Hydrogen bonding in C-substituted nitroanilines: molecular ladders in 2-trifluoromethyl-4-nitroaniline and sheets of R(12) and R(32) rings in 3-trifluoromethyl-4-nitroaniline

In 2-tri­fluoro­methyl-4-nitro­aniline, C₇H₅F₃N₂O₂, (I), the mol­ecules lie across a mirror plane in space group Pnma. The mol­ecules are linked by paired N-H...O hydrogen bonds to form a C(8)[R(6)] chain of rings, pairs of which are linked into a molecular ladder by a single C-H...O hydrogen bond. The isomeric 3-tri­fluoro­methyl-4-nitro­aniline, (II), has Z' = 2 in space group P2₁/c. Each mol­ecule is linked to four others by N-H...O hydrogen bonds to form sheets built from alternating R(12) and R(32) rings.

S1. Comment

In the structure of 4-nitroaniline (Tonogaki et al., 1993), each molecule is linked to four others by means of N—H···O hydrogen bonds, and the molecules are thereby linked into (4,4) nets (Batten & Robson, 1998). The resulting sheets, which contain a single type of R₄⁴(22) rings, are weakly linked by aromatic π···π stacking interactions. Introduction of a single methyl group in 2-methyl-4-nitroaniline gives rise to a different structure in the form of a three-dimensional framework, even though each molecule is still linked to four others by N—H···O hydrogen bonds (Ferguson et al., 2001). The structure now consists of two intersecting sets of sheets built from a single type of R₈⁸(54) ring. However, entirely different patterns of N—H···O hydrogen bonds are observed in the two polymorphs of 2-iodo-4-nitroaniline (McWilliam et al., 2001). In the triclinic polymorph, the molecules are linked into chains via a rather unusual supramolecular synthon comprising pairs of N—H···O hydrogen bonds forming an R₂²(6) ring, while in the orthorhombic polymorph, each molecule acts as just a single donor and single acceptor of N—H···O hydrogen bonds, with formation of simple C(8) chains. In both polymorphs, the chains are further linked into sheets by means of I···NO₂ interactions.

Continuing our study of C-substituted nitroanilines (Cannon et al., 2001; Ferguson et al., 2001; Glidewell et al., 2001; McWilliam et al., 2001; Zakaria et al., 2001; Garden et al., 2001), we have now investigated the isomeric pair 2-trifluoromethyl-4-nitroaniline, (I), and 3-trifluoromethyl-4-nitroaniline, (II), which exhibit yet further modes of supramolecular aggregation. \sch

Compound (I) (Fig. 1) crystallizes in space group Pnma with Z' = 1/2, so that all the atoms, apart from two of the F atoms, lie on a mirror plane, selected as that at 1/4. The molecules are linked into chains by N—H···O hydrogen bonds (Table 1) and these chains are linked in pairs by a single C—H···O hydrogen bond. The amino atom N1 in the molecule at (x, 1/4, z) acts as a hydrogen-bond donor via H11 and H12 to O1 and O2, respectively, in the molecule at (x - 1, 1/4, z), so generating by translation a C(8)[R₂²(6)] chain of rings parallel to [100] (Fig. 2), where the R₂²(6) ring is necessarily planar. Four such chains run through each unit cell. A pair of chains related by the 2₁ screw axis along (x, 1/4, 1/4) are weakly linked by a soft hydrogen bond: atom C6 in the molecule at (x, 1/4, z) acts as a hydrogen-bond donor to O2 in the molecule at (x - 1/2, 1/4, 1/2 - z), while atom C6 at (x - 1/2, 1/4, 1/2 - z) in turn acts as a donor to O2 at (x - 1, 1/4, z). This combination of hard and soft hydrogen bonds thus generates a molecular ladder, in which a pair of [100] chains play the role of the uprights, while the C—H···O hydrogen bonds provide the rungs. Between the rungs, there are R₃²(12) rings (Fig. 2). The C(8)[R₂²(6)] chain of rings in (I) is thus analogous to that in triclinic 2-iodo-4-nitroaniline (McWilliam et al., 2001). In this latter compound, the linking of the chains into sheets again involves chains of like polarity, related to one another by translation. Two molecular ladders pass through each unit cell in (I), at y = 1/4 and y = 3/4, but there are no direction-specific interactions between neighbouring ladders.

Compound (II) crystallizes in space group P2₁/c with Z' = 2, and each molecule (Fig. 3) is linked to four others, via N—H···O hydrogen bonds (Table 3), into sheets parallel to (101). The formation of these sheets can readily be analysed in terms of three distinct one-dimensional motifs. There are two spiral chains parallel to [010], each comprising one type of molecule only, and a translational chain parallel to [101] containing both types of molecule.

Atom N11 in the type 1 molecule at (x, y, z) acts as a hydrogen-bond donor, via H12, to O12 in the type 1 molecule at (x - 1, 1/2 + y, 1/2 - z), so producing a C(8) chain parallel to [010] generated by the 2₁ screw axis along (-1/2, y, 1/4) (Fig. 4). Similarly, atom N21 in the type 2 molecule at (x, y, z) acts as a donor, via H22, to O21 in the type 2 molecule at (-x, y - 1/2, 3/2 - z), producing another C(8) spiral, this time generated by the 2₁ axis along (0, y, 3/4). Within the asymmetric unit, atom N21 acts as a donor, via H21, to O11, while atom N11 at (x, y, z) acts as a donor, via H11, to O22 at (x - 1, y, z - 1). The combination of the [101] chain with the two independent [010] chains generates a (101) sheet built of R₄⁴(12) and R₄⁴(32) rings, alternating in checkerboard fashion (Fig. 4). The interior of the large rings is occupied by the CF₃ groups, the conformations of which are such that the two sets of F atoms are meshed together.

The (101) sheets in (II) are weakly linked by aromatic π···π stacking interactions. For the aromatic rings of molecules in adjacent sheets, the minimum distance between the ring centroids of a type 1 molecule at (x, y, z) and a type 2 molecule at (x - 1, 1/2 - y, z - 1/2) is 3.552 (2) Å, with the planes separated by 3.385 (3) Å.

The bond lengths in (I) and (II) present no unexpected features. In compound (II), there is evidence from the exocyclic bond angles (Table 2) for significant repulsion between the adjacent nitro and trifluoromethyl groups.

S2. Experimental

Samples of compounds (I) and (II) were purchased from Aldrich. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethanol.

S3. Refinement

Compound (I) crystallized in the orthorhombic system. The systematic absences permitted space groups Pna2₁ and Pnma; Pnma was selected, and confirmed by the analysis. For compound (II), the space group P2₁/c was uniquely assigned from the systematic absences. H atoms were treated as riding, with C—H = 0.95 and N—H = 0.88 Å.

Computing details

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of the molecule of (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. Part of the crystal structure of (I) showing the linking of pairs of C(8)[R2^2(6)] chains of rings into a molecular ladder. The atoms marked with a star (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (1 + x, 1/4, z), (x - 1, 1/4, z), (x - 1/2, 1/4, 1/2 - z) and (1/2 + x, 1/4, 1/2 - z), respectively.
	Fig. 3. A view of the two independent molecules of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. Part of the crystal structure of (II) showing the formation of a (101) sheet built from R4^4(12) and R4^4(32) rings. The atoms marked with a star (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (x - 1, 1/2 + y, 1/2 - z), (x, 1 + y, z), (-x, 1/2 + y, 3/2 - z) and (x - 1, y, z - 1), respectively.

(I) 2-Trifluoromethyl-4-nitroaniline

Crystal data

C7H5F3N2O2	F(000) = 416
Mr = 206.13	Dx = 1.754 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 961 reflections
a = 9.0274 (4) Å	θ = 2.7–27.6°
b = 6.5933 (4) Å	µ = 0.18 mm^−1
c = 13.1170 (8) Å	T = 150 K
V = 780.73 (8) Å^3	Block, red
Z = 4	0.20 × 0.15 × 0.01 mm

Data collection

Nonius KappaCCD diffractometer	961 independent reflections
Radiation source: fine-focus sealed X-ray tube	725 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ϕ scans, and ω scans with κ offsets	θmax = 27.6°, θmin = 2.7°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −9→11
Tmin = 0.987, Tmax = 0.998	k = −8→8
3944 measured reflections	l = −16→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0691P)^2 + 0.053P] where P = (Fo^2 + 2Fc^2)/3
961 reflections	(Δ/σ)max = 0.001
82 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the `size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	−0.02222 (19)	0.2500	0.01210 (14)	0.0256 (5)
C1	0.1272 (2)	0.2500	0.01781 (15)	0.0192 (5)
C2	0.2192 (2)	0.2500	−0.07008 (15)	0.0188 (5)
C3	0.3712 (2)	0.2500	−0.06062 (15)	0.0191 (5)
C4	0.4351 (2)	0.2500	0.03545 (15)	0.0186 (5)
C5	0.3483 (2)	0.2500	0.12311 (15)	0.0219 (5)
C6	0.1968 (2)	0.2500	0.11432 (16)	0.0238 (5)
C7	0.1532 (2)	0.2500	−0.17425 (15)	0.0250 (5)
F1	0.06499 (11)	0.41227 (17)	−0.19085 (7)	0.0370 (4)
F3	0.25374 (15)	0.2500	−0.24767 (9)	0.0459 (5)
N2	0.59518 (19)	0.2500	0.04274 (13)	0.0222 (4)
O1	0.66780 (16)	0.2500	−0.03648 (11)	0.0310 (4)
O2	0.65362 (17)	0.2500	0.12830 (11)	0.0325 (4)
H12	−0.0756	0.2500	0.0683	0.031*
H11	−0.0662	0.2500	−0.0478	0.031*
H3	0.4320	0.2500	−0.1197	0.023*
H5	0.3935	0.2500	0.1885	0.026*
H6	0.1376	0.2500	0.1742	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0151 (9)	0.0348 (13)	0.0269 (10)	0.000	0.0023 (7)	0.000
C1	0.0168 (10)	0.0195 (12)	0.0214 (10)	0.000	0.0017 (8)	0.000
C2	0.0172 (10)	0.0233 (12)	0.0158 (10)	0.000	−0.0024 (8)	0.000
C3	0.0184 (9)	0.0244 (12)	0.0144 (9)	0.000	0.0020 (8)	0.000
C4	0.0166 (10)	0.0217 (12)	0.0175 (9)	0.000	−0.0018 (8)	0.000
C5	0.0247 (11)	0.0276 (12)	0.0134 (9)	0.000	−0.0025 (8)	0.000
C6	0.0285 (11)	0.0293 (12)	0.0138 (9)	0.000	0.0049 (9)	0.000
C7	0.0194 (10)	0.0364 (14)	0.0193 (10)	0.000	−0.0053 (8)	0.000
F1	0.0389 (6)	0.0414 (7)	0.0308 (5)	0.0069 (4)	−0.0145 (4)	0.0058 (4)
F3	0.0280 (8)	0.0960 (15)	0.0136 (6)	0.000	−0.0010 (5)	0.000
N2	0.0193 (9)	0.0249 (11)	0.0224 (9)	0.000	−0.0058 (7)	0.000
O1	0.0154 (8)	0.0502 (12)	0.0274 (8)	0.000	0.0031 (7)	0.000
O2	0.0253 (8)	0.0487 (11)	0.0235 (8)	0.000	−0.0109 (7)	0.000

Geometric parameters (Å, º)

N1—C1	1.351 (3)	C4—N2	1.448 (3)
N1—H11	0.8800	C5—C6	1.373 (3)
N1—H12	0.8800	C5—H5	0.9500
C1—C6	1.413 (3)	C6—H6	0.9500
C1—C2	1.421 (3)	C7—F3	1.324 (2)
C2—C3	1.377 (3)	C7—F1^i	1.3511 (17)
C2—C7	1.491 (3)	C7—F1	1.3511 (17)
C3—C4	1.386 (3)	N2—O1	1.229 (2)
C3—H3	0.9500	N2—O2	1.240 (2)
C4—C5	1.392 (3)
C1—N1—H11	120.0	C6—C5—C4	119.46 (18)
C1—N1—H12	120.0	C6—C5—H5	120.3
H11—N1—H12	120.0	C4—C5—H5	120.3
N1—C1—C6	119.56 (18)	C5—C6—C1	121.20 (18)
N1—C1—C2	122.60 (18)	C5—C6—H6	119.4
C6—C1—C2	117.83 (19)	C1—C6—H6	119.4
C3—C2—C1	120.61 (17)	F3—C7—F1^i	106.67 (12)
C3—C2—C7	118.76 (17)	F3—C7—F1	106.67 (12)
C1—C2—C7	120.63 (18)	F1^i—C7—F1	104.72 (17)
C2—C3—C4	119.78 (18)	F3—C7—C2	113.10 (17)
C2—C3—H3	120.1	F1^i—C7—C2	112.54 (11)
C4—C3—H3	120.1	F1—C7—C2	112.54 (11)
C3—C4—C5	121.11 (18)	O1—N2—O2	122.57 (16)
C3—C4—N2	118.40 (17)	O1—N2—C4	118.46 (15)
C5—C4—N2	120.49 (17)	O2—N2—C4	118.97 (16)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O1^ii	0.88	2.41	2.870 (2)	113
N1—H12···O2^ii	0.88	2.57	3.299 (2)	141
C6—H6···O2^iii	0.95	2.59	3.398 (3)	143

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

(II) 3-Trifluoromethyl-4-nitroaniline

Crystal data

C7H5F3N2O2	F(000) = 832
Mr = 206.13	Dx = 1.752 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3541 reflections
a = 7.1048 (2) Å	θ = 3.0–27.5°
b = 15.3832 (5) Å	µ = 0.18 mm^−1
c = 14.3091 (6) Å	T = 150 K
β = 91.9102 (12)°	Plate, yellow
V = 1563.04 (9) Å^3	0.40 × 0.16 × 0.10 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	3541 independent reflections
Radiation source: fine-focus sealed X-ray tube	2369 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.812, Tmax = 0.983	k = −17→19
12016 measured reflections	l = −17→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0617P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3541 reflections	Δρmax = 0.26 e Å^−3
254 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0153 (19)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the `size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N11	−0.6318 (2)	0.44448 (11)	0.07857 (11)	0.0299 (4)
C11	−0.5772 (2)	0.38575 (12)	0.14419 (12)	0.0203 (4)
C12	−0.5337 (2)	0.41245 (12)	0.23643 (12)	0.0196 (4)
C13	−0.4776 (2)	0.35482 (11)	0.30538 (11)	0.0180 (4)
C14	−0.4639 (2)	0.26582 (11)	0.28128 (12)	0.0190 (4)
C15	−0.5097 (2)	0.23876 (12)	0.19038 (12)	0.0217 (4)
C16	−0.5656 (2)	0.29701 (12)	0.12290 (12)	0.0218 (4)
C17	−0.4507 (2)	0.39216 (12)	0.40263 (13)	0.0235 (4)
F11	−0.51135 (15)	0.47424 (7)	0.40579 (7)	0.0308 (3)
F12	−0.27187 (14)	0.39329 (7)	0.43395 (7)	0.0336 (3)
F13	−0.55087 (16)	0.34846 (8)	0.46541 (7)	0.0354 (3)
N12	−0.4002 (2)	0.19935 (10)	0.34611 (11)	0.0238 (4)
O11	−0.31463 (19)	0.22002 (9)	0.41879 (9)	0.0336 (4)
O12	−0.4301 (2)	0.12258 (9)	0.32571 (10)	0.0395 (4)
N21	−0.1232 (2)	0.10727 (10)	0.57317 (11)	0.0288 (4)
C21	−0.0653 (2)	0.16737 (12)	0.63724 (12)	0.0210 (4)
C22	−0.0513 (2)	0.25579 (12)	0.61228 (12)	0.0212 (4)
C23	0.0046 (2)	0.31808 (12)	0.67648 (12)	0.0203 (4)
C24	0.0481 (2)	0.29196 (12)	0.76917 (12)	0.0213 (4)
C25	0.0405 (2)	0.20458 (12)	0.79359 (13)	0.0228 (4)
C26	−0.0158 (2)	0.14327 (12)	0.72908 (12)	0.0231 (4)
C27	0.0342 (2)	0.40838 (12)	0.63987 (13)	0.0262 (4)
F21	0.05603 (16)	0.40859 (7)	0.54741 (8)	0.0374 (3)
F22	0.18993 (14)	0.44588 (7)	0.67764 (8)	0.0343 (3)
F23	−0.11002 (15)	0.46208 (7)	0.65539 (9)	0.0398 (3)
N22	0.0947 (2)	0.35281 (11)	0.84365 (11)	0.0267 (4)
O21	0.0298 (2)	0.42728 (10)	0.83940 (10)	0.0384 (4)
O22	0.19263 (19)	0.32704 (10)	0.91097 (10)	0.0377 (4)
H11	−0.6609	0.4273	0.0212	0.036*
H12	−0.6383	0.5000	0.0931	0.036*
H12A	−0.5433	0.4724	0.2516	0.024*
H15	−0.5020	0.1788	0.1751	0.026*
H16	−0.5967	0.2773	0.0614	0.026*
H22	−0.1301	0.0521	0.5891	0.035*
H21	−0.1538	0.1234	0.5157	0.035*
H22A	−0.0813	0.2728	0.5497	0.025*
H25	0.0746	0.1872	0.8556	0.027*
H26	−0.0213	0.0839	0.7469	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0488 (10)	0.0235 (9)	0.0169 (8)	0.0033 (7)	−0.0083 (7)	0.0008 (7)
C11	0.0212 (9)	0.0243 (11)	0.0155 (9)	−0.0006 (7)	−0.0015 (7)	0.0016 (8)
C12	0.0235 (9)	0.0176 (9)	0.0177 (9)	−0.0015 (7)	−0.0004 (7)	−0.0013 (8)
C13	0.0177 (8)	0.0210 (10)	0.0153 (9)	−0.0021 (7)	−0.0008 (6)	−0.0006 (7)
C14	0.0196 (8)	0.0192 (10)	0.0181 (10)	−0.0005 (7)	−0.0004 (7)	0.0036 (8)
C15	0.0221 (9)	0.0201 (10)	0.0229 (10)	−0.0005 (7)	0.0000 (7)	−0.0044 (8)
C16	0.0250 (9)	0.0251 (11)	0.0153 (9)	−0.0001 (7)	−0.0003 (7)	−0.0026 (8)
C17	0.0289 (10)	0.0225 (11)	0.0190 (10)	−0.0011 (8)	−0.0022 (7)	0.0024 (8)
F11	0.0495 (6)	0.0231 (6)	0.0197 (6)	0.0050 (5)	−0.0019 (5)	−0.0050 (5)
F12	0.0373 (6)	0.0357 (7)	0.0267 (6)	−0.0030 (5)	−0.0140 (5)	−0.0022 (5)
F13	0.0528 (7)	0.0363 (7)	0.0176 (6)	−0.0050 (5)	0.0086 (5)	0.0038 (5)
N12	0.0266 (8)	0.0220 (9)	0.0229 (9)	0.0000 (6)	0.0003 (6)	0.0024 (7)
O11	0.0454 (8)	0.0322 (9)	0.0223 (7)	0.0019 (6)	−0.0123 (6)	0.0032 (6)
O12	0.0626 (10)	0.0165 (8)	0.0387 (9)	0.0009 (7)	−0.0092 (7)	0.0037 (6)
N21	0.0390 (9)	0.0217 (9)	0.0252 (9)	−0.0020 (7)	−0.0065 (7)	0.0001 (7)
C21	0.0177 (8)	0.0221 (10)	0.0230 (10)	0.0002 (7)	−0.0003 (7)	−0.0020 (8)
C22	0.0207 (9)	0.0237 (10)	0.0189 (10)	−0.0004 (7)	−0.0035 (7)	0.0021 (8)
C23	0.0177 (8)	0.0214 (10)	0.0217 (10)	0.0014 (7)	−0.0007 (7)	0.0018 (8)
C24	0.0210 (9)	0.0238 (10)	0.0189 (9)	0.0008 (7)	−0.0010 (7)	−0.0039 (8)
C25	0.0232 (9)	0.0267 (11)	0.0183 (9)	0.0027 (7)	−0.0007 (7)	0.0046 (8)
C26	0.0264 (9)	0.0198 (10)	0.0231 (10)	0.0009 (7)	−0.0001 (7)	0.0044 (8)
C27	0.0295 (10)	0.0229 (11)	0.0256 (11)	−0.0011 (8)	−0.0066 (8)	0.0003 (8)
F21	0.0556 (7)	0.0309 (7)	0.0254 (7)	−0.0088 (5)	−0.0051 (5)	0.0079 (5)
F22	0.0349 (6)	0.0292 (7)	0.0380 (7)	−0.0112 (5)	−0.0094 (5)	0.0041 (5)
F23	0.0412 (7)	0.0246 (7)	0.0528 (8)	0.0085 (5)	−0.0097 (5)	0.0004 (6)
N22	0.0282 (8)	0.0296 (10)	0.0225 (9)	−0.0017 (7)	0.0007 (7)	−0.0031 (7)
O21	0.0557 (9)	0.0252 (9)	0.0341 (9)	0.0047 (7)	−0.0023 (7)	−0.0067 (7)
O22	0.0431 (8)	0.0456 (10)	0.0234 (8)	0.0032 (7)	−0.0131 (6)	−0.0038 (7)

Geometric parameters (Å, º)

N11—C11	1.351 (2)	N21—C21	1.356 (2)
N11—H11	0.8800	N21—H22	0.8800
N11—H11	0.8800	N21—H21	0.8800
C11—C16	1.402 (2)	C21—C26	1.399 (2)
C11—C12	1.407 (2)	C21—C22	1.411 (3)
C12—C13	1.375 (2)	C22—C23	1.377 (2)
C12—H12A	0.9500	C22—H22A	0.9500
C13—C14	1.416 (2)	C23—C24	1.410 (2)
C13—C17	1.512 (2)	C23—C27	1.502 (3)
C14—C15	1.394 (2)	C24—C25	1.390 (2)
C14—N12	1.443 (2)	C24—N22	1.448 (2)
C15—C16	1.366 (2)	C25—C26	1.370 (3)
C15—H15	0.9500	C25—H25	0.9500
C16—H16	0.9500	C26—H26	0.9500
C17—F12	1.333 (2)	C27—F21	1.337 (2)
C17—F11	1.335 (2)	C27—F23	1.340 (2)
C17—F13	1.345 (2)	C27—F22	1.345 (2)
N12—O11	1.2291 (19)	N22—O22	1.235 (2)
N12—O12	1.2331 (19)	N22—O21	1.236 (2)
C11—N11—H11	120.0	C21—N21—H21	120.0
C11—N11—H12	120.0	C21—N21—H22	120.0
H11—N11—H12	120.0	H21—N21—H22	120.0
N11—C11—C16	121.20 (16)	N21—C21—C26	121.03 (17)
N11—C11—C12	120.39 (17)	N21—C21—C22	120.57 (16)
C16—C11—C12	118.40 (16)	C26—C21—C22	118.40 (16)
C13—C12—C11	122.28 (17)	C23—C22—C21	121.56 (16)
C13—C12—H12A	118.9	C23—C22—H22A	119.2
C11—C12—H12A	118.9	C21—C22—H22A	119.2
C12—C13—C14	117.97 (15)	C22—C23—C24	118.59 (17)
C12—C13—C17	116.11 (16)	C22—C23—C27	116.85 (16)
C14—C13—C17	125.73 (15)	C24—C23—C27	124.24 (16)
C15—C14—C13	120.01 (16)	C25—C24—C23	120.17 (16)
C13—C14—N12	123.44 (15)	C23—C24—N22	123.06 (16)
C15—C14—N12	116.53 (16)	C25—C24—N22	116.73 (16)
C16—C15—C14	121.12 (17)	C26—C25—C24	120.61 (17)
C16—C15—H15	119.4	C26—C25—H25	119.7
C14—C15—H15	119.4	C24—C25—H25	119.7
C15—C16—C11	120.18 (16)	C25—C26—C21	120.60 (17)
C15—C16—H16	119.9	C25—C26—H26	119.7
C11—C16—H16	119.9	C21—C26—H26	119.7
F12—C17—F11	106.33 (14)	F21—C27—F23	106.08 (14)
F12—C17—F13	107.56 (14)	F21—C27—F22	105.99 (14)
F11—C17—F13	105.75 (14)	F23—C27—F22	106.99 (15)
F12—C17—C13	113.85 (14)	F21—C27—C23	111.69 (15)
F11—C17—C13	111.06 (14)	F23—C27—C23	113.31 (15)
F13—C17—C13	111.81 (14)	F22—C27—C23	112.29 (14)
O11—N12—O12	121.63 (15)	O22—N22—O21	122.39 (16)
O11—N12—C14	119.75 (15)	O22—N22—C24	118.41 (16)
O12—N12—C14	118.60 (15)	O21—N22—C24	119.14 (15)
O11—N12—C14—C13	−16.7 (2)	O21—N22—C24—C23	28.1 (2)
O11—N12—C14—C15	162.0 (2)	O21—N22—C24—C25	−149.5 (2)
O12—N12—C14—C13	164.8 (2)	O22—N22—C24—C23	−154.6 (2)
O12—N12—C14—C15	−16.4 (2)	O22—N22—C24—C25	27.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O22^i	0.88	2.42	3.221 (2)	152
N11—H12···O12^ii	0.88	2.26	3.088 (2)	157
N21—H21···O11	0.88	2.31	3.088 (2)	148
N21—H22···O21^iii	0.88	2.28	3.101 (2)	155
C16—H16···F13^iv	0.95	2.40	3.180 (2)	139
C26—H26···F23^iii	0.95	2.50	3.347 (2)	149

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