rac-1,1,1,6,6,6-Hexa­chloro­hex-3-yne-2,5-diol hemihydrate

Detert, H.; Schollmeyer, D.

doi:10.1107/S2414314617012366

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 8| August 2017| x171236

https://doi.org/10.1107/S2414314617012366

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rac-1,1,1,6,6,6-Hexachlorohex-3-yne-2,5-diol hemihydrate

Heiner Detert ^a ^* and Dieter Schollmeyer ^a

^aUniversity of Mainz, Institut of Organic Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 25 August 2017; accepted 25 August 2017; online 30 August 2017)

The asymmetric unit of the title compound, C₆H₄Cl₆O₂·0.5H₂O, contains one molecule of 1,1,1,6,6,6-hexachlorohex-3-yne-2,5-diol and half a water molecule located on a twofold rotation axis. In the crystal, pairs of hexachlorohexynediol molecules form centrosymmetric dimers connected via pairwise O—H⋯O hydrogen bonds. These dimers are connected by water molecules, resulting in layers parallel to the ab plane.

Keywords: crystal structure; centrosymmetric dimer; layer structure; organochlorine compound; alkyne.

CCDC reference: 1570830

Structure description

Highly chlorinated compounds are of current interest because they are intermediates in the formation of environmental pollutants (Taylor et al., 2000 ) and they are useful as chemical substrates (Rahimi et al., 2009 ; Schmidt et al., 2009 ). Furthermore, their rearrangements (McIntosh et al., 2014 ; Schollmeyer & Detert, 2017 ; Detert et al., 2009 ) are a topic in its own right. The monoclinic unit cell contains four centrosymmetric dimers composed of one molecule with an R,R-configuration, one with an S,S-configuration and four water molecules, the latter is located on a twofold rotation axis.

In the monoclinic crystal, the hexachlorohexynediol molecules adopt a gauche conformation [C1—C2⋯C5—C6 = 30.4 (2)°] with a nonperfect C2 symmetry (Fig. 1). The C—Cl bonds of the trichloromethyl groups vary between 1.756 (3) (C6—Cl4) and 1.776 (3) Å (C1—Cl2). With bond angles of 176.9 (3) and 175.8 (3)° and a torsion angle of 3 (10)°, the alkyne unit is not perfectly linear. An R,R- and an S,S-configured diole are connected via short hydrogen bonds [O1—H1O⋯O2ⁱⁱ = 2.725 (3) Å] to a centrosymmetric dimer (Table 1). A C—H⋯O hydrogen bond [C5—H5⋯O1ⁱ = 3.297 (4) Å] forms a chain parallel to the b axis. Hydrogen bonds between atoms O1 and O2 to the water molecule [O2—H2O⋯O3ⁱ = 2.773 (3) Å and O3—H3O⋯O1 = 2.999 (3) Å] connect these chains into layers in the ab plane (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.98 (4)	2.50 (4)	3.297 (4)	139 (3)
O1—H1O⋯O2ⁱⁱ	0.72 (4)	2.01 (4)	2.725 (3)	168 (4)
O2—H2O⋯O3ⁱ	0.75 (4)	2.02 (4)	2.773 (3)	175 (4)
O3—H3O⋯O1	0.90 (5)	2.29 (5)	2.999 (3)	135 (5)
O3—H3O⋯Cl1	0.90 (5)	2.83 (5)	3.5120 (8)	134 (4)
O3—H3O⋯Cl2	0.90 (5)	3.06 (5)	3.895 (3)	155 (5)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1.

Figure 1
View of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Part of the packing diagram, viewed along the b axis. Hydrogen bonds are shown with dashed lines.

Synthesis and crystallization

The title compound was prepared from ethyl magnesium bromide, acetylene and chloral according to Gorgues et al. (1986 ) and Dupont (1910 ) followed by aqueous work-up. A mixture of three stereoisomers was obtained. Recrystallization from ethanol solution gave the title compound. ¹H NMR: (CDCl₃/DMSO-d₆, 400 MHz): δ 7.05 (2H, OH), 4.79 (2H, CH, ¹J_CH = 154 Hz). Recrystallization from chloroform solution yielded colourless crystals (m.p. 408 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were located in difference Fourier maps and were refined with isotropic displacement parameters.

Table 2
Experimental details

Crystal data
Chemical formula	2C₆H₄Cl₆O₂·H₂O
M_r	659.60
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	193
a, b, c (Å)	19.8354 (11), 5.8480 (2), 21.7082 (13)
β (°)	108.321 (4)
V (Å³)	2390.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.41
Crystal size (mm)	0.39 × 0.07 × 0.06

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Integration (X-RED32; Stoe & Cie, 2006b )
T_min, T_max	0.714, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	6305, 2965, 2202
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.090, 1.03
No. of reflections	2965
No. of parameters	152
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.57
Computer programs: X-AREA (Stoe & Cie, 2006a ), X-RED32 (Stoe & Cie, 2006b), SIR2004 (Altomare et al., 1999 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1570830

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617012366/bt4062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012366/bt4062Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2006a); cell refinement: X-AREA (Stoe & Cie, 2006a); data reduction: X-RED32 (Stoe & Cie, 2006b); program(s) used to solve structure: SIR2004 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

rac-1,1,1,6,6,6-Hexachlorohex-3-yne-2,5-diol hemihydrate top

Crystal data top

2C₆H₄Cl₆O₂·H₂O	D_x = 1.833 Mg m⁻³
M_r = 659.60	Melting point: 408 K
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 19.8354 (11) Å	Cell parameters from 5782 reflections
b = 5.8480 (2) Å	θ = 3.4–28.3°
c = 21.7082 (13) Å	µ = 1.41 mm⁻¹
β = 108.321 (4)°	T = 193 K
V = 2390.5 (2) Å³	Column, colourless
Z = 4	0.39 × 0.07 × 0.06 mm
F(000) = 1304

Data collection top

Stoe IPDS 2T diffractometer	2965 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2202 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.026
rotation method scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: integration (X-RED32; Stoe & Cie, 2006b)	h = −26→26
T_min = 0.714, T_max = 0.933	k = −7→6
6305 measured reflections	l = −24→28

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	All H-atom parameters refined
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0295P)² + 6.4827P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2965 reflections	Δρ_max = 0.59 e Å⁻³
152 parameters	Δρ_min = −0.57 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
C1	0.58326 (13)	0.4054 (5)	0.37414 (13)	0.0269 (5)
C2	0.56624 (13)	0.4444 (5)	0.43828 (13)	0.0268 (5)
H2	0.5573 (14)	0.608 (5)	0.4386 (13)	0.026 (7)*
C3	0.50278 (14)	0.3142 (5)	0.43757 (12)	0.0296 (6)
C4	0.45026 (15)	0.2097 (5)	0.43394 (13)	0.0314 (6)
C5	0.38356 (15)	0.0835 (5)	0.42428 (13)	0.0303 (6)
H5	0.3951 (17)	−0.077 (6)	0.4347 (16)	0.046 (9)*
C6	0.34051 (13)	0.0815 (5)	0.35171 (13)	0.0270 (5)
O1	0.62524 (11)	0.3777 (4)	0.49119 (10)	0.0345 (5)
H1O	0.637 (2)	0.484 (7)	0.5082 (19)	0.051 (12)*
O2	0.34423 (13)	0.1915 (5)	0.46020 (11)	0.0489 (7)
H2O	0.319 (2)	0.114 (7)	0.4692 (19)	0.059 (13)*
O3	0.7500	0.0752 (6)	0.5000	0.0380 (7)
H3O	0.717 (3)	0.171 (10)	0.475 (3)	0.12 (2)*
Cl1	0.59756 (4)	0.11144 (12)	0.36352 (4)	0.03662 (17)
Cl2	0.66181 (4)	0.55802 (13)	0.37759 (4)	0.04003 (19)
Cl3	0.51257 (4)	0.50491 (14)	0.30818 (3)	0.04010 (19)
Cl4	0.38978 (5)	−0.05417 (17)	0.30774 (4)	0.0551 (3)
Cl5	0.26084 (4)	−0.07339 (13)	0.34107 (4)	0.03746 (18)
Cl6	0.31978 (4)	0.36244 (14)	0.32294 (5)	0.0547 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0242 (12)	0.0244 (12)	0.0341 (13)	0.0017 (10)	0.0119 (10)	0.0002 (11)
C2	0.0232 (12)	0.0271 (14)	0.0300 (13)	−0.0016 (10)	0.0083 (10)	0.0002 (11)
C3	0.0268 (13)	0.0357 (15)	0.0257 (12)	−0.0011 (11)	0.0075 (10)	0.0015 (11)
C4	0.0302 (14)	0.0358 (15)	0.0292 (13)	−0.0032 (12)	0.0109 (11)	0.0016 (12)
C5	0.0311 (14)	0.0315 (15)	0.0312 (14)	−0.0084 (12)	0.0138 (11)	−0.0003 (12)
C6	0.0251 (12)	0.0271 (13)	0.0312 (13)	−0.0024 (10)	0.0123 (10)	−0.0012 (11)
O1	0.0297 (10)	0.0338 (12)	0.0349 (11)	−0.0043 (9)	0.0028 (8)	−0.0005 (9)
O2	0.0507 (14)	0.0622 (16)	0.0484 (13)	−0.0332 (13)	0.0367 (11)	−0.0271 (12)
O3	0.0278 (15)	0.0455 (18)	0.0381 (16)	0.000	0.0066 (12)	0.000
Cl1	0.0322 (3)	0.0265 (3)	0.0517 (4)	0.0022 (3)	0.0140 (3)	−0.0071 (3)
Cl2	0.0346 (4)	0.0347 (4)	0.0601 (5)	−0.0071 (3)	0.0282 (3)	−0.0022 (3)
Cl3	0.0384 (4)	0.0489 (4)	0.0334 (3)	0.0119 (3)	0.0118 (3)	0.0097 (3)
Cl4	0.0544 (5)	0.0652 (6)	0.0615 (5)	−0.0178 (4)	0.0408 (4)	−0.0298 (5)
Cl5	0.0301 (3)	0.0397 (4)	0.0436 (4)	−0.0134 (3)	0.0130 (3)	−0.0058 (3)
Cl6	0.0418 (4)	0.0358 (4)	0.0742 (6)	−0.0033 (3)	0.0004 (4)	0.0202 (4)

Geometric parameters (Å, º) top

C1—C2	1.549 (4)	C5—O2	1.414 (3)
C1—Cl3	1.758 (3)	C5—C6	1.538 (4)
C1—Cl1	1.769 (3)	C5—H5	0.98 (4)
C1—Cl2	1.776 (3)	C6—Cl4	1.756 (3)
C2—O1	1.413 (3)	C6—Cl6	1.760 (3)
C2—C3	1.467 (4)	C6—Cl5	1.772 (3)
C2—H2	0.97 (3)	O1—H1O	0.72 (4)
C3—C4	1.189 (4)	O2—H2O	0.75 (4)
C4—C5	1.471 (4)	O3—H3O	0.90 (5)

C2—C1—Cl3	109.87 (17)	O2—C5—C4	108.9 (2)
C2—C1—Cl1	110.43 (19)	O2—C5—C6	110.1 (2)
Cl3—C1—Cl1	109.56 (15)	C4—C5—C6	109.5 (2)
C2—C1—Cl2	108.92 (18)	O2—C5—H5	116 (2)
Cl3—C1—Cl2	109.42 (14)	C4—C5—H5	108 (2)
Cl1—C1—Cl2	108.62 (14)	C6—C5—H5	104 (2)
O1—C2—C3	110.7 (2)	C5—C6—Cl4	109.60 (19)
O1—C2—C1	109.4 (2)	C5—C6—Cl6	110.4 (2)
C3—C2—C1	110.1 (2)	Cl4—C6—Cl6	109.69 (15)
O1—C2—H2	111.8 (17)	C5—C6—Cl5	108.81 (18)
C3—C2—H2	110.6 (17)	Cl4—C6—Cl5	108.90 (15)
C1—C2—H2	104.0 (17)	Cl6—C6—Cl5	109.37 (14)
C4—C3—C2	176.9 (3)	C2—O1—H1O	104 (3)
C3—C4—C5	175.8 (3)	C5—O2—H2O	114 (3)

Cl3—C1—C2—O1	−176.19 (18)	O2—C5—C6—Cl4	−179.75 (18)
Cl1—C1—C2—O1	62.8 (2)	C4—C5—C6—Cl4	60.5 (3)
Cl2—C1—C2—O1	−56.3 (3)	O2—C5—C6—Cl6	59.3 (3)
Cl3—C1—C2—C3	62.0 (3)	C4—C5—C6—Cl6	−60.5 (3)
Cl1—C1—C2—C3	−59.0 (3)	O2—C5—C6—Cl5	−60.8 (3)
Cl2—C1—C2—C3	−178.21 (19)	C4—C5—C6—Cl5	179.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.98 (4)	2.50 (4)	3.297 (4)	139 (3)
O1—H1O···O2ⁱⁱ	0.72 (4)	2.01 (4)	2.725 (3)	168 (4)
O2—H2O···O3ⁱ	0.75 (4)	2.02 (4)	2.773 (3)	175 (4)
O3—H3O···O1	0.90 (5)	2.29 (5)	2.999 (3)	135 (5)
O3—H3O···Cl1	0.90 (5)	2.83 (5)	3.5120 (8)	134 (4)
O3—H3O···Cl2	0.90 (5)	3.06 (5)	3.895 (3)	155 (5)

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

Acknowledgements

The authors are grateful to Anna Weber for the preparation of the title compound.

References

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