Hydroxonium triaqua­bis(biuret-κ2O,O′)dichloridolanthanum(III) dichloride dihydrate

Harrison, W.T.A.

doi:10.1107/S1600536808010349

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Pages m681-m682

doi:10.1107/S1600536808010349

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Hydroxonium triaquabis(biuret-κ²O,O′)dichloridolanthanum(III) dichloride dihydrate

William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 10 April 2008; accepted 15 April 2008; online 18 April 2008)

In the title compound, (H₃O)[LaCl₂(C₂H₅N₃O₂)₂(H₂O)₃]Cl₂·2H₂O, the La atom is bonded to seven O atoms (arising from two O,O′-bidentate biuret molecules and three water molecules) and two chloride ions in an irregular arrangement. A network of N—H⋯O, N—H⋯Cl, O—H⋯O and O—H⋯Cl hydrogen bonds helps to establish the packing, leading to a three-dimensional network. The La atom, one Cl atom and four O atoms lie on a crystallographic mirror plane.

Related literature

For related structures, see: Carugo et al. (1992 ); Rogers et al. (1993 ); Su et al. (2006 ); Haddad (1987 , 1988 ); Harrison (2008a ,b ). For related literature, see: Brese & O'Keeffe (1991 ).

Experimental

Crystal data

(H₃O)[LaCl₂(C₂H₅N₃O₂)₂(H₂O)₃]Cl₂·2H₂O
M_r = 596.00
Orthorhombic, C m c 2₁
a = 17.6252 (7) Å
b = 6.8868 (3) Å
c = 17.0447 (7) Å
V = 2068.91 (15) Å³
Z = 4
Mo Kα radiation
μ = 2.63 mm⁻¹
T = 293 (2) K
0.30 × 0.23 × 0.17 mm

Data collection

Bruker SMART1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.486, T_max = 0.636
11912 measured reflections
3793 independent reflections
3716 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.042
S = 1.09
3793 reflections
121 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.67 e Å⁻³
Absolute structure: Flack (1983 ), 1805 Friedel pairs
Flack parameter: 0.001 (9)

Table 1
Selected bond lengths (Å)

La1—O3	2.503 (2)
La1—O2	2.5313 (13)
La1—O1	2.5318 (14)
La1—O4	2.542 (2)
La1—O5	2.562 (2)
La1—Cl1	2.9606 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2ⁱ	0.86	2.94	3.643 (3)	141
N1—H2⋯Cl1ⁱⁱ	0.86	2.83	3.574 (3)	145
N2—H3⋯Cl1ⁱⁱ	0.86	2.28	3.1399 (14)	173
N3—H4⋯O7ⁱⁱ	0.86	2.12	2.927 (3)	156
N3—H5⋯Cl2	0.86	2.75	3.3835 (18)	132
O3—H6⋯Cl2ⁱ	0.85	2.28	3.1181 (16)	168
O4—H7⋯Cl2ⁱⁱⁱ	0.84	2.32	3.1396 (17)	164
O5—H8⋯Cl1^iv	0.75	2.44	3.1566 (17)	160
O6—H9⋯O2ⁱⁱⁱ	0.88	2.23	3.044 (3)	153
O6—H10⋯O7	0.86	2.35	2.941 (3)	126
O6—H10⋯O7^v	0.86	2.35	2.941 (3)	126
O7—H11⋯Cl2^vi	0.86	2.48	3.264 (3)	151
O7—H12⋯O1^vii	0.84	2.09	2.922 (2)	168
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) -x, y+1, z; (v) -x+1, y, z; (vi) x, y-1, z; (vii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010349/fj2113sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010349/fj2113Isup2.hkl

checkCIF report

Comment top

No complexes of lanthanum(III) with biuret (biur), H₂N—CO—NH—CO—NH₂ (or C₂H₅N₃O₂) have been structurally characterized. The structures of two samarium-biuret complexes, Sm(biur)₄.(NO₃)₃ (Haddad, 1987) and Sm(biur)₄.(ClO₄)₃ (Haddad, 1988) have been described. In both cases, an SmO₈ square antiprismatic coordination arises for the metal ion. Based on X-ray photographs, it was suggested that all the Ln(biur)₄.(NO₃)₃ and Ln(biur)₄.(ClO₄)₃ compounds are isostructural with their samarium prototypes. In this paper, we describe the synthesis and structure of the title compound, (I), in which three different ligands are bonded to the trivalent cation.

Compound (I) is an ionic salt containing a new [La(biur)₂(H₂O)₅Cl₂]⁺ complex ion. The complete cation is generated by crystallographic mirror symmetry, with La and the three water O atoms lying on the reflecting plane. A hydroxonium cation (with its O6 atom with site symmetry m), an uncoordinated chloride ion (Cl2) and an uncoordinated water molecule (O7) complete the structure (Fig. 1) of (I).

The resulting LaO₇Cl₂ polyhedral geometry in (I) (Table 1) can only be described as irregular. The Brese & O'Keeffe (1991) bond-valence sum for La1 in (I) of 3.29 is significantly larger than the expected value of 3.00. A local LaO₇Cl₂ grouping has been seen in various other compounds, including [LaCl₂(H₂O)(C₁₂H₂₄O₆)]⁺.Cl^- (Rogers et al., 1993) and [La(H₂O)₄Cl(C₃H₇O₃]²⁺.2Cl^-.H₂O (Su et al., 2006), but otherwise these phases have no similarity to (I).

The O,O-bidenate coordination of the biuret molecule to the lanthanum ion in (I) results in a six-membered chelate ring that is non-planar. As noted previously (Carugo et al., 1992), the biuret molecule can be regarded as two planar amide fragments linked by the NH bridge. Here, the dihedral angle betwen the N1/C1/O1/N2 and N2/C2/O2/N3 units is 5.06 (10)°. The lanthanum cation deviates from the N1/C1/O1/N2 and N2/C2/O2/N3 mean planes by 0.894 (4)Å and 0.606 (4) Å, respectively.

The component species in (I) are linked by a dense array of N—H···O, N—H···Cl, O—H···Cl and O—H···O hydrogen bonds (Table 2) resulting in a three-dimensional network. Of note are the [001] chains resulting from the O—H···O hydrogen bonds involving the complex cation, H₃O6 and H₂O7 (Fig. 2).

The structure of (I) is different to those of the recently reported (Harrison, 2008a,b) M(biur)₂(H₂)₄.Cl₃ (M = Gd, Y) phases, perhaps because the larger La³⁺ cation can accommodate nine atoms in its coordination sphere.

Related literature top

For related structures, see: Carugo et al. (1992); Rogers et al. (1993); Su et al. (2006); Haddad (1987, 1988); Harrison (2008a,b)

For related literature, see: Brese & O'Keeffe (1991).

Experimental top

0.1 M Aqueous solutions of LaCl₃ (10 ml) and biuret (10 ml) were mixed and a small quantity of dilute hydrochloric acid was added, to result in a colourless solution. Colourless blocks of (I) grew over several days as the water slowly evaporated.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Symmetry code: (i) -x, y, z.
	Fig. 2. Fragment of the packing for (I) displaying the hydrogen bonds (shows an double dashed lines) leading to chains arising from the complex cation, the hydroxonium ion and the uncoordinated water molecule. Symmetry code: (i) 1/2 - x, 1/2 + y, z.

Hydroxonium triaquabis(biuret-κ²O,O')dichloridolanthanum(III) dichloride dihydrate top

Crystal data top

(H₃O)[LaCl₂(C₂H₅N₃O₂)₂(H₂O)₃]Cl₂·2H₂O	F(000) = 1176
M_r = 596.00	D_x = 1.913 Mg m⁻³
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 4771 reflections
a = 17.6252 (7) Å	θ = 2.3–32.5°
b = 6.8868 (3) Å	µ = 2.63 mm⁻¹
c = 17.0447 (7) Å	T = 293 K
V = 2068.91 (15) Å³	Block, colourless
Z = 4	0.30 × 0.23 × 0.17 mm

Data collection top

Bruker SMART1000 CCD diffractometer	3793 independent reflections
Radiation source: fine-focus sealed tube	3716 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 32.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −26→26
T_min = 0.486, T_max = 0.636	k = −10→9
11912 measured reflections	l = −24→25

Refinement top

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)] = 0.016	H-atom parameters constrained
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.0242P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3793 reflections	Δρ_max = 0.70 e Å⁻³
121 parameters	Δρ_min = −0.67 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1805 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.001 (9)

Crystal data top

(H₃O)[LaCl₂(C₂H₅N₃O₂)₂(H₂O)₃]Cl₂·2H₂O	V = 2068.91 (15) Å³
M_r = 596.00	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 17.6252 (7) Å	µ = 2.63 mm⁻¹
b = 6.8868 (3) Å	T = 293 K
c = 17.0447 (7) Å	0.30 × 0.23 × 0.17 mm

Data collection top

Bruker SMART1000 CCD diffractometer	3793 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	3716 reflections with I > 2σ(I)
T_min = 0.486, T_max = 0.636	R_int = 0.018
11912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.042	Δρ_max = 0.70 e Å⁻³
S = 1.09	Δρ_min = −0.67 e Å⁻³
3793 reflections	Absolute structure: Flack (1983), 1805 Friedel pairs
121 parameters	Absolute structure parameter: 0.001 (9)
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	0.0000	0.234447 (14)	0.341713 (14)	0.01947 (3)
Cl1	0.10789 (2)	−0.09170 (6)	0.32281 (3)	0.03634 (12)
C1	0.18755 (10)	0.3315 (3)	0.40149 (12)	0.0293 (4)
C2	0.17044 (10)	0.4278 (3)	0.26382 (12)	0.0290 (3)
N1	0.24102 (12)	0.2964 (3)	0.45518 (14)	0.0459 (5)
H1	0.2283	0.2650	0.5022	0.055*
H2	0.2882	0.3052	0.4427	0.055*
N2	0.21433 (7)	0.3826 (2)	0.32868 (11)	0.0344 (4)
H3	0.2628	0.3870	0.3229	0.041*
N3	0.20884 (11)	0.4877 (3)	0.20138 (13)	0.0445 (4)
H4	0.1851	0.5181	0.1591	0.053*
H5	0.2575	0.4963	0.2032	0.053*
O1	0.11900 (8)	0.3202 (3)	0.41736 (8)	0.0333 (3)
O2	0.10047 (7)	0.41314 (19)	0.26393 (8)	0.0298 (3)
O3	0.0000	0.0881 (4)	0.47616 (14)	0.0488 (7)
H6	0.0406	0.0729	0.5026	0.059*
O4	0.0000	0.1452 (4)	0.19698 (13)	0.0384 (5)
H7	0.0377	0.0935	0.1750	0.046*
O5	0.0000	0.5850 (3)	0.39200 (13)	0.0388 (5)
H8	−0.0323	0.6527	0.3843	0.047*
Cl2	0.36579 (3)	0.51610 (15)	0.08766 (5)	0.04627 (14)
O6	0.5000	0.1924 (5)	0.17243 (18)	0.0617 (7)
H9	0.4686	0.1472	0.2081	0.074*
H10	0.5000	0.1363	0.1273	0.074*
O7	0.39583 (14)	−0.0187 (4)	0.06811 (12)	0.0695 (6)
H11	0.3960	−0.1404	0.0560	0.083*
H12	0.3976	0.0476	0.0265	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.01375 (4)	0.02565 (5)	0.01902 (5)	0.000	0.000	0.00102 (8)
Cl1	0.01972 (15)	0.03484 (19)	0.0545 (3)	0.00363 (13)	0.00053 (17)	−0.00126 (18)
C1	0.0219 (8)	0.0309 (9)	0.0351 (9)	−0.0001 (6)	−0.0063 (7)	−0.0041 (7)
C2	0.0240 (7)	0.0303 (8)	0.0325 (9)	−0.0042 (6)	0.0059 (7)	−0.0006 (7)
N1	0.0305 (9)	0.0593 (11)	0.0479 (11)	0.0024 (8)	−0.0163 (9)	0.0009 (10)
N2	0.0164 (5)	0.0455 (7)	0.0412 (11)	−0.0021 (5)	0.0022 (6)	0.0039 (7)
N3	0.0322 (9)	0.0584 (11)	0.0430 (10)	−0.0067 (8)	0.0141 (8)	0.0071 (9)
O1	0.0228 (6)	0.0510 (8)	0.0260 (6)	−0.0028 (6)	−0.0025 (5)	−0.0012 (6)
O2	0.0211 (6)	0.0395 (7)	0.0288 (6)	−0.0032 (5)	0.0006 (5)	0.0062 (6)
O3	0.0248 (10)	0.086 (2)	0.0352 (13)	0.000	0.000	0.0282 (12)
O4	0.0265 (10)	0.0609 (15)	0.0279 (10)	0.000	0.000	−0.0113 (10)
O5	0.0301 (10)	0.0299 (9)	0.0564 (14)	0.000	0.000	−0.0004 (9)
Cl2	0.03018 (19)	0.0726 (4)	0.0360 (2)	0.0037 (3)	−0.0008 (3)	−0.0124 (2)
O6	0.076 (2)	0.0640 (16)	0.0453 (16)	0.000	0.000	0.0068 (14)
O7	0.0972 (16)	0.0730 (12)	0.0384 (10)	0.0050 (13)	−0.0051 (10)	0.0115 (10)

Geometric parameters (Å, º) top

La1—O3	2.503 (2)	C2—N2	1.385 (3)
La1—O2	2.5313 (13)	N1—H1	0.8600
La1—O2ⁱ	2.5313 (12)	N1—H2	0.8600
La1—O1	2.5318 (14)	N2—H3	0.8600
La1—O1ⁱ	2.5318 (14)	N3—H4	0.8600
La1—O4	2.542 (2)	N3—H5	0.8600
La1—O5	2.562 (2)	O3—H6	0.8522
La1—Cl1ⁱ	2.9606 (4)	O4—H7	0.8418
La1—Cl1	2.9606 (4)	O5—H8	0.7477
C1—O1	1.241 (2)	O6—H9	0.8786
C1—N1	1.336 (3)	O6—H10	0.8615
C1—N2	1.374 (3)	O7—H11	0.8631
C2—O2	1.237 (2)	O7—H12	0.8446
C2—N3	1.327 (3)

O3—La1—O2	132.46 (4)	O2—La1—Cl1	82.10 (3)
O3—La1—O2ⁱ	132.46 (4)	O2ⁱ—La1—Cl1	139.57 (4)
O2—La1—O2ⁱ	88.78 (6)	O1—La1—Cl1	72.56 (4)
O3—La1—O1	68.14 (5)	O1ⁱ—La1—Cl1	139.86 (4)
O2—La1—O1	64.78 (4)	O4—La1—Cl1	73.20 (5)
O2ⁱ—La1—O1	137.12 (5)	O5—La1—Cl1	138.709 (15)
O3—La1—O1ⁱ	68.14 (5)	Cl1ⁱ—La1—Cl1	79.930 (17)
O2—La1—O1ⁱ	137.12 (5)	O1—C1—N1	121.8 (2)
O2ⁱ—La1—O1ⁱ	64.78 (4)	O1—C1—N2	123.21 (16)
O1—La1—O1ⁱ	111.87 (7)	N1—C1—N2	115.01 (18)
O3—La1—O4	142.27 (9)	O2—C2—N3	122.33 (19)
O2—La1—O4	67.01 (5)	O2—C2—N2	122.51 (17)
O2ⁱ—La1—O4	67.01 (5)	N3—C2—N2	115.16 (17)
O1—La1—O4	123.41 (3)	C1—N1—H1	120.0
O1ⁱ—La1—O4	123.41 (3)	C1—N1—H2	120.0
O3—La1—O5	94.19 (9)	H1—N1—H2	120.0
O2—La1—O5	73.56 (5)	C1—N2—C2	125.93 (14)
O2ⁱ—La1—O5	73.56 (5)	C1—N2—H3	117.0
O1—La1—O5	67.03 (4)	C2—N2—H3	117.0
O1ⁱ—La1—O5	67.03 (4)	C2—N3—H4	120.0
O4—La1—O5	123.54 (8)	C2—N3—H5	120.0
O3—La1—Cl1ⁱ	78.13 (5)	H4—N3—H5	120.0
O2—La1—Cl1ⁱ	139.57 (4)	C1—O1—La1	135.26 (12)
O2ⁱ—La1—Cl1ⁱ	82.10 (3)	C2—O2—La1	137.53 (12)
O1—La1—Cl1ⁱ	139.86 (4)	La1—O3—H6	122.3
O1ⁱ—La1—Cl1ⁱ	72.56 (4)	La1—O4—H7	122.3
O4—La1—Cl1ⁱ	73.20 (5)	La1—O5—H8	121.9
O5—La1—Cl1ⁱ	138.709 (15)	H9—O6—H10	117.3
O3—La1—Cl1	78.13 (5)	H11—O7—H12	108.9

O1—C1—N2—C2	−0.1 (3)	Cl1ⁱ—La1—O1—C1	103.6 (2)
N1—C1—N2—C2	−179.32 (19)	Cl1—La1—O1—C1	54.6 (2)
O2—C2—N2—C1	−5.1 (3)	N3—C2—O2—La1	159.25 (15)
N3—C2—N2—C1	174.93 (19)	N2—C2—O2—La1	−20.7 (3)
N1—C1—O1—La1	−149.81 (17)	O3—La1—O2—C2	21.4 (2)
N2—C1—O1—La1	31.0 (3)	O2ⁱ—La1—O2—C2	175.02 (16)
O3—La1—O1—C1	138.5 (2)	O1—La1—O2—C2	29.91 (18)
O2—La1—O1—C1	−34.7 (2)	O1ⁱ—La1—O2—C2	125.52 (18)
O2ⁱ—La1—O1—C1	−91.9 (2)	O4—La1—O2—C2	−119.5 (2)
O1ⁱ—La1—O1—C1	−167.88 (17)	O5—La1—O2—C2	101.81 (19)
O4—La1—O1—C1	−0.6 (2)	Cl1ⁱ—La1—O2—C2	−108.69 (18)
O5—La1—O1—C1	−116.7 (2)	Cl1—La1—O2—C2	−44.48 (18)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2ⁱⁱ	0.86	2.94	3.643 (3)	141
N1—H2···Cl1ⁱⁱⁱ	0.86	2.83	3.574 (3)	145
N2—H3···Cl1ⁱⁱⁱ	0.86	2.28	3.1399 (14)	173
N3—H4···O7ⁱⁱⁱ	0.86	2.12	2.927 (3)	156
N3—H5···Cl2	0.86	2.75	3.3835 (18)	132
O3—H6···Cl2ⁱⁱ	0.85	2.28	3.1181 (16)	168
O4—H7···Cl2^iv	0.84	2.32	3.1396 (17)	164
O5—H8···Cl1^v	0.75	2.44	3.1566 (17)	160
O6—H9···O2^iv	0.88	2.23	3.044 (3)	153
O6—H10···O7	0.86	2.35	2.941 (3)	126
O6—H10···O7^vi	0.86	2.35	2.941 (3)	126
O7—H11···Cl2^vii	0.86	2.48	3.264 (3)	151
O7—H12···O1^viii	0.84	2.09	2.922 (2)	168

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

Experimental details

Crystal data
Chemical formula	(H₃O)[LaCl₂(C₂H₅N₃O₂)₂(H₂O)₃]Cl₂·2H₂O
M_r	596.00
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	293
a, b, c (Å)	17.6252 (7), 6.8868 (3), 17.0447 (7)
V (Å³)	2068.91 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.63
Crystal size (mm)	0.30 × 0.23 × 0.17

Data collection
Diffractometer	Bruker SMART1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.486, 0.636
No. of measured, independent and observed [I > 2σ(I)] reflections	11912, 3793, 3716
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.042, 1.09
No. of reflections	3793
No. of parameters	121
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.67
Absolute structure	Flack (1983), 1805 Friedel pairs
Absolute structure parameter	0.001 (9)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

La1—O3	2.503 (2)	La1—O4	2.542 (2)
La1—O2	2.5313 (13)	La1—O5	2.562 (2)
La1—O1	2.5318 (14)	La1—Cl1	2.9606 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2ⁱ	0.86	2.94	3.643 (3)	141
N1—H2···Cl1ⁱⁱ	0.86	2.83	3.574 (3)	145
N2—H3···Cl1ⁱⁱ	0.86	2.28	3.1399 (14)	173
N3—H4···O7ⁱⁱ	0.86	2.12	2.927 (3)	156
N3—H5···Cl2	0.86	2.75	3.3835 (18)	132
O3—H6···Cl2ⁱ	0.85	2.28	3.1181 (16)	168
O4—H7···Cl2ⁱⁱⁱ	0.84	2.32	3.1396 (17)	164
O5—H8···Cl1^iv	0.75	2.44	3.1566 (17)	160
O6—H9···O2ⁱⁱⁱ	0.88	2.23	3.044 (3)	153
O6—H10···O7	0.86	2.35	2.941 (3)	126
O6—H10···O7^v	0.86	2.35	2.941 (3)	126
O7—H11···Cl2^vi	0.86	2.48	3.264 (3)	151
O7—H12···O1^vii	0.84	2.09	2.922 (2)	168

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

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