rac-Methyl 4-azido-3-hydr-oxy-3-(2-nitro-phen-yl)butanoate.

In the title compound, C(11)H(12)N(4)O(5), the mean plane through the nitro substituent on the benzene ring is inclined to the benzene mean plane by 85.8 (2)°, which avoids steric inter-actions with the ortho substituents. The hydr-oxy group is involved in bifurcated hydrogen bonds. The first is an intra-molecular O-H⋯O hydrogen bond, involving the ester carbonyl O atom, which gives rise to the formation of a boat-like hydrogen-bonded chelate ring. The second is an inter-molecular O-H⋯N hydrogen bond involving the first N atom of the azide group of a symmetry-related mol-ecule. In the crystal structure this leads to the formation of a polmer chain extending in the c-axis direction.

Related literature

For literature related to the anti­tumor properties of rhazinilam, see: Bonneau et al. (2007 ▶). For literature related to the synthesis and structure–activity relationships of rhazinilam analogues, see: Decor et al. (2006 ▶); Baudoin et al. (2002 ▶); Ghosez et al. (2001 ▶); Rubio & Bornmann (2001 ▶); Dupont et al. (2000 ▶, 1999 ▶); Alazard et al. (1996 ▶). For details of the Mukaiyama reaction, see: Mukaiyama et al. (1974 ▶). For literature related to the synthesis of pyrrolinone precursors, see: Vallat (2004 ▶); Vallat et al. (2009 ▶).

Experimental

Crystal data

C11H12N4O5

M = 280.25

Monoclinic,

a = 9.4772 (11) Å

b = 14.0710 (12) Å

c = 10.1861 (12) Å

β = 110.496 (13)°

V = 1272.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 153 (2) K

0.40 × 0.30 × 0.30 mm

Data collection

Stoe IPDS diffractometer

Absorption correction: none

8743 measured reflections

2451 independent reflections

1587 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.088

S = 0.87

2451 reflections

230 parameters

All H-atom parameters refined

Δρmax = 0.23 e Å−3

Δρmin = −0.21 e Å−3

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 2000 ▶); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808043857/lh2749sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043857/lh2749Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H12N4O5	F(000) = 584
Mr = 280.25	Dx = 1.463 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5300 reflections
a = 9.4772 (11) Å	θ = 2.6–25.8°
b = 14.0710 (12) Å	µ = 0.12 mm−1
c = 10.1861 (12) Å	T = 153 K
β = 110.496 (13)°	Plate, colourless
V = 1272.4 (2) Å3	0.40 × 0.30 × 0.30 mm
Z = 4

Stoe IPDS diffractometer	1587 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.074
graphite	θmax = 25.9°, θmin = 2.5°
φ oscillation scans	h = −11→11
8743 measured reflections	k = −17→17
2451 independent reflections	l = −12→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	All H-atom parameters refined
wR(F2) = 0.088	w = 1/[σ2(Fo2) + (0.0487P)2] where P = (Fo2 + 2Fc2)/3
S = 0.87	(Δ/σ)max < 0.001
2451 reflections	Δρmax = 0.23 e Å−3
230 parameters	Δρmin = −0.21 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0087 (18)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
O1	0.32528 (17)	−0.00702 (10)	0.18798 (17)	0.0599 (6)
O2	0.39794 (16)	0.06178 (11)	0.39169 (15)	0.0653 (5)
O3	0.20867 (11)	0.19457 (8)	0.17217 (12)	0.0272 (4)
O4	0.13982 (13)	0.26155 (8)	0.41688 (11)	0.0370 (4)
O5	−0.07815 (12)	0.34053 (9)	0.35528 (11)	0.0372 (4)
N1	0.30233 (17)	0.02628 (11)	0.28967 (16)	0.0424 (5)
N2	−0.03288 (14)	0.22705 (10)	−0.10334 (13)	0.0321 (4)
N3	0.08103 (17)	0.25861 (10)	−0.12165 (13)	0.0340 (5)
N4	0.17267 (19)	0.29547 (14)	−0.15016 (17)	0.0535 (6)
C1	0.1474 (2)	0.01792 (12)	0.29231 (16)	0.0330 (5)
C2	0.1235 (3)	−0.06299 (14)	0.35997 (18)	0.0472 (7)
C3	−0.0179 (3)	−0.07913 (17)	0.3639 (2)	0.0574 (9)
C4	−0.1334 (3)	−0.01579 (16)	0.3016 (2)	0.0524 (8)
C5	−0.1057 (2)	0.06436 (14)	0.23568 (19)	0.0391 (6)
C6	0.03622 (18)	0.08457 (11)	0.22890 (15)	0.0277 (5)
C7	0.05471 (16)	0.17238 (11)	0.14778 (15)	0.0253 (5)
C8	−0.01067 (19)	0.14495 (13)	−0.00855 (16)	0.0293 (5)
C9	0.02297 (16)	0.28584 (12)	0.32851 (16)	0.0263 (5)
C10	−0.02665 (18)	0.25954 (13)	0.17665 (17)	0.0293 (5)
C11	−0.0434 (3)	0.36959 (19)	0.4988 (2)	0.0489 (8)
H2	0.210 (2)	−0.1090 (17)	0.404 (2)	0.062 (6)*
H3	−0.039 (3)	−0.1301 (18)	0.409 (2)	0.071 (7)*
H3O	0.242 (2)	0.2153 (14)	0.253 (2)	0.043 (6)*
H4	−0.235 (3)	−0.0267 (16)	0.307 (2)	0.064 (6)*
H5	−0.183 (2)	0.1080 (15)	0.186 (2)	0.053 (6)*
H8A	0.0553 (19)	0.0951 (13)	−0.0298 (16)	0.032 (4)*
H8B	−0.113 (2)	0.1209 (12)	−0.0262 (17)	0.035 (4)*
H10A	−0.0016 (19)	0.3118 (13)	0.1284 (17)	0.037 (5)*
H10B	−0.133 (2)	0.2515 (14)	0.1442 (19)	0.047 (5)*
H11A	−0.035 (3)	0.315 (2)	0.560 (3)	0.084 (8)*
H11B	−0.128 (3)	0.4060 (17)	0.497 (2)	0.067 (7)*
H11C	0.044 (3)	0.4065 (17)	0.525 (2)	0.062 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0611 (9)	0.0464 (10)	0.0834 (11)	0.0058 (7)	0.0395 (8)	−0.0098 (8)
O2	0.0494 (8)	0.0595 (10)	0.0596 (9)	0.0016 (7)	−0.0151 (7)	0.0141 (8)
O3	0.0215 (6)	0.0308 (7)	0.0259 (6)	−0.0016 (5)	0.0039 (4)	−0.0006 (5)
O4	0.0298 (6)	0.0426 (8)	0.0307 (6)	0.0080 (5)	0.0006 (5)	−0.0054 (5)
O5	0.0262 (6)	0.0445 (8)	0.0401 (7)	0.0067 (5)	0.0108 (5)	−0.0081 (5)
N1	0.0440 (9)	0.0276 (9)	0.0482 (10)	0.0104 (7)	0.0069 (8)	0.0091 (7)
N2	0.0236 (7)	0.0413 (9)	0.0279 (7)	−0.0005 (6)	0.0048 (5)	0.0044 (6)
N3	0.0352 (8)	0.0377 (9)	0.0257 (7)	0.0053 (7)	0.0063 (6)	0.0049 (6)
N4	0.0431 (10)	0.0645 (12)	0.0571 (10)	−0.0023 (9)	0.0228 (8)	0.0169 (9)
C1	0.0452 (10)	0.0269 (10)	0.0264 (8)	−0.0012 (8)	0.0118 (7)	−0.0025 (7)
C2	0.0829 (15)	0.0269 (11)	0.0336 (10)	−0.0010 (11)	0.0226 (10)	0.0010 (8)
C3	0.109 (2)	0.0334 (13)	0.0435 (12)	−0.0247 (13)	0.0437 (13)	−0.0082 (9)
C4	0.0721 (15)	0.0475 (14)	0.0494 (12)	−0.0280 (12)	0.0360 (11)	−0.0173 (10)
C5	0.0432 (10)	0.0397 (11)	0.0370 (9)	−0.0133 (9)	0.0174 (8)	−0.0097 (9)
C6	0.0341 (9)	0.0255 (9)	0.0229 (7)	−0.0046 (7)	0.0091 (7)	−0.0049 (6)
C7	0.0201 (7)	0.0260 (9)	0.0269 (8)	−0.0015 (6)	0.0045 (6)	0.0003 (6)
C8	0.0272 (9)	0.0297 (10)	0.0272 (8)	−0.0021 (7)	0.0047 (7)	−0.0003 (7)
C9	0.0230 (8)	0.0223 (9)	0.0322 (8)	−0.0018 (7)	0.0080 (7)	0.0002 (7)
C10	0.0226 (8)	0.0299 (10)	0.0304 (9)	0.0017 (7)	0.0032 (7)	0.0012 (7)
C11	0.0456 (12)	0.0569 (15)	0.0476 (12)	0.0028 (11)	0.0207 (10)	−0.0157 (11)

O1—N1	1.224 (2)	C5—C6	1.400 (3)
O2—N1	1.221 (2)	C6—C7	1.530 (2)
O3—C7	1.426 (2)	C7—C10	1.531 (2)
O4—C9	1.206 (2)	C7—C8	1.542 (2)
O5—C9	1.330 (2)	C9—C10	1.497 (2)
O5—C11	1.441 (2)	C2—H2	1.02 (2)
O3—H3O	0.825 (19)	C3—H3	0.91 (2)
N1—C1	1.483 (3)	C4—H4	1.00 (3)
N2—C8	1.473 (2)	C5—H5	0.95 (2)
N2—N3	1.240 (2)	C8—H8A	1.012 (19)
N3—N4	1.133 (2)	C8—H8B	0.983 (19)
C1—C6	1.389 (2)	C10—H10A	0.959 (18)
C1—C2	1.390 (3)	C10—H10B	0.95 (2)
C2—C3	1.374 (4)	C11—H11A	0.98 (3)
C3—C4	1.382 (4)	C11—H11B	0.95 (3)
C4—C5	1.384 (3)	C11—H11C	0.93 (3)
C9—O5—C11	116.57 (15)	O4—C9—C10	125.11 (15)
C7—O3—H3O	105.2 (14)	C7—C10—C9	113.54 (14)
O1—N1—O2	125.32 (18)	C1—C2—H2	119.6 (12)
O2—N1—C1	117.49 (15)	C3—C2—H2	121.7 (12)
O1—N1—C1	117.11 (15)	C2—C3—H3	122.3 (18)
N3—N2—C8	116.57 (14)	C4—C3—H3	117.5 (18)
N2—N3—N4	171.07 (18)	C3—C4—H4	120.1 (13)
N1—C1—C6	122.19 (15)	C5—C4—H4	120.3 (13)
C2—C1—C6	123.7 (2)	C4—C5—H5	122.8 (13)
N1—C1—C2	114.10 (18)	C6—C5—H5	114.6 (12)
C1—C2—C3	118.7 (2)	N2—C8—H8A	111.1 (10)
C2—C3—C4	120.3 (2)	N2—C8—H8B	104.2 (10)
C3—C4—C5	119.6 (3)	C7—C8—H8A	109.8 (9)
C4—C5—C6	122.56 (19)	C7—C8—H8B	106.8 (10)
C1—C6—C7	125.77 (16)	H8A—C8—H8B	111.5 (15)
C5—C6—C7	118.97 (15)	C7—C10—H10A	106.5 (11)
C1—C6—C5	115.17 (16)	C7—C10—H10B	112.4 (12)
O3—C7—C6	112.72 (13)	C9—C10—H10A	107.2 (10)
O3—C7—C10	110.15 (13)	C9—C10—H10B	107.4 (11)
C6—C7—C8	105.96 (13)	H10A—C10—H10B	109.6 (16)
O3—C7—C8	104.56 (13)	O5—C11—H11A	111.3 (17)
C8—C7—C10	110.58 (13)	O5—C11—H11B	104.1 (12)
C6—C7—C10	112.49 (13)	O5—C11—H11C	108.2 (13)
N2—C8—C7	113.22 (14)	H11A—C11—H11B	109 (2)
O4—C9—O5	123.38 (14)	H11A—C11—H11C	113 (2)
O5—C9—C10	111.52 (14)	H11B—C11—H11C	111 (2)
C11—O5—C9—O4	−1.0 (3)	C4—C5—C6—C1	0.5 (3)
C11—O5—C9—C10	179.32 (17)	C4—C5—C6—C7	177.10 (16)
O1—N1—C1—C2	91.99 (19)	C1—C6—C7—O3	−15.3 (2)
O1—N1—C1—C6	−86.4 (2)	C1—C6—C7—C8	98.52 (18)
O2—N1—C1—C2	−84.7 (2)	C1—C6—C7—C10	−140.54 (16)
O2—N1—C1—C6	96.86 (19)	C5—C6—C7—O3	168.49 (14)
N3—N2—C8—C7	78.29 (18)	C5—C6—C7—C8	−77.74 (18)
N1—C1—C2—C3	−177.75 (16)	C5—C6—C7—C10	43.21 (19)
C6—C1—C2—C3	0.6 (3)	O3—C7—C8—N2	−73.41 (17)
N1—C1—C6—C5	177.43 (15)	C6—C7—C8—N2	167.29 (14)
N1—C1—C6—C7	1.1 (2)	C10—C7—C8—N2	45.12 (19)
C2—C1—C6—C5	−0.8 (2)	O3—C7—C10—C9	−69.34 (17)
C2—C1—C6—C7	−177.19 (15)	C6—C7—C10—C9	57.34 (19)
C1—C2—C3—C4	0.0 (3)	C8—C7—C10—C9	175.59 (14)
C2—C3—C4—C5	−0.3 (3)	O4—C9—C10—C7	19.8 (2)
C3—C4—C5—C6	0.1 (3)	O5—C9—C10—C7	−160.54 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O4	0.825 (19)	2.30 (2)	2.9439 (16)	135.5 (18)
O3—H3O···N2i	0.825 (19)	2.27 (2)	2.9193 (18)	135.6 (18)
C10—H10B···O4ii	0.95 (2)	2.557 (19)	3.350 (2)	141.0 (15)
C11—H11B···O1iii	0.95 (3)	2.57 (2)	3.268 (3)	130.9 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O4	0.825 (19)	2.30 (2)	2.9439 (16)	135.5 (18)
O3—H3O⋯N2i	0.825 (19)	2.27 (2)	2.9193 (18)	135.6 (18)
C10—H10B⋯O4ii	0.95 (2)	2.557 (19)	3.350 (2)	141.0 (15)
C11—H11B⋯O1iii	0.95 (3)	2.57 (2)	3.268 (3)	130.9 (16)

Symmetry codes: (i) ; (ii) ; (iii) , .