4-Eth­oxy­carbonyl-N,N,N-trimethyl­anilinium iodide

Tang, X.-Y.

doi:10.1107/S1600536811049361

organic compounds

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Volume 67| Part 12| December 2011| Page o3454

https://doi.org/10.1107/S1600536811049361

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4-Ethoxycarbonyl-N,N,N-trimethylanilinium iodide

Xiao-Yan Tang ^a ^*

^aCollege of Chemistry & Materials Engineering, Jiangsu Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu, 215500 Jiangsu, People's Republic of China
^*Correspondence e-mail: chemxytang@hotmail.com

(Received 3 November 2011; accepted 18 November 2011; online 30 November 2011)

In the title molecular salt, C₁₂H₁₈NO₂⁺·I⁻, the C atoms of the ethyl group are disordered over two sets of sites [occupancies of 0.76 (4) and 0.24 (4)]. In the crystal, ion pairs linked by weak C—H⋯I interactions occur.

Related literature

The title compound is a key intermediate in the preparation of carboxylates. A wide variety of model metal carboxylic compounds has been prepared with the aim of mimicing the structures and functions of the active sites of metal metalloenzymes, see: Liu et al. (2004 ).

Experimental

Crystal data

C₁₂H₁₈NO₂⁺·I⁻
M_r = 335.17
Triclinic, $[P \overline 1]$
a = 7.4790 (15) Å
b = 10.008 (2) Å
c = 10.158 (2) Å
α = 71.16 (3)°
β = 83.30 (3)°
γ = 84.62 (3)°
V = 713.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.23 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.594, T_max = 0.644
7462 measured reflections
3258 independent reflections
2708 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.082
S = 1.14
3258 reflections
169 parameters
38 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯I1ⁱ	0.93	3.02	3.932 (4)	166
Symmetry code: (i) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008) and ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXTL/PC and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811049361/bx2381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049361/bx2381Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811049361/bx2381Isup3.cml

checkCIF report

Comment top

Recently, the chemistry of metal complexes of carboxylates has been receiving an increasing attention. To date, a wide variety of model metal carboxylic compounds has been prepared with the aim to mimic the structures and functions of the active sites of metal metalloenzymes [Liu et al., 2004]. The title compound (I), is a key intermediate in the preparation of carboxylates, which we are designing for the synthesis of metal complexes. The structure of the title compound, [C₁₂H₁₈NO₂]⁺.I^-, comprises discrete ions which are interconected by weak C—H···I hydrogen bonds. These hydrogen bonds appear to complement the Coulombic interaction and help to stabilize the structure further.The molecular structure is stabilize by one intramolecular C—H···O hydrogen bond. The C atoms of ethyl group are disorder over two occupied positions [0.76 (4)/0.24 (4)].

Related literature top

For a metal compound with a similar structure, see: Liu et al. (2004).

For related literature, see: Johnson (1976).

Experimental top

The title compound was synthesized by reaction of 4-Dimethylamino-benzoic acid ethyl ester (0.966 g, 5 mmol) and Iodomethane (0.710 g, 5 mmol) in acetone (40 ml). The solution was vigorously stirring for 24 h to afford white precipitates. The precipitates were collected by filtration, re-dissolved in MeOH (10 ml) then allowed to stand for several days to produce white crystals (I). Yield: 1.44 g (86%). The crystal used for the crystal structure determination was obtained directly from the above preparation. Analysis, found: C, 43.32; H, 5.31; N, 4.12%. calculated. for C₁₂H₁₈INO₂: C, 43.00; H, 5.41; N, 4.18%.

Structure description top

For a metal compound with a similar structure, see: Liu et al. (2004).

For related literature, see: Johnson (1976).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008) and ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. ORTEP-II (Johnson, 1976) plot of complex (I) at the 30% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii. The C11 and C12 atoms of ethyl group are disorder over two sites.

4-Ethoxycarbonyl-N,N,N-trimethylanilinium iodide top

Crystal data top

C₁₂H₁₈NO₂⁺·I⁻	Z = 2
M_r = 335.17	F(000) = 332
Triclinic, P1	D_x = 1.560 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4790 (15) Å	Cell parameters from 7462 reflections
b = 10.008 (2) Å	θ = 3.7–27.5°
c = 10.158 (2) Å	µ = 2.23 mm⁻¹
α = 71.16 (3)°	T = 293 K
β = 83.30 (3)°	Block, colourless
γ = 84.62 (3)°	0.3 × 0.2 × 0.2 mm
V = 713.4 (2) Å³

Data collection top

Rigaku SCXmini diffractometer	3258 independent reflections
Radiation source: fine-focus sealed tube	2708 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −9→9
T_min = 0.594, T_max = 0.644	k = −12→12
7462 measured reflections	l = −12→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.025P)² + 0.3117P] where P = (F_o² + 2F_c²)/3
3258 reflections	(Δ/σ)_max = 0.006
169 parameters	Δρ_max = 0.32 e Å⁻³
38 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₂H₁₈NO₂⁺·I⁻	γ = 84.62 (3)°
M_r = 335.17	V = 713.4 (2) Å³
Triclinic, P1	Z = 2
a = 7.4790 (15) Å	Mo Kα radiation
b = 10.008 (2) Å	µ = 2.23 mm⁻¹
c = 10.158 (2) Å	T = 293 K
α = 71.16 (3)°	0.3 × 0.2 × 0.2 mm
β = 83.30 (3)°

Data collection top

Rigaku SCXmini diffractometer	3258 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2708 reflections with I > 2σ(I)
T_min = 0.594, T_max = 0.644	R_int = 0.032
7462 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	38 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.14	Δρ_max = 0.32 e Å⁻³
3258 reflections	Δρ_min = −0.37 e Å⁻³
169 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.

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	Occ. (<1)
I1	0.20239 (3)	0.72149 (3)	0.14771 (3)	0.06381 (12)
N1	1.2692 (4)	0.2438 (3)	0.1056 (3)	0.0486 (7)
O1	0.5587 (4)	0.3017 (4)	0.5043 (3)	0.0916 (11)
O2	0.6021 (5)	0.0665 (4)	0.5856 (4)	0.1038 (12)
C7	1.3112 (6)	0.1205 (5)	0.0509 (5)	0.0749 (13)
H7A	1.3263	0.0352	0.1276	0.112*
H7B	1.4203	0.1350	−0.0106	0.112*
H7C	1.2137	0.1126	0.0007	0.112*
C9	1.2508 (6)	0.3751 (4)	−0.0189 (4)	0.0627 (10)
H9A	1.1514	0.3682	−0.0678	0.094*
H9B	1.3598	0.3842	−0.0804	0.094*
H9C	1.2294	0.4566	0.0123	0.094*
C8	1.4246 (5)	0.2575 (5)	0.1829 (5)	0.0694 (12)
H8A	1.4024	0.3406	0.2114	0.104*
H8B	1.5344	0.2649	0.1225	0.104*
H8C	1.4352	0.1756	0.2638	0.104*
C4	1.1010 (4)	0.2256 (4)	0.2045 (4)	0.0462 (8)
C3	1.0206 (6)	0.0988 (4)	0.2559 (5)	0.0686 (12)
H3	1.0645	0.0225	0.2258	0.082*
C5	1.0316 (5)	0.3386 (4)	0.2463 (5)	0.0661 (12)
H5	1.0852	0.4248	0.2101	0.079*
C2	0.8712 (6)	0.0872 (5)	0.3544 (5)	0.0755 (13)
H2	0.8174	0.0012	0.3912	0.091*
C6	0.8824 (6)	0.3245 (5)	0.3419 (5)	0.0719 (12)
H6	0.8352	0.4019	0.3690	0.086*
C1	0.8022 (5)	0.1976 (5)	0.3980 (4)	0.0578 (10)
C10	0.6433 (6)	0.1801 (6)	0.5068 (4)	0.0692 (12)
C11	0.4077 (14)	0.311 (2)	0.6100 (10)	0.079 (4)	0.76 (4)
H11B	0.4195	0.3899	0.6433	0.095*	0.76 (4)
H11A	0.4065	0.2247	0.6891	0.095*	0.76 (4)
C12	0.2393 (16)	0.3312 (14)	0.5389 (12)	0.083 (3)	0.76 (4)
H12A	0.2379	0.4206	0.4660	0.125*	0.76 (4)
H12B	0.1366	0.3295	0.6055	0.125*	0.76 (4)
H12C	0.2349	0.2565	0.4994	0.125*	0.76 (4)
C11A	0.397 (4)	0.233 (6)	0.602 (4)	0.093 (11)	0.24 (4)
H11C	0.3381	0.1699	0.5672	0.111*	0.24 (4)
H11D	0.4249	0.1857	0.6974	0.111*	0.24 (4)
C12A	0.301 (7)	0.370 (6)	0.581 (6)	0.126 (17)	0.24 (4)
H12D	0.3747	0.4323	0.6029	0.188*	0.24 (4)
H12E	0.1907	0.3594	0.6419	0.188*	0.24 (4)
H12F	0.2732	0.4094	0.4860	0.188*	0.24 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.05640 (17)	0.05706 (18)	0.0804 (2)	−0.01560 (12)	0.00974 (13)	−0.02719 (14)
N1	0.0453 (16)	0.0458 (17)	0.0531 (18)	−0.0050 (13)	0.0003 (14)	−0.0144 (14)
O1	0.0593 (18)	0.123 (3)	0.067 (2)	0.0124 (19)	0.0189 (16)	−0.0077 (19)
O2	0.101 (3)	0.109 (3)	0.083 (2)	−0.041 (2)	0.025 (2)	−0.007 (2)
C7	0.076 (3)	0.058 (3)	0.094 (3)	−0.010 (2)	0.024 (3)	−0.038 (2)
C9	0.069 (3)	0.054 (2)	0.056 (2)	−0.0056 (19)	0.005 (2)	−0.0074 (18)
C8	0.044 (2)	0.101 (3)	0.063 (3)	−0.017 (2)	−0.0006 (19)	−0.023 (2)
C4	0.0404 (18)	0.044 (2)	0.052 (2)	−0.0057 (15)	0.0008 (16)	−0.0140 (16)
C3	0.078 (3)	0.055 (3)	0.076 (3)	−0.021 (2)	0.011 (2)	−0.027 (2)
C5	0.053 (2)	0.050 (2)	0.084 (3)	−0.0090 (18)	0.018 (2)	−0.013 (2)
C2	0.076 (3)	0.070 (3)	0.075 (3)	−0.037 (2)	0.020 (2)	−0.017 (2)
C6	0.055 (2)	0.061 (3)	0.089 (3)	−0.003 (2)	0.019 (2)	−0.019 (2)
C1	0.048 (2)	0.066 (3)	0.055 (2)	−0.0092 (18)	−0.0023 (18)	−0.014 (2)
C10	0.057 (2)	0.101 (4)	0.045 (2)	−0.025 (3)	−0.002 (2)	−0.012 (2)
C11	0.055 (5)	0.118 (11)	0.058 (4)	−0.005 (5)	0.018 (4)	−0.026 (5)
C12	0.062 (6)	0.105 (7)	0.078 (6)	−0.004 (4)	0.015 (4)	−0.031 (4)
C11A	0.078 (17)	0.12 (3)	0.087 (17)	−0.043 (18)	0.029 (13)	−0.046 (18)
C12A	0.08 (3)	0.19 (4)	0.12 (3)	−0.02 (2)	0.06 (3)	−0.08 (3)

Geometric parameters (Å, º) top

N1—C4	1.501 (5)	C3—H3	0.9300
N1—C7	1.503 (5)	C5—C6	1.377 (5)
N1—C9	1.510 (5)	C5—H5	0.9300
N1—C8	1.516 (5)	C2—C1	1.356 (6)
O1—C10	1.312 (6)	C2—H2	0.9300
O1—C11	1.483 (9)	C6—C1	1.376 (6)
O1—C11A	1.54 (3)	C6—H6	0.9300
O2—C10	1.204 (5)	C1—C10	1.507 (6)
C7—H7A	0.9600	C11—C12	1.49 (2)
C7—H7B	0.9600	C11—H11B	0.9700
C7—H7C	0.9600	C11—H11A	0.9700
C9—H9A	0.9600	C12—H12A	0.9600
C9—H9B	0.9600	C12—H12B	0.9600
C9—H9C	0.9600	C12—H12C	0.9600
C8—H8A	0.9600	C11A—C12A	1.46 (8)
C8—H8B	0.9600	C11A—H11C	0.9700
C8—H8C	0.9600	C11A—H11D	0.9700
C4—C5	1.370 (5)	C12A—H12D	0.9600
C4—C3	1.374 (5)	C12A—H12E	0.9600
C3—C2	1.397 (6)	C12A—H12F	0.9600

C4—N1—C7	111.8 (3)	C6—C5—C4	119.9 (4)
C4—N1—C9	111.2 (3)	C6—C5—H5	120.0
C7—N1—C9	107.3 (3)	C4—C5—H5	120.0
C4—N1—C8	108.3 (3)	C1—C2—C3	122.0 (4)
C7—N1—C8	109.4 (3)	C1—C2—H2	119.0
C9—N1—C8	108.8 (3)	C3—C2—H2	119.0
C10—O1—C11	121.3 (8)	C5—C6—C1	121.1 (4)
C10—O1—C11A	94 (2)	C5—C6—H6	119.5
C11—O1—C11A	31.7 (16)	C1—C6—H6	119.5
N1—C7—H7A	109.5	C2—C1—C6	118.3 (4)
N1—C7—H7B	109.5	C2—C1—C10	120.5 (4)
H7A—C7—H7B	109.5	C6—C1—C10	121.2 (4)
N1—C7—H7C	109.5	O2—C10—O1	125.2 (5)
H7A—C7—H7C	109.5	O2—C10—C1	122.7 (5)
H7B—C7—H7C	109.5	O1—C10—C1	112.1 (4)
N1—C9—H9A	109.5	O1—C11—C12	106.3 (9)
N1—C9—H9B	109.5	O1—C11—H11B	110.5
H9A—C9—H9B	109.5	C12—C11—H11B	110.5
N1—C9—H9C	109.5	O1—C11—H11A	110.5
H9A—C9—H9C	109.5	C12—C11—H11A	110.5
H9B—C9—H9C	109.5	H11B—C11—H11A	108.7
N1—C8—H8A	109.5	C12A—C11A—O1	91 (4)
N1—C8—H8B	109.5	C12A—C11A—H11C	113.5
H8A—C8—H8B	109.5	O1—C11A—H11C	113.5
N1—C8—H8C	109.5	C12A—C11A—H11D	113.5
H8A—C8—H8C	109.5	O1—C11A—H11D	113.5
H8B—C8—H8C	109.5	H11C—C11A—H11D	110.8
C5—C4—C3	120.3 (4)	C11A—C12A—H12D	109.5
C5—C4—N1	118.1 (3)	C11A—C12A—H12E	109.5
C3—C4—N1	121.7 (3)	H12D—C12A—H12E	109.5
C4—C3—C2	118.4 (4)	C11A—C12A—H12F	109.5
C4—C3—H3	120.8	H12D—C12A—H12F	109.5
C2—C3—H3	120.8	H12E—C12A—H12F	109.5

C7—N1—C4—C5	−170.5 (4)	C5—C6—C1—C2	−1.5 (7)
C9—N1—C4—C5	−50.5 (5)	C5—C6—C1—C10	177.6 (4)
C8—N1—C4—C5	69.0 (4)	C11—O1—C10—O2	5.2 (10)
C7—N1—C4—C3	11.5 (5)	C11A—O1—C10—O2	−11.3 (17)
C9—N1—C4—C3	131.4 (4)	C11—O1—C10—C1	−174.8 (8)
C8—N1—C4—C3	−109.1 (4)	C11A—O1—C10—C1	168.7 (16)
C5—C4—C3—C2	−2.1 (7)	C2—C1—C10—O2	20.7 (7)
N1—C4—C3—C2	175.9 (4)	C6—C1—C10—O2	−158.4 (5)
C3—C4—C5—C6	1.1 (7)	C2—C1—C10—O1	−159.3 (4)
N1—C4—C5—C6	−177.0 (4)	C6—C1—C10—O1	21.6 (6)
C4—C3—C2—C1	1.3 (7)	C10—O1—C11—C12	−104.2 (13)
C4—C5—C6—C1	0.7 (7)	C11A—O1—C11—C12	−72 (4)
C3—C2—C1—C6	0.5 (7)	C10—O1—C11A—C12A	−174 (4)
C3—C2—C1—C10	−178.7 (4)	C11—O1—C11A—C12A	34 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···I1ⁱ	0.93	3.02	3.932 (4)	166
C11—H11A···O2	0.97	2.46	2.792 (18)	100

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₈NO₂⁺·I⁻
M_r	335.17
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4790 (15), 10.008 (2), 10.158 (2)
α, β, γ (°)	71.16 (3), 83.30 (3), 84.62 (3)
V (Å³)	713.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.23
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.594, 0.644
No. of measured, independent and observed [I > 2σ(I)] reflections	7462, 3258, 2708
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.082, 1.14
No. of reflections	3258
No. of parameters	169
No. of restraints	38
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.37

Computer programs: CrystalClear (Rigaku, 2005), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008) and ORTEPII (Johnson, 1976), SHELXTL/PC (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···I1ⁱ	0.93	3.02	3.932 (4)	166.4
C11—H11A···O2	0.97	2.46	2.792 (18)	99.9

Symmetry code: (i) x+1, y, z.

Acknowledgements

This work was supported by the Natural Science Foundation of the Education Commission of Jiangsu Province of China (No.11KJB150001) and a start-up grant from the Changshu Institute of Technology (No. ky2009069).

References

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Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
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