Two isomorphous lanthanide crotonate complexes: di-[mu]-but-2-enoato-bis­[diaqua­bis­(but-2-enoato)dysprosium(III)] adenine monosolvate hepta­hydrate and the samarium(II) analogue

The asymmetric unit of the title dimeric compounds, [Ln₂(C₄H₅O₂)₆(H₂O)₄]·C₅H₅N₅·7H₂O, with Ln = Dy, (I), and Sm, (II), consists of an Ln^III cation, three crotonate (but-2-enoate) anions and two coordinated water mol­ecules forming the neutral complex, cocrystallized with half of an external adenine mol­ecule and 3.5 water mol­ecules. The metal complex has crystallographic inversion symmetry. The LnO₉ coordination polyhedra are connected through the sharing of a single edge to form isolated dimeric units, with Ln...Ln separations of 4.1766 (12) Å for (I) and 4.2340 (12) Å for (II). The unbound adenine mol­ecule and one of the solvent water mol­ecules are disordered around an inversion centre into two overlapping, equally populated, units. The structure is sustained by a complex hydrogen-bonding scheme involving all possible O-H and N-H groups as donors, and crotonate and water O and adenine N atoms as acceptors. The system is compared with recently published related compounds.

S1. Comment

Homonuclear systems with ligands that serve as molecular bridges between metal centres have received considerable attention through the years (Fujita et al., 1994; Lu & Babb, 2001; Thompson, 2002). A point of interest in these systems is the possibility of introducing extra ligands as bridges and thus obtaining grid structures and/or clusters, which are appealing not only structurally but also for their potential application in ion exchange, catalysis, molecular absorption, optical, electronic and magnetic areas (Ma et al., 2000; Wang et al., 2002; Xu et al., 2002; Benelli & Gatteschi, 2002; Pan et al., 2004). We have for some time focused our attention on the efficiency of crotonic acid (Hcrot) to couple Ln^III ions and as a result we have described the synthesis and structural and magnetic characterization of a number of lanthanide complexes displaying these types of bridges. In parallel, our investigation of carboxylate complexes has showed that the incorporation of some purine derivatives, like 2,6-diaminopurine (dap), might facilitate crystallization, either through their inclusion as neutral co-crystallization agents (Atria et al., 2009) or as counterions (Atria, Morel et al., 2011), or even as coordinating ligands (Atria, Corsini et al., 2011; Atria, Garland & Baggio, 2011). We also tried adenine (ade), and the first outcome with this ligand [a La complex with a one-dimensional structure, {La(crot)₃(H₂O)₂.(ade).H₂O}_n, (III)] has been described recently (Atria et al., 2012).

We present herein another example of the crotonate–adenine system, viz. the title Ln dimers (Ln = Dy, Sm), formulated as Ln₂(crot)₆(H₂O)₄.ade.7H₂O, with Ln = Dy in (I) and Ln = Sm in (II). The two structures are isomorphous and accordingly we shall discuss only one of them in detail, (I), with only marginal reference to the second, (II).

Fig. 1 shows the centrosymmetric dimeric unit for both (I) and (II). The asymmetric unit consists of an Ln cation, three crotonate anions and two coordinated water molecules determining the neutral complex, completed by an external adenine, disordered around an inversion centre, a solvent water molecule in similar conditions and three further, fully occupied, solvent water molecules. The three crotonate anions (distinguished by their trailing number, 1, 2 or 3) act in a chelating way. Unit 3 has, in addition, one of its carboxylate O atoms (O13) shared with a neigbouring coordination polyhedron (Fig. 1), thus giving rise to the central Ln₂O₂ loop defining the dimeric unit, with Ln···Ln separations of 4.1766 (12) Å for (I) and 4.2340 (12) Å for (II). The seven sites thus provided to the cation environment by the carboxylate O atoms are expanded by two aqua O atoms to a nine-coordination polyhedron, with Ln—O ranges of 2.3504 (19)–2.5524 (19) Å for (I) and 2.4057 (16)–2.5739 (15)Å for (II) (see Tables 1 and 3 for details). The dimeric linkage is reinforced by a strong intra-dimeric hydrogen bond involving atoms O1W and O11ⁱ [symmetry code: (i) 1 - x, 1 - y, -z; Tables 2 and 4, first entry].

This type of dimeric unit occurs rather frequently among Ln crotonates. In particular, we have recently found it in our structural study of the family of lanthanocrotonate diaminopurine analogues, viz. di-µ-but-2-enoato-bis[diaquabis(but-2-enoato)Ln].2,6-diaminopurine disolvate, with Ln = Ho or Dy [(IV); Atria et al., 2009], or Ln = Nd (Atria, Astete et al., 2011), where the [Ln(Crot)₃(H₂O)₂]₂ dinuclear structure is extremely similar to the present one. However, the coordination environments and the resulting hydrogen-bonding schemes are different, and this will be commented on below in the light of the electronic state of their constituents.

The La–adenine analogue, (III), presents a different configuration around the cation, with two carboxylates sharing one of their coordinated O atoms with neighbouring cations, giving rise to chains (instead of dimers) of ten-coordinated (instead of nine-coordinated) polyhedra. The LaO₁₀ coordination assembly in (III) is a slightly distorted bicapped square antiprism. In contrast, the LnO₉ one in (I) and (II) consists of five O atoms in equatorial positions, describing a rather planar structure [mean deviation 0.112 (2) Å], capped by one O atom above the plane and a triangular array below (Fig. 1, inset). The Dy cation, in turn, lies 0.502 (2) Å below the pentagonal mean plane.

The neutral adenine molecule (hereinafter ade⁰) is basically planar, with a maximum deviation of 0.042 Å for atom N5, and it almost engulfs an inversion centre, 0.0329 (2) Å away from the least-squares plane (shown as a cross in Fig. 2). In addition, the solvent water molecule O6W is also quasi-coplanar [deviation 0.2620 (12) Å], and so both the adenine molecule and this solvent water molecule are forced to be 0.50:0.50 disordered around the inversion centre. Their symmetry-related images superimpose each other in such a way that the NH₂ group in one of the images almost coincides with the OH₂ group in the other (Fig. 2). The metrics of the ade⁰ group are normal, and it presents the same prototropic state (distribution of single and double bonds) as in the La analogue [Atria et al., 2012; form (b) in Scheme 2 of that work] with protonation at N2. We shall not discuss the point any further, but the interested reader is referred to this latter report for a brief discussion of the subject. The molecule does not take part in coordination but it plays, in conjunction with the solvent water molecules, a significant role in the general cohesion. Table 2 presents the hydrogen-bonding interactions in which all available O—H and N—H groups act as donors, and all possible O and N atoms act as acceptors; the exceptions to this are based on steric impossibilities, viz. shielding (among atoms O1W and O2W, both coordinated to Dy1, and O13, engaged in the Dy—O—Dy bridge) or protonation (on the nitrogen side, only protonated atoms N2 and N5 do not accept hydrogen bonds). Figs. 3(a) and 3(b) present two different views of the web-like structure woven by these interactions, which hold the isolated dimers in place. Simple inspection of these figures shows that both the dimers and most of the solvent water molecules lie in planar arrays parallel to (001) at z = 0, shown in both views in projection as horizontal strips in heavy lining. In addition, the disordered ade⁰ and O6W molecules serve as connectors between these two-dimensional structures; this linkage is achieved through hydrogen bonds 2 to 10 in Table 2. The internal cohesion of the planes (made up of dimers and solvent water molecules) is in turn achieved by a large number of hydrogen bonds involving only water H atoms as donors on one side and water and carboxylate O atoms as acceptors on the other (entries 11 to 17 in Tables 2 and 4). Fig. 4 shows a thin (001) layer around z = 0 (thus excluding the disordered part at z ~0.50), where the most significant hydrogen-bonding loops (A to E) arising from these interactions are identified. There are three centrosymmetric loops: A, graph-set R₄⁴(8) (Bernstein et al., 1995); B, R₄⁴(12); and C, R₄⁴(20), and two non-centrosymmetric ones: D, R₃³(8), and E, R₃³(8).

The present Dy structure, (I), with its very complex interaction scheme involving all available coordinated O atoms, provides an example of the influence which the hydrogen-bonding interactions might have on the O-atom coordination capabilities and even the valence state of the coordinated cations, as second-order receptors of these interactions. In this respect it is worth comparing the structure of (I) with the above-mentioned Dy diamine purine analogue, (IV), which presents an almost identical dimeric structure but a looser hydrogen-bonding `web'. For the sake of comparison, some relevant values will be given in the order (I)/(IV). (a) Overall Dy—O coordination range 2.3504 (19)–2.5524 (19)/2.3457 (17)–2.5257 (17) Å. (b) Bridging Dy···Dy 4.1766 (12)/4.0412 (13) Å. (c) Shortest Dy—O bridge 2.3784 (18)/2.3464 (17) Å. (d) Longest Dy—O bridge 2.5524 (19)/2.5021 (17) Å. All these figures point to a stronger involvement in coordination in (IV) (with weaker and sparser hydrogen-bonds) compared with (I) (showing a stronger and denser hydrogen-bonding network), a fact confirmed by a bond-valence calculation for Dy (using PLATON; Spek, 2009), resulting in 2.94 valence units for (IV) versus 2.81 valence units for (I).

Related literature

For related literature, see: Atria et al. (2009, 2012); Atria, Astete, Garland & Baggio (2011); Atria, Corsini, Herrera, Garland & Baggio (2011); Atria, Garland & Baggio (2011); Atria, Morel, Garland & Baggio (2011); Benelli & Gatteschi (2002); Bernstein et al. (1995); Fujita et al. (1994); Lu & Babb (2001); Ma et al. (2000); Pan et al. (2004); Spek (2009); Thompson (2002); Wang et al. (2002); Xu et al. (2002).

S2. Experimental

Complexes (I) and (II) were synthesized by similar methods. A mixture of the appropriate oxide (Dy₂O₃ or Sm₂O₃, 1 mmol) and crotonic acid (6 mmol) was dissolved in water (100 ml), followed by the addition of the adenine ligand (1 mmol) dissolved in ethanol (40 ml). The resulting mixture was refluxed for 24 h, filtered while hot and then concentrated to 25 ml [in vacuo, by evaporation, by heating?]. The filtrate was left to stand at room temperature and suitable crystals for single-crystal X-ray diffraction appeared. These were used without further processing.

S3. Refinement

The unbound adenine and one of the solvent water molecules are disordered around an inversion centre into two almost overlapping, equally populated, units.

All the H atoms were clearly seen in a difference Fourier map but they were treated differently in refinement. C-bound H atoms were repositioned at their expected locations and allowed to ride, with C—H = 0.95–0.98 Å, and with U_iso(H) = 1.2–1.5U_eq(C)]. H atoms attached to N and O were refined with restrained distances of N—H = O—H = 0.85 (1) Å and free U_iso(H).

The extinction parameters had a significant effect on the refinement so they were retained, in spite of their small value.

Computing details

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

Figures

	Fig. 1. The molecular structures of (I) (left) and (II) (right). Displacement ellipsoids are drawn at the 40% probability level, with independent (symmetry-related) atoms in heavy (hollow) bonds and filled (empty) ellipsoids. Inset: the coordination assembly of the lanthanide cation. [Symmetry code: (i) -x + 1, -y + 1, -z.]
	Fig. 2. A schematic view showing the way in which the disordered adenine and solvent water molecule O6W overlap. [Symmetry code: (ii) -x + 2, -y, -z + 1.]
	Fig. 3. Packing views of (I) (a) projected down [100] and (b) projected down [010]
	Fig. 4. A [001] packing view of a thin (001) slab of (I), centred at z = 0 and showing the different hydrogen-bonding loops connecting the dimers. Centrosymmetric loops: A, as L1 [O4W···H2WB—O2W—H2WA] + L1^i; B, as L2 [O21—Dy1—O12···(H5WB—O5W—H5WA)^iii] + L2^ii; C, as L3 [(O12—Dy1—O11)^v···H3WA—O3W···H4WB—O4W—H4WA···O5W—H5WB] + L3^iv,. Non-centrosymmetric loops: D, as O21—Dy1—O2W—H2WA···(O4W—H4WA···O5W—H5WA)^i, and E, as H2WB—O2W—Dy1—O13—(Dy1—O11)^v···H3WA—O3W···H4WB—O4W. [Symmetry codes: (i): 2 - x, 1 - y, -z; (ii): 1 - x, 2 - y, -z; (iii): -1 + x, 1 + y, z; (iv): 2 - x, -y, -z; (v): 1 - x, 1 - y, -z.]

(I) di-µ-but-2-enoato-bis[diaquabis(but-2-enoato)dysprosium(III)] adenine monosolvate heptahydrate

Crystal data

[Dy(C4H5O2)6(H2O)4]·C5H5N5·7H2O	Z = 1
Mr = 1168.80	F(000) = 582
Triclinic, P1	Dx = 1.771 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.614 (3) Å	Cell parameters from 9064 reflections
b = 10.808 (3) Å	θ = 1.9–27.7°
c = 11.338 (3) Å	µ = 3.47 mm^−1
α = 73.075 (4)°	T = 291 K
β = 83.958 (5)°	Block, colourless
γ = 61.833 (5)°	0.22 × 0.20 × 0.12 mm
V = 1096.1 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4253 independent reflections
Radiation source: fine-focus sealed tube	4178 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
CCD rotation images, thin slices scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −13→13
Tmin = 0.42, Tmax = 0.66	k = −13→13
8551 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.046	w = 1/[σ^2(Fo^2) + (0.014P)^2 + 1.0859P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.003
4253 reflections	Δρmax = 0.86 e Å^−3
365 parameters	Δρmin = −0.60 e Å^−3
22 restraints	Extinction correction: SHELXL97 Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0105 (4)

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	Occ. (<1)
C1	0.9952 (9)	0.0288 (10)	0.3358 (8)	0.0349 (16)	0.50
H1	1.0051	0.0211	0.2554	0.042*	0.50
C2	1.0259 (6)	−0.0372 (7)	0.5351 (6)	0.0293 (12)	0.50
C3	1.0027 (7)	−0.0260 (7)	0.7275 (7)	0.0306 (13)	0.50
H3	1.0251	−0.0722	0.8111	0.037*	0.50
C4	0.8690 (6)	0.1884 (7)	0.5801 (7)	0.0263 (13)	0.50
C5	0.9286 (7)	0.1073 (8)	0.4928 (7)	0.0260 (12)	0.50
N1	0.9087 (19)	0.1513 (14)	0.3623 (18)	0.031 (2)	0.50
N2	1.0713 (6)	−0.0894 (6)	0.4354 (7)	0.0363 (12)	0.50
H2	1.142 (7)	−0.172 (6)	0.436 (10)	0.044*	0.50
N3	1.0698 (17)	−0.1118 (12)	0.6519 (17)	0.027 (2)	0.50
N4	0.9093 (5)	0.1145 (5)	0.7001 (4)	0.0308 (10)	0.50
N5	0.781 (2)	0.3295 (16)	0.550 (2)	0.036 (3)	0.50
H5A	0.760 (9)	0.389 (6)	0.593 (6)	0.044*	0.50
H5B	0.728 (8)	0.379 (7)	0.485 (5)	0.044*	0.50
O6W	1.234 (2)	−0.3712 (14)	0.449 (2)	0.041 (3)	0.50
H6WA	1.287 (7)	−0.427 (7)	0.513 (4)	0.049*	0.50
H6WB	1.288 (6)	−0.384 (8)	0.389 (4)	0.049*	0.50
Dy1	0.554568 (11)	0.588410 (11)	0.115150 (9)	0.02228 (6)
O11	0.35882 (19)	0.79135 (19)	−0.02367 (17)	0.0292 (4)
O21	0.5573 (2)	0.8066 (2)	−0.02418 (18)	0.0340 (4)
C11	0.4292 (3)	0.8640 (3)	−0.0623 (2)	0.0272 (5)
C21	0.3647 (3)	1.0109 (3)	−0.1493 (3)	0.0370 (6)
H21	0.4218	1.0569	−0.1758	0.044*
C31	0.2324 (3)	1.0807 (3)	−0.1918 (3)	0.0376 (6)
H31	0.1768	1.0330	−0.1649	0.045*
C41	0.1620 (4)	1.2294 (4)	−0.2792 (3)	0.0541 (9)
H41A	0.1351	1.2232	−0.3547	0.081*
H41B	0.2273	1.2702	−0.2961	0.081*
H41C	0.0783	1.2907	−0.2431	0.081*
O12	0.4564 (2)	0.7708 (2)	0.22721 (18)	0.0384 (5)
O22	0.6161 (2)	0.5532 (2)	0.32690 (18)	0.0401 (5)
C12	0.5266 (3)	0.6822 (3)	0.3263 (2)	0.0319 (6)
C22	0.5028 (4)	0.7265 (4)	0.4422 (3)	0.0430 (7)
H22	0.5478	0.6542	0.5143	0.052*
C32	0.4233 (4)	0.8592 (4)	0.4504 (3)	0.0436 (7)
H32	0.3791	0.9318	0.3782	0.052*
C42	0.3981 (4)	0.9033 (5)	0.5674 (3)	0.0558 (9)
H42A	0.4608	0.8229	0.6320	0.084*
H42B	0.3005	0.9307	0.5895	0.084*
H42C	0.4167	0.9847	0.5558	0.084*
O13	0.40146 (19)	0.4809 (2)	0.07176 (16)	0.0283 (4)
O23	0.3693 (2)	0.5420 (2)	0.24319 (18)	0.0350 (4)
C13	0.3417 (3)	0.4837 (3)	0.1755 (2)	0.0257 (5)
C23	0.2481 (3)	0.4138 (3)	0.2125 (3)	0.0356 (6)
H23	0.2367	0.3690	0.1586	0.043*
C33	0.1798 (4)	0.4100 (4)	0.3150 (3)	0.0437 (7)
H33	0.1911	0.4550	0.3688	0.052*
C43	0.0849 (5)	0.3389 (5)	0.3527 (4)	0.0621 (11)
H43A	0.0849	0.2938	0.2912	0.093*
H43B	−0.0107	0.4112	0.3607	0.093*
H43C	0.1196	0.2661	0.4304	0.093*
O1W	0.6943 (2)	0.3338 (2)	0.18512 (19)	0.0349 (4)
H1WA	0.758 (3)	0.278 (3)	0.242 (2)	0.042*
H1WB	0.692 (3)	0.279 (3)	0.146 (2)	0.042*
O2W	0.8024 (2)	0.5409 (2)	0.0973 (2)	0.0373 (4)
H2WA	0.838 (3)	0.599 (2)	0.071 (3)	0.045*
H2WB	0.862 (3)	0.4606 (17)	0.085 (3)	0.045*
O3W	0.9127 (3)	0.1509 (4)	−0.0703 (3)	0.0624 (7)
H3WA	0.834 (3)	0.161 (5)	−0.039 (3)	0.075*
H3WB	0.911 (4)	0.139 (5)	−0.140 (2)	0.075*
O4W	1.0226 (3)	0.3070 (3)	0.0195 (3)	0.0541 (6)
H4WA	1.090 (3)	0.232 (3)	0.065 (3)	0.065*
H4WB	0.986 (4)	0.272 (4)	−0.017 (3)	0.065*
O5W	1.2607 (2)	0.0781 (3)	0.1488 (3)	0.0529 (6)
H5WB	1.305 (3)	−0.0134 (11)	0.166 (4)	0.064*
H5WA	1.318 (3)	0.110 (3)	0.114 (3)	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.040 (4)	0.047 (5)	0.023 (4)	−0.022 (4)	0.002 (4)	−0.014 (4)
C2	0.028 (3)	0.029 (4)	0.028 (4)	−0.010 (3)	0.001 (2)	−0.009 (3)
C3	0.030 (3)	0.032 (3)	0.026 (3)	−0.013 (2)	0.001 (3)	−0.005 (3)
C4	0.026 (3)	0.030 (3)	0.028 (3)	−0.016 (3)	0.001 (2)	−0.009 (2)
C5	0.026 (3)	0.032 (4)	0.023 (3)	−0.015 (3)	0.005 (3)	−0.011 (3)
N1	0.035 (5)	0.020 (6)	0.032 (4)	−0.009 (5)	−0.001 (3)	−0.007 (5)
N2	0.034 (3)	0.034 (3)	0.038 (4)	−0.008 (2)	0.002 (3)	−0.020 (3)
N3	0.027 (5)	0.011 (6)	0.037 (6)	−0.002 (5)	−0.006 (4)	−0.005 (4)
N4	0.034 (2)	0.034 (2)	0.025 (2)	−0.015 (2)	0.0024 (18)	−0.0097 (19)
N5	0.038 (6)	0.031 (8)	0.031 (4)	−0.005 (7)	0.006 (4)	−0.016 (6)
O6W	0.040 (4)	0.035 (7)	0.034 (4)	0.001 (6)	−0.001 (3)	−0.023 (6)
Dy1	0.02409 (8)	0.02101 (8)	0.02058 (8)	−0.00905 (5)	0.00095 (4)	−0.00661 (5)
O11	0.0298 (9)	0.0264 (9)	0.0321 (10)	−0.0139 (8)	0.0011 (8)	−0.0076 (8)
O21	0.0293 (10)	0.0303 (10)	0.0390 (11)	−0.0141 (8)	−0.0021 (8)	−0.0031 (8)
C11	0.0301 (13)	0.0255 (12)	0.0265 (12)	−0.0122 (11)	0.0021 (10)	−0.0093 (10)
C21	0.0356 (15)	0.0327 (15)	0.0394 (16)	−0.0178 (13)	−0.0014 (12)	−0.0006 (12)
C31	0.0354 (15)	0.0343 (15)	0.0365 (15)	−0.0147 (13)	−0.0008 (12)	−0.0026 (12)
C41	0.0465 (19)	0.0424 (19)	0.051 (2)	−0.0103 (15)	−0.0080 (16)	0.0030 (16)
O12	0.0570 (13)	0.0267 (10)	0.0292 (10)	−0.0159 (9)	−0.0012 (9)	−0.0099 (8)
O22	0.0430 (12)	0.0385 (11)	0.0309 (10)	−0.0088 (9)	−0.0049 (9)	−0.0142 (9)
C12	0.0366 (15)	0.0376 (15)	0.0281 (13)	−0.0212 (13)	0.0022 (11)	−0.0113 (12)
C22	0.0499 (19)	0.0495 (19)	0.0295 (15)	−0.0196 (15)	0.0002 (13)	−0.0165 (14)
C32	0.057 (2)	0.0534 (19)	0.0369 (16)	−0.0351 (17)	0.0112 (14)	−0.0222 (14)
C42	0.071 (2)	0.074 (3)	0.050 (2)	−0.046 (2)	0.0265 (18)	−0.0406 (19)
O13	0.0317 (10)	0.0330 (10)	0.0236 (9)	−0.0169 (8)	0.0077 (7)	−0.0113 (8)
O23	0.0425 (11)	0.0457 (12)	0.0315 (10)	−0.0284 (10)	0.0125 (8)	−0.0208 (9)
C13	0.0265 (12)	0.0250 (12)	0.0238 (12)	−0.0102 (10)	0.0042 (10)	−0.0084 (10)
C23	0.0390 (15)	0.0459 (17)	0.0328 (14)	−0.0276 (14)	0.0070 (12)	−0.0138 (13)
C33	0.0500 (19)	0.061 (2)	0.0360 (16)	−0.0377 (17)	0.0120 (14)	−0.0178 (15)
C43	0.070 (3)	0.088 (3)	0.051 (2)	−0.060 (2)	0.0189 (18)	−0.015 (2)
O1W	0.0408 (11)	0.0229 (9)	0.0351 (11)	−0.0080 (8)	−0.0131 (9)	−0.0066 (8)
O2W	0.0294 (10)	0.0343 (11)	0.0476 (12)	−0.0146 (9)	0.0023 (9)	−0.0112 (10)
O3W	0.0448 (14)	0.087 (2)	0.0557 (16)	−0.0329 (14)	0.0057 (12)	−0.0179 (15)
O4W	0.0462 (14)	0.0402 (13)	0.0647 (17)	−0.0110 (11)	−0.0043 (12)	−0.0126 (12)
O5W	0.0364 (12)	0.0411 (13)	0.0701 (17)	−0.0155 (10)	0.0061 (11)	−0.0056 (12)

Geometric parameters (Å, º)

C1—N1	1.309 (11)	C41—H41A	0.9600
C1—N2	1.392 (11)	C41—H41B	0.9600
C1—H1	0.9300	C41—H41C	0.9600
C2—N3	1.332 (19)	O12—C12	1.270 (3)
C2—N2	1.353 (9)	O22—C12	1.262 (3)
C2—C5	1.372 (10)	C12—C22	1.484 (4)
C3—N4	1.325 (8)	C22—C32	1.303 (5)
C3—N3	1.346 (12)	C22—H22	0.9300
C3—H3	0.9300	C32—C42	1.493 (4)
C4—N5	1.317 (16)	C32—H32	0.9300
C4—N4	1.356 (8)	C42—H42A	0.9600
C4—C5	1.414 (10)	C42—H42B	0.9600
C5—N1	1.42 (2)	C42—H42C	0.9600
N2—H2	0.85 (3)	O13—C13	1.278 (3)
N5—H5A	0.85 (3)	O23—C13	1.254 (3)
N5—H5B	0.85 (3)	C13—C23	1.474 (4)
O6W—H6WA	0.85 (3)	C23—C33	1.304 (4)
O6W—H6WB	0.85 (3)	C23—H23	0.9300
Dy1—O1W	2.3504 (19)	C33—C43	1.496 (4)
Dy1—O13^i	2.3784 (18)	C33—H33	0.9300
Dy1—O12	2.4142 (19)	C43—H43A	0.9600
Dy1—O2W	2.428 (2)	C43—H43B	0.9600
Dy1—O22	2.429 (2)	C43—H43C	0.9600
Dy1—O21	2.4380 (19)	O1W—H1WA	0.85 (3)
Dy1—O11	2.4456 (19)	O1W—H1WB	0.85 (3)
Dy1—O23	2.4763 (19)	O2W—H2WA	0.85 (3)
Dy1—O13	2.5524 (19)	O2W—H2WB	0.85 (3)
O11—C11	1.285 (3)	O3W—H3WA	0.85 (3)
O21—C11	1.262 (3)	O3W—H3WB	0.85 (3)
C11—C21	1.472 (4)	O4W—H4WA	0.85 (3)
C21—C31	1.304 (4)	O4W—H4WB	0.85 (3)
C21—H21	0.9300	O5W—H5WB	0.85 (3)
C31—C41	1.490 (4)	O5W—H5WA	0.85 (3)
C31—H31	0.9300
N1—C1—N2	115.9 (13)	C12—Dy1—C11	99.06 (8)
N1—C1—H1	122.1	O1W—Dy1—C13	76.86 (7)
N2—C1—H1	122.1	O13^i—Dy1—C13	90.17 (6)
N3—C2—N2	126.3 (8)	O12—Dy1—C13	97.81 (7)
N3—C2—C5	126.7 (9)	O2W—Dy1—C13	150.45 (7)
N2—C2—C5	107.0 (5)	O22—Dy1—C13	95.97 (7)
N4—C3—N3	129.4 (9)	O21—Dy1—C13	134.50 (7)
N4—C3—H3	115.3	O11—Dy1—C13	81.24 (7)
N3—C3—H3	115.3	O23—Dy1—C13	25.28 (7)
N5—C4—N4	119.6 (12)	O13—Dy1—C13	25.97 (6)
N5—C4—C5	123.6 (12)	C12—Dy1—C13	96.60 (7)
N4—C4—C5	116.7 (6)	C11—Dy1—C13	108.14 (7)
C2—C5—C4	117.8 (7)	C11—O11—Dy1	93.57 (15)
C2—C5—N1	111.6 (9)	C11—O21—Dy1	94.55 (15)
C4—C5—N1	130.6 (7)	O21—C11—O11	118.5 (2)
C1—N1—C5	100.9 (13)	O21—C11—C21	119.6 (2)
C2—N2—C1	104.7 (6)	O11—C11—C21	121.9 (2)
C2—N2—H2	125 (8)	O21—C11—Dy1	59.08 (13)
C1—N2—H2	130 (8)	O11—C11—Dy1	59.50 (13)
C2—N3—C3	110.6 (10)	C21—C11—Dy1	176.8 (2)
C3—N4—C4	118.6 (5)	C31—C21—C11	124.2 (3)
C4—N5—H5A	128 (5)	C31—C21—H21	117.9
C4—N5—H5B	126 (5)	C11—C21—H21	117.9
H5A—N5—H5B	105 (3)	C21—C31—C41	126.2 (3)
H6WA—O6W—H6WB	105 (3)	C21—C31—H31	116.9
O1W—Dy1—O13^i	77.86 (7)	C41—C31—H31	116.9
O1W—Dy1—O12	130.44 (7)	C31—C41—H41A	109.5
O13^i—Dy1—O12	151.64 (7)	C31—C41—H41B	109.5
O1W—Dy1—O2W	73.62 (7)	H41A—C41—H41B	109.5
O13^i—Dy1—O2W	82.42 (7)	C31—C41—H41C	109.5
O12—Dy1—O2W	102.24 (7)	H41A—C41—H41C	109.5
O1W—Dy1—O22	77.62 (7)	H41B—C41—H41C	109.5
O13^i—Dy1—O22	152.62 (7)	C12—O12—Dy1	93.62 (17)
O12—Dy1—O22	53.65 (7)	C12—O22—Dy1	93.15 (16)
O2W—Dy1—O22	79.14 (7)	O22—C12—O12	119.4 (2)
O1W—Dy1—O21	142.06 (7)	O22—C12—C22	119.4 (3)
O13^i—Dy1—O21	80.99 (7)	O12—C12—C22	121.2 (3)
O12—Dy1—O21	74.00 (7)	O22—C12—Dy1	60.09 (14)
O2W—Dy1—O21	72.64 (7)	O12—C12—Dy1	59.45 (14)
O22—Dy1—O21	112.09 (7)	C22—C12—Dy1	174.9 (2)
O1W—Dy1—O11	146.32 (6)	C32—C22—C12	124.8 (3)
O13^i—Dy1—O11	76.92 (6)	C32—C22—H22	117.6
O12—Dy1—O11	77.48 (7)	C12—C22—H22	117.6
O2W—Dy1—O11	124.12 (7)	C22—C32—C42	124.7 (3)
O22—Dy1—O11	130.37 (6)	C22—C32—H32	117.6
O21—Dy1—O11	53.26 (6)	C42—C32—H32	117.6
O1W—Dy1—O23	84.06 (7)	C32—C42—H42A	109.5
O13^i—Dy1—O23	115.44 (6)	C32—C42—H42B	109.5
O12—Dy1—O23	75.01 (7)	H42A—C42—H42B	109.5
O2W—Dy1—O23	147.98 (7)	C32—C42—H42C	109.5
O22—Dy1—O23	73.77 (7)	H42A—C42—H42C	109.5
O21—Dy1—O23	133.71 (7)	H42B—C42—H42C	109.5
O11—Dy1—O23	86.96 (7)	C13—O13—Dy1^i	150.93 (17)
O1W—Dy1—O13	74.47 (7)	C13—O13—Dy1	93.02 (15)
O13^i—Dy1—O13	64.26 (7)	Dy1^i—O13—Dy1	115.74 (7)
O12—Dy1—O13	119.54 (7)	C13—O23—Dy1	97.26 (15)
O2W—Dy1—O13	137.72 (7)	O23—C13—O13	118.2 (2)
O22—Dy1—O13	119.67 (7)	O23—C13—C23	122.9 (2)
O21—Dy1—O13	122.79 (6)	O13—C13—C23	118.8 (2)
O11—Dy1—O13	74.63 (6)	O23—C13—Dy1	57.46 (13)
O23—Dy1—O13	51.19 (6)	O13—C13—Dy1	61.01 (13)
O1W—Dy1—C12	103.80 (8)	C23—C13—Dy1	173.30 (19)
O13^i—Dy1—C12	173.22 (7)	C33—C23—C13	124.9 (3)
O12—Dy1—C12	26.93 (8)	C33—C23—H23	117.5
O2W—Dy1—C12	91.72 (8)	C13—C23—H23	117.5
O22—Dy1—C12	26.76 (8)	C23—C33—C43	125.0 (3)
O21—Dy1—C12	94.06 (8)	C23—C33—H33	117.5
O11—Dy1—C12	103.87 (8)	C43—C33—H33	117.5
O23—Dy1—C12	71.33 (7)	C33—C43—H43A	109.5
O13—Dy1—C12	122.50 (7)	C33—C43—H43B	109.5
O1W—Dy1—C11	155.90 (7)	H43A—C43—H43B	109.5
O13^i—Dy1—C11	78.55 (7)	C33—C43—H43C	109.5
O12—Dy1—C11	73.09 (7)	H43A—C43—H43C	109.5
O2W—Dy1—C11	98.39 (7)	H43B—C43—H43C	109.5
O22—Dy1—C11	123.99 (7)	H1WA—O1W—H1WB	105 (3)
O21—Dy1—C11	26.36 (7)	H2WA—O2W—H2WB	106 (3)
O11—Dy1—C11	26.93 (7)	H3WA—O3W—H3WB	105 (3)
O23—Dy1—C11	110.74 (7)	H4WA—O4W—H4WB	104 (3)
O13—Dy1—C11	99.53 (7)	H5WB—O5W—H5WA	107 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O11^i	0.85 (3)	1.99 (3)	2.807 (3)	162 (3)
N2—H2···N5^ii	0.85 (3)	1.47 (3)	2.278 (14)	158 (11)
N2—H2···O6W	0.85 (3)	1.86 (3)	2.663 (14)	156 (10)
N5—H5A···O23^iii	0.85 (3)	2.28 (3)	2.99 (2)	143 (8)
N5—H5B···O22	0.85 (3)	2.13 (3)	2.95 (2)	161 (7)
O6W—H6WA···O22^ii	0.85 (3)	1.96 (3)	2.80 (2)	172 (7)
O6W—H6WB···O23^iv	0.85 (3)	1.98 (3)	2.779 (19)	156 (8)
O3W—H3WB···N4^v	0.85 (3)	1.90 (3)	2.749 (5)	178 (4)
O1W—H1WA···N1	0.85 (3)	1.89 (3)	2.742 (19)	176 (3)
O1W—H1WA···N3^ii	0.85 (3)	2.03 (3)	2.857 (16)	165 (3)
O2W—H2WA···O4W^vi	0.85 (3)	2.18 (3)	3.001 (3)	163 (3)
O2W—H2WB···O4W	0.85 (3)	1.99 (3)	2.814 (3)	164 (3)
O3W—H3WA···O11^i	0.85 (3)	1.96 (3)	2.806 (3)	173 (5)
O4W—H4WA···O5W	0.85 (3)	1.88 (3)	2.724 (3)	170 (4)
O4W—H4WB···O3W	0.85 (3)	2.05 (3)	2.890 (4)	168 (3)
O5W—H5WB···O12^iv	0.85 (3)	2.06 (3)	2.879 (3)	164 (4)
O5W—H5WA···O21^vi	0.85 (3)	1.98 (3)	2.820 (3)	176 (4)

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

(II) di-µ-but-2-enoato-bis[diaquabis(but-2-enoato)samarium(III)] adenine monosolvate heptahydrate

Crystal data

[Sm(C4H5O2)6(H2O)4]·C5H5N5·7H2O	Z = 1
Mr = 1144.50	F(000) = 574
Triclinic, P1	Dx = 1.716 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.633 (3) Å	Cell parameters from 9182 reflections
b = 10.847 (3) Å	θ = 1.9–27.9°
c = 11.397 (3) Å	µ = 2.71 mm^−1
α = 73.126 (4)°	T = 291 K
β = 83.926 (4)°	Block, colourless
γ = 61.784 (5)°	0.28 × 0.24 × 0.14 mm
V = 1107.7 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4295 independent reflections
Radiation source: fine-focus sealed tube	4154 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
CCD rotation images, thin slices scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −13→13
Tmin = 0.44, Tmax = 0.68	k = −13→13
8609 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.043	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 0.3677P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
4295 reflections	Δρmax = 0.53 e Å^−3
365 parameters	Δρmin = −0.50 e Å^−3
22 restraints	Extinction correction: SHELXL97 Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0148 (5)

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	Occ. (<1)
C1	0.9976 (7)	0.0253 (8)	0.3387 (6)	0.0359 (12)	0.50
H1	1.0101	0.0166	0.2589	0.043*	0.50
C2	1.0248 (5)	−0.0369 (6)	0.5371 (5)	0.0292 (10)	0.50
C3	1.0006 (5)	−0.0246 (5)	0.7278 (6)	0.0315 (10)	0.50
H3	1.0230	−0.0697	0.8111	0.038*	0.50
C4	0.8680 (4)	0.1890 (5)	0.5787 (5)	0.0250 (10)	0.50
C5	0.9279 (6)	0.1064 (7)	0.4928 (6)	0.0254 (10)	0.50
N1	0.9088 (14)	0.1490 (12)	0.3640 (13)	0.0318 (19)	0.50
N2	1.0709 (5)	−0.0907 (5)	0.4388 (6)	0.0335 (10)	0.50
H2	1.144 (5)	−0.169 (5)	0.435 (8)	0.040*	0.50
N3	1.0674 (13)	−0.1108 (10)	0.6531 (12)	0.0281 (18)	0.50
N4	0.9069 (4)	0.1165 (4)	0.6991 (3)	0.0301 (8)	0.50
N5	0.775 (3)	0.334 (2)	0.549 (2)	0.038 (3)	0.50
H5A	0.754 (8)	0.380 (8)	0.603 (5)	0.045*	0.50
H5B	0.746 (7)	0.400 (6)	0.481 (4)	0.045*	0.50
O6W	1.226 (2)	−0.3692 (17)	0.4500 (18)	0.048 (3)	0.50
H6WA	1.281 (7)	−0.385 (9)	0.507 (4)	0.058*	0.50
H6WB	1.279 (7)	−0.387 (9)	0.390 (5)	0.058*	0.50
Sm1	0.555267 (9)	0.589467 (9)	0.115954 (8)	0.02219 (5)
O11	0.35694 (15)	0.79566 (15)	−0.02599 (14)	0.0298 (3)
O21	0.55475 (16)	0.81166 (16)	−0.02557 (15)	0.0341 (3)
C11	0.4270 (2)	0.8674 (2)	−0.06356 (19)	0.0268 (4)
C21	0.3624 (3)	1.0138 (3)	−0.1506 (2)	0.0380 (5)
H21	0.4195	1.0596	−0.1769	0.046*
C31	0.2311 (3)	1.0829 (3)	−0.1928 (2)	0.0385 (5)
H31	0.1756	1.0354	−0.1660	0.046*
C41	0.1607 (3)	1.2310 (3)	−0.2801 (3)	0.0541 (7)
H41A	0.1261	1.2257	−0.3520	0.081*
H41B	0.2285	1.2680	−0.3029	0.081*
H41C	0.0821	1.2947	−0.2415	0.081*
O12	0.45474 (19)	0.77277 (16)	0.23143 (14)	0.0376 (4)
O22	0.61570 (18)	0.55584 (18)	0.33015 (14)	0.0399 (4)
C12	0.5244 (2)	0.6846 (3)	0.3297 (2)	0.0327 (5)
C22	0.5008 (3)	0.7288 (3)	0.4445 (2)	0.0435 (6)
H22	0.5461	0.6568	0.5161	0.052*
C32	0.4214 (3)	0.8610 (3)	0.4528 (2)	0.0444 (6)
H32	0.3771	0.9329	0.3809	0.053*
C42	0.3955 (3)	0.9068 (4)	0.5684 (3)	0.0567 (8)
H42A	0.4561	0.8267	0.6337	0.085*
H42B	0.2974	0.9367	0.5891	0.085*
H42C	0.4162	0.9865	0.5567	0.085*
O13	0.40052 (15)	0.48138 (16)	0.07408 (13)	0.0282 (3)
O23	0.36698 (18)	0.54108 (19)	0.24571 (15)	0.0360 (4)
C13	0.3409 (2)	0.4831 (2)	0.17792 (18)	0.0258 (4)
C23	0.2478 (2)	0.4128 (3)	0.2140 (2)	0.0361 (5)
H23	0.2370	0.3683	0.1600	0.043*
C33	0.1795 (3)	0.4085 (3)	0.3161 (2)	0.0433 (6)
H33	0.1904	0.4530	0.3701	0.052*
C43	0.0850 (4)	0.3372 (4)	0.3529 (3)	0.0629 (8)
H43A	0.0924	0.2847	0.2955	0.094*
H43B	−0.0122	0.4101	0.3534	0.094*
H43C	0.1141	0.2710	0.4335	0.094*
O1W	0.69952 (18)	0.32990 (16)	0.18569 (15)	0.0367 (4)
H1WA	0.763 (2)	0.274 (2)	0.2418 (17)	0.044*
H1WB	0.694 (3)	0.278 (2)	0.146 (2)	0.044*
O2W	0.80789 (16)	0.54076 (18)	0.09538 (16)	0.0376 (4)
H2WA	0.847 (2)	0.594 (2)	0.072 (2)	0.045*
H2WB	0.866 (2)	0.4587 (14)	0.085 (3)	0.045*
O3W	0.9125 (2)	0.1513 (3)	−0.0702 (2)	0.0648 (6)
H3WA	0.833 (2)	0.161 (4)	−0.040 (3)	0.078*
H3WB	0.913 (3)	0.133 (4)	−0.1372 (19)	0.078*
O4W	1.0245 (2)	0.3047 (2)	0.0189 (2)	0.0515 (5)
H4WA	1.087 (3)	0.229 (2)	0.067 (2)	0.062*
H4WB	0.985 (3)	0.274 (3)	−0.019 (2)	0.062*
O5W	1.26049 (19)	0.0783 (2)	0.1491 (2)	0.0534 (5)
H5WB	1.298 (3)	−0.0123 (11)	0.173 (3)	0.064*
H5WA	1.324 (2)	0.102 (3)	0.117 (3)	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.041 (3)	0.050 (4)	0.022 (3)	−0.023 (3)	0.002 (3)	−0.014 (3)
C2	0.029 (3)	0.033 (3)	0.028 (3)	−0.014 (2)	0.000 (2)	−0.011 (2)
C3	0.033 (2)	0.030 (2)	0.027 (3)	−0.0134 (19)	−0.003 (2)	−0.003 (2)
C4	0.025 (2)	0.028 (2)	0.026 (2)	−0.0155 (19)	−0.0017 (16)	−0.0058 (18)
C5	0.029 (3)	0.036 (3)	0.015 (3)	−0.016 (2)	−0.001 (2)	−0.008 (3)
N1	0.034 (5)	0.026 (5)	0.035 (4)	−0.011 (4)	0.001 (3)	−0.012 (3)
N2	0.033 (2)	0.029 (3)	0.036 (3)	−0.0066 (19)	−0.001 (2)	−0.018 (2)
N3	0.027 (4)	0.013 (5)	0.033 (5)	0.000 (4)	−0.006 (3)	−0.004 (3)
N4	0.0347 (19)	0.0304 (18)	0.0247 (18)	−0.0147 (16)	0.0006 (15)	−0.0077 (15)
N5	0.041 (4)	0.049 (7)	0.022 (3)	−0.018 (6)	−0.001 (3)	−0.012 (5)
O6W	0.051 (4)	0.055 (7)	0.035 (4)	−0.014 (5)	0.003 (3)	−0.026 (5)
Sm1	0.02521 (7)	0.02167 (7)	0.01990 (7)	−0.01037 (5)	0.00044 (4)	−0.00677 (4)
O11	0.0298 (7)	0.0267 (7)	0.0329 (8)	−0.0137 (6)	−0.0004 (6)	−0.0066 (6)
O21	0.0306 (8)	0.0307 (8)	0.0386 (9)	−0.0156 (7)	−0.0030 (7)	−0.0022 (7)
C11	0.0310 (10)	0.0258 (10)	0.0246 (10)	−0.0129 (8)	0.0022 (8)	−0.0092 (8)
C21	0.0366 (12)	0.0321 (11)	0.0423 (13)	−0.0181 (10)	−0.0033 (10)	−0.0006 (10)
C31	0.0362 (12)	0.0362 (12)	0.0370 (13)	−0.0148 (10)	−0.0018 (10)	−0.0041 (10)
C41	0.0499 (15)	0.0410 (14)	0.0501 (16)	−0.0105 (12)	−0.0072 (13)	0.0015 (12)
O12	0.0560 (10)	0.0282 (8)	0.0272 (8)	−0.0164 (7)	−0.0015 (7)	−0.0101 (6)
O22	0.0445 (9)	0.0378 (9)	0.0296 (8)	−0.0092 (7)	−0.0057 (7)	−0.0137 (7)
C12	0.0397 (12)	0.0383 (12)	0.0275 (11)	−0.0230 (10)	0.0022 (9)	−0.0112 (10)
C22	0.0521 (15)	0.0508 (15)	0.0301 (12)	−0.0220 (12)	0.0000 (11)	−0.0174 (11)
C32	0.0589 (15)	0.0552 (15)	0.0371 (13)	−0.0373 (13)	0.0122 (12)	−0.0224 (12)
C42	0.0750 (19)	0.077 (2)	0.0489 (16)	−0.0506 (17)	0.0263 (14)	−0.0423 (15)
O13	0.0327 (7)	0.0337 (8)	0.0221 (7)	−0.0178 (6)	0.0066 (6)	−0.0111 (6)
O23	0.0455 (9)	0.0489 (9)	0.0317 (8)	−0.0319 (8)	0.0148 (7)	−0.0233 (7)
C13	0.0268 (9)	0.0253 (9)	0.0229 (10)	−0.0105 (8)	0.0037 (8)	−0.0074 (8)
C23	0.0418 (12)	0.0478 (13)	0.0314 (12)	−0.0295 (11)	0.0078 (10)	−0.0155 (10)
C33	0.0508 (14)	0.0604 (16)	0.0359 (13)	−0.0383 (13)	0.0116 (11)	−0.0187 (12)
C43	0.0704 (19)	0.089 (2)	0.0521 (17)	−0.0609 (19)	0.0171 (15)	−0.0143 (16)
O1W	0.0442 (9)	0.0238 (7)	0.0361 (9)	−0.0089 (7)	−0.0151 (7)	−0.0064 (6)
O2W	0.0295 (8)	0.0367 (9)	0.0472 (10)	−0.0159 (7)	0.0023 (7)	−0.0116 (8)
O3W	0.0491 (11)	0.0968 (17)	0.0560 (13)	−0.0395 (12)	0.0094 (10)	−0.0243 (12)
O4W	0.0452 (10)	0.0408 (10)	0.0628 (13)	−0.0145 (8)	−0.0030 (9)	−0.0139 (9)
O5W	0.0382 (9)	0.0394 (10)	0.0699 (14)	−0.0157 (8)	0.0043 (9)	−0.0021 (9)

Geometric parameters (Å, º)

C1—N1	1.321 (8)	C41—H41A	0.9600
C1—N2	1.385 (8)	C41—H41B	0.9600
C1—H1	0.9300	C41—H41C	0.9600
C2—N3	1.328 (14)	O12—C12	1.266 (3)
C2—N2	1.353 (7)	O22—C12	1.268 (3)
C2—C5	1.368 (8)	C12—C22	1.478 (3)
C3—N4	1.334 (6)	C22—C32	1.303 (4)
C3—N3	1.345 (9)	C22—H22	0.9300
C3—H3	0.9300	C32—C42	1.494 (3)
C4—N4	1.364 (7)	C32—H32	0.9300
C4—N5	1.36 (2)	C42—H42A	0.9600
C4—C5	1.415 (8)	C42—H42B	0.9600
C5—N1	1.411 (16)	C42—H42C	0.9600
N2—H2	0.85 (3)	O13—C13	1.283 (2)
N5—H5A	0.85 (3)	O23—C13	1.250 (3)
N5—H5B	0.85 (3)	C13—C23	1.475 (3)
O6W—H6WA	0.85 (3)	C23—C33	1.307 (3)
O6W—H6WB	0.85 (3)	C23—H23	0.9300
Sm1—O1W	2.4057 (16)	C33—C43	1.498 (3)
Sm1—O13^i	2.4314 (15)	C33—H33	0.9300
Sm1—O12	2.4576 (16)	C43—H43A	0.9600
Sm1—O22	2.4695 (17)	C43—H43B	0.9600
Sm1—O21	2.4785 (16)	C43—H43C	0.9600
Sm1—O2W	2.4792 (17)	O1W—H1WA	0.85 (3)
Sm1—O11	2.4956 (15)	O1W—H1WB	0.85 (3)
Sm1—O23	2.5273 (16)	O2W—H2WA	0.85 (3)
Sm1—O13	2.5739 (15)	O2W—H2WB	0.85 (3)
O11—C11	1.277 (3)	O3W—H3WA	0.85 (3)
O21—C11	1.263 (3)	O3W—H3WB	0.85 (3)
C11—C21	1.474 (3)	O4W—H4WA	0.85 (3)
C21—C31	1.299 (3)	O4W—H4WB	0.85 (3)
C21—H21	0.9300	O5W—H5WB	0.85 (3)
C31—C41	1.491 (3)	O5W—H5WA	0.85 (3)
C31—H31	0.9300
N1—C1—N2	115.6 (10)	C12—Sm1—C11	99.31 (7)
N1—C1—H1	122.2	O1W—Sm1—C13	77.05 (6)
N2—C1—H1	122.2	O13^i—Sm1—C13	90.14 (5)
N3—C2—N2	125.8 (6)	O12—Sm1—C13	97.28 (6)
N3—C2—C5	127.7 (8)	O22—Sm1—C13	95.60 (6)
N2—C2—C5	106.5 (4)	O21—Sm1—C13	134.01 (5)
N4—C3—N3	129.0 (7)	O2W—Sm1—C13	150.24 (6)
N4—C3—H3	115.5	O11—Sm1—C13	81.74 (5)
N3—C3—H3	115.5	O23—Sm1—C13	24.88 (5)
N4—C4—N5	118.7 (10)	O13—Sm1—C13	25.72 (5)
N4—C4—C5	116.8 (4)	C12—Sm1—C13	95.96 (6)
N5—C4—C5	124.5 (10)	C11—Sm1—C13	108.04 (6)
C2—C5—C4	117.3 (6)	C11—O11—Sm1	93.58 (12)
C2—C5—N1	112.4 (8)	C11—O21—Sm1	94.76 (12)
C4—C5—N1	130.3 (6)	O21—C11—O11	119.25 (18)
C1—N1—C5	100.5 (10)	O21—C11—C21	119.14 (19)
C2—N2—C1	105.0 (5)	O11—C11—C21	121.60 (19)
C2—N2—H2	128 (6)	O21—C11—Sm1	59.26 (10)
C1—N2—H2	125 (6)	O11—C11—Sm1	60.08 (10)
C2—N3—C3	110.5 (7)	C21—C11—Sm1	176.69 (16)
C3—N4—C4	118.5 (4)	C31—C21—C11	124.3 (2)
C4—N5—H5A	119 (5)	C31—C21—H21	117.9
C4—N5—H5B	133 (5)	C11—C21—H21	117.9
H5A—N5—H5B	105 (3)	C21—C31—C41	126.3 (2)
H6WA—O6W—H6WB	106 (3)	C21—C31—H31	116.8
O1W—Sm1—O13^i	77.55 (5)	C41—C31—H31	116.8
O1W—Sm1—O12	130.25 (6)	C31—C41—H41A	109.5
O13^i—Sm1—O12	152.16 (5)	C31—C41—H41B	109.5
O1W—Sm1—O22	78.31 (5)	H41A—C41—H41B	109.5
O13^i—Sm1—O22	153.22 (5)	C31—C41—H41C	109.5
O12—Sm1—O22	52.77 (5)	H41A—C41—H41C	109.5
O1W—Sm1—O21	142.17 (6)	H41B—C41—H41C	109.5
O13^i—Sm1—O21	81.01 (5)	C12—O12—Sm1	94.01 (13)
O12—Sm1—O21	74.54 (6)	C12—O22—Sm1	93.40 (13)
O22—Sm1—O21	112.27 (6)	O12—C12—O22	119.6 (2)
O1W—Sm1—O2W	73.24 (6)	O12—C12—C22	121.1 (2)
O13^i—Sm1—O2W	81.98 (5)	O22—C12—C22	119.3 (2)
O12—Sm1—O2W	103.04 (6)	O12—C12—Sm1	59.61 (11)
O22—Sm1—O2W	80.11 (6)	O22—C12—Sm1	60.16 (11)
O21—Sm1—O2W	73.19 (5)	C22—C12—Sm1	175.49 (17)
O1W—Sm1—O11	146.23 (5)	C32—C22—C12	124.9 (2)
O13^i—Sm1—O11	76.52 (5)	C32—C22—H22	117.6
O12—Sm1—O11	78.05 (5)	C12—C22—H22	117.6
O22—Sm1—O11	130.17 (5)	C22—C32—C42	125.4 (3)
O21—Sm1—O11	52.28 (5)	C22—C32—H32	117.3
O2W—Sm1—O11	123.46 (5)	C42—C32—H32	117.3
O1W—Sm1—O23	84.26 (6)	C32—C42—H42A	109.5
O13^i—Sm1—O23	115.01 (5)	C32—C42—H42B	109.5
O12—Sm1—O23	74.76 (6)	H42A—C42—H42B	109.5
O22—Sm1—O23	73.66 (6)	C32—C42—H42C	109.5
O21—Sm1—O23	133.33 (5)	H42A—C42—H42C	109.5
O2W—Sm1—O23	148.37 (6)	H42B—C42—H42C	109.5
O11—Sm1—O23	87.44 (6)	C13—O13—Sm1^i	150.42 (13)
O1W—Sm1—O13	74.62 (6)	C13—O13—Sm1	93.72 (12)
O13^i—Sm1—O13	64.49 (5)	Sm1^i—O13—Sm1	115.51 (5)
O12—Sm1—O13	118.86 (5)	C13—O23—Sm1	96.82 (12)
O22—Sm1—O13	119.24 (5)	O23—C13—O13	118.59 (19)
O21—Sm1—O13	122.45 (5)	O23—C13—C23	122.71 (19)
O2W—Sm1—O13	137.55 (5)	O13—C13—C23	118.67 (19)
O11—Sm1—O13	74.86 (5)	O23—C13—Sm1	58.30 (11)
O23—Sm1—O13	50.53 (5)	O13—C13—Sm1	60.56 (10)
O1W—Sm1—C12	104.15 (6)	C23—C13—Sm1	173.30 (15)
O13^i—Sm1—C12	173.89 (5)	C33—C23—C13	124.8 (2)
O12—Sm1—C12	26.38 (6)	C33—C23—H23	117.6
O22—Sm1—C12	26.44 (6)	C13—C23—H23	117.6
O21—Sm1—C12	94.42 (6)	C23—C33—C43	124.9 (3)
O2W—Sm1—C12	92.84 (6)	C23—C33—H33	117.6
O11—Sm1—C12	103.93 (6)	C43—C33—H33	117.6
O23—Sm1—C12	71.09 (6)	C33—C43—H43A	109.5
O13—Sm1—C12	121.59 (6)	C33—C43—H43B	109.5
O1W—Sm1—C11	155.38 (6)	H43A—C43—H43B	109.5
O13^i—Sm1—C11	78.36 (6)	C33—C43—H43C	109.5
O12—Sm1—C11	73.83 (6)	H43A—C43—H43C	109.5
O22—Sm1—C11	123.90 (6)	H43B—C43—H43C	109.5
O21—Sm1—C11	25.97 (5)	H1WA—O1W—H1WB	107 (3)
O2W—Sm1—C11	98.45 (6)	H2WA—O2W—H2WB	107 (3)
O11—Sm1—C11	26.33 (5)	H3WA—O3W—H3WB	105 (3)
O23—Sm1—C11	110.69 (6)	H4WA—O4W—H4WB	105 (3)
O13—Sm1—C11	99.34 (6)	H5WB—O5W—H5WA	108 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O11^i	0.85 (3)	2.00 (3)	2.823 (2)	165 (2)
N2—H2···N5^ii	0.85 (3)	1.54 (3)	2.325 (19)	154 (8)
N2—H2···O6W	0.85 (3)	1.88 (3)	2.640 (17)	149 (7)
N5—H5A···O23^iii	0.85 (3)	2.17 (3)	2.96 (2)	154 (6)
N5—H5B···O22	0.85 (3)	2.08 (3)	2.90 (2)	162 (6)
O6W—H6WA···O22^ii	0.85 (3)	2.14 (3)	2.82 (2)	137 (7)
O6W—H6WB···O23^iv	0.85 (3)	1.97 (3)	2.79 (2)	163 (6)
O1W—H1WA···N1	0.85 (3)	1.88 (3)	2.729 (15)	178 (3)
O1W—H1WA···N3^ii	0.85 (3)	2.00 (3)	2.833 (12)	166 (2)
O3W—H3WB···N4^v	0.85 (3)	1.93 (3)	2.772 (4)	172 (4)
O2W—H2WA···O4W^vi	0.85 (3)	2.14 (3)	2.958 (3)	165 (2)
O2W—H2WB···O4W	0.85 (3)	2.00 (3)	2.814 (3)	161 (2)
O3W—H3WA···O11^i	0.85 (3)	1.96 (3)	2.808 (3)	174 (4)
O4W—H4WA···O5W	0.85 (3)	1.89 (3)	2.715 (3)	164 (3)
O4W—H4WB···O3W	0.85 (3)	2.06 (3)	2.886 (3)	164 (3)
O5W—H5WB···O12^iv	0.85 (3)	2.07 (3)	2.875 (2)	160 (3)
O5W—H5WA···O21^vi	0.85 (3)	1.98 (3)	2.815 (2)	170 (3)

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