry code (i) −x, 1 − y, 1 − z], and C25—H25···F232ⁱⁱ, with N25···F231ⁱⁱ 2.947 (2) Å and C25—N25···F231ⁱⁱ 91.2 (2)° [symmetry code (ii) x, 3/2 − y, z − 1/2], but the status of such dipolar contacts, in terms of their possible structural significance, has not yet been established.

Experimental top

The title compound was obtained using the procedure published by Torres et al. (1999) [m.p. 459–460 K; literature m.p. 461–462 K (Torres et al., 1999)]. Crystals of (I) suitable for single-crystal X-ray diffraction were obtained by slow evaporation of a solution in acetonitrile.

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle , 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The two independent molecules in compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a chain of rings along (1/2, y, 1/4). For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a chain of rings along (0, y, 3/4). For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a (101) sheet of R₂²(8) and R₄⁶_{(34) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.}

3,3-Difluoro-5-nitro-1H-indol-2(3H)-one top

Crystal data top

C₈H₄F₂N₂O₃	F(000) = 864
M_r = 214.13	D_x = 1.797 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3611 reflections
a = 11.0529 (4) Å	θ = 3.1–27.5°
b = 15.4381 (6) Å	µ = 0.17 mm⁻¹
c = 9.2768 (4) Å	T = 120 K
β = 90.951 (2)°	Block, yellow
V = 1582.74 (11) Å³	0.04 × 0.04 × 0.03 mm
Z = 8

Data collection top

Bruker-Nonius KappaCCD diffractometer	3611 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −11→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −19→20
T_min = 0.980, T_max = 0.995	l = −12→12
18600 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0405P)² + 0.7598P] where P = (F_o² + 2F_c²)/3
3611 reflections	(Δ/σ)_max = 0.001
271 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₈H₄F₂N₂O₃	V = 1582.74 (11) Å³
M_r = 214.13	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.0529 (4) Å	µ = 0.17 mm⁻¹
b = 15.4381 (6) Å	T = 120 K
c = 9.2768 (4) Å	0.04 × 0.04 × 0.03 mm
β = 90.951 (2)°

Data collection top

Bruker-Nonius KappaCCD diffractometer	3611 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2980 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.995	R_int = 0.033
18600 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.04	Δρ_max = 0.31 e Å⁻³
3611 reflections	Δρ_min = −0.24 e Å⁻³
271 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F131	−0.04435 (7)	0.75196 (5)	0.68875 (9)	0.0225 (2)
F132	0.06701 (8)	0.74983 (5)	0.88442 (9)	0.0231 (2)
O12	0.22009 (9)	0.73174 (7)	0.63905 (11)	0.0235 (2)
O151	−0.29573 (10)	0.53040 (7)	1.05503 (12)	0.0301 (3)
O152	−0.23822 (9)	0.39721 (6)	1.02704 (11)	0.0239 (2)
N11	0.13652 (11)	0.59334 (8)	0.64370 (13)	0.0212 (3)
N15	−0.23069 (10)	0.47540 (8)	0.99992 (13)	0.0194 (3)
C12	0.14473 (13)	0.67972 (9)	0.67466 (15)	0.0191 (3)
C13	0.03345 (13)	0.70129 (9)	0.76904 (15)	0.0180 (3)
C13A	−0.01902 (12)	0.61490 (9)	0.80219 (15)	0.0172 (3)
C14	−0.11111 (12)	0.59184 (9)	0.89226 (15)	0.0175 (3)
C15	−0.13848 (12)	0.50402 (9)	0.89886 (14)	0.0175 (3)
C16	−0.07966 (13)	0.44197 (9)	0.81771 (15)	0.0209 (3)
C17	0.01354 (13)	0.46609 (9)	0.72587 (16)	0.0217 (3)
C17A	0.04350 (12)	0.55325 (9)	0.72094 (15)	0.0185 (3)
F231	0.57606 (8)	0.56843 (5)	0.34072 (9)	0.0236 (2)
F232	0.44907 (8)	0.57528 (5)	0.15914 (9)	0.0239 (2)
O22	0.32454 (11)	0.58867 (7)	0.43013 (13)	0.0324 (3)
O251	0.78901 (9)	0.79173 (7)	−0.05958 (11)	0.0239 (2)
O252	0.79517 (9)	0.91845 (6)	0.04203 (11)	0.0236 (2)
N21	0.39276 (11)	0.72992 (7)	0.39912 (13)	0.0194 (3)
N25	0.75454 (10)	0.84455 (7)	0.03053 (12)	0.0175 (2)
C22	0.39055 (13)	0.64264 (9)	0.37930 (15)	0.0210 (3)
C23	0.49404 (13)	0.62130 (9)	0.27326 (15)	0.0185 (3)
C23A	0.54302 (12)	0.70766 (9)	0.23409 (15)	0.0170 (3)
C24	0.63337 (12)	0.72974 (9)	0.14063 (14)	0.0167 (3)
C25	0.65924 (12)	0.81772 (9)	0.12913 (14)	0.0165 (3)
C26	0.59836 (13)	0.88096 (9)	0.20610 (15)	0.0198 (3)
C27	0.50592 (13)	0.85779 (9)	0.29936 (16)	0.0216 (3)
C27A	0.48003 (12)	0.77018 (9)	0.31233 (15)	0.0174 (3)
H11	0.1836	0.5662	0.5829	0.025*
H14	−0.1537	0.6336	0.9470	0.021*
H16	−0.1028	0.3829	0.8245	0.025*
H17	0.0546	0.4245	0.6692	0.026*
H21	0.3455	0.7579	0.4588	0.023*
H24	0.6757	0.6874	0.0870	0.020*
H26	0.6197	0.9402	0.1952	0.024*
H27	0.4626	0.9002	0.3517	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F131	0.0225 (4)	0.0205 (4)	0.0244 (5)	0.0020 (3)	0.0020 (3)	0.0053 (3)
F132	0.0289 (5)	0.0210 (4)	0.0195 (4)	−0.0045 (4)	0.0034 (3)	−0.0041 (3)
O12	0.0216 (5)	0.0255 (5)	0.0237 (6)	−0.0041 (4)	0.0053 (4)	0.0027 (4)
O151	0.0303 (6)	0.0212 (5)	0.0395 (7)	0.0025 (5)	0.0195 (5)	−0.0032 (5)
O152	0.0254 (5)	0.0165 (5)	0.0301 (6)	−0.0018 (4)	0.0057 (4)	0.0039 (4)
N11	0.0219 (6)	0.0209 (6)	0.0210 (6)	0.0002 (5)	0.0092 (5)	−0.0013 (5)
N15	0.0188 (6)	0.0181 (6)	0.0215 (6)	−0.0012 (5)	0.0040 (5)	0.0003 (5)
C12	0.0196 (7)	0.0220 (7)	0.0156 (6)	0.0006 (6)	0.0008 (5)	0.0030 (5)
C13	0.0202 (7)	0.0171 (7)	0.0167 (7)	−0.0002 (5)	0.0013 (5)	−0.0006 (5)
C13A	0.0193 (7)	0.0156 (6)	0.0168 (7)	0.0007 (5)	0.0012 (5)	0.0009 (5)
C14	0.0180 (7)	0.0167 (6)	0.0180 (6)	0.0021 (5)	0.0042 (5)	−0.0009 (5)
C15	0.0155 (6)	0.0187 (7)	0.0184 (7)	0.0000 (5)	0.0038 (5)	0.0007 (5)
C16	0.0222 (7)	0.0169 (7)	0.0236 (7)	0.0005 (6)	0.0047 (6)	−0.0011 (5)
C17	0.0236 (7)	0.0187 (7)	0.0230 (7)	0.0022 (6)	0.0075 (6)	−0.0032 (6)
C17A	0.0187 (7)	0.0205 (7)	0.0165 (7)	0.0001 (6)	0.0039 (5)	0.0005 (5)
F231	0.0249 (4)	0.0188 (4)	0.0271 (5)	0.0032 (3)	0.0030 (3)	0.0041 (3)
F232	0.0270 (5)	0.0226 (4)	0.0222 (4)	−0.0065 (4)	0.0029 (3)	−0.0048 (3)
O22	0.0337 (6)	0.0247 (6)	0.0395 (7)	−0.0076 (5)	0.0199 (5)	−0.0020 (5)
O251	0.0259 (5)	0.0242 (5)	0.0219 (5)	0.0021 (4)	0.0100 (4)	−0.0019 (4)
O252	0.0243 (5)	0.0196 (5)	0.0272 (6)	−0.0056 (4)	0.0059 (4)	0.0015 (4)
N21	0.0191 (6)	0.0184 (6)	0.0208 (6)	0.0001 (5)	0.0084 (5)	−0.0010 (5)
N25	0.0165 (6)	0.0184 (6)	0.0177 (6)	0.0015 (5)	0.0024 (4)	0.0019 (4)
C22	0.0204 (7)	0.0210 (7)	0.0217 (7)	−0.0015 (6)	0.0053 (5)	−0.0016 (6)
C23	0.0192 (7)	0.0173 (7)	0.0190 (7)	−0.0012 (5)	0.0027 (5)	−0.0009 (5)
C23A	0.0177 (6)	0.0162 (7)	0.0172 (6)	−0.0002 (5)	0.0014 (5)	0.0000 (5)
C24	0.0162 (6)	0.0171 (7)	0.0169 (7)	0.0018 (5)	0.0025 (5)	−0.0019 (5)
C25	0.0151 (6)	0.0181 (7)	0.0164 (6)	−0.0006 (5)	0.0031 (5)	0.0018 (5)
C26	0.0209 (7)	0.0149 (7)	0.0236 (7)	0.0000 (5)	0.0037 (5)	0.0000 (5)
C27	0.0223 (7)	0.0183 (7)	0.0243 (7)	0.0022 (6)	0.0065 (6)	−0.0021 (6)
C27A	0.0162 (6)	0.0191 (7)	0.0170 (7)	0.0002 (5)	0.0034 (5)	0.0006 (5)

Geometric parameters (Å, º) top

N11—C12	1.3668 (19)	N21—C22	1.3602 (18)
C12—C13	1.5576 (19)	C22—C23	1.5562 (19)
C13—C13A	1.4886 (19)	C23—C23A	1.4863 (19)
C13A—C14	1.3744 (19)	C23A—C24	1.3761 (19)
C14—C15	1.3907 (19)	C24—C25	1.3925 (19)
C15—C16	1.3868 (19)	C25—C26	1.3899 (19)
C16—C17	1.3980 (19)	C26—C27	1.3963 (19)
C17—C17A	1.387 (2)	C27—C27A	1.388 (2)
C17A—N11	1.4064 (17)	C27A—N21	1.4109 (17)
C13A—C17A	1.4031 (19)	C23A—C27A	1.3999 (19)
C12—O12	1.2070 (17)	C22—O22	1.2085 (18)
C13—F131	1.3728 (16)	C23—F231	1.3641 (16)
C13—F132	1.3534 (16)	C23—F232	1.3620 (16)
C15—N15	1.4644 (17)	C25—N25	1.4662 (17)
N15—O151	1.2294 (15)	N25—O251	1.2327 (15)
N15—O152	1.2361 (15)	N25—O252	1.2301 (15)
N11—H11	0.88	N21—H21	0.88
C14—H14	0.95	C24—H24	0.95
C16—H16	0.95	C26—H26	0.95
C17—H17	0.95	C27—H27	0.95

C12—N11—C17A	111.65 (12)	C22—N21—C27A	111.73 (11)
C12—N11—H11	124.2	C22—N21—H21	124.1
C17A—N11—H11	124.2	C27A—N21—H21	124.1
N11—C12—C13	106.05 (11)	N21—C22—C23	106.46 (11)
N11—C12—O12	129.45 (13)	N21—C22—O22	129.78 (13)
O12—C12—C13	124.51 (13)	O22—C22—C23	123.75 (13)
F131—C13—F132	105.94 (11)	F231—C23—F232	106.00 (11)
C12—C13—C13A	103.80 (11)	C22—C23—C23A	103.84 (11)
F132—C13—C13A	115.80 (11)	F232—C23—C23A	114.05 (11)
F131—C13—C13A	112.33 (11)	F231—C23—C23A	114.01 (11)
F132—C13—C12	110.75 (11)	F232—C23—C22	109.82 (11)
F131—C13—C12	108.07 (11)	F231—C23—C22	109.06 (11)
C14—C13A—C17A	121.81 (13)	C24—C23A—C27A	121.88 (13)
C14—C13A—C13	130.75 (13)	C24—C23A—C23	130.34 (13)
C17A—C13A—C13	107.44 (12)	C27A—C23A—C23	107.78 (12)
C13A—C14—C15	116.30 (12)	C23A—C24—C25	116.23 (12)
C13A—C14—H14	121.8	C23A—C24—H24	121.9
C15—C14—H14	121.8	C25—C24—H24	121.9
C16—C15—C14	123.03 (13)	C26—C25—C24	122.95 (12)
C16—C15—N15	118.47 (12)	C26—C25—N25	118.75 (12)
C14—C15—N15	118.46 (12)	C24—C25—N25	118.29 (12)
O151—N15—O152	123.23 (12)	O252—N25—O251	123.77 (12)
O151—N15—C15	118.41 (11)	O252—N25—C25	118.23 (11)
O152—N15—C15	118.35 (11)	O251—N25—C25	118.00 (11)
C15—C16—C17	120.25 (13)	C25—C26—C27	120.26 (13)
C15—C16—H16	119.9	C25—C26—H26	119.9
C17—C16—H16	119.9	C27—C26—H26	119.9
C17A—C17—C16	117.21 (13)	C27A—C27—C26	117.21 (13)
C17A—C17—H17	121.4	C27A—C27—H27	121.4
C16—C17—H17	121.4	C26—C27—H27	121.4
C17—C17A—C13A	121.36 (13)	C27—C27A—C23A	121.45 (12)
C17—C17A—N11	128.38 (13)	C27—C27A—N21	128.50 (13)
C13A—C17A—N11	110.24 (12)	C23A—C27A—N21	110.05 (12)

C17A—N11—C12—O12	172.40 (14)	C27A—N21—C22—O22	−176.36 (16)
C17A—N11—C12—C13	−7.80 (15)	C27A—N21—C22—C23	3.73 (16)
O12—C12—C13—F132	−46.13 (18)	O22—C22—C23—F232	54.01 (19)
N11—C12—C13—F132	134.05 (12)	N21—C22—C23—F232	−126.07 (12)
O12—C12—C13—F131	69.50 (17)	O22—C22—C23—F231	−61.74 (18)
N11—C12—C13—F131	−110.32 (12)	N21—C22—C23—F231	118.17 (12)
O12—C12—C13—C13A	−171.05 (13)	O22—C22—C23—C23A	176.35 (15)
N11—C12—C13—C13A	9.13 (14)	N21—C22—C23—C23A	−3.73 (15)
F132—C13—C13A—C14	51.4 (2)	F232—C23—C23A—C24	−58.4 (2)
F131—C13—C13A—C14	−70.49 (19)	F231—C23—C23A—C24	63.6 (2)
C12—C13—C13A—C14	173.01 (14)	C22—C23—C23A—C24	−177.87 (14)
F132—C13—C13A—C17A	−128.87 (13)	F232—C23—C23A—C27A	121.93 (13)
F131—C13—C13A—C17A	109.24 (13)	F231—C23—C23A—C27A	−116.12 (13)
C12—C13—C13A—C17A	−7.26 (14)	C22—C23—C23A—C27A	2.43 (15)
C17A—C13A—C14—C15	0.3 (2)	C27A—C23A—C24—C25	0.5 (2)
C13—C13A—C14—C15	179.97 (14)	C23—C23A—C24—C25	−179.17 (14)
C13A—C14—C15—C16	−1.5 (2)	C23A—C24—C25—C26	−0.2 (2)
C13A—C14—C15—N15	176.25 (12)	C23A—C24—C25—N25	−179.79 (12)
C16—C15—N15—O151	−168.87 (13)	C26—C25—N25—O252	15.50 (19)
C14—C15—N15—O151	13.26 (19)	C24—C25—N25—O252	−164.89 (12)
C16—C15—N15—O152	12.06 (19)	C26—C25—N25—O251	−164.24 (13)
C14—C15—N15—O152	−165.81 (13)	C24—C25—N25—O251	15.37 (18)
C14—C15—C16—C17	1.3 (2)	C24—C25—C26—C27	−0.5 (2)
N15—C15—C16—C17	−176.48 (13)	N25—C25—C26—C27	179.07 (13)
C15—C16—C17—C17A	0.2 (2)	C25—C26—C27—C27A	0.9 (2)
C16—C17—C17A—C13A	−1.4 (2)	C26—C27—C27A—C23A	−0.7 (2)
C16—C17—C17A—N11	176.66 (14)	C26—C27—C27A—N21	179.38 (14)
C14—C13A—C17A—C17	1.2 (2)	C24—C23A—C27A—C27	−0.1 (2)
C13—C13A—C17A—C17	−178.54 (13)	C23—C23A—C27A—C27	179.67 (13)
C14—C13A—C17A—N11	−177.20 (13)	C24—C23A—C27A—N21	179.91 (13)
C13—C13A—C17A—N11	3.04 (16)	C23—C23A—C27A—N21	−0.36 (16)
C12—N11—C17A—C17	−174.99 (15)	C22—N21—C27A—C27	177.70 (14)
C12—N11—C17A—C13A	3.29 (17)	C22—N21—C27A—C23A	−2.27 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O22	0.88	2.15	2.8959 (17)	142
N11—H11···O252ⁱ	0.88	2.57	3.2972 (16)	140
N21—H21···O12	0.88	2.23	2.9561 (16)	140
N21—H21···O152ⁱⁱ	0.88	2.46	3.1774 (15)	139
C14—H14···O251ⁱⁱⁱ	0.95	2.52	3.3102 (18)	140
C17—H17···O252ⁱ	0.95	2.59	3.3708 (18)	140
C24—H24···O151^iv	0.95	2.46	3.2766 (18)	144

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+3/2; (iii) x−1, y, z+1; (iv) x+1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₈H₄F₂N₂O₃
M_r	214.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	11.0529 (4), 15.4381 (6), 9.2768 (4)
β (°)	90.951 (2)
V (Å³)	1582.74 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.04 × 0.04 × 0.03

Data collection
Diffractometer	Bruker-Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.980, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	18600, 3611, 2980
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.04
No. of reflections	3611
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.24

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle , 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top

N11—C12	1.3668 (19)	N21—C22	1.3602 (18)
C12—C13	1.5576 (19)	C22—C23	1.5562 (19)
C13—C13A	1.4886 (19)	C23—C23A	1.4863 (19)
C13A—C14	1.3744 (19)	C23A—C24	1.3761 (19)
C14—C15	1.3907 (19)	C24—C25	1.3925 (19)
C15—C16	1.3868 (19)	C25—C26	1.3899 (19)
C16—C17	1.3980 (19)	C26—C27	1.3963 (19)
C17—C17A	1.387 (2)	C27—C27A	1.388 (2)
C17A—N11	1.4064 (17)	C27A—N21	1.4109 (17)
C13A—C17A	1.4031 (19)	C23A—C27A	1.3999 (19)
C12—O12	1.2070 (17)	C22—O22	1.2085 (18)
C13—F131	1.3728 (16)	C23—F231	1.3641 (16)
C13—F132	1.3534 (16)	C23—F232	1.3620 (16)
C15—N15	1.4644 (17)	C25—N25	1.4662 (17)
N15—O151	1.2294 (15)	N25—O251	1.2327 (15)
N15—O152	1.2361 (15)	N25—O252	1.2301 (15)

N11—C12—C13	106.05 (11)	N21—C22—C23	106.46 (11)
N11—C12—O12	129.45 (13)	N21—C22—O22	129.78 (13)
O12—C12—C13	124.51 (13)	O22—C22—C23	123.75 (13)
F131—C13—F132	105.94 (11)	F231—C23—F232	106.00 (11)
C12—C13—C13A	103.80 (11)	C22—C23—C23A	103.84 (11)

C14—C15—N15—O151	13.26 (19)	C24—C25—N25—O251	15.37 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O22	0.88	2.15	2.8959 (17)	142
N11—H11···O252ⁱ	0.88	2.57	3.2972 (16)	140
N21—H21···O12	0.88	2.23	2.9561 (16)	140
N21—H21···O152ⁱⁱ	0.88	2.46	3.1774 (15)	139
C14—H14···O251ⁱⁱⁱ	0.95	2.52	3.3102 (18)	140
C17—H17···O252ⁱ	0.95	2.59	3.3708 (18)	140
C24—H24···O151^iv	0.95	2.46	3.2766 (18)	144

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+3/2; (iii) x−1, y, z+1; (iv) x+1, y, z−1.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Volume 61| Part 1| January 2005| Pages o57-o59

doi:10.1107/S0108270104031026

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