Redetermination at 180 K of a layered lanthanide–organic framework

Silva, P.; Fernandes, J.A.; Almeida Paz, F.A.

doi:10.1107/S1600536812005508

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m294-m295

doi:10.1107/S1600536812005508

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Redetermination at 180 K of a layered lanthanide–organic framework

Patrícia Silva,^a José A. Fernandes ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 13 January 2012; accepted 7 February 2012; online 17 February 2012)

The asymmetric unit of the title compound, poly[(μ₄-{[bis(hydrogen phosphonatomethyl)azaniumyl]methyl}phosphonato)lanthanum(III)], [La(C₃H₉NO₉P₃)]_n, comprises an La³⁺ center and a H₃nmp³⁻ anion (where H₃nmp³⁻ is a residue of partially deprotonated nitrilotris(methylenephosphonic acid), namely {[bis(hydrogen phosphonatomethyl)azaniumyl]methyl}phosphonate). This study concerns a structural redetermination using single-crystal X-ray diffraction data, collected at the low temperature of 180 K, of a recently investigated material whose structural details have been proposed from powder X-ray diffraction studies [Silva et al. (2011 ). J. Am. Chem. Soc. 133, 15120–15138]. The main difference between the two models rests on the position of the H atoms. While two H atoms were modeled as attached to the same phosphonate group in the powder determination, in the current model, the same H atoms are instead distributed among two of these groups. The sample studied was an inversion twin.

Related literature

For general background to the preparation of coordination compounds using lanthanide oxides, see: Liu et al. (2006 ). For previous research studies from our group on metal–organic frameworks (MOFs), see: Silva et al. (2011); Cunha-Silva et al. (2007 ); Cunha-Silva, Ananias et al. (2009 ); Cunha-Silva, Lima et al. (2009 ); Shi et al. (2008 ); Paz et al. (2004 , 2005 ). For single-crystal structural studies on MOFs having residues of (carboxymethyl)iminodi(methylphosphonic acid), see: Tang et al. (2006 ). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999 ). For a description of the Flack parameter, see: Flack (1983 ).

Experimental

Crystal data

[La(C₃H₉NO₉P₃)]
M_r = 434.93
Orthorhombic, P c a 2₁
a = 9.144 (3) Å
b = 11.727 (4) Å
c = 9.823 (3) Å
V = 1053.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.55 mm⁻¹
T = 180 K
0.05 × 0.05 × 0.01 mm

Data collection

Bruker X8 KappaCCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.804, T_max = 0.978
31245 measured reflections
2728 independent reflections
1980 reflections with I > 2σ(I)
R_int = 0.107

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.109
S = 1.02
2728 reflections
158 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 3.98 e Å⁻³
Δρ_min = −1.63 e Å⁻³
Absolute structure: Flack (1983), Friedel pairs 1229
Flack parameter: 0.44 (4)

Table 1
Selected bond lengths (Å)

La1—O1ⁱ	2.466 (6)
La1—O1ⁱⁱ	2.701 (6)
La1—O2ⁱⁱⁱ	2.549 (7)
La1—O2ⁱⁱ	2.665 (7)
La1—O3	2.530 (6)
La1—O3ⁱⁱⁱ	2.916 (6)
La1—O4ⁱⁱⁱ	2.565 (6)
La1—O7	2.480 (6)
La1—O8ⁱ	2.502 (6)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+1, z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O3	0.93	2.05	2.725 (9)	128
N1—H1C⋯O8ⁱ	0.93	2.50	3.298 (9)	143
O6—H6⋯O5^iv	0.84	1.90	2.680 (8)	153
O9—H9⋯O5^v	0.84	1.85	2.478 (8)	130
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y, z+{\script{1\over 2}}]$ ; (v) x-1, y, z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2005 ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812005508/gk2450sup1.cif

Supporting information file. DOI: 10.1107/S1600536812005508/gk2450Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005508/gk2450Isup3.hkl

checkCIF report

Comment top

During the past decade our research group has been highly active in the design, synthesis and structural characterization of multi-dimensional coordination polymers, also commonly denominated by metal-organic frameworks (MOFs) (Cunha-Silva, Lima et al., 2009; Cunha-Silva et al., 2007; Paz et al., 2004; Paz et al., 2005; Shi et al., 2008; Silva et al., 2011). The title material, [La(H₃nmp)] (1) [where H₃nmp^3- is a residue of partially deprotonated nitrilotris(methylenephosphonic acid)], was recently isolated for the first time as microcrystalline powders which prevented a priori a straightforward structural elucidation using single-crystal X-ray diffraction studies (Silva et al., 2011). Structural details were, ultimately, unveiled using laboratory powder X-ray diffraction studies (PXRD) at ambient temperature. Indeed, materials belonging to this class of compounds are usually isolated as microcrystalline powders, as found using (carboxymethyl)iminodi(methylphosphonic acid) (Cunha-Silva, Ananias et al., 2009; Cunha-Silva, Lima et al., 2009) and also nitrilotris(methylenephosphonic acid) (H₆nmp) (Cunha-Silva et al., 2007; Silva et al., 2011). A search in the literature reveals a sole publication containing two single-crystal structural determinations of MOFs combining residues of (carboxymethyl)iminodi(methylphosphonic acid) and rare-earth elements (Tang et al., 2006). To the best of our knowledge the structural determination reported in the communication is the first based on single-crystal data for materials combining residues of H₆nmp and rare-earth elements.

Changes in the synthetic route allowed us to obtain single crystals of 1 which were used for a detailed single-crystal X-ray diffraction study. We note that differences from the original synthetic procedure are solely based on two essential features: (i) the metal precursor, which we have changed from LaCl₃^.7H₂O to La₂O₃; (ii) the heating method, we now employ typical static conditions for the hydrothermal synthesis, instead of the two previously used techniques, a dynamic (with constant rotation) hydrothermal synthesis and microwave heating.

The asymmetric unit of the title compound (see Scheme and Figure 1) comprises a La³⁺ metal center and a whole H₃nmp^3- anion. The single La³⁺ center is nine-coordinated, {LaO₉}, to a total of seven phosphonate groups arising from four symmetry-related H₃nmp^3- anionic ligands, with the coordination polyhedron resembling a highly distorted tricapped trigonal prism. Conversely, the H₃nmp^3- anion coordinates to a total of four symmetry-related La³⁺ metal centers, with such connectivity leading to the formation of a two-dimensional coordination polymer perpendicular to the [010] direction of the unit cell.

The crystal structure unveiled from single-crystal X-ray diffraction resembles that previously described by us and based on powder X-ray diffraction data (Silva et al., 2011): (i) both structures were solved in the Pca2₁ orthorhombic space group; (ii) despite the differences in temperature from the two data sets, the unit cell parameters are very similar; (iii) the coordinates of the non-hydrogen atoms in the two models are highly superimposable with the differences on spatial positions being smaller than ca 0.23 Å (Figure 2). For example, the La—O distances range from 2.466 (6) to 2.916 (6) Å in the single-crystal structural determination (Table 1) and from 2.487 (12) to 2.932 (11) Å in the powder model.

The main difference between the two models resides on the position of the hydrogen atoms. While two H atoms were modeled as attached to the same phosphonate group in the powder determination, in the current model the same hydrogen atoms are instead distributed among two of such groups. In the powder determination the location of the hydrogen atoms was inferred from NMR data of similar compounds (Cunha-Silva et al., 2007). In opposition, in the present single-crystal determination the observed P—O distances were used for the location of the same hydrogen atoms. The hydrogen bonding network present in the crystal is, thus, slightly distinct from that suggested by the previous powder X-ray studies. N1—H1 interacts with two neighboring phosphonate groups coordinated to the metal center (O1 and O8), in a typical bifurcated motif. The O5, O6 and O9 oxygen atoms belonging to the protonated phosphonate groups (P2 and P3) are engaged in strong O—H···O hydrogen bonds (d_D···A below ca 2.50 Å) forming a discrete chain represented by the graph set motif D₂¹(4) (Grell et al., 1999). Individual two-dimensional layers close pack along the [010] direction of the unit cell as depicted in Figure 3. We note the absence of strong supramolecular interactions between adjacent layers and only weak C—H···O contacts (not shown) are present.

Related literature top

For general background to the preparation of coordination compounds using lanthanide oxides, see: Liu et al. (2006). For previous research studies from our group on metal–organic frameworks (MOFs), see: Silva et al. (2011); Cunha-Silva et al. (2007); Cunha-Silva, Ananias et al. (2009); Cunha-Silva, Lima et al. (2009); Shi et al. (2008); Paz et al. (2004, 2005). For single-crystal structural studies on MOFs having residues of (carboxymethyl)iminodi(methylphosphonic acid), see: Tang et al. (2006). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999). For a description of the Flack parameter, see: Flack (1983).

Experimental top

Chemicals have been purchased from commercial sources and were used as received without further purification.

A reactive mixture containing nitrilotris(methylenephosphonic acid) (H₆nmp, 0.26 g, 0.87 mmol, Fluka, 97%) and La₂O₃ (0.14 g, 0.43 mmol, Inframat Advanced Materials, 99.995%) in ca 10 g of distilled water (molar ratios of about 2: 1: 1300) was stirred thoroughly in open air (ambient temperature) for 5 minutes. The resulting homogeneous suspension was transferred into an adapted teflon-lined Parr Instruments reaction vessel (autoclave with internal volume of ca 24 ml) which was then placed inside a preheated oven at 165 °C. The reaction took place under static conditions over a period of 72 h.

The isolated material consisted systematically of physical mixtures composed of the desired material (the two-dimensional MOF structure) alongside with other products. It was possible, however, to isolate from these mixtures a crystal suitable for single-crystal X-ray diffraction data collection (Figure 4).

The reaction conditions highlighted above were fine tuned in order to find the optimal parameters which allowed the isolation of [La(H₃nmp)] (1) as a phase pure compound. Optimal conditions: (i) temperature of 160 °C or 190 °C; (ii) reaction time of 72 h; (iii) pH value of the initial reactive mixture ca 1. After reacting, the reaction vessel had to be quenched in cold water to drastically and rapidly decrease the temperature to close to the ambient one. White suspensions are typically isolated with the final product being recovered by vacuum filtration, washed with copious amounts of distilled water and then air-dried overnight.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound showing all non-H atoms represented as displacement ellipsoids drawn at the 50% probability level and H atoms as small spheres with arbitrary radius. The coordination sphere of the La1 center has been completed for clarity and the atomic labeling is provided for all non-H atoms. Symmetry transformations used to generate equivalent atoms: (i) 1/2-x, y, 1/2+z, (ii) -1/2+x, 1-y, z, (iii) 1-x, 1-y, 1/2+z.
	Fig. 2. Overlay of the asymmetric unit of the title compound: in pink there are the coordinates of the single-crystal determination and in blue those as derived from the powder X-ray diffraction studies.
	Fig. 3. Schematic representation of the crystal packing of the title compound viewed in perspective along the [001] direction of the unit cell. Two-dimensional [La(H₃nmp)] networks close pack perpendicular to the b-axis of the unit cell mediated by weak C—H···O contacts (not shown). Intralayer N—H···O and O—H···O hydrogen bonds are depicted as dashed blue lines and the La³⁺ metallic centers are depicted as green polyhedra. See Table 2 for geometrical details on the represented hydrogen bonding interactions.
	Fig. 4. SEM images showing the two main different morphologies of crystallite aggregates isolated directly from the reaction vessels: (top) phase-pure [La(H₃nmp)] isolated as a microcrystalline powder; (bottom) physical mixture of the desired material (square platelet crystals) alongside with other by-products (needle shaped).

poly[(µ₄-{[bis(hydrogen phosphonatomethyl)azaniumyl]methyl}phosphonato)lanthanum(III)] top

Crystal data top

[La(C₃H₉NO₉P₃)]	F(000) = 832
M_r = 434.93	D_x = 2.743 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3599 reflections
a = 9.144 (3) Å	θ = 3.5–22.9°
b = 11.727 (4) Å	µ = 4.55 mm⁻¹
c = 9.823 (3) Å	T = 180 K
V = 1053.3 (6) Å³	Plate, colourless
Z = 4	0.05 × 0.05 × 0.01 mm

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	2728 independent reflections
Radiation source: fine-focus sealed tube	1980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.107
ω and ϕ scans	θ_max = 29.1°, θ_min = 4.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.804, T_max = 0.978	k = −15→16
31245 measured reflections	l = −13→12

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0552P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.109	(Δ/σ)_max = 0.001
S = 1.02	Δρ_max = 3.98 e Å⁻³
2728 reflections	Δρ_min = −1.63 e Å⁻³
158 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0026 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), Friedel pairs 1229
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.44 (4)

Crystal data top

[La(C₃H₉NO₉P₃)]	V = 1053.3 (6) Å³
M_r = 434.93	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 9.144 (3) Å	µ = 4.55 mm⁻¹
b = 11.727 (4) Å	T = 180 K
c = 9.823 (3) Å	0.05 × 0.05 × 0.01 mm

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	2728 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1980 reflections with I > 2σ(I)
T_min = 0.804, T_max = 0.978	R_int = 0.107
31245 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.109	Δρ_max = 3.98 e Å⁻³
S = 1.02	Δρ_min = −1.63 e Å⁻³
2728 reflections	Absolute structure: Flack (1983), Friedel pairs 1229
158 parameters	Absolute structure parameter: 0.44 (4)
1 restraint

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.

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) top

	x	y	z	U_iso*/U_eq
La1	0.24189 (4)	0.50484 (3)	0.3327 (2)	0.01280 (14)
N1	0.4362 (7)	0.2034 (6)	0.1755 (7)	0.0138 (15)
H1C	0.4234	0.2632	0.2366	0.017*
P1	0.5445 (2)	0.40513 (17)	0.0750 (3)	0.0137 (4)
P2	0.7084 (2)	0.1567 (2)	0.2951 (2)	0.0195 (5)
P3	0.1566 (2)	0.26939 (17)	0.0838 (3)	0.0160 (4)
O1	0.4924 (6)	0.4633 (7)	−0.0534 (7)	0.0171 (16)
O2	0.7098 (5)	0.4276 (4)	0.0878 (6)	0.0151 (11)
O3	0.4646 (7)	0.4334 (5)	0.2059 (7)	0.0167 (14)
O4	0.7137 (6)	0.2775 (5)	0.3365 (9)	0.0232 (13)
O5	0.8051 (6)	0.1208 (5)	0.1770 (6)	0.0235 (15)
O6	0.7461 (6)	0.0712 (5)	0.4149 (6)	0.0172 (13)
H6	0.7437	0.1062	0.4895	0.026*
O7	0.1320 (6)	0.3460 (5)	0.2011 (6)	0.0191 (13)
O8	0.2064 (6)	0.3201 (5)	−0.0494 (6)	0.0189 (13)
O9	0.0235 (7)	0.1894 (6)	0.0523 (7)	0.027 (2)
H9	−0.0065	0.1599	0.1250	0.040*
C1	0.5143 (8)	0.2523 (8)	0.0560 (8)	0.016 (2)
H1A	0.4561	0.2382	−0.0273	0.019*
H1B	0.6097	0.2134	0.0452	0.019*
C2	0.5238 (9)	0.1137 (8)	0.2501 (9)	0.018 (2)
H2A	0.5293	0.0446	0.1924	0.022*
H2B	0.4709	0.0928	0.3345	0.022*
C3	0.2869 (9)	0.1609 (8)	0.1421 (9)	0.0147 (18)
H3A	0.2460	0.1235	0.2241	0.018*
H3B	0.2958	0.1020	0.0704	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0123 (2)	0.0165 (2)	0.0097 (2)	−0.0002 (2)	0.0000 (3)	−0.0002 (3)
N1	0.011 (3)	0.014 (4)	0.016 (4)	0.000 (3)	−0.001 (3)	−0.003 (3)
P1	0.0134 (9)	0.0172 (10)	0.0104 (10)	−0.0007 (8)	0.0000 (10)	−0.0005 (12)
P2	0.0169 (10)	0.0224 (13)	0.0194 (13)	−0.0018 (9)	−0.0002 (9)	0.0023 (10)
P3	0.0134 (9)	0.0199 (10)	0.0147 (10)	−0.0015 (8)	−0.0002 (10)	0.0001 (14)
O1	0.017 (3)	0.020 (4)	0.014 (4)	0.001 (2)	−0.004 (2)	0.013 (3)
O2	0.011 (2)	0.021 (3)	0.014 (3)	0.000 (2)	0.005 (3)	0.001 (3)
O3	0.023 (3)	0.014 (4)	0.014 (3)	−0.003 (3)	0.002 (3)	0.000 (3)
O4	0.024 (3)	0.019 (3)	0.027 (3)	0.001 (2)	0.000 (4)	−0.001 (4)
O5	0.015 (3)	0.030 (4)	0.025 (4)	−0.007 (3)	0.004 (3)	−0.010 (3)
O6	0.019 (3)	0.014 (3)	0.018 (3)	−0.003 (2)	0.001 (3)	0.001 (3)
O7	0.016 (3)	0.025 (4)	0.016 (3)	−0.001 (2)	−0.002 (3)	0.000 (3)
O8	0.019 (3)	0.022 (4)	0.016 (3)	−0.002 (3)	0.004 (3)	0.006 (3)
O9	0.019 (4)	0.035 (4)	0.026 (5)	−0.006 (3)	−0.002 (3)	−0.004 (3)
C1	0.019 (4)	0.024 (5)	0.005 (6)	−0.006 (3)	0.003 (3)	0.002 (4)
C2	0.019 (4)	0.015 (5)	0.022 (5)	−0.003 (3)	0.000 (3)	0.000 (4)
C3	0.010 (4)	0.012 (4)	0.022 (5)	0.002 (3)	−0.001 (3)	0.002 (4)

Geometric parameters (Å, º) top

La1—O1ⁱ	2.466 (6)	P2—O4	1.475 (6)
La1—O1ⁱⁱ	2.701 (6)	P2—O5	1.518 (6)
La1—O2ⁱⁱⁱ	2.549 (7)	P2—O6	1.584 (7)
La1—O2ⁱⁱ	2.665 (7)	P2—C2	1.817 (8)
La1—O3	2.530 (6)	P3—O7	1.478 (6)
La1—O3ⁱⁱⁱ	2.916 (6)	P3—O8	1.508 (6)
La1—O4ⁱⁱⁱ	2.565 (6)	P3—O9	1.567 (6)
La1—O7	2.480 (6)	P3—C3	1.835 (9)
La1—O8ⁱ	2.502 (6)	O6—H6	0.8400
N1—C1	1.489 (10)	O9—H9	0.8400
N1—C3	1.490 (10)	C1—H1A	0.9900
N1—C2	1.512 (11)	C1—H1B	0.9900
N1—H1C	0.9300	C2—H2A	0.9900
P1—O1	1.511 (7)	C2—H2B	0.9900
P1—O3	1.515 (7)	C3—H3A	0.9900
P1—O2	1.540 (5)	C3—H3B	0.9900
P1—C1	1.823 (10)

O1ⁱ—La1—O7	74.7 (2)	C2—N1—H1C	106.2
O1ⁱ—La1—O8ⁱ	77.5 (2)	O1—P1—O3	117.2 (3)
O7—La1—O8ⁱ	70.58 (19)	O1—P1—O2	107.4 (3)
O1ⁱ—La1—O3	149.0 (2)	O3—P1—O2	111.5 (4)
O7—La1—O3	79.7 (2)	O1—P1—C1	108.1 (4)
O8ⁱ—La1—O3	77.8 (2)	O3—P1—C1	103.2 (4)
O1ⁱ—La1—O2ⁱⁱⁱ	112.92 (19)	O2—P1—C1	109.0 (3)
O7—La1—O2ⁱⁱⁱ	72.2 (2)	O1—P1—La1^iv	55.4 (2)
O8ⁱ—La1—O2ⁱⁱⁱ	136.7 (2)	O3—P1—La1^iv	147.0 (3)
O3—La1—O2ⁱⁱⁱ	74.4 (2)	O2—P1—La1^iv	54.2 (2)
O1ⁱ—La1—O4ⁱⁱⁱ	95.9 (2)	C1—P1—La1^iv	109.6 (3)
O7—La1—O4ⁱⁱⁱ	135.6 (2)	O1—P1—La1^v	132.2 (3)
O8ⁱ—La1—O4ⁱⁱⁱ	150.9 (3)	O3—P1—La1^v	62.7 (3)
O3—La1—O4ⁱⁱⁱ	114.7 (2)	O2—P1—La1^v	48.9 (2)
O2ⁱⁱⁱ—La1—O4ⁱⁱⁱ	72.1 (2)	C1—P1—La1^v	118.6 (3)
O1ⁱ—La1—O2ⁱⁱ	77.1 (2)	La1^iv—P1—La1^v	97.44 (6)
O7—La1—O2ⁱⁱ	141.3 (2)	O4—P2—O5	117.3 (4)
O8ⁱ—La1—O2ⁱⁱ	77.91 (19)	O4—P2—O6	113.3 (4)
O3—La1—O2ⁱⁱ	115.33 (19)	O5—P2—O6	105.4 (3)
O2ⁱⁱⁱ—La1—O2ⁱⁱ	144.5 (2)	O4—P2—C2	111.4 (4)
O4ⁱⁱⁱ—La1—O2ⁱⁱ	73.0 (2)	O5—P2—C2	106.1 (4)
O1ⁱ—La1—O1ⁱⁱ	128.4 (3)	O6—P2—C2	101.9 (4)
O7—La1—O1ⁱⁱ	133.2 (2)	O7—P3—O8	118.9 (3)
O8ⁱ—La1—O1ⁱⁱ	76.0 (2)	O7—P3—O9	113.5 (4)
O3—La1—O1ⁱⁱ	61.7 (2)	O8—P3—O9	107.4 (4)
O2ⁱⁱⁱ—La1—O1ⁱⁱ	116.8 (2)	O7—P3—C3	106.1 (4)
O4ⁱⁱⁱ—La1—O1ⁱⁱ	86.9 (2)	O8—P3—C3	110.4 (4)
O2ⁱⁱ—La1—O1ⁱⁱ	54.57 (17)	O9—P3—C3	98.7 (4)
O1ⁱ—La1—O3ⁱⁱⁱ	59.15 (18)	P1—O1—La1^vi	137.9 (3)
O7—La1—O3ⁱⁱⁱ	67.16 (19)	P1—O1—La1^iv	97.2 (3)
O8ⁱ—La1—O3ⁱⁱⁱ	125.26 (18)	La1^vi—O1—La1^iv	124.5 (3)
O3—La1—O3ⁱⁱⁱ	124.9 (3)	P1—O2—La1^v	104.1 (3)
O2ⁱⁱⁱ—La1—O3ⁱⁱⁱ	54.55 (17)	P1—O2—La1^iv	97.9 (3)
O4ⁱⁱⁱ—La1—O3ⁱⁱⁱ	70.84 (19)	La1^v—O2—La1^iv	140.9 (2)
O2ⁱⁱ—La1—O3ⁱⁱⁱ	118.15 (17)	P1—O3—La1	151.4 (4)
O1ⁱⁱ—La1—O3ⁱⁱⁱ	157.6 (2)	P1—O3—La1^v	89.8 (3)
O1ⁱ—La1—P1ⁱⁱ	104.7 (2)	La1—O3—La1^v	114.0 (3)
O7—La1—P1ⁱⁱ	150.21 (15)	P2—O4—La1^v	162.8 (5)
O8ⁱ—La1—P1ⁱⁱ	80.14 (15)	P2—O6—H6	109.5
O3—La1—P1ⁱⁱ	89.10 (16)	P3—O7—La1	143.2 (3)
O2ⁱⁱⁱ—La1—P1ⁱⁱ	131.17 (12)	P3—O8—La1^vi	143.2 (4)
O4ⁱⁱⁱ—La1—P1ⁱⁱ	74.15 (18)	P3—O9—H9	109.5
O2ⁱⁱ—La1—P1ⁱⁱ	27.94 (11)	N1—C1—P1	111.7 (6)
O1ⁱⁱ—La1—P1ⁱⁱ	27.43 (14)	N1—C1—H1A	109.3
O3ⁱⁱⁱ—La1—P1ⁱⁱ	138.88 (14)	P1—C1—H1A	109.3
O1ⁱ—La1—P1ⁱⁱⁱ	86.30 (16)	N1—C1—H1B	109.3
O7—La1—P1ⁱⁱⁱ	67.49 (15)	P1—C1—H1B	109.3
O8ⁱ—La1—P1ⁱⁱⁱ	137.68 (15)	H1A—C1—H1B	107.9
O3—La1—P1ⁱⁱⁱ	99.78 (19)	N1—C2—P2	114.6 (6)
O2ⁱⁱⁱ—La1—P1ⁱⁱⁱ	27.06 (11)	N1—C2—H2A	108.6
O4ⁱⁱⁱ—La1—P1ⁱⁱⁱ	68.66 (18)	P2—C2—H2A	108.6
O2ⁱⁱ—La1—P1ⁱⁱⁱ	136.09 (12)	N1—C2—H2B	108.6
O1ⁱⁱ—La1—P1ⁱⁱⁱ	140.31 (18)	P2—C2—H2B	108.6
O3ⁱⁱⁱ—La1—P1ⁱⁱⁱ	27.49 (13)	H2A—C2—H2B	107.6
P1ⁱⁱ—La1—P1ⁱⁱⁱ	142.12 (7)	N1—C3—P3	115.6 (6)
C1—N1—C3	113.2 (6)	N1—C3—H3A	108.4
C1—N1—C2	113.3 (7)	P3—C3—H3A	108.4
C3—N1—C2	111.0 (6)	N1—C3—H3B	108.4
C1—N1—H1C	106.2	P3—C3—H3B	108.4
C3—N1—H1C	106.2	H3A—C3—H3B	107.4

O3—P1—O1—La1^vi	−45.7 (9)	O2ⁱⁱ—La1—O3—La1^v	−15.9 (3)
O2—P1—O1—La1^vi	−172.1 (6)	O1ⁱⁱ—La1—O3—La1^v	−5.6 (3)
C1—P1—O1—La1^vi	70.4 (7)	O3ⁱⁱⁱ—La1—O3—La1^v	149.2 (3)
La1^iv—P1—O1—La1^vi	172.0 (9)	P1ⁱⁱ—La1—O3—La1^v	−6.0 (2)
La1^v—P1—O1—La1^vi	−122.4 (5)	P1ⁱⁱⁱ—La1—O3—La1^v	137.0 (2)
O3—P1—O1—La1^iv	142.3 (3)	O5—P2—O4—La1^v	28.8 (13)
O2—P1—O1—La1^iv	15.8 (4)	O6—P2—O4—La1^v	152.0 (11)
C1—P1—O1—La1^iv	−101.7 (3)	C2—P2—O4—La1^v	−93.7 (12)
La1^v—P1—O1—La1^iv	65.6 (4)	O8—P3—O7—La1	−47.7 (7)
O1—P1—O2—La1^v	131.3 (4)	O9—P3—O7—La1	−175.5 (6)
O3—P1—O2—La1^v	1.5 (4)	C3—P3—O7—La1	77.3 (7)
C1—P1—O2—La1^v	−111.8 (3)	O1ⁱ—La1—O7—P3	−179.2 (6)
La1^iv—P1—O2—La1^v	147.4 (3)	O8ⁱ—La1—O7—P3	−97.3 (6)
O1—P1—O2—La1^iv	−16.1 (4)	O3—La1—O7—P3	−16.8 (6)
O3—P1—O2—La1^iv	−145.8 (3)	O2ⁱⁱⁱ—La1—O7—P3	60.0 (6)
C1—P1—O2—La1^iv	100.8 (3)	O4ⁱⁱⁱ—La1—O7—P3	98.1 (6)
La1^v—P1—O2—La1^iv	−147.4 (3)	O2ⁱⁱ—La1—O7—P3	−134.7 (5)
O1—P1—O3—La1	22.1 (9)	O1ⁱⁱ—La1—O7—P3	−50.4 (7)
O2—P1—O3—La1	146.5 (7)	O3ⁱⁱⁱ—La1—O7—P3	118.3 (6)
C1—P1—O3—La1	−96.6 (8)	P1ⁱⁱ—La1—O7—P3	−86.3 (7)
La1^iv—P1—O3—La1	89.8 (8)	P1ⁱⁱⁱ—La1—O7—P3	88.5 (6)
La1^v—P1—O3—La1	147.8 (8)	O7—P3—O8—La1^vi	−4.8 (7)
O1—P1—O3—La1^v	−125.7 (4)	O9—P3—O8—La1^vi	125.8 (6)
O2—P1—O3—La1^v	−1.3 (3)	C3—P3—O8—La1^vi	−127.7 (6)
C1—P1—O3—La1^v	115.6 (3)	C3—N1—C1—P1	113.8 (6)
La1^iv—P1—O3—La1^v	−58.1 (5)	C2—N1—C1—P1	−118.5 (6)
O1ⁱ—La1—O3—P1	91.8 (9)	O1—P1—C1—N1	−129.9 (5)
O7—La1—O3—P1	57.4 (8)	O3—P1—C1—N1	−5.0 (7)
O8ⁱ—La1—O3—P1	129.6 (8)	O2—P1—C1—N1	113.6 (6)
O2ⁱⁱⁱ—La1—O3—P1	−16.9 (7)	La1^iv—P1—C1—N1	171.3 (5)
O4ⁱⁱⁱ—La1—O3—P1	−78.3 (8)	La1^v—P1—C1—N1	60.8 (6)
O2ⁱⁱ—La1—O3—P1	−160.3 (7)	C1—N1—C2—P2	50.9 (9)
O1ⁱⁱ—La1—O3—P1	−149.9 (8)	C3—N1—C2—P2	179.7 (6)
O3ⁱⁱⁱ—La1—O3—P1	4.8 (7)	O4—P2—C2—N1	37.7 (8)
P1ⁱⁱ—La1—O3—P1	−150.3 (8)	O5—P2—C2—N1	−91.0 (7)
P1ⁱⁱⁱ—La1—O3—P1	−7.4 (8)	O6—P2—C2—N1	158.9 (6)
O1ⁱ—La1—O3—La1^v	−123.8 (4)	C1—N1—C3—P3	−63.3 (8)
O7—La1—O3—La1^v	−158.2 (3)	C2—N1—C3—P3	167.8 (6)
O8ⁱ—La1—O3—La1^v	−86.1 (3)	O7—P3—C3—N1	−65.8 (7)
O2ⁱⁱⁱ—La1—O3—La1^v	127.5 (3)	O8—P3—C3—N1	64.2 (7)
O4ⁱⁱⁱ—La1—O3—La1^v	66.1 (4)	O9—P3—C3—N1	176.5 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3	0.93	2.05	2.725 (9)	128
N1—H1C···O8ⁱ	0.93	2.50	3.298 (9)	143
O6—H6···O5^vii	0.84	1.90	2.680 (8)	153
O9—H9···O5^viii	0.84	1.85	2.478 (8)	130

Symmetry codes: (i) −x+1/2, y, z+1/2; (vii) −x+3/2, y, z+1/2; (viii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[La(C₃H₉NO₉P₃)]
M_r	434.93
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	180
a, b, c (Å)	9.144 (3), 11.727 (4), 9.823 (3)
V (Å³)	1053.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.55
Crystal size (mm)	0.05 × 0.05 × 0.01

Data collection
Diffractometer	Bruker X8 KappaCCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.804, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	31245, 2728, 1980
R_int	0.107
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.109, 1.02
No. of reflections	2728
No. of parameters	158
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.98, −1.63
Absolute structure	Flack (1983), Friedel pairs 1229
Absolute structure parameter	0.44 (4)

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected bond lengths (Å) top

La1—O1ⁱ	2.466 (6)	La1—O3ⁱⁱⁱ	2.916 (6)
La1—O1ⁱⁱ	2.701 (6)	La1—O4ⁱⁱⁱ	2.565 (6)
La1—O2ⁱⁱⁱ	2.549 (7)	La1—O7	2.480 (6)
La1—O2ⁱⁱ	2.665 (7)	La1—O8ⁱ	2.502 (6)
La1—O3	2.530 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3	0.93	2.05	2.725 (9)	128
N1—H1C···O8ⁱ	0.93	2.50	3.298 (9)	143
O6—H6···O5^iv	0.84	1.90	2.680 (8)	153
O9—H9···O5^v	0.84	1.85	2.478 (8)	130

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

Acknowledgements

This work was financially supported by FEDER through the Operational Programme for Competitiveness Factors – COMPETE, and by Portuguese national funding through Fundação para a Ciência e a Tecnologia (FCT, Portugal), under the research and development project PTDC/QUI-QUI/098098/2008 (FCOMP-01-0124-FEDER-010785). We are also grateful to FCT for the PhD and postdoctoral research grants Nos. SFRH/BD/46601/2008 (to PS) and SFRH/BPD/63736/2009 (to JAF), respectively, and for specific funding towards the purchase of the single-crystal X-ray diffractometer.

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