Interpenetrating supramolecular lattices in 4,4′-bi­pyridine–2,3,5,6-tetra­hydroxy-1,4-benzo­quinone (3/2)

4,4′-Bi­pyridine (BPY) and 2,3,5,6-tetra­hydroxy-1,4-benzo­quinone (THBQ) crystallize in a 3:2 ratio as a neutral molecular adduct, 3C₁₀H₈N₂·2C₆H₄O₆, in space group P. There are two independent and centrosymmetric THBQ mol­ecules and two different BPY mol­ecules in the asymmetric unit, one of which lies about an inversion centre. The molecules link together through O—H...O and O—H...N hydrogen bonds to form three interpenetrating networks which create a `superlattice' of three times the volume of the primitive cell.

S1. Comment

To investigate a variety of molecular interactions in the solid state, in particular N—H···O and O—H···N hydrogen bonds, we have produced new cocrystals of 4,4-bipyridine (BPY) and tetrahydroxybenzoquinone (THBQ). Cocrystals of organic acids and bipyridines have been studied extensively and have been observed to form a wide variety of intermolecular hydrogen bonds (Reetz et al., 1994; MacLean et al., 1999; Lough et al., 2000). We have reported recently the structure of BPY with 2,5-dihydroxybenzoquinone (Cowan et al., 2001), and as a natural progression of the series, we have investigated BPY with THBQ and present here the structure of 4,4'-bipyridine–tetrahydroxybenzoquinone (3/2).

There are two independent centrosymmetric molecules of THBQ in the structure. One THBQ molecule shows a spiral arrangement of the hydroxy H atoms similar to that observed by Kulpe (1965), while the other adopts a `crab-like' conformation with the O—-H bonds almost parallel to the quinone C═O groups. The geometry of the non-H atoms in both THBQ molecules is not significantly different from that observed by Kulpe (1965).

There are also two independent BPY molecules in the structure, one of which lies across an inversion centre; the other is complete within the asymmetric unit. In the complete BPY molecule, the pyridine rings are twisted at 19.9° with respect to each other, while the other BPY is required to be planar by symmetry. The twist in the unique BPY optimizes three weak C—H···O hydrogen bonds [C14···O2ⁱ, C16···O6 and C18···O4ⁱⁱ; symmetry codes: (i) x, y - 1, z; (ii) x - 1, y - 1, z].

There are four conventional hydrogen bonds in the asymmetric unit. Each of the four hydroxy groups is a donor and each of the pyridine N atoms is an acceptor. The other potential acceptor is O5 which acts both as a donor and as an acceptor. The carbonyl groups could be regarded as acceptors for intramolecular hydrogen bonds, but the O—H···O angles are unacceptable (O2–H2···O1 108°, O3–H3···O1 105° and O6–H6···O4 106°) and similarly for a possible intramolecular hydrogen bond between H5 and O6 (O5—H5···O6 102°).

Three different hydrogen-bonded chains are formed in the crystal; two arise from O—H···N hydrogen bonds and the third one from O—H···O hydrogen bonds (Fig. 2). Chains of THBQ propagate along the [111] direction, connected by O—H···O hydrogen bonds (O2···O5). Chains of BPY and THBQ propagate along the [210] direction connected by O—H···N hydrogen bonds (O6···N3) and further O—H···N hydrogen-bonded chains of BPY and THBQ are formed along the [131] direction [O3···N1ⁱⁱⁱ and O5···N2; symmetry code: (iii) x + 1, y + 2, z].

When these three non-collinear chains intersect with one another, two-dimensional rings are created which connect together to form a three-dimensional supramolecular lattice. In the lattice, the THBQ molecules act as four-connecting (molecule containing C1) and six-connecting (molecule containing C4) nodes and the BPY molecules act only as links. The [111] and [131] chains link into planar sheets incorporating both types of node. The [210] chains connect the sheets via the six-connecting nodes after spanning two intervening planes.

The supramolecular structure can also be described by a supercell with axes of a' = 16.798 Å [210], b' = 17.096 Å [120], c' = 13.547 Å [111], α' = 108.8°, β' = 117.8° and γ' = 51.8° and with a volume of 2709 ų, three times that of the primitive unit cell.

The three separate `lattices' which create an interpenetrating mesh within the supercell are shown in Fig. 3. Examination of the structure with PLATON (Spek, 1990) showed that there are no cavities of significant size within this structure. A similar structural motif occurs in cocrystals of a 3:2 ratio of BPY and trimesic acid (Sharma & Zaworotko, 1996), in which three two-dimensional interpenetrating hydrogen-bonded grids are formed but, unlike the present structure, large voids are formed in the crystal.

S2. Experimental

4,4'-Bipyridine (156 mg, 1 mmol) and tetrahydroxybenzoquinone dihydrate (156 mg, 1 mmol) were dissolved in methanol and water producing a deep-red solution. Crystals suitable for X-ray structure determination were obtained by slow evaporation of the solvent at room temperature.

S3. Refinement

All H atoms were found in the difference Fourier maps and were refined with isotropic displacement parameters fixed to their parent atoms; the C–H and O–H distances all refined to within standard ranges.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecules of the title adduct shown with 50% probability displacement ellipsoids. The dashed lines indicate hydrogen bonds. [Symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -1 - x, -y, -z; (iii) 2 - x, 2 - y, -z; (iv) 1 - x, -y, 1 - z.]
	Fig. 2. View of the molecular packing showing the formation of hydrogen-bonded chains, which link together to form a three-dimensional lattice. The dashed lines indicate hydrogen bonds and the parallelograms highlight the chains linked into rings. H atoms have been omitted for clarity.
	Fig. 3. Packing diagram viewed close to the [111] direction. The primitive unit cell and the supercell based on [111], [210] and [120] have been indicated. The separate interpenetrating lattices are coloured differently. H atoms and some molecules have been omitted for clarity.

4,4'-bipyridine–tetrahydroxybenzoquinone (3/2)

Crystal data

3C10H8N2·2C6H4O6	Z = 1
Mr = 812.74	F(000) = 422
Triclinic, P1	Dx = 1.492 Mg m^−3
a = 8.8856 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0728 (9) Å	Cell parameters from 910 reflections
c = 12.9288 (11) Å	θ = 9.3–22.1°
α = 109.164 (5)°	µ = 0.11 mm^−1
β = 92.476 (5)°	T = 100 K
γ = 111.074 (5)°	Irregular, brown
V = 903.17 (14) Å^3	0.6 × 0.4 × 0.3 mm

Data collection

Bruker SMART CCD diffractometer	4127 independent reflections
Radiation source: fine-focus sealed tube	2628 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.754, Tmax = 1.000	k = −11→11
9859 measured reflections	l = −16→16

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)] = 0.038	Hydrogen site location: difference Fourier map
wR(F^2) = 0.067	Only H-atom coordinates refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.02P)^2] where P = (Fo^2 + 2Fc^2)/3
4127 reflections	(Δ/σ)max < 0.001
319 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.89557 (18)	0.82743 (19)	0.47812 (12)	0.0173 (3)
O1	0.80029 (12)	0.68015 (13)	0.46000 (8)	0.0227 (3)
C2	0.86208 (18)	0.92017 (19)	0.41054 (12)	0.0176 (3)
O2	0.72974 (13)	0.83418 (14)	0.32649 (9)	0.0249 (3)
H2	0.6954 (19)	0.728 (2)	0.3104 (13)	0.030*
C3	0.95777 (18)	1.08520 (19)	0.43304 (12)	0.0179 (3)
O3	0.92496 (13)	1.16916 (13)	0.37192 (9)	0.0236 (3)
H3	1.0132 (18)	1.278 (2)	0.3861 (12)	0.028*
C4	0.66918 (18)	0.56848 (18)	0.04832 (12)	0.0177 (3)
O4	0.81671 (12)	0.63116 (13)	0.08719 (9)	0.0248 (3)
C5	0.54347 (18)	0.49434 (18)	0.10817 (12)	0.0168 (3)
O5	0.60280 (12)	0.49760 (13)	0.20800 (8)	0.0200 (3)
H5	0.5311 (18)	0.421 (2)	0.2284 (12)	0.024*
C6	0.38340 (18)	0.43229 (18)	0.06343 (12)	0.0169 (3)
O6	0.26616 (13)	0.36837 (13)	0.11753 (9)	0.0229 (3)
H6	0.1592 (19)	0.3159 (19)	0.0754 (13)	0.028*
N1	0.11089 (15)	−0.52917 (15)	0.36960 (10)	0.0211 (3)
C10	0.2677 (2)	−0.4212 (2)	0.41080 (13)	0.0241 (4)
H10	0.3327 (18)	−0.4490 (19)	0.4552 (13)	0.029*
C11	0.3392 (2)	−0.2698 (2)	0.39293 (13)	0.0213 (4)
H11	0.4556 (18)	−0.2026 (18)	0.4251 (12)	0.026*
C12	0.24512 (18)	−0.22625 (18)	0.32817 (12)	0.0176 (3)
C13	0.31481 (18)	−0.06245 (18)	0.30901 (12)	0.0170 (3)
C14	0.4832 (2)	0.0273 (2)	0.32274 (13)	0.0225 (4)
H14	0.5627 (18)	−0.0103 (19)	0.3446 (12)	0.027*
C15	0.5411 (2)	0.1781 (2)	0.30252 (13)	0.0224 (4)
H15	0.6599 (19)	0.2402 (19)	0.3125 (12)	0.027*
N2	0.44245 (15)	0.24380 (15)	0.27038 (10)	0.0205 (3)
C16	0.28094 (19)	0.15788 (19)	0.25806 (12)	0.0203 (4)
H16	0.2088 (17)	0.2016 (18)	0.2328 (12)	0.024*
C17	0.21196 (19)	0.00584 (19)	0.27529 (12)	0.0194 (4)
H17	0.0941 (18)	−0.0507 (18)	0.2634 (12)	0.023*
C18	0.08324 (19)	−0.33958 (19)	0.28373 (13)	0.0195 (4)
H18	0.0077 (18)	−0.3228 (18)	0.2364 (12)	0.023*
C19	0.0219 (2)	−0.4879 (2)	0.30598 (13)	0.0207 (4)
H19	−0.0942 (18)	−0.5659 (19)	0.2762 (12)	0.025*
N3	−0.06220 (15)	0.20248 (16)	0.04592 (10)	0.0234 (3)
C20	−0.1387 (2)	0.0781 (2)	0.08389 (14)	0.0258 (4)
H20	−0.0655 (18)	0.0469 (19)	0.1263 (12)	0.031*
C21	−0.30727 (19)	−0.0022 (2)	0.06882 (13)	0.0247 (4)
H21	−0.3562 (18)	−0.0915 (19)	0.1031 (12)	0.030*
C22	−0.40869 (18)	0.04258 (18)	0.01029 (12)	0.0194 (3)
C23	−0.32893 (19)	0.1733 (2)	−0.02812 (13)	0.0219 (4)
H23	−0.3991 (17)	0.2072 (18)	−0.0750 (12)	0.026*
C24	−0.15926 (19)	0.2476 (2)	−0.00853 (13)	0.0231 (4)
H24	−0.1011 (18)	0.3389 (19)	−0.0339 (12)	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0220 (9)	0.0142 (9)	0.0179 (8)	0.0093 (7)	0.0078 (7)	0.0057 (7)
O1	0.0274 (6)	0.0141 (6)	0.0236 (6)	0.0038 (5)	0.0023 (5)	0.0083 (5)
C2	0.0170 (8)	0.0172 (9)	0.0182 (8)	0.0063 (7)	0.0022 (7)	0.0068 (7)
O2	0.0290 (7)	0.0135 (6)	0.0281 (6)	0.0047 (5)	−0.0050 (5)	0.0083 (5)
C3	0.0214 (9)	0.0171 (9)	0.0188 (8)	0.0087 (7)	0.0060 (7)	0.0096 (7)
O3	0.0277 (7)	0.0152 (6)	0.0280 (6)	0.0047 (5)	−0.0009 (5)	0.0129 (5)
C4	0.0210 (9)	0.0105 (8)	0.0202 (8)	0.0064 (7)	0.0010 (7)	0.0042 (7)
O4	0.0201 (6)	0.0283 (7)	0.0262 (6)	0.0057 (5)	0.0014 (5)	0.0149 (5)
C5	0.0232 (9)	0.0114 (8)	0.0159 (8)	0.0059 (7)	0.0025 (7)	0.0061 (7)
O5	0.0220 (6)	0.0162 (6)	0.0197 (6)	0.0013 (5)	0.0007 (5)	0.0114 (5)
C6	0.0221 (9)	0.0117 (8)	0.0181 (8)	0.0069 (7)	0.0062 (7)	0.0063 (7)
O6	0.0176 (6)	0.0276 (7)	0.0224 (6)	0.0039 (5)	0.0030 (5)	0.0136 (5)
N1	0.0275 (8)	0.0161 (7)	0.0210 (7)	0.0090 (6)	0.0047 (6)	0.0080 (6)
C10	0.0305 (10)	0.0209 (9)	0.0238 (9)	0.0110 (8)	0.0022 (8)	0.0111 (8)
C11	0.0235 (9)	0.0184 (9)	0.0213 (9)	0.0068 (8)	0.0022 (7)	0.0083 (8)
C12	0.0247 (9)	0.0143 (8)	0.0147 (8)	0.0084 (7)	0.0062 (7)	0.0052 (7)
C13	0.0241 (9)	0.0149 (8)	0.0127 (8)	0.0083 (7)	0.0049 (7)	0.0050 (7)
C14	0.0267 (10)	0.0195 (9)	0.0224 (9)	0.0093 (8)	0.0025 (7)	0.0094 (8)
C15	0.0208 (9)	0.0202 (9)	0.0236 (9)	0.0040 (8)	0.0014 (7)	0.0099 (8)
N2	0.0253 (8)	0.0153 (7)	0.0194 (7)	0.0065 (6)	0.0031 (6)	0.0065 (6)
C16	0.0260 (10)	0.0193 (9)	0.0208 (9)	0.0124 (8)	0.0068 (7)	0.0097 (7)
C17	0.0221 (9)	0.0175 (9)	0.0195 (9)	0.0077 (7)	0.0072 (7)	0.0078 (7)
C18	0.0241 (9)	0.0178 (9)	0.0196 (9)	0.0102 (7)	0.0053 (7)	0.0084 (7)
C19	0.0217 (9)	0.0161 (9)	0.0219 (9)	0.0052 (7)	0.0048 (7)	0.0065 (7)
N3	0.0210 (7)	0.0233 (8)	0.0218 (8)	0.0063 (6)	0.0048 (6)	0.0060 (6)
C20	0.0243 (10)	0.0268 (10)	0.0255 (10)	0.0097 (8)	0.0037 (7)	0.0093 (8)
C21	0.0250 (10)	0.0203 (9)	0.0278 (10)	0.0077 (8)	0.0060 (8)	0.0089 (8)
C22	0.0222 (8)	0.0140 (8)	0.0176 (8)	0.0071 (7)	0.0055 (7)	0.0002 (7)
C23	0.0241 (9)	0.0192 (9)	0.0201 (9)	0.0089 (7)	0.0055 (7)	0.0041 (7)
C24	0.0245 (9)	0.0180 (9)	0.0227 (9)	0.0053 (8)	0.0072 (7)	0.0057 (8)

Geometric parameters (Å, º)

C1—O1	1.2333 (16)	C12—C13	1.4989 (19)
C1—C3^i	1.475 (2)	C13—C14	1.393 (2)
C1—C2	1.4833 (19)	C13—C17	1.3997 (19)
C2—C3	1.3515 (19)	C14—C15	1.395 (2)
C2—O2	1.3585 (17)	C14—H14	0.956 (15)
O2—H2	0.844 (16)	C15—N2	1.3428 (18)
C3—O3	1.3509 (16)	C15—H15	0.980 (15)
C3—C1^i	1.475 (2)	N2—C16	1.3368 (18)
O3—H3	0.965 (15)	C16—C17	1.391 (2)
C4—O4	1.2304 (17)	C16—H16	0.963 (14)
C4—C5	1.475 (2)	C17—H17	0.965 (14)
C4—C6^ii	1.496 (2)	C18—C19	1.390 (2)
C5—C6	1.347 (2)	C18—H18	0.974 (14)
C5—O5	1.3600 (16)	C19—H19	0.987 (14)
O5—H5	0.882 (15)	N3—C24	1.3409 (19)
C6—O6	1.3438 (16)	N3—C20	1.3482 (19)
C6—C4^ii	1.496 (2)	C20—C21	1.382 (2)
O6—H6	0.941 (15)	C20—H20	1.004 (14)
N1—C10	1.3406 (19)	C21—C22	1.399 (2)
N1—C19	1.3419 (18)	C21—H21	1.020 (14)
C10—C11	1.392 (2)	C22—C23	1.403 (2)
C10—H10	0.948 (15)	C22—C22^iii	1.492 (3)
C11—C12	1.396 (2)	C23—C24	1.384 (2)
C11—H11	0.978 (15)	C23—H23	1.039 (14)
C12—C18	1.390 (2)	C24—H24	0.973 (14)
O1—C1—C3^i	121.26 (12)	C13—C14—C15	119.41 (14)
O1—C1—C2	119.76 (13)	C13—C14—H14	123.1 (9)
C3^i—C1—C2	118.97 (12)	C15—C14—H14	117.5 (9)
C3—C2—O2	121.13 (13)	N2—C15—C14	123.41 (15)
C3—C2—C1	121.26 (13)	N2—C15—H15	117.9 (8)
O2—C2—C1	117.59 (13)	C14—C15—H15	118.7 (8)
C2—O2—H2	111.6 (11)	C16—N2—C15	116.98 (12)
O3—C3—C2	120.81 (13)	N2—C16—C17	123.66 (14)
O3—C3—C1^i	119.47 (13)	N2—C16—H16	117.8 (8)
C2—C3—C1^i	119.66 (12)	C17—C16—H16	118.5 (8)
C3—O3—H3	112.8 (9)	C16—C17—C13	119.34 (15)
O4—C4—C5	122.15 (13)	C16—C17—H17	119.3 (8)
O4—C4—C6^ii	118.59 (13)	C13—C17—H17	121.4 (8)
C5—C4—C6^ii	119.26 (12)	C19—C18—C12	119.53 (14)
C6—C5—O5	125.16 (13)	C19—C18—H18	116.4 (8)
C6—C5—C4	119.71 (13)	C12—C18—H18	124.1 (8)
O5—C5—C4	115.12 (12)	N1—C19—C18	123.42 (15)
C5—O5—H5	111.8 (9)	N1—C19—H19	117.5 (8)
O6—C6—C5	121.00 (13)	C18—C19—H19	119.1 (8)
O6—C6—C4^ii	118.01 (12)	C24—N3—C20	116.28 (13)
C5—C6—C4^ii	120.98 (13)	N3—C20—C21	123.58 (15)
C6—O6—H6	114.2 (9)	N3—C20—H20	116.0 (8)
C10—N1—C19	116.96 (13)	C21—C20—H20	120.5 (8)
N1—C10—C11	123.47 (15)	C20—C21—C22	120.20 (15)
N1—C10—H10	118.1 (9)	C20—C21—H21	119.0 (8)
C11—C10—H10	118.4 (9)	C22—C21—H21	120.7 (8)
C10—C11—C12	119.25 (15)	C21—C22—C23	116.14 (14)
C10—C11—H11	116.4 (8)	C21—C22—C22^iii	122.34 (16)
C12—C11—H11	124.3 (8)	C23—C22—C22^iii	121.52 (17)
C18—C12—C11	117.35 (14)	C24—C23—C22	119.76 (15)
C18—C12—C13	121.28 (13)	C24—C23—H23	121.3 (8)
C11—C12—C13	121.36 (13)	C22—C23—H23	118.8 (8)
C14—C13—C17	117.18 (13)	N3—C24—C23	124.02 (15)
C14—C13—C12	121.89 (13)	N3—C24—H24	114.7 (8)
C17—C13—C12	120.93 (13)	C23—C24—H24	121.3 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5	0.84 (2)	1.91 (2)	2.692 (2)	153 (2)
O3—H3···N1^iv	0.97 (2)	1.74 (2)	2.651 (2)	155 (1)
O5—H5···N2	0.88 (2)	1.79 (2)	2.635 (2)	161 (1)
O6—H6···N3	0.94 (2)	1.82 (2)	2.707 (2)	157 (1)
C14—H14···O2^v	0.94 (2)	2.36 (2)	3.268 (2)	158 (1)
C16—H16···O6	0.96 (1)	2.40 (1)	3.066 (2)	126 (1)
C18—H18···O4^vi	0.97 (1)	2.34 (2)	3.274 (2)	162 (1)

Symmetry codes: (iv) x+1, y+2, z; (v) x, y−1, z; (vi) x−1, y−1, z.