Two isomorphous crotonatolanthanide complexes: tetra-μ-but-2-enoato-bis­[diaqua­(but-2-enoato)Ln]–2,6-diamino­purine (1/2) (Ln = Dy and Ho)

The title isomorphous compounds, tetra-μ-but-2-enoato-bis­[diaqua­(but-2-enoato)dysprosium(III)]–2,6-diamino­purine (1/2), [Dy₂(C₄H₅O₂)₆(H₂O)₄]·2C₅H₆N₆, and tetra-μ-but-2-enoato-bis­[diaqua­(but-2-enoato)holmium(III)]–2,6-diaminopurine (1/2), [Ho₂(C₄H₅O₂)₆(H₂O)₄]·2C₅H₆N₆, consist of [Ln(crot)₃(H₂O)₂]₂ dimers (crot is crotonate or but-2-enoate; Ln is the lanthanide cation), built up around inversion centres and completed by 2,6-diamino­purine mol­ecules. The lanthanide cation is coordinated by three chelating crotonate units and two water mol­ecules. One of the chelating carboxyl­ate groups acts also in a bridging mode sharing one O atom with both cations and the final result is a pair of DyO₉ tricapped prismatic polyhedra linked to each other through a central (Dy—O)₂ loop. A feature of the structures is the existence of a complex inter­molecular inter­action scheme involving two sets of tightly inter­linked non-inter­secting one-dimensional structures, one of them formed by the [Dy(crot)₃(H₂O)₂]₂ dimers (running along [100] and linked by O—H...O hydrogen bonds) and the second formed by 2,6-diamino­purine mol­ecules (evolving along [010] linked by N—H...N hydrogen bonds).

S1. Comment

We report here structural work on two isomorphous Ln complexes, formulated as [Ln(crot)₃(H₂O)₂]₂.2(dap) [crot is crotonate or but-2-enoate, C₄H₅O₂; dap is 2,6-diaminopurine, C₅H₆N₆; and Ln = Dy for compound (I) and Ho for (II)]. These are the first cases in which a free unsubstituted 2,6-diaminopurine molecule is reported to take part in a crystal structure, although some closely related substituted analogues have already been the subject of structural work (Singh & Hodgson, 1975; Simundza et al., 1970; Sakore et al., 1969 etc.). For the sake of simplicity we shall only describe the Dy isologue, (I), as representative of the pair of compounds, but numerical data for both compounds are freely available in the archived CIF.

The structure for the Dy complex, shown in Fig. 1, consists of [Dy(crot)₃(H₂O)₂]₂ dimers, along with 2,6-diaminopurine molecules. The dimer is build up around an inversion centre. The unique Dy cation is coordinated by three chelating crotonate units and two water molecules. One of the O atoms (O23) from one of the crotonate carboxylate groups acts also in a bridging mode, and the result is a pair of DyO₉ polyhedra [with Dy—O distances in the range 2.3457 (17) to 2.5257 (17) Å] presenting a tricapped prismatic coordination geometry linked to form a dimer through a central (Dy—O)₂ loop leading to a Dy···Dy distance of 4.0407 (2) Å. This type of carboxylate-linked [Ln(COO)₃(H₂O)₂]₂ dimer is well known in the literature: we could trace 36 of them in a Cambridge Structural Database search (CSD; 2009 Version; Allen, 2002), the vast majority (22 cases) with acetate and only one (an isomorphous family) with butenoate (Rizzi et al., 2003, Atria et al., 2006). The dimers are further linked by hydrogen bonding (see below).

The dimensions of the crotonate ligands and 2,6-diaminepurine molecule are normal, with non-H atoms in the latter one laying in a plane (within experimental error). The most significant deviation from planarity is to be found in the amine H atoms, with a conspicuous pyramidal arrangement around N2 (evidencing an N-atom hybridization with a significan sp³ contribution) and a rather flattened one in N6 (suggesting a predominat sp² character). If N-pyramidality is measured by χ_N (the angle between the C—N vector and the NH₂ plane; Allen et al., 1995), for which the ideal values are 0 (for pure sp²) and 54.7° (for pure sp³), the corresponding values for both N atoms in the case of (I) are χ_N2 = 42.3° (mostly sp³) and χ_N6 = 15.5° (mostly sp²). This is consistent with the C2—N2 bond length [1.360 (3)Å] being longer than the C6—N6 bond length [1.346 (3)Å], suggesting a smaller delocalization in the former. The existence of a large number of efficient hydrogen-bonding donors and acceptors in the structure leads to a complex intermolecular interaction scheme involving two sets of tightly interlinked, non-intersecting hydrogen-bonded one-dimensional structures, one of them running along the crystallographic a-axis direction and formed by the [Dy(crot)₃(H₂O)₂]₂ dimers, the second evolving along the b-axis direction and formed by 2,6-diaminopurine molecules.

Both types of chains embed two sets of inversion centres. In the case of the dimeric chain shown in Fig. 2, the same centre (site A1) that relates the two molecules in the dimer through a four-atom coordination loop also links them through an R₂²(8) hydrogen-bonded ring (Bernstein et al., 1995), almost at right angles to the former loop, via O1W—H1WA···O11ⁱ hydrogen bonds (Table 1). The second centre (site A2) links neighbouring dimers into chains through two centrosymmetric R₂²(8) motifs involving O1W—H1WB···O2W^v and O2W—H2A···O12^v hydrogen bonds (Table 1) as well as two non-centrosymmetric R₂²(6) motifs. A much simpler situation arises in the 2,6-diaminopurine chain (Fig. 3), which also utilizes two independent inversion centres and gives rise to two almost identical centrosymmetric R₂²(8) motifs involving N2—H2A···N3^iv and N6—H8A···N1ⁱⁱⁱ hydrogen bonds, denoted as B1 and B2 in Fig. 3.

The two perpendicular, non-intersecting families of chains (the `dimeric' one, running parallel to [100] at y ≈ z ≈ 0, and the 2,6-diaminopurine one, parallel to [010] at x ≈ z ≈ 1/2) interact at their point of maximal approach through a variety of hydrogen bonds in which there are donors and acceptors on both sides (Fig. 3 and Table 1). These hydrogen bonds give rise to three noncentrosymmetric (sites C1, C3 and C4 in Fig. 3) and one centrosymmetric (site C2) hydrogen-bonded rings, with graph-set descriptors R₄⁴(14), R₂²(7), R₃²(9), R₃³(12) and R₄⁴(14), respectively.

There are also inter-dimeric interactions of the π–π type mediated by symmetry-related crotonate double bonds, as in the case between C21═C31 and its (-x, -y + 1, -z) image, characterized by an intercentroid distance of 3.588 (1) Å and a slippage angle of 26.6 (1)°. These interactions link along the [001] direction the dimeric chains that run along [100].

Related literature

For related literature, see: Allen (2002); Atria et al. (2006); Bernstein et al. (1995); Rizzi et al. (2003); Sakore et al. (1969); Simundza et al. (1970); Singh & Hodgson (1975).

S2. Experimental

Complexes (I) and (II) were synthesized by similar methods: a mixture of Ln₂O₃ (Ln = Dy or Ho, 1 mmol) and crotonic acid (3 mmol) was dissolved in water (100 mmol), and then the 2,6-diaminopurine ligand (1 mmol) dissolved in methanol (10 ml) was added. The resulting mixture was refluxed for 24 h, filtered while hot and then concentrated to 25 ml. The filtrate was left at room temperature. On standing, colorless crystals suitable for single-crystal X-ray diffraction appeared, which were used without further processing.

S3. Refinement

All H atoms were clearly seen in a difference Fourier; C—H and (non-amino) N—H groups were, however, subsequently idealized at their expected positions and allowed to ride (C—H = 0.93–0.98Å and N–H = 0.88Å). Amino N atoms were in a partially hybridized state, N6 being mostly sp² and N2 being mostly sp³; the corresponding H-atom geometry around them followed this scheme with a distorted planar environment around N6 and an important pyramidalization around N2. These H atoms, as well as those corresponding to water molecules, were refined with metric restraints for a few cycles, after which they were allowed to ride. For all H atoms, isotropic displacement factors were taken as U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C).

Computing details

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. : A displacement ellipsoid plot of (I), drawn at the 40% probability level, with independent (symmetry-related) atoms indicated by bold (fine) bonds and filled (empty) ellipsoids. [Symmetry code: (i) -x, -y, -z.]
	Fig. 2. : A view of the packing of (I), projected down c, showing the `dimeric' chains and their internal hydrogen-bonding linkage (see text). For clarity, only the carboxylate end of the butenoate units have been drawn. [Symmetry codes: (i) -x, -y, -z; (v) -x + 1, -y, -z.]
	Fig. 3. : A view of the packing of (I), projected along the a axis, showing on the projection plane (running vertically, in hollow bonds) the `solvate' chains. The `dimeric' chains are perpendicular to the latter and are shown coming out of the plane (in bold, full bonds). Intra- and inter-chain hydrogen bonds are shown as broken lines. For clarity, only the carboxylate ends of the butenoate units have been drawn. [Symmetry codes: (i) -x, -y, -z; (ii) x, y + 1, z; (iii) -x + 1, -y + 2, -z + 1; (iv) -x + 1, -y + 1, -z + 1; (v) -x + 1, -y, -z; (vi) -x + 1, -y + 1, -z; (vii) x - 1, y - 1, z.]

(I) tetra-µ-but-2-enoato-bis[diaqua(µ₂-but-2-enoato)dysprosium(III)]–2,6- diaminopurine (1/2)

Crystal data

[Dy2(C4H5O2)6(H2O)4]·2C5H6N6	Z = 1
Mr = 1207.86	F(000) = 598
Triclinic, P1	Dx = 1.792 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6441 (2) Å	Cell parameters from 4220 reflections
b = 11.1173 (3) Å	θ = 1.9–25.7°
c = 13.3944 (3) Å	µ = 3.39 mm^−1
α = 101.234 (2)°	T = 150 K
β = 107.521 (3)°	Block, colourless
γ = 106.587 (2)°	0.18 × 0.12 × 0.10 mm
V = 1119.51 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4676 independent reflections
Radiation source: fine-focus sealed tube	4487 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
phi and ω scans	θmax = 27.8°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→10
Tmin = 0.60, Tmax = 0.71	k = −14→14
9254 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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.047	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0249P)^2 + 0.9935P] where P = (Fo^2 + 2Fc^2)/3
4676 reflections	(Δ/σ)max = 0.001
292 parameters	Δρmax = 1.43 e Å^−3
0 restraints	Δρmin = −0.57 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.

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

	x	y	z	Uiso*/Ueq
Dy1	0.257311 (13)	0.111249 (10)	0.062817 (8)	0.01299 (4)
O11	0.1170 (2)	0.25418 (16)	0.11431 (14)	0.0173 (3)
O21	0.2650 (2)	0.31148 (17)	0.01214 (14)	0.0186 (4)
C11	0.1808 (3)	0.3380 (2)	0.0702 (2)	0.0163 (5)
C21	0.1601 (3)	0.4664 (2)	0.0901 (2)	0.0205 (5)
H21	0.1926	0.5224	0.0488	0.025*
C31	0.0976 (4)	0.5061 (3)	0.1640 (2)	0.0253 (6)
H31	0.0601	0.4460	0.2012	0.030*
C41	0.0810 (4)	0.6370 (3)	0.1938 (3)	0.0348 (7)
H41A	0.1285	0.6912	0.1526	0.052*
H41B	0.1458	0.6814	0.2729	0.052*
H41C	−0.0424	0.6245	0.1755	0.052*
O12	0.5466 (2)	0.09731 (17)	0.16405 (14)	0.0187 (4)
O22	0.5166 (2)	0.28831 (16)	0.19531 (14)	0.0187 (4)
C12	0.6126 (3)	0.2203 (2)	0.2119 (2)	0.0167 (5)
C22	0.7970 (3)	0.2890 (3)	0.2868 (2)	0.0251 (6)
H22	0.8344	0.3799	0.3254	0.030*
C32	0.9119 (4)	0.2331 (3)	0.3033 (2)	0.0282 (6)
H32	0.8724	0.1415	0.2660	0.034*
C42	1.1011 (4)	0.3009 (4)	0.3761 (3)	0.0379 (7)
H42A	1.1223	0.3910	0.4172	0.057*
H42B	1.1719	0.3036	0.3310	0.057*
H42C	1.1328	0.2524	0.4278	0.057*
O13	0.2538 (2)	0.07059 (17)	0.23275 (14)	0.0176 (3)
O23	0.0012 (2)	−0.02447 (16)	0.09435 (13)	0.0160 (3)
C13	0.0967 (3)	−0.0049 (2)	0.19510 (19)	0.0147 (5)
C23	0.0180 (3)	−0.0758 (2)	0.2606 (2)	0.0184 (5)
H23	−0.1026	−0.1294	0.2283	0.022*
C33	0.1084 (3)	−0.0677 (3)	0.3621 (2)	0.0205 (5)
H33	0.2262	−0.0078	0.3950	0.025*
C43	0.0401 (4)	−0.1454 (3)	0.4297 (2)	0.0277 (6)
H43A	−0.0839	−0.1993	0.3884	0.042*
H43B	0.0543	−0.0849	0.4985	0.042*
H43C	0.1052	−0.2029	0.4464	0.042*
O1W	0.2293 (2)	−0.11385 (17)	−0.00070 (15)	0.0203 (4)
H1WA	0.1304	−0.1717	−0.0430	0.024*
H1WB	0.3110	−0.1412	0.0009	0.024*
O2W	0.4087 (2)	0.11358 (17)	−0.05853 (15)	0.0190 (4)
H2WA	0.4032	0.0383	−0.0904	0.023*
H2WB	0.4129	0.1620	−0.0999	0.023*
N1	0.5034 (3)	0.8160 (2)	0.45832 (17)	0.0185 (4)
C2	0.4950 (3)	0.6955 (3)	0.4701 (2)	0.0189 (5)
N2	0.4658 (3)	0.6733 (2)	0.56031 (19)	0.0258 (5)
H2A	0.4847	0.6047	0.5770	0.031*
H2B	0.5141	0.7464	0.6161	0.031*
N3	0.5091 (3)	0.5967 (2)	0.40318 (17)	0.0181 (4)
C4	0.5358 (3)	0.6285 (2)	0.3163 (2)	0.0155 (5)
C5	0.5447 (3)	0.7457 (2)	0.2926 (2)	0.0171 (5)
C6	0.5281 (3)	0.8431 (2)	0.3691 (2)	0.0170 (5)
N6	0.5406 (3)	0.9634 (2)	0.35924 (19)	0.0224 (5)
H6A	0.5231	1.0186	0.4075	0.027*
H6B	0.5357	0.9757	0.2956	0.027*
N7	0.5749 (3)	0.7412 (2)	0.19575 (18)	0.0190 (4)
C8	0.5844 (3)	0.6242 (2)	0.1645 (2)	0.0196 (5)
H8	0.6038	0.5930	0.0998	0.024*
N9	0.5633 (3)	0.5532 (2)	0.23454 (17)	0.0178 (4)
H9	0.5668	0.4738	0.2285	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Dy1	0.01263 (6)	0.01285 (6)	0.01376 (6)	0.00496 (4)	0.00504 (4)	0.00418 (4)
O11	0.0185 (9)	0.0146 (8)	0.0212 (9)	0.0069 (7)	0.0096 (7)	0.0062 (7)
O21	0.0212 (9)	0.0184 (9)	0.0191 (9)	0.0085 (7)	0.0096 (7)	0.0069 (7)
C11	0.0116 (11)	0.0165 (11)	0.0155 (11)	0.0040 (9)	0.0006 (9)	0.0024 (9)
C21	0.0188 (12)	0.0154 (12)	0.0252 (13)	0.0067 (10)	0.0049 (10)	0.0067 (10)
C31	0.0244 (14)	0.0219 (13)	0.0275 (14)	0.0105 (11)	0.0063 (11)	0.0055 (11)
C41	0.0339 (16)	0.0269 (15)	0.0398 (18)	0.0184 (13)	0.0080 (14)	0.0006 (13)
O12	0.0177 (9)	0.0178 (9)	0.0212 (9)	0.0084 (7)	0.0072 (7)	0.0048 (7)
O22	0.0172 (8)	0.0141 (8)	0.0219 (9)	0.0054 (7)	0.0047 (7)	0.0044 (7)
C12	0.0160 (12)	0.0202 (12)	0.0146 (11)	0.0057 (9)	0.0077 (9)	0.0058 (9)
C22	0.0165 (13)	0.0285 (14)	0.0223 (14)	0.0033 (11)	0.0039 (11)	0.0039 (11)
C32	0.0225 (14)	0.0351 (16)	0.0259 (14)	0.0097 (12)	0.0079 (12)	0.0104 (12)
C42	0.0213 (15)	0.056 (2)	0.0341 (17)	0.0137 (14)	0.0058 (13)	0.0162 (15)
O13	0.0141 (8)	0.0192 (9)	0.0170 (9)	0.0035 (7)	0.0041 (7)	0.0070 (7)
O23	0.0164 (8)	0.0167 (8)	0.0147 (8)	0.0064 (7)	0.0047 (7)	0.0058 (7)
C13	0.0175 (12)	0.0150 (11)	0.0150 (11)	0.0088 (9)	0.0079 (9)	0.0043 (9)
C23	0.0156 (12)	0.0181 (12)	0.0214 (13)	0.0040 (9)	0.0077 (10)	0.0081 (10)
C33	0.0202 (12)	0.0207 (13)	0.0203 (13)	0.0062 (10)	0.0093 (10)	0.0052 (10)
C43	0.0309 (15)	0.0316 (15)	0.0240 (14)	0.0090 (12)	0.0130 (12)	0.0154 (12)
O1W	0.0149 (8)	0.0162 (9)	0.0276 (10)	0.0059 (7)	0.0069 (7)	0.0033 (7)
O2W	0.0266 (9)	0.0160 (8)	0.0217 (9)	0.0113 (7)	0.0133 (8)	0.0096 (7)
N1	0.0198 (11)	0.0192 (10)	0.0168 (10)	0.0075 (8)	0.0067 (8)	0.0061 (8)
C2	0.0161 (12)	0.0219 (13)	0.0180 (12)	0.0053 (10)	0.0059 (10)	0.0080 (10)
N2	0.0363 (13)	0.0235 (12)	0.0209 (11)	0.0123 (10)	0.0124 (10)	0.0094 (9)
N3	0.0184 (10)	0.0175 (10)	0.0175 (10)	0.0056 (8)	0.0054 (8)	0.0074 (8)
C4	0.0126 (11)	0.0144 (11)	0.0167 (12)	0.0029 (9)	0.0040 (9)	0.0045 (9)
C5	0.0144 (11)	0.0181 (12)	0.0164 (12)	0.0035 (9)	0.0045 (9)	0.0061 (10)
C6	0.0135 (11)	0.0157 (11)	0.0193 (12)	0.0040 (9)	0.0039 (9)	0.0058 (10)
N6	0.0314 (12)	0.0201 (11)	0.0227 (11)	0.0138 (10)	0.0136 (10)	0.0100 (9)
N7	0.0205 (11)	0.0166 (10)	0.0210 (11)	0.0060 (8)	0.0097 (9)	0.0065 (9)
C8	0.0198 (12)	0.0203 (12)	0.0194 (12)	0.0057 (10)	0.0098 (10)	0.0064 (10)
N9	0.0208 (11)	0.0140 (10)	0.0190 (10)	0.0065 (8)	0.0081 (9)	0.0050 (8)

Geometric parameters (Å, º)

Dy1—O23^i	2.3455 (16)	C13—C23	1.475 (3)
Dy1—O2W	2.3733 (17)	C23—C33	1.319 (4)
Dy1—O11	2.3770 (16)	C23—H23	0.9500
Dy1—O1W	2.3969 (17)	C33—C43	1.500 (4)
Dy1—O22	2.4025 (17)	C33—H33	0.9500
Dy1—O13	2.4126 (17)	C43—H43A	0.9800
Dy1—O21	2.4397 (17)	C43—H43B	0.9800
Dy1—O23	2.5021 (16)	C43—H43C	0.9800
Dy1—O12	2.5256 (17)	O1W—H1WA	0.8474
O11—C11	1.281 (3)	O1W—H1WB	0.8415
O21—C11	1.262 (3)	O2W—H2WA	0.8435
C11—C21	1.472 (3)	O2W—H2WB	0.8453
C21—C31	1.324 (4)	N1—C6	1.349 (3)
C21—H21	0.9500	N1—C2	1.363 (3)
C31—C41	1.493 (4)	C2—N3	1.335 (3)
C31—H31	0.9500	C2—N2	1.360 (3)
C41—H41A	0.9800	N2—H2A	0.8800
C41—H41B	0.9800	N2—H2B	0.8800
C41—H41C	0.9800	N3—C4	1.344 (3)
O12—C12	1.265 (3)	C4—N9	1.368 (3)
O22—C12	1.273 (3)	C4—C5	1.387 (3)
C12—C22	1.474 (3)	C5—N7	1.393 (3)
C22—C32	1.302 (4)	C5—C6	1.410 (3)
C22—H22	0.9500	C6—N6	1.346 (3)
C32—C42	1.497 (4)	N6—H6A	0.8800
C32—H32	0.9500	N6—H6B	0.8800
C42—H42A	0.9800	N7—C8	1.320 (3)
C42—H42B	0.9800	C8—N9	1.359 (3)
C42—H42C	0.9800	C8—H8	0.9500
O13—C13	1.255 (3)	N9—H9	0.8800
O23—C13	1.289 (3)
O23^i—Dy1—O2W	87.01 (6)	C22—C32—C42	125.5 (3)
O23^i—Dy1—O11	80.90 (6)	C22—C32—H32	117.2
O2W—Dy1—O11	129.89 (6)	C42—C32—H32	117.2
O23^i—Dy1—O1W	77.97 (6)	C32—C42—H42A	109.5
O2W—Dy1—O1W	76.10 (6)	C32—C42—H42B	109.5
O11—Dy1—O1W	145.35 (6)	H42A—C42—H42B	109.5
O23^i—Dy1—O22	152.87 (6)	C32—C42—H42C	109.5
O2W—Dy1—O22	86.39 (6)	H42A—C42—H42C	109.5
O11—Dy1—O22	83.29 (6)	H42B—C42—H42C	109.5
O1W—Dy1—O22	125.53 (6)	C13—O13—Dy1	96.52 (14)
O23^i—Dy1—O13	120.01 (6)	C13—O23—Dy1^i	155.67 (16)
O2W—Dy1—O13	144.27 (6)	C13—O23—Dy1	91.43 (14)
O11—Dy1—O13	80.58 (6)	Dy1^i—O23—Dy1	112.89 (6)
O1W—Dy1—O13	86.61 (6)	O13—C13—O23	118.9 (2)
O22—Dy1—O13	78.53 (6)	O13—C13—C23	122.5 (2)
O23^i—Dy1—O21	80.52 (6)	O23—C13—C23	118.5 (2)
O2W—Dy1—O21	75.77 (6)	C33—C23—C13	122.6 (2)
O11—Dy1—O21	54.36 (6)	C33—C23—H23	118.7
O1W—Dy1—O21	145.21 (6)	C13—C23—H23	118.7
O22—Dy1—O21	72.35 (6)	C23—C33—C43	125.2 (2)
O13—Dy1—O21	128.00 (6)	C23—C33—H33	117.4
O23^i—Dy1—O23	67.11 (6)	C43—C33—H33	117.4
O2W—Dy1—O23	143.48 (6)	C33—C43—H43A	109.5
O11—Dy1—O23	72.91 (5)	C33—C43—H43B	109.5
O1W—Dy1—O23	73.67 (6)	H43A—C43—H43B	109.5
O22—Dy1—O23	128.17 (6)	C33—C43—H43C	109.5
O13—Dy1—O23	52.93 (5)	H43A—C43—H43C	109.5
O21—Dy1—O23	121.61 (5)	H43B—C43—H43C	109.5
O23^i—Dy1—O12	147.84 (6)	Dy1—O1W—H1WA	119.5
O2W—Dy1—O12	73.15 (6)	Dy1—O1W—H1WB	126.4
O11—Dy1—O12	131.23 (6)	H1WA—O1W—H1WB	112.2
O1W—Dy1—O12	72.91 (6)	Dy1—O2W—H2WA	113.7
O22—Dy1—O12	52.64 (6)	Dy1—O2W—H2WB	125.7
O13—Dy1—O12	71.94 (6)	H2WA—O2W—H2WB	110.5
O21—Dy1—O12	117.14 (6)	C6—N1—C2	118.5 (2)
O23—Dy1—O12	115.84 (5)	N3—C2—N2	116.5 (2)
C11—O11—Dy1	93.81 (14)	N3—C2—N1	128.0 (2)
C11—O21—Dy1	91.39 (14)	N2—C2—N1	115.5 (2)
O21—C11—O11	119.9 (2)	C2—N2—H2A	115.8
O21—C11—C21	120.4 (2)	C2—N2—H2B	111.3
O11—C11—C21	119.7 (2)	H2A—N2—H2B	114.5
C31—C21—C11	122.0 (2)	C2—N3—C4	111.6 (2)
C31—C21—H21	119.0	N3—C4—N9	127.2 (2)
C11—C21—H21	119.0	N3—C4—C5	126.9 (2)
C21—C31—C41	125.6 (3)	N9—C4—C5	105.9 (2)
C21—C31—H31	117.2	C4—C5—N7	109.7 (2)
C41—C31—H31	117.2	C4—C5—C6	116.5 (2)
C31—C41—H41A	109.5	N7—C5—C6	133.7 (2)
C31—C41—H41B	109.5	N6—C6—N1	118.3 (2)
H41A—C41—H41B	109.5	N6—C6—C5	123.2 (2)
C31—C41—H41C	109.5	N1—C6—C5	118.5 (2)
H41A—C41—H41C	109.5	C6—N6—H6A	119.2
H41B—C41—H41C	109.5	C6—N6—H6B	117.9
C12—O12—Dy1	91.33 (14)	H6A—N6—H6B	120.5
C12—O22—Dy1	96.88 (14)	C8—N7—C5	104.5 (2)
O12—C12—O22	119.1 (2)	N7—C8—N9	112.9 (2)
O12—C12—C22	122.6 (2)	N7—C8—H8	123.6
O22—C12—C22	118.3 (2)	N9—C8—H8	123.6
C32—C22—C12	124.2 (3)	C8—N9—C4	107.0 (2)
C32—C22—H22	117.9	C8—N9—H9	126.5
C12—C22—H22	117.9	C4—N9—H9	126.5
O23^i—Dy1—O11—C11	−89.04 (14)	O21—Dy1—O13—C13	106.53 (14)
O2W—Dy1—O11—C11	−10.74 (16)	O23—Dy1—O13—C13	2.44 (13)
O1W—Dy1—O11—C11	−141.95 (14)	O12—Dy1—O13—C13	−142.72 (15)
O22—Dy1—O11—C11	68.84 (14)	O23^i—Dy1—O23—C13	179.49 (17)
O13—Dy1—O11—C11	148.27 (14)	O2W—Dy1—O23—C13	131.21 (13)
O21—Dy1—O11—C11	−4.23 (13)	O11—Dy1—O23—C13	−93.37 (13)
O23—Dy1—O11—C11	−157.76 (14)	O1W—Dy1—O23—C13	95.92 (13)
O12—Dy1—O11—C11	92.55 (15)	O22—Dy1—O23—C13	−26.76 (15)
O23^i—Dy1—O21—C11	89.83 (14)	O13—Dy1—O23—C13	−2.36 (12)
O2W—Dy1—O21—C11	179.12 (14)	O21—Dy1—O23—C13	−118.54 (13)
O11—Dy1—O21—C11	4.28 (13)	O12—Dy1—O23—C13	34.75 (14)
O1W—Dy1—O21—C11	142.19 (14)	O23^i—Dy1—O23—Dy1^i	0.0
O22—Dy1—O21—C11	−90.15 (14)	O2W—Dy1—O23—Dy1^i	−48.28 (12)
O13—Dy1—O21—C11	−31.04 (16)	O11—Dy1—O23—Dy1^i	87.14 (7)
O23—Dy1—O21—C11	34.29 (15)	O1W—Dy1—O23—Dy1^i	−83.57 (7)
O12—Dy1—O21—C11	−118.66 (13)	O22—Dy1—O23—Dy1^i	153.75 (6)
Dy1—O21—C11—O11	−7.5 (2)	O13—Dy1—O23—Dy1^i	178.14 (10)
Dy1—O21—C11—C21	170.7 (2)	O21—Dy1—O23—Dy1^i	61.97 (9)
Dy1—O11—C11—O21	7.7 (2)	O12—Dy1—O23—Dy1^i	−144.74 (6)
Dy1—O11—C11—C21	−170.54 (19)	Dy1—O13—C13—O23	−4.3 (2)
O21—C11—C21—C31	−169.1 (2)	Dy1—O13—C13—C23	173.62 (19)
O11—C11—C21—C31	9.1 (4)	Dy1^i—O23—C13—O13	−177.0 (2)
C11—C21—C31—C41	176.6 (3)	Dy1—O23—C13—O13	4.1 (2)
O23^i—Dy1—O12—C12	151.05 (14)	Dy1^i—O23—C13—C23	5.0 (5)
O2W—Dy1—O12—C12	96.81 (14)	Dy1—O23—C13—C23	−173.88 (18)
O11—Dy1—O12—C12	−31.91 (17)	O13—C13—C23—C33	−1.9 (4)
O1W—Dy1—O12—C12	177.06 (15)	O23—C13—C23—C33	176.0 (2)
O22—Dy1—O12—C12	−1.74 (13)	C13—C23—C33—C43	−174.8 (2)
O13—Dy1—O12—C12	−90.93 (14)	C6—N1—C2—N3	0.3 (4)
O21—Dy1—O12—C12	33.17 (15)	C6—N1—C2—N2	−178.5 (2)
O23—Dy1—O12—C12	−121.35 (14)	N2—C2—N3—C4	179.3 (2)
O23^i—Dy1—O22—C12	−146.00 (15)	N1—C2—N3—C4	0.5 (4)
O2W—Dy1—O22—C12	−69.76 (14)	C2—N3—C4—N9	177.0 (2)
O11—Dy1—O22—C12	159.37 (15)	C2—N3—C4—C5	−1.5 (3)
O1W—Dy1—O22—C12	0.32 (17)	N3—C4—C5—N7	179.7 (2)
O13—Dy1—O22—C12	77.67 (14)	N9—C4—C5—N7	0.9 (3)
O21—Dy1—O22—C12	−145.96 (15)	N3—C4—C5—C6	1.6 (4)
O23—Dy1—O22—C12	97.32 (15)	N9—C4—C5—C6	−177.2 (2)
O12—Dy1—O22—C12	1.74 (13)	C2—N1—C6—N6	−178.4 (2)
Dy1—O12—C12—O22	3.0 (2)	C2—N1—C6—C5	−0.3 (3)
Dy1—O12—C12—C22	−177.1 (2)	C4—C5—C6—N6	177.4 (2)
Dy1—O22—C12—O12	−3.2 (2)	N7—C5—C6—N6	−0.1 (4)
Dy1—O22—C12—C22	176.90 (19)	C4—C5—C6—N1	−0.6 (3)
O12—C12—C22—C32	6.2 (4)	N7—C5—C6—N1	−178.1 (2)
O22—C12—C22—C32	−173.9 (3)	C4—C5—N7—C8	−0.4 (3)
C12—C22—C32—C42	178.1 (3)	C6—C5—N7—C8	177.2 (3)
O23^i—Dy1—O13—C13	4.42 (16)	C5—N7—C8—N9	−0.3 (3)
O2W—Dy1—O13—C13	−129.98 (14)	N7—C8—N9—C4	0.9 (3)
O11—Dy1—O13—C13	78.09 (14)	N3—C4—N9—C8	−179.8 (2)
O1W—Dy1—O13—C13	−69.60 (14)	C5—C4—N9—C8	−1.1 (3)
O22—Dy1—O13—C13	163.09 (14)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O22	0.88	1.91	2.775 (3)	166
N6—H6B···O12^ii	0.88	2.43	3.257 (3)	157
N6—H6A···N1^iii	0.88	2.42	3.300 (3)	175
N2—H2A···N3^iv	0.88	2.32	3.190 (3)	171
N2—H2B···O13^iv	0.88	2.43	3.256 (3)	158
O1W—H1WB···O2W^v	0.84	2.22	2.987 (2)	152
O1W—H1WA···O11^i	0.85	1.91	2.716 (2)	159
O2W—H2WB···N7^vi	0.85	1.84	2.681 (3)	176
O2W—H2WA···O12^v	0.84	1.87	2.683 (2)	163
C8—H8···O21^vi	0.95	2.37	3.128 (3)	136
C23—H23···N7^vii	0.95	2.60	3.525 (3)	164
C33—H33···N1^iv	0.95	2.57	3.469 (3)	157

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

(II) tetra-µ-but-2-enoato-bis[diaqua(µ₂-but-2-enoato)holmium(III)]–2,6- diaminopurine (1/2)

Crystal data

[Ho2(C4H5O2)6(H2O)4]·2C5H6N6	Z = 1
Mr = 1212.72	F(000) = 600
Triclinic, P1	Dx = 1.794 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.644 (2) Å	Cell parameters from 3982 reflections
b = 11.141 (3) Å	θ = 2.0–24.9°
c = 13.412 (3) Å	µ = 3.58 mm^−1
α = 101.360 (3)°	T = 150 K
β = 107.537 (4)°	Block, colourless
γ = 106.518 (4)°	0.22 × 0.18 × 0.12 mm
V = 1122.9 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4612 independent reflections
Radiation source: fine-focus sealed tube	4337 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
phi and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→10
Tmin = 0.40, Tmax = 0.65	k = −14→14
8804 measured reflections	l = −17→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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.35	w = 1/[σ^2(Fo^2) + (0.0249P)^2 + 0.9935P] where P = (Fo^2 + 2Fc^2)/3
4612 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 2.52 e Å^−3
0 restraints	Δρmin = −1.73 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.

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

	x	y	z	Uiso*/Ueq
Ho1	0.25679 (2)	0.110951 (16)	0.062756 (13)	0.01423 (7)
O11	0.1172 (3)	0.2539 (3)	0.1150 (2)	0.0203 (6)
O21	0.2634 (3)	0.3097 (3)	0.0114 (2)	0.0191 (6)
C11	0.1800 (5)	0.3367 (4)	0.0702 (3)	0.0157 (7)
C21	0.1596 (5)	0.4651 (4)	0.0899 (3)	0.0212 (8)
H21	0.1924	0.5211	0.0488	0.025*
C31	0.0962 (5)	0.5045 (4)	0.1641 (3)	0.0250 (9)
H31	0.0583	0.4445	0.2009	0.030*
C41	0.0799 (6)	0.6356 (5)	0.1939 (4)	0.0364 (11)
H41A	0.1212	0.6875	0.1495	0.055*
H41B	0.1505	0.6823	0.2720	0.055*
H41C	−0.0425	0.6231	0.1796	0.055*
O12	0.5457 (3)	0.0963 (3)	0.1628 (2)	0.0194 (6)
O22	0.5145 (3)	0.2871 (3)	0.1949 (2)	0.0198 (6)
C12	0.6114 (5)	0.2200 (4)	0.2118 (3)	0.0177 (8)
C22	0.7958 (5)	0.2892 (5)	0.2868 (4)	0.0277 (9)
H22	0.8329	0.3799	0.3258	0.033*
C32	0.9114 (6)	0.2328 (5)	0.3029 (4)	0.0295 (10)
H32	0.8723	0.1417	0.2646	0.035*
C42	1.1007 (6)	0.3005 (6)	0.3767 (4)	0.0393 (12)
H42A	1.1228	0.3919	0.4151	0.059*
H42B	1.1726	0.2994	0.3326	0.059*
H42C	1.1301	0.2546	0.4307	0.059*
O13	0.2536 (3)	0.0706 (3)	0.2318 (2)	0.0194 (6)
O23	0.0009 (3)	−0.0248 (3)	0.0934 (2)	0.0170 (5)
C13	0.0970 (5)	−0.0048 (4)	0.1952 (3)	0.0162 (7)
C23	0.0178 (5)	−0.0754 (4)	0.2600 (3)	0.0206 (8)
H23	−0.1026	−0.1293	0.2275	0.025*
C33	0.1089 (5)	−0.0663 (4)	0.3625 (3)	0.0202 (8)
H33	0.2263	−0.0058	0.3960	0.024*
C43	0.0396 (6)	−0.1452 (5)	0.4295 (4)	0.0291 (10)
H43A	−0.0820	−0.2034	0.3859	0.044*
H43B	0.0460	−0.0852	0.4961	0.044*
H43C	0.1098	−0.1982	0.4502	0.044*
O1W	0.2294 (3)	−0.1121 (3)	−0.0002 (2)	0.0208 (6)
H1WA	0.1305	−0.1700	−0.0426	0.025*
H1WB	0.3111	−0.1395	0.0013	0.025*
O2W	0.4071 (3)	0.1132 (3)	−0.0584 (2)	0.0185 (6)
H2WA	0.4016	0.0379	−0.0902	0.022*
H2WB	0.4113	0.1616	−0.0997	0.022*
N1	0.5042 (4)	0.8160 (3)	0.4581 (3)	0.0194 (7)
C2	0.4952 (5)	0.6949 (4)	0.4698 (3)	0.0197 (8)
N2	0.4659 (5)	0.6736 (4)	0.5604 (3)	0.0258 (8)
H2A	0.4848	0.6049	0.5771	0.031*
H2B	0.5141	0.7467	0.6161	0.031*
N3	0.5087 (4)	0.5965 (3)	0.4029 (3)	0.0191 (7)
C4	0.5350 (5)	0.6282 (4)	0.3158 (3)	0.0166 (7)
C5	0.5453 (5)	0.7452 (4)	0.2924 (3)	0.0174 (8)
C6	0.5279 (5)	0.8428 (4)	0.3685 (3)	0.0183 (8)
N6	0.5404 (5)	0.9631 (3)	0.3591 (3)	0.0240 (7)
H6A	0.5229	1.0183	0.4073	0.029*
H6B	0.5355	0.9754	0.2954	0.029*
N7	0.5741 (4)	0.7403 (3)	0.1949 (3)	0.0207 (7)
C8	0.5838 (5)	0.6241 (4)	0.1642 (3)	0.0197 (8)
H8	0.6031	0.5928	0.0995	0.024*
N9	0.5632 (4)	0.5530 (3)	0.2341 (3)	0.0186 (7)
H9	0.5673	0.4740	0.2280	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ho1	0.01397 (10)	0.01972 (10)	0.01286 (10)	0.00658 (7)	0.00691 (7)	0.00974 (7)
O11	0.0211 (14)	0.0245 (14)	0.0219 (14)	0.0095 (11)	0.0122 (11)	0.0134 (12)
O21	0.0195 (14)	0.0248 (14)	0.0211 (14)	0.0107 (11)	0.0114 (11)	0.0147 (11)
C11	0.0135 (17)	0.0227 (19)	0.0122 (17)	0.0071 (14)	0.0032 (14)	0.0103 (15)
C21	0.0171 (19)	0.024 (2)	0.024 (2)	0.0081 (15)	0.0062 (16)	0.0109 (16)
C31	0.023 (2)	0.025 (2)	0.026 (2)	0.0092 (17)	0.0076 (17)	0.0080 (17)
C41	0.036 (3)	0.035 (3)	0.039 (3)	0.022 (2)	0.011 (2)	0.006 (2)
O12	0.0183 (14)	0.0236 (14)	0.0207 (14)	0.0102 (11)	0.0084 (11)	0.0109 (11)
O22	0.0213 (14)	0.0215 (14)	0.0186 (13)	0.0083 (11)	0.0076 (11)	0.0099 (11)
C12	0.0187 (19)	0.030 (2)	0.0111 (17)	0.0104 (16)	0.0090 (14)	0.0122 (15)
C22	0.018 (2)	0.036 (2)	0.026 (2)	0.0077 (17)	0.0053 (17)	0.0119 (19)
C32	0.026 (2)	0.040 (3)	0.023 (2)	0.0121 (19)	0.0083 (18)	0.0125 (19)
C42	0.020 (2)	0.064 (3)	0.036 (3)	0.015 (2)	0.008 (2)	0.024 (3)
O13	0.0168 (14)	0.0250 (14)	0.0159 (13)	0.0047 (11)	0.0058 (10)	0.0103 (11)
O23	0.0159 (13)	0.0225 (14)	0.0150 (13)	0.0060 (10)	0.0065 (10)	0.0110 (11)
C13	0.0175 (18)	0.0213 (19)	0.0148 (17)	0.0113 (15)	0.0072 (14)	0.0082 (15)
C23	0.0168 (19)	0.025 (2)	0.024 (2)	0.0051 (15)	0.0104 (16)	0.0148 (17)
C33	0.021 (2)	0.027 (2)	0.0176 (19)	0.0070 (16)	0.0121 (16)	0.0116 (16)
C43	0.034 (2)	0.040 (3)	0.022 (2)	0.013 (2)	0.0158 (18)	0.0185 (19)
O1W	0.0150 (13)	0.0244 (14)	0.0259 (15)	0.0098 (11)	0.0079 (11)	0.0103 (12)
O2W	0.0252 (15)	0.0229 (14)	0.0211 (14)	0.0130 (11)	0.0176 (12)	0.0159 (11)
N1	0.0206 (17)	0.0238 (17)	0.0176 (16)	0.0096 (13)	0.0076 (13)	0.0113 (13)
C2	0.0152 (18)	0.028 (2)	0.0174 (19)	0.0055 (15)	0.0059 (15)	0.0139 (16)
N2	0.036 (2)	0.0302 (19)	0.0192 (17)	0.0131 (16)	0.0160 (15)	0.0157 (15)
N3	0.0191 (17)	0.0242 (17)	0.0166 (16)	0.0075 (13)	0.0068 (13)	0.0119 (13)
C4	0.0153 (18)	0.0213 (19)	0.0118 (17)	0.0039 (14)	0.0039 (14)	0.0083 (15)
C5	0.0161 (18)	0.0232 (19)	0.0150 (18)	0.0054 (15)	0.0065 (14)	0.0124 (15)
C6	0.0123 (18)	0.0237 (19)	0.0175 (18)	0.0066 (14)	0.0022 (14)	0.0088 (15)
N6	0.034 (2)	0.0277 (18)	0.0225 (18)	0.0166 (15)	0.0171 (15)	0.0161 (15)
N7	0.0215 (17)	0.0256 (17)	0.0180 (16)	0.0071 (14)	0.0096 (13)	0.0120 (14)
C8	0.023 (2)	0.0228 (19)	0.0158 (18)	0.0056 (15)	0.0110 (15)	0.0094 (15)
N9	0.0201 (17)	0.0216 (16)	0.0176 (16)	0.0067 (13)	0.0085 (13)	0.0127 (13)

Geometric parameters (Å, º)

Ho1—O23^i	2.335 (3)	O13—C13	1.252 (5)
Ho1—O2W	2.365 (3)	O23—C13	1.302 (4)
Ho1—O11	2.376 (3)	C13—C23	1.471 (5)
Ho1—O1W	2.380 (3)	C23—C33	1.330 (5)
Ho1—O22	2.391 (3)	C23—H23	0.9500
Ho1—O13	2.403 (3)	C33—C43	1.508 (5)
Ho1—O21	2.436 (3)	C33—H33	0.9500
Ho1—O23	2.498 (3)	C43—H43A	0.9800
Ho1—O12	2.522 (3)	C43—H43B	0.9800
Ho1—C11	2.769 (4)	C43—H43C	0.9800
Ho1—C13	2.844 (4)	O1W—H1WA	0.8477
Ho1—C12	2.846 (4)	O1W—H1WB	0.8416
O11—C11	1.279 (4)	O2W—H2WA	0.8443
O21—C11	1.268 (4)	O2W—H2WB	0.8474
C11—C21	1.472 (5)	N1—C6	1.353 (5)
C21—C31	1.333 (6)	N1—C2	1.372 (5)
C21—H21	0.9500	C2—N3	1.330 (5)
C31—C41	1.494 (6)	C2—N2	1.364 (5)
C31—H31	0.9500	N2—H2A	0.8818
C41—H41A	0.9800	N2—H2B	0.8803
C41—H41B	0.9800	N3—C4	1.348 (5)
C41—H41C	0.9800	C4—N9	1.370 (5)
O12—C12	1.275 (5)	C4—C5	1.385 (5)
O22—C12	1.273 (5)	C5—N7	1.397 (5)
C12—C22	1.475 (5)	C5—C6	1.412 (6)
C22—C32	1.312 (6)	C6—N6	1.348 (5)
C22—H22	0.9500	N6—H6A	0.8802
C32—C42	1.501 (6)	N6—H6B	0.8814
C32—H32	0.9500	N7—C8	1.314 (5)
C42—H42A	0.9800	C8—N9	1.360 (5)
C42—H42B	0.9800	C8—H8	0.9500
C42—H42C	0.9800	N9—H9	0.8800
O23^i—Ho1—O2W	87.01 (9)	C31—C41—H41B	109.5
O23^i—Ho1—O11	81.00 (9)	H41A—C41—H41B	109.5
O2W—Ho1—O11	129.89 (9)	C31—C41—H41C	109.5
O23^i—Ho1—O1W	78.12 (9)	H41A—C41—H41C	109.5
O2W—Ho1—O1W	76.17 (9)	H41B—C41—H41C	109.5
O11—Ho1—O1W	145.46 (9)	C12—O12—Ho1	91.0 (2)
O23^i—Ho1—O22	152.83 (9)	C12—O22—Ho1	97.2 (2)
O2W—Ho1—O22	86.56 (9)	O22—C12—O12	118.8 (3)
O11—Ho1—O22	83.03 (9)	O22—C12—C22	118.4 (4)
O1W—Ho1—O22	125.53 (9)	O12—C12—C22	122.8 (4)
O23^i—Ho1—O13	119.94 (9)	O22—C12—Ho1	56.45 (19)
O2W—Ho1—O13	144.35 (9)	O12—C12—Ho1	62.38 (19)
O11—Ho1—O13	80.47 (9)	C22—C12—Ho1	174.2 (3)
O1W—Ho1—O13	86.51 (9)	C32—C22—C12	123.8 (4)
O22—Ho1—O13	78.49 (9)	C32—C22—H22	118.1
O23^i—Ho1—O21	80.23 (9)	C12—C22—H22	118.1
O2W—Ho1—O21	75.54 (9)	C22—C32—C42	125.3 (5)
O11—Ho1—O21	54.56 (9)	C22—C32—H32	117.3
O1W—Ho1—O21	144.99 (9)	C42—C32—H32	117.3
O22—Ho1—O21	72.60 (9)	C32—C42—H42A	109.5
O13—Ho1—O21	128.31 (9)	C32—C42—H42B	109.5
O23^i—Ho1—O23	66.89 (10)	H42A—C42—H42B	109.5
O2W—Ho1—O23	143.26 (9)	C32—C42—H42C	109.5
O11—Ho1—O23	73.05 (9)	H42A—C42—H42C	109.5
O1W—Ho1—O23	73.54 (9)	H42B—C42—H42C	109.5
O22—Ho1—O23	128.27 (9)	C13—O13—Ho1	97.2 (2)
O13—Ho1—O23	53.09 (8)	C13—O23—Ho1^i	155.5 (2)
O21—Ho1—O23	121.62 (9)	C13—O23—Ho1	91.4 (2)
O23^i—Ho1—O12	147.64 (9)	Ho1^i—O23—Ho1	113.11 (10)
O2W—Ho1—O12	73.02 (9)	O13—C13—O23	118.2 (3)
O11—Ho1—O12	131.33 (9)	O13—C13—C23	123.4 (3)
O1W—Ho1—O12	72.60 (9)	O23—C13—C23	118.3 (3)
O22—Ho1—O12	52.94 (9)	O13—C13—Ho1	56.93 (19)
O13—Ho1—O12	72.14 (9)	O23—C13—Ho1	61.41 (19)
O21—Ho1—O12	117.37 (9)	C23—C13—Ho1	174.7 (3)
O23—Ho1—O12	115.96 (9)	C33—C23—C13	122.3 (4)
O23^i—Ho1—C11	81.37 (10)	C33—C23—H23	118.9
O2W—Ho1—C11	102.77 (10)	C13—C23—H23	118.9
O11—Ho1—C11	27.45 (10)	C23—C33—C43	124.8 (4)
O1W—Ho1—C11	159.49 (10)	C23—C33—H33	117.6
O22—Ho1—C11	74.39 (10)	C43—C33—H33	117.6
O13—Ho1—C11	103.99 (10)	C33—C43—H43A	109.5
O21—Ho1—C11	27.24 (10)	C33—C43—H43B	109.5
O23—Ho1—C11	98.47 (10)	H43A—C43—H43B	109.5
O12—Ho1—C11	127.17 (10)	C33—C43—H43C	109.5
O23^i—Ho1—C13	94.11 (10)	H43A—C43—H43C	109.5
O2W—Ho1—C13	153.41 (10)	H43B—C43—H43C	109.5
O11—Ho1—C13	76.31 (10)	Ho1—O1W—H1WA	119.5
O1W—Ho1—C13	78.08 (10)	Ho1—O1W—H1WB	126.5
O22—Ho1—C13	103.29 (10)	H1WA—O1W—H1WB	112.2
O13—Ho1—C13	25.90 (10)	Ho1—O2W—H2WA	113.6
O21—Ho1—C13	130.86 (10)	Ho1—O2W—H2WB	125.8
O23—Ho1—C13	27.22 (9)	H2WA—O2W—H2WB	110.5
O12—Ho1—C13	93.08 (10)	C6—N1—C2	118.6 (3)
C11—Ho1—C13	103.66 (11)	N3—C2—N2	116.9 (4)
O23^i—Ho1—C12	165.03 (10)	N3—C2—N1	127.8 (4)
O2W—Ho1—C12	78.08 (10)	N2—C2—N1	115.2 (4)
O11—Ho1—C12	107.65 (10)	C2—N2—H2A	115.5
O1W—Ho1—C12	99.19 (10)	C2—N2—H2B	111.5
O22—Ho1—C12	26.34 (10)	H2A—N2—H2B	114.5
O13—Ho1—C12	74.22 (9)	C2—N3—C4	111.6 (3)
O21—Ho1—C12	94.70 (10)	N3—C4—N9	127.1 (3)
O23—Ho1—C12	126.84 (9)	N3—C4—C5	127.2 (4)
O12—Ho1—C12	26.62 (10)	N9—C4—C5	105.7 (3)
C11—Ho1—C12	100.60 (11)	C4—C5—N7	110.0 (3)
C13—Ho1—C12	99.77 (10)	C4—C5—C6	116.6 (3)
C11—O11—Ho1	93.6 (2)	N7—C5—C6	133.4 (4)
C11—O21—Ho1	91.2 (2)	N6—C6—N1	118.1 (4)
O21—C11—O11	120.1 (3)	N6—C6—C5	123.7 (4)
O21—C11—C21	120.0 (3)	N1—C6—C5	118.2 (3)
O11—C11—C21	119.9 (3)	C6—N6—H6A	119.4
O21—C11—Ho1	61.59 (19)	C6—N6—H6B	117.8
O11—C11—Ho1	58.90 (19)	H6A—N6—H6B	120.5
C21—C11—Ho1	171.8 (3)	C8—N7—C5	104.2 (3)
C31—C21—C11	121.5 (4)	N7—C8—N9	113.2 (3)
C31—C21—H21	119.3	N7—C8—H8	123.4
C11—C21—H21	119.3	N9—C8—H8	123.4
C21—C31—C41	125.2 (4)	C8—N9—C4	106.8 (3)
C21—C31—H31	117.4	C8—N9—H9	126.6
C41—C31—H31	117.4	C4—N9—H9	126.6
C31—C41—H41A	109.5
O23^i—Ho1—O11—C11	−88.6 (2)	C13—Ho1—C12—O12	77.2 (2)
O2W—Ho1—O11—C11	−10.2 (3)	O22—C12—C22—C32	−173.6 (4)
O1W—Ho1—O11—C11	−141.9 (2)	O12—C12—C22—C32	5.8 (7)
O22—Ho1—O11—C11	69.4 (2)	C12—C22—C32—C42	178.8 (4)
O13—Ho1—O11—C11	148.8 (2)	O23^i—Ho1—O13—C13	4.5 (3)
O21—Ho1—O11—C11	−4.22 (19)	O2W—Ho1—O13—C13	−129.9 (2)
O23—Ho1—O11—C11	−157.0 (2)	O11—Ho1—O13—C13	78.3 (2)
O12—Ho1—O11—C11	93.0 (2)	O1W—Ho1—O13—C13	−69.6 (2)
C13—Ho1—O11—C11	174.9 (2)	O22—Ho1—O13—C13	163.0 (2)
C12—Ho1—O11—C11	78.8 (2)	O21—Ho1—O13—C13	106.4 (2)
O23^i—Ho1—O21—C11	90.1 (2)	O23—Ho1—O13—C13	2.4 (2)
O2W—Ho1—O21—C11	179.5 (2)	O12—Ho1—O13—C13	−142.5 (2)
O11—Ho1—O21—C11	4.25 (19)	C11—Ho1—O13—C13	92.5 (2)
O1W—Ho1—O21—C11	142.5 (2)	C12—Ho1—O13—C13	−170.2 (2)
O22—Ho1—O21—C11	−89.6 (2)	O23^i—Ho1—O23—C13	179.8 (3)
O13—Ho1—O21—C11	−30.5 (2)	O2W—Ho1—O23—C13	131.6 (2)
O23—Ho1—O21—C11	35.1 (2)	O11—Ho1—O23—C13	−93.0 (2)
O12—Ho1—O21—C11	−118.7 (2)	O1W—Ho1—O23—C13	95.9 (2)
C13—Ho1—O21—C11	3.1 (3)	O22—Ho1—O23—C13	−26.7 (2)
C12—Ho1—O21—C11	−104.1 (2)	O13—Ho1—O23—C13	−2.3 (2)
Ho1—O21—C11—O11	−7.5 (3)	O21—Ho1—O23—C13	−118.9 (2)
Ho1—O21—C11—C21	170.8 (3)	O12—Ho1—O23—C13	35.3 (2)
Ho1—O11—C11—O21	7.7 (3)	C11—Ho1—O23—C13	−103.4 (2)
Ho1—O11—C11—C21	−170.5 (3)	C12—Ho1—O23—C13	6.7 (3)
O23^i—Ho1—C11—O21	−85.4 (2)	O23^i—Ho1—O23—Ho1^i	0.0
O2W—Ho1—C11—O21	−0.5 (2)	O2W—Ho1—O23—Ho1^i	−48.19 (19)
O11—Ho1—C11—O21	−172.5 (3)	O11—Ho1—O23—Ho1^i	87.26 (12)
O1W—Ho1—C11—O21	−85.1 (3)	O1W—Ho1—O23—Ho1^i	−83.84 (12)
O22—Ho1—C11—O21	82.2 (2)	O22—Ho1—O23—Ho1^i	153.56 (10)
O13—Ho1—C11—O21	155.8 (2)	O13—Ho1—O23—Ho1^i	177.97 (16)
O23—Ho1—C11—O21	−150.3 (2)	O21—Ho1—O23—Ho1^i	61.35 (14)
O12—Ho1—C11—O21	77.8 (2)	O12—Ho1—O23—Ho1^i	−144.45 (10)
C13—Ho1—C11—O21	−177.6 (2)	C11—Ho1—O23—Ho1^i	76.79 (12)
C12—Ho1—C11—O21	79.5 (2)	C13—Ho1—O23—Ho1^i	−179.8 (3)
O23^i—Ho1—C11—O11	87.1 (2)	C12—Ho1—O23—Ho1^i	−173.08 (11)
O2W—Ho1—C11—O11	172.0 (2)	Ho1—O13—C13—O23	−4.1 (4)
O1W—Ho1—C11—O11	87.4 (3)	Ho1—O13—C13—C23	173.7 (3)
O22—Ho1—C11—O11	−105.3 (2)	Ho1^i—O23—C13—O13	−176.6 (4)
O13—Ho1—C11—O11	−31.8 (2)	Ho1—O23—C13—O13	3.9 (3)
O21—Ho1—C11—O11	172.5 (3)	Ho1^i—O23—C13—C23	5.5 (8)
O23—Ho1—C11—O11	22.2 (2)	Ho1—O23—C13—C23	−174.0 (3)
O12—Ho1—C11—O11	−109.8 (2)	Ho1^i—O23—C13—Ho1	179.5 (6)
C13—Ho1—C11—O11	−5.1 (2)	O23^i—Ho1—C13—O13	−176.1 (2)
C12—Ho1—C11—O11	−108.0 (2)	O2W—Ho1—C13—O13	92.4 (3)
O21—C11—C21—C31	−169.8 (4)	O11—Ho1—C13—O13	−96.4 (2)
O11—C11—C21—C31	8.4 (6)	O1W—Ho1—C13—O13	107.0 (2)
C11—C21—C31—C41	176.5 (4)	O22—Ho1—C13—O13	−17.1 (2)
O23^i—Ho1—O12—C12	151.6 (2)	O21—Ho1—C13—O13	−95.5 (2)
O2W—Ho1—O12—C12	97.3 (2)	O23—Ho1—C13—O13	−175.9 (4)
O11—Ho1—O12—C12	−31.3 (2)	O12—Ho1—C13—O13	35.5 (2)
O1W—Ho1—O12—C12	177.7 (2)	C11—Ho1—C13—O13	−94.0 (2)
O22—Ho1—O12—C12	−1.43 (19)	C12—Ho1—C13—O13	9.6 (2)
O13—Ho1—O12—C12	−90.3 (2)	O13—C13—C23—C33	−1.6 (6)
O21—Ho1—O12—C12	34.2 (2)	O23—C13—C23—C33	176.3 (4)
O23—Ho1—O12—C12	−121.1 (2)	C13—C23—C33—C43	−174.3 (4)
C11—Ho1—O12—C12	3.9 (3)	C6—N1—C2—N3	0.6 (6)
C13—Ho1—O12—C12	−105.8 (2)	C6—N1—C2—N2	−178.1 (3)
O23^i—Ho1—O22—C12	−146.4 (2)	N2—C2—N3—C4	179.1 (3)
O2W—Ho1—O22—C12	−69.8 (2)	N1—C2—N3—C4	0.4 (6)
O11—Ho1—O22—C12	159.3 (2)	C2—N3—C4—N9	176.5 (4)
O1W—Ho1—O22—C12	0.5 (3)	C2—N3—C4—C5	−1.1 (5)
O13—Ho1—O22—C12	77.6 (2)	N3—C4—C5—N7	179.9 (4)
O21—Ho1—O22—C12	−145.7 (2)	N9—C4—C5—N7	1.9 (4)
O23—Ho1—O22—C12	97.4 (2)	N3—C4—C5—C6	0.7 (6)
O12—Ho1—O22—C12	1.4 (2)	N9—C4—C5—C6	−177.3 (3)
C11—Ho1—O22—C12	−174.1 (2)	C2—N1—C6—N6	−178.6 (3)
C13—Ho1—O22—C12	85.2 (2)	C2—N1—C6—C5	−1.1 (5)
Ho1—O22—C12—O12	−2.6 (4)	C4—C5—C6—N6	177.8 (4)
O23^i—Ho1—C12—O12	−80.5 (4)	N7—C5—C6—N6	−1.1 (7)
O2W—Ho1—C12—O12	−75.8 (2)	C4—C5—C6—N1	0.5 (5)
O11—Ho1—C12—O12	155.8 (2)	N7—C5—C6—N1	−178.5 (4)
O1W—Ho1—C12—O12	−2.2 (2)	C4—C5—N7—C8	−1.2 (4)
O22—Ho1—C12—O12	177.4 (4)	C6—C5—N7—C8	177.8 (4)
O13—Ho1—C12—O12	81.5 (2)	C5—N7—C8—N9	0.1 (4)
O21—Ho1—C12—O12	−150.0 (2)	N7—C8—N9—C4	1.1 (5)
O23—Ho1—C12—O12	74.1 (2)	N3—C4—N9—C8	−179.8 (4)
C11—Ho1—C12—O12	−176.8 (2)	C5—C4—N9—C8	−1.8 (4)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O22	0.88	1.93	2.788 (4)	166
N6—H6B···O12^ii	0.88	2.44	3.272 (4)	157
N6—H6A···N1^iii	0.88	2.43	3.308 (5)	175
N2—H2A···N3^iv	0.88	2.33	3.199 (5)	171
N2—H2B···O13^iv	0.88	2.43	3.262 (5)	158
O1W—H1WB···O2W^v	0.84	2.23	3.005 (4)	152
O1W—H1WA···O11^i	0.85	1.91	2.722 (4)	160
O2W—H2WB···N7^vi	0.85	1.85	2.693 (4)	176
O2W—H2WA···O12^v	0.84	1.86	2.678 (4)	162
C8—H8···O21^vi	0.95	2.38	3.136 (5)	136
C23—H23···N7^vii	0.95	2.61	3.534 (5)	164
C33—H33···N1^iv	0.95	2.56	3.457 (5)	158

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