catena-Poly[[[diaqua­[trans-3-(4-pyri­dyl)acrylato]samarium(III)]-di-[mu]-trans-3-(4-pyrid­yl)acrylato] dihydrate]

In the title compound, {[Sm(4-pya)₃(H₂O)₂]·2H₂O}_n [4-pya is trans-3-(4-pyrid­yl)acrylate, C₈H₆NO₂], each Sm^III atom is ten-coordinated and has a bicapped square-antiprismatic coordination geometry. There is a crystallographic center of symmetry at the mid-point of the Sm...Sm line within each [Sm(4-pya)₃(H₂O)₂]₂ dimer. Each dimer is inter­connected by two pairs of bridging 4-pya ligands to form a one-dimensional chain. Neighboring chains are connected via hydrogen bonds to form a three-dimensional network.

S1. Comment

Over the past few decades, there has been considerable interest in the coordination chemistry of lanthanide compounds due to their unique structures and their potential applications in advanced materials, such as Ln-doped semiconductors (Taniguchi & Takahei, 1993), and catalytic (Costes et al., 1997; Bencini et al., 1985), magnetic (Lisowski & Starynowicz, 1999), fluorescent (Alexander, 1995; Bermudez et al., 2001), and nonlinear optical materials (Reinhard & Gudel, 2002). As is well known, ligands containing a combination of N and O donor atoms are good building blocks for the formation of various lanthanide coordination compounds (Liang et al., 2000; Pan et al., 2000; Ma et al., 1999; Costes et al., 2002; Ouchi et al., 1988; Kim et al., 2004). Trans-4-pyridylacrylic acid (4-Hpya) is one such interesting multifunctional ligand. Four coordination modes of 4-pya have been observed in the crystal structures of transition metal complexes of this ligand (Evans & Lin, 2001; Zhang et al., 2000; Liu et al., 2001). However, the chemistry of lanthanide complexes of 4-Hpya is less well studied (Zhou et al., 2003). Owing to the large radii and the strong oxophilicity of Ln^III ions, we anticipated that coordination of 4-Hpya by Ln^III metals may lead to the formation of new compounds with different coordination modes. In this regard, we carried out the reaction of Sm₂O₃ with 4-Hpya by hydrothermal synthesis. We report here the crystal structure of (I).

Complex (I) crystallizes in space group P-1 and the asymmetric unit contains one-half of an [Sm(4-pya)₃(H₂O)₂]₂ dimer and two solvent water molecules. Complex (I) has a one-dimensional chain structure extended along the a axis (Fig. 1). Each repeating [Sm(4-pya)₃(H₂O)₂]₂ dimer within the chain is interconnected by four tridentate bridging 4-pya anions. There is a crystallographic center of symmetry at the midpoint of the Sm1···Sm1ⁱ [symmetry code: (i) 1 − x, 1 − y, 1 − z] line within the dimer. The Sm1 center coordinates to eight O atoms of 4-pya ligands and two O atoms of water molecules, forming a bicapped square-antiprismatic coordination geometry. The Sm···Sm contact within the dimer is 4.303 (1) Å, shorter than the Sm···Sm separation [4.468 (1) Å] between dimers. Both Sm···Sm contacts are too long to include metal–metal interactions. In the dimer, the 4-pya ligand exhibits two coordination modes. In neither of the two modes does the N atom of the pyridyl group bond to Sm. In one mode, the 4-pya ligand chelates the Sm^III center via atoms O1 and O2 to form an SmO₂C four-membered ring. In the other mode, 4-pya acts as a tridentate ligand, chelating the Sm1 ion via atoms O3ⁱ and O4ⁱ and bridging the Sm1ⁱ ion via atom O3ⁱ. Because of the existence of the different coordination modes of 4-pya, the Sm1—O bond distances range from 2.404 (2) Å to 2.713 (2) Å (Table 1). The Sm1—O1 bond length is comparable to that of the Sm1—O2 bond, implying that atoms O1 and O2 of this 4-pya ligand are almost symmetrically bound to atom Sm1. However, the 4-pya ligand carrying O3ⁱ and O4ⁱ binds to Sm1 in an unsymmetric way as the Sm1—O3ⁱ bond is 0.24 (2) Å longer than the Sm1—O4ⁱ bond. It is noted that the Sm1—O3ⁱ bond length is the longest among all the Sm1—O bonds. This may be ascribed to the fact that atom O3ⁱ strongly binds to atom Sm1ⁱ of the same dimer with Sm1ⁱ—O3ⁱ = 2.487 (2) Å. Interestingly, the structure of (I) differs from that reported in the lanthanide/3-pya complex La[(C₈H₆NO₂)₃]_n (3-pya is trans-4-pyridylacrylate; Zhou et al., 2003). Each La^III ion in the latter complex is eight-coordinated with seven O atoms and one N atom from the 3-pya ligand, forming a two-dimensional network.

In the unit cell of (I), the coordinated water molecules interact with the O atoms of the 4-pya ligands to form intramolecular hydrogen bonds (O8—H27···O1 and O7—H25···O2; Table 2). Furthermore, one of the free water molecules and the coordinated water molecules interact with the O and N atoms of the 4-pya ligands of the adjacent chains to afford intermolecular hydrogen bonds, thereby forming a three-dimensional hydrogen-bonded network (Fig. 2).

S2. Experimental

4-Hpya was prepared as reported previously (Alcalde et al., 1992). Other reagents were obtained from commercial sources and used as received. A mixture of Sm₂O₃ (0.06 g, 0.17 mmol), 4-Hpya (0.15 g, 1 mmol) and water (10 ml) was heated in a stainless-steel reactor with a Teflon liner at 413 K for 4 d and then cooled slowly to room temperature. The resulting colorless crystals were collected by filtration, washed with ethanol and then air-dried (yield 8%, 0.018 g). The crystal used for the structure determination was obtained directly from the above preparation. Analysis found: C 43.59, H 3.86, N 6.38%; calculated for C₄₈H₅₂Sm₂N₆O₂₀: C 43.23, H 3.93, N 6.30%. Spectroscopic analysis: IR (KBr, cm⁻¹): 3238 (m), 3045 (m), 1646 (s), 1601 (s), 1544 (s), 1404 (s), 1253 (m), 990 (m), 822 (m), 744 (m), 590 (m).

S3. Refinement

The positions of the H atoms of the water molecules were located from difference Fourier maps and were refined freely along with isotropic displacement parameters. All other hydrogen atoms were placed in geometrically idealized positions (C—H = 0.95 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. An ORTEPII (Johnson, 1976) view of the dimeric unit and atom labelling for (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 2, −y + 1, −z + 1.]
	Fig. 2. A packing diagram (looking down the a axis) for (I), showing the three-dimensional network formed by hydrogen bonds (dotted lines) between the polymeric chains.

catena-Poly[[[diaqua[trans-3-(4-pyridyl)acrylato]samarium(III)]-di-µ-trans- 3-(4-pyridyl)acrylato] dihydrate]

Crystal data

[Sm(C8H6NO2)3(H2O)2]·2H2O	Z = 2
Mr = 666.83	F(000) = 666
Triclinic, P1	Dx = 1.672 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.2459 (8) Å	Cell parameters from 5348 reflections
b = 12.6631 (15) Å	θ = 3.1–25.3°
c = 14.3286 (16) Å	µ = 2.28 mm^−1
α = 111.782 (2)°	T = 193 K
β = 98.825 (2)°	Block, colorless
γ = 100.605 (2)°	0.35 × 0.15 × 0.10 mm
V = 1324.7 (3) Å^3

Data collection

Rigaku Mercury diffractometer	4571 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.4°, θmin = 3.1°
/w scans	h = −9→9
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→15
Tmin = 0.678, Tmax = 0.796	l = −17→17
13165 measured reflections	720 standard reflections every 6 reflections
4840 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0293P)^2 + 0.9553P] where P = (Fo^2 + 2Fc^2)/3
4812 reflections	(Δ/σ)max = 0.011
338 parameters	Δρmax = 0.95 e Å^−3
12 restraints	Δρmin = −0.70 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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 (Ų)

	x	y	z	Uiso*/Ueq
Sm1	0.781720 (19)	0.565469 (13)	0.529619 (11)	0.01467 (7)
O1	0.8531 (3)	0.4493 (2)	0.63592 (17)	0.0232 (5)
O2	0.6943 (3)	0.5701 (2)	0.69022 (17)	0.0201 (5)
O3	0.5300 (3)	0.39386 (19)	0.47128 (17)	0.0196 (5)
O4	0.3006 (3)	0.2467 (2)	0.41408 (19)	0.0235 (5)
O5	0.8865 (3)	0.41318 (19)	0.41783 (16)	0.0187 (5)
O6	0.9950 (3)	0.2866 (2)	0.31192 (18)	0.0244 (5)
O7	0.6364 (3)	0.5384 (2)	0.35607 (17)	0.0202 (5)
H25	0.5329 (18)	0.499 (3)	0.335 (2)	0.024*
H26	0.679 (3)	0.533 (3)	0.3049 (16)	0.024*
O8	0.9550 (3)	0.6918 (2)	0.46166 (18)	0.0212 (5)
H27	1.016 (4)	0.658 (3)	0.425 (2)	0.025*
H28	0.908 (4)	0.732 (3)	0.437 (2)	0.025*
O9	1.1028 (5)	0.0278 (4)	0.2276 (3)	0.0782 (12)
H29	1.142 (7)	0.086 (3)	0.286 (2)	0.094*
H30	1.017 (5)	0.039 (5)	0.195 (4)	0.094*
O10	1.1122 (8)	−0.2044 (5)	0.2021 (9)	0.183 (4)
H31	1.168 (13)	−0.153 (8)	0.185 (10)	0.220*
H32	1.033 (10)	−0.179 (9)	0.227 (8)	0.220*
N1	0.7293 (4)	0.5283 (4)	1.1685 (3)	0.0452 (9)
N2	0.7913 (4)	−0.1654 (3)	0.3829 (2)	0.0318 (7)
N3	0.2294 (7)	0.0697 (3)	−0.0816 (3)	0.0696 (14)
C1	0.7771 (4)	0.4988 (3)	0.7022 (2)	0.0184 (4)
C2	0.7835 (4)	0.4750 (3)	0.7964 (3)	0.0240 (8)
H2	0.8237	0.4105	0.7998	0.029*
C3	0.7338 (4)	0.5428 (3)	0.8756 (3)	0.0250 (8)
H3	0.6910	0.6041	0.8669	0.030*
C4	0.7365 (5)	0.5351 (3)	0.9754 (3)	0.0282 (8)
C5	0.6781 (5)	0.6164 (4)	1.0492 (3)	0.0345 (9)
H5	0.6396	0.6764	1.0351	0.041*
C6	0.6766 (6)	0.6094 (4)	1.1426 (4)	0.0506 (6)
H6	0.6357	0.6656	1.1915	0.061*
C7	0.7863 (6)	0.4511 (4)	1.0978 (4)	0.0506 (6)
H7	0.8261	0.3932	1.1149	0.061*
C8	0.7915 (5)	0.4496 (4)	1.0014 (3)	0.0339 (9)
H8	0.8317	0.3915	0.9538	0.041*
C9	0.4602 (4)	0.2839 (3)	0.4367 (2)	0.0184 (4)
C10	0.5702 (4)	0.2026 (3)	0.4264 (3)	0.0201 (7)
H10	0.6901	0.2341	0.4470	0.024*
C11	0.5067 (4)	0.0868 (3)	0.3892 (3)	0.0237 (7)
H11	0.3868	0.0571	0.3644	0.028*
C12	0.6071 (4)	0.0005 (3)	0.3833 (3)	0.0235 (7)
C13	0.5276 (5)	−0.1110 (3)	0.3732 (3)	0.0280 (8)
H13	0.4081	−0.1336	0.3648	0.034*
C14	0.6238 (5)	−0.1889 (3)	0.3753 (3)	0.0313 (9)
H14	0.5676	−0.2636	0.3712	0.038*
C15	0.8654 (5)	−0.0597 (3)	0.3876 (3)	0.0328 (9)
H15	0.9835	−0.0421	0.3901	0.039*
C16	0.7809 (5)	0.0259 (3)	0.3892 (3)	0.0278 (8)
H16	0.8405	0.1003	0.3942	0.033*
C17	0.8716 (4)	0.3278 (3)	0.3312 (2)	0.0184 (4)
C18	0.7059 (4)	0.2804 (3)	0.2541 (3)	0.0221 (7)
H18	0.6088	0.3015	0.2757	0.027*
C19	0.6880 (5)	0.2100 (3)	0.1566 (3)	0.0298 (8)
H19	0.7853	0.1869	0.1369	0.036*
C20	0.5275 (6)	0.1645 (3)	0.0754 (3)	0.0383 (10)
C21	0.5313 (7)	0.1257 (4)	−0.0281 (3)	0.0522 (13)
H21	0.6368	0.1305	−0.0473	0.063*
C22	0.3791 (6)	0.0798 (4)	−0.1032 (4)	0.0506 (6)
H22	0.3835	0.0544	−0.1738	0.061*
C23	0.2235 (6)	0.1081 (4)	0.0171 (3)	0.0506 (6)
H23	0.1154	0.1025	0.0331	0.061*
C24	0.3689 (6)	0.1562 (4)	0.0986 (3)	0.0462 (11)
H24	0.3600	0.1827	0.1684	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.01735 (10)	0.01504 (10)	0.01451 (10)	0.00717 (7)	0.00520 (7)	0.00734 (7)
O1	0.0270 (13)	0.0300 (13)	0.0220 (12)	0.0168 (11)	0.0130 (10)	0.0137 (11)
O2	0.0222 (12)	0.0250 (12)	0.0175 (11)	0.0104 (10)	0.0065 (10)	0.0110 (10)
O3	0.0254 (12)	0.0160 (11)	0.0199 (12)	0.0076 (10)	0.0062 (10)	0.0087 (10)
O4	0.0188 (12)	0.0206 (12)	0.0338 (14)	0.0079 (10)	0.0074 (10)	0.0123 (11)
O5	0.0219 (12)	0.0177 (11)	0.0165 (11)	0.0084 (9)	0.0049 (9)	0.0055 (9)
O6	0.0220 (12)	0.0247 (13)	0.0242 (13)	0.0096 (10)	0.0064 (10)	0.0056 (10)
O7	0.0184 (12)	0.0286 (13)	0.0177 (12)	0.0072 (10)	0.0064 (10)	0.0128 (10)
O8	0.0231 (12)	0.0226 (13)	0.0276 (13)	0.0132 (10)	0.0106 (11)	0.0157 (11)
O9	0.062 (3)	0.073 (3)	0.060 (3)	0.000 (2)	−0.010 (2)	0.002 (2)
O10	0.079 (4)	0.084 (4)	0.297 (10)	0.043 (3)	0.003 (5)	−0.012 (5)
N1	0.0357 (19)	0.068 (3)	0.0241 (17)	−0.0066 (18)	0.0021 (15)	0.0218 (18)
N2	0.048 (2)	0.0274 (17)	0.0269 (17)	0.0247 (15)	0.0095 (15)	0.0121 (14)
N3	0.091 (4)	0.034 (2)	0.052 (3)	0.000 (2)	−0.031 (2)	0.0101 (19)
C1	0.0211 (10)	0.0206 (10)	0.0171 (9)	0.0076 (8)	0.0053 (8)	0.0105 (8)
C2	0.0256 (18)	0.0321 (19)	0.0217 (18)	0.0127 (16)	0.0070 (15)	0.0162 (16)
C3	0.0268 (18)	0.0304 (19)	0.0227 (18)	0.0081 (16)	0.0051 (15)	0.0162 (16)
C4	0.0287 (19)	0.036 (2)	0.0210 (18)	0.0036 (16)	0.0060 (16)	0.0146 (16)
C5	0.042 (2)	0.037 (2)	0.0227 (19)	0.0061 (19)	0.0101 (18)	0.0111 (17)
C6	0.0548 (15)	0.0495 (14)	0.0379 (13)	0.0026 (12)	−0.0008 (11)	0.0176 (11)
C7	0.0548 (15)	0.0495 (14)	0.0379 (13)	0.0026 (12)	−0.0008 (11)	0.0176 (11)
C8	0.034 (2)	0.048 (2)	0.030 (2)	0.0127 (19)	0.0109 (17)	0.0242 (19)
C9	0.0211 (10)	0.0206 (10)	0.0171 (9)	0.0076 (8)	0.0053 (8)	0.0105 (8)
C10	0.0202 (17)	0.0235 (18)	0.0235 (17)	0.0108 (14)	0.0086 (14)	0.0136 (15)
C11	0.0256 (18)	0.0217 (18)	0.0258 (18)	0.0102 (15)	0.0067 (15)	0.0099 (15)
C12	0.0310 (19)	0.0207 (17)	0.0194 (17)	0.0121 (15)	0.0062 (15)	0.0065 (14)
C13	0.037 (2)	0.0231 (18)	0.0278 (19)	0.0127 (16)	0.0125 (17)	0.0107 (16)
C14	0.053 (3)	0.0217 (18)	0.029 (2)	0.0190 (18)	0.0167 (19)	0.0151 (16)
C15	0.036 (2)	0.034 (2)	0.028 (2)	0.0196 (18)	0.0050 (17)	0.0087 (17)
C16	0.036 (2)	0.0189 (17)	0.0263 (19)	0.0123 (16)	0.0030 (16)	0.0057 (15)
C17	0.0211 (10)	0.0206 (10)	0.0171 (9)	0.0076 (8)	0.0053 (8)	0.0105 (8)
C18	0.0246 (18)	0.0222 (17)	0.0205 (17)	0.0065 (14)	0.0027 (14)	0.0107 (15)
C19	0.037 (2)	0.0264 (19)	0.0246 (19)	0.0089 (17)	0.0031 (16)	0.0098 (16)
C20	0.054 (3)	0.0217 (19)	0.027 (2)	0.0034 (18)	−0.0075 (19)	0.0067 (16)
C21	0.080 (4)	0.037 (2)	0.025 (2)	0.011 (2)	−0.006 (2)	0.0066 (19)
C22	0.0548 (15)	0.0495 (14)	0.0379 (13)	0.0026 (12)	−0.0008 (11)	0.0176 (11)
C23	0.0548 (15)	0.0495 (14)	0.0379 (13)	0.0026 (12)	−0.0008 (11)	0.0176 (11)
C24	0.045 (3)	0.038 (2)	0.040 (2)	−0.002 (2)	−0.012 (2)	0.013 (2)

Geometric parameters (Å, º)

Sm1—O5	2.404 (2)	C3—C4	1.465 (5)
Sm1—O7	2.457 (2)	C3—H3	0.9500
Sm1—O4^i	2.471 (2)	C4—C5	1.393 (5)
Sm1—O3	2.488 (2)	C4—C8	1.396 (5)
Sm1—O2	2.499 (2)	C5—C6	1.376 (6)
Sm1—O8	2.508 (2)	C5—H5	0.9500
Sm1—O6^ii	2.519 (2)	C6—H6	0.9500
Sm1—O1	2.557 (2)	C7—C8	1.381 (6)
Sm1—O5^ii	2.659 (2)	C7—H7	0.9500
Sm1—O3^i	2.712 (2)	C8—H8	0.9500
O1—C1	1.254 (4)	C9—C10	1.475 (4)
O2—C1	1.272 (4)	C10—C11	1.327 (5)
O3—C9	1.273 (4)	C10—H10	0.9500
O3—Sm1^i	2.712 (2)	C11—C12	1.473 (5)
O4—C9	1.259 (4)	C11—H11	0.9500
O4—Sm1^i	2.471 (2)	C12—C13	1.387 (5)
O5—C17	1.278 (4)	C12—C16	1.393 (5)
O5—Sm1^ii	2.659 (2)	C13—C14	1.380 (5)
O6—C17	1.249 (4)	C13—H13	0.9500
O6—Sm1^ii	2.519 (2)	C14—H14	0.9500
O7—H25	0.848 (10)	C15—C16	1.387 (5)
O7—H26	0.848 (10)	C15—H15	0.9500
O8—H27	0.84 (3)	C16—H16	0.9500
O8—H28	0.84 (4)	C17—C18	1.480 (5)
O9—H29	0.85 (3)	C18—C19	1.316 (5)
O9—H30	0.85 (5)	C18—H18	0.9500
O10—H31	0.86 (12)	C19—C20	1.479 (5)
O10—H32	0.85 (10)	C19—H19	0.9500
N1—C7	1.336 (6)	C20—C21	1.385 (6)
N1—C6	1.334 (6)	C20—C24	1.393 (6)
N2—C14	1.337 (5)	C21—C22	1.387 (6)
N2—C15	1.338 (5)	C21—H21	0.9500
N3—C23	1.327 (6)	C22—H22	0.9500
N3—C22	1.313 (7)	C23—C24	1.394 (6)
C1—C2	1.483 (4)	C23—H23	0.9500
C2—C3	1.320 (5)	C24—H24	0.9500
C2—H2	0.9500
O5—Sm1—O7	77.38 (7)	C3—C2—C1	120.5 (3)
O5—Sm1—O4^i	154.64 (8)	C3—C2—H2	119.8
O7—Sm1—O4^i	83.76 (8)	C1—C2—H2	119.8
O5—Sm1—O3	79.83 (7)	C2—C3—C4	128.0 (3)
O7—Sm1—O3	74.40 (7)	C2—C3—H3	116.0
O4^i—Sm1—O3	111.35 (7)	C4—C3—H3	116.0
O5—Sm1—O2	125.51 (7)	C5—C4—C8	117.0 (3)
O7—Sm1—O2	135.99 (7)	C5—C4—C3	118.8 (3)
O4^i—Sm1—O2	79.84 (7)	C8—C4—C3	124.2 (3)
O3—Sm1—O2	74.19 (7)	C6—C5—C4	119.7 (4)
O5—Sm1—O8	83.36 (7)	C6—C5—H5	120.2
O7—Sm1—O8	67.87 (8)	C4—C5—H5	120.2
O4^i—Sm1—O8	73.84 (7)	N1—C6—C5	123.8 (5)
O3—Sm1—O8	141.18 (7)	N1—C6—H6	118.1
O2—Sm1—O8	141.99 (8)	C5—C6—H6	118.1
O5—Sm1—O6^ii	113.49 (7)	N1—C7—C8	124.5 (5)
O7—Sm1—O6^ii	141.26 (8)	N1—C7—H7	117.7
O4^i—Sm1—O6^ii	72.14 (8)	C8—C7—H7	117.7
O3—Sm1—O6^ii	142.43 (7)	C7—C8—C4	118.6 (4)
O2—Sm1—O6^ii	69.65 (7)	C7—C8—H8	120.7
O8—Sm1—O6^ii	76.38 (8)	C4—C8—H8	120.7
O5—Sm1—O1	75.81 (7)	O4—C9—O3	120.1 (3)
O7—Sm1—O1	141.76 (8)	O4—C9—C10	121.3 (3)
O4^i—Sm1—O1	128.45 (7)	O3—C9—C10	118.6 (3)
O3—Sm1—O1	74.43 (7)	C11—C10—C9	122.0 (3)
O2—Sm1—O1	51.50 (7)	C11—C10—H10	119.0
O8—Sm1—O1	134.11 (7)	C9—C10—H10	119.0
O6^ii—Sm1—O1	75.36 (8)	C10—C11—C12	125.4 (3)
O5—Sm1—O5^ii	63.65 (8)	C10—C11—H11	117.3
O7—Sm1—O5^ii	122.22 (7)	C12—C11—H11	117.3
O4^i—Sm1—O5^ii	115.00 (7)	C13—C12—C16	117.5 (3)
O3—Sm1—O5^ii	131.89 (7)	C13—C12—C11	119.4 (3)
O2—Sm1—O5^ii	101.70 (7)	C16—C12—C11	123.1 (3)
O8—Sm1—O5^ii	66.80 (7)	C14—C13—C12	119.4 (4)
O6^ii—Sm1—O5^ii	50.04 (7)	C14—C13—H13	120.3
O1—Sm1—O5^ii	67.31 (7)	C12—C13—H13	120.3
O5—Sm1—O3^i	133.91 (7)	N2—C14—C13	123.9 (3)
O7—Sm1—O3^i	69.11 (7)	N2—C14—H14	118.1
O4^i—Sm1—O3^i	49.83 (7)	C13—C14—H14	118.1
O3—Sm1—O3^i	61.58 (8)	N2—C15—C16	124.2 (4)
O2—Sm1—O3^i	69.10 (7)	N2—C15—H15	117.9
O8—Sm1—O3^i	110.69 (7)	C16—C15—H15	117.9
O6^ii—Sm1—O3^i	112.47 (7)	C15—C16—C12	118.7 (3)
O1—Sm1—O3^i	113.26 (7)	C15—C16—H16	120.7
O5^ii—Sm1—O3^i	162.44 (7)	C12—C16—H16	120.7
C1—O1—Sm1	92.57 (18)	O6—C17—O5	120.5 (3)
C1—O2—Sm1	94.83 (18)	O6—C17—C18	121.0 (3)
C9—O3—Sm1	152.5 (2)	O5—C17—C18	118.5 (3)
C9—O3—Sm1^i	89.06 (18)	C19—C18—C17	122.4 (3)
Sm1—O3—Sm1^i	118.42 (8)	C19—C18—H18	118.8
C9—O4—Sm1^i	100.81 (19)	C17—C18—H18	118.8
C17—O5—Sm1	151.5 (2)	C18—C19—C20	124.7 (4)
C17—O5—Sm1^ii	90.87 (18)	C18—C19—H19	117.7
Sm1—O5—Sm1^ii	116.35 (8)	C20—C19—H19	117.7
C17—O6—Sm1^ii	98.24 (19)	C21—C20—C24	117.7 (4)
Sm1—O7—H25	116 (2)	C21—C20—C19	120.0 (4)
Sm1—O7—H26	128 (2)	C24—C20—C19	122.3 (4)
H25—O7—H26	110.1 (16)	C20—C21—C22	119.1 (5)
Sm1—O8—H27	114 (2)	C20—C21—H21	120.4
Sm1—O8—H28	119 (2)	C22—C21—H21	120.4
H27—O8—H28	111.5 (17)	N3—C22—C21	123.4 (5)
H29—O9—H30	109 (5)	N3—C22—H22	118.3
H31—O10—H32	109 (11)	C21—C22—H22	118.3
C7—N1—C6	116.3 (4)	N3—C23—C24	122.9 (5)
C14—N2—C15	116.2 (3)	N3—C23—H23	118.6
C23—N3—C22	118.3 (4)	C24—C23—H23	118.6
O1—C1—O2	120.9 (3)	C20—C24—C23	118.7 (4)
O1—C1—C2	120.1 (3)	C20—C24—H24	120.7
O2—C1—C2	119.0 (3)	C23—C24—H24	120.7
O5—Sm1—O1—C1	−167.9 (2)	Sm1—O1—C1—C2	−174.9 (3)
O7—Sm1—O1—C1	−121.1 (2)	Sm1—O2—C1—O1	−5.0 (3)
O4^i—Sm1—O1—C1	20.5 (2)	Sm1—O2—C1—C2	174.8 (3)
O3—Sm1—O1—C1	−84.69 (19)	O1—C1—C2—C3	166.5 (3)
O2—Sm1—O1—C1	−2.72 (18)	O2—C1—C2—C3	−13.2 (5)
O8—Sm1—O1—C1	126.41 (19)	C1—C2—C3—C4	−177.8 (3)
O6^ii—Sm1—O1—C1	72.72 (19)	C2—C3—C4—C5	179.8 (4)
O5^ii—Sm1—O1—C1	125.1 (2)	C2—C3—C4—C8	−1.4 (6)
O3^i—Sm1—O1—C1	−35.8 (2)	C8—C4—C5—C6	−0.1 (6)
O5—Sm1—O2—C1	20.5 (2)	C3—C4—C5—C6	178.8 (4)
O7—Sm1—O2—C1	131.08 (19)	C7—N1—C6—C5	0.2 (7)
O4^i—Sm1—O2—C1	−159.1 (2)	C4—C5—C6—N1	0.3 (7)
O3—Sm1—O2—C1	85.14 (19)	C6—N1—C7—C8	−0.9 (7)
O8—Sm1—O2—C1	−112.6 (2)	N1—C7—C8—C4	1.1 (7)
O6^ii—Sm1—O2—C1	−84.48 (19)	C5—C4—C8—C7	−0.5 (6)
O1—Sm1—O2—C1	2.69 (18)	C3—C4—C8—C7	−179.4 (4)
O5^ii—Sm1—O2—C1	−45.40 (19)	Sm1^i—O4—C9—O3	−4.5 (3)
O3^i—Sm1—O2—C1	150.2 (2)	Sm1^i—O4—C9—C10	174.0 (2)
O5—Sm1—O3—C9	24.9 (4)	Sm1—O3—C9—O4	−174.9 (3)
O7—Sm1—O3—C9	104.5 (4)	Sm1^i—O3—C9—O4	4.0 (3)
O4^i—Sm1—O3—C9	−178.8 (4)	Sm1—O3—C9—C10	6.5 (6)
O2—Sm1—O3—C9	−106.7 (4)	Sm1^i—O3—C9—C10	−174.5 (3)
O8—Sm1—O3—C9	90.7 (4)	O4—C9—C10—C11	2.7 (5)
O6^ii—Sm1—O3—C9	−90.6 (4)	O3—C9—C10—C11	−178.8 (3)
O1—Sm1—O3—C9	−53.1 (4)	C9—C10—C11—C12	−175.4 (3)
O5^ii—Sm1—O3—C9	−15.0 (5)	C10—C11—C12—C13	160.5 (3)
O3^i—Sm1—O3—C9	178.8 (5)	C10—C11—C12—C16	−18.3 (6)
O5—Sm1—O3—Sm1^i	−153.94 (10)	C16—C12—C13—C14	3.6 (5)
O7—Sm1—O3—Sm1^i	−74.34 (9)	C11—C12—C13—C14	−175.3 (3)
O4^i—Sm1—O3—Sm1^i	2.35 (11)	C15—N2—C14—C13	−0.6 (5)
O2—Sm1—O3—Sm1^i	74.44 (9)	C12—C13—C14—N2	−2.6 (6)
O8—Sm1—O3—Sm1^i	−88.18 (13)	C14—N2—C15—C16	2.6 (5)
O6^ii—Sm1—O3—Sm1^i	90.53 (13)	N2—C15—C16—C12	−1.4 (6)
O1—Sm1—O3—Sm1^i	128.09 (10)	C13—C12—C16—C15	−1.8 (5)
O5^ii—Sm1—O3—Sm1^i	166.11 (7)	C11—C12—C16—C15	177.1 (3)
O3^i—Sm1—O3—Sm1^i	0.0	Sm1^ii—O6—C17—O5	−6.3 (3)
O7—Sm1—O5—C17	−25.2 (4)	Sm1^ii—O6—C17—C18	172.7 (3)
O4^i—Sm1—O5—C17	−68.1 (5)	Sm1—O5—C17—O6	169.2 (3)
O3—Sm1—O5—C17	51.0 (4)	Sm1^ii—O5—C17—O6	5.9 (3)
O2—Sm1—O5—C17	113.1 (4)	Sm1—O5—C17—C18	−9.9 (6)
O8—Sm1—O5—C17	−93.9 (4)	Sm1^ii—O5—C17—C18	−173.1 (3)
O6^ii—Sm1—O5—C17	−165.9 (4)	O6—C17—C18—C19	−13.1 (5)
O1—Sm1—O5—C17	127.3 (4)	O5—C17—C18—C19	166.0 (3)
O5^ii—Sm1—O5—C17	−161.3 (5)	C17—C18—C19—C20	−177.2 (3)
O3^i—Sm1—O5—C17	18.5 (5)	C18—C19—C20—C21	158.2 (4)
O7—Sm1—O5—Sm1^ii	136.10 (10)	C18—C19—C20—C24	−23.3 (6)
O4^i—Sm1—O5—Sm1^ii	93.21 (18)	C24—C20—C21—C22	−0.6 (6)
O3—Sm1—O5—Sm1^ii	−147.77 (10)	C19—C20—C21—C22	178.0 (4)
O2—Sm1—O5—Sm1^ii	−85.68 (11)	C23—N3—C22—C21	1.7 (7)
O8—Sm1—O5—Sm1^ii	67.37 (9)	C20—C21—C22—N3	−0.7 (7)
O6^ii—Sm1—O5—Sm1^ii	−4.63 (11)	C22—N3—C23—C24	−1.4 (7)
O1—Sm1—O5—Sm1^ii	−71.42 (9)	C21—C20—C24—C23	0.9 (6)
O5^ii—Sm1—O5—Sm1^ii	0.0	C19—C20—C24—C23	−177.6 (4)
O3^i—Sm1—O5—Sm1^ii	179.81 (7)	N3—C23—C24—C20	0.1 (7)
Sm1—O1—C1—O2	4.9 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H25···O2^i	0.85 (1)	1.83 (1)	2.675 (3)	171 (3)
O7—H26···N1^iii	0.85 (1)	2.04 (1)	2.870 (4)	166 (3)
O8—H27···O1^ii	0.84 (3)	1.93 (3)	2.741 (3)	162 (3)
O8—H28···N2^iv	0.84 (4)	2.05 (4)	2.883 (4)	177 (3)
O9—H29···O4^v	0.85 (3)	2.17 (2)	2.997 (4)	163 (6)
O9—H30···N3^vi	0.85 (5)	2.22 (4)	2.913 (6)	138 (5)

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