2-Methyl­propan-2-aminium 2-(meth­oxy­carbon­yl)benzoate

Li, J.

doi:10.1107/S1600536811037688

organic compounds

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Volume 67| Part 10| October 2011| Page o2705

https://doi.org/10.1107/S1600536811037688

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2-Methylpropan-2-aminium 2-(methoxycarbonyl)benzoate

Jian Li ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ljwfu@163.com

(Received 11 August 2011; accepted 15 September 2011; online 30 September 2011)

In the title compound, C₄H₁₂N⁺·C₉H₇O₄⁻, two C atoms and the N atom of the cation lie on a mirror plane, while all the atoms of the anion are disordered about a mirror plane. In the crystal, N—H⋯O hydrogen bonds link the components into chains along [010]. In the anion, the mean planes of the methoxycarbonyl and carboxylate groups form dihedral angles of 83.0 (2) and 83.2 (2)°, respectively, with the aromatic ring.

Related literature

For the applications of phthalimides and N-substituted phthalimides, see: Lima et al. (2002 ). For related structures, see: Li (2011 ); Liang (2011 ).

Experimental

Crystal data

C₄H₁₂N⁺·C₉H₇O₄⁻
M_r = 253.29
Monoclinic, P 2₁ /m
a = 9.2939 (8) Å
b = 7.0159 (6) Å
c = 10.5536 (11) Å
β = 103.322 (1)°
V = 669.63 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.49 × 0.43 × 0.32 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.956, T_max = 0.971
4353 measured reflections
1797 independent reflections
1137 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.137
S = 1.03
1797 reflections
152 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N⋯O4	0.925 (18)	1.749 (19)	2.674 (3)	178.3 (17)
N1—H2N⋯O3ⁱ	0.925 (18)	2.042 (18)	2.926 (3)	159.4 (16)
N1—H1N⋯O3ⁱⁱ	0.92 (3)	1.96 (2)	2.825 (3)	156 (1)
N1—H1N⋯O3ⁱⁱⁱ	0.92 (3)	1.96 (2)	2.825 (3)	156 (1)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z]$ ; (ii) -x+2, -y+1, -z+2; (iii) $[-x+2, y+{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811037688/lh5313sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037688/lh5313Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811037688/lh5313Isup3.cml

checkCIF report

Comment top

Phthalimides and N-substituted phthalimides are animportant class of compounds because of their interesting biological activities (Lima et al., 2002). Tert-butylaminium 2-(methoxycarbonyl)benzoate is an intermediate in the preparation of N-substituted phthalimides. The crystal structures of propan-1-aminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate N,N-dimethylformamide monosolvate (Li, 2011) and butane-1,4-diaminium bis[3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate] (Liang, 2011) have already been reported. In this paper, the structure of the title compound is reported. The asymmetric unit of the title compound, 2-methylpropan-2-aminium 2-(methoxycarbonyl)benzoate, (I), is shown in Fig. 1. Atoms C11 and C11a of the cation lie symmetrically on a mirror plane (C10C12N1) while all the atoms of the anion are disordered over a mirror plane. In the crystal, N—H···O hydrogen bonds link the components into one-dimensional chains along [010].

Related literature top

For the applications of phthalimides and N-substituted phthalimides, see: Lima et al. (2002). For related structures, see: Li (2011); Liang (2011).

Experimental top

A mixture of phthalic anhydride (1.52 g, 0.01 mol) and methanol (15 ml) was refluxed for 30 min. Then tert-butylamine (0.73 g, 0.01 mol) was added to the above solution and mixed for 30 min at room temperature. The solution was kept at room temperature for 5 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.

Structure description top

For the applications of phthalimides and N-substituted phthalimides, see: Lima et al. (2002). For related structures, see: Li (2011); Liang (2011).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I), drawn with 30% probability ellipsoids. The disorder is not shown (symmetry code (a): x, -y+3/2, z).
	Fig. 2. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines.

2-Methylpropan-2-aminium 2-(methoxycarbonyl)benzoate top

Crystal data top

C₄H₁₂N⁺·C₉H₇O₄⁻	F(000) = 272
M_r = 253.29	D_x = 1.256 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1362 reflections
a = 9.2939 (8) Å	θ = 2.6–25.8°
b = 7.0159 (6) Å	µ = 0.09 mm⁻¹
c = 10.5536 (11) Å	T = 298 K
β = 103.322 (1)°	Block, colorless
V = 669.63 (11) Å³	0.49 × 0.43 × 0.32 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1797 independent reflections
Radiation source: fine-focus sealed tube	1137 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
φ and ω scans	θ_max = 28.4°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→11
T_min = 0.956, T_max = 0.971	k = −9→9
4353 measured reflections	l = −6→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0609P)² + 0.1129P] where P = (F_o² + 2F_c²)/3
1797 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.16 e Å⁻³
14 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₄H₁₂N⁺·C₉H₇O₄⁻	V = 669.63 (11) Å³
M_r = 253.29	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 9.2939 (8) Å	µ = 0.09 mm⁻¹
b = 7.0159 (6) Å	T = 298 K
c = 10.5536 (11) Å	0.49 × 0.43 × 0.32 mm
β = 103.322 (1)°

Data collection top

Bruker SMART CCD diffractometer	1797 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1137 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.971	R_int = 0.021
4353 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	14 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.16 e Å⁻³
1797 reflections	Δρ_min = −0.17 e Å⁻³
152 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.8688 (2)	0.2267 (9)	0.39796 (18)	0.0599 (11)	0.50
O2	0.9747 (2)	0.2711 (10)	0.60624 (19)	0.0596 (10)	0.50
O3	0.8655 (3)	0.1366 (4)	0.8604 (3)	0.0541 (7)	0.50
O4	0.8413 (3)	0.4448 (4)	0.8097 (3)	0.0544 (7)	0.50
C1	0.8655 (3)	0.2433 (7)	0.5222 (2)	0.0440 (7)	0.50
C2	0.8117 (3)	0.2730 (9)	0.7889 (2)	0.0366 (9)	0.50
C3	0.7136 (3)	0.2236 (5)	0.5430 (2)	0.0470 (9)	0.50
C4	0.6905 (3)	0.2377 (6)	0.6689 (2)	0.0407 (6)	0.50
C5	0.5479 (3)	0.2184 (7)	0.6863 (3)	0.0574 (13)	0.50
H5A	0.5315	0.2273	0.7698	0.069*	0.50
C6	0.4291 (3)	0.1862 (4)	0.5818 (3)	0.0547 (9)	0.50
H6A	0.3342	0.1727	0.5955	0.066*	0.50
C7	0.4520 (4)	0.1743 (4)	0.4584 (3)	0.0566 (9)	0.50
H7A	0.3725	0.1551	0.3879	0.068*	0.50
C8	0.5922 (3)	0.1906 (3)	0.4389 (3)	0.0483 (8)	0.50
H8A	0.6070	0.1797	0.3551	0.058*	0.50
C9	1.0136 (3)	0.2437 (12)	0.3673 (3)	0.0716 (11)	0.5
H9A	1.0025	0.2370	0.2747	0.107*	0.50
H9B	1.0762	0.1417	0.4083	0.107*	0.50
H9C	1.0573	0.3637	0.3989	0.107*	0.50
N1	0.87003 (19)	0.7500	0.96516 (19)	0.0428 (5)
C10	0.7457 (2)	0.7500	1.0343 (2)	0.0417 (5)
C11	0.76193 (19)	0.5723 (3)	1.11787 (18)	0.0606 (5)
H11A	0.7587	0.4617	1.0637	0.091*
H11B	0.6826	0.5666	1.1621	0.091*
H11C	0.8547	0.5761	1.1808	0.091*
C12	0.6025 (2)	0.7500	0.9300 (2)	0.0601 (7)
H12A	0.5986	0.8615	0.8766	0.090*	0.50
H12B	0.5200	0.7504	0.9706	0.090*
H12C	0.5983	0.6381	0.8769	0.090*	0.50
H2N	0.8597 (18)	0.643 (2)	0.9127 (18)	0.060 (5)*
H1N	0.960 (3)	0.7500	1.024 (3)	0.060 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0603 (11)	0.080 (3)	0.0415 (9)	−0.011 (2)	0.0155 (8)	−0.014 (2)
O2	0.0444 (9)	0.088 (3)	0.0444 (9)	−0.012 (2)	0.0060 (7)	−0.006 (2)
O3	0.0524 (14)	0.0535 (17)	0.0458 (16)	−0.0050 (13)	−0.0106 (12)	0.0165 (13)
O4	0.0625 (17)	0.0448 (16)	0.0515 (17)	−0.0075 (12)	0.0042 (13)	−0.0091 (12)
C1	0.0504 (12)	0.0467 (15)	0.0338 (12)	0.006 (5)	0.0073 (10)	−0.014 (4)
C2	0.0340 (9)	0.042 (2)	0.0338 (10)	0.0011 (13)	0.0088 (8)	0.0018 (14)
C3	0.0417 (12)	0.059 (3)	0.0369 (12)	0.0012 (18)	0.0015 (9)	−0.0022 (19)
C4	0.0364 (10)	0.0458 (15)	0.0364 (11)	0.005 (3)	0.0014 (8)	0.001 (3)
C5	0.0396 (12)	0.086 (4)	0.0453 (13)	−0.001 (2)	0.0064 (10)	0.001 (2)
C6	0.0357 (14)	0.056 (2)	0.068 (2)	−0.0041 (11)	0.0018 (14)	−0.0015 (14)
C7	0.0465 (16)	0.059 (2)	0.0528 (18)	−0.0036 (13)	−0.0126 (14)	−0.0040 (14)
C8	0.0556 (17)	0.046 (2)	0.0366 (14)	−0.0011 (12)	−0.0028 (12)	−0.0038 (11)
C9	0.0723 (18)	0.086 (3)	0.0611 (19)	−0.015 (5)	0.0253 (15)	0.032 (5)
N1	0.0340 (9)	0.0543 (12)	0.0378 (10)	0.000	0.0037 (7)	0.000
C10	0.0327 (10)	0.0499 (12)	0.0418 (11)	0.000	0.0069 (8)	0.000
C11	0.0581 (10)	0.0617 (11)	0.0619 (10)	−0.0050 (8)	0.0137 (8)	0.0120 (9)
C12	0.0361 (11)	0.0756 (17)	0.0636 (15)	0.000	0.0010 (11)	0.000

Geometric parameters (Å, º) top

O1—C1	1.323 (3)	C8—H8A	0.9300
O1—C9	1.460 (3)	C9—H9A	0.9600
O2—C1	1.200 (3)	C9—H9B	0.9600
O3—C2	1.249 (6)	C9—H9C	0.9600
O4—C2	1.244 (7)	N1—C10	1.501 (3)
C1—C3	1.484 (4)	N1—H2N	0.925 (18)
C2—C4	1.509 (3)	N1—H1N	0.92 (3)
C3—C4	1.397 (4)	C10—C11ⁱ	1.515 (2)
C3—C8	1.400 (4)	C10—C11	1.515 (2)
C4—C5	1.386 (4)	C10—C12	1.519 (3)
C5—C6	1.388 (4)	C11—H11A	0.9600
C5—H5A	0.9300	C11—H11B	0.9600
C6—C7	1.370 (5)	C11—H11C	0.9600
C6—H6A	0.9300	C12—H12A	0.9600
C7—C8	1.369 (5)	C12—H12B	0.9600
C7—H7A	0.9300	C12—H12C	0.9600

C1—O1—C9	116.4 (2)	O1—C9—H9B	109.5
O2—C1—O1	122.5 (2)	H9A—C9—H9B	109.5
O2—C1—C3	125.3 (2)	O1—C9—H9C	109.5
O1—C1—C3	112.2 (2)	H9A—C9—H9C	109.5
O4—C2—O3	126.5 (4)	H9B—C9—H9C	109.5
O4—C2—C4	113.5 (3)	C10—N1—H2N	107.8 (11)
O3—C2—C4	119.9 (3)	C10—N1—H1N	110.8 (15)
C4—C3—C8	119.0 (3)	H2N—N1—H1N	110.9 (13)
C4—C3—C1	119.6 (2)	N1—C10—C11ⁱ	107.38 (11)
C8—C3—C1	121.4 (2)	N1—C10—C11	107.38 (11)
C5—C4—C3	118.7 (2)	C11ⁱ—C10—C11	110.77 (19)
C5—C4—C2	117.2 (2)	N1—C10—C12	106.99 (18)
C3—C4—C2	124.1 (2)	C11ⁱ—C10—C12	112.01 (11)
C4—C5—C6	121.4 (3)	C11—C10—C12	112.01 (11)
C4—C5—H5A	119.3	C10—C11—H11A	109.5
C6—C5—H5A	119.3	C10—C11—H11B	109.5
C7—C6—C5	119.7 (3)	H11A—C11—H11B	109.5
C7—C6—H6A	120.1	C10—C11—H11C	109.5
C5—C6—H6A	120.1	H11A—C11—H11C	109.5
C8—C7—C6	120.0 (3)	H11B—C11—H11C	109.5
C8—C7—H7A	120.0	C10—C12—H12A	109.5
C6—C7—H7A	120.0	C10—C12—H12B	109.5
C7—C8—C3	121.2 (3)	H12A—C12—H12B	109.5
C7—C8—H8A	119.4	C10—C12—H12C	109.5
C3—C8—H8A	119.4	H12A—C12—H12C	109.5
O1—C9—H9A	109.5	H12B—C12—H12C	109.5

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N···O4	0.925 (18)	1.749 (19)	2.674 (3)	178.3 (17)
N1—H2N···O3ⁱⁱ	0.925 (18)	2.042 (18)	2.926 (3)	159.4 (16)
N1—H1N···O3ⁱⁱⁱ	0.92 (3)	1.96 (2)	2.825 (3)	156 (1)
N1—H1N···O3^iv	0.92 (3)	1.96 (2)	2.825 (3)	156 (1)

Symmetry codes: (ii) x, −y+1/2, z; (iii) −x+2, −y+1, −z+2; (iv) −x+2, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N⁺·C₉H₇O₄⁻
M_r	253.29
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	9.2939 (8), 7.0159 (6), 10.5536 (11)
β (°)	103.322 (1)
V (Å³)	669.63 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.49 × 0.43 × 0.32

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.956, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	4353, 1797, 1137
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.137, 1.03
No. of reflections	1797
No. of parameters	152
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N···O4	0.925 (18)	1.749 (19)	2.674 (3)	178.3 (17)
N1—H2N···O3ⁱ	0.925 (18)	2.042 (18)	2.926 (3)	159.4 (16)
N1—H1N···O3ⁱⁱ	0.92 (3)	1.96 (2)	2.825 (3)	156.1 (3)
N1—H1N···O3ⁱⁱⁱ	0.92 (3)	1.96 (2)	2.825 (3)	156.1 (3)

Symmetry codes: (i) x, −y+1/2, z; (ii) −x+2, −y+1, −z+2; (iii) −x+2, y+1/2, −z+2.

Acknowledgements

The author thanks Shandong Provincial Natural Science Foundation, China (grant No. ZR2009BL027) for support.

References

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