Hexa μ α methyl­acrylato bis­­[(1,10 phenanthroline)lanthanum(III)] dihydrate

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(1)metal-organic papers Acta Crystallographica Section E. Structure Reports Online. Hexa-l-a-methylacrylato-bis[(1,10-phenanthroline)lanthanum(III)] dihydrate. ISSN 1600-5368. Yue Zhu,a,b Wei-Min Lu,a* Meng Maa and Fang Chena. Correspondence e-mail: weimlu2000@163.com. The title compound, [La2(C4H5O2)6(C12H8N2)2]2H2O, is a discrete centrosymmetric homodinuclear complex, which is structurally very similar to a previously studied analogue. The LaIII atoms are bridged by two bidentate and two tridentate carboxylate groups, with an La  La separation of ˚ . Each LaIII atom exhibits a distorted tricapped 4.0807 (4) A trigonal prismatic coordination formed by seven O atoms of bridging methylacrylate groups and two N atoms of the bidentate chelating 1,10-phenanthroline ligands.. Key indicators. Comment. a. Chemistry Department, Zhejiang University (Xixi Campus), Hangzhou, Zhejiang 310028, People’s Republic of China, and bMedical School, Hangzhou Teachers’ College, Hangzhou 310012, People’s Republic of China. Single-crystal X-ray study T = 293 K ˚ Mean (C–C) = 0.009 A R factor = 0.035 wR factor = 0.112 Data-to-parameter ratio = 17.8 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.. # 2005 International Union of Crystallography Printed in Great Britain – all rights reserved. m2044. Zhu et al.. . Received 17 August 2005 Accepted 13 September 2005 Online 21 September 2005. Molecular magnetic compounds, such as molecular ferro- and ferrimagnets, organic magnets, single-molecule magnets and high-spin molecules, have recently attracted attention (Miller & Drillon, 2001a,b, 2002; Christou et al., 2000). Efforts to obtain molecular magnets containing rare-earth ions have been less numerous because the interactions between pairs of f electrons are expected to be small, producing measurable effects only at extremely low temperatures, but the number of new reported compounds in which rare-earth ions are magnetically coupled to transition-metal ions and/or organic radicals is rapidly increasing. In recent years, we have pursued a project on the structures and properties of heteronuclear complexes of rare-earth and transition metals bridged by carboxyl groups (Wu et al., 2002, 2003, 2004; Zhu et al., 2005). The title complex, (I), was unexpectedly obtained during the preparation of a lanthanum–iron complex.. Fig. 1 shows the molecular structure of the title complex; selected bond distances are listed in Table 1.. [La2(C4H5O2)6(C12H8N2)2]2H2O. doi:10.1107/S1600536805028928. Acta Cryst. (2005). E61, m2044–m2046.

(2) metal-organic papers added and the pH was adjusted to 4.1 with 0.1 M HL. An ethanol solution (5 ml) of 1,10-phenanthroline (200 mg, 1.0 mmol) was added to the mixture with stirring. The filtrate was allowed to stand at room temperature, and colourless single crystals suitable for X-ray diffraction precipitated after a few days. Analysis calculated for C48H50La2N4O14: C 49.41, H 4.15, N 4.80, La 23.81%; found: C 49.56, H 4.18, N 4.76, La 23.63%.. Crystal data. Figure 1 The molecule of the title complex, with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted. Unlabelled atoms are related to labelled atoms by the symmetry operator (2  x; 1  y; 1  z).. Compound (I) is structurally very similar to another La analogue, (II), in which the water molecule is replaced by an -methylacrylic acid molecule (Lu, et al., 1996). As one would expect, the surroundings of the central atoms in the two complexes are the same. This means that the LaIII atoms, with the coordination geometry of a distorted tricapped trigonal prism, are linked to each other by bidentate and tridentate carboxylate groups to form a centrosymmetric dimeric unit. Each LaIII atom is nine-coordinated by two N atoms of the phenanthroline ligand and seven O atoms from three different coordination modes of six carboxylate groups. The detailed coordination modes of -methylacrylate groups in (II) are also fully applicable to the title complex. The La  Lai separation ˚ ; symmetry code as in Table 1] in the dimer just [4.0807 (4) A exceeds the sum of two atomic radii and is slightly longer than ˚ ] in (II). that [4.0456 (4) A The structure of the title complex has two distinct La—O ˚ and distances; the average La—Obridging bond length is 2.498 A ˚ , which are similar to those (2.494 and La—Ochelating is 2.606 A ˚ ) of (II). The La—Ochelating distance is significantly 2.612 A larger than the sum of the covalent radii of the two atoms, as is to be expected because the (O—La—O)chelating angles of about 50 indicate ring strain. The phenanthroline ligands possess local C2v symmetry. The average La—N bond distance ˚ and is nearly the same as the corresponding La—N is 2.708 A ˚ ) in (II). A water molecule is connected to distance (2.709 A atom O1 by a hydrogen bond. Comparison of structures (I) and (II) shows that it is uncertain whether water or a free -methylacrylic acid molecule will be included in the complex during the growth of the crystal.. Experimental LaL32H2O [430 mg, 1.0 mmol; HL = CH2C(CH3)COOH] was dissolved in water (5 ml). A 1 M solution of Fe(NO3)3 (1.0 ml) was Acta Cryst. (2005). E61, m2044–m2046. [La2(C4H5O2)6(C12H8N2)2]2H2O Mr = 1184.74 Triclinic, P1 ˚ a = 10.8815 (4) A ˚ b = 11.0081 (5) A ˚ c = 11.7412 (7) A  = 69.229 (2)  = 77.892 (4)  = 68.091 (2) ˚3 V = 1215.16 (10) A. Z=1 Dx = 1.619 Mg m3 Mo K radiation Cell parameters from 6732 reflections  = 2.5–27.5  = 1.80 mm1 T = 293 (2) K Chunk, colourless 0.21  0.18  0.14 mm. Data collection 5471 independent reflections 5112 reflections with I > 2(I) Rint = 0.045 max = 27.5 h = 13 ! 14 k = 13 ! 14 l = 15 ! 15. Rigaku R-AXIS RAPID diffractometer ! scans Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.703, Tmax = 0.786 11677 measured reflections. Refinement Refinement on F 2 R[F 2 > 2(F 2)] = 0.035 wR(F 2) = 0.112 S = 1.24 5471 reflections 307 parameters H-atom parameters constrained. w = 1/[ 2(Fo2) + (0.0611P)2 + 0.7074P] where P = (Fo2 + 2Fc2)/3 (/)max = 0.001 ˚ 3 max = 0.81 e A ˚ 3 min = 1.21 e A. Table 1 ˚ ). Selected bond lengths (A La1—O1 La1—O2 La1—O3 La1—O4 La1—O5. 2.584 2.532 2.592 2.493 2.495. (3) (3) (3) (3) (3). La1—O6 La1—O6i La1—N1 La1—N2. 2.457 2.718 2.699 2.719. (3) (3) (4) (3). Symmetry code: (i) x þ 2; y þ 1; z þ 1.. Table 2 ˚ ,  ). Hydrogen-bond geometry (A D—H  A. D—H. H  A. D  A. D—H  A. O7—HW1  O1. 0.99. 1.88. 2.863 (5). 174. All H atoms were placed in calculated positions (C—H = 0.93– ˚ and O—H = 0.94–0.99 A ˚ ) and included in the final cycles of 0.96 A refinement in a riding model, with Uiso(H) = 1.2Ueq(C) [Uiso(H) = 1.5Ueq(C,O) in the case of the methyl and water H atoms]. The ˚ from atom La1. deepest hole is located 1.0 A Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: CrystalStructure (Rigaku/MSC, 2002); data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, Zhu et al.. . [La2(C4H5O2)6(C12H8N2)2]2H2O. m2045.

(3) metal-organic papers 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).. References Christou, G., Gatteschi, D., Hendrickson, D. N. & Sessoli, R. (2000). MRS Bull. 25, 66–71. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Lu, W. M, Sao, Z. P. & Dong, N. (1996). J. Coord. Chem. 40, 145–155.. m2046. Zhu et al.. . [La2(C4H5O2)6(C12H8N2)2]2H2O. Miller, J. S. & Drillon, M. (2001a). Magnetism: Molecules to Materials I. Weinheim: Wiley-VCH. Miller, J. S. & Drillon, M. (2001b). Magnetism: Molecules to Materials II. Weinheim: Wiley-VCH. Miller, J. S. & Drillon, M. (2002). Magnetism: Molecules to Materials III. Weinheim: Wiley-VCH. Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Rigaku/MSC (2002). CrystalStructure. Version 3.00. Rigaku/MSC, 9009 New Trails Drive, The Woodlands, TX 77381-5209, USA. Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany. Wu, B., Lu, W. M., Wu, F. F. & Zheng, X. M. (2003). Transition Met. Chem. 28, 694–697. Wu, B., Lu, W. M. & Zheng, X. M. (2002). Chin. J. Chem. 20, 846–850. Wu, B., Lu, W. M. & Zheng, X. M. (2004). J. Coord. Chem. 57, 805–812. Zhu, Y., Lu, W. M. & Chen, F. (2005). Acta Cryst. E61, m1610–1612.. Acta Cryst. (2005). E61, m2044–m2046.

(4) supporting information. supporting information Acta Cryst. (2005). E61, m2044–m2046. [doi:10.1107/S1600536805028928]. Hexa-µ-α-methylacrylato-bis[(1,10-phenanthroline)lanthanum(III)] dihydrate Yue Zhu, Wei-Min Lu, Meng Ma and Fang Chen S1. Comment Molecular magnetic compounds, such as molecular ferro- and ferrimagnets, organic magnets, single-molecule magnets and high-spin molecules, have recently attracted attention (Miller & Drillon, 2001a,b, Miller & Drillon, 2002; Christou et al., 2000). Efforts to obtain molecular magnets containing rare-earth ions have been comparatively less numerous because the interactions between pairs of f electrons are expected to be small, producing measurable effects only at extremely low temperatures, but the number of new reported compounds in which rare-earth ions are magnetically coupled to transition-metal ions and/or organic radicals is rapidly increasing. In recent nears, we have pursued a project on the structures and properties of heteronuclear complexes of rare-earth and transition metals bridged by carboxyl groups (Wu et al., 2002, 2003, 2004; Zhu et al., 2005). The title complex, (I), was unexpectedly obtained during the preparation of a lanthanium–iron complex. Fig. 1 shows the molecular structure of the title complex; selected bond distances are listed in Table 1. Compound (I) is isostructural with another La analogue, (II), in which the water molecule is replaced by an α-methylacrylic acid molecule (Lu, et al., 1996). As one would expect, the surroundings of the central atoms in the two complexes are the same. This means that the LaIII atoms, with the coordination geometry of a distorted tricapped trigonal prism, are linked to each other by bidentate and tridentate carboxylate groups to form a centrosymmetric dimeric unit. Each LaIII atom is nine-coordinated by two N atoms of the phenanthroline ligand and seven O atoms from three different coordination modes of six carboxylate groups. The detailed coordination modes of α-methylacrylate groups in (II) are also fully applicable to the title complex. The La···Lai separation [4.0807 (4) Å] in the dimer just exceeds the sum of two atomic radii and is slightly longer than that [4.0456 (4) Å] in (II). The structure of the title complex has two distinct La—O distances; the average La—Obridging bond length is 2.498 Å and La—Ochelating is 2.606 Å, which are similar to those (2.494 and 2.612 Å) of (II). The La—Ochelating distance is significantly larger than the sum of the covalent radii of the two atoms, as is to be expected because the (O—La—O)chelating angles of about 50° indicate ring strain. The phenanthroline ligands possess local C2v symmetry. The average La—N bond distance is 2.708 Å and is nearly the same as the corresponding La—N distance (2.709 Å) in (II). A water molecule is connected with atom O1 by a hydrogen bond. Comparison of structures (I) and (II) shows that it is uncertain whether water or a free α-methylacrylic acid molecule will be included in the complex during the growth of the crystal. S2. Experimental LaL3·2H2O [430 mg, 1.0 mmol; HL = CH2C(CH3)COOH] was dissolved in water (5 ml). A 1 M solution of Fe(NO3)3 (1.0 ml) was added and the pH was adjusted to 4.1 with 0.1 M HL. An ethanol solution (5 ml) of 1,10-phenanthroline (200 mg, 1.0 mmol) was added to the mixture with stirring. The filtrate was allowed to stand at room temperature, and colourless single crystals suitable for X-ray work precipitated after a few days. Analysis calculated for C48H50La2N4O14: C. Acta Cryst. (2005). E61, m2044–m2046. sup-1.

(5) supporting information 49.41, H 4.15, N 4.80, La 23.81%; found: C 49.56, H 4.18, N 4.76, La 23.63%. S3. Refinement All H atoms were placed in calculated positions (C—H = 0.93–0.96 Å and O—H = 0.94–0.99 Å) and included in the final cycles of refinement in a riding model, with Uiso(H) = 1.2Ueq(C) [Uiso(H) = 1.5Ueq(C,O) in the case of the methyl and water H atoms].. Figure 1 Molecule of the title complex, with the displacement ellipsoids drawn at the 30% probability level. The H atoms have been omitted. Hexa-µ-α-methylacrylato-bis[(1,10-phenanthroline)lanthanum(III)] monohydrate Crystal data [La2(C4H5O2)6(C12H8N2)2]·2H2O Mr = 1184.74 Triclinic, P1 Hall symbol: -P 1 a = 10.8815 (4) Å b = 11.0081 (5) Å c = 11.7412 (7) Å α = 69.229 (2)° β = 77.892 (4)° γ = 68.091 (2)° V = 1215.16 (10) Å3. Acta Cryst. (2005). E61, m2044–m2046. Z=1 F(000) = 592 Dx = 1.619 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 6732 reflections θ = 2.5–27.5° µ = 1.80 mm−1 T = 293 K Chunk, colourless 0.21 × 0.18 × 0.14 mm. sup-2.

(6) supporting information Data collection Rigaku R-AXIS RAPID diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 10.0 pixels mm-1 ω scans Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.703, Tmax = 0.786. 11677 measured reflections 5471 independent reflections 5112 reflections with I > 2σ(I) Rint = 0.045 θmax = 27.5°, θmin = 1.9° h = −13→14 k = −13→14 l = −15→15. Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.035 wR(F2) = 0.112 S = 1.24 5471 reflections 307 parameters 0 restraints Primary atom site location: structure-invariant direct methods. Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0611P)2 + 0.7074P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.81 e Å−3 Δρmin = −1.21 e Å−3. Special details Experimental. The elemental analyses on C, H and N were performed using a Carlo-Erba 1110 Elemental Analyzer; La was analyzed by titration with edta. Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2). La1 O1 O2 O3 O4 O5 O6 O7 HW1 HW2 N1 N2 C1 H1. x. y. z. Uiso*/Ueq. 0.856611 (19) 0.8829 (3) 0.6862 (3) 0.8836 (3) 0.7597 (3) 1.0851 (3) 0.9738 (3) 1.1319 (6) 1.0462 1.1882 0.8041 (3) 0.6166 (3) 0.8901 (5) 0.9635. 0.56341 (2) 0.3733 (3) 0.4584 (4) 0.8022 (3) 0.5913 (4) 0.5077 (4) 0.3565 (3) 0.1741 (7) 0.2464 0.2231 0.6969 (4) 0.7603 (4) 0.6631 (5) 0.5840. 0.629075 (19) 0.8378 (3) 0.7671 (3) 0.5132 (3) 0.4432 (3) 0.6836 (3) 0.5647 (3) 0.7938 (7) 0.8026 0.7426 0.7961 (3) 0.6430 (3) 0.8752 (5) 0.8795. 0.02779 (9) 0.0457 (8) 0.0489 (8) 0.0422 (7) 0.0438 (7) 0.0439 (7) 0.0375 (6) 0.115 (2) 0.172* 0.172* 0.0359 (7) 0.0368 (8) 0.0451 (10) 0.054*. Acta Cryst. (2005). E61, m2044–m2046. sup-3.

(7) supporting information C2 H2 C3 H3 C4 C5 H5 C6 H6 C7 C8 H8 C9 H9 C10 H10 C11 C12 C21 C22 C23 H23A H23B C24 H24A H24B H24C C31 C32 C33 H33A H33B H33C C34 H34A H34B C41 C42 C43 H43A H43B C44 H44A H44B H44C. 0.8778 (6) 0.9401 0.7720 (5) 0.7623 0.6786 (5) 0.5628 (6) 0.5534 0.4687 (5) 0.3940 0.4810 (4) 0.3811 (5) 0.3029 0.3983 (5) 0.3309 0.5185 (5) 0.5305 0.5972 (4) 0.6977 (4) 0.7637 (5) 0.7128 (6) 0.5765 (8) 0.5425 0.5192 0.8082 (9) 0.8959 0.8014 0.7914 0.9857 (4) 1.0651 (5) 0.9912 (7) 0.8976 1.0079 1.0202 1.1991 (6) 1.2506 1.2396 0.7965 (4) 0.6936 (5) 0.5669 (5) 0.5028 0.5414 0.7420 (7) 0.8374 0.7077 0.7121. Acta Cryst. (2005). E61, m2044–m2046. 0.7385 (6) 0.7092 0.8566 (6) 0.9098 0.8969 (5) 1.0196 (6) 1.0802 1.0465 (5) 1.1244 0.9589 (5) 0.9788 (6) 1.0529 0.8912 (6) 0.9022 0.7834 (5) 0.7254 0.8439 (4) 0.8124 (4) 0.3758 (5) 0.2818 (6) 0.3067 (9) 0.2482 0.3818 0.1696 (8) 0.1728 0.0846 0.1759 0.7639 (4) 0.8577 (5) 1.0074 (6) 1.0223 1.0451 1.0518 0.8026 (7) 0.8597 0.7077 0.5330 (4) 0.5094 (5) 0.5636 (7) 0.5495 0.6161 0.4241 (9) 0.3937 0.4779 0.3456. 0.9527 (5) 1.0084 0.9452 (5) 0.9950 0.8624 (4) 0.8500 (5) 0.8922 0.7780 (5) 0.7730 0.7100 (4) 0.6393 (5) 0.6357 0.5770 (5) 0.5333 0.5786 (5) 0.5328 0.7101 (4) 0.7895 (4) 0.8480 (4) 0.9582 (5) 0.9799 (7) 1.0467 0.9276 1.0330 (7) 1.0005 1.0344 1.1147 0.4459 (4) 0.3814 (4) 0.3431 (7) 0.3637 0.2563 0.3845 0.3649 (7) 0.3275 0.3909 0.3618 (4) 0.3115 (5) 0.3435 (6) 0.3130 0.3967 0.2268 (8) 0.2166 0.1488 0.2603. 0.0541 (13) 0.065* 0.0516 (12) 0.062* 0.0435 (10) 0.0533 (12) 0.064* 0.0524 (12) 0.063* 0.0419 (10) 0.0520 (12) 0.062* 0.0551 (13) 0.066* 0.0462 (11) 0.055* 0.0347 (8) 0.0343 (8) 0.0395 (9) 0.0533 (12) 0.097 (3) 0.116* 0.116* 0.094 (3) 0.140* 0.140* 0.140* 0.0341 (8) 0.0421 (10) 0.0686 (17) 0.103* 0.103* 0.103* 0.0661 (16) 0.079* 0.079* 0.0357 (9) 0.0450 (10) 0.0668 (17) 0.080* 0.080* 0.084 (2) 0.126* 0.126* 0.126*. sup-4.

(8) supporting information Atomic displacement parameters (Å2). La1 O1 O2 O3 O4 O5 O6 O7 N1 N2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C21 C22 C23 C24 C31 C32 C33 C34 C41 C42 C43 C44. U11. U22. U33. U12. U13. U23. 0.02322 (12) 0.0392 (17) 0.0365 (17) 0.0370 (16) 0.0328 (15) 0.0290 (14) 0.0366 (15) 0.102 (5) 0.0342 (17) 0.0277 (16) 0.039 (2) 0.054 (3) 0.057 (3) 0.048 (2) 0.057 (3) 0.045 (3) 0.032 (2) 0.031 (2) 0.031 (2) 0.034 (2) 0.0309 (19) 0.0330 (19) 0.042 (2) 0.066 (3) 0.081 (5) 0.114 (6) 0.036 (2) 0.050 (3) 0.078 (4) 0.051 (3) 0.032 (2) 0.037 (2) 0.036 (3) 0.059 (4). 0.03225 (13) 0.0472 (17) 0.057 (2) 0.0335 (14) 0.0575 (19) 0.064 (2) 0.0353 (14) 0.107 (4) 0.0396 (18) 0.0416 (18) 0.055 (3) 0.074 (3) 0.066 (3) 0.045 (2) 0.050 (3) 0.046 (3) 0.040 (2) 0.056 (3) 0.072 (3) 0.058 (3) 0.036 (2) 0.036 (2) 0.042 (2) 0.060 (3) 0.117 (7) 0.088 (5) 0.0344 (19) 0.043 (2) 0.045 (3) 0.062 (3) 0.040 (2) 0.058 (3) 0.106 (5) 0.119 (6). 0.02808 (13) 0.0439 (18) 0.048 (2) 0.0501 (19) 0.0450 (18) 0.0425 (17) 0.0426 (17) 0.115 (5) 0.0309 (17) 0.0377 (19) 0.041 (2) 0.045 (3) 0.044 (3) 0.040 (2) 0.055 (3) 0.054 (3) 0.039 (2) 0.050 (3) 0.051 (3) 0.047 (3) 0.0279 (19) 0.032 (2) 0.035 (2) 0.041 (3) 0.073 (5) 0.070 (5) 0.034 (2) 0.038 (2) 0.078 (4) 0.090 (5) 0.037 (2) 0.049 (3) 0.077 (4) 0.114 (6). −0.00983 (9) −0.0183 (14) −0.0214 (15) −0.0112 (12) −0.0098 (14) −0.0157 (14) −0.0136 (12) 0.009 (4) −0.0092 (14) −0.0089 (14) −0.013 (2) −0.025 (3) −0.025 (3) −0.018 (2) −0.015 (2) −0.005 (2) −0.0060 (17) 0.001 (2) −0.008 (2) −0.014 (2) −0.0103 (16) −0.0146 (16) −0.0184 (19) −0.039 (3) −0.060 (5) −0.062 (5) −0.0127 (16) −0.025 (2) −0.031 (3) −0.034 (3) −0.0128 (17) −0.019 (2) −0.025 (3) −0.030 (4). −0.00116 (8) −0.0075 (13) −0.0065 (14) 0.0056 (13) −0.0093 (13) −0.0025 (12) −0.0019 (12) −0.034 (4) −0.0038 (13) −0.0038 (13) −0.0073 (18) −0.012 (2) 0.001 (2) 0.0058 (18) 0.010 (2) 0.006 (2) 0.0039 (16) −0.0021 (19) −0.010 (2) −0.0086 (18) 0.0036 (15) 0.0026 (15) −0.0009 (17) −0.001 (2) 0.011 (4) −0.030 (4) −0.0078 (16) 0.0001 (18) −0.002 (3) 0.017 (3) −0.0099 (16) −0.0107 (19) −0.006 (2) −0.011 (4). −0.00921 (9) 0.0005 (14) −0.0006 (16) −0.0115 (13) −0.0219 (15) −0.0207 (15) −0.0130 (13) −0.044 (4) −0.0098 (14) −0.0101 (15) −0.015 (2) −0.021 (3) −0.029 (2) −0.0173 (19) −0.028 (2) −0.016 (2) −0.0048 (18) −0.011 (2) −0.013 (3) −0.015 (2) −0.0032 (15) −0.0083 (16) −0.0094 (18) −0.005 (2) 0.011 (4) 0.028 (4) −0.0089 (16) −0.0090 (19) −0.004 (3) −0.026 (3) −0.0082 (17) −0.018 (2) −0.048 (4) −0.077 (5). Geometric parameters (Å, º) La1—O1 La1—O2 La1—O3 La1—O4 La1—O5 La1—O6 La1—O6i La1—N1. Acta Cryst. (2005). E61, m2044–m2046. 2.584 (3) 2.532 (3) 2.592 (3) 2.493 (3) 2.495 (3) 2.457 (3) 2.718 (3) 2.699 (4). C6—H6 C7—C8 C7—C11 C8—C9 C8—H8 C9—C10 C9—H9 C10—H10. 0.9300 1.411 (7) 1.417 (6) 1.344 (8) 0.9300 1.398 (7) 0.9300 0.9300. sup-5.

(9) supporting information La1—N2 La1—C21 La1—C31 La1—La1i O1—C21 O2—C21 O3—C31 O4—C41 O5—C41i O6—C31i O6—La1i O7—HW1 O7—HW2 N1—C1 N1—C12 N2—C10 N2—C11 C1—C2 C1—H1 C2—C3 C2—H2 C3—C4 C3—H3 C4—C12 C4—C5 C5—C6 C5—H5 C6—C7. 2.719 (3) 2.932 (5) 3.025 (4) 4.0812 (5) 1.267 (5) 1.262 (6) 1.247 (5) 1.253 (5) 1.263 (5) 1.275 (5) 2.718 (3) 0.9889 0.9436 1.317 (6) 1.353 (5) 1.333 (6) 1.346 (6) 1.392 (7) 0.9300 1.367 (8) 0.9300 1.396 (7) 0.9300 1.409 (6) 1.450 (7) 1.344 (8) 0.9300 1.410 (8). C11—C12 C21—C22 C22—C23 C22—C24 C23—H23A C23—H23B C24—H24A C24—H24B C24—H24C C31—O6i C31—C32 C32—C34 C32—C33 C33—H33A C33—H33B C33—H33C C34—H34A C34—H34B C41—O5i C41—C42 C42—C43 C42—C44 C43—H43A C43—H43B C44—H44A C44—H44B C44—H44C. 1.450 (6) 1.493 (7) 1.389 (9) 1.425 (9) 0.9300 0.9300 0.9600 0.9600 0.9600 1.275 (5) 1.491 (6) 1.355 (8) 1.484 (7) 0.9600 0.9600 0.9600 0.9300 0.9300 1.263 (5) 1.508 (6) 1.314 (7) 1.491 (8) 0.9300 0.9300 0.9600 0.9600 0.9600. O1—La1—O2 O1—La1—O3 O1—La1—O4 O1—La1—O5 O1—La1—O6 O1—La1—O6i O1—La1—N1 O1—La1—N2 O2—La1—O3 O2—La1—O4 O2—La1—O5 O2—La1—O6 O2—La1—O6i O2—La1—N1 O2—La1—N2 O3—La1—O4 O3—La1—O5 O3—La1—O6 O3—La1—O6i. 50.95 (10) 142.83 (11) 130.93 (12) 73.18 (11) 78.78 (11) 135.08 (10) 74.92 (11) 108.10 (11) 140.11 (11) 91.21 (12) 123.99 (11) 91.88 (12) 163.02 (12) 82.83 (12) 69.10 (11) 86.02 (11) 82.51 (11) 124.43 (10) 48.72 (9). C3—C2—C1 C3—C2—H2 C1—C2—H2 C2—C3—C4 C2—C3—H3 C4—C3—H3 C3—C4—C12 C3—C4—C5 C12—C4—C5 C6—C5—C4 C6—C5—H5 C4—C5—H5 C5—C6—C7 C5—C6—H6 C7—C6—H6 C6—C7—C8 C6—C7—C11 C8—C7—C11 C9—C8—C7. 118.6 (5) 120.7 120.7 119.5 (5) 120.3 120.3 118.0 (5) 122.9 (5) 119.1 (5) 120.6 (5) 119.7 119.7 121.4 (5) 119.3 119.3 123.2 (4) 120.6 (5) 116.2 (5) 120.4 (4). Acta Cryst. (2005). E61, m2044–m2046. sup-6.

(10) supporting information O3—La1—N1 O3—La1—N2 O4—La1—O5 O4—La1—O6 O4—La1—O6i O4—La1—N1 O4—La1—N2 O5—La1—O6 O5—La1—O6i O5—La1—N1 O5—La1—N2 O6—La1—O6i O6—La1—N1 O6—La1—N2 N1—La1—O6i N1—La1—N2 O6i—La1—N2 O6—La1—C21 O4—La1—C21 O5—La1—C21 O2—La1—C21 O1—La1—C21 O3—La1—C21 N1—La1—C21 O6i—La1—C21 N2—La1—C21 O6—La1—C31 O4—La1—C31 O5—La1—C31 O2—La1—C31 O1—La1—C31 O3—La1—C31 N1—La1—C31 O6i—La1—C31 N2—La1—C31 C21—La1—C31 O6—La1—La1i O4—La1—La1i O5—La1—La1i O2—La1—La1i O1—La1—La1i O3—La1—La1i N1—La1—La1i O6i—La1—La1i N2—La1—La1i C21—La1—La1i C31—La1—La1i C21—O1—La1. Acta Cryst. (2005). E61, m2044–m2046. 73.11 (11) 71.41 (10) 135.27 (11) 71.82 (10) 73.86 (10) 137.58 (10) 78.01 (11) 79.63 (10) 66.15 (10) 79.00 (11) 136.47 (11) 76.00 (11) 149.92 (10) 143.90 (11) 113.60 (10) 60.58 (11) 114.23 (10) 84.63 (12) 111.75 (12) 98.71 (12) 25.37 (12) 25.58 (11) 150.28 (12) 77.97 (12) 157.10 (11) 88.62 (12) 100.92 (11) 81.84 (11) 70.44 (11) 162.64 (11) 142.99 (11) 24.10 (10) 91.58 (11) 24.92 (10) 93.83 (11) 166.40 (12) 40.26 (7) 68.11 (7) 67.81 (8) 131.05 (9) 110.77 (8) 84.31 (7) 141.96 (8) 35.74 (6) 139.44 (8) 123.87 (9) 60.66 (8) 92.8 (3). C9—C8—H8 C7—C8—H8 C8—C9—C10 C8—C9—H9 C10—C9—H9 N2—C10—C9 N2—C10—H10 C9—C10—H10 N2—C11—C7 N2—C11—C12 C7—C11—C12 N1—C12—C4 N1—C12—C11 C4—C12—C11 O2—C21—O1 O2—C21—C22 O1—C21—C22 O2—C21—La1 O1—C21—La1 C22—C21—La1 C23—C22—C24 C23—C22—C21 C24—C22—C21 C22—C23—H23A C22—C23—H23B H23A—C23—H23B C22—C24—H24A C22—C24—H24B H24A—C24—H24B C22—C24—H24C H24A—C24—H24C H24B—C24—H24C O3—C31—O6i O3—C31—C32 O6i—C31—C32 O3—C31—La1 O6i—C31—La1 C32—C31—La1 C34—C32—C33 C34—C32—C31 C33—C32—C31 C32—C33—H33A C32—C33—H33B H33A—C33—H33B C32—C33—H33C H33A—C33—H33C H33B—C33—H33C C32—C34—H34A. 119.8 119.8 119.4 (5) 120.3 120.3 122.7 (5) 118.7 118.7 123.1 (4) 118.6 (4) 118.3 (4) 122.0 (4) 118.1 (4) 119.7 (4) 121.0 (4) 119.1 (4) 119.9 (4) 59.3 (2) 61.7 (2) 178.4 (3) 124.0 (6) 118.4 (5) 117.6 (5) 120.0 120.0 120.0 109.5 109.5 109.5 109.5 109.5 109.5 120.9 (4) 119.7 (4) 119.4 (4) 58.1 (2) 64.0 (2) 166.3 (3) 124.1 (5) 118.8 (4) 117.1 (4) 109.5 109.5 109.5 109.5 109.5 109.5 120.0. sup-7.

(11) supporting information C21—O2—La1 C31—O3—La1 C41—O4—La1 C41i—O5—La1 C31i—O6—La1 C31i—O6—La1i La1—O6—La1i HW1—O7—HW2 C1—N1—C12 C1—N1—La1 C12—N1—La1 C10—N2—C11 C10—N2—La1 C11—N2—La1 N1—C1—C2 N1—C1—H1 C2—C1—H1. 95.3 (3) 97.8 (2) 134.4 (3) 137.8 (3) 164.9 (3) 91.1 (3) 104.00 (11) 104.2 118.0 (4) 121.0 (3) 120.4 (3) 118.0 (4) 121.9 (3) 120.0 (3) 124.0 (5) 118.0 118.0. C32—C34—H34B H34A—C34—H34B O4—C41—O5i O4—C41—C42 O5i—C41—C42 C43—C42—C44 C43—C42—C41 C44—C42—C41 C42—C43—H43A C42—C43—H43B H43A—C43—H43B C42—C44—H44A C42—C44—H44B H44A—C44—H44B C42—C44—H44C H44A—C44—H44C H44B—C44—H44C. 120.0 120.0 125.0 (4) 118.8 (4) 116.2 (4) 123.0 (5) 119.4 (5) 117.6 (4) 120.0 120.0 120.0 109.5 109.5 109.5 109.5 109.5 109.5. Symmetry code: (i) −x+2, −y+1, −z+1.. Hydrogen-bond geometry (Å, º) D—H···A. D—H. H···A. D···A. D—H···A. O7—HW1···O1. 0.99. 1.88. 2.863 (5). 174. Acta Cryst. (2005). E61, m2044–m2046. sup-8.

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