Poly[tris­(μ4-5-amino­isophthalato)diaqua­dilanthanum(III)]

Weng-Thim, T.; Adnan, R.; Fun, H.-K.; Jebas, S.R.

doi:10.1107/S1600536808018849

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m971-m972

doi:10.1107/S1600536808018849

Open

access

Poly[tris(μ₄-5-aminoisophthalato)diaquadilanthanum(III)]

Tham Weng-Thim,^a Rohana Adnan,^a Hoong-Kun Fun ^b ^* and Samuel Robinson Jebas ^b ‡

^aSchool of Chemical Science, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 31 May 2008; accepted 22 June 2008; online 28 June 2008)

The title compound, [La₂(C₈H₅NO₄)₃(H₂O)₂]_n, is a three-dimensional network coordination polymer in which each La^III ion is nine-coordinated by eight carboxylate O atoms from six 5-aminoisophthalate ligands and one O atom from a water molecule. One organic ligand lies on a twofold rotation axis. O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds are observed in the crystal structure.

Related literature

For related literature on metal carboxylate complexes, see: Eddaoudi et al. (2002 ); Tao et al. (2000 ); Zheng et al. (2004 ). For related literature on aromatic polycarboxylic acids, see: Eddaoudi et al. (2000 ); Li et al. (1999 ); Lo et al. (2000 ); Qu et al. (2005 ); Rosi et al. (2002 ). For the coordination modes of lanthanides, see: Bond et al. (2000 ); Saleh et al. (1998 ). For bond length and angle data, see: Glunnlaugson et al. (2004 ); Zheng et al. (2003 ); Drew et al. (2000 ).

Experimental

Crystal data

[La₂(C₈H₅NO₄)₃(H₂O)₂]
M_r = 851.24
Orthorhombic, P b c n
a = 12.2525 (3) Å
b = 8.0521 (2) Å
c = 25.6820 (6) Å
V = 2533.74 (11) Å³
Z = 4
Mo Kα radiation
μ = 3.41 mm⁻¹
T = 100.0 (1) K
0.36 × 0.31 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.313, T_max = 0.822
68438 measured reflections
7718 independent reflections
6892 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.074
S = 1.16
7718 reflections
208 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.54 e Å⁻³
Δρ_min = −1.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1OW⋯O5ⁱ	0.84	2.02	2.8354 (16)	164
O1W—H2OW⋯N1ⁱⁱ	0.84	2.02	2.817 (2)	157
N1—H1N1⋯O4ⁱⁱⁱ	0.90 (1)	2.28 (2)	3.0929 (17)	150 (3)
N2—H1N2⋯O4^iv	0.84 (1)	2.60 (2)	3.1953 (12)	129 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) x+1, y, z; (iii) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018849/ci2610sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018849/ci2610Isup2.hkl

checkCIF report

Comment top

In recent years, interest has been focused on metal carboxylate complexes due to their potential applications as material for molecular recognition, ion exchange, catalysis and luminescence (Eddaoudi et al., 2002; Tao et al., 2000; Zheng et al., 2004). Aromatic polycarboxylic acids such as 1,4-benzenedicarboxylic acid and 1,3-benzenedicarboxylic acid are used extensively in the synthesis of this type of coordination polymer (Eddaoudi et al., 2000; Li et al., 1999; Lo et al., 2000; Qu et al., 2005; Rosi et al., 2002).

Aminoisophthalic acid is a potential multidentate ligand with trifunctional group that may generate structures of higher dimensions containing networks or channels. It's two carboxylic groups may be completely or partially deprotonated and thus results in versatile coordination modes. Meanwhile, lanthanide ions are known for their ability to display diverse coordination modes and high coordination number (Bond et al., 2000; Saleh et al., 1998). In addition to that, hard acid lanthanide ions prefer to coordinate with carboxyl groups belonging to hard base. In this paper, we report the crystal structure of a polymeric coordination complex formed from hydrothermal reaction between trivalent lanthanum ion and aminoisophthalic acid.

In the crystal structure of the title compound, each La^III ion is nine-coordinated by eight carboxylate O atoms from six 5-aminoisophthalate ligands and one O atom from a water molecule. The La—O bond lengths [2.4076 (11) Å-2.8015 (12) Å] and bond angles around the La^III ion agree well with the values reported for related lanthanum complexes (Glunnlaugson et al., 2004; Zheng et al., 2003; Drew et al., 2000).

The O—H···O, O—H···N and N—H···O hydrogen bonds are observed in the crystal structure (Fig. 2).

Related literature top

For related literature on metal carboxylate complexes, see: Eddaoudi et al. (2002); Tao et al. (2000); Zheng et al. (2004). For related literature on aromatic polycarboxylic acids, see: Eddaoudi et al. (2000); Li et al. (1999); Lo et al. (2000); Qu et al. (2005); Rosi et al. (2002). For the coordination modes of lanthanides, see: Bond et al. (2000); Saleh et al. (1998). For bond length and angle data, see: Glunnlaugson et al. (2004); Zheng et al. (2003); Drew et al. (2000).

Experimental top

A mixture of 5-aminoisophthalic acid (0.273 g, 1.5 mmol), sodium hydroxide (0.120 g, 3 mmol) and distilled water (20 ml) was heated till boiling. The solution was left to cool and then poured into a 40 ml Teflon tube with La(NO₃).6H₂O (0.433 g, 1.0 mmol). The Teflon tube was sealed and heated at 403 K for 60 h, and then allowed to cool to room temperature. Pale clear-pink crystals obtained were filtered, washed with distilled water and left to dry in air (yield: 52% based on La).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. Part of the three-dimensional coordination polymer, showing the coordination environment of the La^III ion. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (A) 1/2-x, -1/2+y, z; (B) 1/2+x, 1/2-y, -z; (C) -x, 1-y, -z.]
	Fig. 2. A view of part of the coordination polymer of the title compound. Hydrogen bonds are shown as dashed lines.

Poly[tris(µ₄-5-aminoisophthalato)diaquadilanthanum(III)] top

Crystal data top

[La₂(C₈H₅NO₄)₃(H₂O)₂]	F(000) = 1640
M_r = 851.24	D_x = 2.221 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 9864 reflections
a = 12.2525 (3) Å	θ = 2.3–45.2°
b = 8.0521 (2) Å	µ = 3.41 mm⁻¹
c = 25.6820 (6) Å	T = 100 K
V = 2533.74 (11) Å³	Plate, pink
Z = 4	0.36 × 0.31 × 0.06 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7718 independent reflections
Radiation source: fine-focus sealed tube	6892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 40.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −22→21
T_min = 0.313, T_max = 0.822	k = −14→14
68438 measured reflections	l = −45→44

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0368P)² + 1.5159P] where P = (F_o² + 2F_c²)/3
7718 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 1.54 e Å⁻³
5 restraints	Δρ_min = −1.24 e Å⁻³

Crystal data top

[La₂(C₈H₅NO₄)₃(H₂O)₂]	V = 2533.74 (11) Å³
M_r = 851.24	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 12.2525 (3) Å	µ = 3.41 mm⁻¹
b = 8.0521 (2) Å	T = 100 K
c = 25.6820 (6) Å	0.36 × 0.31 × 0.06 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7718 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	6892 reflections with I > 2σ(I)
T_min = 0.313, T_max = 0.822	R_int = 0.040
68438 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	5 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 1.54 e Å⁻³
7718 reflections	Δρ_min = −1.24 e Å⁻³
208 parameters

Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.305761 (5)	0.465168 (9)	0.094499 (3)	0.00725 (3)
O1	0.11915 (9)	0.55822 (16)	0.09118 (5)	0.01427 (19)
O2	0.29520 (8)	0.76545 (14)	0.14936 (5)	0.01260 (17)
O3	0.36750 (11)	0.54193 (13)	0.18450 (5)	0.0161 (2)
O4	0.03641 (8)	0.77482 (13)	0.12749 (5)	0.01283 (17)
O5	−0.11694 (8)	0.16092 (13)	−0.01083 (4)	0.01261 (17)
O6	−0.27525 (9)	0.27524 (13)	−0.03252 (4)	0.01193 (16)
O1W	0.48255 (8)	0.60804 (14)	0.07751 (5)	0.01474 (18)
H1OW	0.5115	0.6313	0.0488	0.018*
H2OW	0.5309	0.6145	0.1009	0.018*
N1	−0.35537 (11)	0.53130 (17)	0.15151 (6)	0.0164 (2)
N2	0.5000	1.2332 (3)	0.2500	0.0265 (5)
C1	−0.16182 (11)	0.57505 (17)	0.13169 (6)	0.0116 (2)
H1	−0.1544	0.6421	0.1610	0.014*
C2	−0.26282 (11)	0.50210 (18)	0.12013 (6)	0.0117 (2)
C3	−0.27434 (10)	0.40880 (17)	0.07446 (6)	0.0112 (2)
H3	−0.3426	0.3692	0.0647	0.013*
C4	−0.18356 (10)	0.37549 (16)	0.04371 (6)	0.0102 (2)
C5	−0.08197 (11)	0.44158 (16)	0.05646 (6)	0.0108 (2)
H5	−0.0209	0.4155	0.0365	0.013*
C6	−0.07239 (11)	0.54677 (16)	0.09915 (6)	0.0100 (2)
C7	0.03462 (10)	0.63224 (16)	0.10726 (6)	0.01037 (19)
C8	0.35819 (11)	0.69799 (17)	0.18250 (6)	0.0111 (2)
C9	0.42765 (11)	0.80015 (16)	0.21813 (6)	0.0114 (2)
C10	0.42555 (12)	0.97334 (16)	0.21897 (6)	0.0123 (2)
H10	0.3747	1.0303	0.1989	0.015*
C11	0.5000	1.0623 (3)	0.2500	0.0135 (3)
C12	0.5000	0.7136 (2)	0.2500	0.0124 (3)
H12	0.5000	0.5981	0.2500	0.015*
C13	−0.19263 (10)	0.26435 (17)	−0.00240 (6)	0.0099 (2)
H1N1	−0.399 (2)	0.443 (2)	0.1564 (11)	0.023 (7)*
H1N2	0.5414 (19)	1.281 (3)	0.2714 (9)	0.028 (7)*
H2N1	−0.342 (2)	0.571 (3)	0.1839 (6)	0.018 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.00651 (4)	0.00736 (4)	0.00789 (4)	−0.00013 (2)	0.00015 (2)	−0.00035 (2)
O1	0.0076 (4)	0.0187 (5)	0.0165 (5)	0.0020 (3)	0.0003 (3)	−0.0007 (4)
O2	0.0128 (4)	0.0130 (4)	0.0120 (5)	0.0016 (3)	−0.0042 (3)	0.0008 (3)
O3	0.0223 (5)	0.0101 (4)	0.0160 (5)	0.0014 (3)	−0.0076 (4)	−0.0013 (3)
O4	0.0122 (4)	0.0111 (4)	0.0153 (5)	−0.0026 (3)	−0.0004 (3)	−0.0009 (3)
O5	0.0127 (4)	0.0129 (4)	0.0122 (5)	0.0030 (3)	−0.0022 (3)	−0.0024 (3)
O6	0.0107 (4)	0.0133 (4)	0.0118 (5)	0.0004 (3)	−0.0025 (3)	−0.0001 (3)
O1W	0.0108 (4)	0.0170 (5)	0.0163 (5)	−0.0029 (3)	0.0008 (3)	0.0023 (4)
N1	0.0108 (5)	0.0231 (6)	0.0153 (6)	−0.0028 (4)	0.0031 (4)	−0.0054 (4)
N2	0.0457 (13)	0.0095 (7)	0.0244 (11)	0.000	−0.0211 (10)	0.000
C1	0.0093 (5)	0.0122 (5)	0.0133 (6)	−0.0010 (3)	0.0002 (4)	−0.0023 (4)
C2	0.0098 (5)	0.0130 (5)	0.0123 (6)	−0.0006 (4)	0.0004 (4)	−0.0012 (4)
C3	0.0098 (4)	0.0119 (5)	0.0120 (6)	−0.0009 (3)	−0.0003 (4)	−0.0010 (4)
C4	0.0109 (5)	0.0092 (5)	0.0104 (6)	−0.0003 (3)	−0.0007 (4)	−0.0009 (4)
C5	0.0102 (4)	0.0107 (5)	0.0114 (6)	−0.0003 (3)	−0.0001 (4)	−0.0004 (4)
C6	0.0086 (5)	0.0095 (5)	0.0120 (6)	−0.0004 (3)	−0.0008 (4)	−0.0002 (4)
C7	0.0088 (4)	0.0114 (5)	0.0109 (5)	−0.0007 (3)	−0.0011 (4)	0.0010 (4)
C8	0.0119 (5)	0.0113 (5)	0.0101 (5)	0.0013 (3)	−0.0021 (4)	−0.0015 (4)
C9	0.0133 (5)	0.0108 (5)	0.0102 (5)	0.0003 (3)	−0.0032 (4)	−0.0008 (4)
C10	0.0164 (5)	0.0093 (5)	0.0113 (6)	0.0018 (3)	−0.0036 (4)	−0.0004 (4)
C11	0.0190 (8)	0.0098 (7)	0.0116 (8)	0.000	−0.0038 (6)	0.000
C12	0.0144 (7)	0.0098 (7)	0.0129 (8)	0.000	−0.0046 (6)	0.000
C13	0.0106 (5)	0.0100 (5)	0.0093 (5)	−0.0003 (3)	−0.0004 (4)	−0.0001 (4)

Geometric parameters (Å, º) top

La1—O1	2.4076 (11)	N1—H2N1	0.91 (1)
La1—O2ⁱ	2.4701 (11)	N2—C11	1.377 (3)
La1—O1W	2.4912 (10)	N2—H1N2	0.84 (1)
La1—O3	2.5093 (12)	C1—C6	1.397 (2)
La1—O5ⁱⁱ	2.5585 (11)	C1—C2	1.4016 (19)
La1—O4ⁱ	2.6089 (10)	C1—H1	0.93
La1—O6ⁱⁱⁱ	2.6538 (11)	C2—C3	1.400 (2)
La1—O6ⁱⁱ	2.6955 (11)	C3—C4	1.3902 (19)
La1—O2	2.8015 (12)	C3—H3	0.93
O1—C7	1.2643 (18)	C4—C5	1.3927 (18)
O2—C8	1.2708 (17)	C4—C13	1.489 (2)
O2—La1^iv	2.4701 (11)	C5—C6	1.390 (2)
O3—C8	1.2628 (17)	C5—H5	0.93
O4—C7	1.2604 (17)	C6—C7	1.4953 (18)
O4—La1^iv	2.6089 (10)	C8—C9	1.4961 (19)
O5—C13	1.2651 (17)	C9—C12	1.3933 (17)
O5—La1^v	2.5585 (11)	C9—C10	1.3949 (19)
O6—C13	1.2771 (17)	C10—C11	1.4071 (18)
O6—La1ⁱⁱⁱ	2.6538 (11)	C10—H10	0.93
O6—La1^v	2.6955 (11)	C11—C10^vi	1.4071 (18)
O1W—H1OW	0.84	C12—C9^vi	1.3933 (17)
O1W—H2OW	0.84	C12—H12	0.93
N1—C2	1.411 (2)	C13—La1^v	3.0017 (14)
N1—H1N1	0.90 (1)

O1—La1—O2ⁱ	75.36 (4)	C2—N1—H1N1	115.5 (19)
O1—La1—O1W	132.52 (4)	C2—N1—H2N1	116.3 (18)
O2ⁱ—La1—O1W	146.72 (4)	H1N1—N1—H2N1	105 (2)
O1—La1—O3	104.02 (4)	C11—N2—H1N2	117 (2)
O2ⁱ—La1—O3	77.64 (4)	C6—C1—C2	119.84 (13)
O1W—La1—O3	77.61 (4)	C6—C1—H1	120.1
O1—La1—O5ⁱⁱ	116.44 (4)	C2—C1—H1	120.1
O2ⁱ—La1—O5ⁱⁱ	113.96 (4)	C3—C2—C1	119.43 (12)
O1W—La1—O5ⁱⁱ	73.40 (4)	C3—C2—N1	119.13 (12)
O3—La1—O5ⁱⁱ	139.45 (4)	C1—C2—N1	121.25 (13)
O1—La1—O4ⁱ	153.93 (4)	C4—C3—C2	119.92 (12)
O2ⁱ—La1—O4ⁱ	78.67 (3)	C4—C3—H3	120.0
O1W—La1—O4ⁱ	71.56 (4)	C2—C3—H3	120.0
O3—La1—O4ⁱ	67.80 (4)	C3—C4—C5	120.51 (13)
O5ⁱⁱ—La1—O4ⁱ	76.42 (4)	C3—C4—C13	120.55 (11)
O1—La1—O6ⁱⁱⁱ	66.41 (4)	C5—C4—C13	118.91 (12)
O2ⁱ—La1—O6ⁱⁱⁱ	141.66 (3)	C6—C5—C4	119.58 (13)
O1W—La1—O6ⁱⁱⁱ	69.74 (4)	C6—C5—H5	120.2
O3—La1—O6ⁱⁱⁱ	113.64 (3)	C4—C5—H5	120.2
O5ⁱⁱ—La1—O6ⁱⁱⁱ	82.01 (4)	C5—C6—C1	120.32 (12)
O4ⁱ—La1—O6ⁱⁱⁱ	139.64 (3)	C5—C6—C7	117.66 (12)
O1—La1—O6ⁱⁱ	81.54 (4)	C1—C6—C7	121.98 (12)
O2ⁱ—La1—O6ⁱⁱ	71.63 (4)	O4—C7—O1	123.35 (13)
O1W—La1—O6ⁱⁱ	123.26 (4)	O4—C7—C6	119.47 (12)
O3—La1—O6ⁱⁱ	146.29 (3)	O1—C7—C6	117.12 (12)
O5ⁱⁱ—La1—O6ⁱⁱ	49.86 (3)	O3—C8—O2	120.49 (13)
O4ⁱ—La1—O6ⁱⁱ	92.45 (3)	O3—C8—C9	118.09 (12)
O6ⁱⁱⁱ—La1—O6ⁱⁱ	99.18 (3)	O2—C8—C9	121.33 (12)
O1—La1—O2	72.86 (4)	O3—C8—La1	55.20 (8)
O2ⁱ—La1—O2	104.59 (4)	O2—C8—La1	68.49 (8)
O1W—La1—O2	74.31 (4)	C9—C8—La1	157.57 (9)
O3—La1—O2	48.55 (3)	C12—C9—C10	120.17 (13)
O5ⁱⁱ—La1—O2	141.45 (3)	C12—C9—C8	116.50 (12)
O4ⁱ—La1—O2	112.21 (3)	C10—C9—C8	123.28 (13)
O6ⁱⁱⁱ—La1—O2	67.38 (3)	C9—C10—C11	120.37 (14)
O6ⁱⁱ—La1—O2	154.13 (3)	C9—C10—H10	119.8
C7—O1—La1	155.94 (10)	C11—C10—H10	119.8
C8—O2—La1^iv	164.67 (10)	N2—C11—C10	120.59 (9)
C8—O2—La1	86.55 (8)	N2—C11—C10^vi	120.59 (9)
La1^iv—O2—La1	107.35 (4)	C10—C11—C10^vi	118.81 (18)
C8—O3—La1	100.39 (9)	C9^vi—C12—C9	119.99 (18)
C7—O4—La1^iv	114.46 (9)	C9^vi—C12—H12	120.0
C13—O5—La1^v	97.67 (9)	C9—C12—H12	120.0
C13—O6—La1ⁱⁱⁱ	121.94 (9)	O5—C13—O6	121.52 (13)
C13—O6—La1^v	90.94 (8)	O5—C13—C4	118.50 (12)
La1ⁱⁱⁱ—O6—La1^v	105.27 (4)	O6—C13—C4	119.99 (12)
La1—O1W—H1OW	128.6	O5—C13—La1^v	57.64 (7)
La1—O1W—H2OW	120.9	O6—C13—La1^v	63.88 (8)
H1OW—O1W—H2OW	108.3	C4—C13—La1^v	175.99 (9)

O2ⁱ—La1—O1—C7	81.4 (3)	La1—O3—C8—O2	21.93 (16)
O1W—La1—O1—C7	−77.4 (3)	La1—O3—C8—C9	−154.83 (11)
O3—La1—O1—C7	8.5 (3)	La1^iv—O2—C8—O3	−174.7 (3)
O5ⁱⁱ—La1—O1—C7	−168.8 (2)	La1—O2—C8—O3	−19.25 (14)
O4ⁱ—La1—O1—C7	76.4 (3)	La1^iv—O2—C8—C9	1.9 (5)
O6ⁱⁱⁱ—La1—O1—C7	−101.5 (3)	La1—O2—C8—C9	157.41 (13)
O6ⁱⁱ—La1—O1—C7	154.5 (3)	La1^iv—O2—C8—La1	−155.5 (4)
O2—La1—O1—C7	−29.2 (3)	O1—La1—C8—O3	120.56 (10)
C13ⁱⁱ—La1—O1—C7	172.0 (3)	O2ⁱ—La1—C8—O3	45.09 (10)
C8—La1—O1—C7	−13.0 (3)	O1W—La1—C8—O3	−104.47 (10)
O1—La1—O2—C8	138.62 (9)	O5ⁱⁱ—La1—C8—O3	−97.27 (11)
O2ⁱ—La1—O2—C8	69.33 (7)	O4ⁱ—La1—C8—O3	−33.35 (10)
O1W—La1—O2—C8	−76.18 (9)	O6ⁱⁱⁱ—La1—C8—O3	−173.07 (10)
O3—La1—O2—C8	10.99 (8)	O6ⁱⁱ—La1—C8—O3	58.48 (19)
O5ⁱⁱ—La1—O2—C8	−110.23 (9)	O2—La1—C8—O3	159.76 (15)
O4ⁱ—La1—O2—C8	−14.18 (9)	C13ⁱⁱ—La1—C8—O3	−82.2 (2)
O6ⁱⁱⁱ—La1—O2—C8	−150.35 (9)	O1—La1—C8—O2	−39.20 (9)
O6ⁱⁱ—La1—O2—C8	147.23 (9)	O2ⁱ—La1—C8—O2	−114.68 (7)
C13ⁱⁱ—La1—O2—C8	−148.28 (9)	O1W—La1—C8—O2	95.77 (9)
O1—La1—O2—La1^iv	−47.98 (4)	O3—La1—C8—O2	−159.76 (15)
O2ⁱ—La1—O2—La1^iv	−117.27 (6)	O5ⁱⁱ—La1—C8—O2	102.97 (9)
O1W—La1—O2—La1^iv	97.22 (5)	O4ⁱ—La1—C8—O2	166.88 (8)
O3—La1—O2—La1^iv	−175.61 (7)	O6ⁱⁱⁱ—La1—C8—O2	27.17 (8)
O5ⁱⁱ—La1—O2—La1^iv	63.17 (6)	O6ⁱⁱ—La1—C8—O2	−101.28 (16)
O4ⁱ—La1—O2—La1^iv	159.22 (4)	C13ⁱⁱ—La1—C8—O2	118.03 (17)
O6ⁱⁱⁱ—La1—O2—La1^iv	23.04 (4)	O1—La1—C8—C9	−159.9 (3)
O6ⁱⁱ—La1—O2—La1^iv	−39.37 (10)	O2ⁱ—La1—C8—C9	124.7 (3)
C13ⁱⁱ—La1—O2—La1^iv	25.12 (10)	O1W—La1—C8—C9	−24.9 (2)
C8—La1—O2—La1^iv	173.40 (11)	O3—La1—C8—C9	79.6 (3)
O1—La1—O3—C8	−62.50 (10)	O5ⁱⁱ—La1—C8—C9	−17.7 (3)
O2ⁱ—La1—O3—C8	−133.75 (10)	O4ⁱ—La1—C8—C9	46.2 (3)
O1W—La1—O3—C8	68.68 (10)	O6ⁱⁱⁱ—La1—C8—C9	−93.5 (3)
O5ⁱⁱ—La1—O3—C8	113.71 (10)	O6ⁱⁱ—La1—C8—C9	138.1 (2)
O4ⁱ—La1—O3—C8	143.60 (11)	O2—La1—C8—C9	−120.7 (3)
O6ⁱⁱⁱ—La1—O3—C8	7.57 (11)	C13ⁱⁱ—La1—C8—C9	−2.6 (4)
O6ⁱⁱ—La1—O3—C8	−158.30 (8)	O3—C8—C9—C12	1.7 (2)
O2—La1—O3—C8	−11.23 (8)	O2—C8—C9—C12	−175.02 (12)
C13ⁱⁱ—La1—O3—C8	152.93 (9)	La1—C8—C9—C12	−64.5 (3)
C6—C1—C2—C3	−3.4 (2)	O3—C8—C9—C10	179.15 (15)
C6—C1—C2—N1	−178.49 (14)	O2—C8—C9—C10	2.4 (2)
C1—C2—C3—C4	6.3 (2)	La1—C8—C9—C10	112.9 (2)
N1—C2—C3—C4	−178.49 (14)	C12—C9—C10—C11	3.2 (2)
C2—C3—C4—C5	−3.4 (2)	C8—C9—C10—C11	−174.17 (12)
C2—C3—C4—C13	174.65 (13)	C9—C10—C11—N2	178.42 (11)
C3—C4—C5—C6	−2.5 (2)	C9—C10—C11—C10^vi	−1.58 (11)
C13—C4—C5—C6	179.43 (13)	C10—C9—C12—C9^vi	−1.58 (11)
C4—C5—C6—C1	5.4 (2)	C8—C9—C12—C9^vi	175.93 (14)
C4—C5—C6—C7	−172.14 (13)	La1^v—O5—C13—O6	0.96 (15)
C2—C1—C6—C5	−2.4 (2)	La1^v—O5—C13—C4	−178.75 (10)
C2—C1—C6—C7	174.99 (13)	La1ⁱⁱⁱ—O6—C13—O5	−109.60 (13)
La1^iv—O4—C7—O1	29.15 (18)	La1^v—O6—C13—O5	−0.90 (14)
La1^iv—O4—C7—C6	−147.91 (10)	La1ⁱⁱⁱ—O6—C13—C4	70.10 (15)
La1—O1—C7—O4	42.8 (3)	La1^v—O6—C13—C4	178.80 (11)
La1—O1—C7—C6	−140.0 (2)	La1ⁱⁱⁱ—O6—C13—La1^v	−108.70 (8)
C5—C6—C7—O4	147.88 (14)	C3—C4—C13—O5	−138.65 (14)
C1—C6—C7—O4	−29.6 (2)	C5—C4—C13—O5	39.5 (2)
C5—C6—C7—O1	−29.36 (19)	C3—C4—C13—O6	41.6 (2)
C1—C6—C7—O1	153.14 (14)	C5—C4—C13—O6	−140.26 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1OW···O5^iv	0.84	2.02	2.8354 (16)	164
O1W—H2OW···N1^vii	0.84	2.02	2.817 (2)	157
N1—H1N1···O4^viii	0.90 (1)	2.28 (2)	3.0929 (17)	150 (3)
N2—H1N2···O4^ix	0.84 (1)	2.60 (2)	3.1953 (12)	129 (2)

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

Experimental details

Crystal data
Chemical formula	[La₂(C₈H₅NO₄)₃(H₂O)₂]
M_r	851.24
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	100
a, b, c (Å)	12.2525 (3), 8.0521 (2), 25.6820 (6)
V (Å³)	2533.74 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.41
Crystal size (mm)	0.36 × 0.31 × 0.06

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.313, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	68438, 7718, 6892
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.904

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.074, 1.16
No. of reflections	7718
No. of parameters	208
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.54, −1.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1OW···O5ⁱ	0.84	2.02	2.8354 (16)	164
O1W—H2OW···N1ⁱⁱ	0.84	2.02	2.817 (2)	157
N1—H1N1···O4ⁱⁱⁱ	0.90 (1)	2.28 (2)	3.0929 (17)	150 (3)
N2—H1N2···O4^iv	0.84 (1)	2.60 (2)	3.1953 (12)	129 (2)

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

Footnotes

‡Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

FHK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post-doctoral fellowship.

References

Bond, D. L., Clark, D. L., Donohoe, R. J., Gordon, J. C., Gordon, P. L., Keogh, D. W., Scott, B. L., Tait, C. D. & Watkin, J. G. (2000). Inorg. Chem. 39, 3934–3937. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Drew, M. G. B., Hudson, M. J., Iveson, P. B., Madic, C. & Russel, M. L. (2000). J. Chem. Soc. Dalton Trans. pp. 2711–2720. Web of Science CSD CrossRef Google Scholar
Eddaoudi, M., Kim, J., Rosi, N., Vodak, D., Wochter, J., OKeeffe, M. & Yaghi, O. (2002). Mater. Sci. 295, 469–472. CAS Google Scholar
Eddaoudi, M., Li, H. & Yaghi, O. M. (2000). J. Am. Chem. Soc. 122, 1391–1397. Web of Science CrossRef CAS Google Scholar
Glunnlaugson, T., Leonard, J. P., Mulready, S. & Nieuwenhuyzen, M. (2004). Tetrahedron, 60, 105–113. Google Scholar
Li, H., Eddaoudi, M., O'Keeffe, M. & Yaghi, O. M. (1999). Nature (London), 402, 276–279. CAS Google Scholar
Lo, S. M. F., Chui, S. S. Y., Shek, L. Y., Lin, Z., Zhang, X. X., Wen, G. H. & Williams, I. D. (2000). J. Am. Chem. Soc. 122, 6293–6294. Web of Science CSD CrossRef CAS Google Scholar
Qu, Y. L., Ke, Y. X., Lu, S. M., Fan, R., Pan, G. Q. & Li, J. M. (2005). J. Mol. Struct. 734, 7–13. Web of Science CSD CrossRef CAS Google Scholar
Rosi, N. L., Eddaoudi, M., Kim, J., O'Keeffe, M. & Yaghi, O. M. (2002). Angew. Chem. 41, 284–287. CrossRef CAS Google Scholar
Saleh, M. I., Salhin, A., Saad, B., Zain, S. M., Rahman, N. A. & Ariffin, Z. (1998). J. Mol. Struct. 448, 63–68. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tao, J., Tong, M. L., Shi, J. X., Chen, X. M. & Ng, S. W. (2000). Chem. Commun. pp. 2043–2044. Web of Science CSD CrossRef Google Scholar
Zheng, X.-J. & Jin, L.-P. (2003). Polyhedron, 22, 2617–2624. Web of Science CSD CrossRef CAS Google Scholar
Zheng, S. L., Yang, J. H., Yu, X. L., Chen, X. M. & Wong, W. T. (2004). Inorg. Chem. 43, 830–838. Web of Science CSD CrossRef PubMed CAS Google Scholar