(1S,2E,6R,7aR)-1,6-Dihy­droxy-2-(4-nitro­benzyl­idene)-2,3,5,6,7,7a-hexa­hydro-1H-pyrrolizin-3-one

Oliveira, F.L.; Freire, K.R.L.; Aparicio, R.; Coelho, F.

doi:10.1107/S1600536812018235

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1570-o1571

doi:10.1107/S1600536812018235

Open

access

(1S,2E,6R,7aR)-1,6-Dihydroxy-2-(4-nitrobenzylidene)-2,3,5,6,7,7a-hexahydro-1H-pyrrolizin-3-one

F. L. Oliveira,^a K. R. L. Freire,^b R. Aparicio ^a ^* and F. Coelho ^b

^aLaboratory of Structural Biology and Crystallography, Institute of Chemistry, University of Campinas, CP6154, CEP13083-970, Campinas, SP, Brazil, and ^bLaboratory of Synthesis of Natural Products and Drugs, Institute of Chemistry, University of Campinas, CP6154, CEP13083-970, Campinas, SP, Brazil
^*Correspondence e-mail: aparicio@iqm.unicamp.br

(Received 17 March 2012; accepted 23 April 2012; online 28 April 2012)

The crystal structure of the title compound, C₁₄H₁₄N₂O₅, contains two distinct conformers in the asymmetric unit. The compound has three defined stereocenters, two of them contiguous, and a C=C double bond with an E conformation. The stereocenters exhibit the same chirality in both conformers, with significant differences in the conformation of the five-membered rings of the pyrrolizine unit (both either in a twist or in an envelope form) and in the dihedral angles between the corresponding mean planes and the benzene rings. A prominent feature is a change from almost coplanar rings in one conformer to a new conformation in the second conformer, in which the mean plane of a five-membered ring is almost perpendicular to the benzene ring, with a dihedral angle 87.19 (8)°; the corresponding angle in the first conformer is 14.02 (10)°. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds. Crystallographic data were essential to confirm the configuration of the double bond, which was unclear from the available two-dimensional NMR data. In addition, reliable Flack and Hooft parameters were obtained, allowing for the correct absolute structure to be determined.

Related literature

For the preparation of the title compound, see: Freire et al. (2011 ). For the use of this type of compound as LFA-1 (Lymphocyte Function-Associated Antigen-1) inhibitors, see: Baumann (2007 ). For related structures, see: Oliveira et al. (2012a ,b ).

Experimental

Crystal data

C₁₄H₁₄N₂O₅
M_r = 290.27
Monoclinic, P 2₁
a = 6.8289 (6) Å
b = 7.0433 (6) Å
c = 26.618 (3) Å
β = 92.335 (4)°
V = 1279.2 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.98 mm⁻¹
T = 100 K
0.39 × 0.23 × 0.06 mm

Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: numerical (SADABS; Bruker, 2010 ) T_min = 0.844, T_max = 1.000
41060 measured reflections
4038 independent reflections
3986 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.067
S = 1.01
4038 reflections
383 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ) and Hooft et al. (2008 ); Hooft parameter = 0.04(4), 1539 Bijvoet pairs
Flack parameter: 0.03 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1′ⁱ	0.82	1.93	2.7303 (14)	166
O1—H1A⋯O2ⁱⁱ	0.82	1.89	2.6993 (15)	169
O3′—H3′⋯O3ⁱⁱⁱ	0.82	1.95	2.7585 (15)	171
O1′—H1A′⋯O3′^iv	0.82	1.93	2.7451 (15)	174
C1′—H1′⋯O2′ⁱⁱ	0.98	2.52	3.3655 (17)	144
C1′—H1′⋯O5′^v	0.98	2.55	3.3242 (19)	136
C10—H10⋯O1^vi	0.93	2.54	3.126 (2)	121
C12′—H12′⋯O3′^vii	0.93	2.57	3.5014 (18)	174
C13—H13⋯O4ⁱ	0.93	2.51	3.2644 (19)	138
C13′—H13′⋯O5′ⁱ	0.93	2.51	3.1160 (18)	123
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) x, y-1, z; (iv) x, y+1, z; (v) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+2]$ ; (vii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018235/pv2525sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018235/pv2525Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812018235/pv2525Isup3.cml

checkCIF report

Comment top

The title compound, a new asymmetric benzyl-pyrrolizidinone, has been prepared from a Morita-Baylis-Hillman adduct using a straight forward synthetic sequence developed in our laboratory (Freire et al., 2011). It can be used as a prototype to design new mediators of the activity of LFA-1 (lymphocyte function-associated antigen 1), with potential applications in the treatment of autoimmune diseases and as anti-inflammatory drugs (Baumann, 2007). The title compound has three defined stereocenters, two of them contiguous, and a double bond with E configuration, an information which was not clear from two-dimensional-NOESY NMR studies. A crystal structure determination of the titlte compound has allowed us to establish its correct configuration, which is reported in this article.

In the crystal structure of the title compound, an asymmetric unit contains two distinct conformers, molecule 1 (Fig. 1) and molecule 2 (Fig. 2), whose stereocenters exhibit the same chirality. In molecule 1, the five membered rings N1/C3/C2/C1/C7A and N1/C5/C6/C7/C7A of the pyrrolizine moiety exhibit C1- and C7-envelope conformations, respectively, with C1 and C7 atoms displaced from the mean-planes formed by the remaining rings atoms by 0.3194 (14) and 0.592 (2) Å, respectively. The mean planes of these rings have a dihedral angle of 23.47 (10)°, and are almost coplanar to the benzene ring, with which they form dihedral angles of 24.52 (9)° and 14.02 (10)°, respectively. The molecule 2 exhibits the rings N1'/C7A'/C1'/C2'/C3' and N1'/C7A'/C7'/C6'/C5' in a twisted conformation on C7A'-C1' and N1'-C7A', respectively, with a dihedral angle between their mean planes equal to 58.07 (8)°. The dihedral angle between the mean planes of the ring N1'/C7A'/C1'/C2'/C3' and the benzene ring is 34.75 (7)°. The ring N1'/C7A'/C7'/C6'/C5' is almost perpendicular to the latter with a corresponding angle equal to 87.19 (8)°. The atom C1' lies 0.3200 (14) Å out of the plane formed by the rest of the ring atoms (N1'/C7A'/C2'/C3'). The corresponding measurement for the atom C7A' in relation to the mean plane formed by the other atoms in the ring (N1'/C7'/C6'/C5') is 0.4771 (13) Å. In the crystal, the molecules are held together by intermolecular hydrogen bonds (Tab. 1 and Fig. 3).

Related literature top

For the preparation of the title compound, see: Freire et al. (2011). For the use of this type of compound as LFA-1 (Lymphocyte Function-Associated Antigen-1) inhibitors, see: Baumann (2007). For related structures, see: Oliveira et al. (2012a,b).

Experimental top

The title compound was prepared by a synthetic sequence recently described in the literature (Freire et al., 2011) and purified by flash silica gel column chromatography (CH₂Cl₂ : MeOH – solvent gradient: 100:0 to 95:05) to afford 0.07 g (as a white solid) in 83% yield. It was then recrystallized using the liquid-vapor saturation method, dissolved in ethanol and crystallized subject to the vapor pressure of a second less polar liquid (ethyl ether), in a closed camera, providing the slow formation of crystals.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of molecule 1 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of molecule 2 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 3. A view of the hydrogen bonding interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity.

(1S,2E,6R,7aR)-1,6-Dihydroxy-2- (4-nitrobenzylidene)-2,3,5,6,7,7a-hexahydro-1H-pyrrolizin-3-one top

Crystal data top

C₁₄H₁₄N₂O₅	F(000) = 608
M_r = 290.27	D_x = 1.507 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
a = 6.8289 (6) Å	Cell parameters from 4038 reflections
b = 7.0433 (6) Å	θ = 1.7–67.8°
c = 26.618 (3) Å	µ = 0.98 mm⁻¹
β = 92.335 (4)°	T = 100 K
V = 1279.2 (2) Å³	Plate, orange
Z = 4	0.39 × 0.23 × 0.06 mm

Data collection top

Bruker Kappa APEXII DUO diffractometer	4038 independent reflections
Radiation source: fine-focus sealed tube	3986 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Bruker APEX CCD area–detector scans	θ_max = 67.8°, θ_min = 1.7°
Absorption correction: numerical (SADABS; Bruker, 2010)	h = −8→8
T_min = 0.844, T_max = 1.000	k = −8→6
41060 measured reflections	l = −31→31

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0419P)² + 0.3034P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
4038 reflections	Δρ_max = 0.15 e Å⁻³
383 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983) and Hooft et al. (2008); Hooft parameter = 0.04(4), 1539 Bijvoet pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (11)

Crystal data top

C₁₄H₁₄N₂O₅	V = 1279.2 (2) Å³
M_r = 290.27	Z = 4
Monoclinic, P2₁	Cu Kα radiation
a = 6.8289 (6) Å	µ = 0.98 mm⁻¹
b = 7.0433 (6) Å	T = 100 K
c = 26.618 (3) Å	0.39 × 0.23 × 0.06 mm
β = 92.335 (4)°

Data collection top

Bruker Kappa APEXII DUO diffractometer	4038 independent reflections
Absorption correction: numerical (SADABS; Bruker, 2010)	3986 reflections with I > 2σ(I)
T_min = 0.844, T_max = 1.000	R_int = 0.037
41060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.067	Δρ_max = 0.15 e Å⁻³
S = 1.01	Δρ_min = −0.16 e Å⁻³
4038 reflections	Absolute structure: Flack (1983) and Hooft et al. (2008); Hooft parameter = 0.04(4), 1539 Bijvoet pairs
383 parameters	Absolute structure parameter: 0.03 (11)
1 restraint

Special details top

Experimental. [α]D²⁰ + 28° (c 2, MeOH); IR (Film, ν_max): 3308, 2974, 2924, 2864, 1699, 1671, 1644, 1596, 1523, 1513, 1435, 1381, 1346, 1314, 1264, 1244, 1220, 1202, 1133, 1104, 1075, 1055 cm^-1; ¹H NMR (400 MHz, CD₃OD) δ 1.49 (ddd, J = 13.2, 8.3, 5.1 Hz, 1H, H-7 A); 2.49 (ddd, J = 13.3, 7.4, 6.2 Hz, 1H, H-7B); 3.38 (dd, J = 12.4, 5.8 Hz, 1H, H-5 A); 3.68 (dd, J = 12.4, 3.0 Hz, 1H, H-5B); 3.80 (td, J = 8.1, 2.4 Hz, 1H, H-7 C); 4.56 (qd, J = 5.8, 3.3 Hz 1H, H-6); 5.01 (t, J = 2.4 Hz, 1H, H-1); 7.45 (d, J = 2.3 Hz, 1H, H-4); 8.01 (d, J = 8.8 Hz, 2H, Ar); 8.26 (d, J = 8.9 Hz, 2H, Ar); ¹³C NMR (62.5 MHz, CD₃CN) 39.2; 53.3; 68.4; 71.5; 72.5; 124.3; 132.4; 133.2; 140.5; 141.8; 148.6; 170.9; HRMS (ESI-TOF) m/z Calc. for C₁₄H₁₅N₂O₅ [M + H]⁺: 291.0981. Found 291.0989.

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
O4	0.39324 (16)	0.4194 (2)	1.13861 (4)	0.0321 (3)
O3	1.01737 (15)	0.58119 (18)	0.71964 (4)	0.0225 (2)
H3	1.1038	0.5564	0.7002	0.034*
O5	0.64579 (19)	0.4992 (2)	1.18584 (4)	0.0403 (3)
O2	1.35576 (15)	0.51910 (18)	0.90371 (4)	0.0242 (3)
O1	0.69151 (14)	0.31660 (18)	0.90951 (4)	0.0229 (2)
H1A	0.5821	0.3645	0.9071	0.034*
O4'	−0.02923 (16)	0.27989 (18)	0.37824 (4)	0.0276 (3)
O3'	0.64995 (14)	−0.31144 (17)	0.68320 (4)	0.0213 (2)
H3'	0.7590	−0.3523	0.6914	0.032*
O5'	−0.20844 (14)	0.44237 (19)	0.42810 (4)	0.0253 (2)
O2'	0.89538 (14)	0.19376 (18)	0.63315 (4)	0.0246 (2)
O1'	0.32974 (14)	0.45702 (17)	0.66785 (4)	0.0208 (2)
H1A'	0.4302	0.5197	0.6722	0.031*
N1	1.11842 (16)	0.4299 (2)	0.84513 (4)	0.0190 (3)
N2'	−0.05497 (17)	0.3612 (2)	0.41818 (5)	0.0200 (3)
C8'	0.3952 (2)	0.3245 (2)	0.53145 (5)	0.0186 (3)
N1'	0.67054 (17)	0.15506 (19)	0.69496 (5)	0.0182 (3)
N2	0.5662 (2)	0.4640 (2)	1.14448 (5)	0.0268 (3)
C11	0.6877 (2)	0.4734 (2)	1.10041 (6)	0.0230 (3)
C10	0.6000 (2)	0.5089 (3)	1.05377 (6)	0.0243 (3)
H10	0.4657	0.5303	1.0504	0.029*
C9	0.7149 (2)	0.5122 (3)	1.01205 (6)	0.0231 (3)
H9	0.6577	0.5391	0.9805	0.028*
C8	0.9165 (2)	0.4754 (2)	1.01693 (5)	0.0204 (3)
C4	1.0493 (2)	0.4734 (2)	0.97498 (5)	0.0203 (3)
H4	1.1813	0.4820	0.9848	0.024*
C2	1.0161 (2)	0.4615 (2)	0.92537 (5)	0.0182 (3)
C1	0.83077 (19)	0.4455 (2)	0.89178 (5)	0.0181 (3)
H1	0.7706	0.5712	0.8877	0.022*
C7A	0.9103 (2)	0.3801 (2)	0.84114 (5)	0.0184 (3)
H7C	0.8963	0.2421	0.8379	0.022*
C7	0.84455 (19)	0.4745 (3)	0.79203 (5)	0.0200 (3)
H7A	0.8157	0.6079	0.7970	0.024*
H7B	0.7298	0.4122	0.7770	0.024*
C6	1.0236 (2)	0.4485 (3)	0.75953 (5)	0.0197 (3)
H6	1.0251	0.3191	0.7460	0.024*
C12	0.8871 (2)	0.4445 (3)	1.10728 (6)	0.0242 (3)
H12	0.9440	0.4252	1.1392	0.029*
C13	0.9999 (2)	0.4452 (3)	1.06502 (6)	0.0224 (3)
H13	1.1343	0.4251	1.0689	0.027*
C5	1.2005 (2)	0.4771 (3)	0.79686 (5)	0.0219 (3)
H5A	1.3075	0.3927	0.7893	0.026*
H5B	1.2468	0.6073	0.7964	0.026*
C3	1.1863 (2)	0.4727 (2)	0.89175 (5)	0.0187 (3)
C11'	0.1040 (2)	0.3571 (2)	0.45687 (6)	0.0184 (3)
C10'	0.0645 (2)	0.4121 (2)	0.50562 (5)	0.0185 (3)
H10'	−0.0580	0.4598	0.5130	0.022*
C9'	0.2104 (2)	0.3945 (2)	0.54290 (6)	0.0193 (3)
H9'	0.1857	0.4294	0.5757	0.023*
C4'	0.5558 (2)	0.2916 (2)	0.56866 (5)	0.0193 (3)
H4'	0.6804	0.2868	0.5558	0.023*
C2'	0.5490 (2)	0.2677 (2)	0.61826 (5)	0.0179 (3)
C3'	0.7287 (2)	0.2047 (2)	0.64785 (5)	0.0186 (3)
C5'	0.7559 (2)	−0.0070 (2)	0.72222 (6)	0.0220 (3)
H5A'	0.7835	0.0247	0.7573	0.026*
H5B'	0.8765	−0.0475	0.7074	0.026*
C6'	0.5976 (2)	−0.1640 (2)	0.71715 (5)	0.0190 (3)
H6'	0.5717	−0.2175	0.7502	0.023*
C7'	0.4137 (2)	−0.0660 (3)	0.69485 (5)	0.0200 (3)
H7A'	0.3879	−0.1059	0.6603	0.024*
H7B'	0.3006	−0.0968	0.7142	0.024*
C7A'	0.4561 (2)	0.1466 (2)	0.69725 (5)	0.0176 (3)
H7C'	0.4138	0.1998	0.7291	0.021*
C1'	0.3793 (2)	0.2681 (2)	0.65274 (5)	0.0169 (3)
H1'	0.2651	0.2069	0.6362	0.020*
C13'	0.4305 (2)	0.2780 (2)	0.48130 (6)	0.0199 (3)
H13'	0.5548	0.2371	0.4732	0.024*
C12'	0.2860 (2)	0.2915 (2)	0.44377 (5)	0.0198 (3)
H12'	0.3100	0.2577	0.4108	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0276 (6)	0.0393 (8)	0.0296 (6)	0.0024 (6)	0.0041 (4)	0.0055 (6)
O3	0.0216 (5)	0.0263 (6)	0.0200 (5)	0.0046 (5)	0.0061 (4)	0.0038 (5)
O5	0.0488 (7)	0.0514 (9)	0.0208 (6)	−0.0125 (7)	0.0030 (5)	−0.0045 (6)
O2	0.0145 (5)	0.0288 (7)	0.0290 (6)	0.0000 (5)	−0.0015 (4)	−0.0011 (5)
O1	0.0162 (5)	0.0249 (6)	0.0280 (5)	−0.0014 (5)	0.0051 (4)	0.0020 (5)
O4'	0.0290 (6)	0.0305 (7)	0.0233 (5)	−0.0010 (5)	0.0004 (4)	−0.0059 (5)
O3'	0.0184 (5)	0.0207 (6)	0.0247 (5)	0.0009 (5)	−0.0004 (4)	−0.0056 (5)
O5'	0.0194 (5)	0.0293 (7)	0.0272 (5)	0.0044 (5)	0.0025 (4)	0.0036 (5)
O2'	0.0146 (5)	0.0271 (6)	0.0322 (5)	0.0012 (5)	0.0031 (4)	0.0004 (5)
O1'	0.0176 (5)	0.0155 (6)	0.0296 (5)	0.0005 (4)	0.0043 (4)	−0.0030 (5)
N1	0.0135 (5)	0.0232 (7)	0.0204 (6)	0.0020 (6)	0.0018 (4)	−0.0001 (6)
N2'	0.0218 (6)	0.0180 (7)	0.0205 (6)	−0.0023 (6)	0.0027 (5)	0.0034 (5)
C8'	0.0214 (7)	0.0141 (8)	0.0205 (7)	−0.0017 (6)	0.0036 (6)	0.0026 (6)
N1'	0.0153 (6)	0.0176 (7)	0.0215 (6)	0.0003 (5)	−0.0026 (5)	−0.0014 (5)
N2	0.0366 (7)	0.0233 (8)	0.0206 (6)	0.0000 (7)	0.0035 (5)	0.0014 (6)
C11	0.0309 (8)	0.0168 (9)	0.0216 (7)	−0.0010 (7)	0.0046 (6)	−0.0016 (7)
C10	0.0246 (7)	0.0254 (9)	0.0229 (7)	0.0033 (7)	0.0010 (6)	−0.0015 (7)
C9	0.0272 (8)	0.0226 (9)	0.0192 (7)	0.0040 (7)	−0.0011 (6)	−0.0010 (7)
C8	0.0243 (7)	0.0162 (8)	0.0206 (7)	−0.0016 (7)	0.0000 (5)	−0.0024 (6)
C4	0.0184 (7)	0.0185 (9)	0.0238 (7)	0.0003 (6)	−0.0015 (5)	0.0004 (7)
C2	0.0170 (7)	0.0159 (8)	0.0217 (7)	0.0015 (6)	0.0007 (5)	0.0016 (6)
C1	0.0160 (6)	0.0182 (8)	0.0201 (7)	0.0005 (6)	0.0013 (5)	0.0007 (7)
C7A	0.0146 (6)	0.0179 (8)	0.0228 (7)	−0.0010 (6)	0.0003 (5)	0.0001 (6)
C7	0.0146 (6)	0.0249 (9)	0.0204 (7)	0.0008 (6)	0.0005 (5)	0.0005 (7)
C6	0.0190 (7)	0.0207 (8)	0.0194 (7)	0.0010 (7)	0.0018 (5)	−0.0003 (7)
C12	0.0326 (8)	0.0200 (9)	0.0195 (7)	−0.0045 (7)	−0.0043 (6)	0.0007 (7)
C13	0.0231 (7)	0.0187 (8)	0.0251 (7)	−0.0019 (7)	−0.0023 (6)	−0.0003 (7)
C5	0.0169 (7)	0.0283 (9)	0.0210 (7)	0.0003 (7)	0.0047 (5)	−0.0013 (7)
C3	0.0187 (7)	0.0145 (8)	0.0228 (7)	0.0034 (6)	−0.0004 (5)	0.0008 (6)
C11'	0.0200 (7)	0.0140 (8)	0.0214 (7)	−0.0016 (6)	0.0014 (5)	0.0032 (6)
C10'	0.0181 (6)	0.0151 (8)	0.0226 (7)	0.0013 (6)	0.0057 (5)	0.0012 (6)
C9'	0.0226 (7)	0.0166 (8)	0.0192 (7)	−0.0001 (6)	0.0048 (6)	0.0009 (6)
C4'	0.0176 (6)	0.0158 (8)	0.0248 (7)	−0.0009 (6)	0.0056 (6)	−0.0001 (6)
C2'	0.0164 (7)	0.0134 (8)	0.0239 (7)	0.0001 (6)	0.0012 (5)	−0.0005 (6)
C3'	0.0173 (7)	0.0147 (8)	0.0238 (7)	−0.0008 (6)	0.0002 (5)	−0.0035 (7)
C5'	0.0217 (7)	0.0198 (9)	0.0240 (7)	0.0001 (7)	−0.0054 (5)	−0.0009 (7)
C6'	0.0202 (7)	0.0197 (9)	0.0172 (6)	0.0013 (7)	0.0014 (5)	0.0003 (6)
C7'	0.0181 (6)	0.0197 (8)	0.0222 (7)	−0.0012 (7)	−0.0014 (5)	0.0009 (7)
C7A'	0.0150 (6)	0.0200 (9)	0.0179 (7)	0.0002 (6)	0.0008 (5)	−0.0025 (6)
C1'	0.0169 (7)	0.0149 (8)	0.0190 (6)	0.0007 (6)	0.0006 (5)	−0.0032 (6)
C13'	0.0191 (7)	0.0171 (8)	0.0240 (7)	0.0018 (6)	0.0080 (6)	0.0031 (7)
C12'	0.0233 (7)	0.0181 (8)	0.0182 (6)	−0.0003 (7)	0.0052 (6)	0.0004 (6)

Geometric parameters (Å, º) top

O4—N2	1.2262 (18)	C1—C7A	1.5439 (19)
O3—C6	1.414 (2)	C1—H1	0.9800
O3—H3	0.8200	C7A—C7	1.518 (2)
O5—N2	1.2328 (18)	C7A—H7C	0.9800
O2—C3	1.2321 (19)	C7—C6	1.5374 (18)
O1—C1	1.4100 (19)	C7—H7A	0.9700
O1—H1A	0.8200	C7—H7B	0.9700
O4'—N2'	1.2266 (18)	C6—C5	1.5455 (19)
O3'—C6'	1.4316 (19)	C6—H6	0.9800
O3'—H3'	0.8200	C12—C13	1.389 (2)
O5'—N2'	1.2319 (17)	C12—H12	0.9300
O2'—C3'	1.2209 (18)	C13—H13	0.9300
O1'—C1'	1.434 (2)	C5—H5A	0.9700
O1'—H1A'	0.8200	C5—H5B	0.9700
N1—C3	1.3409 (19)	C11'—C12'	1.384 (2)
N1—C5	1.4608 (18)	C11'—C10'	1.391 (2)
N1—C7A	1.4637 (17)	C10'—C9'	1.383 (2)
N2'—C11'	1.4657 (19)	C10'—H10'	0.9300
C8'—C9'	1.400 (2)	C9'—H9'	0.9300
C8'—C13'	1.405 (2)	C4'—C2'	1.334 (2)
C8'—C4'	1.466 (2)	C4'—H4'	0.9300
N1'—C3'	1.3760 (19)	C2'—C3'	1.498 (2)
N1'—C5'	1.461 (2)	C2'—C1'	1.5073 (19)
N1'—C7A'	1.4696 (17)	C5'—C6'	1.549 (2)
N2—C11	1.4655 (19)	C5'—H5A'	0.9700
C11—C10	1.379 (2)	C5'—H5B'	0.9700
C11—C12	1.381 (2)	C6'—C7'	1.531 (2)
C10—C9	1.386 (2)	C6'—H6'	0.9800
C10—H10	0.9300	C7'—C7A'	1.526 (2)
C9—C8	1.402 (2)	C7'—H7A'	0.9700
C9—H9	0.9300	C7'—H7B'	0.9700
C8—C13	1.396 (2)	C7A'—C1'	1.537 (2)
C8—C4	1.467 (2)	C7A'—H7C'	0.9800
C4—C2	1.333 (2)	C1'—H1'	0.9800
C4—H4	0.9300	C13'—C12'	1.379 (2)
C2—C3	1.497 (2)	C13'—H13'	0.9300
C2—C1	1.5236 (19)	C12'—H12'	0.9300

C6—O3—H3	109.5	C12—C13—H13	119.2
C1—O1—H1A	109.5	C8—C13—H13	119.2
C6'—O3'—H3'	109.5	N1—C5—C6	102.60 (11)
C1'—O1'—H1A'	109.5	N1—C5—H5A	111.2
C3—N1—C5	129.22 (13)	C6—C5—H5A	111.2
C3—N1—C7A	114.76 (11)	N1—C5—H5B	111.2
C5—N1—C7A	113.38 (11)	C6—C5—H5B	111.2
O4'—N2'—O5'	123.76 (13)	H5A—C5—H5B	109.2
O4'—N2'—C11'	118.14 (12)	O2—C3—N1	125.74 (13)
O5'—N2'—C11'	118.08 (12)	O2—C3—C2	127.10 (13)
C9'—C8'—C13'	118.70 (13)	N1—C3—C2	107.10 (12)
C9'—C8'—C4'	124.39 (13)	C12'—C11'—C10'	122.56 (14)
C13'—C8'—C4'	116.89 (13)	C12'—C11'—N2'	118.47 (13)
C3'—N1'—C5'	121.79 (13)	C10'—C11'—N2'	118.92 (13)
C3'—N1'—C7A'	111.93 (11)	C9'—C10'—C11'	118.88 (13)
C5'—N1'—C7A'	109.02 (12)	C9'—C10'—H10'	120.6
O4—N2—O5	123.54 (13)	C11'—C10'—H10'	120.6
O4—N2—C11	118.90 (12)	C10'—C9'—C8'	120.32 (14)
O5—N2—C11	117.55 (13)	C10'—C9'—H9'	119.8
C10—C11—C12	122.37 (14)	C8'—C9'—H9'	119.8
C10—C11—N2	119.32 (14)	C2'—C4'—C8'	129.29 (14)
C12—C11—N2	118.31 (13)	C2'—C4'—H4'	115.4
C11—C10—C9	119.04 (15)	C8'—C4'—H4'	115.4
C11—C10—H10	120.5	C4'—C2'—C3'	119.78 (13)
C9—C10—H10	120.5	C4'—C2'—C1'	131.40 (13)
C10—C9—C8	120.56 (14)	C3'—C2'—C1'	108.31 (12)
C10—C9—H9	119.7	O2'—C3'—N1'	125.71 (13)
C8—C9—H9	119.7	O2'—C3'—C2'	127.20 (13)
C13—C8—C9	118.40 (14)	N1'—C3'—C2'	107.07 (12)
C13—C8—C4	117.06 (13)	N1'—C5'—C6'	104.55 (11)
C9—C8—C4	124.50 (13)	N1'—C5'—H5A'	110.8
C2—C4—C8	131.99 (14)	C6'—C5'—H5A'	110.8
C2—C4—H4	114.0	N1'—C5'—H5B'	110.8
C8—C4—H4	114.0	C6'—C5'—H5B'	110.8
C4—C2—C3	118.93 (13)	H5A'—C5'—H5B'	108.9
C4—C2—C1	133.59 (13)	O3'—C6'—C7'	107.72 (12)
C3—C2—C1	107.43 (11)	O3'—C6'—C5'	112.42 (12)
O1—C1—C2	114.00 (12)	C7'—C6'—C5'	105.71 (13)
O1—C1—C7A	111.46 (13)	O3'—C6'—H6'	110.3
C2—C1—C7A	102.77 (11)	C7'—C6'—H6'	110.3
O1—C1—H1	109.5	C5'—C6'—H6'	110.3
C2—C1—H1	109.5	C7A'—C7'—C6'	105.95 (12)
C7A—C1—H1	109.5	C7A'—C7'—H7A'	110.5
N1—C7A—C7	102.11 (11)	C6'—C7'—H7A'	110.5
N1—C7A—C1	103.90 (11)	C7A'—C7'—H7B'	110.5
C7—C7A—C1	121.27 (13)	C6'—C7'—H7B'	110.5
N1—C7A—H7C	109.6	H7A'—C7'—H7B'	108.7
C7—C7A—H7C	109.6	N1'—C7A'—C7'	103.06 (12)
C1—C7A—H7C	109.6	N1'—C7A'—C1'	104.75 (11)
C7A—C7—C6	102.61 (11)	C7'—C7A'—C1'	117.14 (12)
C7A—C7—H7A	111.2	N1'—C7A'—H7C'	110.5
C6—C7—H7A	111.2	C7'—C7A'—H7C'	110.5
C7A—C7—H7B	111.2	C1'—C7A'—H7C'	110.5
C6—C7—H7B	111.2	O1'—C1'—C2'	111.62 (12)
H7A—C7—H7B	109.2	O1'—C1'—C7A'	112.18 (11)
O3—C6—C5	113.29 (13)	C2'—C1'—C7A'	102.81 (11)
O3—C6—C7	110.09 (12)	O1'—C1'—H1'	110.0
C5—C6—C7	103.96 (11)	C2'—C1'—H1'	110.0
O3—C6—H6	109.8	C7A'—C1'—H1'	110.0
C5—C6—H6	109.8	C12'—C13'—C8'	121.81 (13)
C7—C6—H6	109.8	C12'—C13'—H13'	119.1
C11—C12—C13	117.93 (14)	C8'—C13'—H13'	119.1
C11—C12—H12	121.0	C13'—C12'—C11'	117.65 (13)
C13—C12—H12	121.0	C13'—C12'—H12'	121.2
C12—C13—C8	121.61 (14)	C11'—C12'—H12'	121.2

O4—N2—C11—C10	26.1 (2)	O4'—N2'—C11'—C12'	11.0 (2)
O5—N2—C11—C10	−154.96 (17)	O5'—N2'—C11'—C12'	−170.61 (15)
O4—N2—C11—C12	−153.41 (17)	O4'—N2'—C11'—C10'	−166.52 (15)
O5—N2—C11—C12	25.5 (2)	O5'—N2'—C11'—C10'	11.9 (2)
C12—C11—C10—C9	1.3 (3)	C12'—C11'—C10'—C9'	−2.3 (2)
N2—C11—C10—C9	−178.18 (16)	N2'—C11'—C10'—C9'	175.13 (14)
C11—C10—C9—C8	1.6 (3)	C11'—C10'—C9'—C8'	0.7 (2)
C10—C9—C8—C13	−3.3 (3)	C13'—C8'—C9'—C10'	1.8 (2)
C10—C9—C8—C4	179.20 (16)	C4'—C8'—C9'—C10'	−176.78 (15)
C13—C8—C4—C2	165.53 (19)	C9'—C8'—C4'—C2'	20.8 (3)
C9—C8—C4—C2	−16.9 (3)	C13'—C8'—C4'—C2'	−157.82 (17)
C8—C4—C2—C3	177.05 (17)	C8'—C4'—C2'—C3'	170.07 (16)
C8—C4—C2—C1	0.0 (3)	C8'—C4'—C2'—C1'	−0.8 (3)
C4—C2—C1—O1	−43.3 (3)	C5'—N1'—C3'—O2'	−36.3 (2)
C3—C2—C1—O1	139.45 (13)	C7A'—N1'—C3'—O2'	−167.84 (16)
C4—C2—C1—C7A	−164.06 (19)	C5'—N1'—C3'—C2'	141.93 (13)
C3—C2—C1—C7A	18.68 (16)	C7A'—N1'—C3'—C2'	10.41 (17)
C3—N1—C7A—C7	140.96 (14)	C4'—C2'—C3'—O2'	10.2 (3)
C5—N1—C7A—C7	−22.39 (18)	C1'—C2'—C3'—O2'	−177.00 (16)
C3—N1—C7A—C1	14.10 (18)	C4'—C2'—C3'—N1'	−168.00 (15)
C5—N1—C7A—C1	−149.25 (14)	C1'—C2'—C3'—N1'	4.77 (17)
O1—C1—C7A—N1	−141.64 (12)	C3'—N1'—C5'—C6'	−103.79 (15)
C2—C1—C7A—N1	−19.14 (16)	C7A'—N1'—C5'—C6'	28.93 (15)
O1—C1—C7A—C7	104.60 (16)	N1'—C5'—C6'—O3'	107.05 (14)
C2—C1—C7A—C7	−132.91 (14)	N1'—C5'—C6'—C7'	−10.21 (15)
N1—C7A—C7—C6	36.32 (15)	O3'—C6'—C7'—C7A'	−131.16 (13)
C1—C7A—C7—C6	151.00 (14)	C5'—C6'—C7'—C7A'	−10.78 (15)
C7A—C7—C6—O3	−159.78 (13)	C3'—N1'—C7A'—C7'	102.01 (14)
C7A—C7—C6—C5	−38.13 (16)	C5'—N1'—C7A'—C7'	−35.68 (14)
C10—C11—C12—C13	−2.3 (3)	C3'—N1'—C7A'—C1'	−21.04 (17)
N2—C11—C12—C13	177.18 (16)	C5'—N1'—C7A'—C1'	−158.73 (12)
C11—C12—C13—C8	0.5 (3)	C6'—C7'—C7A'—N1'	27.53 (14)
C9—C8—C13—C12	2.2 (3)	C6'—C7'—C7A'—C1'	141.91 (12)
C4—C8—C13—C12	179.95 (16)	C4'—C2'—C1'—O1'	−84.7 (2)
C3—N1—C5—C6	−161.69 (16)	C3'—C2'—C1'—O1'	103.71 (14)
C7A—N1—C5—C6	−1.32 (18)	C4'—C2'—C1'—C7A'	154.90 (17)
O3—C6—C5—N1	143.86 (13)	C3'—C2'—C1'—C7A'	−16.73 (15)
C7—C6—C5—N1	24.36 (16)	N1'—C7A'—C1'—O1'	−97.99 (13)
C5—N1—C3—O2	−19.5 (3)	C7'—C7A'—C1'—O1'	148.58 (12)
C7A—N1—C3—O2	−179.69 (15)	N1'—C7A'—C1'—C2'	22.06 (15)
C5—N1—C3—C2	157.98 (16)	C7'—C7A'—C1'—C2'	−91.37 (14)
C7A—N1—C3—C2	−2.17 (18)	C9'—C8'—C13'—C12'	−3.0 (2)
C4—C2—C3—O2	−11.3 (3)	C4'—C8'—C13'—C12'	175.74 (15)
C1—C2—C3—O2	166.43 (16)	C8'—C13'—C12'—C11'	1.5 (2)
C4—C2—C3—N1	171.22 (16)	C10'—C11'—C12'—C13'	1.2 (2)
C1—C2—C3—N1	−11.05 (17)	N2'—C11'—C12'—C13'	−176.23 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1′ⁱ	0.82	1.93	2.7303 (14)	166
O1—H1A···O2ⁱⁱ	0.82	1.89	2.6993 (15)	169
O3′—H3′···O3ⁱⁱⁱ	0.82	1.95	2.7585 (15)	171
O1′—H1A′···O3′^iv	0.82	1.93	2.7451 (15)	174
C1′—H1′···O2′ⁱⁱ	0.98	2.52	3.3655 (17)	144
C1′—H1′···O5′^v	0.98	2.55	3.3242 (19)	136
C10—H10···O1^vi	0.93	2.54	3.126 (2)	121
C12′—H12′···O3′^vii	0.93	2.57	3.5014 (18)	174
C13—H13···O4ⁱ	0.93	2.51	3.2644 (19)	138
C13′—H13′···O5′ⁱ	0.93	2.51	3.1160 (18)	123

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₂O₅
M_r	290.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	6.8289 (6), 7.0433 (6), 26.618 (3)
β (°)	92.335 (4)
V (Å³)	1279.2 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.39 × 0.23 × 0.06

Data collection
Diffractometer	Bruker Kappa APEXII DUO diffractometer
Absorption correction	Numerical (SADABS; Bruker, 2010)
T_min, T_max	0.844, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	41060, 4038, 3986
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.067, 1.01
No. of reflections	4038
No. of parameters	383
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16
Absolute structure	Flack (1983) and Hooft et al. (2008); Hooft parameter = 0.04(4), 1539 Bijvoet pairs
Absolute structure parameter	0.03 (11)

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1'ⁱ	0.82	1.93	2.7303 (14)	165.7
O1—H1A···O2ⁱⁱ	0.82	1.89	2.6993 (15)	169.0
O3'—H3'···O3ⁱⁱⁱ	0.82	1.95	2.7585 (15)	170.7
O1'—H1A'···O3'^iv	0.82	1.93	2.7451 (15)	174.4
C1'—H1'···O2'ⁱⁱ	0.98	2.52	3.3655 (17)	144.0
C1'—H1'···O5'^v	0.98	2.55	3.3242 (19)	136.0
C10—H10···O1^vi	0.93	2.54	3.126 (2)	121.0
C12'—H12'···O3'^vii	0.93	2.57	3.5014 (18)	174.0
C13—H13···O4ⁱ	0.93	2.51	3.2644 (19)	138.0
C13'—H13'···O5'ⁱ	0.93	2.51	3.1160 (18)	123.0

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

Acknowledgements

The authors acknowledge the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for financial support. FLO and KRLF were supported by bursaries from CAPES and CNPq, respectively. KRLF is currently a FAPESP post-doctoral fellow. RA and FC are recipients of research grants from CNPq.

References

Baumann, K. O. (2007). WO Patent 2007039286; Chem. Abstr. 146, 421836. Google Scholar
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Freire, K. R. L., Tormena, C. F. & Coelho, F. (2011). Synlett, 14, 2059–2063. Google Scholar
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96–103. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oliveira, F. L., Freire, K. R. L., Aparicio, R. & Coelho, F. (2012a). Acta Cryst. E68, o586. CSD CrossRef IUCr Journals Google Scholar
Oliveira, F. L., Freire, K. R. L., Aparicio, R. & Coelho, F. (2012b). Acta Cryst. E68, o587. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1570-o1571

doi:10.1107/S1600536812018235

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

(1S,2E,6R,7aR)-1,6-Dihy­dr­oxy-2-(4-nitro­benzyl­­idene)-2,3,5,6,7,7a-hexa­hydro-1H-pyrrolizin-3-one

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(1S,2E,6R,7aR)-1,6-Dihydroxy-2-(4-nitrobenzylidene)-2,3,5,6,7,7a-hexahydro-1H-pyrrolizin-3-one