2,3-Dichloro-1,4-hydro-quinone 2,3-dichloro-1,4-benzoquinone monohydrate: a quinhydrone-type 1:1 donor-acceptor [D-A] charge-transfer complex.

IN THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND (SYSTEMATIC NAME: 2,3-dichloro-benzene-1,4-diol 2,3-dichloro-cyclo-hexa-2,5-diene-1,4-dione monohydrate), C(6)H(4)Cl(2)O(2)·C(6)H(2)Cl(2)O(2)·H(2)O, the 2,3-dichloro-1,4-hydro-quinone donor (D) and the 2,3-dichloro-1,4-benzoquinone acceptor (A) mol-ecules form alternating stacks along [100]. Their mol-ecular planes [maximum deviations for non-H atoms: 0.0133 (14) (D) and 0.0763 (14) Å (A)] are inclined to one another by 1.45 (3)° and are thus almost parallel. There are π-π inter-actions involving the D and A mol-ecules, with centroid-centroid distances of 3.5043 (9) and 3.9548 (9) Å. Inter-molecular O-H⋯O hydrogen bonds involving the water mol-ecule and the hy-droxy and ketone groups lead to the formation of two-dimensional networks lying parallel to (001). These networks are linked by C-H⋯O inter-actions, forming a three-dimensional structure.

Related literature

For prototypical examples of similar organic redox systems, see: Yi et al. (2009a ▶,b ▶). For details concerning quinhydrone, a 1:1 hydro­quinone-quinone adduct, and a well known mol­ecular charge-transfer (CT) complex, see: Foster (1969 ▶). For structural studies of different polymorphs of quinhydrone, see: Matsuda et al. (1958 ▶); Sakurai (1965 ▶,1968 ▶). For details concerning quinhydrone analogues, see: Bouvet et al. (2006 ▶,2007 ▶); Patil et al. (1984 ▶); Yamamura et al. (2007 ▶). For a detailed computational study on the stacking energies and the electron density topology in quinhydrone, see: Gonzalez Moa et al. (2007 ▶).

Experimental

Crystal data

C6H4Cl2O2·C6H2Cl2O2·H2O

M = 373.98

Monoclinic,

a = 7.15329 (14) Å

b = 7.19541 (15) Å

c = 27.2811 (5) Å

β = 92.9738 (18)°

V = 1402.29 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.86 mm−1

T = 173 K

0.3 × 0.2 × 0.07 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.859, T max = 0.942

19255 measured reflections

3138 independent reflections

2653 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.077

S = 1.04

3138 reflections

198 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041377/su2322sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811041377/su2322Isup2.mol

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041377/su2322Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811041377/su2322Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H4Cl2O2·C6H2Cl2O2·H2O	F(000) = 752
Mr = 373.98	Dx = 1.771 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7958 reflections
a = 7.15329 (14) Å	θ = 2.8–27.5°
b = 7.19541 (15) Å	µ = 0.86 mm−1
c = 27.2811 (5) Å	T = 173 K
β = 92.9738 (18)°	Plate, red
V = 1402.29 (5) Å3	0.3 × 0.2 × 0.07 mm
Z = 4

Siemens SMART 1K CCD area-detector diffractometer	3138 independent reflections
Radiation source: fine-focus sealed tube	2653 reflections with I > 2σ(I)
graphite	Rint = 0.026
rotation method scans	θmax = 27.9°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.859, Tmax = 0.942	k = −9→9
19255 measured reflections	l = −35→35

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0429P)2 + 0.583P] where P = (Fo2 + 2Fc2)/3
3138 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

	x	y	z	Uiso*/Ueq
C1	0.7866 (2)	0.9165 (2)	0.38598 (7)	0.0220 (4)
O1	0.72734 (19)	1.07053 (18)	0.37504 (5)	0.0299 (3)
C2	0.8432 (2)	0.7822 (3)	0.34779 (6)	0.0216 (4)
Cl2	0.81893 (7)	0.85660 (7)	0.288391 (16)	0.03021 (13)
C3	0.9107 (2)	0.6140 (3)	0.36016 (6)	0.0220 (4)
Cl3	0.97542 (7)	0.45526 (7)	0.317735 (18)	0.03252 (13)
C4	0.9362 (2)	0.5565 (2)	0.41269 (7)	0.0229 (4)
O4	1.00840 (19)	0.40868 (18)	0.42426 (5)	0.0305 (3)
C5	0.8731 (2)	0.6879 (3)	0.44963 (7)	0.0252 (4)
H5	0.8808	0.6525	0.4832	0.030*
C6	0.8052 (3)	0.8555 (3)	0.43743 (7)	0.0251 (4)
H6	0.7682	0.9370	0.4625	0.030*
C11	0.3767 (2)	0.7229 (2)	0.33596 (6)	0.0194 (3)
O11	0.43186 (18)	0.60154 (17)	0.30131 (4)	0.0245 (3)
H11	0.4304	0.6550	0.2739	0.037*
C12	0.3915 (2)	0.6700 (2)	0.38514 (6)	0.0185 (3)
Cl12	0.47890 (6)	0.45165 (6)	0.399712 (15)	0.02360 (11)
C13	0.3366 (2)	0.7902 (2)	0.42204 (6)	0.0196 (3)
Cl13	0.35592 (7)	0.72408 (6)	0.482946 (16)	0.02805 (12)
C14	0.2652 (2)	0.9655 (2)	0.40960 (6)	0.0206 (4)
O14	0.2109 (2)	1.07750 (18)	0.44656 (5)	0.0289 (3)
H14	0.1681	1.1775	0.4347	0.043*
C15	0.2513 (2)	1.0172 (2)	0.36060 (6)	0.0220 (4)
H15	0.2035	1.1366	0.3519	0.026*
C16	0.3058 (2)	0.8979 (2)	0.32418 (6)	0.0213 (4)
H16	0.2947	0.9361	0.2908	0.026*
O20	0.4387 (2)	0.7413 (2)	0.21375 (5)	0.0325 (3)
H20A	0.393 (3)	0.691 (4)	0.1903 (10)	0.049*
H20B	0.472 (4)	0.834 (4)	0.2061 (10)	0.049*

	U11	U22	U33	U12	U13	U23
C1	0.0203 (8)	0.0230 (9)	0.0224 (9)	−0.0010 (7)	−0.0011 (7)	0.0017 (7)
O1	0.0371 (7)	0.0239 (7)	0.0283 (7)	0.0054 (6)	−0.0032 (6)	0.0030 (5)
C2	0.0203 (8)	0.0282 (9)	0.0160 (8)	−0.0027 (7)	−0.0002 (7)	0.0021 (7)
Cl2	0.0329 (2)	0.0399 (3)	0.0178 (2)	0.0027 (2)	0.00070 (17)	0.00536 (19)
C3	0.0190 (8)	0.0246 (9)	0.0226 (9)	−0.0017 (7)	0.0023 (7)	−0.0043 (7)
Cl3	0.0360 (3)	0.0321 (3)	0.0298 (3)	0.0031 (2)	0.00496 (19)	−0.00926 (19)
C4	0.0195 (8)	0.0235 (9)	0.0254 (9)	−0.0020 (7)	−0.0005 (7)	0.0027 (7)
O4	0.0315 (7)	0.0243 (7)	0.0356 (8)	0.0055 (6)	−0.0008 (6)	0.0056 (6)
C5	0.0266 (9)	0.0297 (9)	0.0193 (9)	0.0005 (8)	0.0012 (7)	0.0028 (7)
C6	0.0267 (9)	0.0281 (9)	0.0206 (9)	0.0021 (8)	0.0022 (7)	−0.0022 (7)
C11	0.0206 (8)	0.0185 (8)	0.0190 (8)	−0.0021 (7)	0.0013 (6)	−0.0019 (6)
O11	0.0373 (7)	0.0196 (6)	0.0169 (6)	0.0037 (5)	0.0047 (5)	0.0002 (5)
C12	0.0188 (8)	0.0144 (7)	0.0223 (9)	0.0003 (6)	−0.0001 (6)	0.0023 (6)
Cl12	0.0305 (2)	0.0166 (2)	0.0236 (2)	0.00314 (17)	0.00040 (17)	0.00279 (16)
C13	0.0214 (8)	0.0210 (8)	0.0163 (8)	−0.0018 (7)	0.0002 (6)	0.0022 (7)
Cl13	0.0374 (3)	0.0288 (2)	0.0179 (2)	0.0034 (2)	0.00093 (17)	0.00261 (17)
C14	0.0219 (8)	0.0178 (8)	0.0221 (9)	−0.0007 (7)	0.0021 (7)	−0.0025 (7)
O14	0.0412 (8)	0.0213 (6)	0.0245 (7)	0.0081 (6)	0.0043 (6)	−0.0023 (5)
C15	0.0241 (9)	0.0161 (8)	0.0257 (9)	0.0005 (7)	−0.0009 (7)	0.0034 (7)
C16	0.0232 (9)	0.0220 (8)	0.0186 (9)	−0.0001 (7)	0.0004 (7)	0.0041 (7)
O20	0.0539 (9)	0.0238 (7)	0.0192 (7)	−0.0103 (7)	−0.0027 (6)	0.0009 (5)

C1—O1	1.218 (2)	C11—C12	1.393 (2)
C1—C6	1.470 (3)	O11—H11	0.8400
C1—C2	1.493 (2)	C12—C13	1.400 (2)
C2—C3	1.340 (3)	C12—Cl12	1.7292 (16)
C2—Cl2	1.7070 (17)	C13—C14	1.396 (2)
C3—C4	1.494 (2)	C13—Cl13	1.7270 (17)
C3—Cl3	1.7069 (18)	C14—O14	1.363 (2)
C4—O4	1.217 (2)	C14—C15	1.386 (2)
C4—C5	1.470 (3)	O14—H14	0.8400
C5—C6	1.335 (3)	C15—C16	1.384 (2)
C5—H5	0.9500	C15—H15	0.9500
C6—H6	0.9500	C16—H16	0.9500
C11—O11	1.360 (2)	O20—H20A	0.79 (3)
C11—C16	1.389 (2)	O20—H20B	0.74 (3)
O1—C1—C6	121.26 (17)	C16—C11—C12	118.64 (16)
O1—C1—C2	121.44 (16)	C11—O11—H11	109.5
C6—C1—C2	117.30 (15)	C11—C12—C13	120.89 (15)
C3—C2—C1	121.09 (15)	C11—C12—Cl12	118.58 (13)
C3—C2—Cl2	122.70 (14)	C13—C12—Cl12	120.53 (13)
C1—C2—Cl2	116.21 (13)	C14—C13—C12	119.78 (15)
C2—C3—C4	121.08 (16)	C14—C13—Cl13	119.55 (13)
C2—C3—Cl3	122.71 (14)	C12—C13—Cl13	120.68 (13)
C4—C3—Cl3	116.20 (13)	O14—C14—C15	123.05 (15)
O4—C4—C5	121.72 (17)	O14—C14—C13	117.98 (15)
O4—C4—C3	121.32 (17)	C15—C14—C13	118.96 (16)
C5—C4—C3	116.95 (15)	C14—O14—H14	109.5
C6—C5—C4	122.04 (16)	C16—C15—C14	121.10 (16)
C6—C5—H5	119.0	C16—C15—H15	119.4
C4—C5—H5	119.0	C14—C15—H15	119.4
C5—C6—C1	121.43 (17)	C15—C16—C11	120.63 (16)
C5—C6—H6	119.3	C15—C16—H16	119.7
C1—C6—H6	119.3	C11—C16—H16	119.7
O11—C11—C16	122.47 (15)	H20A—O20—H20B	108 (3)
O11—C11—C12	118.89 (15)
O1—C1—C2—C3	179.07 (17)	O11—C11—C12—C13	179.97 (15)
C6—C1—C2—C3	−0.9 (2)	C16—C11—C12—C13	−0.1 (3)
O1—C1—C2—Cl2	−0.3 (2)	O11—C11—C12—Cl12	−0.2 (2)
C6—C1—C2—Cl2	179.69 (13)	C16—C11—C12—Cl12	179.74 (13)
C1—C2—C3—C4	−1.5 (3)	C11—C12—C13—C14	0.2 (3)
Cl2—C2—C3—C4	177.83 (13)	Cl12—C12—C13—C14	−179.57 (13)
C1—C2—C3—Cl3	179.46 (13)	C11—C12—C13—Cl13	−179.82 (13)
Cl2—C2—C3—Cl3	−1.2 (2)	Cl12—C12—C13—Cl13	0.4 (2)
C2—C3—C4—O4	−175.28 (17)	C12—C13—C14—O14	179.13 (15)
Cl3—C3—C4—O4	3.8 (2)	Cl13—C13—C14—O14	−0.8 (2)
C2—C3—C4—C5	3.7 (2)	C12—C13—C14—C15	−0.4 (3)
Cl3—C3—C4—C5	−177.23 (13)	Cl13—C13—C14—C15	179.68 (13)
O4—C4—C5—C6	175.42 (18)	O14—C14—C15—C16	−179.12 (16)
C3—C4—C5—C6	−3.5 (3)	C13—C14—C15—C16	0.4 (3)
C4—C5—C6—C1	1.2 (3)	C14—C15—C16—C11	−0.2 (3)
O1—C1—C6—C5	−178.88 (17)	O11—C11—C16—C15	180.00 (16)
C2—C1—C6—C5	1.1 (3)	C12—C11—C16—C15	0.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O20	0.84	1.76	2.5947 (18)	173
O14—H14···O4i	0.84	2.03	2.8381 (18)	161
O20—H20A···O1ii	0.79 (3)	2.12 (3)	2.914 (2)	177 (3)
O20—H20B···O11iii	0.74 (3)	2.06 (3)	2.7899 (19)	169 (3)
C6—H6···O14iv	0.95	2.48	3.209 (2)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O20	0.84	1.76	2.5947 (18)	173
O14—H14⋯O4i	0.84	2.03	2.8381 (18)	161
O20—H20A⋯O1ii	0.79 (3)	2.12 (3)	2.914 (2)	177 (3)
O20—H20B⋯O11iii	0.74 (3)	2.06 (3)	2.7899 (19)	169 (3)
C6—H6⋯O14iv	0.95	2.48	3.209 (2)	134

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .