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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 606-608

Isolation of 3-amino-4-nitro­benzyl acetate: evidence of an undisclosed impurity in 5-amino-2-nitro­benzoic acid

aDepartment of Chemistry and Physics, Armstrong State University, 11935 Abercorn Street, Savannah GA 31419, USA
*Correspondence e-mail: Brandon.Quillian@armstrong.edu

Edited by S. Parkin, University of Kentucky, USA (Received 4 March 2015; accepted 5 May 2015; online 13 May 2015)

Yellow crystals of the title compound 3-amino-4-nitro­benzyl acetate, C9H10N2O4, were isolated from the reaction of acetic anhydride with (5-amino-2-nitro­phen­yl)methanol, prepared from reduction of commerically available 5-amino-2-nitro­benzoic acid with borane–THF. The mol­ecule is essentially planar (r.m.s. deviation = 0.028 Å). The mol­ecules are linked by inter­molecular N—H⋯O hydrogen-bonding inter­actions between the carbonyl and amine groups, forming a zigzag chain along the b-axis direction lying in a plane parallel to (-102). The chains are stacked along the c axis by ππ inter­actions [centroid–centroid distances = 3.6240 (3) and 3.5855 (4) Å]. A strong intra­molecular N—H⋯O hydrogen-bonding inter­action is observed between the nitro group and the amine group [2.660 (2) Å].

1. Chemical Context

Often commercially available chemicals are sold with minor impurities in the range 1–5%; the user may choose to `use as received' or further purify. The identities of the impurities are rarely disclosed in fine chemicals. Though these impurities may serve as benign spectators, in some cases they might hinder reactivity and/or produce undesirable by-products that are difficult to separate from the desired product. Therefore, it is important to identify these impurities to allow the users to decide if further purification is warranted. We recently purchased 5-amino-2-nitro­benzoic acid from Acros Organics© (5 g, 97%, AC33074-0050) for our ongoing studies of photo-induced deca­rboxylation of ortho-nitro­benzyl esters (Cabane et al., 2010[Cabane, E., Malinova, V. & Meier, W. (2010). Macromol. Chem. Phys. 211, 1847-1856.]; Pocker et al., 1978[Pocker, Y., Davison, B. L. & Deits, T. L. (1978). J. Am. Chem. Soc. 100, 3564-3567.]). The isolation of the title compound, 3-amino-4-nitro­benzyl acetate, after the reaction of crude (5-amino-2-nitro­phen­yl)methanol, prepared from the reduction of 5-amino-2-nitro­benzoic acid, with acetic anhydride suggests 3-amino-4-nitro­benzoic acid is an impurity in the commercially available starting material.

[Scheme 1]

2. Structural Commentary

The asymmetric unit of the title compound (Fig. 1[link]) displays an essentially planar mol­ecule (r.m.s.d. 0.028 Å) with the amine, nitro and acetate groups resting in the plane of the arene. The carbonyl, C=O [1.208 (2) Å], and ester, C—O [1.3477 (19) Å], bond distances are unassuming. The nitro bond distances [O1—N1 1.2500 (16) and O2—N1 1.2401 (17) Å] are similar to those in N-(3-chloro­phen­yl)-3-nitro­pyridin-2-amine [1.222 (2) and 1.245 (2) Å] (Aznan et al., 2011[Aznan, A. M. A., Abdullah, Z., Ng, S. W. & Tiekink, E. R. T. (2011). Acta Cryst. E67, o3076.]). Atom O1 of the nitro group is involved in strong intra­molecular hydrogen bonding [graph set S1, 1(6)] between H2B of the amine at a distance of 2.06 (2) Å, forming a rigid, thermodynamically stable six-membered ring (Fig. 1[link]). The elongated O1—N1 bond distance, as compared to the O2—N1 distance, is consistent with resonance-assisted hydrogen bonding between O1 and H2B (Beck & Mo, 2006[Beck, J. F. & Mo, Y. (2006). J. Comput. Chem. 4, 455-466.]).

[Figure 1]
Figure 1
A displacement ellipsoid plot of 3-amino-4-nitro­benzyl acetate (50% probability level). C-bound H atoms have been omitted for clarity.

3. Supra­molecular Features

The crystal structure of 3-amino-4-nitro­benzyl acetate has inter­esting supra­molecular features. The mol­ecules are arranged in layers held together by inter­molecular N2—H2A⋯O4 [3.005 (2) Å] hydrogen bonding [graph set C1,1(9)] inter­actions between the carbonyl and amine groups forming a zigzag chain along the b-axis direction (Fig. 2[link] and Table 1[link]) lying in a plane parallel to ([\overline{1}]02). A view of a single layer along the ab plane, observed down the c axis (Fig. 2[link]) provides a representative illustration of the hydrogen-bonding inter­actions of 3-amino-4-nitro­benzyl acetate. Observing the unit cell along the b-axis (Fig. 3[link]) shows four layers along the c axis separated at a distance of 3.3163 (10) Å with the arene groups stacked one above the other. The chains stack along the c axis by ππ inter­actions [centroid–centroid distances = 3.6240 (3) Å (symmetry code 1 − x, 1 − y, 1 − z) and 3.5855 (4) Å (symmetry code 1 − x, y, [{3\over 2}] − z)].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯O4i 0.83 (2) 2.18 (2) 3.005 (2) 171.5 (17)
N2—H2B⋯O1 0.84 (2) 2.06 (2) 2.6600 (19) 128.0 (16)
N2—H2B⋯O1ii 0.84 (2) 2.44 (2) 3.1443 (19) 142.7 (16)
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1].
[Figure 2]
Figure 2
A single of layer of the unit cell of 3-amino-4-nitro­benzoic acid through the ab plane (observed down the c axis), highlighting the hydrogen-bonding motif.
[Figure 3]
Figure 3
A displacement ellipsoid plot of the unit cell of 3-amino-4-nitro­benzoic acid observed down the b axis.

4. Database Survey

For a related benzyl acetate structure, see Kasuga et al. (2015[Kasuga, N. C., Saito, Y., Sato, H. & Yamaguchi, K. (2015). Acta Cryst. E71, 483-486.]). For alkyl- and aryl-3-amino-4-nitro-benzoates and benzoic acids displaying similar intramolecular hydrogen bonding between the amino and nitro groups, see: Narendra Babu et al. (2009[Narendra Babu, S. N., Abdul Rahim, A. S., Abd Hamid, S., Balasubramani, K. & Fun, H.-K. (2009). Acta Cryst. E65, o2070-o2071.]); Abdul Rahim et al. (2010[Abdul Rahim, A. S., Abd Hamid, S., Narendra Babu, S. N., Loh, W.-S. & Fun, H.-K. (2010). Acta Cryst. E66, o846-o847.]); Yoon et al. (2011[Yoon, Y. K., Ali, M. A., Choon, T. S., Loh, W.-S. & Fun, H.-K. (2011). Acta Cryst. E67, o2606.]); Yoon et al. (2012[Yoon, Y. K., Manogaran, E., Ali, M. A., Arshad, S. & Razak, I. A. (2012). Acta Cryst. E68, o1684.]).

5. Synthesis and Crystallization

(5-Amino-2-nitro­phen­yl)methanol: (5-amino-2-nitro­phen­yl)methanol was prepared by a modified literature protocol (Yoon et al. 1973[Yoon, N. M., Pak, C. S., Krishnamurthy, S. & Stocky, T. P. (1973). J. Org. Chem. 38, 2786-2792.]). To a solution of 5-amino-2-nitro­benzoic acid (97%, 1.5 g, 8.2 mmol) dissolved in tetra­hydro­furan (10 mL), borane–THF (27.6 mL, 1.0 M in THF, 27.6 mmol) was added dropwise by dropping funnel over 30 minutes. The reaction was stirred overnight at room temperature. The reaction was quenched with aqueous potassium hydroxide (2.45 M) until pH 11 was reached and continued to be stirred for 6 h, resulting in a greenish-brown solution. The solution was treated with a saturated solution of potassium carbonate followed by treatment with hydro­chloric acid until pH 1 was reached. The reaction mixture was extracted with diethyl ether three times; organic portions were collected and dried with anhydrous sodium sulfate overnight. The solution was filtered under vacuum, the filtrate was collected and all solvent removed under rotary evaporation to give a green powder (0.68 g, 49%). 1H NMR, (300 MHz, acetone-d6) δ: 4.61 (t, 1H, –OH, 3JHH = 5.3 Hz), 4.95 (d, 2H, CH2, 3JHH = 5.3 Hz) , 6.03 (bs, 2H, NH2), 6.63 (dd, 1H, Ar-H, 3JHH = 8.8 Hz, 3JHH = 2.3 Hz), 7.07 (m, 1H, Ar-H), 8.02 (dd, 1H, 3JHH = 9.4 Hz, 3JHH = 3.0 Hz) (Aujard et al. 2006[Aujard, I., Benbrahim, C., Gouget, M., Ruel, O., Baudin, J.-B., Neveu, P. & Jullien, L. (2006). Chem. Eur. J. 12, 6865-6879.]). Note: minor impurities were observed in the base line in the aromatic region.

3-Amino-4-nitro­benzyl acetate: (5-amino-2-nitro­phen­yl)methanol (10 mg, 0.0595 mmol) and tri­ethyl­amine (17 µL, 0.119 mmol) were dissolved in aceto­nitrile-d6 (0.7 mL) and added to an NMR tube. Acetic anhydride (11.2 µL, 0.119 mmol) was added to the tube via a syringe. The tube was held at room temperature overnight. On completion of the reaction the solvent was removed in vacuo and the residue was reconstituted in a minimum amount of methyl­ene chloride. The sample was loaded on a column of silica and eluted with an ethyl acetate/hexane solution (70/30 v/v %). The separated solutions were allowed to slowly evaporate at room temperature. The parent compound (5-amino-2-nitro­benzyl acetate) elutes first and is isolated as a yellow powder. 1H NMR (300 MHz, CDCl3) δ: 2.10 (s, 3H, CH3), 4.35 (bs, 2H, NH2), 5.50 (s, 2H, CH2), 6.55 (dd, 1H, Ar-H, 3JHH = 8.9 Hz, 5JHH = 2.5 Hz), 6.68 (m, 1H, Ar-H), 8.09 (dd, 1H, Ar-H, 3JHH = 8.9 Hz, 5JHH = 2.5 Hz) (Serafinowski et al. 2008[Serafinowski, P. J. & Garland, P. B. (2008). Org. Biomol. Chem. 6, 3284-3291.]). Yellow crystals of the title compound were isolated (less than 1 mg) in later eluate. 1H NMR (300 MHz, CDCl3) δ: 2.19 (s, 3H, CH3), 5.53 (s, 2H, CH2), 7.44 (bs, 2H, NH2), 7.65 (dd, 1H, Ar-H, 3JHH = 8.9 Hz, 5JHH = 2.5 Hz), 7.75 (m, 1H, Ar-H), 8.15 (d, 1H, Ar-H, 3JHH = 8.9 Hz).

5.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. Hydrogen atoms were refined freely.

Table 2
Experimental details

Crystal data
Chemical formula C9H10N2O4
Mr 210.19
Crystal system, space group Monoclinic, C2/c
Temperature (K) 173
a, b, c (Å) 14.4803 (15), 11.4054 (11), 13.0936 (13)
β (°) 116.341 (8)
V3) 1937.9 (4)
Z 8
Radiation type Mo Kα
μ (mm−1) 0.12
Crystal size (mm) 0.25 × 0.25 × 0.10
 
Data collection
Diffractometer Rigaku Mercury375R
Absorption correction Multi-scan (REQAB; Rigaku, 1998[Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan.])
Tmin, Tmax 0.840, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 8409, 1759, 1348
Rint 0.045
(sin θ/λ)max−1) 0.601
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.098, 1.06
No. of reflections 1759
No. of parameters 176
H-atom treatment All H-atom parameters refined
Δρmax, Δρmin (e Å−3) 0.21, −0.17
Computer programs: CrystalClear-SM Expert (Rigaku, 2014), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2013 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Supporting information


Chemical Context top

Often commercially available chemicals are sold with minor impurities in the range 1–5% that the user may choose to `use as received' or further purify. The identities of the impurities are rarely disclosed in fine chemicals. Though these impurities may serve as benign spe­cta­tors, in some cases they might hinder reactivity and/or produce undesirable by-products that are difficult to separate from the desired product. Therefore, it is important to identify these impurities to allow the users to decide if further purification is warranted. We recently purchased 5-amino-2-nitro­benzoic acid from Acros Organics© (5 g, 97%, AC33074-0050) for our ongoing studies of photo-induced de­carboxyl­ation of ortho-nitro­benzyl esters (Cabane et al., 2010; Pocker et al., 1978). The isolation of the title compound, 3-amino-4-nitro­benzyl acetate, after the reaction of crude (5-amino-2-nitro­phenyl)­methanol, prepared from the reduction of 5-amino-2-nitro­benzoic acid, with acetic anhydride (2) suggests 3-amino-4-nitro­benzoic acid is an impurity in the commercially available starting material.

Structural Commentary top

The asymmetric unit of the title compound (Fig. 1) displays an essentially planar molecule (r.m.s.d. 0.028 Å) with the amine, nitro and acetate groups resting in the plane of the arene. The carbonyl, CO [1.208 (2) Å], and ester, C—O [1.3477 (19) Å], bond distances are unassuming. The nitro bond distances [O1—N1 1.2500 (16) and O2—N1 1.2401 (17) Å] are similar to those in N-(3-chloro­phenyl)-3-nitro­pyridin-2-amine [1.222 (2) and 1.245 (2) Å; Aznan et al., 2011). Atom O1 of the nitro group is involved in strong intra­molecular hydrogen bonding [graph set S1, 1(6)] between H2B of the amine at a distance of 2.06 (2) Å, forming a rigid, thermodynamically stable six-membered ring. The elongated O1—N1 bond distance, as compared to the O2—N1 distance, is consistent with resonance-assisted hydrogen bonding between O1 and H2B (Beck & Mo, 2006).

Supra­molecular Features top

The crystal structure of 3-amino-4-nitro­benzyl acetate has inter­esting supra­molecular features. The molecules are arranged in layers held together by inter­molecular N2—H2A···O4 [3.005 (2) Å] hydrogen bonding [graph set C1,1(9)] inter­actions between the carbonyl and amine groups forming a zigzag chain along the b-axis direction (Fig. 2 and (Table 1) in a sheet structure parallel to (102). A view of a single layer along the ab plane, observed down the c axis (Fig. 2) provides a representative illustration of the hydrogen-bonding inter­actions of 3-amino-4-nitro­benzyl acetate. Observing the unit cell along the b-axis (Fig. 3) shows four layers along the c axis separated at a distance of 3.3163 (10) Å with the arene groups hovering over each other. The chains are stacked along the c axis by ππ inter­actions [centroid–centroid distance = 3.6240 (3) Å, symmetry code 1 - x, 1 - y, 1 - z and centroid–centroid distance = 3.5855 (4) Å, symmetry code 1 - x, y, 3/2 - z].

Database Survey top

For related structures, see Kasuga et al. (2015). For related alkyl- and aryl-amino-nitro benzoates and benzoic acids see: Narendra Babu et al. (2009); Abdul Rahim et al. (2010); Yoon et al. (2011); Yoon et al. (2012).

Synthesis and Crystallization top

(5-Amino-2-nitro­phenyl)­methanol: (5-amino-2-nitro­phenyl)­methanol was prepared by a modified literature protocol (Yoon et al. 1973). To a solution of 5-amino-2-nitro­benzoic acid (97%, 1.5 g, 8.2 mmol) dissolved in tetra­hydro­furan (10 mL), borane–THF (27.6 mL, 1.0 M in THF, 27.6 mmol) was added dropwise by dropping funnel over 30 minutes. The reaction was stirred overnight at room temperature. The reaction was quenched with aqueous potassium hydroxide (2.45 M) until pH 11 was reached and continued to be stirred for 6 hours, resulting in a greenish-brown solution. The solution was treated with a saturated solution of potassium carbonate followed by treatment with hydro­chloric acid until pH 1 was reached. The reaction mixture was extracted with di­ethyl ether three times; organic portions were collected and dried with anhydrous sodium sulfate overnight. The solution was filtered under vacuum, the filtrate was collected and all solvent removed under rotary evaporation to give a green powder (0.68 g, 49%). 1H NMR, (300 MHz, acetone-d6) δ: 4.61 (t, 1H, –OH, 3JHH = 5.3 Hz), 4.95 (d, 2H, CH2, 3JHH = 5.3 Hz ), 6.03 (bs, 2H, NH2), 6.63 (dd, 1H, Ar—H, 3JHH = 8.8 Hz, 3JHH = 2.3 Hz), 7.07 (m, 1H, Ar—H), 8.02 (dd, 1H, 3JHH = 9.4 Hz, 3JHH = 3.0 Hz) (Aujard et al. 2006). Note: minor impurities were observed in the base line in the aromatic region.

3-Amino-4-nitro­benzyl acetate: (5-amino-2-nitro­phenyl)­methanol (10 mg, 0.0595 mmol) and tri­ethyl­amine (17 µL, 0.119 mmol) were dissolved in aceto­nitrile-d6 (0.7 mL) and added to an NMR tube. Acetic anhydride (11.2 µL, 0.119 mmol) was added to the tube via a syringe. The tube was held at room temperature and allowed to react overnight. All solvent was removed in vacuo and the residue was reconstituted in a minimum amount of methyl­ene chloride. The sample was loaded on a column of silica and eluted with an ethyl acetate/hexane solution (70/30 v/v %). The separated solutions were allowed to slowly evaporate at room temperature. The parent compound (5-amino-2-nitro­benzyl acetate) elutes first and is isolated as a yellow powder. 1H NMR (300 MHz, CDCl3) δ: 2.10 (s, 3H, CH3), 4.35 (bs, 2H, NH2), 5.50 (s, 2H, CH2), 6.55 (dd, 1H, Ar—H, 3JHH = 8.9 Hz, 5JHH = 2.5 Hz), 6.68 (m, 1H, Ar—H), 8.09 (dd, 1H, Ar—H, 3JHH = 8.9 Hz, 5JHH = 2.5 Hz) (Serafinowski et al. 2008). Yellow crystals of the title compound were isolated (less than 1 mg) in later eluate. 1H NMR (300 MHz, CDCl3) δ: 2.19 (s, 3H, CH3), 5.53 (s, 2H, CH2), 7.44 (bs, 2H, NH2), 7.65 (dd, 1H, Ar—H, 3JHH = 8.9 Hz, 5JHH = 2.5 Hz), 7.75 (m, 1H, Ar—H), 8.15 (d, 1H, Ar—H, 3JHH = 8.9 Hz).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were refined freely.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2014); cell refinement: CrystalClear-SM Expert (Rigaku, 2014); data reduction: CrystalClear-SM Expert (Rigaku, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. A displacement ellipsoid plot of 3-amino-4-nitrobenzyl acetate (50% probability level). Some H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A single of layer of the unit cell of 3-amino-4-nitrobenzoic acid through the ab plane (observed down the c axis), highlighting the hydrogen-bonding motif.
[Figure 3] Fig. 3. A displacement ellipsoid plot of the unit cell of 3-amino-4-nitrobenzoic acid observed down the b axis.
3-Amino-4-nitrobenzyl acetate top
Crystal data top
C9H10N2O4F(000) = 880
Mr = 210.19Dx = 1.441 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71075 Å
a = 14.4803 (15) ÅCell parameters from 513 reflections
b = 11.4054 (11) Åθ = 1.6–25.4°
c = 13.0936 (13) ŵ = 0.12 mm1
β = 116.341 (8)°T = 173 K
V = 1937.9 (4) Å3Prism, yellow
Z = 80.25 × 0.25 × 0.10 mm
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
1759 independent reflections
Radiation source: Sealed Tube1348 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.045
Detector resolution: 13.6612 pixels mm-1θmax = 25.3°, θmin = 2.4°
profile data from ω scansh = 1717
Absorption correction: multi-scan
(REQAB; Rigaku, 1998)
k = 1313
Tmin = 0.840, Tmax = 1.000l = 1515
8409 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037All H-atom parameters refined
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0578P)2 + 0.2118P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1759 reflectionsΔρmax = 0.21 e Å3
176 parametersΔρmin = 0.17 e Å3
0 restraints
Crystal data top
C9H10N2O4V = 1937.9 (4) Å3
Mr = 210.19Z = 8
Monoclinic, C2/cMo Kα radiation
a = 14.4803 (15) ŵ = 0.12 mm1
b = 11.4054 (11) ÅT = 173 K
c = 13.0936 (13) Å0.25 × 0.25 × 0.10 mm
β = 116.341 (8)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
1759 independent reflections
Absorption correction: multi-scan
(REQAB; Rigaku, 1998)
1348 reflections with I > 2σ(I)
Tmin = 0.840, Tmax = 1.000Rint = 0.045
8409 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.098All H-atom parameters refined
S = 1.06Δρmax = 0.21 e Å3
1759 reflectionsΔρmin = 0.17 e Å3
176 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O30.74138 (8)0.43515 (9)0.74195 (10)0.0324 (3)
O10.23008 (8)0.61948 (10)0.50492 (11)0.0418 (3)
O20.18245 (8)0.43814 (10)0.46692 (11)0.0436 (3)
O40.86707 (9)0.30050 (11)0.79735 (12)0.0456 (4)
N10.25141 (9)0.51321 (11)0.50551 (11)0.0288 (3)
N20.42892 (12)0.67596 (12)0.60612 (12)0.0300 (3)
H2A0.4821 (16)0.7166 (16)0.6337 (16)0.036 (5)*
H2B0.3700 (16)0.7046 (15)0.5821 (16)0.039 (5)*
C60.43920 (11)0.55950 (12)0.60073 (12)0.0228 (3)
C10.35704 (10)0.47782 (13)0.55271 (12)0.0245 (3)
C40.55919 (11)0.39372 (13)0.64720 (12)0.0252 (3)
C50.54112 (10)0.51152 (13)0.64747 (11)0.0228 (3)
H50.5978 (13)0.5675 (14)0.6814 (13)0.024 (4)*
C20.37680 (12)0.35678 (14)0.54982 (13)0.0295 (4)
H20.3212 (13)0.3041 (14)0.5154 (15)0.031 (4)*
C30.47512 (12)0.31496 (14)0.59587 (14)0.0312 (4)
H30.4895 (13)0.2318 (16)0.5930 (15)0.033 (4)*
C70.66619 (11)0.34199 (14)0.69873 (14)0.0296 (4)
H7A0.6780 (14)0.2874 (16)0.7620 (16)0.040 (5)*
H7B0.6772 (12)0.2957 (14)0.6407 (15)0.032 (4)*
C80.84105 (11)0.40198 (15)0.79024 (13)0.0307 (4)
C90.91100 (13)0.50537 (18)0.83137 (18)0.0419 (5)
H9A0.8961 (16)0.5562 (19)0.7680 (19)0.055 (6)*
H9B0.9809 (17)0.4806 (16)0.8703 (17)0.046 (5)*
H9C0.8934 (17)0.554 (2)0.881 (2)0.067 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0175 (5)0.0288 (6)0.0445 (7)0.0021 (4)0.0080 (5)0.0018 (5)
O10.0242 (6)0.0319 (7)0.0621 (8)0.0054 (5)0.0128 (6)0.0060 (5)
O20.0194 (6)0.0411 (7)0.0601 (8)0.0073 (5)0.0085 (6)0.0033 (6)
O40.0271 (6)0.0400 (8)0.0605 (8)0.0089 (5)0.0111 (6)0.0009 (6)
N10.0188 (6)0.0314 (8)0.0327 (7)0.0002 (5)0.0083 (5)0.0031 (6)
N20.0199 (7)0.0271 (8)0.0379 (8)0.0002 (6)0.0082 (6)0.0025 (6)
C60.0214 (7)0.0266 (8)0.0210 (7)0.0013 (6)0.0098 (6)0.0011 (6)
C10.0180 (7)0.0307 (8)0.0234 (7)0.0004 (6)0.0078 (6)0.0027 (6)
C40.0210 (7)0.0312 (8)0.0239 (7)0.0010 (6)0.0104 (6)0.0002 (6)
C50.0198 (8)0.0271 (8)0.0212 (7)0.0025 (6)0.0086 (6)0.0011 (6)
C20.0218 (8)0.0283 (9)0.0358 (9)0.0063 (7)0.0105 (7)0.0029 (7)
C30.0279 (8)0.0238 (9)0.0406 (9)0.0004 (6)0.0142 (7)0.0017 (7)
C70.0237 (8)0.0262 (8)0.0363 (9)0.0007 (6)0.0110 (7)0.0024 (7)
C80.0211 (8)0.0379 (10)0.0305 (8)0.0056 (7)0.0091 (7)0.0011 (7)
C90.0214 (9)0.0483 (12)0.0489 (11)0.0017 (8)0.0091 (8)0.0015 (9)
Geometric parameters (Å, º) top
O3—C71.4449 (19)C4—C31.419 (2)
O3—C81.3477 (19)C4—C71.509 (2)
O1—N11.2500 (16)C5—H50.978 (17)
O2—N11.2401 (17)C2—H20.944 (17)
O4—C81.208 (2)C2—C31.362 (2)
N1—C11.4303 (19)C3—H30.975 (18)
N2—H2A0.83 (2)C7—H7A0.988 (19)
N2—H2B0.83 (2)C7—H7B0.994 (17)
N2—C61.342 (2)C8—C91.491 (3)
C6—C11.419 (2)C9—H9A0.96 (2)
C6—C51.4320 (19)C9—H9B0.95 (2)
C1—C21.414 (2)C9—H9C0.97 (2)
C4—C51.369 (2)
C8—O3—C7116.19 (12)C3—C2—C1120.94 (14)
O1—N1—C1119.36 (12)C3—C2—H2119.5 (10)
O2—N1—O1121.00 (12)C4—C3—H3118.7 (10)
O2—N1—C1119.64 (13)C2—C3—C4119.75 (15)
H2A—N2—H2B122.7 (17)C2—C3—H3121.5 (10)
C6—N2—H2A118.1 (12)O3—C7—C4109.47 (13)
C6—N2—H2B119.1 (12)O3—C7—H7A108.3 (11)
N2—C6—C1125.60 (13)O3—C7—H7B109.9 (9)
N2—C6—C5118.24 (13)C4—C7—H7A112.5 (10)
C1—C6—C5116.16 (13)C4—C7—H7B110.3 (10)
C6—C1—N1122.12 (13)H7A—C7—H7B106.2 (14)
C2—C1—N1117.02 (13)O3—C8—C9111.22 (14)
C2—C1—C6120.86 (13)O4—C8—O3122.52 (15)
C5—C4—C3119.84 (14)O4—C8—C9126.26 (15)
C5—C4—C7122.83 (14)C8—C9—H9A108.1 (13)
C3—C4—C7117.33 (14)C8—C9—H9B110.5 (11)
C6—C5—H5116.3 (9)C8—C9—H9C110.8 (13)
C4—C5—C6122.40 (13)H9A—C9—H9B115.0 (17)
C4—C5—H5121.3 (9)H9A—C9—H9C102.2 (18)
C1—C2—H2119.6 (10)H9B—C9—H9C110.0 (17)
O1—N1—C1—C60.9 (2)C5—C6—C1—N1178.48 (13)
O1—N1—C1—C2179.17 (13)C5—C6—C1—C21.44 (19)
O2—N1—C1—C6178.35 (13)C5—C4—C3—C21.7 (2)
O2—N1—C1—C21.6 (2)C5—C4—C7—O32.0 (2)
N1—C1—C2—C3178.07 (14)C3—C4—C5—C62.1 (2)
N2—C6—C1—N11.2 (2)C3—C4—C7—O3177.40 (13)
N2—C6—C1—C2178.91 (14)C7—O3—C8—O40.1 (2)
N2—C6—C5—C4179.13 (13)C7—O3—C8—C9179.98 (14)
C6—C1—C2—C31.9 (2)C7—C4—C5—C6178.49 (13)
C1—C6—C5—C40.5 (2)C7—C4—C3—C2178.86 (15)
C1—C2—C3—C40.2 (2)C8—O3—C7—C4179.68 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4i0.83 (2)2.18 (2)3.005 (2)171.5 (17)
N2—H2B···O10.84 (2)2.06 (2)2.6600 (19)128.0 (16)
N2—H2B···O1ii0.84 (2)2.44 (2)3.1443 (19)142.7 (16)
Symmetry codes: (i) x+3/2, y+1/2, z+3/2; (ii) x+1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4i0.83 (2)2.18 (2)3.005 (2)171.5 (17)
N2—H2B···O10.84 (2)2.06 (2)2.6600 (19)128.0 (16)
N2—H2B···O1ii0.84 (2)2.44 (2)3.1443 (19)142.7 (16)
Symmetry codes: (i) x+3/2, y+1/2, z+3/2; (ii) x+1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formulaC9H10N2O4
Mr210.19
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)14.4803 (15), 11.4054 (11), 13.0936 (13)
β (°) 116.341 (8)
V3)1937.9 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.25 × 0.25 × 0.10
Data collection
DiffractometerRigaku Mercury375R (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
(REQAB; Rigaku, 1998)
Tmin, Tmax0.840, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8409, 1759, 1348
Rint0.045
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.098, 1.06
No. of reflections1759
No. of parameters176
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.21, 0.17

Computer programs: CrystalClear-SM Expert (Rigaku, 2014), SHELXT (Sheldrick, 2015a), SHELXL2013 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

Acknowledgments are made to Armstrong State University and to the Donors of the American Chemical Society Petroleum Research Fund for support (or partial support) of this research (PRF No. 53848-UNI3). Additional support was provided by the NSF–STEP Program under Award No. DUE-0856593.

References

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Volume 71| Part 6| June 2015| Pages 606-608
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