Methyl 2-(3,5-dinitro­benzamido)-3-methyl­butano­ate

Li, X.; Zhao, Y.

doi:10.1107/S1600536812040895

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3098

doi:10.1107/S1600536812040895

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Methyl 2-(3,5-dinitrobenzamido)-3-methylbutanoate

Xiaokun Li ^a ^* and Yuqing Zhao ^b

^aCollege of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou, 450008, People's Republic of China, and ^bSchool of Civil Engineering and Communication, North China University of Water Source and Electric Power, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: li96052122@126.com

(Received 12 July 2012; accepted 28 September 2012; online 10 October 2012)

In the title compound, C₁₃H₁₅N₃O₇, the dihedral angle between the amide plane (r.m.s. deviation = 0.008 Å) and the benzene ring is 33.2 (2)°. In the crystal, molecules are connected by N–H⋯O=C hydrogen bonds, forming a chain along the b-axis direction.

Related literature

For the biological activity of related compounds, see: Sykes et al. (1999 ).

Experimental

Crystal data

C₁₃H₁₅N₃O₇
M_r = 325.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.060 (2) Å
b = 9.412 (3) Å
c = 23.321 (6) Å
V = 1549.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.43 × 0.32 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.660, T_max = 0.746
9197 measured reflections
3580 independent reflections
3003 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.131
S = 1.03
3580 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O5ⁱ	0.86	2.12	2.949 (2)	161
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812040895/kp2434sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812040895/kp2434Isup2.hkl

checkCIF report

Comment top

Nitro and ester groups widely exist in variety of biologically active compounds that could be used as prodrugs (Sykes et al., 1999). We synthesized the title compound and determined its crystal structure (Fig. 1) whereas its biological activily is planned to be examined as well. In the crystal of the title compound, the carbonyl group acts as an acceptor and the amide group is a proton donor in the intermolecular N–H···O=C hydrogen bond, forming a chain along the b axis (Table 1, Fig. 2).

Related literature top

Nitro and ester groups occur widely in many biologically active compounds, see: Sykes et al. (1999).

Experimental top

To a solution of methyl 2-amino-3-methylbutanoate hydrochloride (0.8 g, 5 mmol) and triethylamine (0.5 mL) in dry methylene chloride (100 mL) was added to 3,5-dinitrobenzoyl chloride (1.1 g, 5 mmol)in dry methylene chloride (50 mL) at 273 K. The mixture was allowed to warm to room temperature for 0.5 h. After concentrating, the residue was subjected to chromatography(petroleum ether/ acetone, 4:1) to provide the product as a white crystal (1.2 g, 71.1%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the molecular strcuture of the title compound; the displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the hydrogen bonded chain running in the [100] direction. The hydrogen bonds are shown as dashed lines.

Methyl 2-(3,5-dinitrobenzamido)-3-methylbutanoate top

Crystal data top

C₁₃H₁₅N₃O₇	F(000) = 680
M_r = 325.28	D_x = 1.394 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9233 reflections
a = 7.060 (2) Å	θ = 1.0–22.7°
b = 9.412 (3) Å	µ = 0.12 mm⁻¹
c = 23.321 (6) Å	T = 296 K
V = 1549.8 (7) Å³	Block, colourless
Z = 4	0.43 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3580 independent reflections
Radiation source: fine-focus sealed tube	3003 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
phi and ω scans	θ_max = 27.7°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
T_min = 0.660, T_max = 0.746	k = −12→12
9197 measured reflections	l = −26→30

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0802P)² + 0.1123P] where P = (F_o² + 2F_c²)/3
3580 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₃H₁₅N₃O₇	V = 1549.8 (7) Å³
M_r = 325.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.060 (2) Å	µ = 0.12 mm⁻¹
b = 9.412 (3) Å	T = 296 K
c = 23.321 (6) Å	0.43 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3580 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3003 reflections with I > 2σ(I)
T_min = 0.660, T_max = 0.746	R_int = 0.023
9197 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
3580 reflections	Δρ_min = −0.18 e Å⁻³
208 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. C10, C11, C13 and C12 belong to terminal alkyl chains which show signs of disorder and have higher thermal parameters.

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

	x	y	z	U_iso*/U_eq
C1	1.2857 (3)	0.28856 (19)	0.10037 (8)	0.0526 (4)
C2	1.2504 (3)	0.23672 (19)	0.15455 (8)	0.0503 (4)
H2A	1.3390	0.1801	0.1732	0.060*
C3	1.0795 (2)	0.27084 (17)	0.18071 (7)	0.0453 (4)
C4	0.9487 (3)	0.35376 (18)	0.15216 (8)	0.0469 (4)
H4A	0.8350	0.3785	0.1696	0.056*
C5	0.9895 (3)	0.39948 (18)	0.09717 (7)	0.0495 (4)
C6	1.1576 (3)	0.3692 (2)	0.07014 (8)	0.0521 (4)
H6A	1.1834	0.4015	0.0333	0.062*
C7	1.0425 (2)	0.21140 (17)	0.23943 (7)	0.0460 (4)
C8	0.8869 (3)	0.2398 (2)	0.33103 (8)	0.0557 (4)
H8A	0.9465	0.1466	0.3358	0.067*
C9	0.9790 (4)	0.3399 (3)	0.37526 (9)	0.0671 (6)
C10	0.5694 (5)	0.3567 (4)	0.3394 (2)	0.1160 (12)
H15A	0.4365	0.3390	0.3442	0.174*
H15B	0.5902	0.4049	0.3036	0.174*
H15C	0.6142	0.4149	0.3703	0.174*
C11	0.5992 (4)	0.1150 (4)	0.29434 (14)	0.0947 (9)
H14A	0.4656	0.1019	0.2998	0.142*
H14B	0.6627	0.0253	0.2983	0.142*
H14C	0.6221	0.1526	0.2567	0.142*
C12	1.0720 (6)	0.3594 (4)	0.47134 (13)	0.1166 (13)
H12A	1.0668	0.3069	0.5066	0.175*
H12B	1.0072	0.4483	0.4760	0.175*
H12C	1.2018	0.3769	0.4613	0.175*
C13	0.6744 (4)	0.2186 (3)	0.33924 (11)	0.0735 (6)
H13A	0.6560	0.1746	0.3769	0.088*
N1	1.4675 (3)	0.2555 (2)	0.07277 (9)	0.0671 (5)
N2	0.8475 (3)	0.48375 (18)	0.06597 (7)	0.0613 (4)
N5	0.9379 (2)	0.29050 (15)	0.27435 (6)	0.0506 (4)
H5A	0.9000	0.3728	0.2632	0.061*
O1	1.5804 (3)	0.1847 (3)	0.09906 (10)	0.0990 (6)
O2	1.4962 (3)	0.3026 (2)	0.02520 (8)	0.0877 (6)
O3	0.8739 (3)	0.5050 (2)	0.01510 (7)	0.0856 (5)
O4	0.7125 (3)	0.5274 (2)	0.09269 (7)	0.0781 (5)
O5	1.1072 (2)	0.09485 (13)	0.25244 (6)	0.0596 (4)
O6	0.9809 (3)	0.2774 (2)	0.42582 (6)	0.0897 (6)
O7	1.0395 (5)	0.4534 (3)	0.36573 (10)	0.1163 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0540 (10)	0.0489 (9)	0.0547 (10)	−0.0103 (8)	0.0075 (8)	−0.0126 (8)
C2	0.0526 (9)	0.0426 (8)	0.0556 (10)	−0.0011 (7)	−0.0013 (8)	−0.0040 (7)
C3	0.0525 (9)	0.0375 (7)	0.0460 (8)	−0.0054 (7)	−0.0006 (7)	−0.0030 (7)
C4	0.0503 (9)	0.0439 (8)	0.0464 (8)	−0.0035 (7)	−0.0001 (7)	−0.0047 (7)
C5	0.0614 (10)	0.0427 (8)	0.0445 (8)	−0.0027 (8)	−0.0047 (8)	−0.0028 (7)
C6	0.0639 (11)	0.0497 (9)	0.0426 (8)	−0.0102 (8)	0.0046 (8)	−0.0043 (7)
C7	0.0500 (9)	0.0402 (8)	0.0477 (8)	−0.0039 (7)	−0.0024 (7)	0.0004 (7)
C8	0.0658 (11)	0.0549 (10)	0.0463 (9)	0.0091 (9)	0.0023 (8)	0.0045 (8)
C9	0.0770 (14)	0.0720 (13)	0.0523 (11)	0.0169 (12)	−0.0047 (10)	−0.0061 (9)
C10	0.0821 (19)	0.094 (2)	0.172 (4)	0.0177 (17)	0.034 (2)	0.017 (2)
C11	0.0834 (18)	0.099 (2)	0.102 (2)	−0.0206 (17)	−0.0107 (15)	0.0137 (17)
C12	0.152 (3)	0.130 (3)	0.0680 (16)	0.019 (3)	−0.0295 (19)	−0.0348 (17)
C13	0.0736 (14)	0.0762 (14)	0.0707 (13)	−0.0033 (12)	0.0113 (11)	0.0167 (11)
N1	0.0613 (10)	0.0632 (10)	0.0769 (12)	−0.0070 (9)	0.0174 (9)	−0.0107 (9)
N2	0.0743 (11)	0.0594 (9)	0.0504 (9)	0.0028 (9)	−0.0069 (8)	0.0018 (7)
N5	0.0629 (9)	0.0432 (7)	0.0456 (7)	0.0071 (7)	0.0047 (6)	0.0055 (6)
O1	0.0641 (10)	0.1110 (14)	0.1218 (16)	0.0183 (11)	0.0206 (10)	0.0107 (13)
O2	0.0948 (13)	0.0910 (12)	0.0773 (11)	−0.0046 (11)	0.0372 (10)	−0.0117 (9)
O3	0.1103 (15)	0.0954 (12)	0.0511 (8)	0.0146 (12)	−0.0049 (9)	0.0146 (8)
O4	0.0800 (11)	0.0881 (11)	0.0661 (9)	0.0258 (9)	−0.0040 (8)	0.0041 (8)
O5	0.0776 (9)	0.0431 (6)	0.0580 (7)	0.0098 (6)	0.0016 (7)	0.0035 (6)
O6	0.1274 (15)	0.0904 (11)	0.0512 (8)	0.0167 (12)	−0.0109 (9)	−0.0112 (8)
O7	0.162 (2)	0.0923 (13)	0.0946 (14)	−0.0369 (15)	−0.0343 (14)	−0.0015 (12)

Geometric parameters (Å, º) top

C1—C6	1.375 (3)	C9—O6	1.318 (3)
C1—C2	1.377 (3)	C10—C13	1.497 (4)
C1—N1	1.469 (3)	C10—H15A	0.9600
C2—C3	1.390 (3)	C10—H15B	0.9600
C2—H2A	0.9300	C10—H15C	0.9600
C3—C4	1.380 (3)	C11—C13	1.526 (4)
C3—C7	1.502 (2)	C11—H14A	0.9600
C4—C5	1.383 (3)	C11—H14B	0.9600
C4—H4A	0.9300	C11—H14C	0.9600
C5—C6	1.373 (3)	C12—O6	1.462 (3)
C5—N2	1.471 (3)	C12—H12A	0.9600
C6—H6A	0.9300	C12—H12B	0.9600
C7—O5	1.226 (2)	C12—H12C	0.9600
C7—N5	1.328 (2)	C13—H13A	0.9800
C8—N5	1.451 (2)	N1—O1	1.206 (3)
C8—C13	1.525 (3)	N1—O2	1.212 (3)
C8—C9	1.541 (3)	N2—O4	1.211 (2)
C8—H8A	0.9800	N2—O3	1.217 (2)
C9—O7	1.171 (3)	N5—H5A	0.8600

C6—C1—C2	123.15 (18)	H15A—C10—H15B	109.5
C6—C1—N1	117.83 (18)	C13—C10—H15C	109.5
C2—C1—N1	119.02 (19)	H15A—C10—H15C	109.5
C1—C2—C3	118.55 (18)	H15B—C10—H15C	109.5
C1—C2—H2A	120.7	C13—C11—H14A	109.5
C3—C2—H2A	120.7	C13—C11—H14B	109.5
C4—C3—C2	119.99 (17)	H14A—C11—H14B	109.5
C4—C3—C7	122.29 (16)	C13—C11—H14C	109.5
C2—C3—C7	117.70 (16)	H14A—C11—H14C	109.5
C3—C4—C5	118.94 (17)	H14B—C11—H14C	109.5
C3—C4—H4A	120.5	O6—C12—H12A	109.5
C5—C4—H4A	120.5	O6—C12—H12B	109.5
C6—C5—C4	122.75 (17)	H12A—C12—H12B	109.5
C6—C5—N2	118.28 (16)	O6—C12—H12C	109.5
C4—C5—N2	118.97 (17)	H12A—C12—H12C	109.5
C5—C6—C1	116.59 (17)	H12B—C12—H12C	109.5
C5—C6—H6A	121.7	C10—C13—C8	111.9 (2)
C1—C6—H6A	121.7	C10—C13—C11	112.6 (3)
O5—C7—N5	123.84 (16)	C8—C13—C11	109.9 (2)
O5—C7—C3	119.61 (16)	C10—C13—H13A	107.4
N5—C7—C3	116.54 (14)	C8—C13—H13A	107.4
N5—C8—C13	113.70 (18)	C11—C13—H13A	107.4
N5—C8—C9	107.70 (17)	O1—N1—O2	123.8 (2)
C13—C8—C9	114.29 (18)	O1—N1—C1	118.12 (19)
N5—C8—H8A	106.9	O2—N1—C1	118.0 (2)
C13—C8—H8A	106.9	O4—N2—O3	124.5 (2)
C9—C8—H8A	106.9	O4—N2—C5	117.71 (17)
O7—C9—O6	125.0 (2)	O3—N2—C5	117.81 (19)
O7—C9—C8	125.7 (2)	C7—N5—C8	120.85 (15)
O6—C9—C8	109.3 (2)	C7—N5—H5A	119.6
C13—C10—H15A	109.5	C8—N5—H5A	119.6
C13—C10—H15B	109.5	C9—O6—C12	114.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O5ⁱ	0.86	2.12	2.949 (2)	161

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅N₃O₇
M_r	325.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	7.060 (2), 9.412 (3), 23.321 (6)
V (Å³)	1549.8 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.43 × 0.32 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.660, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9197, 3580, 3003
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.131, 1.03
No. of reflections	3580
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O5ⁱ	0.86	2.12	2.949 (2)	161.2

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

Acknowledgements

The author thanks North China University of Water Source and Electric Power for supporting this study.

References

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