Crystal structure of diiso­propyl­aminium di­chloro­acetate

Sun, W.; Shan, G.

doi:10.1107/S2056989015007586

organic compounds

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Page o361

https://doi.org/10.1107/S2056989015007586

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Crystal structure of diisopropylaminium dichloroacetate

Wei Sun ^a and Guangzhi Shan ^a ^*

^aInstitute of Medicinal Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Tiantan Xili 1#, Beijing, People's Republic of China
^*Correspondence e-mail: shanguangzhi@imb.pumc.edu.cn

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 30 March 2015; accepted 17 April 2015; online 30 April 2015)

In the title compound, C₆H₁₆N⁺·C₂HCl₂O₂⁻, the cation exhibits non-crystallographic C₂ symmetry. In the crystal, the components are linked by N—H⋯O and C—H⋯O hydrogen bonds into chains propagating along [010].

Keywords: crystal structure; diisopropylamine dichlorocacetate; hydrogen bonding.

CCDC reference: 1060114

1. Related literature

For the background to the biological activity of the title compound, see: Gelernt & Herbert (2009 ); Yamane et al. (2014 ); Liu et al. (2015 ). For a related structure, see: Yu & Qian (2009 ).

2. Experimental

2.1. Crystal data

C₆H₁₆N⁺·C₂HCl₂O₂⁻
M_r = 230.13
Monoclinic, P 2₁ /c
a = 10.0272 (2) Å
b = 9.04914 (17) Å
c = 13.6496 (3) Å
β = 106.433 (2)°
V = 1187.94 (4) Å³
Z = 4
Cu Kα radiation
μ = 4.71 mm⁻¹
T = 120 K
0.36 × 0.28 × 0.24 mm

2.2. Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ) T_min = 0.662, T_max = 1.000
11039 measured reflections
2107 independent reflections
1911 reflections with I > 2σ(I)
R_int = 0.026

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.092
S = 1.03
2107 reflections
122 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.92	1.87	2.788 (2)	177
N1—H1B⋯O2ⁱⁱ	0.92	1.90	2.757 (2)	154
C6—H6⋯O1ⁱⁱⁱ	1.00	2.38	3.258 (2)	146
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: OLEX2 (Dolomanov et al., 2009 ), SHELXTL, PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1060114

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015007586/gk2629sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989015007586/gk2629Isup2.cml

checkCIF report

Comment top

Diisopropylaminium dichlorocacetate (DADA) is the effective constituent of Vitamin B15 (Gelernt et al., 2009). Recently, DADA has been found as a potential PDK4 inhibitor for treatment of severe influenza (Yamane et al., 2014). Moreover the desirable therapeutic effects of colorectal cancer in mat is shown (Liu et al., 2015). No data about the crystal structure of diisopropylaminium dichlorocacetate has been reported so far.

The title molecule is shown in Fig. 1. The asymmetric unit contains one diisopropylaminium cation and one dichloroacetate anion. In the crystal structure, the cations and anions are linked by intermolecular N—H···O and C—H···O hydrogen bonds (Table 1, Fig.2) to form chains propagating along [010].

Related literature top

For the background to the biological activity of the title compound, see: Gelernt & Herbert (2009); Yamane et al. (2014); Liu et al. (2015). For a related structure, see: Yu & Qian (2009).

Experimental top

Single crystals suitable for X-ray analysis were obtained by slow solvent evaporation from a solution of the title compound in a dichloromethane/cyclohexane mixture (1:1 v/v) at room temperature.

Structure description top

For the background to the biological activity of the title compound, see: Gelernt & Herbert (2009); Yamane et al. (2014); Liu et al. (2015). For a related structure, see: Yu & Qian (2009).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); 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: OLEX2 (Dolomanov et al., 2009), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound. The displacement parameters are shown at the 30% probability level.
	Fig. 2. Crystal packing of the title compound, viewed down the b direction. Dashed lines indicate hydrogen bonds.

Bis(propan-2-yl)azanium 2,2-dichloroacetate top

Crystal data top

C₆H₁₆N⁺·C₂HCl₂O₂⁻	F(000) = 488
M_r = 230.13	D_x = 1.287 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.0272 (2) Å	Cell parameters from 5039 reflections
b = 9.04914 (17) Å	θ = 4.6–66.9°
c = 13.6496 (3) Å	µ = 4.71 mm⁻¹
β = 106.433 (2)°	T = 120 K
V = 1187.94 (4) Å³	Block, colourless
Z = 4	0.36 × 0.28 × 0.24 mm

Data collection top

Agilent Xcalibur Atlas Gemini ultra diffractometer	2107 independent reflections
Radiation source: sealed X-ray tube, Enhance Ultra (Cu) X-ray Source	1911 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4674 pixels mm^-1	θ_max = 66.9°, θ_min = 4.6°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −7→10
T_min = 0.662, T_max = 1.000	l = −16→16
11039 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0344P)² + 1.3398P] where P = (F_o² + 2F_c²)/3
2107 reflections	(Δ/σ)_max < 0.001
122 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Crystal data top

C₆H₁₆N⁺·C₂HCl₂O₂⁻	V = 1187.94 (4) Å³
M_r = 230.13	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.0272 (2) Å	µ = 4.71 mm⁻¹
b = 9.04914 (17) Å	T = 120 K
c = 13.6496 (3) Å	0.36 × 0.28 × 0.24 mm
β = 106.433 (2)°

Data collection top

Agilent Xcalibur Atlas Gemini ultra diffractometer	2107 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	1911 reflections with I > 2σ(I)
T_min = 0.662, T_max = 1.000	R_int = 0.026
11039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.03	Δρ_max = 0.81 e Å⁻³
2107 reflections	Δρ_min = −0.85 e Å⁻³
122 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat with a nominal stability of 0.1 K. .

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
Cl1	0.53986 (5)	0.16195 (6)	0.60806 (5)	0.04006 (18)
Cl2	0.62278 (7)	−0.05527 (9)	0.76920 (6)	0.0651 (3)
O1	0.86608 (14)	−0.08510 (15)	0.66082 (12)	0.0292 (3)
O2	0.84614 (15)	0.15792 (15)	0.68081 (12)	0.0308 (3)
N1	0.15036 (16)	−0.05351 (17)	0.75375 (12)	0.0202 (3)
H1A	0.0563	−0.0607	0.7230	0.024*
H1B	0.1801	−0.1441	0.7822	0.024*
C2	0.80092 (19)	0.0312 (2)	0.66498 (14)	0.0216 (4)
C3	0.2208 (2)	−0.0234 (2)	0.67193 (15)	0.0268 (4)
H3	0.3218	−0.0050	0.7050	0.032*
C6	0.1729 (2)	0.0574 (2)	0.83878 (15)	0.0256 (4)
H6	0.1401	0.1563	0.8087	0.031*
C4	0.1577 (2)	0.1123 (3)	0.61147 (17)	0.0331 (5)
H4A	0.0568	0.0998	0.5855	0.050*
H4B	0.1972	0.1253	0.5540	0.050*
H4C	0.1785	0.1995	0.6558	0.050*
C1	0.6441 (2)	0.0036 (2)	0.65013 (17)	0.0291 (5)
H1	0.6122	−0.0772	0.5989	0.035*
C7	0.0847 (3)	0.0110 (3)	0.90727 (17)	0.0362 (5)
H7A	−0.0130	0.0049	0.8669	0.054*
H7B	0.0943	0.0840	0.9619	0.054*
H7C	0.1158	−0.0858	0.9373	0.054*
C5	0.2054 (3)	−0.1610 (3)	0.60590 (18)	0.0421 (6)
H5A	0.2486	−0.2451	0.6483	0.063*
H5B	0.2513	−0.1450	0.5522	0.063*
H5C	0.1065	−0.1815	0.5747	0.063*
C8	0.3249 (2)	0.0689 (3)	0.8971 (2)	0.0436 (6)
H8A	0.3593	−0.0283	0.9247	0.065*
H8B	0.3363	0.1395	0.9533	0.065*
H8C	0.3779	0.1029	0.8511	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0265 (3)	0.0351 (3)	0.0558 (4)	0.0130 (2)	0.0072 (2)	0.0078 (2)
Cl2	0.0341 (3)	0.0849 (5)	0.0860 (5)	0.0143 (3)	0.0328 (3)	0.0510 (4)
O1	0.0201 (7)	0.0203 (7)	0.0470 (9)	0.0020 (6)	0.0090 (6)	−0.0021 (6)
O2	0.0266 (7)	0.0206 (7)	0.0473 (9)	−0.0036 (6)	0.0139 (6)	−0.0056 (6)
N1	0.0162 (7)	0.0192 (8)	0.0250 (8)	0.0001 (6)	0.0055 (6)	0.0007 (6)
C2	0.0188 (9)	0.0231 (10)	0.0229 (9)	0.0003 (8)	0.0056 (7)	0.0012 (7)
C3	0.0173 (9)	0.0376 (12)	0.0271 (10)	−0.0007 (8)	0.0091 (8)	0.0046 (9)
C6	0.0270 (10)	0.0204 (10)	0.0292 (10)	0.0020 (8)	0.0078 (8)	−0.0026 (8)
C4	0.0333 (12)	0.0334 (12)	0.0334 (11)	−0.0038 (9)	0.0106 (9)	0.0076 (9)
C1	0.0187 (10)	0.0231 (10)	0.0434 (12)	0.0032 (8)	0.0053 (9)	0.0030 (9)
C7	0.0416 (13)	0.0394 (13)	0.0313 (11)	0.0023 (10)	0.0161 (10)	−0.0025 (10)
C5	0.0558 (15)	0.0426 (14)	0.0327 (12)	0.0147 (12)	0.0201 (11)	0.0021 (10)
C8	0.0314 (12)	0.0473 (14)	0.0466 (14)	−0.0040 (11)	0.0020 (10)	−0.0203 (12)

Geometric parameters (Å, º) top

Cl1—C1	1.771 (2)	C6—C8	1.511 (3)
Cl2—C1	1.780 (2)	C4—H4A	0.9800
O1—C2	1.248 (2)	C4—H4B	0.9800
O2—C2	1.230 (2)	C4—H4C	0.9800
N1—H1A	0.9200	C1—H1	1.0000
N1—H1B	0.9200	C7—H7A	0.9800
N1—C3	1.505 (2)	C7—H7B	0.9800
N1—C6	1.503 (2)	C7—H7C	0.9800
C2—C1	1.548 (3)	C5—H5A	0.9800
C3—H3	1.0000	C5—H5B	0.9800
C3—C4	1.514 (3)	C5—H5C	0.9800
C3—C5	1.519 (3)	C8—H8A	0.9800
C6—H6	1.0000	C8—H8B	0.9800
C6—C7	1.516 (3)	C8—H8C	0.9800

H1A—N1—H1B	107.3	H4B—C4—H4C	109.5
C3—N1—H1A	108.1	Cl1—C1—Cl2	109.02 (12)
C3—N1—H1B	108.1	Cl1—C1—H1	108.8
C6—N1—H1A	108.1	Cl2—C1—H1	108.8
C6—N1—H1B	108.1	C2—C1—Cl1	113.38 (14)
C6—N1—C3	116.92 (15)	C2—C1—Cl2	107.99 (14)
O1—C2—C1	112.56 (16)	C2—C1—H1	108.8
O2—C2—O1	128.50 (18)	C6—C7—H7A	109.5
O2—C2—C1	118.92 (17)	C6—C7—H7B	109.5
N1—C3—H3	108.9	C6—C7—H7C	109.5
N1—C3—C4	109.89 (16)	H7A—C7—H7B	109.5
N1—C3—C5	107.58 (17)	H7A—C7—H7C	109.5
C4—C3—H3	108.9	H7B—C7—H7C	109.5
C4—C3—C5	112.62 (18)	C3—C5—H5A	109.5
C5—C3—H3	108.9	C3—C5—H5B	109.5
N1—C6—H6	108.7	C3—C5—H5C	109.5
N1—C6—C7	107.75 (16)	H5A—C5—H5B	109.5
N1—C6—C8	111.19 (16)	H5A—C5—H5C	109.5
C7—C6—H6	108.7	H5B—C5—H5C	109.5
C8—C6—H6	108.7	C6—C8—H8A	109.5
C8—C6—C7	111.81 (19)	C6—C8—H8B	109.5
C3—C4—H4A	109.5	C6—C8—H8C	109.5
C3—C4—H4B	109.5	H8A—C8—H8B	109.5
C3—C4—H4C	109.5	H8A—C8—H8C	109.5
H4A—C4—H4B	109.5	H8B—C8—H8C	109.5
H4A—C4—H4C	109.5

O1—C2—C1—Cl1	−157.58 (15)	C3—N1—C6—C7	175.93 (16)
O1—C2—C1—Cl2	81.51 (19)	C3—N1—C6—C8	−61.2 (2)
O2—C2—C1—Cl1	23.8 (2)	C6—N1—C3—C4	−67.1 (2)
O2—C2—C1—Cl2	−97.11 (19)	C6—N1—C3—C5	169.99 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.92	1.87	2.788 (2)	177
N1—H1B···O2ⁱⁱ	0.92	1.90	2.757 (2)	154
C6—H6···O1ⁱⁱⁱ	1.00	2.38	3.258 (2)	146

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.92	1.87	2.788 (2)	177.3
N1—H1B···O2ⁱⁱ	0.92	1.90	2.757 (2)	154.2
C6—H6···O1ⁱⁱⁱ	1.00	2.38	3.258 (2)	146.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2.

Acknowledgements

This work was supported by the National S&T Major Special Project on Major New Drug Innovation (2012ZX09301002-001-019)

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