Poly[[penta­aqua­(μ₄-pyridine-2,4,6-tri­carboxyl­ato)(μ₃-pyridine-2,4,6-tri­carboxyl­ato)disamarium(III)] mono­hydrate]

Abstract

The asymmetric unit of the title compound, {[Sm₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O}_n, contains two independent Sm^III ions, two pyridine-2,4,6-tricarboxyl­ate (ptc) ligands, five aqua ligands and one lattice water mol­ecule. One Sm^III ion is nine-coordinated by one N and five O atoms from the three ptc ligands and three aqua ligands in a distorted monocapped square antiprismatic geometry, and the other is eight-coordinated by one N and five O atoms from three ptc ligands and two aqua ligands in a 4,4′-bicapped trigonal anti­prismatic geometry. The ptc ligands brigde the Sm^III ions into a three-dimensional polymeric framework. Extensive O—H⋯O hydrogen bonding is observed in the crystal structure.

Related literature  

For related compounds, see: Gao et al. (2006 ▶); Ghosh & Bharadwaj (2005 ▶); Li et al. (2008 ▶); Wang et al. (2007 ▶).

Experimental  

Crystal data  

• [Sm₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O

• M _r = 825.01

• Monoclinic,

• a = 18.426 (4) Å

• b = 6.9082 (14) Å

• c = 18.583 (4) Å

• β = 111.98 (3)°

• V = 2193.6 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 5.40 mm⁻¹

• T = 293 K

• 0.43 × 0.28 × 0.21 mm

Data collection  

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.177, T _max = 0.321

• 20300 measured reflections

• 4963 independent reflections

• 4776 reflections with I > 2σ(I)

• R _int = 0.035

Refinement  

• R[F ² > 2σ(F ²)] = 0.018

• wR(F ²) = 0.041

• S = 1.19

• 4963 reflections

• 344 parameters

• H-atom parameters constrained

• Δρ_max = 0.69 e Å⁻³

• Δρ_min = −0.84 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O14i	0.82	1.87	2.686 (3)	172
O7—H7B⋯O2ii	0.86	1.80	2.645 (3)	165
O8—H8A⋯O12iii	0.89	1.83	2.727 (3)	177
O8—H8B⋯O9iv	0.87	2.38	2.831 (3)	113
O9—H9A⋯O6i	0.87	1.84	2.698 (3)	171
O9—H9B⋯O5i	0.93	2.55	3.052 (3)	114
O16—H16A⋯O4i	0.82	2.31	3.075 (3)	157
O16—H16B⋯O15v	0.79	1.97	2.747 (3)	171
O17—H17A⋯O18vi	0.84	1.86	2.697 (3)	176
O17—H17B⋯O5vii	0.80	1.96	2.731 (3)	162
O18—H18A⋯O14viii	0.85	2.06	2.905 (3)	174
O18—H18B⋯O13	0.82	1.93	2.736 (3)	168

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

supplementary crystallographic information

Comment

In recent years, research of lanthanide pyridine-2,4,6-tricarboxylate coordination polymers has been of great interest in the fields of molecule adsorption, host-guest interaction and luminescence materials (Gao et al., 2006; Li et al., 2008; Wang et al., 2007;) etc. The compound {[Pr(H₂O)₂(ptc)].2H₂O} reported by Ghosh et al. (2005) represents an example of three-dimensional MOF, which could potentially be utilized as an adsorption material. In this contribution, we report the structure of the title compound.

The asymmetric unit of title compound contains two Sm^III ions (Sm1, Sm2), two ptc ligands (denoted as ptc1 and ptc2 ligands, which contain N1 and N2 atoms, respectively) (H₃ptc = pyridine-2,4,6-tricarboxylate), five aqua ligands and one lattice water molecule as illustrated in Fig. 1. The Sm1 and Sm2 are respectively 9- and 8-coordinated with the ligating atoms occupying the corners of distorted monocapped square anti-prism and 4,4'-bicapped trigonal anti-prism, respectively. The bond distances about the Sm1 and Sm2 atoms fall in the regions 2.406-2.587 Å and 2.359-2.529 Å, the corresponding bond angles are in the regions 50.9-147.8° and 63.3-159.7°, respectively.

Each ptc1 ligand links four Sm^III centers with the 4-carboxylate bonded to two metal ions in syn-syn bridging fashion and the 2-carboxylate coordinated to two metal ions in anti-syn bridging fashion, while each ptc2 ligand connects three Sm^III centers with the 4-carboxylate chelating one metal ion and the 2-carboxylate bridging two metal ions in anti-anti bridging fashions.

Both ptc1 and ptc2 ligands coordinate Sm1 atoms to form a linear [Sm(ptc)₂] metallo-ligand, which, in turn, bridges the Sm2 atoms to generate one-dimensional ribbon-like chains with rectangular and 8-membered rhombic rings alternating (Fig. 2). Within the rectangular ring, the two adjacent ptc1 and ptc2 ligands orientate approximately parallelly to each other with a dihedral angle of 7.4° and the mean interplanar distance of 3.33 Å suggests significant intrachain π···π stacking interactions. The resulting one-dimensional chains donate carboxylate O atoms (O1 and O10) to coordinate with Sm atoms from two neighboring chains to construct a three-dimensional framework (Fig. 3).

Experimental

All chemicals were obtained from commerical sources and were used as obtained. A mixture of SmCl₃.nH₂O (0.60 mmol), pyridine-2,4,6-tricarboxylic acid (0.0537 g, 0.25 mmol), Malonic acid (0.0261 g, 0.25 mmol), NaOH (1 ml, 1 M) and H₂O (20 ml) was sealed into a 23 ml Teflon-lined stainless autoclave, which was heated up to 180°C, at which temperature the reactor was held for 3 days, and then cooled to room temperature. A mixture of brownish deposit and a small amount of colourless block-liked crystals were obtained.

Refinement

H atoms bonded to C atoms were palced in geometrically calculated position, and were refined using a riding model, with U_iso(H) = 1.2 U_eq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O–H distances fixed as initially found and with U_iso(H) values set at 1.2 Ueq(O).

Figures

Fig. 1.

A portion of the crystal structure showing the atomic numbering and 45% probability dispalcement ellipsoids [symmetry codes: (i) 1/2-x, -1/2+y, 1/2-z; (ii) x, y, 1+z; (iii) 1-x, 1-y, 1-z; (iv) 1/2-x, -1/2+y, 3/2-z].

Fig. 2.

The one-dimensional chain with the rectangular and 8-membered rhombic rings.

Fig. 3.

The three-dimensional metal-organic framework in the title compound.

Crystal data

[Sm2(C8H2NO6)2(H2O)5]·H2O	F(000) = 1576
Mr = 825.01	Dx = 2.498 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 19369 reflections
a = 18.426 (4) Å	θ = 3.2–27.5°
b = 6.9082 (14) Å	µ = 5.40 mm−1
c = 18.583 (4) Å	T = 293 K
β = 111.98 (3)°	Block, colorless
V = 2193.6 (8) Å3	0.43 × 0.28 × 0.21 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	4963 independent reflections
Radiation source: fine-focus sealed tube	4776 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 0 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −23→23
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −8→8
Tmin = 0.177, Tmax = 0.321	l = −24→22
20300 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.018	H-atom parameters constrained
wR(F2) = 0.041	w = 1/[σ2(Fo2) + (0.0066P)2 + 3.5019P] where P = (Fo2 + 2Fc2)/3
S = 1.19	(Δ/σ)max = 0.002
4963 reflections	Δρmax = 0.69 e Å−3
344 parameters	Δρmin = −0.84 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00244 (6)

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	0.373309 (7)	0.222784 (18)	0.378119 (7)	0.01049 (4)
Sm2	0.374965 (8)	0.250031 (17)	0.896720 (7)	0.01111 (5)
N1	0.42996 (13)	0.3322 (3)	0.27802 (12)	0.0125 (4)
C1	0.38355 (15)	0.4105 (3)	0.21147 (15)	0.0127 (5)
C2	0.40694 (15)	0.4323 (3)	0.14877 (15)	0.0139 (5)
H2A	0.3735	0.4861	0.1023	0.017*
C3	0.48176 (15)	0.3710 (3)	0.15774 (15)	0.0125 (5)
C4	0.53246 (15)	0.3029 (4)	0.22948 (15)	0.0136 (5)
H4A	0.5840	0.2707	0.2377	0.016*
C5	0.50357 (15)	0.2846 (3)	0.28859 (15)	0.0119 (5)
C6	0.30319 (15)	0.4640 (4)	0.20964 (15)	0.0145 (5)
O1	0.26044 (11)	0.5719 (3)	0.15807 (11)	0.0185 (4)
O2	0.28618 (11)	0.3912 (3)	0.26427 (11)	0.0206 (4)
C7	0.50797 (15)	0.3719 (3)	0.08959 (14)	0.0124 (5)
O3	0.45938 (12)	0.3160 (3)	0.02671 (11)	0.0219 (4)
O4	0.57737 (11)	0.4236 (3)	0.10278 (11)	0.0172 (4)
C8	0.55086 (16)	0.2082 (4)	0.36836 (16)	0.0146 (5)
O5	0.62134 (12)	0.1852 (3)	0.38807 (12)	0.0278 (5)
O6	0.51110 (11)	0.1716 (3)	0.41069 (11)	0.0183 (4)
O7	0.36682 (12)	−0.0503 (3)	0.29113 (11)	0.0220 (4)
H7B	0.3178	−0.0743	0.2654	0.026*
H7A	0.3869	−0.0502	0.2585	0.026*
O8	0.40849 (13)	0.5640 (3)	0.39790 (13)	0.0267 (5)
H8A	0.4563	0.6135	0.4218	0.032*
H8B	0.3682	0.5986	0.4083	0.032*
O9	0.37653 (13)	−0.0753 (3)	0.45208 (12)	0.0232 (4)
H9A	0.4159	−0.0992	0.4946	0.028*
H9B	0.3363	−0.1166	0.4672	0.028*
N2	0.38147 (13)	0.2822 (3)	0.76366 (13)	0.0126 (4)
C9	0.31935 (15)	0.3494 (3)	0.70511 (15)	0.0136 (5)
C10	0.31717 (16)	0.3588 (4)	0.62931 (15)	0.0164 (5)
H10A	0.2726	0.4017	0.5888	0.020*
C11	0.38335 (16)	0.3023 (4)	0.61614 (15)	0.0144 (5)
C12	0.44856 (17)	0.2360 (3)	0.67751 (16)	0.0142 (5)
H12A	0.4938	0.2004	0.6699	0.017*
C13	0.44461 (16)	0.2242 (3)	0.75073 (16)	0.0135 (5)
C14	0.25231 (16)	0.4146 (4)	0.72805 (15)	0.0148 (5)
O10	0.19320 (12)	0.4815 (3)	0.67583 (11)	0.0210 (4)
O11	0.26175 (12)	0.3950 (3)	0.79795 (11)	0.0232 (4)
C15	0.38312 (17)	0.3038 (4)	0.53467 (15)	0.0157 (5)
O12	0.44658 (13)	0.2832 (3)	0.52504 (12)	0.0221 (4)
O13	0.31898 (12)	0.3173 (3)	0.47848 (11)	0.0212 (4)
C16	0.50960 (15)	0.1461 (3)	0.82233 (15)	0.0134 (5)
O14	0.57112 (12)	0.0880 (3)	0.81788 (11)	0.0206 (4)
O15	0.49458 (12)	0.1467 (3)	0.88390 (11)	0.0198 (4)
O16	0.39568 (13)	−0.0498 (3)	0.97353 (11)	0.0244 (4)
H16B	0.4251	−0.0676	1.0162	0.029*
H16A	0.3898	−0.1564	0.9530	0.029*
O17	0.28096 (12)	0.3100 (3)	0.95460 (13)	0.0283 (5)
H17B	0.2358	0.3132	0.9261	0.034*
H17A	0.2806	0.2465	0.9929	0.034*
O18	0.21204 (15)	0.6072 (3)	0.41898 (14)	0.0374 (6)
H18B	0.2389	0.5106	0.4367	0.045*
H18A	0.1688	0.5550	0.3908	0.045*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Sm1	0.00985 (8)	0.01369 (7)	0.00821 (7)	0.00008 (4)	0.00368 (6)	0.00015 (4)
Sm2	0.00839 (8)	0.01720 (7)	0.00731 (7)	−0.00064 (4)	0.00243 (6)	−0.00005 (4)
N1	0.0109 (11)	0.0167 (10)	0.0101 (10)	0.0002 (8)	0.0040 (9)	0.0003 (8)
C1	0.0095 (12)	0.0143 (11)	0.0133 (12)	0.0001 (9)	0.0032 (10)	0.0017 (9)
C2	0.0132 (13)	0.0169 (11)	0.0101 (12)	−0.0002 (9)	0.0026 (10)	0.0028 (9)
C3	0.0128 (13)	0.0136 (11)	0.0118 (12)	−0.0032 (9)	0.0055 (10)	−0.0006 (9)
C4	0.0108 (13)	0.0162 (11)	0.0144 (13)	−0.0015 (9)	0.0055 (11)	−0.0011 (10)
C5	0.0115 (13)	0.0128 (10)	0.0111 (12)	−0.0005 (9)	0.0041 (11)	0.0002 (9)
C6	0.0113 (13)	0.0184 (12)	0.0133 (12)	0.0010 (9)	0.0042 (10)	−0.0015 (10)
O1	0.0137 (10)	0.0243 (9)	0.0164 (10)	0.0060 (7)	0.0045 (8)	0.0061 (8)
O2	0.0128 (10)	0.0339 (10)	0.0171 (10)	0.0053 (8)	0.0079 (8)	0.0105 (8)
C7	0.0137 (13)	0.0127 (10)	0.0105 (12)	0.0009 (9)	0.0044 (10)	0.0024 (9)
O3	0.0208 (11)	0.0313 (10)	0.0112 (10)	−0.0046 (8)	0.0031 (9)	−0.0038 (8)
O4	0.0150 (10)	0.0224 (9)	0.0158 (9)	−0.0015 (7)	0.0077 (8)	0.0010 (7)
C8	0.0127 (13)	0.0158 (11)	0.0140 (13)	0.0001 (9)	0.0036 (11)	−0.0002 (10)
O5	0.0108 (11)	0.0466 (13)	0.0235 (12)	0.0054 (9)	0.0035 (9)	0.0103 (10)
O6	0.0137 (10)	0.0295 (10)	0.0121 (9)	0.0051 (8)	0.0053 (8)	0.0073 (8)
O7	0.0143 (10)	0.0353 (11)	0.0188 (10)	−0.0037 (8)	0.0090 (9)	−0.0115 (9)
O8	0.0268 (12)	0.0190 (9)	0.0329 (12)	−0.0045 (8)	0.0098 (10)	−0.0050 (8)
O9	0.0273 (12)	0.0248 (10)	0.0169 (10)	0.0035 (8)	0.0074 (9)	0.0062 (8)
N2	0.0114 (11)	0.0163 (9)	0.0095 (11)	0.0000 (8)	0.0033 (9)	0.0004 (8)
C9	0.0136 (13)	0.0157 (11)	0.0113 (12)	0.0018 (9)	0.0044 (10)	0.0009 (9)
C10	0.0168 (14)	0.0197 (12)	0.0111 (13)	0.0039 (10)	0.0034 (11)	0.0030 (10)
C11	0.0173 (14)	0.0152 (11)	0.0114 (13)	0.0001 (9)	0.0062 (11)	−0.0017 (10)
C12	0.0137 (14)	0.0169 (12)	0.0128 (13)	0.0007 (9)	0.0058 (12)	−0.0007 (9)
C13	0.0131 (14)	0.0140 (11)	0.0133 (13)	−0.0002 (9)	0.0049 (11)	−0.0013 (9)
C14	0.0139 (13)	0.0171 (11)	0.0126 (12)	0.0028 (9)	0.0039 (10)	0.0006 (10)
O10	0.0170 (11)	0.0284 (10)	0.0149 (10)	0.0110 (8)	0.0029 (8)	0.0043 (8)
O11	0.0167 (11)	0.0417 (12)	0.0124 (10)	0.0096 (9)	0.0067 (9)	0.0040 (8)
C15	0.0216 (14)	0.0164 (11)	0.0105 (13)	0.0019 (10)	0.0076 (11)	−0.0003 (10)
O12	0.0175 (11)	0.0370 (11)	0.0136 (10)	0.0003 (8)	0.0077 (9)	−0.0027 (8)
O13	0.0180 (11)	0.0347 (11)	0.0099 (9)	0.0068 (8)	0.0042 (8)	−0.0007 (8)
C16	0.0129 (13)	0.0135 (11)	0.0132 (12)	−0.0016 (9)	0.0042 (10)	0.0001 (9)
O14	0.0137 (10)	0.0303 (10)	0.0194 (10)	0.0067 (8)	0.0079 (9)	0.0014 (8)
O15	0.0152 (10)	0.0336 (10)	0.0113 (9)	0.0068 (8)	0.0057 (8)	0.0043 (8)
O16	0.0297 (12)	0.0225 (10)	0.0140 (10)	0.0053 (8)	0.0002 (9)	0.0034 (8)
O17	0.0111 (11)	0.0532 (13)	0.0215 (11)	0.0062 (9)	0.0071 (9)	0.0058 (10)
O18	0.0347 (15)	0.0383 (13)	0.0323 (13)	0.0133 (10)	0.0046 (11)	−0.0015 (10)

Geometric parameters (Å, º)

Sm1—O6	2.406 (2)	O3—Sm2vi	2.377 (2)
Sm1—O2	2.422 (2)	O4—Sm2iv	2.4185 (18)
Sm1—O8	2.436 (2)	C8—O5	1.221 (3)
Sm1—O7	2.4582 (19)	C8—O6	1.285 (3)
Sm1—O9	2.4642 (19)	O7—H7B	0.8654
Sm1—O13	2.5110 (18)	O7—H7A	0.8193
Sm1—O1i	2.5243 (19)	O8—H8A	0.8930
Sm1—N1	2.564 (2)	O8—H8B	0.8667
Sm1—O12	2.587 (2)	O9—H9A	0.8662
Sm1—C15	2.901 (3)	O9—H9B	0.9304
Sm2—O10ii	2.3600 (19)	N2—C9	1.333 (3)
Sm2—O3iii	2.377 (2)	N2—C13	1.335 (3)
Sm2—O17	2.3925 (19)	C9—C10	1.396 (3)
Sm2—O15	2.4120 (19)	C9—C14	1.518 (3)
Sm2—O4iv	2.4185 (19)	C10—C11	1.387 (3)
Sm2—O11	2.420 (2)	C10—H10A	0.9300
Sm2—O16	2.463 (2)	C11—C12	1.389 (4)
Sm2—N2	2.530 (2)	C11—C15	1.512 (3)
N1—C1	1.327 (3)	C12—C13	1.392 (4)
N1—C5	1.337 (3)	C12—H12A	0.9300
C1—C2	1.394 (3)	C13—C16	1.518 (4)
C1—C6	1.514 (3)	C14—O10	1.245 (3)
C2—C3	1.391 (4)	C14—O11	1.252 (3)
C2—H2A	0.9300	O10—Sm2vii	2.3600 (19)
C3—C4	1.393 (4)	C15—O13	1.254 (3)
C3—C7	1.515 (3)	C15—O12	1.256 (3)
C4—C5	1.394 (3)	C16—O14	1.234 (3)
C4—H4A	0.9300	C16—O15	1.274 (3)
C5—C8	1.506 (4)	O16—H16B	0.7852
C6—O1	1.237 (3)	O16—H16A	0.8179
C6—O2	1.273 (3)	O17—H17B	0.8023
O1—Sm1v	2.5243 (19)	O17—H17A	0.8383
C7—O3	1.238 (3)	O18—H18B	0.8223
C7—O4	1.260 (3)	O18—H18A	0.8524
O6—Sm1—O2	125.63 (6)	C2—C1—C6	124.1 (2)
O6—Sm1—O8	84.72 (7)	C3—C2—C1	118.0 (2)
O2—Sm1—O8	73.68 (8)	C3—C2—H2A	121.0
O6—Sm1—O7	80.78 (7)	C1—C2—H2A	121.0
O2—Sm1—O7	86.62 (7)	C2—C3—C4	119.8 (2)
O8—Sm1—O7	141.88 (7)	C2—C3—C7	120.7 (2)
O6—Sm1—O9	86.22 (7)	C4—C3—C7	119.5 (2)
O2—Sm1—O9	139.32 (7)	C3—C4—C5	117.9 (2)
O8—Sm1—O9	140.81 (7)	C3—C4—H4A	121.1
O7—Sm1—O9	73.17 (7)	C5—C4—H4A	121.1
O6—Sm1—O13	121.87 (7)	N1—C5—C4	121.8 (2)
O2—Sm1—O13	101.87 (6)	N1—C5—C8	114.3 (2)
O8—Sm1—O13	78.10 (7)	C4—C5—C8	123.8 (2)
O7—Sm1—O13	138.87 (7)	O1—C6—O2	125.5 (2)
O9—Sm1—O13	74.70 (7)	O1—C6—C1	119.9 (2)
O6—Sm1—O1i	147.10 (6)	O2—C6—C1	114.6 (2)
O2—Sm1—O1i	72.76 (7)	C6—O1—Sm1v	136.93 (16)
O8—Sm1—O1i	128.16 (7)	C6—O2—Sm1	127.30 (17)
O7—Sm1—O1i	72.87 (6)	O3—C7—O4	126.5 (2)
O9—Sm1—O1i	67.72 (7)	O3—C7—C3	116.3 (2)
O13—Sm1—O1i	71.60 (7)	O4—C7—C3	117.1 (2)
O6—Sm1—N1	63.12 (7)	C7—O3—Sm2vi	170.38 (18)
O2—Sm1—N1	62.70 (7)	C7—O4—Sm2iv	127.27 (16)
O8—Sm1—N1	70.53 (7)	O5—C8—O6	125.2 (3)
O7—Sm1—N1	71.46 (6)	O5—C8—C5	120.0 (2)
O9—Sm1—N1	136.02 (6)	O6—C8—C5	114.8 (2)
O13—Sm1—N1	147.78 (7)	C8—O6—Sm1	127.38 (17)
O1i—Sm1—N1	123.39 (7)	Sm1—O7—H7B	107.1
O6—Sm1—O12	70.93 (7)	Sm1—O7—H7A	124.1
O2—Sm1—O12	139.30 (7)	H7B—O7—H7A	104.9
O8—Sm1—O12	71.36 (7)	Sm1—O8—H8A	127.1
O7—Sm1—O12	134.07 (7)	Sm1—O8—H8B	95.7
O9—Sm1—O12	69.64 (7)	H8A—O8—H8B	123.4
O13—Sm1—O12	50.94 (7)	Sm1—O9—H9A	120.4
O1i—Sm1—O12	114.82 (7)	Sm1—O9—H9B	124.7
N1—Sm1—O12	121.65 (7)	H9A—O9—H9B	99.0
O6—Sm1—C15	96.45 (8)	C9—N2—C13	119.8 (2)
O2—Sm1—C15	123.75 (7)	C9—N2—Sm2	119.21 (16)
O8—Sm1—C15	75.45 (7)	C13—N2—Sm2	120.87 (18)
O7—Sm1—C15	140.98 (7)	N2—C9—C10	122.1 (2)
O9—Sm1—C15	67.82 (7)	N2—C9—C14	114.5 (2)
O13—Sm1—C15	25.51 (7)	C10—C9—C14	123.4 (2)
O1i—Sm1—C15	92.01 (7)	C11—C10—C9	118.0 (2)
N1—Sm1—C15	141.37 (7)	C11—C10—H10A	121.0
O12—Sm1—C15	25.64 (7)	C9—C10—H10A	121.0
O10ii—Sm2—O3iii	137.50 (7)	C10—C11—C12	119.7 (2)
O10ii—Sm2—O17	94.18 (8)	C10—C11—C15	120.1 (2)
O3iii—Sm2—O17	79.54 (8)	C12—C11—C15	120.1 (2)
O10ii—Sm2—O15	91.23 (7)	C11—C12—C13	118.5 (2)
O3iii—Sm2—O15	83.25 (7)	C11—C12—H12A	120.8
O17—Sm2—O15	159.69 (7)	C13—C12—H12A	120.8
O10ii—Sm2—O4iv	148.20 (7)	N2—C13—C12	121.8 (3)
O3iii—Sm2—O4iv	73.67 (7)	N2—C13—C16	113.8 (2)
O17—Sm2—O4iv	99.20 (7)	C12—C13—C16	124.4 (2)
O15—Sm2—O4iv	86.13 (7)	O10—C14—O11	126.2 (2)
O10ii—Sm2—O11	76.61 (8)	O10—C14—C9	117.2 (2)
O3iii—Sm2—O11	137.89 (7)	O11—C14—C9	116.6 (2)
O17—Sm2—O11	72.89 (7)	C14—O10—Sm2vii	149.34 (19)
O15—Sm2—O11	127.43 (6)	C14—O11—Sm2	125.26 (16)
O4iv—Sm2—O11	79.98 (7)	O13—C15—O12	121.9 (2)
O10ii—Sm2—O16	66.67 (7)	O13—C15—C11	118.9 (2)
O3iii—Sm2—O16	70.83 (7)	O12—C15—C11	119.2 (3)
O17—Sm2—O16	82.31 (7)	O13—C15—Sm1	59.59 (13)
O15—Sm2—O16	81.90 (7)	O12—C15—Sm1	63.06 (14)
O4iv—Sm2—O16	143.57 (7)	C11—C15—Sm1	168.04 (17)
O11—Sm2—O16	133.64 (7)	C15—O12—Sm1	91.30 (17)
O10ii—Sm2—N2	73.77 (7)	C15—O13—Sm1	94.91 (15)
O3iii—Sm2—N2	136.39 (7)	O14—C16—O15	125.1 (3)
O17—Sm2—N2	137.00 (8)	O14—C16—C13	120.0 (2)
O15—Sm2—N2	63.27 (7)	O15—C16—C13	114.9 (2)
O4iv—Sm2—N2	76.81 (6)	C16—O15—Sm2	127.11 (17)
O11—Sm2—N2	64.22 (7)	Sm2—O16—H16B	128.1
O16—Sm2—N2	125.92 (7)	Sm2—O16—H16A	121.5
C1—N1—C5	120.1 (2)	H16B—O16—H16A	104.5
C1—N1—Sm1	120.05 (16)	Sm2—O17—H17B	117.1
C5—N1—Sm1	119.15 (16)	Sm2—O17—H17A	121.9
N1—C1—C2	122.0 (2)	H17B—O17—H17A	103.8
N1—C1—C6	113.8 (2)	H18B—O18—H18A	100.8

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O14viii	0.82	1.87	2.686 (3)	172
O7—H7B···O2i	0.86	1.80	2.645 (3)	165
O8—H8A···O12iv	0.89	1.83	2.727 (3)	177
O8—H8B···O9ix	0.87	2.38	2.831 (3)	113
O9—H9A···O6viii	0.87	1.84	2.698 (3)	171
O9—H9B···O5viii	0.93	2.55	3.052 (3)	114
O16—H16A···O4viii	0.82	2.31	3.075 (3)	157
O16—H16B···O15x	0.79	1.97	2.747 (3)	171
O17—H17A···O18ii	0.84	1.86	2.697 (3)	176
O17—H17B···O5xi	0.80	1.96	2.731 (3)	162
O18—H18A···O14xii	0.85	2.06	2.905 (3)	174
O18—H18B···O13	0.82	1.93	2.736 (3)	168

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (viii) −x+1, −y, −z+1; (ix) x, y+1, z; (x) −x+1, −y, −z+2; (xi) x−1/2, −y+1/2, z+1/2; (xii) x−1/2, −y+1/2, z−1/2.