2-(2-Chloro­phen­yl)-5-methyl-1,3-dioxane-5-carboxylic acid

Jia, G.-K.; Yuan, L.; Zhang, M.; Yuan, X.-Y.

doi:10.1107/S1600536812025019

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2037

https://doi.org/10.1107/S1600536812025019

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2-(2-Chlorophenyl)-5-methyl-1,3-dioxane-5-carboxylic acid

Guo-Kai Jia,^a Lin Yuan,^b ^* Min Zhang ^b and Xian-You Yuan ^b

^aCollege of Chemistry, Xiangtan University, Xiangtan Hunan 411105, People's Republic of China, and ^bDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China
^*Correspondence e-mail: yuanxianzhangmin@163.com

(Received 14 May 2012; accepted 1 June 2012; online 13 June 2012)

In the title compound, C₁₂H₁₃ClO₄, the 1,3-dioxane ring adopts a chair conformation and the 2-chlorobenzene and methyl substituents occupy equatorial sites. The carboxyl group is in an axial inclination. In the crystal, carboxylic acid inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R₂²(8) loops.

Related literature

For background to protecting groups, see: He et al. (2004 ). For related structures, see: Laing et al. (1984 ); Sun et al. (2010 ); Wang et al. (2010 ).

Experimental

Crystal data

C₁₂H₁₃ClO₄
M_r = 256.67
Monoclinic, P 2₁ /c
a = 9.4452 (3) Å
b = 13.9413 (5) Å
c = 9.37059 (18) Å
β = 102.145 (2)°
V = 1206.28 (6) Å³
Z = 4
Cu Kα radiation
μ = 2.83 mm⁻¹
T = 153 K
0.46 × 0.42 × 0.23 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2006 ) T_min = 0.356, T_max = 0.562
5864 measured reflections
2089 independent reflections
1902 reflections with I > 2σ(I)
R_int = 0.023
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.084
S = 1.07
2089 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O3ⁱ	0.72 (2)	1.92 (2)	2.6323 (18)	170 (3)
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: CrysAlis PRO (Agilent, 2006); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812025019/hb6799sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025019/hb6799Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025019/hb6799Isup3.cml

checkCIF report

Comment top

The title compound was synthesized to be used as a protection of carbonyl or synthetic intermediate in organic syntheses (He et al., 2004).

In the title compound, C₁₂H₁₃ClO₄, the 1,3-dioxane ring adopts a chair conformation and the 2-chlorophenyl substituent occupies an equatorial site (Fig. 1). In the crystal, adjacent molecules are connected by O—H···O hydrogen bonding interactions between the oxygen atoms O₃ and O₄ into a dimer (Fig. 2). The crystal structures of some similar 1,3-dioxanes have been reported (Laing et al., 1984; Sun et al., 2010; Wang et al., 2010).

Related literature top

For background to protecting groups, see: He et al. (2004). For related structures, see: Laing et al. (1984); Sun et al. (2010); Wang et al. (2010).

Experimental top

2,2-bis(hydroxymethyl propionic acid (6.7 g, 0.05 mol), 2-chlorobenzaldehyde (7.0 g, 0.05 mol), N,N-dimethylformamide (30 ml), cyclohexane (15 ml), and p-toluenesulfonic acid monohydrate (1 g, 0.005 mol) were heated and stirred at 353 K for 5 h. Diethyl ether (50 ml) and NaHCO3 (0.42 g, 5 mmol) were added to dissolve the residue after DMF and cyclohexane were evaporated under reduced pressure. The organic solution was washed with water (100 ml), and dried with anhydrous sodium sulfate for 3 h. The resulting solution was filtered and evaporated, and the product was recrystallized from ethyl acetate to give 8.3 g of colorless blocks (yield 65%; m.p. 424.2 K).

Structure description top

The title compound was synthesized to be used as a protection of carbonyl or synthetic intermediate in organic syntheses (He et al., 2004).

For background to protecting groups, see: He et al. (2004). For related structures, see: Laing et al. (1984); Sun et al. (2010); Wang et al. (2010).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2006); cell refinement: CrysAlis PRO (Agilent, 2006); data reduction: CrysAlis PRO (Agilent, 2006); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A view of the packing of the title compound

2-(2-Chlorophenyl)-5-methyl-1,3-dioxane-5-carboxylic acid top

Crystal data top

C₁₂H₁₃ClO₄	F(000) = 536
M_r = 256.67	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.4452 (3) Å	Cell parameters from 5864 reflections
b = 13.9413 (5) Å	θ = 4.8–67.0°
c = 9.37059 (18) Å	µ = 2.83 mm⁻¹
β = 102.145 (2)°	T = 153 K
V = 1206.28 (6) Å³	Block, colorless
Z = 4	0.46 × 0.42 × 0.23 mm

Data collection top

Agilent Xcalibur Atlas Gemini ultra diffractometer	2089 independent reflections
Radiation source: fine-focus sealed tube	1902 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 67.0°, θ_min = 4.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2006)	h = −10→11
T_min = 0.356, T_max = 0.562	k = −16→15
5864 measured reflections	l = −10→11

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0395P)² + 0.6772P] where P = (F_o² + 2F_c²)/3
2089 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₂H₁₃ClO₄	V = 1206.28 (6) Å³
M_r = 256.67	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 9.4452 (3) Å	µ = 2.83 mm⁻¹
b = 13.9413 (5) Å	T = 153 K
c = 9.37059 (18) Å	0.46 × 0.42 × 0.23 mm
β = 102.145 (2)°

Data collection top

Agilent Xcalibur Atlas Gemini ultra diffractometer	2089 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2006)	1902 reflections with I > 2σ(I)
T_min = 0.356, T_max = 0.562	R_int = 0.023
5864 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.33 e Å⁻³
2089 reflections	Δρ_min = −0.30 e Å⁻³
158 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
Cl	0.64679 (5)	0.45963 (3)	0.15200 (5)	0.02559 (15)
O1	0.83817 (12)	0.26839 (8)	0.27910 (12)	0.0143 (3)
C9	0.95610 (17)	0.13397 (12)	0.18663 (17)	0.0139 (3)
C8	0.96031 (17)	0.24125 (12)	0.22005 (18)	0.0149 (3)
H8A	1.0508	0.2569	0.2909	0.018*
H8B	0.9596	0.2779	0.1294	0.018*
C10	0.80794 (17)	0.11189 (12)	0.08981 (17)	0.0147 (4)
H10A	0.8003	0.1430	−0.0065	0.018*
H10B	0.7978	0.0418	0.0741	0.018*
C7	0.54853 (18)	0.37904 (12)	0.23610 (19)	0.0193 (4)
C3	0.50347 (18)	0.22009 (12)	0.31020 (18)	0.0181 (4)
H3	0.5253	0.1535	0.3151	0.022*
C5	0.3595 (2)	0.35127 (14)	0.3641 (2)	0.0296 (5)
H5	0.2832	0.3748	0.4062	0.036*
C4	0.39209 (19)	0.25432 (14)	0.3718 (2)	0.0233 (4)
H4	0.3385	0.2115	0.4190	0.028*
C6	0.43677 (19)	0.41421 (14)	0.2957 (2)	0.0275 (4)
H6	0.4135	0.4806	0.2897	0.033*
C1	0.70735 (17)	0.24594 (11)	0.17837 (18)	0.0141 (3)
H1	0.7062	0.2786	0.0831	0.017*
O2	0.69428 (12)	0.14595 (8)	0.15653 (12)	0.0144 (3)
C2	0.58361 (17)	0.28173 (12)	0.24141 (18)	0.0153 (3)
O4	1.05941 (15)	0.10910 (10)	0.43964 (14)	0.0264 (3)
O3	0.91722 (14)	−0.00573 (9)	0.32146 (14)	0.0271 (3)
C12	0.97688 (17)	0.07531 (12)	0.32671 (17)	0.0138 (3)
C11	1.07850 (19)	0.10862 (13)	0.10860 (19)	0.0202 (4)
H11A	1.1703	0.1340	0.1645	0.030*
H11B	1.0580	0.1369	0.0107	0.030*
H11C	1.0854	0.0388	0.1008	0.030*
H4B	1.073 (2)	0.0772 (17)	0.502 (3)	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0236 (2)	0.0145 (2)	0.0385 (3)	0.00062 (17)	0.00616 (19)	0.00353 (18)
O1	0.0115 (6)	0.0153 (6)	0.0155 (6)	0.0004 (5)	0.0014 (4)	−0.0026 (4)
C9	0.0145 (8)	0.0154 (8)	0.0122 (8)	0.0008 (7)	0.0038 (6)	0.0004 (6)
C8	0.0143 (8)	0.0152 (8)	0.0159 (8)	0.0003 (7)	0.0046 (6)	0.0015 (7)
C10	0.0171 (8)	0.0154 (8)	0.0117 (8)	0.0013 (7)	0.0034 (6)	−0.0018 (6)
C7	0.0146 (8)	0.0167 (8)	0.0245 (9)	−0.0009 (7)	−0.0010 (7)	0.0001 (7)
C3	0.0170 (8)	0.0169 (8)	0.0188 (8)	−0.0004 (7)	0.0000 (7)	−0.0010 (7)
C5	0.0179 (9)	0.0291 (11)	0.0442 (12)	0.0047 (8)	0.0118 (8)	−0.0053 (9)
C4	0.0162 (9)	0.0256 (10)	0.0283 (10)	−0.0016 (8)	0.0052 (7)	−0.0016 (8)
C6	0.0196 (9)	0.0185 (9)	0.0442 (12)	0.0057 (8)	0.0062 (8)	−0.0027 (8)
C1	0.0147 (8)	0.0111 (8)	0.0148 (8)	−0.0009 (7)	−0.0010 (6)	0.0002 (6)
O2	0.0135 (6)	0.0126 (6)	0.0172 (6)	0.0000 (5)	0.0032 (4)	−0.0029 (4)
C2	0.0119 (8)	0.0166 (8)	0.0152 (8)	0.0010 (7)	−0.0025 (6)	−0.0025 (7)
O4	0.0412 (8)	0.0197 (7)	0.0134 (6)	0.0008 (6)	−0.0053 (6)	0.0030 (5)
O3	0.0298 (7)	0.0195 (7)	0.0278 (7)	−0.0068 (6)	−0.0038 (6)	0.0077 (5)
C12	0.0129 (8)	0.0138 (8)	0.0149 (8)	0.0028 (7)	0.0038 (6)	−0.0015 (6)
C11	0.0201 (9)	0.0241 (9)	0.0183 (9)	0.0028 (7)	0.0081 (7)	−0.0014 (7)

Geometric parameters (Å, º) top

Cl—C7	1.7472 (18)	C3—H3	0.9500
O1—C1	1.4230 (19)	C5—C6	1.382 (3)
O1—C8	1.4314 (18)	C5—C4	1.385 (3)
C9—C12	1.524 (2)	C5—H5	0.9500
C9—C8	1.527 (2)	C4—H4	0.9500
C9—C10	1.530 (2)	C6—H6	0.9500
C9—C11	1.534 (2)	C1—O2	1.4106 (19)
C8—H8A	0.9900	C1—C2	1.501 (2)
C8—H8B	0.9900	C1—H1	1.0000
C10—O2	1.4322 (19)	O4—C12	1.266 (2)
C10—H10A	0.9900	O4—H4B	0.72 (2)
C10—H10B	0.9900	O3—C12	1.259 (2)
C7—C6	1.384 (2)	C11—H11A	0.9800
C7—C2	1.395 (2)	C11—H11B	0.9800
C3—C4	1.387 (2)	C11—H11C	0.9800
C3—C2	1.390 (2)

C1—O1—C8	110.09 (12)	C4—C5—H5	119.6
C12—C9—C8	110.85 (13)	C5—C4—C3	119.60 (17)
C12—C9—C10	109.80 (13)	C5—C4—H4	120.2
C8—C9—C10	107.44 (13)	C3—C4—H4	120.2
C12—C9—C11	108.28 (13)	C5—C6—C7	118.96 (17)
C8—C9—C11	109.50 (13)	C5—C6—H6	120.5
C10—C9—C11	110.98 (13)	C7—C6—H6	120.5
O1—C8—C9	110.48 (13)	O2—C1—O1	110.54 (12)
O1—C8—H8A	109.6	O2—C1—C2	109.51 (13)
C9—C8—H8A	109.6	O1—C1—C2	107.77 (13)
O1—C8—H8B	109.6	O2—C1—H1	109.7
C9—C8—H8B	109.6	O1—C1—H1	109.7
H8A—C8—H8B	108.1	C2—C1—H1	109.7
O2—C10—C9	110.51 (12)	C1—O2—C10	109.89 (12)
O2—C10—H10A	109.5	C3—C2—C7	117.99 (15)
C9—C10—H10A	109.5	C3—C2—C1	121.46 (15)
O2—C10—H10B	109.5	C7—C2—C1	120.52 (15)
C9—C10—H10B	109.5	C12—O4—H4B	114.9 (19)
H10A—C10—H10B	108.1	O3—C12—O4	123.95 (15)
C6—C7—C2	121.73 (16)	O3—C12—C9	118.20 (14)
C6—C7—Cl	118.49 (14)	O4—C12—C9	117.75 (15)
C2—C7—Cl	119.78 (13)	C9—C11—H11A	109.5
C4—C3—C2	121.00 (16)	C9—C11—H11B	109.5
C4—C3—H3	119.5	H11A—C11—H11B	109.5
C2—C3—H3	119.5	C9—C11—H11C	109.5
C6—C5—C4	120.71 (17)	H11A—C11—H11C	109.5
C6—C5—H5	119.6	H11B—C11—H11C	109.5

C1—O1—C8—C9	−59.01 (16)	C4—C3—C2—C7	−0.1 (2)
C12—C9—C8—O1	−66.61 (16)	C4—C3—C2—C1	178.11 (15)
C10—C9—C8—O1	53.36 (16)	C6—C7—C2—C3	−0.6 (3)
C11—C9—C8—O1	173.98 (13)	Cl—C7—C2—C3	179.55 (12)
C12—C9—C10—O2	67.01 (16)	C6—C7—C2—C1	−178.79 (16)
C8—C9—C10—O2	−53.64 (16)	Cl—C7—C2—C1	1.4 (2)
C11—C9—C10—O2	−173.32 (13)	O2—C1—C2—C3	19.6 (2)
C6—C5—C4—C3	0.0 (3)	O1—C1—C2—C3	−100.69 (17)
C2—C3—C4—C5	0.4 (3)	O2—C1—C2—C7	−162.29 (14)
C4—C5—C6—C7	−0.6 (3)	O1—C1—C2—C7	77.43 (18)
C2—C7—C6—C5	1.0 (3)	C8—C9—C12—O3	149.70 (15)
Cl—C7—C6—C5	−179.21 (15)	C10—C9—C12—O3	31.1 (2)
C8—O1—C1—O2	64.06 (15)	C11—C9—C12—O3	−90.17 (18)
C8—O1—C1—C2	−176.31 (12)	C8—C9—C12—O4	−33.9 (2)
O1—C1—O2—C10	−64.23 (15)	C10—C9—C12—O4	−152.45 (14)
C2—C1—O2—C10	177.19 (12)	C11—C9—C12—O4	86.24 (18)
C9—C10—O2—C1	59.63 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O3ⁱ	0.72 (2)	1.92 (2)	2.6323 (18)	170 (3)

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃ClO₄
M_r	256.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	9.4452 (3), 13.9413 (5), 9.37059 (18)
β (°)	102.145 (2)
V (Å³)	1206.28 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.83
Crystal size (mm)	0.46 × 0.42 × 0.23

Data collection
Diffractometer	Agilent Xcalibur Atlas Gemini ultra
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2006)
T_min, T_max	0.356, 0.562
No. of measured, independent and observed [I > 2σ(I)] reflections	5864, 2089, 1902
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.084, 1.07
No. of reflections	2089
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.30

Computer programs: CrysAlis PRO (Agilent, 2006), 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
O4—H4B···O3ⁱ	0.72 (2)	1.92 (2)	2.6323 (18)	170 (3)

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

The authors thank the Construction Program of Key Disciplines in Hunan Province (2011–76), the Science and Technology Planning Project of Yongzhou (No. 2011–6), the Key Project of Hunan University of Science and Engineering (No. 2011) and the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province (2012–318) for financial support.

References

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