The binary adduct of 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2^11,14]triaconta-11,13,24,26(1),27,29-hexaene and benzene-1,2,4,5-tetracarboxylic acid

The crystals of the title salt, 6,21-di­aza-3,9,18,24-tetraazoniatri­cyclo­[22.2.2.2^11,14]­triaconta-11,13,24,26(1),27,29-hexaene benzene-1,2,4,5-tetra­carboxyl­ate(4-) hexahydrate, C₂₄H₄₂N₆⁴⁺·C₁₀H₂O₈^4-·6H₂O, are formed by the intermolecular interaction of a macrocyclic hex­amine with a mol­ecule of C₆H₂(COOH)₄ in aqueous solution. Both the cation and the anion are on inversion centres. Hydro­gen bonds are formed between the four ammonium cations in the hex­amine and the four carboxyl­ate anions in the aromatic acid. Stacks exist along the crystallographic a axis in the solid state. The water mol­ecules also take part in a hydrogen-bonding network which joins these stacks together.

S1. Comment

Macrocyclic compounds may form supramolecules if the stereochemistry of the donor atoms and the size and shape of the central cavity are suitable (Lehn, 1985, 1988). We are interested in the interplay of the covalent, ionic and hydrogen-bonding interactions that hold these supramolecules together, and in the dependence of these interactions on the conformation.

The inclusion properties of macrocyclic compounds can be adjusted by controlling the ring size. In the macrocyclic hexamine compound 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2^11,14]triaconta-11,13,24,26 (1),27,29- hexaene, designated L, the two identical diethylenetriamine moieties can be considered as two arms of the molecule, which can coordinate to transition metal ions to form binuclear (Zhu et al., 1998; Jurek & Martell, 1999) and tetranuclear (He et al., 2001) metal complexes. This macrocyclic hexamine also creates a supramolecule, through the intermolecular hydrogen bonding that water molecules form with the hexamine and with other water molecules (He et al., 2000). However, when metal ions are absent from the central cavity, the amino groups (as ammonium cations) become available for electrostatic interactions with carboxylic groups (as carboxylate anions) in a suitable molecule. Here, we show that the centrosymmetric hexamine L and C₆H₂(COOH)₄ form a salt, (I). \sch

The asymmetric unit of the triclinic cell of (I) contains one half of the tetraprotonated LH₄⁴⁺ cation, one half of the C₆H₂(COO)₄^4- anion and three water molecules. The cations adopt a chair-like conformation, with one diethylenetriamine moiety flipped down and the other flipped up. The hydrogen bonding, involving the H atoms at N1 and N3 in LH₄⁴⁺, and the O atoms in C₆H₂(COO)^4-, gives rise to aggregated stacks along the a axis (Fig. 1). The water molecules maintain hydrogen bonds that join the C₆H₂(COO)₄^4- ions of different stacks, yielding a three-dimensional network (Fig. 2). All bond lengths and angles in (I) agree well with the corresponding dimensions of the isolated macrocycle (He et al., 2000). The observed differences from the standard values can be attributed to the participation of some atoms in hydrogen bonding.

The structure of (I) shows that the LH₄⁴⁺ macrocycle adjusts its conformation in order to optimize ionic interactions with C₆H₂(COO)₄^4-.

S2. Experimental

The macrocyclic hexamine L was synthesized according to the procedure of Chen & Martell (1991). Needle-shaped single crystals of the title salt were obtained by mixing a 10 mM aqueous solution of L (1.44 ml) with a 20 mM aqueous solution of C₆H₂(COOH)₄ (0.36 µl) (molar ratio 2:1) and 2.00 M NaOH (3.6 ml). The total volume was 7.40 ml Please check - 1.44 + 3.6 = 5.04 ml. Similar crystals were also obtained using the binuclear Mg^II complex [LMg₂(OH)₂](ClO4)₂ instead of L, and mixing a 20 mM aqueous solution of [LMg₂(OH)₂](ClO₄)₂ (300 ml), a 20 mM aqueous solution of C₆H₂(COOH)₄ (150 µl) and water (250 ml). Spectroscopic analysis for (I): ¹H NMR (D₂O, δ, p.p.m.): 7.28 (s, 8H, ArH in LH₄⁴⁺), 4.11 (s, 8H, ArCH₂ in LH₄⁴⁺), 3.25 (t, 8H, NHCH₂ in LH₄⁴⁺), 3.03 (t, 8H, NHCH₂ in LH₄⁴⁺), 7.16 [s, 2H, ArCH in C₆H₂(COO)₄^4-].

S3. Refinement

H atoms involved in hydrogen bonding were located from a difference Fourier map and their positions and isotropic displacement parameters were refined. All other H atoms were introduced at calculated positions and refined riding on their carrier atoms.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the crystal structure of (I) showing the intermolecular interactions within a stack. Displacement ellipsoids are drawn at the 50% probability level. One of the water molecules, and H atoms not participating in these interactions, have been omitted for clarity.
	Fig. 2. The packing diagram for (I) viewed along the a axis. Only hydrogen bonds with H···A shorter than 2.40 Å are shown.

6,21-diaza-3,9,18,24-tetraazoniatricyclo[22.2.2.2^11,14]triaconta- 11,13,24,26 (1),27,29-hexaene benzene-1,2,4,5-tetracarboxylate hexahydrate

Crystal data

C24H42N6^4+·C10H2O8^4^−·6H2O	Z = 1
Mr = 772.85	F(000) = 414
Triclinic, P1	Dx = 1.434 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0983 (11) Å	Cell parameters from 3621 reflections
b = 9.3947 (15) Å	θ = 7–21°
c = 13.880 (2) Å	µ = 0.11 mm^−1
α = 87.686 (3)°	T = 298 K
β = 79.635 (3)°	Prism, black
γ = 79.498 (3)°	0.2 × 0.2 × 0.1 mm
V = 895.2 (2) Å^3

Data collection

Bruker SMART Query CCD area-detector diffractometer	1669 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 24.7°, θmin = 2.2°
ϕ and ω scans	h = −8→8
4531 measured reflections	k = −10→11
3011 independent reflections	l = −16→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.039P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max < 0.001
3011 reflections	Δρmax = 0.22 e Å^−3
293 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (2)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8509 (4)	0.7251 (3)	−0.0640 (2)	0.0211 (7)
H1A	0.8891	0.6357	−0.0947	0.025*
C2	0.8155 (4)	0.7308 (3)	0.0367 (2)	0.0226 (8)
H2A	0.8290	0.6453	0.0729	0.027*
C3	0.7603 (4)	0.8614 (3)	0.0846 (2)	0.0216 (7)
C4	0.7382 (5)	0.9867 (3)	0.0290 (2)	0.0310 (9)
H4A	0.6995	1.0758	0.0600	0.037*
C5	0.7725 (5)	0.9816 (3)	−0.0711 (2)	0.0310 (9)
H5A	0.7568	1.0674	−0.1069	0.037*
C6	0.8305 (4)	0.8501 (3)	−0.1204 (2)	0.0201 (7)
C7	0.8718 (4)	0.8484 (3)	−0.2298 (2)	0.0245 (8)
H7A	0.7508	0.8773	−0.2543	0.029*
H7B	0.9551	0.9182	−0.2535	0.029*
C8	1.0187 (4)	0.6984 (3)	−0.3769 (2)	0.0248 (8)
H8A	1.0968	0.7715	−0.4001	0.030*
H8B	0.9005	0.7196	−0.4047	0.030*
C9	0.7303 (5)	0.8729 (3)	0.1941 (2)	0.0256 (8)
H9A	0.8492	0.8903	0.2129	0.031*
H9B	0.6287	0.9552	0.2151	0.031*
C10	0.6379 (4)	0.7524 (3)	0.35371 (19)	0.0245 (8)
H10A	0.5416	0.8380	0.3738	0.029*
H10B	0.7569	0.7612	0.3762	0.029*
C11	0.5646 (4)	0.6183 (3)	0.3985 (2)	0.0228 (8)
H11B	0.5504	0.6213	0.4693	0.027*
H11C	0.4380	0.6159	0.3822	0.027*
C12	0.8703 (4)	0.4480 (3)	0.4100 (2)	0.0246 (8)
H12B	0.8277	0.4467	0.4804	0.030*
H12C	0.9545	0.5194	0.3946	0.030*
C13	0.3519 (4)	0.6153 (3)	−0.0037 (2)	0.0168 (7)
C14	0.3762 (4)	0.5523 (3)	0.0870 (2)	0.0162 (7)
C15	0.2411 (4)	0.6218 (3)	0.1773 (2)	0.0174 (7)
C16	0.5260 (4)	0.4341 (3)	0.09131 (19)	0.0164 (7)
C17	0.5522 (5)	0.3541 (3)	0.1858 (2)	0.0191 (7)
H13	0.249 (4)	0.691 (3)	−0.0032 (16)	0.015 (8)*
H31N	0.893 (5)	0.640 (3)	−0.246 (2)	0.050 (12)*
H32N	1.103 (7)	0.669 (5)	−0.231 (3)	0.123 (17)*
H21N	0.628 (4)	0.408 (3)	0.3642 (19)	0.033 (9)*
H11N	0.566 (5)	0.714 (3)	0.223 (2)	0.035 (10)*
H12N	0.793 (5)	0.659 (3)	0.226 (2)	0.060 (11)*
H11W	0.165 (8)	0.771 (6)	0.327 (4)	0.16 (2)*
H12W	0.138 (5)	0.862 (3)	0.415 (2)	0.021 (11)*
H21W	0.149 (5)	0.040 (4)	0.550 (2)	0.062 (13)*
H22W	0.308 (6)	0.049 (4)	0.473 (3)	0.076 (15)*
H31W	0.462 (5)	0.226 (4)	0.347 (3)	0.071 (14)*
H32W	0.573 (5)	0.125 (4)	0.404 (2)	0.042 (12)*
N1	0.6755 (4)	0.7405 (3)	0.24451 (17)	0.0196 (6)
N2	0.7009 (4)	0.4883 (3)	0.36169 (17)	0.0211 (6)
N3	0.9681 (4)	0.7029 (3)	−0.26820 (18)	0.0204 (6)
O1	0.0740 (3)	0.5913 (2)	0.19808 (13)	0.0225 (5)
O2	0.3060 (3)	0.7094 (2)	0.22321 (14)	0.0226 (5)
O3	0.4079 (3)	0.3672 (2)	0.25511 (13)	0.0233 (5)
O4	0.7130 (3)	0.2751 (2)	0.18966 (13)	0.0238 (5)
O5	0.0755 (4)	0.8297 (3)	0.38912 (19)	0.0371 (7)
O6	0.2412 (4)	−0.0139 (2)	0.51266 (18)	0.0292 (6)
O7	0.4589 (4)	0.1539 (3)	0.39240 (19)	0.0431 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0182 (18)	0.0184 (17)	0.0263 (19)	−0.0021 (14)	−0.0035 (14)	−0.0036 (14)
C2	0.026 (2)	0.0186 (17)	0.0233 (18)	−0.0077 (14)	−0.0017 (15)	0.0041 (14)
C3	0.0218 (19)	0.0231 (17)	0.0196 (18)	−0.0080 (14)	0.0013 (15)	0.0002 (14)
C4	0.041 (2)	0.0190 (18)	0.029 (2)	−0.0023 (15)	0.0029 (17)	−0.0036 (15)
C5	0.037 (2)	0.0197 (18)	0.032 (2)	0.0005 (16)	−0.0020 (17)	0.0071 (15)
C6	0.0146 (17)	0.0219 (17)	0.0239 (18)	−0.0061 (14)	−0.0012 (14)	0.0007 (14)
C7	0.0231 (19)	0.0201 (17)	0.0302 (19)	−0.0020 (14)	−0.0059 (15)	−0.0008 (14)
C8	0.0248 (19)	0.0291 (19)	0.0202 (18)	−0.0053 (15)	−0.0032 (15)	0.0030 (14)
C9	0.031 (2)	0.0225 (17)	0.0234 (18)	−0.0124 (15)	0.0010 (16)	0.0016 (14)
C10	0.0220 (19)	0.0273 (18)	0.0220 (18)	−0.0028 (15)	0.0018 (15)	−0.0048 (14)
C11	0.0182 (18)	0.0281 (18)	0.0202 (17)	−0.0041 (14)	0.0019 (14)	−0.0013 (14)
C12	0.0227 (19)	0.0300 (18)	0.0220 (17)	−0.0084 (15)	−0.0026 (15)	0.0002 (14)
C13	0.0101 (17)	0.0152 (16)	0.0243 (18)	−0.0025 (14)	−0.0009 (14)	0.0002 (14)
C14	0.0148 (17)	0.0171 (16)	0.0194 (17)	−0.0104 (13)	−0.0026 (13)	−0.0019 (13)
C15	0.0193 (19)	0.0165 (16)	0.0151 (17)	−0.0022 (14)	−0.0021 (14)	0.0050 (13)
C16	0.0150 (17)	0.0177 (16)	0.0185 (17)	−0.0087 (13)	−0.0023 (14)	−0.0022 (13)
C17	0.023 (2)	0.0164 (16)	0.0199 (18)	−0.0065 (15)	−0.0058 (15)	0.0003 (13)
N1	0.0206 (17)	0.0220 (15)	0.0158 (14)	−0.0051 (13)	−0.0005 (13)	−0.0018 (11)
N2	0.0207 (16)	0.0226 (15)	0.0201 (14)	−0.0055 (12)	−0.0020 (12)	−0.0017 (12)
N3	0.0221 (17)	0.0194 (15)	0.0188 (15)	−0.0074 (13)	0.0019 (13)	0.0016 (12)
O1	0.0170 (12)	0.0267 (12)	0.0230 (12)	−0.0067 (10)	0.0020 (10)	−0.0029 (9)
O2	0.0222 (13)	0.0256 (12)	0.0203 (12)	−0.0077 (10)	0.0002 (10)	−0.0067 (9)
O3	0.0174 (12)	0.0323 (13)	0.0178 (12)	−0.0049 (10)	0.0027 (10)	0.0055 (9)
O4	0.0200 (13)	0.0268 (12)	0.0238 (12)	0.0007 (10)	−0.0068 (10)	−0.0005 (9)
O5	0.0237 (15)	0.0521 (17)	0.0361 (16)	−0.0087 (13)	−0.0005 (13)	−0.0194 (13)
O6	0.0238 (15)	0.0307 (14)	0.0323 (15)	−0.0050 (12)	−0.0018 (12)	−0.0058 (12)
O7	0.0320 (18)	0.0575 (19)	0.0400 (17)	−0.0117 (14)	−0.0086 (14)	0.0251 (14)

Geometric parameters (Å, º)

C1—C2	1.376 (4)	C11—H11C	0.9700
C1—C6	1.384 (4)	C12—N2	1.463 (4)
C1—H1A	0.9300	C12—C8^i	1.500 (3)
C2—C3	1.377 (4)	C12—H12B	0.9700
C2—H2A	0.9300	C12—H12C	0.9700
C3—C4	1.382 (4)	C13—C14	1.394 (4)
C3—C9	1.502 (4)	C13—C16^ii	1.402 (3)
C4—C5	1.367 (4)	C13—H13	0.92 (2)
C4—H4A	0.9300	C14—C16	1.398 (4)
C5—C6	1.395 (4)	C14—C15	1.524 (4)
C5—H5A	0.9300	C15—O1	1.251 (3)
C6—C7	1.495 (4)	C15—O2	1.258 (3)
C7—N3	1.486 (3)	C16—C13^ii	1.402 (3)
C7—H7A	0.9700	C16—C17	1.509 (4)
C7—H7B	0.9700	C17—O4	1.252 (3)
C8—N3	1.487 (3)	C17—O3	1.265 (3)
C8—C12^i	1.500 (4)	N1—H11N	0.96 (3)
C8—H8A	0.9700	N1—H12N	1.03 (3)
C8—H8B	0.9700	N2—H21N	0.99 (3)
C9—N1	1.483 (3)	N3—H31N	0.88 (3)
C9—H9A	0.9700	N3—H32N	1.16 (5)
C9—H9B	0.9700	O5—H11W	1.08 (5)
C10—N1	1.496 (3)	O5—H12W	0.73 (3)
C10—C11	1.518 (4)	O6—H21W	0.85 (3)
C10—H10A	0.9700	O6—H22W	0.92 (4)
C10—H10B	0.9700	O7—H31W	0.91 (4)
C11—N2	1.460 (3)	O7—H32W	0.84 (3)
C11—H11B	0.9700
C2—C1—C6	121.1 (3)	C10—C11—H11B	109.6
C2—C1—H1A	119.4	N2—C11—H11C	109.6
C6—C1—H1A	119.4	C10—C11—H11C	109.6
C3—C2—C1	121.0 (3)	H11B—C11—H11C	108.1
C3—C2—H2A	119.5	N2—C12—C8^i	110.5 (2)
C1—C2—H2A	119.5	N2—C12—H12B	109.5
C2—C3—C4	118.3 (3)	C8^i—C12—H12B	109.5
C2—C3—C9	122.7 (3)	N2—C12—H12C	109.5
C4—C3—C9	119.0 (3)	C8^i—C12—H12C	109.5
C5—C4—C3	120.9 (3)	H12B—C12—H12C	108.1
C5—C4—H4A	119.5	C14—C13—C16^ii	122.5 (3)
C3—C4—H4A	119.5	C14—C13—H13	116.2 (15)
C4—C5—C6	121.2 (3)	C16^ii—C13—H13	121.3 (15)
C4—C5—H5A	119.4	C13—C14—C16	119.2 (2)
C6—C5—H5A	119.4	C13—C14—C15	117.3 (2)
C1—C6—C5	117.4 (3)	C16—C14—C15	123.4 (2)
C1—C6—C7	122.7 (3)	O1—C15—O2	125.3 (3)
C5—C6—C7	119.9 (3)	O1—C15—C14	118.1 (3)
N3—C7—C6	111.8 (2)	O2—C15—C14	116.6 (3)
N3—C7—H7A	109.3	C14—C16—C13^ii	118.3 (2)
C6—C7—H7A	109.3	C14—C16—C17	122.1 (2)
N3—C7—H7B	109.3	C13^ii—C16—C17	119.5 (2)
C6—C7—H7B	109.3	O4—C17—O3	124.0 (3)
H7A—C7—H7B	107.9	O4—C17—C16	118.1 (3)
N3—C8—C12^i	110.4 (2)	O3—C17—C16	117.8 (3)
N3—C8—H8A	109.6	C9—N1—C10	112.9 (2)
C12^i—C8—H8A	109.6	C9—N1—H11N	111.8 (17)
N3—C8—H8B	109.6	C10—N1—H11N	110.4 (17)
C12^i—C8—H8B	109.6	C9—N1—H12N	106.0 (18)
H8A—C8—H8B	108.1	C10—N1—H12N	107.4 (17)
N1—C9—C3	112.3 (2)	H11N—N1—H12N	108 (2)
N1—C9—H9A	109.1	C11—N2—C12	115.8 (2)
C3—C9—H9A	109.1	C11—N2—H21N	108.3 (16)
N1—C9—H9B	109.1	C12—N2—H21N	111.1 (17)
C3—C9—H9B	109.1	C7—N3—C8	113.4 (2)
H9A—C9—H9B	107.9	C7—N3—H31N	109 (2)
N1—C10—C11	109.1 (2)	C8—N3—H31N	111 (2)
N1—C10—H10A	109.9	C7—N3—H32N	106 (2)
C11—C10—H10A	109.9	C8—N3—H32N	113 (2)
N1—C10—H10B	109.9	H31N—N3—H32N	104 (3)
C11—C10—H10B	109.9	H11W—O5—H12W	109 (4)
H10A—C10—H10B	108.3	H21W—O6—H22W	106 (3)
N2—C11—C10	110.1 (2)	H31W—O7—H32W	109 (3)
N2—C11—H11B	109.6
C6—C1—C2—C3	−0.6 (5)	C16—C14—C15—O1	−101.6 (3)
C1—C2—C3—C4	1.0 (5)	C13—C14—C15—O2	−96.7 (3)
C1—C2—C3—C9	−176.8 (3)	C16—C14—C15—O2	80.6 (3)
C2—C3—C4—C5	−0.8 (5)	C13—C14—C16—C13^ii	0.9 (4)
C9—C3—C4—C5	177.1 (3)	C15—C14—C16—C13^ii	−176.4 (3)
C3—C4—C5—C6	0.1 (5)	C13—C14—C16—C17	−175.6 (3)
C2—C1—C6—C5	−0.1 (4)	C15—C14—C16—C17	7.1 (4)
C2—C1—C6—C7	178.6 (3)	C14—C16—C17—O4	−162.4 (3)
C4—C5—C6—C1	0.4 (5)	C13^ii—C16—C17—O4	21.2 (4)
C4—C5—C6—C7	−178.4 (3)	C14—C16—C17—O3	19.9 (4)
C1—C6—C7—N3	−10.0 (4)	C13^ii—C16—C17—O3	−156.5 (3)
C5—C6—C7—N3	168.7 (3)	C3—C9—N1—C10	−177.9 (2)
C2—C3—C9—N1	−26.7 (4)	C11—C10—N1—C9	174.7 (2)
C4—C3—C9—N1	155.5 (3)	C10—C11—N2—C12	81.5 (3)
N1—C10—C11—N2	54.5 (3)	C8^i—C12—N2—C11	171.1 (2)
C16^ii—C13—C14—C16	−0.9 (5)	C6—C7—N3—C8	−177.7 (2)
C16^ii—C13—C14—C15	176.5 (3)	C12^i—C8—N3—C7	175.3 (3)
C13—C14—C15—O1	81.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31N···O3^ii	0.88 (3)	2.17 (4)	2.837 (4)	132 (3)
N3—H31N···O1^ii	0.88 (3)	2.23 (3)	2.942 (3)	138 (3)
N3—H32N···O4^i	1.16 (5)	1.69 (5)	2.726 (3)	146 (4)
N1—H11N···O2	0.96 (3)	1.85 (3)	2.759 (4)	157 (2)
N1—H12N···O1^iii	1.03 (3)	1.95 (3)	2.891 (3)	151 (3)
O5—H11W···O2	1.08 (5)	1.66 (5)	2.727 (3)	170 (5)
O5—H12W···O6^iv	0.73 (3)	2.12 (3)	2.835 (4)	163 (3)
O6—H21W···O5^v	0.85 (3)	1.91 (4)	2.753 (3)	169 (3)
O5—H11W···O2	1.08 (5)	1.66 (5)	2.727 (3)	170 (5)
O6—H22W···O7	0.92 (4)	1.80 (4)	2.722 (4)	174 (3)
O7—H31W···O3	0.91 (4)	1.83 (4)	2.730 (3)	166 (4)
O7—H31W···O4	0.91 (4)	2.64 (4)	3.337 (3)	134 (3)
O7—H32W···O6^vi	0.84 (3)	2.03 (3)	2.801 (4)	151 (3)

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