Ethyl 4-(dimethyl­amino)benzoate

Sundar, J.K.; Natarajan, V.; Arivanandhan, M.; Hayakawa, Y.; Natarajan, S.

doi:10.1107/S160053680905541X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o355

https://doi.org/10.1107/S160053680905541X

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Ethyl 4-(dimethylamino)benzoate

J. Kalyana Sundar,^a V. Natarajan,^b M. Arivanandhan,^c ^* Y. Hayakawa ^c and S. Natarajan ^a

^aDepartment of Physics, Madurai Kamaraj University, Madurai 625 021, India, ^bDepartment of Physics, Aditanar College of Arts and Science, Tiruchendur 628 216, India, and ^cNanodevices and Nanomaterials Division, Research Institute of Electronics, Shizuoka University, Hamamatsu 432 8011, Japan
^*Correspondence e-mail: rmarivu@ipc.shizuoka.ac.jp

(Received 22 December 2009; accepted 25 December 2009; online 13 January 2010)

Molecules of the title compound, C₁₁H₁₅NO₂, are essentially planar (r.m.s. deviation = 0.035 Å) and are linked into a chain along the a axis by weak C—H⋯O hydrogen bonds.

Related literature

Benzoic acid and its derivatives are good inhibitors of influenza viruses, see: Luo et al. (1995 ). For the use of benzoic acid derivatives such as 4-aminobenzoic acid as bifunctional organic ligands due to the variety of their coordination modes, see: Amiraslanov et al. (1979 ); Chen & Chen (2002 ); Hauptmann et al. (2000 ). For the use of the title compound as a part of a self-curing two-part system comprising degradable copolymers with applications in medicine and dentistry as root-canal sealants, root-canal filling materials, dental restorative materials, implant materials, bone cements and pulp-capping materials, see: Jia & Jin (2004 ).

Experimental

Crystal data

C₁₁H₁₅NO₂
M_r = 193.24
Monoclinic, P 2₁ /a
a = 12.6949 (8) Å
b = 6.6596 (4) Å
c = 12.8529 (9) Å
β = 98.672 (11)°
V = 1074.20 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.18 × 0.15 × 0.13 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.985, T_max = 0.989
4088 measured reflections
1873 independent reflections
1424 reflections with I > 2σ(I)
R_int = 0.051
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.134
S = 1.05
1873 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.55	3.4682 (19)	168
Symmetry code: (i) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680905541X/ci2998sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680905541X/ci2998Isup2.hkl

checkCIF report

Comment top

Benzoic acid and its derivatives are good inhibitors of influenza viruses (Luo et al., 1995). Some benzoic acid derivatives such as 4-aminobenzoic acid have been extensively reported in coordination chemistry as bifunctional organic ligands due to the varieties of their coordination modes (Chen & Chen, 2002; Amiraslanov et al., 1979; Hauptmann et al., 2000). The title compound, a tertiary amine, is used as a part of self-curing two part system for dental/ medical compositions comprising degradable copolymers which are suitable for use as root canal sealants, root canal filling materials, dental restorative materials, implant materials, bone cements and pulp capping materials (Jia et al., 2004).

The molecule of the title compound, C₁₁H₁₅N O₂, is essentially planar (r.m.s. deviation 0.035 Å). The molecules are linked into a chain along the a axis by weak C—H···O hydrogen bonds.

Related literature top

Benzoic acid and its derivatives are good inhibitors of influenza viruses, see: Luo et al. (1995). For the use of benzoic acid derivatives such as 4-aminobenzoic acid as bifunctional organic ligands due to the variety of their coordination modes, see: Amiraslanov et al. (1979); Chen & Chen (2002); Hauptmann et al. (2000). For the use of the title compound as a part of a self-curing two-part system comprising degradable copolymers with applications in medicine and dentistry as root-canal sealants, root-canal filling materials, dental restorative materials, implant materials, bone cements and pulp-capping materials, see: Jia & Jin (2004);

Experimental top

Ethyl 4-(dimethylamino)benzoate (EDMAB) obtained from Sigma–Aldrich, India, was dissolved in ethanol. The saturated solution was transferred to a crystallizer and covered by a perforated polyethylene sheet for controlled evaporation at room temperature. Colourless crystals were harvested, after five days

Structure description top

Benzoic acid and its derivatives are good inhibitors of influenza viruses, see: Luo et al. (1995). For the use of benzoic acid derivatives such as 4-aminobenzoic acid as bifunctional organic ligands due to the variety of their coordination modes, see: Amiraslanov et al. (1979); Chen & Chen (2002); Hauptmann et al. (2000). For the use of the title compound as a part of a self-curing two-part system comprising degradable copolymers with applications in medicine and dentistry as root-canal sealants, root-canal filling materials, dental restorative materials, implant materials, bone cements and pulp-capping materials, see: Jia & Jin (2004);

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Ethyl 4-(dimethylamino)benzoate top

Crystal data top

C₁₁H₁₅NO₂	F(000) = 416
M_r = 193.24	D_x = 1.195 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 25 reflections
a = 12.6949 (8) Å	θ = 2–25°
b = 6.6596 (4) Å	µ = 0.08 mm⁻¹
c = 12.8529 (9) Å	T = 293 K
β = 98.672 (11)°	Block, colourless
V = 1074.20 (12) Å³	0.18 × 0.15 × 0.13 mm
Z = 4

Data collection top

Nonius MACH-3 diffractometer	1424 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 25.0°, θ_min = 3.2°
ω–2θ scans	h = −1→15
Absorption correction: ψ scan (North et al., 1968)	k = −7→7
T_min = 0.985, T_max = 0.989	l = −15→15
4088 measured reflections	3 standard reflections every 60 min
1873 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0618P)² + 0.2249P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1873 reflections	Δρ_max = 0.16 e Å⁻³
131 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (3)

Crystal data top

C₁₁H₁₅NO₂	V = 1074.20 (12) Å³
M_r = 193.24	Z = 4
Monoclinic, P2₁/a	Mo Kα radiation
a = 12.6949 (8) Å	µ = 0.08 mm⁻¹
b = 6.6596 (4) Å	T = 293 K
c = 12.8529 (9) Å	0.18 × 0.15 × 0.13 mm
β = 98.672 (11)°

Data collection top

Nonius MACH-3 diffractometer	1424 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.051
T_min = 0.985, T_max = 0.989	3 standard reflections every 60 min
4088 measured reflections	intensity decay: none
1873 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.05	Δρ_max = 0.16 e Å⁻³
1873 reflections	Δρ_min = −0.14 e Å⁻³
131 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 > 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.

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

	x	y	z	U_iso*/U_eq
O1	0.40072 (9)	0.08183 (18)	0.88044 (9)	0.0572 (4)
O2	0.54776 (10)	0.0855 (2)	0.80386 (11)	0.0707 (4)
C1	0.34843 (11)	−0.5441 (3)	0.66547 (12)	0.0469 (4)
C4	0.42325 (12)	−0.1813 (3)	0.76552 (12)	0.0461 (4)
N1	0.31326 (11)	−0.7203 (3)	0.61807 (13)	0.0627 (5)
C7	0.46496 (12)	0.0065 (3)	0.81690 (12)	0.0497 (4)
C3	0.32462 (12)	−0.2619 (3)	0.77847 (12)	0.0479 (4)
H3	0.2828	−0.1950	0.8208	0.057*
C6	0.44776 (12)	−0.4608 (3)	0.65238 (13)	0.0528 (5)
H6	0.4900	−0.5262	0.6098	0.063*
C2	0.28788 (12)	−0.4375 (3)	0.73023 (13)	0.0491 (4)
H2	0.2217	−0.4869	0.7405	0.059*
C5	0.48322 (12)	−0.2852 (3)	0.70133 (13)	0.0531 (5)
H5	0.5492	−0.2343	0.6913	0.064*
C8	0.43523 (14)	0.2641 (3)	0.93720 (13)	0.0574 (5)
H8A	0.4448	0.3713	0.8884	0.069*
H8B	0.5023	0.2419	0.9829	0.069*
C1A	0.37347 (16)	−0.8242 (3)	0.54815 (15)	0.0685 (5)
H1A1	0.3762	−0.7437	0.4867	0.103*
H1A2	0.3397	−0.9501	0.5277	0.103*
H1A3	0.4445	−0.8481	0.5835	0.103*
C2A	0.21248 (14)	−0.8068 (3)	0.63395 (17)	0.0690 (6)
H2A1	0.2090	−0.8138	0.7080	0.103*
H2A2	0.2062	−0.9395	0.6044	0.103*
H2A3	0.1553	−0.7247	0.6000	0.103*
C9	0.34993 (18)	0.3176 (3)	1.00051 (16)	0.0767 (6)
H9A	0.2835	0.3340	0.9545	0.115*
H9B	0.3683	0.4409	1.0376	0.115*
H9C	0.3431	0.2125	1.0502	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0615 (7)	0.0553 (8)	0.0586 (7)	−0.0047 (6)	0.0215 (6)	−0.0083 (6)
O2	0.0583 (7)	0.0663 (9)	0.0929 (10)	−0.0141 (7)	0.0289 (7)	−0.0111 (7)
C1	0.0436 (8)	0.0519 (10)	0.0451 (8)	0.0024 (7)	0.0062 (6)	0.0041 (7)
C4	0.0448 (8)	0.0495 (10)	0.0459 (8)	0.0027 (7)	0.0129 (7)	0.0052 (7)
N1	0.0543 (8)	0.0650 (11)	0.0710 (10)	−0.0081 (7)	0.0163 (7)	−0.0160 (8)
C7	0.0481 (8)	0.0529 (10)	0.0500 (9)	0.0034 (8)	0.0132 (7)	0.0061 (8)
C3	0.0465 (8)	0.0507 (10)	0.0500 (9)	0.0056 (7)	0.0186 (7)	0.0041 (7)
C6	0.0470 (8)	0.0591 (11)	0.0560 (10)	0.0024 (8)	0.0200 (7)	−0.0052 (8)
C2	0.0399 (8)	0.0560 (11)	0.0535 (9)	0.0010 (7)	0.0139 (7)	0.0055 (8)
C5	0.0431 (8)	0.0622 (12)	0.0578 (10)	−0.0045 (8)	0.0198 (7)	−0.0025 (8)
C8	0.0711 (11)	0.0483 (10)	0.0526 (10)	−0.0032 (9)	0.0089 (8)	−0.0005 (8)
C1A	0.0794 (13)	0.0657 (13)	0.0612 (11)	0.0003 (11)	0.0133 (9)	−0.0123 (10)
C2A	0.0613 (11)	0.0597 (12)	0.0851 (13)	−0.0125 (10)	0.0083 (9)	−0.0028 (10)
C9	0.0951 (15)	0.0653 (13)	0.0750 (13)	0.0003 (12)	0.0296 (11)	−0.0139 (11)

Geometric parameters (Å, º) top

O1—C7	1.3361 (19)	C2—H2	0.9300
O1—C8	1.449 (2)	C5—H5	0.9300
O2—C7	1.2095 (19)	C8—C9	1.493 (2)
C1—N1	1.365 (2)	C8—H8A	0.9700
C1—C2	1.408 (2)	C8—H8B	0.9700
C1—C6	1.411 (2)	C1A—H1A1	0.9600
C4—C5	1.389 (2)	C1A—H1A2	0.9600
C4—C3	1.395 (2)	C1A—H1A3	0.9600
C4—C7	1.475 (3)	C2A—H2A1	0.9600
N1—C1A	1.442 (2)	C2A—H2A2	0.9600
N1—C2A	1.446 (2)	C2A—H2A3	0.9600
C3—C2	1.372 (2)	C9—H9A	0.9600
C3—H3	0.9300	C9—H9B	0.9600
C6—C5	1.372 (3)	C9—H9C	0.9600
C6—H6	0.9300

C7—O1—C8	117.15 (13)	O1—C8—C9	106.59 (14)
N1—C1—C2	121.76 (14)	O1—C8—H8A	110.4
N1—C1—C6	121.51 (14)	C9—C8—H8A	110.4
C2—C1—C6	116.73 (16)	O1—C8—H8B	110.4
C5—C4—C3	117.49 (16)	C9—C8—H8B	110.4
C5—C4—C7	119.76 (14)	H8A—C8—H8B	108.6
C3—C4—C7	122.75 (14)	N1—C1A—H1A1	109.5
C1—N1—C1A	121.48 (15)	N1—C1A—H1A2	109.5
C1—N1—C2A	121.10 (15)	H1A1—C1A—H1A2	109.5
C1A—N1—C2A	117.40 (16)	N1—C1A—H1A3	109.5
O2—C7—O1	123.00 (17)	H1A1—C1A—H1A3	109.5
O2—C7—C4	124.59 (15)	H1A2—C1A—H1A3	109.5
O1—C7—C4	112.41 (13)	N1—C2A—H2A1	109.5
C2—C3—C4	121.61 (15)	N1—C2A—H2A2	109.5
C2—C3—H3	119.2	H2A1—C2A—H2A2	109.5
C4—C3—H3	119.2	N1—C2A—H2A3	109.5
C5—C6—C1	121.20 (14)	H2A1—C2A—H2A3	109.5
C5—C6—H6	119.4	H2A2—C2A—H2A3	109.5
C1—C6—H6	119.4	C8—C9—H9A	109.5
C3—C2—C1	121.24 (15)	C8—C9—H9B	109.5
C3—C2—H2	119.4	H9A—C9—H9B	109.5
C1—C2—H2	119.4	C8—C9—H9C	109.5
C6—C5—C4	121.73 (15)	H9A—C9—H9C	109.5
C6—C5—H5	119.1	H9B—C9—H9C	109.5
C4—C5—H5	119.1

C2—C1—N1—C1A	177.23 (16)	C7—C4—C3—C2	−179.64 (15)
C6—C1—N1—C1A	−3.2 (3)	N1—C1—C6—C5	−179.15 (16)
C2—C1—N1—C2A	−1.0 (3)	C2—C1—C6—C5	0.5 (2)
C6—C1—N1—C2A	178.53 (16)	C4—C3—C2—C1	0.1 (2)
C8—O1—C7—O2	−1.5 (2)	N1—C1—C2—C3	179.19 (15)
C8—O1—C7—C4	178.51 (13)	C6—C1—C2—C3	−0.4 (2)
C5—C4—C7—O2	3.6 (3)	C1—C6—C5—C4	−0.2 (3)
C3—C4—C7—O2	−176.55 (16)	C3—C4—C5—C6	−0.2 (2)
C5—C4—C7—O1	−176.49 (14)	C7—C4—C5—C6	179.69 (15)
C3—C4—C7—O1	3.4 (2)	C7—O1—C8—C9	179.26 (15)
C5—C4—C3—C2	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.55	3.4682 (19)	168

Symmetry code: (i) x−1/2, −y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅NO₂
M_r	193.24
Crystal system, space group	Monoclinic, P2₁/a
Temperature (K)	293
a, b, c (Å)	12.6949 (8), 6.6596 (4), 12.8529 (9)
β (°)	98.672 (11)
V (Å³)	1074.20 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.18 × 0.15 × 0.13

Data collection
Diffractometer	Nonius MACH-3
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.985, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	4088, 1873, 1424
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.134, 1.05
No. of reflections	1873
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.14

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.55	3.4682 (19)	168

Symmetry code: (i) x−1/2, −y−1/2, z.

Acknowledgements

The authors thank the DST for the FIST programme.

References

Amiraslanov, I. R., Mamedov, Kh. S., Movsumov, E. M., Musaev, F. N. & Nadzhafov, G. N. (1979). Zh. Strukt. Khim. 20, 1075–1080. CAS Google Scholar
Chen, H. J. & Chen, X. M. (2002). Inorg. Chim. Acta, 329, 13–21. Web of Science CSD CrossRef CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany. Google Scholar
Hauptmann, R., Kondo, M. & Kitagawa, S. (2000). Z. Kristallogr. New Cryst. Struct. 215, 169–172. CAS Google Scholar
Jia, W.-T. & Jin, S.-H. (2004). US Patent No. 6787584. Google Scholar
Luo, M., Jedrzejas, M. J., Singh, S., White, C. L., Brouillette, W. J., Air, G. M. & Laver, W. G. (1995). Acta Cryst. D51, 504–510. CrossRef CAS Web of Science IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar