Dimethyl­ammonium 2-[(2-oxo-2H-chromen-7-yl)­oxy]acetate

Dong, F.-X.

doi:10.1107/S1600536811012761

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1105

doi:10.1107/S1600536811012761

Open

access

Dimethylammonium 2-[(2-oxo-2H-chromen-7-yl)oxy]acetate

Feng-Xia Dong ^a ^*

^aState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China
^*Correspondence e-mail: dongfx@jlu.edu.cn

(Received 1 April 2011; accepted 6 April 2011; online 13 April 2011)

In the title salt, C₂H₈N⁺·C₁₁H₇O₅⁻, the acetate group is twisted out of the plane of the coumarin ring system with a C—O—C—C torsion angle of 76.3 (2)°. In the crystal, N—H⋯O hydrogen bonds link the cations and anions into chains propagating in [100].

Related literature

For the synthesis, see Matsuda et al. (2000 ).

Experimental

Crystal data

C₂H₈N⁺·C₁₁H₇O₅⁻
M_r = 265.26
Triclinic, $[P \overline 1]$
a = 6.714 (5) Å
b = 8.146 (7) Å
c = 12.767 (12) Å
α = 83.33 (4)°
β = 79.16 (3)°
γ = 67.78 (3)°
V = 634.1 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.44 × 0.22 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.955, T_max = 0.986
6310 measured reflections
2881 independent reflections
1878 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.131
S = 0.93
2881 reflections
182 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4	0.90 (1)	1.92 (1)	2.799 (2)	166 (2)
N1—H1B⋯O5ⁱ	0.90 (1)	1.86 (1)	2.729 (3)	160 (2)
Symmetry code: (i) x-1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012761/ng5144sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012761/ng5144Isup2.hkl

checkCIF report

Comment top

Coumarin derivatives have been widely studied due to the applications in medicine and optical materials. In this paper, we report the synthesis and crystal structure of the title compound, which is a type of carboxyl modified coumarin derivative.

In the title compound, the acetate group twist outside the plane of coumarin group with a C7—O3—C10—C11 torsion angle of 76.3 (2). The hydrogen atom of carboxyl transfer to the dimethylamine molecule forming N—H···O hydrogen bonding interaction (Figure 1).

In the crystal structure of the title compound, the N—H···O hydrogen bonds bewteen coumarin anions and dimethylammonium cations link them to form a chain structure (Figure 2, Table 1).

Related literature top

For the synthesis, see Matsuda et al. (2000).

Experimental top

A mixture of 7-hydroxycoumarin (0.16 g, 1.0 mmol), potassium carbonate (0.20 g, 1.4 mmol), ethyl bromoacetate (0.20 g, 1.2 mmol), and dry acetone (30 ml) was refluxed for 4 h while stirring in a N₂ atmosphere. After removal of salt by filtration, the resulting ester was recrystallized from ethanol. After then, the carboxylic acid derivatives was obtained through refluxing in sodium hydroxide solution and protonized with HCl. Mix the obtained carboxylic acid derivatives with dimethylamine with molar ratio of 1:1 in methanol, needle-like crystals of title compound were obtained after several days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms. Dashed lines indicate the hydrogen-bonding interactions.
	Fig. 2. A partial packing view, showing the hydrogen-bonding chain structure. Dashed lines indicate the hydrogen bonds, no involving H atoms have been omitted for clarity.

Dimethylammonium 2-[(2-oxo-2H-chromen-7-yl)oxy]acetate top

Crystal data top

C₂H₈N⁺·C₁₁H₇O₅⁻	Z = 2
M_r = 265.26	F(000) = 280
Triclinic, P1	D_x = 1.389 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.714 (5) Å	Cell parameters from 4269 reflections
b = 8.146 (7) Å	θ = 3.1–27.5°
c = 12.767 (12) Å	µ = 0.11 mm⁻¹
α = 83.33 (4)°	T = 293 K
β = 79.16 (3)°	Block, colorless
γ = 67.78 (3)°	0.44 × 0.22 × 0.14 mm
V = 634.1 (9) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2881 independent reflections
Radiation source: fine-focus sealed tube	1878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.955, T_max = 0.986	k = −10→10
6310 measured reflections	l = −16→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0824P)² + 0.0078P] where P = (F_o² + 2F_c²)/3
2881 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.17 e Å⁻³
2 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂H₈N⁺·C₁₁H₇O₅⁻	γ = 67.78 (3)°
M_r = 265.26	V = 634.1 (9) Å³
Triclinic, P1	Z = 2
a = 6.714 (5) Å	Mo Kα radiation
b = 8.146 (7) Å	µ = 0.11 mm⁻¹
c = 12.767 (12) Å	T = 293 K
α = 83.33 (4)°	0.44 × 0.22 × 0.14 mm
β = 79.16 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2881 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1878 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.986	R_int = 0.026
6310 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	2 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.17 e Å⁻³
2881 reflections	Δρ_min = −0.16 e Å⁻³
182 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
N1	0.1702 (2)	0.71671 (17)	0.56112 (12)	0.0410 (3)
C1	0.4408 (3)	0.6603 (2)	1.12637 (14)	0.0474 (4)
C2	0.2575 (3)	0.6054 (3)	1.16133 (14)	0.0509 (4)
H2	0.2490	0.5412	1.2261	0.061*
C3	0.0990 (3)	0.6456 (2)	1.10186 (14)	0.0492 (4)
H3	−0.0200	0.6120	1.1270	0.059*
C4	0.1103 (2)	0.7390 (2)	1.00064 (12)	0.0390 (4)
C5	−0.0479 (2)	0.7886 (2)	0.93318 (14)	0.0469 (4)
H5	−0.1734	0.7628	0.9553	0.056*
C6	−0.0222 (2)	0.8737 (2)	0.83609 (13)	0.0441 (4)
H6	−0.1294	0.9053	0.7929	0.053*
C7	0.1668 (2)	0.9134 (2)	0.80145 (12)	0.0352 (3)
C8	0.3255 (2)	0.8682 (2)	0.86578 (12)	0.0377 (4)
H8	0.4510	0.8942	0.8435	0.045*
C9	0.2930 (2)	0.7836 (2)	0.96401 (12)	0.0366 (4)
C10	0.3639 (2)	1.0429 (2)	0.66355 (12)	0.0366 (4)
H10A	0.3951	1.0951	0.7201	0.044*
H10B	0.3299	1.1324	0.6057	0.044*
C11	0.5675 (2)	0.8869 (2)	0.62315 (12)	0.0340 (3)
C12	0.1952 (3)	0.7031 (3)	0.44443 (15)	0.0557 (5)
H12A	0.0662	0.6949	0.4271	0.084*
H12B	0.3187	0.5991	0.4223	0.084*
H12C	0.2168	0.8065	0.4081	0.084*
C13	0.1659 (3)	0.5537 (3)	0.62202 (18)	0.0646 (5)
H13A	0.2810	0.4530	0.5894	0.097*
H13B	0.0281	0.5430	0.6225	0.097*
H13C	0.1856	0.5584	0.6940	0.097*
O1	0.5856 (2)	0.6407 (2)	1.17600 (11)	0.0675 (4)
O2	0.45322 (16)	0.74415 (16)	1.02652 (9)	0.0459 (3)
O3	0.17667 (14)	0.99754 (15)	0.70317 (8)	0.0410 (3)
O4	0.54894 (16)	0.75011 (15)	0.60073 (10)	0.0472 (3)
O5	0.73879 (16)	0.91839 (17)	0.61151 (11)	0.0571 (4)
H1B	0.040 (2)	0.802 (2)	0.5816 (16)	0.067 (6)*
H1A	0.279 (2)	0.747 (3)	0.5738 (16)	0.068 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0340 (6)	0.0366 (7)	0.0567 (9)	−0.0137 (5)	−0.0116 (6)	−0.0086 (6)
C1	0.0462 (9)	0.0598 (11)	0.0368 (9)	−0.0195 (8)	−0.0072 (7)	−0.0023 (8)
C2	0.0554 (10)	0.0640 (11)	0.0366 (9)	−0.0294 (9)	−0.0012 (8)	0.0013 (8)
C3	0.0459 (9)	0.0642 (11)	0.0437 (10)	−0.0311 (8)	0.0046 (7)	−0.0071 (9)
C4	0.0322 (7)	0.0512 (9)	0.0375 (9)	−0.0207 (6)	0.0018 (6)	−0.0102 (7)
C5	0.0318 (7)	0.0694 (11)	0.0474 (10)	−0.0274 (7)	−0.0002 (7)	−0.0124 (9)
C6	0.0289 (7)	0.0650 (11)	0.0413 (9)	−0.0179 (7)	−0.0062 (6)	−0.0105 (8)
C7	0.0275 (7)	0.0447 (8)	0.0315 (8)	−0.0107 (6)	−0.0008 (6)	−0.0087 (7)
C8	0.0267 (7)	0.0534 (9)	0.0358 (8)	−0.0189 (6)	−0.0009 (6)	−0.0046 (7)
C9	0.0280 (7)	0.0492 (9)	0.0345 (8)	−0.0152 (6)	−0.0035 (6)	−0.0080 (7)
C10	0.0345 (7)	0.0388 (8)	0.0361 (8)	−0.0131 (6)	−0.0043 (6)	−0.0026 (7)
C11	0.0302 (7)	0.0415 (8)	0.0315 (8)	−0.0125 (6)	−0.0090 (6)	−0.0007 (6)
C12	0.0580 (10)	0.0542 (10)	0.0547 (11)	−0.0179 (8)	−0.0144 (9)	−0.0018 (9)
C13	0.0706 (12)	0.0565 (11)	0.0663 (13)	−0.0243 (10)	−0.0181 (10)	0.0147 (10)
O1	0.0595 (8)	0.1038 (11)	0.0491 (8)	−0.0383 (8)	−0.0243 (6)	0.0135 (8)
O2	0.0351 (5)	0.0709 (8)	0.0374 (6)	−0.0263 (5)	−0.0095 (5)	0.0047 (6)
O3	0.0282 (5)	0.0550 (7)	0.0365 (6)	−0.0115 (4)	−0.0052 (4)	−0.0019 (5)
O4	0.0392 (6)	0.0417 (6)	0.0615 (8)	−0.0118 (5)	−0.0088 (5)	−0.0145 (6)
O5	0.0301 (5)	0.0638 (8)	0.0809 (10)	−0.0189 (5)	−0.0076 (6)	−0.0134 (7)

Geometric parameters (Å, º) top

N1—C13	1.466 (3)	C7—O3	1.361 (2)
N1—C12	1.480 (3)	C7—C8	1.381 (2)
N1—H1B	0.904 (9)	C8—C9	1.381 (2)
N1—H1A	0.899 (9)	C8—H8	0.9300
C1—O1	1.209 (2)	C9—O2	1.378 (2)
C1—O2	1.378 (2)	C10—O3	1.4287 (19)
C1—C2	1.441 (3)	C10—C11	1.524 (2)
C2—C3	1.341 (3)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.426 (3)	C11—O4	1.238 (2)
C3—H3	0.9300	C11—O5	1.2490 (19)
C4—C9	1.392 (2)	C12—H12A	0.9600
C4—C5	1.404 (2)	C12—H12B	0.9600
C5—C6	1.362 (3)	C12—H12C	0.9600
C5—H5	0.9300	C13—H13A	0.9600
C6—C7	1.406 (2)	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600

C13—N1—C12	112.95 (16)	C9—C8—H8	120.9
C13—N1—H1B	106.2 (13)	C7—C8—H8	120.9
C12—N1—H1B	107.5 (14)	O2—C9—C8	116.35 (13)
C13—N1—H1A	111.7 (14)	O2—C9—C4	120.33 (15)
C12—N1—H1A	107.7 (13)	C8—C9—C4	123.32 (14)
H1B—N1—H1A	110.8 (19)	O3—C10—C11	114.33 (13)
O1—C1—O2	116.32 (16)	O3—C10—H10A	108.7
O1—C1—C2	126.56 (18)	C11—C10—H10A	108.7
O2—C1—C2	117.12 (15)	O3—C10—H10B	108.7
C3—C2—C1	120.98 (18)	C11—C10—H10B	108.7
C3—C2—H2	119.5	H10A—C10—H10B	107.6
C1—C2—H2	119.5	O4—C11—O5	127.04 (13)
C2—C3—C4	120.98 (15)	O4—C11—C10	119.35 (13)
C2—C3—H3	119.5	O5—C11—C10	113.50 (14)
C4—C3—H3	119.5	N1—C12—H12A	109.5
C9—C4—C5	116.59 (16)	N1—C12—H12B	109.5
C9—C4—C3	118.16 (15)	H12A—C12—H12B	109.5
C5—C4—C3	125.24 (14)	N1—C12—H12C	109.5
C6—C5—C4	121.69 (14)	H12A—C12—H12C	109.5
C6—C5—H5	119.2	H12B—C12—H12C	109.5
C4—C5—H5	119.2	N1—C13—H13A	109.5
C5—C6—C7	119.80 (14)	N1—C13—H13B	109.5
C5—C6—H6	120.1	H13A—C13—H13B	109.5
C7—C6—H6	120.1	N1—C13—H13C	109.5
O3—C7—C8	124.62 (13)	H13A—C13—H13C	109.5
O3—C7—C6	115.05 (13)	H13B—C13—H13C	109.5
C8—C7—C6	120.33 (15)	C9—O2—C1	122.27 (13)
C9—C8—C7	118.24 (13)	C7—O3—C10	117.87 (11)

C7—O3—C10—C11	76.32 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.90 (1)	1.92 (1)	2.799 (2)	166 (2)
N1—H1B···O5ⁱ	0.90 (1)	1.86 (1)	2.729 (3)	160 (2)

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂H₈N⁺·C₁₁H₇O₅⁻
M_r	265.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.714 (5), 8.146 (7), 12.767 (12)
α, β, γ (°)	83.33 (4), 79.16 (3), 67.78 (3)
V (Å³)	634.1 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.44 × 0.22 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.955, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	6310, 2881, 1878
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.131, 0.93
No. of reflections	2881
No. of parameters	182
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.899 (9)	1.917 (11)	2.799 (2)	166.2 (19)
N1—H1B···O5ⁱ	0.904 (9)	1.862 (12)	2.729 (3)	160.1 (19)

Symmetry code: (i) x−1, y, z.

Acknowledgements

The author thanks Jilin University for supporting this study.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Matsuda, T., Mizutani, M. & Arnold, S. C. (2000). Macromolecules, 33, 795–800. CrossRef CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar