The hydrogen-bonded complex bis­(tert-butyl­ammonium) 2,6-di­chloro­phenolate 2,4-di­chloro­phenol–2,4-di­chloro­phenolate tetra­hydro­furan disolvate containing a chiral R₅³(10) hydrogen-bonded ring as a supramolecular synthon

A fixed hydrogen-bonding motif with a high probability of occurring when appropriate functional groups are involved is described as a `supra­molecular hydrogen-bonding synthon'. The identification of these synthons may enable the prediction of accurate crystal structures. The rare chiral hydrogen-bonding motif R₅³(10) was observed previously in a cocrystal of 2,4,6-tri­chloro­phenol, 2,4-di­chloro­phenol and di­cyclo­hexyl­amine. In the title solvated salt, 2C₄H₁₂N⁺·C₆H₃Cl₂O⁻·(C₆H₃Cl₂O⁻·C₆H₄Cl₂O)·2C₄H₈O, five components, namely two tert-butylammonium cations, one 2,4-dichlorophenol molecule, one 2,4-dichloro­phenolate anion and one 2,6-dichlorophenolate anion, are bound by N—H...O and O—H...O hydrogen bonds to form a hydrogen-bonded ring, with the graph-set motif R₅³(10), which is further associated with two pendant tetra­hydro­furan mol­ecules by N—H...O hydrogen bonds. The hydrogen-bonded ring has inter­nal symmetry, with a twofold axis running through the centre of the 2,6-di­chloro­phenolate anion, and is isostructural with a previous and related structure formed from 2,4-di­chloro­phenol, di­cyclo­hexyl­amine and 2,4,6-tri­chloro­phenol. In the title crystal, helical columns are built by the alignment and twisting of the chiral hydrogen-bonded rings, along and across the c axis, and successive pairs of rings are associated with each other through C—H...π inter­actions. Neighbouring helical columns are inversely related and, therefore, no chirality is sustained, in contrast to the previous case.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Bis(tert-butylammonium) 2,6-dichlorophenolate 2,4-dichlorophenolate 2,4-dichlorophenol tetrahydrofuran disolvate

Crystal data

2C4H12N^+·C6H3Cl2O^−·C6H3Cl2O^−·C6H4Cl2O·2C4H8O	F(000) = 1640
Mr = 779.46	Dx = 1.293 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 14.8441 (12) Å	Cell parameters from 2879 reflections
b = 13.2872 (11) Å	θ = 2.1–23.1°
c = 21.0311 (15) Å	µ = 0.47 mm^−1
β = 105.191 (3)°	T = 293 K
V = 4003.2 (5) Å^3	Prism, colorless
Z = 4	0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer	3934 independent reflections
Radiation source: fine-focus sealed tube	2350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
φ and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→18
Tmin = 0.892, Tmax = 0.935	k = −16→16
10530 measured reflections	l = −25→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0964P)^2] where P = (Fo^2 + 2Fc^2)/3
3934 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.32 e Å^−3
1 restraint	Δρmin = −0.32 e Å^−3

Special details

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.

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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.1991 (2)	−0.0150 (2)	0.14329 (15)	0.0509 (7)
C2	0.2370 (2)	−0.0754 (3)	0.19683 (16)	0.0618 (8)
H2	0.2076	−0.0811	0.2307	0.074*
C3	0.3197 (2)	−0.1284 (2)	0.20038 (17)	0.0643 (8)
C4	0.3640 (2)	−0.1185 (3)	0.15022 (17)	0.0649 (9)
H4	0.4189	−0.1536	0.1522	0.078*
C5	0.3258 (2)	−0.0558 (2)	0.09677 (17)	0.0585 (8)
H5	0.3559	−0.0485	0.0634	0.070*
C6	0.24343 (19)	−0.0041 (2)	0.09293 (14)	0.0465 (6)
C7	0.2500	0.4651 (4)	0.0000	0.0648 (13)
C8	0.2441 (2)	0.5239 (2)	−0.05631 (18)	0.0642 (9)
C9	0.2454 (2)	0.6299 (3)	−0.0542 (2)	0.0718 (10)
H9	0.2429	0.6633	−0.0935	0.086*
C10	0.2500	0.6882 (4)	0.0000	0.0741 (14)
H10	0.2500	0.7582	0.0000	0.089*
C11	0.1172 (3)	0.2914 (3)	0.20948 (18)	0.0741 (10)
H11A	0.1815	0.2974	0.2074	0.089*
H11B	0.1082	0.2238	0.2241	0.089*
C12	0.0994 (3)	0.3648 (3)	0.25766 (18)	0.0739 (10)
H12A	0.1523	0.4094	0.2731	0.089*
H12B	0.0868	0.3307	0.2952	0.089*
C13	0.0161 (3)	0.4216 (3)	0.2204 (2)	0.0810 (11)
H13A	0.0259	0.4935	0.2264	0.097*
H13B	−0.0388	0.4026	0.2344	0.097*
C14	0.0058 (2)	0.3924 (3)	0.15013 (18)	0.0705 (10)
H14A	−0.0594	0.3796	0.1287	0.085*
H14B	0.0267	0.4472	0.1271	0.085*
C15	0.0376 (2)	0.2499 (2)	−0.02621 (15)	0.0594 (8)
C16	−0.0350 (2)	0.1841 (2)	−0.01277 (16)	0.0579 (8)
H16A	−0.0133	0.1157	−0.0088	0.087*
H16B	−0.0906	0.1891	−0.0483	0.087*
H16C	−0.0484	0.2046	0.0276	0.087*
C17	0.0044 (2)	0.3600 (2)	−0.03639 (16)	0.0568 (8)
H17A	0.0533	0.4009	−0.0448	0.085*
H17B	−0.0111	0.3837	0.0025	0.085*
H17C	−0.0497	0.3639	−0.0732	0.085*
C18	0.0706 (2)	0.2143 (3)	−0.08504 (16)	0.0650 (9)
H18A	0.1156	0.2610	−0.0933	0.097*
H18B	0.0183	0.2103	−0.1231	0.097*
H18C	0.0988	0.1491	−0.0758	0.097*
Cl1	0.36776 (6)	−0.19802 (7)	0.26861 (4)	0.0711 (3)
Cl2	0.09661 (7)	0.04388 (8)	0.13829 (5)	0.0863 (4)
Cl3	0.23478 (6)	0.46070 (7)	−0.12810 (5)	0.0731 (3)
N1	0.12112 (15)	0.24947 (18)	0.03209 (12)	0.0521 (6)
H1A	0.1638	0.2919	0.0250	0.078*
H1B	0.1450	0.1877	0.0381	0.078*
H1C	0.1041	0.2685	0.0678	0.078*
O1	0.20805 (14)	0.05805 (15)	0.04282 (10)	0.0558 (5)
H1	0.239 (6)	0.064 (4)	0.012 (4)	0.067*	0.50
O2	0.2500	0.3674 (2)	0.0000	0.0656 (8)
O3	0.05771 (17)	0.30728 (18)	0.14689 (12)	0.0716 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0536 (16)	0.0489 (17)	0.0516 (18)	0.0031 (13)	0.0165 (13)	0.0024 (14)
C2	0.070 (2)	0.067 (2)	0.052 (2)	0.0007 (16)	0.0222 (16)	0.0078 (17)
C3	0.0656 (19)	0.063 (2)	0.059 (2)	0.0059 (16)	0.0082 (15)	0.0116 (17)
C4	0.0634 (19)	0.066 (2)	0.062 (2)	0.0101 (16)	0.0093 (16)	0.0183 (17)
C5	0.0537 (17)	0.060 (2)	0.064 (2)	0.0094 (14)	0.0197 (15)	0.0093 (16)
C6	0.0552 (16)	0.0427 (15)	0.0419 (16)	0.0025 (13)	0.0134 (12)	0.0037 (13)
C7	0.052 (2)	0.076 (4)	0.067 (3)	0.000	0.017 (2)	0.000
C8	0.0595 (19)	0.057 (2)	0.078 (2)	−0.0220 (15)	0.0229 (16)	−0.0088 (18)
C9	0.073 (2)	0.062 (2)	0.086 (3)	−0.0099 (17)	0.0310 (19)	0.016 (2)
C10	0.069 (3)	0.077 (3)	0.080 (4)	0.000	0.024 (3)	0.000
C11	0.095 (3)	0.067 (2)	0.068 (2)	0.0114 (18)	0.033 (2)	−0.0109 (19)
C12	0.101 (3)	0.066 (2)	0.062 (2)	−0.004 (2)	0.033 (2)	0.0143 (19)
C13	0.100 (3)	0.067 (2)	0.087 (3)	−0.001 (2)	0.045 (2)	−0.020 (2)
C14	0.078 (2)	0.069 (2)	0.073 (2)	0.0088 (17)	0.0340 (18)	−0.0170 (19)
C15	0.0693 (19)	0.061 (2)	0.0497 (19)	0.0106 (15)	0.0198 (15)	0.0085 (16)
C16	0.0612 (17)	0.0589 (19)	0.0572 (19)	−0.0088 (14)	0.0219 (14)	0.0108 (16)
C17	0.0656 (18)	0.0485 (18)	0.0560 (19)	0.0119 (14)	0.0154 (14)	0.0123 (15)
C18	0.078 (2)	0.066 (2)	0.053 (2)	0.0119 (16)	0.0203 (16)	−0.0039 (17)
Cl1	0.0753 (5)	0.0756 (6)	0.0632 (5)	0.0068 (4)	0.0196 (4)	0.0216 (5)
Cl2	0.0821 (6)	0.1018 (8)	0.0887 (7)	0.0411 (5)	0.0464 (5)	0.0324 (6)
Cl3	0.0834 (6)	0.0701 (6)	0.0747 (6)	0.0028 (4)	0.0365 (5)	−0.0092 (5)
N1	0.0513 (13)	0.0557 (15)	0.0462 (14)	0.0134 (11)	0.0070 (11)	0.0074 (12)
O1	0.0643 (13)	0.0600 (13)	0.0469 (13)	0.0141 (10)	0.0216 (9)	0.0109 (10)
O2	0.077 (2)	0.057 (2)	0.068 (2)	0.000	0.0270 (16)	0.000
O3	0.0872 (16)	0.0744 (16)	0.0591 (15)	−0.0187 (12)	0.0295 (12)	−0.0182 (12)

Geometric parameters (Å, º)

C1—C2	1.378 (4)	C12—H12A	0.9700
C1—C6	1.393 (4)	C12—H12B	0.9700
C1—Cl2	1.689 (3)	C13—C14	1.496 (5)
C2—C3	1.400 (4)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.387 (5)	C14—O3	1.380 (4)
C3—Cl1	1.699 (3)	C14—H14A	0.9700
C4—C5	1.395 (4)	C14—H14B	0.9700
C4—H4	0.9300	C15—C16	1.472 (4)
C5—C6	1.386 (4)	C15—N1	1.498 (4)
C5—H5	0.9300	C15—C18	1.521 (4)
C6—O1	1.334 (3)	C15—C17	1.540 (4)
C7—O2	1.299 (6)	C16—H16A	0.9600
C7—C8	1.402 (4)	C16—H16B	0.9600
C7—C8^i	1.402 (4)	C16—H16C	0.9600
C8—C9	1.409 (4)	C17—H17A	0.9600
C8—Cl3	1.702 (4)	C17—H17B	0.9600
C9—C10	1.365 (5)	C17—H17C	0.9600
C9—H9	0.9300	C18—H18A	0.9600
C10—C9^i	1.365 (5)	C18—H18B	0.9600
C10—H10	0.9300	C18—H18C	0.9600
C11—O3	1.396 (4)	N1—H1A	0.8900
C11—C12	1.479 (5)	N1—H1B	0.8900
C11—H11A	0.9700	N1—H1C	0.8900
C11—H11B	0.9700	O1—H1	0.885 (10)
C12—C13	1.484 (5)
C2—C1—C6	120.6 (3)	C12—C13—H13A	110.9
C2—C1—Cl2	119.3 (2)	C14—C13—H13A	110.9
C6—C1—Cl2	120.1 (2)	C12—C13—H13B	110.9
C1—C2—C3	120.1 (3)	C14—C13—H13B	110.9
C1—C2—H2	120.0	H13A—C13—H13B	108.9
C3—C2—H2	120.0	O3—C14—C13	110.3 (3)
C4—C3—C2	119.7 (3)	O3—C14—H14A	109.6
C4—C3—Cl1	121.1 (3)	C13—C14—H14A	109.6
C2—C3—Cl1	119.1 (3)	O3—C14—H14B	109.6
C3—C4—C5	119.7 (3)	C13—C14—H14B	109.6
C3—C4—H4	120.1	H14A—C14—H14B	108.1
C5—C4—H4	120.1	C16—C15—N1	109.3 (3)
C6—C5—C4	120.6 (3)	C16—C15—C18	112.3 (3)
C6—C5—H5	119.7	N1—C15—C18	106.9 (2)
C4—C5—H5	119.7	C16—C15—C17	111.5 (3)
O1—C6—C5	120.8 (3)	N1—C15—C17	106.5 (3)
O1—C6—C1	119.9 (2)	C18—C15—C17	110.0 (3)
C5—C6—C1	119.3 (3)	C15—C16—H16A	109.5
O2—C7—C8	123.9 (2)	C15—C16—H16B	109.5
O2—C7—C8^i	123.9 (2)	H16A—C16—H16B	109.5
C8—C7—C8^i	112.3 (5)	C15—C16—H16C	109.5
C7—C8—C9	122.2 (4)	H16A—C16—H16C	109.5
C7—C8—Cl3	116.5 (3)	H16B—C16—H16C	109.5
C9—C8—Cl3	121.3 (3)	C15—C17—H17A	109.5
C10—C9—C8	126.2 (4)	C15—C17—H17B	109.5
C10—C9—H9	116.9	H17A—C17—H17B	109.5
C8—C9—H9	116.9	C15—C17—H17C	109.5
C9—C10—C9^i	110.8 (5)	H17A—C17—H17C	109.5
C9—C10—H10	124.6	H17B—C17—H17C	109.5
C9^i—C10—H10	124.6	C15—C18—H18A	109.5
O3—C11—C12	111.3 (3)	C15—C18—H18B	109.5
O3—C11—H11A	109.4	H18A—C18—H18B	109.5
C12—C11—H11A	109.4	C15—C18—H18C	109.5
O3—C11—H11B	109.4	H18A—C18—H18C	109.5
C12—C11—H11B	109.2	H18B—C18—H18C	109.5
H11A—C11—H11B	108.0	C15—N1—H1A	109.5
C11—C12—C13	104.3 (3)	C15—N1—H1B	109.5
C11—C12—H12A	110.9	H1A—N1—H1B	109.5
C13—C12—H12A	110.9	C15—N1—H1C	109.5
C11—C12—H12B	110.9	H1A—N1—H1C	109.5
C13—C12—H12B	110.9	H1B—N1—H1C	109.5
H12A—C12—H12B	108.9	C6—O1—H1	117 (5)
C12—C13—C14	104.2 (3)	C14—O3—C11	107.5 (3)
C6—C1—C2—C3	−1.3 (5)	O2—C7—C8—C9	−179.2 (2)
Cl2—C1—C2—C3	177.1 (3)	C8^i—C7—C8—C9	0.8 (2)
C1—C2—C3—C4	0.9 (5)	O2—C7—C8—Cl3	0.9 (3)
C1—C2—C3—Cl1	177.1 (3)	C8^i—C7—C8—Cl3	−179.1 (3)
C2—C3—C4—C5	0.2 (5)	C7—C8—C9—C10	−1.8 (5)
Cl1—C3—C4—C5	−176.0 (3)	Cl3—C8—C9—C10	178.1 (2)
C3—C4—C5—C6	−0.8 (5)	C8—C9—C10—C9^i	0.9 (2)
C4—C5—C6—O1	178.2 (3)	O3—C11—C12—C13	5.6 (4)
C4—C5—C6—C1	0.4 (5)	C11—C12—C13—C14	−12.4 (4)
C2—C1—C6—O1	−177.1 (3)	C12—C13—C14—O3	16.0 (4)
Cl2—C1—C6—O1	4.4 (4)	C13—C14—O3—C11	−12.8 (4)
C2—C1—C6—C5	0.7 (5)	C12—C11—O3—C14	4.3 (4)
Cl2—C1—C6—C5	−177.8 (2)

Symmetry code: (i) −x+1/2, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	1.81	2.691 (3)	172
N1—H1B···O1	0.89	1.96	2.837 (4)	171
N1—H1C···O3	0.89	2.03	2.915 (4)	176
O1—H1···O1^i	0.89	1.56	2.444 (3)	173

Symmetry code: (i) −x+1/2, y, −z.