Methyl 2-diphenyl­phosphor­yloxy-2-aza­bicyclo­[2.2.1]hept-5-ene-3-exo-carboxyl­ate

Sousa, C.A.D.; Vale, M.L.C.; Rodríguez-Borges, J.E.; Garcia-Mera, X.

doi:10.1107/S160053680804292X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o188

doi:10.1107/S160053680804292X

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Methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-exo-carboxylate

Carlos A. D. Sousa,^a ^* M. Luísa C. Vale,^a José E. Rodríguez-Borges ^a and Xerardo Garcia-Mera ^b

^aCentro de Investigação em Química, Departamento de Química, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687 4169-007, Porto, Portugal, and ^bDepartamento de Química Orgánica, Facultade de Farmacia, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain
^*Correspondence e-mail: carlos.sousa@fc.up.pt

(Received 2 December 2008; accepted 16 December 2008; online 20 December 2008)

In the title compound, C₂₀H₂₀NO₄P, the dihedral angle between the phenyl rings is 68.52 (7)°. In the crystal structure, the molecules are linked by a weak C—H⋯π(arene) interaction along [010] involving the phenyl CH group and the phenyl rings. There are no further significant intermolecular interactions.

Related literature

For the preparation of the precursor of the title compound, see: Sousa et al. (2008 ). For related literature about this type of bicyclic compound and their relevance see: Vale et al. (2006 ), Alves et al. (2006 ), Yoda et al. (1995 ).

Experimental

Crystal data

C₂₀H₂₀NO₄P
M_r = 369.34
Monoclinic, P 2₁ /c
a = 18.4223 (6) Å
b = 8.5522 (3) Å
c = 11.6022 (4) Å
β = 97.1810 (10)°
V = 1813.60 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100 (2) K
0.37 × 0.34 × 0.34 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.871, T_max = 0.940
14828 measured reflections
3717 independent reflections
3172 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.091
S = 1.05
3717 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cg1ⁱ	0.95	2.77	3.566 (2)	142
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of the C15–C20 ring.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053680804292X/bx2188sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680804292X/bx2188Isup2.hkl

checkCIF report

Comment top

The stucture of the title compound, (I), is shown in Fig. 1. It can be seen the existence of three chiral centers at C2 (R), C5 (S) and C6 (R). In the crystalline structure, the molecules are linked by a weak C—H···π interaction, Fig. 2 [H12-πⁱ 2.77 Å, C12-H12-π 142°, C12-π 3.566 (2) Å, symmetry code: (i) 1-x,1/2+y, 1/2-z] along [010] directions. There are no further significant intermolecular interactions.

Related literature top

For the preparation of the precursor of the title compound, see: Sousa et al. (2008). For related literature about this type of bicyclic compound and their relevance see: Vale et al. (2006), Alves et al. (2006), Yoda et al. (1995). Cg1 is the centroid of the C15–C20 ring.

Experimental top

The title compound was synthesized from the previously prepared (3exo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate (Sousa et al. 2008). Equimolar amounts of (3exo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate (0.56 g, 3.3 mmol) and diphenylpfosphinic chloride (0.63 ml, 3.3 mmol), in the presence of 1 eq. of anidrous triethylamine and and a catalytic quantity of DMAP, were let to react overnigth in dichloromethane, at room temperature under argon atmosphere. Water was added and the product was extracted with dichloromethane (3 × 15 ml). The organic layers were dried over sodium sulfate and the solvent was evaporated. The obtained product was purified by flash chromatography (eluent: dichloromethane/diethyl ether 1:1), leading to a light clear yellow oil in 80% yield. Crystals of (I) were made from a slow evaporation of a dichloromethane/hexane solution.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top

	Fig. 1. A view of (I), showing the three chiral carbons C2, C5 and C6 and the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
	Fig. 2. Part of the crystal structute of (I) viewed along the c axis. Dashed lines show C—H···π (arene) interactions. Only H atoms participating in hydrogen bonding are shown. π is the centroid of the ring defined by atoms C15-C20.

Methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-exo- carboxylate top

Crystal data top

C₂₀H₂₀NO₄P	F(000) = 776
M_r = 369.34	D_x = 1.353 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1953 reflections
a = 18.4223 (6) Å	θ = 3.1–25.9°
b = 8.5522 (3) Å	µ = 0.18 mm⁻¹
c = 11.6022 (4) Å	T = 100 K
β = 97.181 (1)°	Prism, colourless
V = 1813.60 (11) Å³	0.37 × 0.34 × 0.34 mm
Z = 4

Data collection top

Bruker ApexII CCD area-detector diffractometer	3717 independent reflections
Radiation source: sealed tube	3172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
phi and ω scans	θ_max = 26.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −23→22
T_min = 0.871, T_max = 0.940	k = 0→10
14828 measured reflections	l = 0→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0429P)² + 0.8843P] where P = (F_o² + 2F_c²)/3
3717 reflections	(Δ/σ)_max = 0.001
236 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₂₀H₂₀NO₄P	V = 1813.60 (11) Å³
M_r = 369.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.4223 (6) Å	µ = 0.18 mm⁻¹
b = 8.5522 (3) Å	T = 100 K
c = 11.6022 (4) Å	0.37 × 0.34 × 0.34 mm
β = 97.181 (1)°

Data collection top

Bruker ApexII CCD area-detector diffractometer	3717 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	3172 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.940	R_int = 0.033
14828 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.05	Δρ_max = 0.29 e Å⁻³
3717 reflections	Δρ_min = −0.41 e Å⁻³
236 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.04005 (8)	0.24766 (17)	0.08174 (13)	0.0156 (3)
H1A	−0.005	0.3099	0.0614	0.019*
H1B	0.0318	0.1646	0.1381	0.019*
C2	0.10739 (8)	0.34831 (17)	0.12086 (13)	0.0140 (3)
H2	0.1038	0.4159	0.1902	0.017*
C3	0.11615 (8)	0.43459 (18)	0.00937 (13)	0.0157 (3)
H3	0.1328	0.539	0.003	0.019*
C4	0.09614 (8)	0.33679 (18)	−0.07788 (13)	0.0170 (3)
H4	0.0965	0.358	−0.1582	0.02*
C5	0.07271 (8)	0.18529 (18)	−0.02579 (13)	0.0152 (3)
H5	0.0408	0.1144	−0.0788	0.018*
C6	0.14566 (8)	0.11298 (17)	0.03659 (12)	0.0124 (3)
H6	0.1849	0.1189	−0.0155	0.015*
C7	0.13407 (7)	−0.05517 (17)	0.07081 (12)	0.0126 (3)
C8	0.10791 (9)	−0.23359 (18)	0.21479 (14)	0.0188 (3)
H8A	0.0638	−0.2759	0.1694	0.028*
H8B	0.1021	−0.2364	0.2976	0.028*
H8C	0.1503	−0.2968	0.201	0.028*
C9	0.37374 (8)	0.32042 (17)	0.19955 (13)	0.0135 (3)
C10	0.39313 (8)	0.28107 (18)	0.09030 (13)	0.0156 (3)
H10	0.3592	0.2281	0.0353	0.019*
C11	0.46227 (8)	0.31986 (19)	0.06275 (14)	0.0196 (3)
H11	0.4758	0.2923	−0.011	0.024*
C12	0.51155 (8)	0.3985 (2)	0.14240 (15)	0.0220 (4)
H12	0.559	0.4232	0.1236	0.026*
C13	0.49180 (9)	0.4412 (2)	0.24924 (15)	0.0228 (4)
H13	0.5253	0.4974	0.3029	0.027*
C14	0.42326 (8)	0.40209 (18)	0.27826 (14)	0.0180 (3)
H14	0.41	0.431	0.3519	0.022*
C15	0.29184 (7)	0.05353 (17)	0.27096 (13)	0.0125 (3)
C16	0.31090 (8)	−0.05303 (18)	0.18853 (13)	0.0156 (3)
H16	0.3218	−0.017	0.1151	0.019*
C17	0.31393 (9)	−0.21192 (18)	0.21417 (14)	0.0190 (3)
H17	0.3284	−0.2841	0.1591	0.023*
C18	0.29590 (8)	−0.26536 (18)	0.31971 (15)	0.0200 (3)
H18	0.2972	−0.3742	0.3364	0.024*
C19	0.27594 (8)	−0.16006 (19)	0.40103 (14)	0.0185 (3)
H19	0.2629	−0.197	0.4729	0.022*
C20	0.27503 (8)	−0.00078 (18)	0.37771 (13)	0.0149 (3)
H20	0.2629	0.0713	0.4346	0.018*
N1	0.16332 (6)	0.21932 (14)	0.13812 (11)	0.0116 (3)
O1	0.11889 (6)	−0.07336 (12)	0.17981 (9)	0.0166 (2)
O2	0.13582 (6)	−0.16137 (12)	0.00278 (9)	0.0190 (2)
O3	0.23563 (5)	0.28855 (12)	0.12671 (9)	0.0131 (2)
O4	0.27071 (6)	0.34776 (12)	0.34900 (9)	0.0158 (2)
P1	0.288697 (19)	0.26111 (4)	0.24650 (3)	0.01112 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0105 (7)	0.0152 (8)	0.0210 (8)	0.0011 (6)	0.0016 (6)	0.0022 (6)
C2	0.0121 (7)	0.0126 (7)	0.0175 (7)	0.0026 (6)	0.0025 (6)	−0.0004 (6)
C3	0.0118 (7)	0.0132 (7)	0.0218 (8)	0.0026 (6)	0.0016 (6)	0.0041 (6)
C4	0.0154 (7)	0.0179 (8)	0.0172 (7)	0.0029 (6)	0.0000 (6)	0.0060 (6)
C5	0.0130 (7)	0.0149 (8)	0.0167 (7)	−0.0011 (6)	−0.0020 (6)	0.0021 (6)
C6	0.0112 (7)	0.0123 (7)	0.0135 (7)	−0.0005 (6)	0.0008 (5)	0.0000 (6)
C7	0.0081 (6)	0.0149 (7)	0.0145 (7)	0.0003 (6)	−0.0001 (5)	−0.0004 (6)
C8	0.0206 (8)	0.0145 (8)	0.0209 (8)	−0.0045 (6)	0.0010 (6)	0.0058 (6)
C9	0.0106 (7)	0.0116 (7)	0.0180 (7)	0.0001 (6)	0.0005 (6)	0.0035 (6)
C10	0.0133 (7)	0.0161 (8)	0.0169 (7)	−0.0018 (6)	−0.0003 (6)	0.0041 (6)
C11	0.0170 (8)	0.0232 (8)	0.0192 (8)	0.0001 (6)	0.0047 (6)	0.0046 (6)
C12	0.0131 (7)	0.0242 (9)	0.0289 (9)	−0.0026 (6)	0.0031 (6)	0.0075 (7)
C13	0.0152 (8)	0.0235 (9)	0.0283 (9)	−0.0056 (7)	−0.0031 (7)	−0.0009 (7)
C14	0.0157 (7)	0.0174 (8)	0.0205 (8)	−0.0009 (6)	0.0002 (6)	−0.0009 (6)
C15	0.0086 (7)	0.0114 (7)	0.0165 (7)	−0.0001 (5)	−0.0021 (5)	0.0011 (6)
C16	0.0139 (7)	0.0163 (8)	0.0162 (7)	0.0004 (6)	0.0008 (6)	0.0004 (6)
C17	0.0188 (8)	0.0145 (8)	0.0226 (8)	0.0031 (6)	−0.0022 (6)	−0.0060 (6)
C18	0.0166 (8)	0.0120 (8)	0.0296 (9)	−0.0001 (6)	−0.0043 (7)	0.0042 (7)
C19	0.0151 (7)	0.0198 (8)	0.0202 (8)	−0.0022 (6)	0.0002 (6)	0.0068 (6)
C20	0.0121 (7)	0.0154 (8)	0.0169 (7)	−0.0008 (6)	0.0008 (6)	−0.0007 (6)
N1	0.0071 (6)	0.0117 (6)	0.0161 (6)	−0.0022 (5)	0.0017 (5)	−0.0004 (5)
O1	0.0224 (6)	0.0119 (5)	0.0163 (5)	−0.0032 (4)	0.0049 (4)	0.0011 (4)
O2	0.0245 (6)	0.0139 (6)	0.0189 (6)	−0.0012 (4)	0.0038 (5)	−0.0031 (5)
O3	0.0079 (5)	0.0142 (5)	0.0168 (5)	−0.0033 (4)	0.0003 (4)	0.0029 (4)
O4	0.0165 (5)	0.0135 (5)	0.0177 (5)	−0.0003 (4)	0.0030 (4)	−0.0014 (4)
P1	0.00981 (19)	0.01024 (19)	0.0131 (2)	−0.00066 (14)	0.00083 (14)	0.00053 (14)

Geometric parameters (Å, º) top

C1—C2	1.531 (2)	C10—C11	1.392 (2)
C1—C5	1.546 (2)	C10—H10	0.95
C1—H1A	0.99	C11—C12	1.386 (2)
C1—H1B	0.99	C11—H11	0.95
C2—N1	1.5057 (18)	C12—C13	1.384 (2)
C2—C3	1.515 (2)	C12—H12	0.95
C2—H2	1	C13—C14	1.388 (2)
C3—C4	1.329 (2)	C13—H13	0.95
C3—H3	0.95	C14—H14	0.95
C4—C5	1.515 (2)	C15—C20	1.393 (2)
C4—H4	0.95	C15—C16	1.397 (2)
C5—C6	1.571 (2)	C15—P1	1.7976 (15)
C5—H5	1	C16—C17	1.391 (2)
C6—N1	1.4915 (18)	C16—H16	0.95
C6—C7	1.514 (2)	C17—C18	1.386 (2)
C6—H6	1	C17—H17	0.95
C7—O2	1.2064 (18)	C18—C19	1.387 (2)
C7—O1	1.3379 (17)	C18—H18	0.95
C8—O1	1.4505 (18)	C19—C20	1.389 (2)
C8—H8A	0.98	C19—H19	0.95
C8—H8B	0.98	C20—H20	0.95
C8—H8C	0.98	N1—O3	1.4786 (15)
C9—C14	1.395 (2)	O3—P1	1.6133 (10)
C9—C10	1.400 (2)	O4—P1	1.4737 (11)
C9—P1	1.7950 (15)

C2—C1—C5	92.89 (11)	C11—C10—H10	120.2
C2—C1—H1A	113.1	C9—C10—H10	120.2
C5—C1—H1A	113.1	C12—C11—C10	120.30 (15)
C2—C1—H1B	113.1	C12—C11—H11	119.8
C5—C1—H1B	113.1	C10—C11—H11	119.8
H1A—C1—H1B	110.5	C13—C12—C11	120.11 (14)
N1—C2—C3	109.04 (11)	C13—C12—H12	119.9
N1—C2—C1	98.23 (11)	C11—C12—H12	119.9
C3—C2—C1	100.92 (12)	C12—C13—C14	120.20 (15)
N1—C2—H2	115.5	C12—C13—H13	119.9
C3—C2—H2	115.5	C14—C13—H13	119.9
C1—C2—H2	115.5	C13—C14—C9	120.14 (15)
C4—C3—C2	107.14 (13)	C13—C14—H14	119.9
C4—C3—H3	126.4	C9—C14—H14	119.9
C2—C3—H3	126.4	C20—C15—C16	119.59 (14)
C3—C4—C5	107.46 (13)	C20—C15—P1	117.59 (11)
C3—C4—H4	126.3	C16—C15—P1	122.82 (11)
C5—C4—H4	126.3	C17—C16—C15	119.85 (14)
C4—C5—C1	100.71 (12)	C17—C16—H16	120.1
C4—C5—C6	104.50 (12)	C15—C16—H16	120.1
C1—C5—C6	99.25 (11)	C18—C17—C16	120.24 (15)
C4—C5—H5	116.6	C18—C17—H17	119.9
C1—C5—H5	116.6	C16—C17—H17	119.9
C6—C5—H5	116.6	C17—C18—C19	120.02 (14)
N1—C6—C7	113.33 (11)	C17—C18—H18	120
N1—C6—C5	102.32 (11)	C19—C18—H18	120
C7—C6—C5	110.74 (12)	C18—C19—C20	120.14 (15)
N1—C6—H6	110.1	C18—C19—H19	119.9
C7—C6—H6	110.1	C20—C19—H19	119.9
C5—C6—H6	110.1	C19—C20—C15	120.11 (14)
O2—C7—O1	123.83 (14)	C19—C20—H20	119.9
O2—C7—C6	121.82 (13)	C15—C20—H20	119.9
O1—C7—C6	114.29 (12)	O3—N1—C6	106.47 (10)
O1—C8—H8A	109.5	O3—N1—C2	107.69 (10)
O1—C8—H8B	109.5	C6—N1—C2	105.28 (11)
H8A—C8—H8B	109.5	C7—O1—C8	115.30 (12)
O1—C8—H8C	109.5	N1—O3—P1	108.68 (8)
H8A—C8—H8C	109.5	O4—P1—O3	116.67 (6)
H8B—C8—H8C	109.5	O4—P1—C9	113.30 (7)
C14—C9—C10	119.54 (13)	O3—P1—C9	98.94 (6)
C14—C9—P1	117.84 (12)	O4—P1—C15	112.04 (7)
C10—C9—P1	122.54 (11)	O3—P1—C15	106.49 (6)
C11—C10—C9	119.67 (14)	C9—P1—C15	108.35 (7)

C5—C1—C2—N1	−60.85 (12)	C18—C19—C20—C15	2.1 (2)
C5—C1—C2—C3	50.47 (12)	C16—C15—C20—C19	−1.2 (2)
N1—C2—C3—C4	68.17 (15)	P1—C15—C20—C19	179.43 (11)
C1—C2—C3—C4	−34.58 (15)	C7—C6—N1—O3	120.70 (12)
C2—C3—C4—C5	0.88 (16)	C5—C6—N1—O3	−120.03 (11)
C3—C4—C5—C1	32.73 (15)	C7—C6—N1—C2	−125.14 (12)
C3—C4—C5—C6	−69.86 (15)	C5—C6—N1—C2	−5.87 (13)
C2—C1—C5—C4	−49.87 (12)	C3—C2—N1—O3	51.25 (14)
C2—C1—C5—C6	56.93 (12)	C1—C2—N1—O3	155.87 (10)
C4—C5—C6—N1	71.20 (13)	C3—C2—N1—C6	−62.06 (14)
C1—C5—C6—N1	−32.48 (13)	C1—C2—N1—C6	42.56 (13)
C4—C5—C6—C7	−167.72 (12)	O2—C7—O1—C8	3.0 (2)
C1—C5—C6—C7	88.59 (13)	C6—C7—O1—C8	−179.72 (12)
N1—C6—C7—O2	−162.95 (13)	C6—N1—O3—P1	−127.24 (9)
C5—C6—C7—O2	82.74 (17)	C2—N1—O3—P1	120.25 (10)
N1—C6—C7—O1	19.76 (17)	N1—O3—P1—O4	−68.47 (10)
C5—C6—C7—O1	−94.56 (14)	N1—O3—P1—C9	169.71 (9)
C14—C9—C10—C11	1.8 (2)	N1—O3—P1—C15	57.44 (9)
P1—C9—C10—C11	−174.85 (12)	C14—C9—P1—O4	18.47 (14)
C9—C10—C11—C12	−0.7 (2)	C10—C9—P1—O4	−164.79 (12)
C10—C11—C12—C13	−1.0 (2)	C14—C9—P1—O3	142.70 (12)
C11—C12—C13—C14	1.6 (3)	C10—C9—P1—O3	−40.56 (14)
C12—C13—C14—C9	−0.4 (2)	C14—C9—P1—C15	−106.51 (13)
C10—C9—C14—C13	−1.3 (2)	C10—C9—P1—C15	70.23 (14)
P1—C9—C14—C13	175.54 (12)	C20—C15—P1—O4	2.24 (13)
C20—C15—C16—C17	−0.9 (2)	C16—C15—P1—O4	−177.14 (11)
P1—C15—C16—C17	178.48 (11)	C20—C15—P1—O3	−126.43 (11)
C15—C16—C17—C18	2.0 (2)	C16—C15—P1—O3	54.19 (13)
C16—C17—C18—C19	−1.1 (2)	C20—C15—P1—C9	127.97 (11)
C17—C18—C19—C20	−1.0 (2)	C16—C15—P1—C9	−51.41 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1ⁱ	0.95	2.77	3.566 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀NO₄P
M_r	369.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	18.4223 (6), 8.5522 (3), 11.6022 (4)
β (°)	97.181 (1)
V (Å³)	1813.60 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.37 × 0.34 × 0.34

Data collection
Diffractometer	Bruker ApexII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.871, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	14828, 3717, 3172
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.091, 1.05
No. of reflections	3717
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.41

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX publication routines (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1ⁱ	0.95	2.77	3.566 (2)	142

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

Acknowledgements

This work was supported by the Centro de Investigação em Química of the University of Porto. The X-ray data were collected at the Unidade de Raios X, RIAIDT, University of Santiago de Compostela. The authors thank Antonio L. Llamas-Saiz for his help and the Fundação para a Ciência e Tecnologia (FCT) and Xunta de Galicia for financial support (grants POCTI/QUI/44471/2002 and 07CSA008203-PR, respectively). CADS thanks the FCT for grant No. SFRH/BD/31526/2006.

References

Altomare, A., Cascarano, C., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Burla, M. C., Polidori, G., Camalli, M. & Spagna, R. (1997). SIR97. University of Bari, Italy. Google Scholar
Alves, M. J., García-Mera, X., Vale, M. L. C., Santos, T. P., Aguiar, F. R. & Rodrígues-Borges, J. E. (2006). Tetrahedron Lett. 47, 7595–7597. Web of Science CrossRef CAS Google Scholar
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sousa, C. A. D., Vale, M. L. C., Rodrígues-Borges, J. E. & García-Mera, X. (2008). Tetrahedron Lett. 49, 5777–5781. Web of Science CSD CrossRef CAS Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vale, M. L. C., Rodrígues-Borges, J. E., Caamaño, O., Fernández, F. & García-Mera, X. (2006). Tetrahedron, 62, 9475–9482. Google Scholar
Yoda, H., Yamazaki, H., Kawauchi, M. & Takabe, K. (1995). Tetrahedron Asymmetry, 6, 2669–2672. CrossRef CAS Web of Science Google Scholar

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Volume 65| Part 1| January 2009| Page o188

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

Methyl 2-di­phenyl­phosphor­yl­oxy-2-aza­bi­cyclo­[2.2.1]hept-5-ene-3-exo-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-exo-carboxylate