catena-Poly[[[tetra­kis(μ-2-butenoato)dicopper(II)]-μ-2-butenoato-[diaqua­(2-butenoato)holmium(III)]-di-μ-2-butenoato-[diaqua­(2-butenoato)holmium(III)]-μ-2-butenoato] trihydrate]

Perec, M.; Garland, M.T.; Baggio, R.

doi:10.1107/S1600536808034296

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Pages m1463-m1464

doi:10.1107/S1600536808034296

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catena-Poly[[[tetrakis(μ-2-butenoato)dicopper(II)]-μ-2-butenoato-[diaqua(2-butenoato)holmium(III)]-di-μ-2-butenoato-[diaqua(2-butenoato)holmium(III)]-μ-2-butenoato] trihydrate]

Mireille Perec,^a Maria Teresa Garland ^b and Ricardo Baggio ^c ^*

^aDepartamento de Química Inorgánica, Analítica y Química Física, INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires, Argentina, ^bDepartamento de Física, Facultad de Ciencias Físicas y Matemáticas and CIMAT, Universidad de Chile, Santiago de Chile, Chile, and ^cDepartamento de Física, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica., Buenos Aires, Argentina
^*Correspondence e-mail: baggio@cnea.gov.ar

(Received 14 October 2008; accepted 20 October 2008; online 25 October 2008)

The title compound {[Cu₂Ho₂(C₄H₅O₂)₁₀(H₂O)₄]·3H₂O}_n, is a one-dimensional 3d/4f organic–inorganic hybrid complex, the Ho^III member of the isotypic lanthanoid series with Ln = Gd^III, Er^III and Y^III. The structure shows an alternation of Cu₂ and Ho₂ dinuclear units bridged by the ligands and hydrogen bonds only. The chains are composed of Cu₂ classical dinuclear η¹:η¹:μ₂ fourfold bridges [Cu⋯Cu = 2.6417 (9) Å] and of Ho₂ units bridged by two η²:η¹:μ₂ carboxylate units. This results in distorted square-based pyramidal CuO₅ units and irregular HoO₉ units. The alternating Cu₂ and Ho₂ units are bridged into linear arrays along the a axis by a set of one η²:η¹:μ₂ carboxylate O atom and two hydrogen bonds with Cu⋯Ho separations of 4.4883 (10) and 4.5086 (10) Å. The distance between adjacent chains, as calculated by the closest and furthest distances between two chains, covers the range 10–14 Å. The H atoms of the water molecules could not be located, but the O⋯O separations for these species suggest the presence of O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Benelli & Gatteschi (2002 ); Kutlu et al. (1997 ); Legendziewicz et al. (2000 ). For the isotypic family, see: Calvo et al. (2008 ). For related literature, see: van Niekerk & Schoening (1953 ). For bond-length data, see: Allen (2002 ).

Experimental

Crystal data

[Cu₂Ho₂(C₄H₅O₂)₁₀(H₂O)₄]·3H₂O
M_r = 1433.85
Monoclinic, P 2₁ /c
a = 13.8856 (17) Å
b = 22.078 (3) Å
c = 19.846 (3) Å
β = 107.152 (2)°
V = 5813.5 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.49 mm⁻¹
T = 291 (2) K
0.24 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.62, T_max = 0.76
34338 measured reflections
12977 independent reflections
9482 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.085
S = 0.93
12977 reflections
653 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Selected bond lengths (Å)

Ho1—O17	2.322 (3)
Ho1—O1W	2.323 (3)
Ho1—O18	2.356 (3)
Ho1—O10	2.362 (4)
Ho1—O29	2.365 (3)
Ho1—O2W	2.386 (3)
Ho1—O20	2.418 (3)
Ho1—O19	2.619 (3)
Ho1—O28	2.789 (4)
Ho2—O28	2.316 (3)
Ho2—O4W	2.322 (3)
Ho2—O26	2.357 (3)
Ho2—O3W	2.368 (3)
Ho2—O25	2.382 (3)
Ho2—O27	2.392 (3)
Ho2—O15	2.443 (3)
Ho2—O16	2.635 (3)
Ho2—O17	2.642 (3)
Cu1—O12	1.939 (3)
Cu1—O13	1.949 (4)
Cu1—O14	1.961 (3)
Cu1—O11	1.978 (3)
Cu1—O16ⁱ	2.215 (3)
Cu2—O21	1.938 (4)
Cu2—O23	1.968 (3)
Cu2—O24	1.971 (3)
Cu2—O22	1.989 (3)
Cu2—O19	2.178 (3)
Symmetry code: (i) x-1, y, z.

Table 2
Short OW⋯O contacts (< 3.00 Å) attributable to hydrogen bonding

OW⋯O	d (Å)	OW⋯O	d (Å)
O1W⋯O18	2.948 (5)	O3W⋯O28	2.957 (5)
O1W⋯O19	2.815 (5)	O4W⋯O14ⁱ	2.645 (5)
O1W⋯O20	2.895 (5)	O4W⋯O15	2.853 (5)
O1W⋯O22	2.763 (5)	O4W⋯O16	2.839 (4)
O1W⋯O5W	2.632 (5)	O4W⋯O27	2.854 (5)
O2W⋯O19	2.900 (5)	O4W⋯O7Wⁱⁱ	2.703 (5)
O2W⋯O23	2.777 (5)	O5W⋯O27ⁱⁱⁱ	2.848 (5)
O2W⋯O25	2.734 (5)	O5W⋯O6W	2.800 (5)
O2W⋯O28	2.905 (5)	O6W⋯O15ⁱⁱⁱ	2.788 (5)
O3W⋯O10	2.675 (5)	O6W⋯O26^iv	2.858 (5)
O3W⋯O11ⁱ	2.766 (5)	O6W⋯O7W	2.867 (5)
Symmetry codes: (i) x+1, y, z; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART-NT (Bruker, 2001 ); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT; 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 and PLATON (Spek (2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034296/hb2821sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034296/hb2821Isup2.hkl

checkCIF report

Comment top

In the field of molecule-based magnetic materials of 3 d and 4f metals with multicarboxylate bridging ligands, a variety of two-dimensional and three-dimensional original structures with interesting magnetic and spectroscopic properties have been discovered (Benelli and Gatteschi, 2002). One-dimensional structures, however, have only been reported in few cases for Ln₂Cu complexes with the trichloroacetate ligand (Kutlu et al.,1997; Legendziewicz et al., 2000)

Aliphatic monocarboxylic acids are expected to have limited bonding ability, since the carboxylate group cannot bridge adjacent large high-nuclear clusters. Monocarboxylates, however, may constitute a route toward one-dimensional 3 d-4f polymers, their main interest being the construction of single chain magnets. We recently used trans-2-butenoic acid in the synthesis and X-ray structure determination of three isostructural Cu^II—Ln^III1-D polymers {[Cu₂Ln₂L₁₀(H₂O)₄].3H₂O}_n(Ln = Gd^III, Er^III, Y^III; HL= trans-2-butenoicacid) (Calvo et al., 2008). The {[Cu₂Ho₂L₁₀(H₂O)₄].3H₂O}_n species had also been synthesized, but no single crystals could be obtained at the time. We now wish to report the crystal data of the isostructural Cu₂Ho₂complex obtained as well shaped needles. They consist of non-centrosymmetric polymeric chains built in the centrosymmetric P2₁/c group by two distinct blocks: one formed by two Cu^II ions bridged by four carboxylate bridges in the η¹:η¹:µ₂ conformation and the other by two Ho^III ions bridged by two carboxylate oxygen atoms in η²:η¹:µ₂ conformation (See Figure 1). Bonds between Cu and Ho metal centers consist of one covalent tridentate carboxylate oxygen atom and two intrachain H-bonds which enhance the stability of the chains.

Each Cu^II atom of the Cu₂dinuclear core provides the basal plane for a square pyramidal arrangement, the apical sites being provided by atoms O16 and O19 common to the Ho₂coordination polyhedra. The Cu₂ block resembles the structure of dinuclear copper acetate monohydrate (Van Niekerk & Schoening, 1953), the main difference being the absence of an embedded inversion symmetry center relating the copper ions, present in the latter. The four independent carboxylato bridges in the Cu₂ structure depart an average of 0.12 Å from a centrosymmetric disposition, as measured by the best fit of the dinuclear unit with its inverted image (XP in the SHELXTL package, Sheldrick, 2008). The four Cu—O—C—O—Cu loops are planar within 0.03 Å, and parallel or perpendicular to each other within a maximum deviation of ca 6°. The Cu···Cu distance within the dinuclear unit is 2.642 (1) Å compared with 2.616 (1) Å in the classical fourfold copper acetate monohydrate. In the Ho₂ block, the metal centers are bridged by two oxygen atoms from two tridentate η²:η¹:µ₂ carboxylates at a Ho···Ho distance of 4.207 (1) Å.The coordination of each holmium (HoO₉) is completed by two chelating carboxylates and two aqua O atoms. Departure from a centrosymmetric arrangement is more important in this block than in the copper one, the mean square deviation from the inverted image being here 0.27 Å. Within a chain, Figure 2, alternate dinuclear units of the same type are related by a unit cell a translation; all the space group symmetry elements are external to the chains and thus relate them into each other. As a consequence of this lack of internal symmetry, alternate Cu—Ho chemical bridges are slightly different: 4.496 and 4.517 Å, respectively. The axis-to-axis separations between a chain and the six neighbouring ones cover the range 10–14 Å. The alkene groups protrude outwards almost normal to the chain direction. Although hydrogen atoms of water molecules could not be found in the late difference Fourier maps, a number of short Ow···OCO₂and Ow···Ow distances, less than 3.00 Å (Table 2), suggests involvement in H-bonding interactions

Related literature top

For related structures, see: Benelli & Gatteschi (2002); Kutlu et al. (1997); Legendziewicz et al. (2000). For an isomorphic family, see: Calvo et al. (2008). For related literature, see: van Niekerk & Schoening (1953). For bond-length data, see: Allen (2002).

Experimental top

The title compound was prepared by the slow addition under constant stirring of Ho₂(CO₃)₃(0.50 g,1 mmol) to an aqueous solution of copper acetate monohydrate (0.40 g, 2 mmol) and trans-2-butenoic acid (0.90 g, 10 mmol) at pH about5. The filtrate was stored in a stoppered flask for two months whereupon green needles of (I) were obtained (75% yield based on Cu). Anal Calcd(found) for C₄₀H₆₄O₂₇Cu₂Ho₂: C, 33.80 (34.20), H, 4.50 (4.75), Cu, 8.95 (9.10)%.IR (KBr disk, cm^-1): 3427(s, vbr, ν(OH)), 1659, 1603 and 1538(versus,ν(CO2)asym), 1449 and 1417(versus, ν(CO2)sym), 1297(m), 1256(m), 1105(w), 967(m),917(w), 857(w), 749(m), 699(w), 651(br, w), 521(w), 461(w), 420(w). The TGA showed that the water loss occurs in the range 80–112 °C (see refinement section for details); decomposition occurs in three overlapping steps, in the range 245–550°C.

Computing details top

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek (2003).

Figures top

	Fig. 1. Molecular view of both dimers, with displacement ellipsoids at a 30% level. H atoms omitted, and carbon atoms not in the carboxylate groups drawn in empty ellipsoids and bonds, for clarity.
	Fig. 2. Schematic view of a chain running along [100]. Possible intrachain H-bonds drawn in broken lines. All H atoms and those carbon atoms not in the carboxylate groups, omitted for clarity. Symmetry codes: (i) 1 + x, y, z; (ii): -1 + x, y, z

catena-Poly[[[tetrakis(µ-2-butenoato)dicopper(II)]-µ-2-butenoato- [diaqua(2-butenoato)holmium(III)]-di-µ-2-butenoato- [diaqua(2-butenoato)holmium(III)]-µ-2-butenoato] trihydrate] top

Crystal data top

[Cu₂Ho₂(C₄H₅O₂)₁₀(H₂O)₄]·3H₂O	F(000) = 2792
M_r = 1433.85	D_x = 1.638 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7221 reflections
a = 13.8856 (17) Å	θ = 2.1–26.8°
b = 22.078 (3) Å	µ = 3.49 mm⁻¹
c = 19.846 (3) Å	T = 291 K
β = 107.152 (2)°	Needles, green
V = 5813.5 (14) Å³	0.24 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	12977 independent reflections
Radiation source: fine-focus sealed tube	9482 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ϕ and ω scans	θ_max = 28.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; (Bruker, 2002)	h = −18→13
T_min = 0.62, T_max = 0.76	k = −29→25
34338 measured reflections	l = −19→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0296P)²] where P = (F_o² + 2F_c²)/3
12977 reflections	(Δ/σ)_max = 0.003
653 parameters	Δρ_max = 1.23 e Å⁻³
30 restraints	Δρ_min = −1.02 e Å⁻³

Crystal data top

[Cu₂Ho₂(C₄H₅O₂)₁₀(H₂O)₄]·3H₂O	V = 5813.5 (14) Å³
M_r = 1433.85	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.8856 (17) Å	µ = 3.49 mm⁻¹
b = 22.078 (3) Å	T = 291 K
c = 19.846 (3) Å	0.24 × 0.10 × 0.08 mm
β = 107.152 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	12977 independent reflections
Absorption correction: multi-scan (SADABS; (Bruker, 2002)	9482 reflections with I > 2σ(I)
T_min = 0.62, T_max = 0.76	R_int = 0.043
34338 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	30 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 0.93	Δρ_max = 1.23 e Å⁻³
12977 reflections	Δρ_min = −1.02 e Å⁻³
653 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ho1	0.843231 (18)	0.783533 (10)	0.670233 (12)	0.03660 (7)
Ho2	1.024471 (17)	0.664760 (10)	0.594522 (11)	0.03346 (7)
Cu1	0.36154 (5)	0.68897 (3)	0.65391 (3)	0.03839 (15)
Cu2	0.51325 (5)	0.74316 (3)	0.62360 (3)	0.04014 (15)
O11	0.3036 (3)	0.77154 (15)	0.64194 (18)	0.0456 (9)
O21	0.4304 (3)	0.81524 (15)	0.61285 (19)	0.0513 (10)
C11	0.3485 (4)	0.8172 (2)	0.6260 (3)	0.0403 (12)
C21	0.2976 (5)	0.8760 (2)	0.6233 (3)	0.0546 (15)
H21	0.2337	0.8768	0.6294	0.065*
C31	0.3377 (6)	0.9269 (3)	0.6128 (4)	0.079 (2)
H31	0.4007	0.9254	0.6053	0.095*
C41	0.2900 (7)	0.9879 (3)	0.6120 (5)	0.130 (4)
H411	0.2243	0.9831	0.6180	0.195*
H412	0.2840	1.0075	0.5678	0.195*
H413	0.3312	1.0122	0.6497	0.195*
O12	0.4345 (3)	0.70699 (16)	0.75125 (18)	0.0511 (10)
O22	0.5570 (3)	0.75996 (17)	0.72663 (18)	0.0515 (10)
C12	0.5109 (4)	0.7396 (2)	0.7686 (3)	0.0417 (12)
C22	0.5494 (4)	0.7565 (3)	0.8436 (3)	0.0545 (15)
H22	0.5406	0.7287	0.8766	0.065*
C32	0.5943 (4)	0.8065 (3)	0.8670 (3)	0.0617 (17)
H32	0.6102	0.8320	0.8346	0.074*
C42	0.6232 (5)	0.8273 (3)	0.9430 (3)	0.082 (2)
H421	0.6212	0.7934	0.9729	0.123*
H422	0.5767	0.8577	0.9484	0.123*
H423	0.6901	0.8438	0.9559	0.123*
O13	0.4443 (3)	0.61669 (15)	0.6601 (2)	0.0546 (10)
O23	0.5778 (3)	0.66311 (15)	0.64296 (19)	0.0499 (9)
C13	0.5324 (4)	0.6173 (2)	0.6572 (3)	0.0441 (13)
C23	0.5903 (5)	0.5598 (2)	0.6700 (3)	0.0575 (16)
H23	0.6581	0.5609	0.6723	0.069*
C33	0.5505 (5)	0.5080 (3)	0.6783 (3)	0.075 (2)
H33	0.4830	0.5079	0.6770	0.090*
C43	0.6053 (6)	0.4482 (3)	0.6898 (4)	0.109 (3)
H431	0.5809	0.4235	0.6485	0.164*
H432	0.5938	0.4280	0.7296	0.164*
H433	0.6763	0.4551	0.6987	0.164*
O14	0.3123 (3)	0.67875 (17)	0.55130 (17)	0.0509 (10)
O24	0.4430 (3)	0.72049 (16)	0.52530 (18)	0.0514 (10)
C14	0.3585 (4)	0.6959 (2)	0.5083 (3)	0.0445 (13)
C24	0.3035 (4)	0.6850 (3)	0.4335 (3)	0.0565 (16)
H24	0.2503	0.6577	0.4237	0.068*
C34	0.3231 (5)	0.7100 (3)	0.3815 (3)	0.0696 (19)
H34	0.3779	0.7362	0.3915	0.084*
C44	0.2657 (5)	0.7010 (3)	0.3048 (3)	0.084 (2)
H441	0.2093	0.6747	0.3011	0.126*
H442	0.3092	0.6831	0.2807	0.126*
H443	0.2419	0.7394	0.2839	0.126*
O15	0.9577 (3)	0.57490 (15)	0.52451 (18)	0.0459 (9)
O25	0.8763 (3)	0.61044 (15)	0.59465 (19)	0.0471 (9)
C15	0.8831 (4)	0.5728 (2)	0.5473 (3)	0.0428 (13)
C25	0.8068 (5)	0.5250 (3)	0.5189 (3)	0.0639 (17)
H25	0.8221	0.4948	0.4911	0.077*
C35	0.7229 (5)	0.5231 (3)	0.5303 (3)	0.0727 (19)
H35	0.7099	0.5522	0.5604	0.087*
C45	0.6403 (5)	0.4769 (3)	0.4990 (4)	0.110 (3)
H451	0.6616	0.4504	0.4678	0.164*
H452	0.5799	0.4976	0.4733	0.164*
H453	0.6275	0.4536	0.5363	0.164*
O16	1.2173 (2)	0.65248 (14)	0.66304 (17)	0.0389 (8)
O26	1.1059 (3)	0.58251 (14)	0.66393 (18)	0.0442 (9)
C16	1.1965 (4)	0.6008 (2)	0.6824 (2)	0.0364 (11)
C26	1.2771 (4)	0.5619 (2)	0.7272 (3)	0.0472 (14)
H26	1.3425	0.5771	0.7414	0.057*
C36	1.2615 (4)	0.5076 (2)	0.7477 (3)	0.0640 (18)
H36	1.1953	0.4938	0.7347	0.077*
C46	1.3410 (5)	0.4654 (3)	0.7906 (4)	0.094 (3)
H461	1.4061	0.4839	0.7995	0.141*
H462	1.3396	0.4283	0.7650	0.141*
H463	1.3281	0.4568	0.8346	0.141*
O17	0.8752 (3)	0.74373 (14)	0.57064 (16)	0.0402 (8)
O27	0.9215 (3)	0.70443 (15)	0.48474 (17)	0.0448 (9)
C17	0.8725 (4)	0.7441 (2)	0.5062 (3)	0.0383 (12)
C27	0.8146 (4)	0.7912 (2)	0.4588 (3)	0.0461 (14)
H27	0.7746	0.8172	0.4758	0.055*
C37	0.8169 (5)	0.7980 (2)	0.3939 (3)	0.0523 (15)
H37	0.8562	0.7712	0.3772	0.063*
C47	0.7609 (6)	0.8460 (3)	0.3448 (3)	0.083 (2)
H471	0.7123	0.8645	0.3641	0.124*
H472	0.7268	0.8281	0.3000	0.124*
H473	0.8074	0.8761	0.3387	0.124*
O18	0.9594 (3)	0.75324 (16)	0.77741 (18)	0.0502 (10)
O28	0.9992 (3)	0.69894 (16)	0.69837 (18)	0.0505 (10)
C18	1.0119 (4)	0.7120 (2)	0.7621 (3)	0.0416 (13)
C28	1.0866 (5)	0.6785 (3)	0.8176 (3)	0.0681 (19)
H28	1.1244	0.6486	0.8042	0.082*
C38	1.1021 (6)	0.6886 (4)	0.8835 (4)	0.104 (3)
H38	1.0625	0.7179	0.8962	0.125*
C48	1.1803 (8)	0.6563 (4)	0.9425 (4)	0.187 (6)
H481	1.2200	0.6300	0.9227	0.281*
H482	1.1469	0.6327	0.9697	0.281*
H483	1.2233	0.6856	0.9725	0.281*
O19	0.6491 (3)	0.78103 (15)	0.60660 (17)	0.0426 (9)
O29	0.7445 (3)	0.85441 (15)	0.58965 (18)	0.0480 (9)
C19	0.6600 (4)	0.8298 (2)	0.5752 (3)	0.0394 (12)
C29	0.5717 (5)	0.8531 (3)	0.5191 (3)	0.0660 (18)
H29	0.5109	0.8325	0.5110	0.079*
C39	0.5738 (6)	0.8983 (3)	0.4821 (4)	0.109 (3)
H39	0.6349	0.9185	0.4903	0.130*
C49	0.4842 (7)	0.9230 (4)	0.4242 (5)	0.185 (5)
H491	0.5080	0.9451	0.3906	0.277*
H492	0.4457	0.9496	0.4447	0.277*
H493	0.4424	0.8901	0.4010	0.277*
O10	0.9850 (3)	0.83683 (15)	0.6588 (2)	0.0540 (10)
O20	0.9038 (3)	0.87976 (15)	0.72448 (18)	0.0488 (9)
C10	0.9735 (4)	0.8813 (2)	0.6968 (3)	0.0444 (13)
C20	1.0431 (4)	0.9329 (2)	0.7057 (3)	0.0562 (16)
H20	1.0967	0.9297	0.6867	0.067*
C30	1.0347 (5)	0.9820 (3)	0.7378 (3)	0.0683 (18)
H30	0.9817	0.9838	0.7575	0.082*
C40	1.1009 (5)	1.0372 (3)	0.7473 (4)	0.094 (3)
H401	1.1487	1.0322	0.7213	0.141*
H402	1.1362	1.0424	0.7964	0.141*
H403	1.0600	1.0723	0.7303	0.141*
O1W	0.7526 (3)	0.80013 (15)	0.74993 (17)	0.0470 (9)
O2W	0.7832 (3)	0.68213 (14)	0.66900 (18)	0.0445 (9)
O3W	1.0957 (2)	0.76302 (14)	0.60445 (18)	0.0432 (9)
O4W	1.1179 (3)	0.65241 (16)	0.51587 (17)	0.0474 (9)
O5W	0.8129 (3)	0.86530 (16)	0.86586 (17)	0.0542 (10)
O6W	0.9477 (3)	0.96277 (14)	0.88853 (18)	0.0541 (10)
O7W	1.0534 (3)	0.85442 (18)	0.87360 (18)	0.0610 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ho1	0.03854 (14)	0.04022 (14)	0.03143 (13)	−0.00543 (11)	0.01091 (10)	−0.00266 (10)
Ho2	0.03031 (13)	0.03573 (13)	0.03362 (13)	−0.00186 (10)	0.00829 (9)	−0.00210 (10)
Cu1	0.0296 (3)	0.0453 (4)	0.0392 (4)	−0.0049 (3)	0.0086 (3)	−0.0007 (3)
Cu2	0.0313 (4)	0.0485 (4)	0.0406 (4)	−0.0052 (3)	0.0106 (3)	−0.0008 (3)
O11	0.041 (2)	0.042 (2)	0.055 (2)	−0.0044 (17)	0.0167 (18)	0.0005 (17)
O21	0.048 (2)	0.045 (2)	0.069 (3)	−0.0020 (19)	0.028 (2)	0.0026 (19)
C11	0.041 (3)	0.042 (3)	0.034 (3)	−0.001 (3)	0.005 (2)	−0.002 (2)
C21	0.062 (4)	0.046 (3)	0.063 (4)	0.001 (3)	0.030 (3)	−0.003 (3)
C31	0.099 (6)	0.048 (4)	0.104 (6)	0.004 (4)	0.050 (5)	0.003 (4)
C41	0.186 (10)	0.043 (4)	0.196 (10)	0.028 (5)	0.109 (8)	0.028 (5)
O12	0.040 (2)	0.071 (3)	0.042 (2)	−0.011 (2)	0.0111 (18)	−0.0002 (19)
O22	0.041 (2)	0.071 (3)	0.043 (2)	−0.014 (2)	0.0136 (18)	−0.0120 (19)
C12	0.033 (3)	0.048 (3)	0.043 (3)	0.005 (3)	0.011 (2)	0.001 (3)
C22	0.040 (3)	0.077 (4)	0.044 (3)	−0.003 (3)	0.009 (3)	0.004 (3)
C32	0.042 (4)	0.083 (4)	0.062 (4)	−0.006 (3)	0.019 (3)	−0.017 (3)
C42	0.068 (5)	0.113 (6)	0.063 (4)	−0.013 (4)	0.018 (4)	−0.030 (4)
O13	0.044 (2)	0.044 (2)	0.081 (3)	0.0001 (19)	0.027 (2)	0.002 (2)
O23	0.039 (2)	0.046 (2)	0.064 (3)	−0.0019 (18)	0.0141 (19)	0.0024 (19)
C13	0.039 (3)	0.050 (3)	0.038 (3)	−0.002 (3)	0.004 (2)	−0.002 (3)
C23	0.053 (4)	0.051 (4)	0.067 (4)	0.011 (3)	0.016 (3)	0.003 (3)
C33	0.088 (6)	0.052 (4)	0.081 (5)	0.008 (4)	0.017 (4)	0.005 (4)
C43	0.148 (9)	0.056 (4)	0.116 (7)	0.026 (5)	0.027 (6)	0.012 (4)
O14	0.036 (2)	0.081 (3)	0.034 (2)	−0.016 (2)	0.0072 (16)	−0.0097 (19)
O24	0.044 (2)	0.069 (3)	0.042 (2)	−0.016 (2)	0.0150 (18)	−0.0040 (19)
C14	0.040 (3)	0.051 (3)	0.041 (3)	−0.001 (3)	0.010 (3)	−0.004 (3)
C24	0.045 (4)	0.079 (4)	0.046 (4)	−0.011 (3)	0.015 (3)	−0.003 (3)
C34	0.066 (5)	0.089 (5)	0.058 (4)	−0.008 (4)	0.024 (4)	0.003 (4)
C44	0.090 (6)	0.123 (6)	0.040 (4)	0.007 (5)	0.019 (4)	0.002 (4)
O15	0.042 (2)	0.043 (2)	0.049 (2)	−0.0077 (18)	0.0093 (18)	−0.0114 (17)
O25	0.040 (2)	0.045 (2)	0.060 (2)	−0.0052 (17)	0.0204 (18)	−0.0024 (18)
C15	0.039 (3)	0.039 (3)	0.045 (3)	−0.003 (3)	0.002 (3)	0.005 (2)
C25	0.045 (4)	0.060 (4)	0.079 (5)	−0.004 (3)	0.008 (3)	−0.011 (3)
C35	0.063 (5)	0.073 (5)	0.075 (5)	−0.012 (4)	0.010 (4)	−0.006 (4)
C45	0.084 (6)	0.090 (5)	0.136 (7)	−0.046 (5)	0.002 (5)	−0.020 (5)
O16	0.036 (2)	0.0381 (19)	0.042 (2)	−0.0043 (16)	0.0115 (16)	0.0031 (16)
O26	0.032 (2)	0.041 (2)	0.054 (2)	−0.0085 (16)	0.0024 (17)	0.0028 (17)
C16	0.038 (3)	0.037 (3)	0.033 (3)	−0.001 (2)	0.009 (2)	−0.004 (2)
C26	0.035 (3)	0.050 (3)	0.049 (3)	−0.006 (3)	0.001 (2)	0.007 (3)
C36	0.051 (4)	0.054 (4)	0.070 (4)	−0.013 (3)	−0.010 (3)	0.015 (3)
C46	0.088 (6)	0.057 (4)	0.105 (6)	0.003 (4)	−0.021 (5)	0.024 (4)
O17	0.049 (2)	0.043 (2)	0.0288 (18)	−0.0020 (17)	0.0107 (16)	−0.0016 (15)
O27	0.044 (2)	0.051 (2)	0.038 (2)	0.0139 (18)	0.0082 (17)	−0.0007 (16)
C17	0.038 (3)	0.039 (3)	0.035 (3)	−0.004 (2)	0.007 (2)	−0.001 (2)
C27	0.057 (4)	0.045 (3)	0.038 (3)	0.014 (3)	0.018 (3)	0.004 (2)
C37	0.072 (4)	0.043 (3)	0.044 (3)	0.007 (3)	0.020 (3)	0.003 (3)
C47	0.121 (7)	0.067 (4)	0.056 (4)	0.017 (4)	0.020 (4)	0.019 (3)
O18	0.047 (2)	0.059 (2)	0.042 (2)	0.006 (2)	0.0083 (18)	−0.0040 (18)
O28	0.056 (3)	0.061 (2)	0.038 (2)	−0.012 (2)	0.0182 (18)	−0.0082 (18)
C18	0.040 (3)	0.051 (3)	0.032 (3)	−0.013 (3)	0.007 (2)	0.002 (2)
C28	0.068 (5)	0.074 (4)	0.051 (4)	0.017 (4)	0.001 (3)	0.005 (3)
C38	0.120 (8)	0.117 (6)	0.053 (5)	0.005 (5)	−0.007 (5)	0.024 (5)
C48	0.213 (13)	0.177 (10)	0.102 (7)	0.000 (9)	−0.061 (7)	0.078 (7)
O19	0.039 (2)	0.048 (2)	0.042 (2)	−0.0068 (17)	0.0119 (16)	0.0040 (17)
O29	0.046 (2)	0.047 (2)	0.055 (2)	−0.0074 (18)	0.0206 (19)	0.0058 (18)
C19	0.042 (3)	0.043 (3)	0.036 (3)	0.002 (3)	0.016 (2)	−0.001 (2)
C29	0.054 (4)	0.086 (5)	0.056 (4)	0.011 (4)	0.015 (3)	0.025 (3)
C39	0.071 (6)	0.119 (7)	0.118 (7)	0.004 (5)	0.001 (5)	0.065 (6)
C49	0.118 (9)	0.217 (11)	0.181 (10)	0.038 (8)	−0.016 (7)	0.143 (9)
O10	0.057 (3)	0.045 (2)	0.069 (3)	−0.0125 (19)	0.032 (2)	−0.0162 (19)
O20	0.050 (2)	0.049 (2)	0.053 (2)	−0.0096 (19)	0.0251 (19)	−0.0109 (18)
C10	0.046 (3)	0.044 (3)	0.044 (3)	0.000 (3)	0.014 (3)	−0.004 (3)
C20	0.060 (4)	0.046 (3)	0.072 (4)	−0.015 (3)	0.034 (3)	−0.014 (3)
C30	0.068 (5)	0.063 (4)	0.083 (5)	−0.017 (4)	0.036 (4)	−0.021 (4)
C40	0.103 (6)	0.060 (4)	0.137 (7)	−0.037 (4)	0.061 (5)	−0.041 (4)
O1W	0.044 (2)	0.060 (2)	0.040 (2)	−0.0070 (18)	0.0162 (17)	−0.0091 (17)
O2W	0.036 (2)	0.044 (2)	0.056 (2)	0.0000 (17)	0.0175 (17)	−0.0007 (17)
O3W	0.038 (2)	0.0354 (18)	0.058 (2)	−0.0041 (16)	0.0184 (18)	−0.0023 (17)
O4W	0.033 (2)	0.074 (3)	0.037 (2)	−0.0042 (18)	0.0130 (16)	−0.0078 (18)
O5W	0.058 (3)	0.060 (2)	0.040 (2)	−0.013 (2)	0.0087 (18)	−0.0083 (18)
O6W	0.069 (3)	0.038 (2)	0.053 (2)	−0.0057 (19)	0.014 (2)	−0.0005 (17)
O7W	0.054 (3)	0.085 (3)	0.041 (2)	0.012 (2)	0.0101 (19)	0.002 (2)

Geometric parameters (Å, º) top

Ho1—O17	2.322 (3)	C34—C44	1.507 (7)
Ho1—O1W	2.323 (3)	C34—H34	0.9300
Ho1—O18	2.356 (3)	C44—H441	0.9600
Ho1—O10	2.362 (4)	C44—H442	0.9600
Ho1—O29	2.365 (3)	C44—H443	0.9600
Ho1—O2W	2.386 (3)	O15—C15	1.247 (6)
Ho1—O20	2.418 (3)	O25—C15	1.279 (6)
Ho1—O19	2.619 (3)	C15—C25	1.484 (7)
Ho1—C10	2.765 (5)	C25—C35	1.251 (7)
Ho1—O28	2.789 (4)	C25—H25	0.9300
Ho2—O28	2.316 (3)	C35—C45	1.523 (7)
Ho2—O4W	2.322 (3)	C35—H35	0.9300
Ho2—O26	2.357 (3)	C45—H451	0.9600
Ho2—O3W	2.368 (3)	C45—H452	0.9600
Ho2—O25	2.382 (3)	C45—H453	0.9600
Ho2—O27	2.392 (3)	O16—C16	1.265 (5)
Ho2—O15	2.443 (3)	O16—Cu1ⁱⁱ	2.215 (3)
Ho2—O16	2.635 (3)	O26—C16	1.267 (5)
Ho2—O17	2.642 (3)	C16—C26	1.481 (6)
Ho2—C17	2.901 (5)	C26—C36	1.305 (6)
Cu1—O12	1.939 (3)	C26—H26	0.9300
Cu1—O13	1.949 (4)	C36—C46	1.503 (7)
Cu1—O14	1.961 (3)	C36—H36	0.9300
Cu1—O11	1.978 (3)	C46—H461	0.9600
Cu1—O16ⁱ	2.215 (3)	C46—H462	0.9600
Cu1—Cu2	2.6417 (9)	C46—H463	0.9600
Cu2—O21	1.938 (4)	O17—C17	1.268 (5)
Cu2—O23	1.968 (3)	O27—C17	1.259 (5)
Cu2—O24	1.971 (3)	C17—C27	1.471 (6)
Cu2—O22	1.989 (3)	C27—C37	1.306 (6)
Cu2—O19	2.178 (3)	C27—H27	0.9300
O11—C11	1.272 (6)	C37—C47	1.493 (6)
O21—C11	1.241 (6)	C37—H37	0.9300
C11—C21	1.472 (6)	C47—H471	0.9600
C21—C31	1.297 (7)	C47—H472	0.9600
C21—H21	0.9300	C47—H473	0.9600
C31—C41	1.499 (7)	O18—C18	1.258 (6)
C31—H31	0.9300	O28—C18	1.258 (5)
C41—H411	0.9600	C18—C28	1.471 (7)
C41—H412	0.9600	C28—C38	1.282 (7)
C41—H413	0.9600	C28—H28	0.9300
O12—C12	1.244 (6)	C38—C48	1.520 (8)
O22—C12	1.273 (6)	C38—H38	0.9300
C12—C22	1.472 (6)	C48—H481	0.9600
C22—C32	1.286 (7)	C48—H482	0.9600
C22—H22	0.9300	C48—H483	0.9600
C32—C42	1.513 (7)	O19—C19	1.274 (5)
C32—H32	0.9300	O29—C19	1.247 (6)
C42—H421	0.9600	C19—C29	1.484 (7)
C42—H422	0.9600	C29—C39	1.244 (7)
C42—H423	0.9600	C29—H29	0.9300
O13—C13	1.241 (6)	C39—C49	1.524 (8)
O23—C13	1.268 (6)	C39—H39	0.9300
C13—C23	1.483 (6)	C49—H491	0.9600
C23—C33	1.302 (7)	C49—H492	0.9600
C23—H23	0.9300	C49—H493	0.9600
C33—C43	1.507 (7)	O10—C10	1.276 (5)
C33—H33	0.9300	O20—C10	1.247 (6)
C43—H431	0.9600	C10—C20	1.471 (6)
C43—H432	0.9600	C20—C30	1.280 (6)
C43—H433	0.9600	C20—H20	0.9300
O14—C14	1.268 (6)	C30—C40	1.504 (7)
O24—C14	1.246 (6)	C30—H30	0.9300
C14—C24	1.474 (6)	C40—H401	0.9600
C24—C34	1.269 (7)	C40—H402	0.9600
C24—H24	0.9300	C40—H403	0.9600

O17—Ho1—O1W	156.53 (12)	H421—C42—H423	109.5
O17—Ho1—O18	114.16 (12)	H422—C42—H423	109.5
O1W—Ho1—O18	78.12 (13)	C13—O13—Cu1	124.0 (4)
O17—Ho1—O10	74.47 (12)	C13—O23—Cu2	122.2 (3)
O1W—Ho1—O10	128.45 (12)	O13—C13—O23	125.5 (5)
O18—Ho1—O10	81.98 (13)	O13—C13—C23	118.4 (5)
O17—Ho1—O29	83.87 (12)	O23—C13—C23	116.2 (5)
O1W—Ho1—O29	91.91 (12)	C33—C23—C13	123.0 (6)
O18—Ho1—O29	154.75 (12)	C33—C23—H23	118.5
O10—Ho1—O29	86.49 (13)	C13—C23—H23	118.5
O17—Ho1—O2W	77.88 (11)	C23—C33—C43	125.1 (7)
O1W—Ho1—O2W	84.11 (12)	C23—C33—H33	117.5
O18—Ho1—O2W	83.50 (12)	C43—C33—H33	117.5
O10—Ho1—O2W	139.90 (12)	C33—C43—H431	109.5
O29—Ho1—O2W	118.86 (12)	C33—C43—H432	109.5
O17—Ho1—O20	125.65 (12)	H431—C43—H432	109.5
O1W—Ho1—O20	75.24 (12)	C33—C43—H433	109.5
O18—Ho1—O20	77.99 (13)	H431—C43—H433	109.5
O10—Ho1—O20	54.19 (12)	H432—C43—H433	109.5
O29—Ho1—O20	77.04 (12)	C14—O14—Cu1	125.1 (3)
O2W—Ho1—O20	154.61 (12)	C14—O24—Cu2	122.1 (3)
O17—Ho1—O19	90.55 (11)	O24—C14—O14	124.8 (5)
O1W—Ho1—O19	69.15 (11)	O24—C14—C24	120.7 (5)
O18—Ho1—O19	139.70 (12)	O14—C14—C24	114.5 (5)
O10—Ho1—O19	137.13 (12)	C34—C24—C14	125.3 (6)
O29—Ho1—O19	51.59 (11)	C34—C24—H24	117.4
O2W—Ho1—O19	70.65 (11)	C14—C24—H24	117.4
O20—Ho1—O19	113.99 (12)	C24—C34—C44	126.0 (6)
O17—Ho1—C10	100.30 (14)	C24—C34—H34	117.0
O1W—Ho1—C10	101.70 (14)	C44—C34—H34	117.0
O18—Ho1—C10	79.30 (14)	C34—C44—H441	109.5
O10—Ho1—C10	27.41 (13)	C34—C44—H442	109.5
O29—Ho1—C10	80.15 (14)	H441—C44—H442	109.5
O2W—Ho1—C10	160.21 (14)	C34—C44—H443	109.5
O20—Ho1—C10	26.79 (13)	H441—C44—H443	109.5
O19—Ho1—C10	129.13 (13)	H442—C44—H443	109.5
O17—Ho1—O28	65.47 (11)	C15—O15—Ho2	92.3 (3)
O1W—Ho1—O28	120.94 (11)	C15—O25—Ho2	94.3 (3)
O18—Ho1—O28	49.06 (11)	O15—C15—O25	119.4 (5)
O10—Ho1—O28	74.49 (12)	O15—C15—C25	117.7 (5)
O29—Ho1—O28	147.11 (11)	O25—C15—C25	122.8 (5)
O2W—Ho1—O28	67.79 (11)	C35—C25—C15	123.7 (6)
O20—Ho1—O28	110.60 (12)	C35—C25—H25	118.2
O19—Ho1—O28	135.29 (10)	C15—C25—H25	118.2
C10—Ho1—O28	93.36 (14)	C25—C35—C45	125.3 (7)
O28—Ho2—O4W	153.86 (12)	C25—C35—H35	117.4
O28—Ho2—O26	84.46 (12)	C45—C35—H35	117.4
O4W—Ho2—O26	92.03 (12)	C35—C45—H451	109.5
O28—Ho2—O3W	78.27 (12)	C35—C45—H452	109.5
O4W—Ho2—O3W	82.01 (12)	H451—C45—H452	109.5
O26—Ho2—O3W	122.71 (11)	C35—C45—H453	109.5
O28—Ho2—O25	78.79 (12)	H451—C45—H453	109.5
O4W—Ho2—O25	126.57 (12)	H452—C45—H453	109.5
O26—Ho2—O25	82.95 (12)	C16—O16—Cu1ⁱⁱ	130.2 (3)
O3W—Ho2—O25	143.21 (12)	C16—O16—Ho2	87.8 (3)
O28—Ho2—O27	118.99 (12)	Cu1ⁱⁱ—O16—Ho2	136.55 (14)
O4W—Ho2—O27	74.51 (12)	C16—O26—Ho2	100.8 (3)
O26—Ho2—O27	150.39 (11)	O16—C16—O26	119.7 (4)
O3W—Ho2—O27	82.13 (12)	O16—C16—C26	120.3 (5)
O25—Ho2—O27	84.32 (12)	O26—C16—C26	120.0 (4)
O28—Ho2—O15	129.71 (12)	C36—C26—C16	123.6 (5)
O4W—Ho2—O15	73.50 (12)	C36—C26—H26	118.2
O26—Ho2—O15	75.11 (11)	C16—C26—H26	118.2
O3W—Ho2—O15	150.52 (12)	C26—C36—C46	125.8 (6)
O25—Ho2—O15	53.73 (12)	C26—C36—H36	117.1
O27—Ho2—O15	75.79 (12)	C46—C36—H36	117.1
O28—Ho2—O16	88.38 (12)	C36—C46—H461	109.5
O4W—Ho2—O16	69.54 (11)	C36—C46—H462	109.5
O26—Ho2—O16	51.66 (10)	H461—C46—H462	109.5
O3W—Ho2—O16	73.46 (11)	C36—C46—H463	109.5
O25—Ho2—O16	133.95 (11)	H461—C46—H463	109.5
O27—Ho2—O16	138.68 (11)	H462—C46—H463	109.5
O15—Ho2—O16	111.57 (11)	C17—O17—Ho1	154.1 (3)
O28—Ho2—O17	68.17 (12)	C17—O17—Ho2	88.5 (3)
O4W—Ho2—O17	121.43 (11)	Ho1—O17—Ho2	115.70 (12)
O26—Ho2—O17	146.01 (11)	C17—O27—Ho2	100.6 (3)
O3W—Ho2—O17	72.35 (11)	O27—C17—O17	118.6 (4)
O25—Ho2—O17	72.57 (11)	O27—C17—C27	121.5 (4)
O27—Ho2—O17	50.84 (10)	O17—C17—C27	119.9 (5)
O15—Ho2—O17	106.72 (11)	O27—C17—Ho2	54.1 (2)
O16—Ho2—O17	141.66 (10)	O17—C17—Ho2	65.6 (3)
O28—Ho2—C17	93.83 (14)	C27—C17—Ho2	167.4 (4)
O4W—Ho2—C17	96.66 (13)	C37—C27—C17	123.0 (5)
O26—Ho2—C17	163.08 (13)	C37—C27—H27	118.5
O3W—Ho2—C17	73.06 (12)	C17—C27—H27	118.5
O25—Ho2—C17	80.22 (13)	C27—C37—C47	124.5 (6)
O27—Ho2—C17	25.24 (11)	C27—C37—H37	117.7
O15—Ho2—C17	93.46 (13)	C47—C37—H37	117.7
O16—Ho2—C17	145.23 (12)	C37—C47—H471	109.5
O17—Ho2—C17	25.92 (11)	C37—C47—H472	109.5
O12—Cu1—O13	88.88 (16)	H471—C47—H472	109.5
O12—Cu1—O14	167.90 (15)	C37—C47—H473	109.5
O13—Cu1—O14	89.40 (16)	H471—C47—H473	109.5
O12—Cu1—O11	90.28 (15)	H472—C47—H473	109.5
O13—Cu1—O11	166.73 (15)	C18—O18—Ho1	106.2 (3)
O14—Cu1—O11	88.65 (15)	C18—O28—Ho2	163.0 (4)
O12—Cu1—O16ⁱ	102.25 (14)	C18—O28—Ho1	85.3 (3)
O13—Cu1—O16ⁱ	103.16 (14)	Ho2—O28—Ho1	110.63 (13)
O14—Cu1—O16ⁱ	89.80 (14)	O18—C18—O28	119.3 (5)
O11—Cu1—O16ⁱ	89.96 (13)	O18—C18—C28	121.0 (5)
O12—Cu1—Cu2	85.23 (11)	O28—C18—C28	119.7 (5)
O13—Cu1—Cu2	83.69 (11)	C38—C28—C18	123.1 (7)
O14—Cu1—Cu2	82.68 (11)	C38—C28—H28	118.5
O11—Cu1—Cu2	83.04 (11)	C18—C28—H28	118.5
O16ⁱ—Cu1—Cu2	169.82 (9)	C28—C38—C48	124.9 (9)
O21—Cu2—O23	168.65 (16)	C28—C38—H38	117.6
O21—Cu2—O24	89.72 (16)	C48—C38—H38	117.6
O23—Cu2—O24	91.67 (15)	C38—C48—H481	109.5
O21—Cu2—O22	87.21 (16)	C38—C48—H482	109.5
O23—Cu2—O22	89.05 (15)	H481—C48—H482	109.5
O24—Cu2—O22	167.66 (15)	C38—C48—H483	109.5
O21—Cu2—O19	100.40 (14)	H481—C48—H483	109.5
O23—Cu2—O19	90.55 (14)	H482—C48—H483	109.5
O24—Cu2—O19	98.19 (14)	C19—O19—Cu2	129.3 (3)
O22—Cu2—O19	94.12 (14)	C19—O19—Ho1	87.9 (3)
O21—Cu2—Cu1	84.83 (11)	Cu2—O19—Ho1	138.47 (15)
O23—Cu2—Cu1	84.07 (11)	C19—O29—Ho1	100.7 (3)
O24—Cu2—Cu1	85.14 (11)	O29—C19—O19	119.7 (5)
O22—Cu2—Cu1	82.68 (11)	O29—C19—C29	122.2 (5)
O19—Cu2—Cu1	173.77 (9)	O19—C19—C29	117.9 (5)
C11—O11—Cu1	123.2 (3)	C39—C29—C19	124.3 (7)
C11—O21—Cu2	123.8 (3)	C39—C29—H29	117.9
O21—C11—O11	124.9 (5)	C19—C29—H29	117.9
O21—C11—C21	118.8 (5)	C29—C39—C49	125.2 (8)
O11—C11—C21	116.3 (5)	C29—C39—H39	117.4
C31—C21—C11	123.1 (6)	C49—C39—H39	117.4
C31—C21—H21	118.4	C39—C49—H491	109.5
C11—C21—H21	118.4	C39—C49—H492	109.5
C21—C31—C41	124.8 (7)	H491—C49—H492	109.5
C21—C31—H31	117.6	C39—C49—H493	109.5
C41—C31—H31	117.6	H491—C49—H493	109.5
C31—C41—H411	109.5	H492—C49—H493	109.5
C31—C41—H412	109.5	C10—O10—Ho1	94.2 (3)
H411—C41—H412	109.5	C10—O20—Ho1	92.3 (3)
C31—C41—H413	109.5	O20—C10—O10	119.3 (5)
H411—C41—H413	109.5	O20—C10—C20	122.4 (5)
H412—C41—H413	109.5	O10—C10—C20	118.3 (5)
C12—O12—Cu1	123.2 (3)	O20—C10—Ho1	60.9 (3)
C12—O22—Cu2	123.2 (3)	O10—C10—Ho1	58.4 (3)
O12—C12—O22	125.1 (5)	C20—C10—Ho1	175.9 (4)
O12—C12—C22	116.9 (5)	C30—C20—C10	124.3 (6)
O22—C12—C22	118.0 (5)	C30—C20—H20	117.9
C32—C22—C12	125.1 (6)	C10—C20—H20	117.9
C32—C22—H22	117.4	C20—C30—C40	127.3 (6)
C12—C22—H22	117.4	C20—C30—H30	116.3
C22—C32—C42	125.4 (6)	C40—C30—H30	116.3
C22—C32—H32	117.3	C30—C40—H401	109.5
C42—C32—H32	117.3	C30—C40—H402	109.5
C32—C42—H421	109.5	H401—C40—H402	109.5
C32—C42—H422	109.5	C30—C40—H403	109.5
H421—C42—H422	109.5	H401—C40—H403	109.5
C32—C42—H423	109.5	H402—C40—H403	109.5

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

Experimental details

Crystal data
Chemical formula	[Cu₂Ho₂(C₄H₅O₂)₁₀(H₂O)₄]·3H₂O
M_r	1433.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	13.8856 (17), 22.078 (3), 19.846 (3)
β (°)	107.152 (2)
V (Å³)	5813.5 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.49
Crystal size (mm)	0.24 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; (Bruker, 2002)
T_min, T_max	0.62, 0.76
No. of measured, independent and observed [I > 2σ(I)] reflections	34338, 12977, 9482
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.085, 0.93
No. of reflections	12977
No. of parameters	653
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −1.02

Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek (2003).

Selected bond lengths (Å) top

Ho1—O17	2.322 (3)	Ho2—O27	2.392 (3)
Ho1—O1W	2.323 (3)	Ho2—O15	2.443 (3)
Ho1—O18	2.356 (3)	Ho2—O16	2.635 (3)
Ho1—O10	2.362 (4)	Ho2—O17	2.642 (3)
Ho1—O29	2.365 (3)	Ho2—C17	2.901 (5)
Ho1—O2W	2.386 (3)	Cu1—O12	1.939 (3)
Ho1—O20	2.418 (3)	Cu1—O13	1.949 (4)
Ho1—O19	2.619 (3)	Cu1—O14	1.961 (3)
Ho1—C10	2.765 (5)	Cu1—O11	1.978 (3)
Ho1—O28	2.789 (4)	Cu1—O16ⁱ	2.215 (3)
Ho2—O28	2.316 (3)	Cu2—O21	1.938 (4)
Ho2—O4W	2.322 (3)	Cu2—O23	1.968 (3)
Ho2—O26	2.357 (3)	Cu2—O24	1.971 (3)
Ho2—O3W	2.368 (3)	Cu2—O22	1.989 (3)
Ho2—O25	2.382 (3)	Cu2—O19	2.178 (3)

Symmetry code: (i) x−1, y, z.

Short OW···O contacts (< 3.00 Å) attributable to hydrogen bonding top

OW···O	d (Å)	OW···O	d (Å)
O1W···O18	2.948 (5)	O3W···O28	2.957 (5)
O1W···O19	2.815 (5)	O4W···O14ⁱ	2.645 (5)
O1W···O20	2.895 (5)	O4W···O15	2.853 (5)
O1W···O22	2.763 (5)	O4W···O16	2.839 (4)
O1W···O5W	2.632 (5)	O4W···O27	2.854 (5)
O2W···O19	2.900 (5)	O4W···O7Wⁱⁱ	2.703 (5)
O2W···O23	2.777 (5)	O5W···O27ⁱⁱⁱ	2.848 (5)
O2W···O25	2.734 (5)	O5W···O6W	2.800 (5)
O2W···O28	2.905 (5)	O6W···O15ⁱⁱⁱ	2.788 (5)
O3W···O10	2.675 (5)	O6W···O26^iv	2.858 (5)
O3W···O11ⁱ	2.766 (5)	O6W···O7W	2.867 (5)

Symmetry codes: (i) x+1, y, z; (ii) x, -y+3/2, z-1/2; (iii) x, -y+3/2, z+1/2; (iv) -x+2, y+1/2, -z+3/2.

Acknowledgements

This work was supported by PIP 5274 and PICT 25409 in Argentina and FONDECYT 1070298 in Chile. MP is a member of CONICET.

References

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