Download citation
Download citation
link to html
The structure of the title compound, {[La(C6H4NO2)2(H2O)4](NO3)}n, consists of an infinite cationic chain, [La(C6H4NO2)2(H2O)4]+, and well separated (NO3) anions. The LaIII atom is eight-coordinated by four O atoms from four isonicotinate ligands and four water mol­ecules. The coordin­ation geometry around the La centre can be described as a distorted square antiprism. The La atoms are bridged by two carboxyl­ate groups of two isonicotinate ligands to form an infinite chain along the c direction. The carboxyl­ate-bridged chains are linked to each other via hydrogen bonds between pyridyl N atoms and coordinated water mol­ecules to form a three-dimensional network with channels in which the nitrate anions are located, and the intermolecular hydrogen bonds are formed between the nitrate anions and cationic chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007918/bt6264sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007918/bt6264Isup2.hkl
Contains datablock I

CCDC reference: 214565

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • H-atom completeness 51%
  • R factor = 0.042
  • wR factor = 0.111
  • Data-to-parameter ratio = 12.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C12 H16 La1 N3 O11 Atom count from the _atom_site data: C12 H8 La1 N3 O11 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C12 H16 La N3 O11 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 48.00 48.00 0.00 H 64.00 32.00 32.00 La 4.00 4.00 0.00 N 12.00 12.00 0.00 O 44.00 44.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? CHEMW_03 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_weight 517.19 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 12.00 144.13 H 1.01 8.00 8.06 N 14.01 3.00 42.02 O 16.00 11.00 175.99 La 138.91 1.00 138.91 Calculated formula weight 509.11 The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01

Comment top

Lanthanide metal polynuclear compounds have attracted increasing interest due to their magnetic and luminescent properties. These compounds were usually prepared by the reaction of rare-earth metal ions with bi- or multidentate ligands, such as nicotinic acid (Starynowicz, 1991, 1993; Kay et al., 1972; Ma et al., 1996), isonicotinic acid (Ma et al., 1999; Zeng et al., 2000) and isonicotinic acid N-oxide (Mao et al., 1998). In recent years, we have reported several complexes of this type with different bridging ligands (Zhang et al., 1999; Cui et al., 1999). We report here the synthesis and crystal structure of a new lanthanum complex with isonicotinic ligand, namely catena-poly[[[tetraaqualanthanum(III)]-di-µ-isoniconitinato-κ2O:O'] nitrate], (I). Since it contains a non-coordinated N atom on the pyridine ring, it can be used as a `metallo ligand' to bind transition metal ions for the preparation of compounds of rare earth and transition metal.

As shown in Fig. 1, the structure of (I) is comprised of an infinite cationic chain [La(C6H4NO2)2(H2O)4]+ and well separated anions (NO3). LaIII ions are eight-coordinated by four O atoms belonging to four different isonicotinic ligands [La—O, average 2.441 (3) Å] and four water molecules [La—OW, average 2.605 (3) Å]. The La centre has a distorted square anti-prism coordination geometry with O—La—O bond angles ranging from 70.14 (9) to 145.17 (10)°. One of the square faces comprises atoms O1, O1A, O2W and O2WA, with a mean deviation of 0.478 Å, and the other is defined by atoms O2, O2A, O1W and O1WA, with the mean deviation of 0.236 Å. The dihedral angle between the two planes is 2.04°. The LaIII atom is displaced 1.388 and 1.370 Å, respectively, from the above two faces. The La atoms are bridged by two syn–syn µ-O,O'-carboxylate groups of isonicotinate ligands to form an infinite chain with La···La separation of 5.154 Å along the c axis. This alignment is similar to that found in [{Eu(L)2(H2O)4}]n.nH2O (L = isonicotinic acid N-oxide; Mao et al., 1998), but differs from those found in Ln(isonicotinate)3(H2O)2 (Ln = Ce, Pr, Nd, Sm, Eu, Tb) (Ma et al., 1999) in which the LnIII atoms are bridged by four syn–syn µ-O,O'-carboxylate groups of isonicotinic ligands (Ln = Ce, Pr, Nd) or coordinated by both two syn-syn µ-O,O'-carboxylate groups and chelating carboxylate groups of isonicotinate ligands (Ln = Sm, Eu, Tb). To our best knowledge, the arrangement in present complex is rare in the lanthanide analogs.

There are two types of intermolecular hydrogen bonds and one intrachain hydrogen bond in the crystal structure. The intrachain hydrogen bond is composed of two waters coordinated to adjacent LaIII ions with O1W···O2W distance of 2.862 (4) Å, as illustrated in Fig. 1. One of the two types of intermolecular hydrogen bonds, formed by the uncoordinated N atoms of isonicotinate ligands and coordinated water molecules between neighbouring chains with O2W···N1 distance of 2.688 (4) Å, links the cationic chains into a three-dimensional network with channels along the c axis in which the nitrate anions are located, as shown in Fig. 2. The other intermolecular hydrogen bonds are formed by the nitrate anions and coordinated water molecules with the O1W···O4 distance of 2.860 (5) Å and O2W···O4 distance of 2.818 (4) Å.

Experimental top

The title complex was prepared by mixing a 1:1 molar ratio of La(NO3)3.xH2O (43.2 mg, 0.1 mmol) and C5H4NCOOH (12.3 mg, 0.1 mmol) in a mixed solvent of H2O/EtOH (v:v = 1:1). The pH of the solution was adjusted to 5.8 with NH3·H2O. The reaction mixture was filtered and colourless single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent.

Refinement top

H atoms bonded to carbon were inserted at calculated positions with isotropic displacement parameters riding on those of their carrier atoms. No H atoms were included for the water molecules.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of the title compound with 40% probability ellipsoids. Hydrogen bonds are represented by dotted lines.
[Figure 2] Fig. 2. View of the packing diagram of the title compound. Dotted lines represent hydrogen bonds. For clarity, only a pair of nitrate anions hydrogen bonding with coordinated water are shown.
catena-Poly[[[tetraaqualanthanum(III)]-di-µ2-isoniconitinato-κ2O:O'] nitrate] top
Crystal data top
[La(C6H4NO2)2(H2O)4](NO3)Dx = 1.914 Mg m3
Mr = 517.19Melting point: not measured K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 9.2732 (12) ÅCell parameters from 2055 reflections
b = 19.963 (3) Åθ = 2.0–25.0°
c = 10.2565 (13) ŵ = 2.44 mm1
β = 109.021 (2)°T = 293 K
V = 1795.0 (4) Å3Prism, colorless
Z = 40.40 × 0.22 × 0.12 mm
F(000) = 1016
Data collection top
Siemens SMART CCD
diffractometer
1574 independent reflections
Radiation source: fine-focus sealed tube1406 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 911
Tmin = 0.530, Tmax = 0.746k = 1223
2844 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.111 w = 1/[σ2(Fo2) + (0.0575P)2 + 24.0948P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.003
1574 reflectionsΔρmax = 0.85 e Å3
125 parametersΔρmin = 1.51 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00285 (18)
Crystal data top
[La(C6H4NO2)2(H2O)4](NO3)V = 1795.0 (4) Å3
Mr = 517.19Z = 4
Monoclinic, C2/cMo Kα radiation
a = 9.2732 (12) ŵ = 2.44 mm1
b = 19.963 (3) ÅT = 293 K
c = 10.2565 (13) Å0.40 × 0.22 × 0.12 mm
β = 109.021 (2)°
Data collection top
Siemens SMART CCD
diffractometer
1574 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1406 reflections with I > 2σ(I)
Tmin = 0.530, Tmax = 0.746Rint = 0.034
2844 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.111H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0575P)2 + 24.0948P]
where P = (Fo2 + 2Fc2)/3
1574 reflectionsΔρmax = 0.85 e Å3
125 parametersΔρmin = 1.51 e Å3
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
xyzUiso*/Ueq
La10.50000.487145 (15)0.75000.02487 (7)
O10.4394 (3)0.39359 (14)0.5849 (3)0.0428 (8)
O20.3967 (3)0.43237 (13)0.3728 (3)0.0399 (8)
N10.3402 (4)0.18481 (17)0.3036 (4)0.0423 (10)
C10.4002 (5)0.1967 (2)0.4389 (4)0.0390 (11)
H1A0.42710.16050.49920.047*
C20.4239 (4)0.26127 (19)0.4927 (4)0.0298 (10)
H2A0.46500.26820.58730.036*
C30.3852 (4)0.31512 (18)0.4029 (4)0.0271 (9)
C40.3245 (4)0.3027 (2)0.2639 (4)0.0318 (10)
H4A0.29780.33790.20110.038*
C50.3038 (5)0.2370 (2)0.2193 (4)0.0385 (11)
H5A0.26220.22900.12510.046*
C60.4094 (4)0.38616 (19)0.4585 (4)0.0287 (9)
N20.50001.0683 (3)0.25000.0377 (13)
O30.50001.1291 (3)0.25000.0686 (17)
O40.4837 (4)1.03588 (19)0.1509 (3)0.0565 (10)
O1W0.7240 (3)0.54390 (16)0.9406 (3)0.0421 (8)
O2W0.2464 (3)0.44155 (13)0.7742 (3)0.0349 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La10.03638 (14)0.01895 (13)0.02163 (12)0.0000.01268 (10)0.000
O10.0650 (17)0.0327 (15)0.0310 (13)0.0056 (13)0.0159 (12)0.0090 (11)
O20.0519 (14)0.0256 (14)0.0467 (14)0.0028 (12)0.0221 (12)0.0072 (12)
N10.0456 (17)0.0310 (18)0.0521 (19)0.0069 (15)0.0184 (15)0.0132 (15)
C10.049 (2)0.027 (2)0.045 (2)0.0005 (17)0.0203 (17)0.0050 (17)
C20.0363 (18)0.031 (2)0.0210 (15)0.0000 (16)0.0074 (13)0.0017 (14)
C30.0308 (16)0.0240 (18)0.0288 (16)0.0028 (14)0.0129 (13)0.0035 (14)
C40.0381 (19)0.032 (2)0.0214 (16)0.0001 (16)0.0046 (15)0.0041 (15)
C50.042 (2)0.041 (2)0.0301 (18)0.0082 (18)0.0097 (16)0.0102 (17)
C60.0331 (16)0.0275 (19)0.0275 (16)0.0050 (15)0.0126 (13)0.0016 (14)
N20.034 (2)0.041 (3)0.043 (2)0.0000.0192 (18)0.000
O30.088 (3)0.042 (3)0.080 (3)0.0000.033 (3)0.000
O40.0564 (16)0.068 (2)0.0509 (16)0.0036 (17)0.0261 (13)0.0122 (16)
O1W0.0481 (14)0.0494 (17)0.0293 (12)0.0077 (14)0.0132 (11)0.0047 (12)
O2W0.0423 (13)0.0287 (14)0.0345 (12)0.0042 (11)0.0134 (11)0.0052 (11)
Geometric parameters (Å, º) top
La1—O2i2.423 (3)C1—C21.391 (6)
La1—O2ii2.423 (3)C1—H1A0.9300
La1—O12.460 (3)C2—C31.385 (5)
La1—O1iii2.460 (3)C2—H2A0.9300
La1—O1W2.602 (3)C3—C41.373 (5)
La1—O1Wiii2.602 (3)C3—C61.518 (5)
La1—O2W2.608 (3)C4—C51.382 (6)
La1—O2Wiii2.608 (3)C4—H4A0.9300
O1—C61.242 (5)C5—H5A0.9300
O2—C61.253 (5)N2—O31.212 (7)
O2—La1ii2.423 (3)N2—O41.255 (4)
N1—C51.326 (5)N2—O4iv1.255 (4)
N1—C11.337 (5)
O2i—La1—O2ii96.94 (14)O1Wiii—La1—O2Wiii127.16 (9)
O2i—La1—O1145.17 (10)O2W—La1—O2Wiii139.15 (12)
O2ii—La1—O1100.71 (10)C6—O1—La1137.1 (3)
O2i—La1—O1iii100.71 (10)C6—O2—La1ii152.9 (3)
O2ii—La1—O1iii145.17 (10)C5—N1—C1117.9 (4)
O1—La1—O1iii81.22 (13)N1—C1—C2122.3 (4)
O2i—La1—O1W71.02 (9)N1—C1—H1A118.8
O2ii—La1—O1W75.40 (9)C2—C1—H1A118.8
O1—La1—O1W142.66 (10)C3—C2—C1118.8 (3)
O1iii—La1—O1W82.30 (9)C3—C2—H2A120.6
O2i—La1—O1Wiii75.40 (9)C1—C2—H2A120.6
O2ii—La1—O1Wiii71.02 (9)C4—C3—C2118.7 (3)
O1—La1—O1Wiii82.30 (9)C4—C3—C6121.3 (3)
O1iii—La1—O1Wiii142.66 (10)C2—C3—C6120.0 (3)
O1W—La1—O1Wiii128.39 (14)C3—C4—C5118.7 (4)
O2i—La1—O2W70.14 (9)C3—C4—H4A120.6
O2ii—La1—O2W143.36 (8)C5—C4—H4A120.6
O1—La1—O2W77.87 (10)N1—C5—C4123.5 (4)
O1iii—La1—O2W71.36 (9)N1—C5—H5A118.3
O1W—La1—O2W127.16 (9)C4—C5—H5A118.3
O1Wiii—La1—O2W72.53 (9)O1—C6—O2125.6 (4)
O2i—La1—O2Wiii143.36 (8)O1—C6—C3117.3 (3)
O2ii—La1—O2Wiii70.14 (9)O2—C6—C3117.1 (3)
O1—La1—O2Wiii71.36 (9)O3—N2—O4121.1 (3)
O1iii—La1—O2Wiii77.87 (10)O3—N2—O4iv121.1 (3)
O1W—La1—O2Wiii72.53 (9)O4—N2—O4iv117.9 (5)
Symmetry codes: (i) x, y+1, z+1/2; (ii) x+1, y+1, z+1; (iii) x+1, y, z+3/2; (iv) x+1, y, z1/2.

Experimental details

Crystal data
Chemical formula[La(C6H4NO2)2(H2O)4](NO3)
Mr517.19
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)9.2732 (12), 19.963 (3), 10.2565 (13)
β (°) 109.021 (2)
V3)1795.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)2.44
Crystal size (mm)0.40 × 0.22 × 0.12
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.530, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
2844, 1574, 1406
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.111, 1.01
No. of reflections1574
No. of parameters125
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0575P)2 + 24.0948P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.85, 1.51

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
La1—O2i2.423 (3)La1—O1Wiii2.602 (3)
La1—O2ii2.423 (3)La1—O2W2.608 (3)
La1—O12.460 (3)La1—O2Wiii2.608 (3)
La1—O1iii2.460 (3)O2—La1ii2.423 (3)
La1—O1W2.602 (3)
O2i—La1—O2ii96.94 (14)O1W—La1—O1Wiii128.39 (14)
O2i—La1—O1145.17 (10)O2i—La1—O2W70.14 (9)
O2ii—La1—O1100.71 (10)O2ii—La1—O2W143.36 (8)
O2i—La1—O1iii100.71 (10)O1—La1—O2W77.87 (10)
O2ii—La1—O1iii145.17 (10)O1iii—La1—O2W71.36 (9)
O1—La1—O1iii81.22 (13)O1W—La1—O2W127.16 (9)
O2i—La1—O1W71.02 (9)O1Wiii—La1—O2W72.53 (9)
O2ii—La1—O1W75.40 (9)O2i—La1—O2Wiii143.36 (8)
O1—La1—O1W142.66 (10)O2ii—La1—O2Wiii70.14 (9)
O1iii—La1—O1W82.30 (9)O1—La1—O2Wiii71.36 (9)
O2i—La1—O1Wiii75.40 (9)O1iii—La1—O2Wiii77.87 (10)
O2ii—La1—O1Wiii71.02 (9)O1W—La1—O2Wiii72.53 (9)
O1—La1—O1Wiii82.30 (9)O1Wiii—La1—O2Wiii127.16 (9)
O1iii—La1—O1Wiii142.66 (10)O2W—La1—O2Wiii139.15 (12)
Symmetry codes: (i) x, y+1, z+1/2; (ii) x+1, y+1, z+1; (iii) x+1, y, z+3/2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds