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

Quillian, B.; Hendricks, J.; Trivitayakhun, M.; Padgett, C.W.

doi:10.1107/S2056989015008750

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S2056989015008750

Open

access

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

Brandon Quillian,^a ^* Jordan Hendricks,^a Matthew Trivitayakhun ^a and Clifford W. Padgett ^a

^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 π–π 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].

Keywords: crystal structure; 3-amino-4-nitrobenzyl acetate; intramolecular; intermolecular; resonance-assisted hydrogen bonding; 5-amino-2-nitrobenzoic acid.

CCDC reference: 1063364

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 ; 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 suggests 3-amino-4-nitrobenzoic acid is an impurity in the commercially available starting material.

2. Structural Commentary

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, 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 ). 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). 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 ).

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 and Table 1) 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) 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 stacked one above the other. The chains stack along the c axis by π–π 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	D⋯A	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
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
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 ). 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 ); Abdul Rahim et al. (2010 ); Yoon et al. (2011 ); Yoon et al. (2012 ).

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 ). 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, ³J_HH = 5.3 Hz), 4.95 (d, 2H, CH₂, ³J_HH = 5.3 Hz) , 6.03 (bs, 2H, NH₂), 6.63 (dd, 1H, Ar-H, ³J_HH = 8.8 Hz, ³J_HH = 2.3 Hz), 7.07 (m, 1H, Ar-H), 8.02 (dd, 1H, ³J_HH = 9.4 Hz, ³J_HH = 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 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, ³J_HH = 8.9 Hz, ⁵J_HH = 2.5 Hz), 6.68 (m, 1H, Ar-H), 8.09 (dd, 1H, Ar-H, ³J_HH = 8.9 Hz, ⁵J_HH = 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, ³J_HH = 8.9 Hz, ⁵J_HH = 2.5 Hz), 7.75 (m, 1H, Ar-H), 8.15 (d, 1H, Ar-H, ³J_HH = 8.9 Hz).

5.1. Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₄
M_r	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)
V (Å³)	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 )
T_min, T_max	0.840, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8409, 1759, 1348
R_int	0.045
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17
Computer programs: CrystalClear-SM Expert (Rigaku, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2013 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1063364

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015008750/pk2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015008750/pk2548Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015008750/pk2548Isup3.cml

checkCIF report

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, 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). 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 π–π 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, ³J_HH = 5.3 Hz), 4.95 (d, 2H, CH₂, ³J_HH = 5.3 Hz ), 6.03 (bs, 2H, NH₂), 6.63 (dd, 1H, Ar—H, ³J_HH = 8.8 Hz, ³J_HH = 2.3 Hz), 7.07 (m, 1H, Ar—H), 8.02 (dd, 1H, ³J_HH = 9.4 Hz, ³J_HH = 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, ³J_HH = 8.9 Hz, ⁵J_HH = 2.5 Hz), 6.68 (m, 1H, Ar—H), 8.09 (dd, 1H, Ar—H, ³J_HH = 8.9 Hz, ⁵J_HH = 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, ³J_HH = 8.9 Hz, ⁵J_HH = 2.5 Hz), 7.75 (m, 1H, Ar—H), 8.15 (d, 1H, Ar—H, ³J_HH = 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

	Fig. 1. A displacement ellipsoid plot of 3-amino-4-nitrobenzyl acetate (50% probability level). Some H atoms have been omitted for clarity.
	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.
	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

C₉H₁₀N₂O₄	F(000) = 880
M_r = 210.19	D_x = 1.441 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
a = 14.4803 (15) Å	Cell parameters from 513 reflections
b = 11.4054 (11) Å	θ = 1.6–25.4°
c = 13.0936 (13) Å	µ = 0.12 mm⁻¹
β = 116.341 (8)°	T = 173 K
V = 1937.9 (4) Å³	Prism, yellow
Z = 8	0.25 × 0.25 × 0.10 mm

Data collection top

Rigaku Mercury375R (2x2 bin mode) diffractometer	1759 independent reflections
Radiation source: Sealed Tube	1348 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.045
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.3°, θ_min = 2.4°
profile data from ω scans	h = −17→17
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −13→13
T_min = 0.840, T_max = 1.000	l = −15→15
8409 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	All H-atom parameters refined
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0578P)² + 0.2118P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1759 reflections	Δρ_max = 0.21 e Å⁻³
176 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints

Crystal data top

C₉H₁₀N₂O₄	V = 1937.9 (4) Å³
M_r = 210.19	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.4803 (15) Å	µ = 0.12 mm⁻¹
b = 11.4054 (11) Å	T = 173 K
c = 13.0936 (13) Å	0.25 × 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)
T_min = 0.840, T_max = 1.000	R_int = 0.045
8409 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.098	All H-atom parameters refined
S = 1.06	Δρ_max = 0.21 e Å⁻³
1759 reflections	Δρ_min = −0.17 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O3	0.74138 (8)	0.43515 (9)	0.74195 (10)	0.0324 (3)
O1	0.23008 (8)	0.61948 (10)	0.50492 (11)	0.0418 (3)
O2	0.18245 (8)	0.43814 (10)	0.46692 (11)	0.0436 (3)
O4	0.86707 (9)	0.30050 (11)	0.79735 (12)	0.0456 (4)
N1	0.25141 (9)	0.51321 (11)	0.50551 (11)	0.0288 (3)
N2	0.42892 (12)	0.67596 (12)	0.60612 (12)	0.0300 (3)
H2A	0.4821 (16)	0.7166 (16)	0.6337 (16)	0.036 (5)*
H2B	0.3700 (16)	0.7046 (15)	0.5821 (16)	0.039 (5)*
C6	0.43920 (11)	0.55950 (12)	0.60073 (12)	0.0228 (3)
C1	0.35704 (10)	0.47782 (13)	0.55271 (12)	0.0245 (3)
C4	0.55919 (11)	0.39372 (13)	0.64720 (12)	0.0252 (3)
C5	0.54112 (10)	0.51152 (13)	0.64747 (11)	0.0228 (3)
H5	0.5978 (13)	0.5675 (14)	0.6814 (13)	0.024 (4)*
C2	0.37680 (12)	0.35678 (14)	0.54982 (13)	0.0295 (4)
H2	0.3212 (13)	0.3041 (14)	0.5154 (15)	0.031 (4)*
C3	0.47512 (12)	0.31496 (14)	0.59587 (14)	0.0312 (4)
H3	0.4895 (13)	0.2318 (16)	0.5930 (15)	0.033 (4)*
C7	0.66619 (11)	0.34199 (14)	0.69873 (14)	0.0296 (4)
H7A	0.6780 (14)	0.2874 (16)	0.7620 (16)	0.040 (5)*
H7B	0.6772 (12)	0.2957 (14)	0.6407 (15)	0.032 (4)*
C8	0.84105 (11)	0.40198 (15)	0.79024 (13)	0.0307 (4)
C9	0.91100 (13)	0.50537 (18)	0.83137 (18)	0.0419 (5)
H9A	0.8961 (16)	0.5562 (19)	0.7680 (19)	0.055 (6)*
H9B	0.9809 (17)	0.4806 (16)	0.8703 (17)	0.046 (5)*
H9C	0.8934 (17)	0.554 (2)	0.881 (2)	0.067 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0175 (5)	0.0288 (6)	0.0445 (7)	0.0021 (4)	0.0080 (5)	−0.0018 (5)
O1	0.0242 (6)	0.0319 (7)	0.0621 (8)	0.0054 (5)	0.0128 (6)	0.0060 (5)
O2	0.0194 (6)	0.0411 (7)	0.0601 (8)	−0.0073 (5)	0.0085 (6)	−0.0033 (6)
O4	0.0271 (6)	0.0400 (8)	0.0605 (8)	0.0089 (5)	0.0111 (6)	−0.0009 (6)
N1	0.0188 (6)	0.0314 (8)	0.0327 (7)	0.0002 (5)	0.0083 (5)	0.0031 (6)
N2	0.0199 (7)	0.0271 (8)	0.0379 (8)	0.0002 (6)	0.0082 (6)	−0.0025 (6)
C6	0.0214 (7)	0.0266 (8)	0.0210 (7)	0.0013 (6)	0.0098 (6)	0.0011 (6)
C1	0.0180 (7)	0.0307 (8)	0.0234 (7)	0.0004 (6)	0.0078 (6)	0.0027 (6)
C4	0.0210 (7)	0.0312 (8)	0.0239 (7)	0.0010 (6)	0.0104 (6)	0.0002 (6)
C5	0.0198 (8)	0.0271 (8)	0.0212 (7)	−0.0025 (6)	0.0086 (6)	−0.0011 (6)
C2	0.0218 (8)	0.0283 (9)	0.0358 (9)	−0.0063 (7)	0.0105 (7)	−0.0029 (7)
C3	0.0279 (8)	0.0238 (9)	0.0406 (9)	−0.0004 (6)	0.0142 (7)	−0.0017 (7)
C7	0.0237 (8)	0.0262 (8)	0.0363 (9)	0.0007 (6)	0.0110 (7)	−0.0024 (7)
C8	0.0211 (8)	0.0379 (10)	0.0305 (8)	0.0056 (7)	0.0091 (7)	0.0011 (7)
C9	0.0214 (9)	0.0483 (12)	0.0489 (11)	−0.0017 (8)	0.0091 (8)	−0.0015 (9)

Geometric parameters (Å, º) top

O3—C7	1.4449 (19)	C4—C3	1.419 (2)
O3—C8	1.3477 (19)	C4—C7	1.509 (2)
O1—N1	1.2500 (16)	C5—H5	0.978 (17)
O2—N1	1.2401 (17)	C2—H2	0.944 (17)
O4—C8	1.208 (2)	C2—C3	1.362 (2)
N1—C1	1.4303 (19)	C3—H3	0.975 (18)
N2—H2A	0.83 (2)	C7—H7A	0.988 (19)
N2—H2B	0.83 (2)	C7—H7B	0.994 (17)
N2—C6	1.342 (2)	C8—C9	1.491 (3)
C6—C1	1.419 (2)	C9—H9A	0.96 (2)
C6—C5	1.4320 (19)	C9—H9B	0.95 (2)
C1—C2	1.414 (2)	C9—H9C	0.97 (2)
C4—C5	1.369 (2)

C8—O3—C7	116.19 (12)	C3—C2—C1	120.94 (14)
O1—N1—C1	119.36 (12)	C3—C2—H2	119.5 (10)
O2—N1—O1	121.00 (12)	C4—C3—H3	118.7 (10)
O2—N1—C1	119.64 (13)	C2—C3—C4	119.75 (15)
H2A—N2—H2B	122.7 (17)	C2—C3—H3	121.5 (10)
C6—N2—H2A	118.1 (12)	O3—C7—C4	109.47 (13)
C6—N2—H2B	119.1 (12)	O3—C7—H7A	108.3 (11)
N2—C6—C1	125.60 (13)	O3—C7—H7B	109.9 (9)
N2—C6—C5	118.24 (13)	C4—C7—H7A	112.5 (10)
C1—C6—C5	116.16 (13)	C4—C7—H7B	110.3 (10)
C6—C1—N1	122.12 (13)	H7A—C7—H7B	106.2 (14)
C2—C1—N1	117.02 (13)	O3—C8—C9	111.22 (14)
C2—C1—C6	120.86 (13)	O4—C8—O3	122.52 (15)
C5—C4—C3	119.84 (14)	O4—C8—C9	126.26 (15)
C5—C4—C7	122.83 (14)	C8—C9—H9A	108.1 (13)
C3—C4—C7	117.33 (14)	C8—C9—H9B	110.5 (11)
C6—C5—H5	116.3 (9)	C8—C9—H9C	110.8 (13)
C4—C5—C6	122.40 (13)	H9A—C9—H9B	115.0 (17)
C4—C5—H5	121.3 (9)	H9A—C9—H9C	102.2 (18)
C1—C2—H2	119.6 (10)	H9B—C9—H9C	110.0 (17)

O1—N1—C1—C6	0.9 (2)	C5—C6—C1—N1	178.48 (13)
O1—N1—C1—C2	−179.17 (13)	C5—C6—C1—C2	−1.44 (19)
O2—N1—C1—C6	−178.35 (13)	C5—C4—C3—C2	−1.7 (2)
O2—N1—C1—C2	1.6 (2)	C5—C4—C7—O3	−2.0 (2)
N1—C1—C2—C3	−178.07 (14)	C3—C4—C5—C6	2.1 (2)
N2—C6—C1—N1	−1.2 (2)	C3—C4—C7—O3	177.40 (13)
N2—C6—C1—C2	178.91 (14)	C7—O3—C8—O4	0.1 (2)
N2—C6—C5—C4	179.13 (13)	C7—O3—C8—C9	179.98 (14)
C6—C1—C2—C3	1.9 (2)	C7—C4—C5—C6	−178.49 (13)
C1—C6—C5—C4	−0.5 (2)	C7—C4—C3—C2	178.86 (15)
C1—C2—C3—C4	−0.2 (2)	C8—O3—C7—C4	−179.68 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+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···A	D—H	H···A	D···A	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+3/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₄
M_r	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)
V (Å³)	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 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.840, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8409, 1759, 1348
R_int	0.045
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	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

Abdul Rahim, A. S., Abd Hamid, S., Narendra Babu, S. N., Loh, W.-S. & Fun, H.-K. (2010). Acta Cryst. E66, o846–o847. Web of Science CrossRef IUCr Journals Google Scholar
Aujard, I., Benbrahim, C., Gouget, M., Ruel, O., Baudin, J.-B., Neveu, P. & Jullien, L. (2006). Chem. Eur. J. 12, 6865–6879. Web of Science CrossRef PubMed CAS Google Scholar
Aznan, A. M. A., Abdullah, Z., Ng, S. W. & Tiekink, E. R. T. (2011). Acta Cryst. E67, o3076. Web of Science CSD CrossRef IUCr Journals Google Scholar
Beck, J. F. & Mo, Y. (2006). J. Comput. Chem. 4, 455–466. Google Scholar
Cabane, E., Malinova, V. & Meier, W. (2010). Macromol. Chem. Phys. 211, 1847–1856. Web of Science CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kasuga, N. C., Saito, Y., Sato, H. & Yamaguchi, K. (2015). Acta Cryst. E71, 483–486. CSD CrossRef IUCr Journals Google Scholar
Narendra Babu, S. N., Abdul Rahim, A. S., Abd Hamid, S., Balasubramani, K. & Fun, H.-K. (2009). Acta Cryst. E65, o2070–o2071. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pocker, Y., Davison, B. L. & Deits, T. L. (1978). J. Am. Chem. Soc. 100, 3564–3567. CrossRef CAS Web of Science Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Serafinowski, P. J. & Garland, P. B. (2008). Org. Biomol. Chem. 6, 3284–3291. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Yoon, Y. K., Ali, M. A., Choon, T. S., Loh, W.-S. & Fun, H.-K. (2011). Acta Cryst. E67, o2606. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yoon, Y. K., Manogaran, E., Ali, M. A., Arshad, S. & Razak, I. A. (2012). Acta Cryst. E68, o1684. CSD CrossRef IUCr Journals Google Scholar
Yoon, N. M., Pak, C. S., Krishnamurthy, S. & Stocky, T. P. (1973). J. Org. Chem. 38, 2786–2792. CrossRef CAS Web of Science 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 71| Part 6| June 2015| Pages 606-608

doi:10.1107/S2056989015008750

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

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Chemical Context

2. Structural Commentary

3. Supra­molecular Features

4. Database Survey

5. Synthesis and Crystallization

5.1. Refinement

Supporting information

Acknowledgements

References

research communications

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

3. Supramolecular Features