Penta­fluoro­phenyl (3R,4R,5R)-5-{[(3R,4R,5R)-5-azido­methyl-3,4-dimeth­oxy-2,3,4,5-tetra­hydro­furan-3-carbonyl­amino]meth­yl}-3,4-dimeth­oxy-2,3,4,5-tetra­hydro­furan-3-carboxyl­ate

Punzo, F.; Cowley, A.R.; Watkin, D.J.; Iezzi Simone, M.; Edwards, A.A.; Tranter, G.E.; Fleet, G.W.J.

doi:10.1107/S1600536805043205

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 2| February 2006| Pages o473-o475

https://doi.org/10.1107/S1600536805043205

Pentafluorophenyl (3R,4R,5R)-5-{[(3R,4R,5R)-5-azidomethyl-3,4-dimethoxy-2,3,4,5-tetrahydrofuran-3-carbonylamino]methyl}-3,4-dimethoxy-2,3,4,5-tetrahydrofuran-3-carboxylate

Francesco Punzo,^a ^*‡ Andrew R. Cowley,^b David J. Watkin,^b Michela Iezzi Simone,^c Alison A. Edwards,^d George E. Tranter ^d and George W. J. Fleet ^c

^aDipartimento di Scienze Chimiche, Facoltà di Farmacia, Università di Catania, Viale A. Doria 6, 95125 Catania, Italy, ^bDepartment of Chemical Crystallography, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, ^cDepartment of Organic Chemistry, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, and ^dBiological Chemistry, Division of Biomedical Sciences, Imperial College, London SW7 2AZ, England
^*Correspondence e-mail: fpunzo@unict.it

(Received 12 December 2005; accepted 25 December 2005; online 7 January 2006)

The crystal structure of the title compound, C₂₂H₂₅F₅N₄O₉, an important intermediate in the synthesis of novel biopolymers containing branched carbon chains, establishes the relative stereochemistry at all six chiral centres of the dipeptide. The structure may indicate a predisposition to the organization of secondary structure by novel dipeptide isosteres. An intermolecular hydrogen bond between the NH group and one of the N atoms of the azide group contributes to the stabilization of the packing.

Comment

Sugar amino acids (SAAs) have been extensively studied as peptidomimetics (Chakraborty et al., 2005 ). δ-Tetrahydrofuran (THF) SAAs such as (1) (Smith et al., 2003 ; Chakraborty et al., 2004 ) have become well established as dipeptide isosteres (Grotenberg et al., 2004 ). Such systems continue to provide an increased understanding of the factors inducing secondary structure and insight into the complex nature of protein folding (Billing & Nilsson, 2005 ; Claridge et al., 2005 ; Long et al., 1999 ) with potential chemotherapeutic activities as integrin antagonists (van Well et al., 2004 ), enkephalin analogues (Montero et al., 2004 ) and somatastatin mimics (Gruner et al., 2002 ). In the past, almost all THF SAAs have contained linear carbon chains, since the only carbohydrate building blocks from which they can be derived have unbranched chains (Bols, 1996 ). Knowledge of the predisposition of monomers to adopt particular secondary structural motif may allow the design of bioactive peptidomimetic libraries.

However, new classes of branched carbohydrates suitable for short syntheses of branched carbon chain SAAs have recently become available by Kiliani or other procedures (Soengas et al., 2005 ; Hotchkiss et al., 2004 ,2006 ). The Ho crossed aldol (Ho, 1979 , 1985 ) was the crucial step in the synthesis of branched SAAs such as (2) (Simone et al., 2005 ). The azidoester (2) was converted by standard peptide procedures into the dimeric pentafluorophenyl ester (3) as a key intermediate for the generation of homooligomers having the branched trans-δ-SAA scaffold (2) as a component.

The crystal structure reported in this paper firmly establishes the relative configuration of the six stereogenic centres in (3); the absolute configuration is consistent with the one determined by the use of D-ribose as the starting material for the synthesis. An intermolecular hydrogen bond between the H atom connected to N10 and N28, the first nitrogen of the azide chain, contributes to the stabilization of the packing.

Figure 1
The structure of (3), with displacement ellipsoids drawn at the 50% probability level. H-atom radii are arbitrary.

Figure 2
Packing diagram of (3), viewed down the a axis. Dashed lines indicate intermolecular hydrogen bonds.

Experimental

Compound (3) was crystallized by dissolving it in dichloromethane, adding a few drops of cyclohexane and allowing the slow competitive evaporation of the two solvents until clear colourless crystals formed.

Crystal data

C₂₂H₂₅F₅N₄O₉
M_r = 584.45
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.18471 (11) Å
b = 11.04142 (15) Å
c = 32.6727 (5) Å
V = 2591.91 (7) Å³
Z = 4
D_x = 1.498 Mg m⁻³
Cu Kα radiation
Cell parameters from 11003 reflections
θ = 4.2–69.3°
μ = 1.22 mm⁻¹
T = 120 K
Lath, colourless
0.50 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer
ω/2θ scans
Absorption correction: multi-scan(CrysAlis; Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis. Oxford Diffraction Ltd, Abingdon, Oxford, England.]$ )T_min = 0.783, T_max = 0.885
11003 measured reflections
4281 independent reflections
3387 reflections with I > 2σ(I)
R_int = 0.020
θ_max = 69.3°
h = −6 → 8
k = −9 → 13
l = −39 → 33

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.081
S = 0.92
4281 reflections
362 parameters
H-atom parameters constrained
w = 1/[σ²(F²) + (0.04P)² + 0.55P] where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max = 0.001
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ), 1237 Friedel pairs
Flack parameter: 0.00 (16)

Table 1
Selected geometric parameters (Å, °)

O1—C17	1.425 (3)
O1—C40	1.418 (4)
O2—C24	1.431 (3)
O2—C25	1.424 (3)
F3—C34	1.334 (3)
F4—C26	1.342 (3)
O5—C18	1.390 (3)
O5—C32	1.387 (3)
O6—C30	1.411 (3)
O6—C38	1.421 (4)
O7—C20	1.222 (3)
O8—C23	1.404 (3)
O8—C36	1.434 (4)
O9—C19	1.409 (3)
O9—C39	1.437 (4)
N10—C20	1.336 (3)
N10—C21	1.450 (3)
F11—C33	1.338 (3)
F12—C35	1.333 (3)
O13—C32	1.180 (3)
F14—C37	1.342 (3)
O15—C22	1.422 (3)
O15—C31	1.403 (3)
N16—N28	1.183 (3)
N16—N29	1.146 (3)
C17—C20	1.537 (3)
C17—C30	1.532 (4)
C17—C31	1.515 (3)
C18—C26	1.383 (4)
C18—C34	1.376 (3)
C19—C23	1.540 (3)
C19—C25	1.532 (4)
C19—C32	1.522 (3)
C21—C24	1.514 (3)
C22—C27	1.502 (4)
C22—C30	1.546 (4)
C23—C24	1.517 (3)
C26—C37	1.355 (4)
C27—N28	1.495 (4)
C33—C34	1.382 (4)
C33—C35	1.364 (5)
C35—C37	1.369 (4)

C17—O1—C40	114.6 (2)
C24—O2—C25	110.12 (19)
C18—O5—C32	115.64 (19)
C30—O6—C38	113.3 (2)
C23—O8—C36	113.0 (2)
C19—O9—C39	114.5 (2)
C20—N10—C21	121.8 (2)
C22—O15—C31	109.17 (19)
N28—N16—N29	172.9 (3)
O1—C17—C20	111.3 (2)
O1—C17—C30	104.20 (19)
C20—C17—C30	113.26 (19)
O1—C17—C31	113.9 (2)
C20—C17—C31	112.2 (2)
C30—C17—C31	101.3 (2)
O5—C18—C26	118.8 (2)
O5—C18—C34	123.2 (3)
C26—C18—C34	118.0 (2)
O9—C19—C23	108.06 (19)
O9—C19—C25	113.9 (2)
C23—C19—C25	102.24 (19)
O9—C19—C32	107.94 (19)
C23—C19—C32	108.4 (2)
C25—C19—C32	115.9 (2)
C17—C20—N10	115.5 (2)
C17—C20—O7	121.0 (2)
N10—C20—O7	123.4 (2)
N10—C21—C24	114.3 (2)
O15—C22—C27	106.1 (2)
O15—C22—C30	106.8 (2)
C27—C22—C30	114.9 (2)
C19—C23—O8	115.53 (19)
C19—C23—C24	103.4 (2)
O8—C23—C24	109.2 (2)
C23—C24—C21	115.6 (2)
C23—C24—O2	104.3 (2)
C21—C24—O2	108.6 (2)
C19—C25—O2	107.9 (2)
C18—C26—F4	118.9 (2)
C18—C26—C37	121.6 (3)
F4—C26—C37	119.5 (3)
C22—C27—N28	112.0 (3)
C27—N28—N16	115.4 (2)
C22—C30—C17	103.0 (2)
C22—C30—O6	111.7 (2)
C17—C30—O6	108.6 (2)
C17—C31—O15	105.3 (2)
C19—C32—O5	111.3 (2)
C19—C32—O13	126.2 (3)
O5—C32—O13	122.4 (2)
F11—C33—C34	119.2 (3)
F11—C33—C35	120.1 (3)
C34—C33—C35	120.6 (3)
C33—C34—C18	120.2 (3)
C33—C34—F3	119.6 (3)
C18—C34—F3	120.2 (3)
F12—C35—C33	119.9 (3)
F12—C35—C37	120.7 (3)
C33—C35—C37	119.4 (3)
F14—C37—C35	119.6 (3)
F14—C37—C26	120.2 (3)
C35—C37—C26	120.2 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H1⋯N28ⁱ	0.94	2.23	3.120 (3)	158
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

The H atoms were located in a difference map, but those attached to C atoms were repositioned geometrically. They were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–98 Å, N—H in the range 0.86–0.89 Å and U_iso(H) in the range 1.2–1.5 times U_eq of the parent atom), after which their positions were refined with riding constraints.

Data collection: CrysAlis (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis. Oxford Diffraction Ltd, Abingdon, Oxford, England.]$ ); cell refinement: CrysAlis; data reduction: CrysAlis; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, 3. DOI: https://doi.org/10.1107/S1600536805043205/ci2001sup1.cif

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S1600536805043205/ci20013sup2.hkl

Computing details top

Data collection: CrysAlis (Oxford Diffraction, 2005); cell refinement: CrysAlis; data reduction: CrysAlis; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Pentafluorophenyl (3R,4R,5R)-5-{[(3R,4R,5R)-5-azidomethyl-3,4-dimethoxy-2,3,4,5-tetrahydrofuran- 3-carbonylamino]methyl}-3,4-dimethoxy-2,3,4,5-tetrahydrofuran-3-carboxylate top

Crystal data top

C₂₂H₂₅F₅N₄O₉	F(000) = 1208
M_r = 584.45	D_x = 1.498 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54248 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11003 reflections
a = 7.18471 (11) Å	θ = 4.2–69.3°
b = 11.04142 (15) Å	µ = 1.22 mm⁻¹
c = 32.6727 (5) Å	T = 120 K
V = 2591.91 (7) Å³	Plate, colourless
Z = 4	0.50 × 0.20 × 0.10 mm

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	3387 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω/2θ scans	θ_max = 69.3°, θ_min = 4.2°
Absorption correction: multi-scan (CrysAlis; Oxford Diffraction, 2005)	h = −6→8
T_min = 0.783, T_max = 0.885	k = −9→13
11003 measured reflections	l = −39→33
4281 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F²) + (0.04P)² + 0.55P] where P = [max(F_o²,0) + 2F_c²]/3
wR(F²) = 0.081	(Δ/σ)_max = 0.001
S = 0.92	Δρ_max = 0.29 e Å⁻³
4281 reflections	Δρ_min = −0.14 e Å⁻³
362 parameters	Absolute structure: Flack (1983), 1237 Friedel pairs
0 restraints	Absolute structure parameter: 0.00 (16)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	U_iso*/U_eq
O1	0.2249 (3)	0.58178 (16)	0.76221 (5)	0.0567
O2	0.1532 (3)	0.66323 (16)	0.60192 (5)	0.0545
F3	0.0797 (3)	0.46794 (18)	0.43728 (5)	0.0810
F4	−0.3609 (2)	0.65310 (16)	0.52301 (5)	0.0728
O5	−0.0124 (3)	0.56503 (15)	0.51413 (5)	0.0521
O6	0.3012 (2)	0.35309 (18)	0.68901 (5)	0.0613
O7	−0.1177 (2)	0.43686 (17)	0.70491 (5)	0.0585
O8	−0.1422 (3)	0.40677 (17)	0.59803 (5)	0.0604
O9	0.2815 (3)	0.37069 (16)	0.57241 (5)	0.0609
N10	0.0521 (3)	0.59896 (18)	0.68589 (6)	0.0432
F11	−0.1759 (3)	0.45764 (19)	0.37705 (5)	0.1000
F12	−0.5202 (3)	0.5498 (2)	0.38863 (6)	0.1035
O13	0.0116 (4)	0.36179 (17)	0.51341 (6)	0.0782
F14	−0.6115 (3)	0.64942 (19)	0.46177 (7)	0.0972
O15	0.2700 (3)	0.3302 (2)	0.78835 (7)	0.0899
N16	0.5502 (3)	0.2964 (2)	0.84412 (7)	0.0578
C17	0.1661 (3)	0.4742 (2)	0.74192 (7)	0.0464
C18	−0.1368 (4)	0.5586 (2)	0.48162 (7)	0.0499
C19	0.1615 (4)	0.4710 (2)	0.56830 (7)	0.0490
C20	0.0187 (3)	0.5017 (2)	0.70912 (7)	0.0433
C21	−0.0763 (3)	0.6374 (2)	0.65421 (7)	0.0470
C22	0.4169 (4)	0.3390 (3)	0.75934 (8)	0.0601
C23	0.0248 (4)	0.4698 (2)	0.60462 (7)	0.0466
C24	−0.0180 (4)	0.6029 (2)	0.61125 (7)	0.0464
C25	0.2586 (4)	0.5935 (3)	0.57352 (7)	0.0535
C26	−0.3142 (4)	0.6050 (3)	0.48672 (8)	0.0569
C27	0.5819 (4)	0.3878 (3)	0.78228 (8)	0.0669
N28	0.6467 (3)	0.3025 (3)	0.81486 (8)	0.0720
N29	0.4711 (4)	0.2836 (3)	0.87426 (8)	0.0762
C30	0.3459 (4)	0.4209 (3)	0.72428 (7)	0.0509
C31	0.1054 (4)	0.3741 (3)	0.77071 (9)	0.0595
C32	0.0506 (4)	0.4548 (2)	0.52899 (7)	0.0536
C33	−0.2226 (6)	0.5058 (3)	0.41321 (8)	0.0713
C34	−0.0917 (4)	0.5098 (3)	0.44416 (8)	0.0604
C35	−0.3964 (5)	0.5523 (3)	0.41902 (9)	0.0712
C36	−0.1239 (5)	0.2786 (3)	0.60382 (10)	0.0801
C37	−0.4410 (4)	0.6028 (3)	0.45602 (10)	0.0664
C38	0.4599 (5)	0.3180 (4)	0.66591 (10)	0.0950
C39	0.4293 (5)	0.3663 (3)	0.54282 (11)	0.0832
C40	0.0981 (6)	0.6264 (3)	0.79185 (10)	0.0845
H211	−0.0899	0.7268	0.6563	0.0663*
H212	−0.1990	0.5981	0.6594	0.0663*
H221	0.4413	0.2586	0.7484	0.0856*
H231	0.0889	0.4387	0.6294	0.0651*
H241	−0.1121	0.6319	0.5909	0.0654*
H251	0.2639	0.6369	0.5467	0.0765*
H252	0.3825	0.5806	0.5845	0.0770*
H271	0.6842	0.4000	0.7632	0.0950*
H272	0.5487	0.4654	0.7955	0.0945*
H301	0.4355	0.4855	0.7174	0.0725*
H311	0.0405	0.3081	0.7561	0.0846*
H312	0.0217	0.4038	0.7920	0.0855*
H361	−0.2449	0.2424	0.6020	0.1410*
H362	−0.0467	0.2455	0.5819	0.1409*
H363	−0.0668	0.2635	0.6306	0.1412*
H381	0.4143	0.2762	0.6411	0.1746*
H382	0.5264	0.3928	0.6588	0.1748*
H383	0.5365	0.2637	0.6820	0.1748*
H391	0.4888	0.2887	0.5447	0.1461*
H392	0.3813	0.3773	0.5154	0.1463*
H393	0.5206	0.4291	0.5487	0.1469*
H401	0.1359	0.7089	0.7991	0.1511*
H402	−0.0278	0.6307	0.7815	0.1514*
H403	0.1014	0.5761	0.8165	0.1516*
H1	0.1579	0.6462	0.6911	0.0652*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0701 (12)	0.0580 (11)	0.0418 (9)	−0.0085 (10)	−0.0070 (9)	−0.0026 (8)
O2	0.0681 (12)	0.0481 (9)	0.0473 (9)	−0.0010 (10)	0.0122 (9)	−0.0067 (8)
F3	0.0903 (13)	0.0974 (13)	0.0553 (10)	0.0168 (11)	0.0111 (9)	−0.0099 (9)
F4	0.0689 (10)	0.0816 (11)	0.0678 (10)	−0.0014 (10)	0.0106 (8)	−0.0130 (9)
O5	0.0641 (11)	0.0503 (10)	0.0419 (9)	0.0025 (9)	−0.0037 (8)	−0.0026 (8)
O6	0.0581 (10)	0.0781 (13)	0.0477 (9)	0.0127 (10)	−0.0068 (9)	−0.0090 (9)
O7	0.0490 (10)	0.0670 (11)	0.0596 (11)	−0.0138 (10)	−0.0093 (9)	0.0138 (9)
O8	0.0615 (12)	0.0573 (11)	0.0623 (11)	−0.0055 (10)	−0.0018 (9)	−0.0073 (9)
O9	0.0726 (12)	0.0576 (11)	0.0525 (10)	0.0174 (10)	0.0026 (9)	−0.0050 (9)
N10	0.0485 (11)	0.0456 (11)	0.0356 (9)	−0.0024 (10)	−0.0001 (9)	0.0003 (9)
F11	0.1528 (19)	0.1045 (15)	0.0428 (9)	0.0021 (14)	−0.0053 (10)	−0.0136 (9)
F12	0.1182 (17)	0.1082 (15)	0.0839 (13)	−0.0086 (14)	−0.0500 (13)	0.0019 (12)
O13	0.1300 (19)	0.0507 (11)	0.0540 (11)	−0.0005 (13)	−0.0259 (12)	−0.0108 (10)
F14	0.0682 (12)	0.1017 (14)	0.1216 (16)	0.0050 (12)	−0.0194 (11)	−0.0081 (13)
O15	0.0483 (11)	0.132 (2)	0.0891 (15)	−0.0158 (13)	−0.0161 (11)	0.0689 (15)
N16	0.0603 (14)	0.0699 (16)	0.0431 (13)	0.0128 (13)	−0.0172 (12)	0.0061 (12)
C17	0.0482 (14)	0.0522 (14)	0.0387 (12)	−0.0092 (13)	−0.0016 (11)	0.0063 (11)
C18	0.0648 (17)	0.0462 (13)	0.0386 (12)	−0.0065 (13)	−0.0009 (12)	0.0043 (11)
C19	0.0594 (15)	0.0471 (13)	0.0405 (12)	0.0093 (13)	−0.0029 (12)	−0.0054 (11)
C20	0.0427 (13)	0.0498 (14)	0.0374 (12)	−0.0014 (13)	0.0030 (10)	−0.0009 (11)
C21	0.0549 (15)	0.0478 (14)	0.0382 (12)	0.0078 (12)	−0.0022 (11)	−0.0008 (11)
C22	0.0642 (17)	0.0643 (17)	0.0519 (15)	0.0067 (15)	−0.0124 (13)	0.0048 (14)
C23	0.0526 (15)	0.0478 (13)	0.0394 (12)	0.0009 (13)	−0.0032 (11)	−0.0006 (11)
C24	0.0513 (15)	0.0482 (14)	0.0398 (12)	0.0054 (13)	−0.0047 (11)	0.0018 (11)
C25	0.0562 (15)	0.0605 (15)	0.0439 (13)	0.0022 (14)	0.0000 (12)	−0.0084 (12)
C26	0.0636 (17)	0.0562 (15)	0.0508 (15)	−0.0062 (15)	−0.0011 (13)	−0.0002 (13)
C27	0.0448 (15)	0.107 (3)	0.0484 (15)	0.0027 (17)	−0.0036 (12)	0.0122 (16)
N28	0.0496 (13)	0.109 (2)	0.0576 (14)	0.0228 (15)	−0.0039 (12)	0.0145 (15)
N29	0.0688 (16)	0.102 (2)	0.0578 (15)	−0.0032 (16)	−0.0082 (13)	0.0114 (15)
C30	0.0470 (13)	0.0645 (16)	0.0412 (12)	−0.0043 (14)	−0.0078 (11)	0.0056 (12)
C31	0.0491 (15)	0.0683 (18)	0.0611 (16)	−0.0084 (14)	−0.0060 (13)	0.0204 (14)
C32	0.0702 (18)	0.0486 (15)	0.0420 (13)	0.0041 (14)	0.0014 (12)	−0.0027 (12)
C33	0.106 (3)	0.070 (2)	0.0379 (14)	−0.007 (2)	−0.0035 (16)	0.0016 (13)
C34	0.0738 (19)	0.0621 (17)	0.0452 (14)	0.0075 (15)	0.0051 (13)	0.0040 (13)
C35	0.085 (2)	0.0665 (19)	0.0619 (18)	−0.0048 (18)	−0.0220 (17)	0.0082 (16)
C36	0.100 (3)	0.0616 (19)	0.079 (2)	−0.017 (2)	0.007 (2)	−0.0011 (17)
C37	0.0646 (19)	0.0568 (17)	0.078 (2)	−0.0052 (16)	−0.0054 (16)	0.0020 (16)
C38	0.074 (2)	0.144 (4)	0.067 (2)	0.035 (2)	−0.0031 (17)	−0.027 (2)
C39	0.095 (2)	0.077 (2)	0.077 (2)	0.0235 (19)	0.0241 (19)	−0.0138 (19)
C40	0.125 (3)	0.073 (2)	0.0558 (17)	0.016 (2)	0.0076 (19)	−0.0088 (16)

Geometric parameters (Å, º) top

O1—C17	1.425 (3)	C21—C24	1.514 (3)
O1—C40	1.418 (4)	C21—H211	0.994
O2—C24	1.431 (3)	C21—H212	0.997
O2—C25	1.424 (3)	C22—C27	1.502 (4)
F3—C34	1.334 (3)	C22—C30	1.546 (4)
F4—C26	1.342 (3)	C22—H221	0.973
O5—C18	1.390 (3)	C23—C24	1.517 (3)
O5—C32	1.387 (3)	C23—H231	0.991
O6—C30	1.411 (3)	C24—H241	1.000
O6—C38	1.421 (4)	C25—H251	0.999
O7—C20	1.222 (3)	C25—H252	0.970
O8—C23	1.404 (3)	C26—C37	1.355 (4)
O8—C36	1.434 (4)	C27—N28	1.495 (4)
O9—C19	1.409 (3)	C27—H271	0.972
O9—C39	1.437 (4)	C27—H272	0.989
N10—C20	1.336 (3)	C30—H301	0.987
N10—C21	1.450 (3)	C31—H311	0.989
N10—H1	0.938	C31—H312	0.976
F11—C33	1.338 (3)	C33—C34	1.382 (4)
F12—C35	1.333 (3)	C33—C35	1.364 (5)
O13—C32	1.180 (3)	C35—C37	1.369 (4)
F14—C37	1.342 (3)	C36—H361	0.959
O15—C22	1.422 (3)	C36—H362	0.976
O15—C31	1.403 (3)	C36—H363	0.980
N16—N28	1.183 (3)	C38—H381	0.989
N16—N29	1.146 (3)	C38—H382	0.982
C17—C20	1.537 (3)	C38—H383	0.969
C17—C30	1.532 (4)	C39—H391	0.960
C17—C31	1.515 (3)	C39—H392	0.968
C18—C26	1.383 (4)	C39—H393	0.974
C18—C34	1.376 (3)	C40—H401	0.980
C19—C23	1.540 (3)	C40—H402	0.967
C19—C25	1.532 (4)	C40—H403	0.978
C19—C32	1.522 (3)

C17—O1—C40	114.6 (2)	C18—C26—C37	121.6 (3)
C24—O2—C25	110.12 (19)	F4—C26—C37	119.5 (3)
C18—O5—C32	115.64 (19)	C22—C27—N28	112.0 (3)
C30—O6—C38	113.3 (2)	C22—C27—H271	109.1
C23—O8—C36	113.0 (2)	N28—C27—H271	107.9
C19—O9—C39	114.5 (2)	C22—C27—H272	109.8
C20—N10—C21	121.8 (2)	N28—C27—H272	108.0
C20—N10—H1	119.3	H271—C27—H272	110.0
C21—N10—H1	118.8	C27—N28—N16	115.4 (2)
C22—O15—C31	109.17 (19)	C22—C30—C17	103.0 (2)
N28—N16—N29	172.9 (3)	C22—C30—O6	111.7 (2)
O1—C17—C20	111.3 (2)	C17—C30—O6	108.6 (2)
O1—C17—C30	104.20 (19)	C22—C30—H301	112.1
C20—C17—C30	113.26 (19)	C17—C30—H301	111.0
O1—C17—C31	113.9 (2)	O6—C30—H301	110.2
C20—C17—C31	112.2 (2)	C17—C31—O15	105.3 (2)
C30—C17—C31	101.3 (2)	C17—C31—H311	111.9
O5—C18—C26	118.8 (2)	O15—C31—H311	109.9
O5—C18—C34	123.2 (3)	C17—C31—H312	112.0
C26—C18—C34	118.0 (2)	O15—C31—H312	110.0
O9—C19—C23	108.06 (19)	H311—C31—H312	107.6
O9—C19—C25	113.9 (2)	C19—C32—O5	111.3 (2)
C23—C19—C25	102.24 (19)	C19—C32—O13	126.2 (3)
O9—C19—C32	107.94 (19)	O5—C32—O13	122.4 (2)
C23—C19—C32	108.4 (2)	F11—C33—C34	119.2 (3)
C25—C19—C32	115.9 (2)	F11—C33—C35	120.1 (3)
C17—C20—N10	115.5 (2)	C34—C33—C35	120.6 (3)
C17—C20—O7	121.0 (2)	C33—C34—C18	120.2 (3)
N10—C20—O7	123.4 (2)	C33—C34—F3	119.6 (3)
N10—C21—C24	114.3 (2)	C18—C34—F3	120.2 (3)
N10—C21—H211	107.7	F12—C35—C33	119.9 (3)
C24—C21—H211	109.9	F12—C35—C37	120.7 (3)
N10—C21—H212	108.2	C33—C35—C37	119.4 (3)
C24—C21—H212	107.1	O8—C36—H361	108.7
H211—C21—H212	109.4	O8—C36—H362	108.9
O15—C22—C27	106.1 (2)	H361—C36—H362	108.3
O15—C22—C30	106.8 (2)	O8—C36—H363	108.9
C27—C22—C30	114.9 (2)	H361—C36—H363	111.4
O15—C22—H221	108.4	H362—C36—H363	110.6
C27—C22—H221	111.6	F14—C37—C35	119.6 (3)
C30—C22—H221	108.7	F14—C37—C26	120.2 (3)
C19—C23—O8	115.53 (19)	C35—C37—C26	120.2 (3)
C19—C23—C24	103.4 (2)	O6—C38—H381	107.3
O8—C23—C24	109.2 (2)	O6—C38—H382	106.6
C19—C23—H231	109.6	H381—C38—H382	111.1
O8—C23—H231	110.5	O6—C38—H383	109.6
C24—C23—H231	108.2	H381—C38—H383	110.2
C23—C24—C21	115.6 (2)	H382—C38—H383	111.8
C23—C24—O2	104.3 (2)	O9—C39—H391	108.4
C21—C24—O2	108.6 (2)	O9—C39—H392	110.8
C23—C24—H241	110.6	H391—C39—H392	109.3
C21—C24—H241	110.4	O9—C39—H393	110.0
O2—C24—H241	106.9	H391—C39—H393	108.8
C19—C25—O2	107.9 (2)	H392—C39—H393	109.5
C19—C25—H251	110.1	O1—C40—H401	108.1
O2—C25—H251	109.4	O1—C40—H402	112.3
C19—C25—H252	109.3	H401—C40—H402	107.3
O2—C25—H252	109.0	O1—C40—H403	110.4
H251—C25—H252	111.1	H401—C40—H403	108.8
C18—C26—F4	118.9 (2)	H402—C40—H403	109.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H1···N28ⁱ	0.94	2.23	3.120 (3)	158

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Footnotes

‡Visiting Scientist at the Department of Chemical Crystallography, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England.

Acknowledgements

Financial support (to AAE) from the EPSRC (grant No. GR/S44105/01) and (to MIS) from the European Community's Human Potential Programme under contract HPRN-CT-2002-00173 is gratefully acknowledged. The authors thank Oxford Diffraction for use of the Gemini R X-ray system.

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