Methyl 2-amino-4,5-di­meth­oxy­benzoate

Hill, T.N.; Patel, N.

doi:10.1107/S1600536813030894

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1779

doi:10.1107/S1600536813030894

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Methyl 2-amino-4,5-dimethoxybenzoate

Tania N. Hill ^a ^* and Naadiya Patel ^a

^aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, PO WITS 2050, Johannesburg, South Africa
^*Correspondence e-mail: tania.hill@gmail.com

(Received 7 November 2013; accepted 11 November 2013; online 16 November 2013)

The title compound, C₁₀H₁₃NO₄, is essentially planar, with an r.m.s. deviation of 0.049 Å. An intramolecular C—H⋯O hydrogen bond occurs and the amino group forms an intramolecular N—H⋯O_ester hydrogen bond; the other H atom forms an intermolecular N—H⋯O_carbonyl hydrogen bond, leading to the formation of a helical chain that runs along the b-axis direction.

CCDC reference: 971313

Related literature

For similar crystal structures, see: Zhang et al. (2009 ); Smith & Elsegood (2002 ).

Experimental

Crystal data

C₁₀H₁₃NO₄
M_r = 211.21
Monoclinic, P 2₁ /c
a = 11.1933 (4) Å
b = 7.7564 (3) Å
c = 13.7728 (5) Å
β = 121.741 (2)°
V = 1016.91 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.5 × 0.29 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.948, T_max = 0.974
9994 measured reflections
2543 independent reflections
2080 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.109
S = 1.05
2543 reflections
147 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2	0.95	2.37	2.7131 (14)	101
N1—H1A⋯O1	0.90 (2)	2.03 (2)	2.702 (2)	131 (2)
N1—H1B⋯O1ⁱ	0.88 (2)	2.10 (2)	2.947 (1)	162 (1)
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 971313

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813030894/ng5347sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030894/ng5347Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813030894/ng5347Isup3.cml

checkCIF report

Comment top

The molecular structure of (I) is presented in Figure 1, and was obtained by recrystallization of the commercially available compound. The title compound consists of an amino (C2) and methoxy (C4 and C5) substituted benzoate which was found to be essentially planar with an r.m.s. deviation of 0.049 Å; the dihedral angles shown in Table 1 further reinforce the planarity of (I). The maximum deviation observed below the calculated mean plane was found for the carbonyl oxygen (O1) at -0.136 (1) Å. Two intramolecular hydrogen bonds found between the phenyl carbon (C6), the amino (N1) and the ester O atoms (O1 and O2) with distances of 2.713 (1) Å and 2.702 (2) Å, effectively lock the ester into the molecular plane. The last hydrogen bond interaction observed between the amino (N1) and an adjacent carbonyl oxygen (O1) (symmetry operator [-x, y + 1/2, -z - 1/2]) with a distance of 2.947 (1) Å results in a helical chain along [0 1 0] (Figure 2).

Related literature top

For similar crystal structures, see: Zhang et al. (2009); Smith & Elsegood (2002).

Experimental top

Methyl 2-amino-4,5-dimethoxybenzoate was obtained commercially. (I) was redissolved in warm MeOH and allowed to cool to room terperature. Yellow crystals suitable for single-crystal diffraction were obtained by slow evaporation over a few days.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. View of (I) (50% probability displacement ellipsoids)
	Fig. 2. Packing of (I) viewed along [0 1 0]. H atoms omitted.

Methyl 2-amino-4,5-dimethoxybenzoate top

Crystal data top

C₁₀H₁₃NO₄	F(000) = 448
M_r = 211.21	D_x = 1.38 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3834 reflections
a = 11.1933 (4) Å	θ = 3.0–28.3°
b = 7.7564 (3) Å	µ = 0.11 mm⁻¹
c = 13.7728 (5) Å	T = 173 K
β = 121.741 (2)°	Cuboid, yellow
V = 1016.91 (7) Å³	0.5 × 0.29 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2543 independent reflections
Radiation source: fine-focus sealed tube	2080 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 512 pixels mm^-1	θ_max = 28.3°, θ_min = 2.1°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −10→10
T_min = 0.948, T_max = 0.974	l = −18→18
9994 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0501P)² + 0.2646P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.109	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.27 e Å⁻³
2543 reflections	Δρ_min = −0.25 e Å⁻³
147 parameters

Crystal data top

C₁₀H₁₃NO₄	V = 1016.91 (7) Å³
M_r = 211.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.1933 (4) Å	µ = 0.11 mm⁻¹
b = 7.7564 (3) Å	T = 173 K
c = 13.7728 (5) Å	0.5 × 0.29 × 0.25 mm
β = 121.741 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2543 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2080 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.974	R_int = 0.035
9994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.27 e Å⁻³
2543 reflections	Δρ_min = −0.25 e Å⁻³
147 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
C1	0.19769 (12)	0.09141 (14)	−0.01177 (10)	0.0237 (2)
C2	0.16865 (12)	0.16680 (14)	−0.11496 (10)	0.0243 (2)
C3	0.22538 (12)	0.33134 (15)	−0.11104 (10)	0.0250 (2)
H3	0.2062	0.3839	−0.1801	0.03*
C4	0.30761 (12)	0.41704 (14)	−0.00949 (10)	0.0239 (2)
C5	0.33814 (12)	0.34050 (14)	0.09484 (9)	0.0234 (2)
C6	0.28295 (12)	0.18137 (14)	0.09202 (9)	0.0235 (2)
H6	0.3024	0.1301	0.1615	0.028*
C7	0.13820 (12)	−0.07648 (14)	−0.01151 (10)	0.0256 (2)
C8	0.13103 (15)	−0.30520 (15)	0.09811 (12)	0.0340 (3)
H8A	0.0291	−0.3006	0.064	0.051*
H8B	0.1763	−0.3421	0.1779	0.051*
H8C	0.1531	−0.3875	0.0558	0.051*
C9	0.33489 (15)	0.66056 (17)	−0.10146 (11)	0.0345 (3)
H9A	0.3706	0.591	−0.1402	0.052*
H9B	0.3805	0.7738	−0.0826	0.052*
H9C	0.2331	0.6751	−0.1518	0.052*
C10	0.44564 (14)	0.36738 (17)	0.29532 (10)	0.0328 (3)
H10A	0.3554	0.3526	0.29	0.049*
H10B	0.5049	0.4467	0.3579	0.049*
H10C	0.4927	0.2554	0.31	0.049*
N1	0.09141 (12)	0.08643 (15)	−0.21889 (9)	0.0326 (3)
O1	0.05611 (10)	−0.15847 (12)	−0.09659 (8)	0.0376 (2)
O2	0.18202 (10)	−0.13617 (11)	0.09315 (7)	0.0324 (2)
O3	0.36486 (9)	0.57535 (10)	0.00121 (7)	0.0293 (2)
O4	0.42222 (9)	0.43624 (10)	0.19078 (7)	0.0279 (2)
H1B	0.0560 (16)	0.1496 (19)	−0.2812 (14)	0.037 (4)*
H1A	0.0410 (18)	−0.007 (3)	−0.2225 (15)	0.056 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0235 (5)	0.0231 (5)	0.0239 (5)	0.0032 (4)	0.0121 (4)	−0.0001 (4)
C2	0.0221 (5)	0.0261 (5)	0.0232 (5)	0.0050 (4)	0.0110 (4)	−0.0010 (4)
C3	0.0261 (6)	0.0278 (6)	0.0223 (5)	0.0056 (4)	0.0137 (5)	0.0038 (4)
C4	0.0248 (6)	0.0229 (5)	0.0268 (5)	0.0033 (4)	0.0155 (5)	0.0024 (4)
C5	0.0236 (5)	0.0249 (5)	0.0219 (5)	0.0017 (4)	0.0121 (4)	−0.0004 (4)
C6	0.0255 (6)	0.0237 (5)	0.0216 (5)	0.0021 (4)	0.0127 (4)	0.0011 (4)
C7	0.0250 (6)	0.0246 (5)	0.0272 (6)	0.0032 (4)	0.0137 (5)	−0.0011 (4)
C8	0.0438 (8)	0.0221 (5)	0.0417 (7)	−0.0015 (5)	0.0263 (6)	0.0015 (5)
C9	0.0402 (7)	0.0328 (6)	0.0336 (6)	0.0003 (5)	0.0214 (6)	0.0092 (5)
C10	0.0398 (7)	0.0348 (6)	0.0218 (6)	−0.0095 (5)	0.0148 (5)	−0.0019 (5)
N1	0.0371 (6)	0.0324 (6)	0.0211 (5)	−0.0008 (5)	0.0102 (5)	−0.0008 (4)
O1	0.0411 (5)	0.0323 (5)	0.0305 (5)	−0.0088 (4)	0.0127 (4)	−0.0055 (4)
O2	0.0431 (5)	0.0241 (4)	0.0295 (4)	−0.0050 (4)	0.0188 (4)	−0.0004 (3)
O3	0.0363 (5)	0.0258 (4)	0.0271 (4)	−0.0031 (3)	0.0176 (4)	0.0029 (3)
O4	0.0341 (5)	0.0271 (4)	0.0215 (4)	−0.0063 (3)	0.0140 (4)	−0.0018 (3)

Geometric parameters (Å, º) top

C1—C2	1.4077 (15)	C8—O2	1.4458 (14)
C1—C6	1.4162 (15)	C8—H8A	0.98
C1—C7	1.4634 (16)	C8—H8B	0.98
C2—N1	1.3722 (15)	C8—H8C	0.98
C2—C3	1.4138 (16)	C9—O3	1.4317 (14)
C3—C4	1.3751 (16)	C9—H9A	0.98
C3—H3	0.95	C9—H9B	0.98
C4—O3	1.3568 (13)	C9—H9C	0.98
C4—C5	1.4203 (15)	C10—O4	1.4247 (14)
C5—O4	1.3692 (13)	C10—H10A	0.98
C5—C6	1.3716 (15)	C10—H10B	0.98
C6—H6	0.95	C10—H10C	0.98
C7—O1	1.2202 (14)	N1—H1B	0.881 (16)
C7—O2	1.3374 (14)	N1—H1A	0.90 (2)

C2—C1—C6	119.31 (10)	H8A—C8—H8B	109.5
C2—C1—C7	120.56 (10)	O2—C8—H8C	109.5
C6—C1—C7	120.12 (10)	H8A—C8—H8C	109.5
N1—C2—C1	123.27 (11)	H8B—C8—H8C	109.5
N1—C2—C3	118.28 (10)	O3—C9—H9A	109.5
C1—C2—C3	118.42 (10)	O3—C9—H9B	109.5
C4—C3—C2	121.47 (10)	H9A—C9—H9B	109.5
C4—C3—H3	119.3	O3—C9—H9C	109.5
C2—C3—H3	119.3	H9A—C9—H9C	109.5
O3—C4—C3	124.97 (10)	H9B—C9—H9C	109.5
O3—C4—C5	114.83 (10)	O4—C10—H10A	109.5
C3—C4—C5	120.20 (10)	O4—C10—H10B	109.5
O4—C5—C6	125.87 (10)	H10A—C10—H10B	109.5
O4—C5—C4	115.28 (10)	O4—C10—H10C	109.5
C6—C5—C4	118.85 (10)	H10A—C10—H10C	109.5
C5—C6—C1	121.75 (10)	H10B—C10—H10C	109.5
C5—C6—H6	119.1	C2—N1—H1B	118.5 (10)
C1—C6—H6	119.1	C2—N1—H1A	117.0 (12)
O1—C7—O2	121.23 (11)	H1B—N1—H1A	116.4 (15)
O1—C7—C1	125.11 (11)	C7—O2—C8	115.77 (9)
O2—C7—C1	113.66 (10)	C4—O3—C9	117.30 (9)
O2—C8—H8A	109.5	C5—O4—C10	116.08 (9)
O2—C8—H8B	109.5

C6—C1—C2—N1	177.57 (11)	C4—C5—C6—C1	0.54 (17)
C7—C1—C2—N1	−3.72 (17)	C2—C1—C6—C5	0.06 (17)
C6—C1—C2—C3	−0.46 (16)	C7—C1—C6—C5	−178.65 (10)
C7—C1—C2—C3	178.25 (10)	C2—C1—C7—O1	−3.96 (18)
N1—C2—C3—C4	−177.87 (11)	C6—C1—C7—O1	174.73 (11)
C1—C2—C3—C4	0.26 (16)	C2—C1—C7—O2	176.09 (10)
C2—C3—C4—O3	−179.49 (10)	C6—C1—C7—O2	−5.22 (15)
C2—C3—C4—C5	0.33 (17)	O1—C7—O2—C8	2.67 (16)
O3—C4—C5—O4	−0.88 (14)	C1—C7—O2—C8	−177.38 (10)
C3—C4—C5—O4	179.28 (10)	C3—C4—O3—C9	1.26 (16)
O3—C4—C5—C6	179.10 (10)	C5—C4—O3—C9	−178.57 (10)
C3—C4—C5—C6	−0.73 (17)	C6—C5—O4—C10	−4.40 (16)
O4—C5—C6—C1	−179.48 (10)	C4—C5—O4—C10	175.59 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2	0.95	2.37	2.7131 (14)	101
N1—H1A···O1	0.90 (2)	2.03 (2)	2.702 (2)	131 (2)
N1—H1B···O1ⁱ	0.88 (2)	2.10 (2)	2.947 (1)	162 (1)

Symmetry code: (i) −x, y+1/2, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2	0.95	2.37	2.7131 (14)	100.5
N1—H1A···O1	0.90 (2)	2.03 (2)	2.702 (2)	131 (2)
N1—H1B···O1ⁱ	0.88 (2)	2.10 (2)	2.947 (1)	162 (1)

Symmetry code: (i) −x, y+1/2, −z−1/2.

Acknowledgements

The University of the Witwatersrand and the Molecular Sciences Institute are thanked for providing the infrastructure and financial support. Special thanks go to Dr Andreas Lemmerer of the University of the Witwatersrand for his contributions and insights toward this project. TNH wishes to thank the University of the Witwatersrand research committee for a postdoctoral fellowship.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Imapct GbR, Bonn, Germany. Google Scholar
Bruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin. USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, M. B. & Elsegood, M. R. J. (2002). Tetrahedron Lett. 43, 1299–1301. Web of Science CSD CrossRef CAS Google Scholar
Zhang, M., Lu, R., Han, L., Wei, W. & Wang, H. (2009). Acta Cryst. E65, o942. Web of Science CSD CrossRef IUCr Journals Google Scholar