Redetermination at 180 K of a layered lanthanide-organic framework.

The asymmetric unit of the title compound, poly[(μ(4)-{[bis-(hydrogen phospho-natometh-yl)aza-nium-yl]meth-yl}phospho-nato)lanthanum(III)], [La(C(3)H(9)NO(9)P(3))](n), comprises an La(3+) center and a H(3)nmp(3-) anion (where H(3)nmp(3-) is a residue of partially deprotonated nitrilo-tris-(methyl-ene-phospho-nic acid), namely {[bis-(hydrogen phospho-natometh-yl)aza-nium-yl]meth-yl}-phos-pho-nate). 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 phospho-nate 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 = 434.93

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.109

S = 1.02

2728 reflections

158 parameters

1 restraint

H-atom parameters constrained

Δρmax = 3.98 e Å−3

Δρmin = −1.63 e Å−3

Absolute structure: Flack (1983 ▶), Friedel pairs 1229

Flack parameter: 0.44 (4)

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812005508/gk2450sup1.cif

Supplementary material file. DOI: 10.1107/S1600536812005508/gk2450Isup2.cdx

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

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

[La(C3H9NO9P3)]	F(000) = 832
Mr = 434.93	Dx = 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

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

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(Fo2) + (0.0552P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 3.98 e Å−3
2728 reflections	Δρmin = −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	Flack parameter: 0.44 (4)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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—La1iv	55.4 (2)
O8i—La1—O2iii	136.7 (2)	O3—P1—La1iv	147.0 (3)
O3—La1—O2iii	74.4 (2)	O2—P1—La1iv	54.2 (2)
O1i—La1—O4iii	95.9 (2)	C1—P1—La1iv	109.6 (3)
O7—La1—O4iii	135.6 (2)	O1—P1—La1v	132.2 (3)
O8i—La1—O4iii	150.9 (3)	O3—P1—La1v	62.7 (3)
O3—La1—O4iii	114.7 (2)	O2—P1—La1v	48.9 (2)
O2iii—La1—O4iii	72.1 (2)	C1—P1—La1v	118.6 (3)
O1i—La1—O2ii	77.1 (2)	La1iv—P1—La1v	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—La1vi	137.9 (3)
O7—La1—O3iii	67.16 (19)	P1—O1—La1iv	97.2 (3)
O8i—La1—O3iii	125.26 (18)	La1vi—O1—La1iv	124.5 (3)
O3—La1—O3iii	124.9 (3)	P1—O2—La1v	104.1 (3)
O2iii—La1—O3iii	54.55 (17)	P1—O2—La1iv	97.9 (3)
O4iii—La1—O3iii	70.84 (19)	La1v—O2—La1iv	140.9 (2)
O2ii—La1—O3iii	118.15 (17)	P1—O3—La1	151.4 (4)
O1ii—La1—O3iii	157.6 (2)	P1—O3—La1v	89.8 (3)
O1i—La1—P1ii	104.7 (2)	La1—O3—La1v	114.0 (3)
O7—La1—P1ii	150.21 (15)	P2—O4—La1v	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—La1vi	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—La1vi	−45.7 (9)	O2ii—La1—O3—La1v	−15.9 (3)
O2—P1—O1—La1vi	−172.1 (6)	O1ii—La1—O3—La1v	−5.6 (3)
C1—P1—O1—La1vi	70.4 (7)	O3iii—La1—O3—La1v	149.2 (3)
La1iv—P1—O1—La1vi	172.0 (9)	P1ii—La1—O3—La1v	−6.0 (2)
La1v—P1—O1—La1vi	−122.4 (5)	P1iii—La1—O3—La1v	137.0 (2)
O3—P1—O1—La1iv	142.3 (3)	O5—P2—O4—La1v	28.8 (13)
O2—P1—O1—La1iv	15.8 (4)	O6—P2—O4—La1v	152.0 (11)
C1—P1—O1—La1iv	−101.7 (3)	C2—P2—O4—La1v	−93.7 (12)
La1v—P1—O1—La1iv	65.6 (4)	O8—P3—O7—La1	−47.7 (7)
O1—P1—O2—La1v	131.3 (4)	O9—P3—O7—La1	−175.5 (6)
O3—P1—O2—La1v	1.5 (4)	C3—P3—O7—La1	77.3 (7)
C1—P1—O2—La1v	−111.8 (3)	O1i—La1—O7—P3	−179.2 (6)
La1iv—P1—O2—La1v	147.4 (3)	O8i—La1—O7—P3	−97.3 (6)
O1—P1—O2—La1iv	−16.1 (4)	O3—La1—O7—P3	−16.8 (6)
O3—P1—O2—La1iv	−145.8 (3)	O2iii—La1—O7—P3	60.0 (6)
C1—P1—O2—La1iv	100.8 (3)	O4iii—La1—O7—P3	98.1 (6)
La1v—P1—O2—La1iv	−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)
La1iv—P1—O3—La1	89.8 (8)	P1iii—La1—O7—P3	88.5 (6)
La1v—P1—O3—La1	147.8 (8)	O7—P3—O8—La1vi	−4.8 (7)
O1—P1—O3—La1v	−125.7 (4)	O9—P3—O8—La1vi	125.8 (6)
O2—P1—O3—La1v	−1.3 (3)	C3—P3—O8—La1vi	−127.7 (6)
C1—P1—O3—La1v	115.6 (3)	C3—N1—C1—P1	113.8 (6)
La1iv—P1—O3—La1v	−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)	La1iv—P1—C1—N1	171.3 (5)
O4iii—La1—O3—P1	−78.3 (8)	La1v—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—La1v	−123.8 (4)	C1—N1—C3—P3	−63.3 (8)
O7—La1—O3—La1v	−158.2 (3)	C2—N1—C3—P3	167.8 (6)
O8i—La1—O3—La1v	−86.1 (3)	O7—P3—C3—N1	−65.8 (7)
O2iii—La1—O3—La1v	127.5 (3)	O8—P3—C3—N1	64.2 (7)
O4iii—La1—O3—La1v	66.1 (4)	O9—P3—C3—N1	176.5 (6)

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···O5vii	0.84	1.90	2.680 (8)	153
O9—H9···O5viii	0.84	1.85	2.478 (8)	130

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) ; (ii) ; (iii) .

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⋯O5iv	0.84	1.90	2.680 (8)	153
O9—H9⋯O5v	0.84	1.85	2.478 (8)	130

Symmetry codes: (i) ; (iv) ; (v) .