Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007918/bt6264sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007918/bt6264Isup2.hkl |
CCDC reference: 214565
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.
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.
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.
[La(C6H4NO2)2(H2O)4](NO3) | Dx = 1.914 Mg m−3 |
Mr = 517.19 | Melting point: not measured K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2732 (12) Å | Cell parameters from 2055 reflections |
b = 19.963 (3) Å | θ = 2.0–25.0° |
c = 10.2565 (13) Å | µ = 2.44 mm−1 |
β = 109.021 (2)° | T = 293 K |
V = 1795.0 (4) Å3 | Prism, colorless |
Z = 4 | 0.40 × 0.22 × 0.12 mm |
F(000) = 1016 |
Siemens SMART CCD diffractometer | 1574 independent reflections |
Radiation source: fine-focus sealed tube | 1406 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→11 |
Tmin = 0.530, Tmax = 0.746 | k = −12→23 |
2844 measured reflections | l = −12→12 |
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)] = 0.042 | H-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 reflections | Δρmax = 0.85 e Å−3 |
125 parameters | Δρmin = −1.51 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00285 (18) |
[La(C6H4NO2)2(H2O)4](NO3) | V = 1795.0 (4) Å3 |
Mr = 517.19 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.2732 (12) Å | µ = 2.44 mm−1 |
b = 19.963 (3) Å | T = 293 K |
c = 10.2565 (13) Å | 0.40 × 0.22 × 0.12 mm |
β = 109.021 (2)° |
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 = 0.746 | Rint = 0.034 |
2844 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0575P)2 + 24.0948P] where P = (Fo2 + 2Fc2)/3 |
1574 reflections | Δρmax = 0.85 e Å−3 |
125 parameters | Δρmin = −1.51 e Å−3 |
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 | 0.5000 | 0.487145 (15) | 0.7500 | 0.02487 (7) | |
O1 | 0.4394 (3) | 0.39359 (14) | 0.5849 (3) | 0.0428 (8) | |
O2 | 0.3967 (3) | 0.43237 (13) | 0.3728 (3) | 0.0399 (8) | |
N1 | 0.3402 (4) | 0.18481 (17) | 0.3036 (4) | 0.0423 (10) | |
C1 | 0.4002 (5) | 0.1967 (2) | 0.4389 (4) | 0.0390 (11) | |
H1A | 0.4271 | 0.1605 | 0.4992 | 0.047* | |
C2 | 0.4239 (4) | 0.26127 (19) | 0.4927 (4) | 0.0298 (10) | |
H2A | 0.4650 | 0.2682 | 0.5873 | 0.036* | |
C3 | 0.3852 (4) | 0.31512 (18) | 0.4029 (4) | 0.0271 (9) | |
C4 | 0.3245 (4) | 0.3027 (2) | 0.2639 (4) | 0.0318 (10) | |
H4A | 0.2978 | 0.3379 | 0.2011 | 0.038* | |
C5 | 0.3038 (5) | 0.2370 (2) | 0.2193 (4) | 0.0385 (11) | |
H5A | 0.2622 | 0.2290 | 0.1251 | 0.046* | |
C6 | 0.4094 (4) | 0.38616 (19) | 0.4585 (4) | 0.0287 (9) | |
N2 | 0.5000 | 1.0683 (3) | −0.2500 | 0.0377 (13) | |
O3 | 0.5000 | 1.1291 (3) | −0.2500 | 0.0686 (17) | |
O4 | 0.4837 (4) | 1.03588 (19) | −0.1509 (3) | 0.0565 (10) | |
O1W | 0.7240 (3) | 0.54390 (16) | 0.9406 (3) | 0.0421 (8) | |
O2W | 0.2464 (3) | 0.44155 (13) | 0.7742 (3) | 0.0349 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.03638 (14) | 0.01895 (13) | 0.02163 (12) | 0.000 | 0.01268 (10) | 0.000 |
O1 | 0.0650 (17) | 0.0327 (15) | 0.0310 (13) | −0.0056 (13) | 0.0159 (12) | −0.0090 (11) |
O2 | 0.0519 (14) | 0.0256 (14) | 0.0467 (14) | −0.0028 (12) | 0.0221 (12) | 0.0072 (12) |
N1 | 0.0456 (17) | 0.0310 (18) | 0.0521 (19) | −0.0069 (15) | 0.0184 (15) | −0.0132 (15) |
C1 | 0.049 (2) | 0.027 (2) | 0.045 (2) | 0.0005 (17) | 0.0203 (17) | 0.0050 (17) |
C2 | 0.0363 (18) | 0.031 (2) | 0.0210 (15) | 0.0000 (16) | 0.0074 (13) | 0.0017 (14) |
C3 | 0.0308 (16) | 0.0240 (18) | 0.0288 (16) | −0.0028 (14) | 0.0129 (13) | −0.0035 (14) |
C4 | 0.0381 (19) | 0.032 (2) | 0.0214 (16) | −0.0001 (16) | 0.0046 (15) | −0.0041 (15) |
C5 | 0.042 (2) | 0.041 (2) | 0.0301 (18) | −0.0082 (18) | 0.0097 (16) | −0.0102 (17) |
C6 | 0.0331 (16) | 0.0275 (19) | 0.0275 (16) | −0.0050 (15) | 0.0126 (13) | −0.0016 (14) |
N2 | 0.034 (2) | 0.041 (3) | 0.043 (2) | 0.000 | 0.0192 (18) | 0.000 |
O3 | 0.088 (3) | 0.042 (3) | 0.080 (3) | 0.000 | 0.033 (3) | 0.000 |
O4 | 0.0564 (16) | 0.068 (2) | 0.0509 (16) | −0.0036 (17) | 0.0261 (13) | 0.0122 (16) |
O1W | 0.0481 (14) | 0.0494 (17) | 0.0293 (12) | −0.0077 (14) | 0.0132 (11) | −0.0047 (12) |
O2W | 0.0423 (13) | 0.0287 (14) | 0.0345 (12) | −0.0042 (11) | 0.0134 (11) | −0.0052 (11) |
La1—O2i | 2.423 (3) | C1—C2 | 1.391 (6) |
La1—O2ii | 2.423 (3) | C1—H1A | 0.9300 |
La1—O1 | 2.460 (3) | C2—C3 | 1.385 (5) |
La1—O1iii | 2.460 (3) | C2—H2A | 0.9300 |
La1—O1W | 2.602 (3) | C3—C4 | 1.373 (5) |
La1—O1Wiii | 2.602 (3) | C3—C6 | 1.518 (5) |
La1—O2W | 2.608 (3) | C4—C5 | 1.382 (6) |
La1—O2Wiii | 2.608 (3) | C4—H4A | 0.9300 |
O1—C6 | 1.242 (5) | C5—H5A | 0.9300 |
O2—C6 | 1.253 (5) | N2—O3 | 1.212 (7) |
O2—La1ii | 2.423 (3) | N2—O4 | 1.255 (4) |
N1—C5 | 1.326 (5) | N2—O4iv | 1.255 (4) |
N1—C1 | 1.337 (5) | ||
O2i—La1—O2ii | 96.94 (14) | O1Wiii—La1—O2Wiii | 127.16 (9) |
O2i—La1—O1 | 145.17 (10) | O2W—La1—O2Wiii | 139.15 (12) |
O2ii—La1—O1 | 100.71 (10) | C6—O1—La1 | 137.1 (3) |
O2i—La1—O1iii | 100.71 (10) | C6—O2—La1ii | 152.9 (3) |
O2ii—La1—O1iii | 145.17 (10) | C5—N1—C1 | 117.9 (4) |
O1—La1—O1iii | 81.22 (13) | N1—C1—C2 | 122.3 (4) |
O2i—La1—O1W | 71.02 (9) | N1—C1—H1A | 118.8 |
O2ii—La1—O1W | 75.40 (9) | C2—C1—H1A | 118.8 |
O1—La1—O1W | 142.66 (10) | C3—C2—C1 | 118.8 (3) |
O1iii—La1—O1W | 82.30 (9) | C3—C2—H2A | 120.6 |
O2i—La1—O1Wiii | 75.40 (9) | C1—C2—H2A | 120.6 |
O2ii—La1—O1Wiii | 71.02 (9) | C4—C3—C2 | 118.7 (3) |
O1—La1—O1Wiii | 82.30 (9) | C4—C3—C6 | 121.3 (3) |
O1iii—La1—O1Wiii | 142.66 (10) | C2—C3—C6 | 120.0 (3) |
O1W—La1—O1Wiii | 128.39 (14) | C3—C4—C5 | 118.7 (4) |
O2i—La1—O2W | 70.14 (9) | C3—C4—H4A | 120.6 |
O2ii—La1—O2W | 143.36 (8) | C5—C4—H4A | 120.6 |
O1—La1—O2W | 77.87 (10) | N1—C5—C4 | 123.5 (4) |
O1iii—La1—O2W | 71.36 (9) | N1—C5—H5A | 118.3 |
O1W—La1—O2W | 127.16 (9) | C4—C5—H5A | 118.3 |
O1Wiii—La1—O2W | 72.53 (9) | O1—C6—O2 | 125.6 (4) |
O2i—La1—O2Wiii | 143.36 (8) | O1—C6—C3 | 117.3 (3) |
O2ii—La1—O2Wiii | 70.14 (9) | O2—C6—C3 | 117.1 (3) |
O1—La1—O2Wiii | 71.36 (9) | O3—N2—O4 | 121.1 (3) |
O1iii—La1—O2Wiii | 77.87 (10) | O3—N2—O4iv | 121.1 (3) |
O1W—La1—O2Wiii | 72.53 (9) | O4—N2—O4iv | 117.9 (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, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [La(C6H4NO2)2(H2O)4](NO3) |
Mr | 517.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.2732 (12), 19.963 (3), 10.2565 (13) |
β (°) | 109.021 (2) |
V (Å3) | 1795.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.44 |
Crystal size (mm) | 0.40 × 0.22 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.530, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2844, 1574, 1406 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.111, 1.01 |
No. of reflections | 1574 |
No. of parameters | 125 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0575P)2 + 24.0948P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.85, −1.51 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
La1—O2i | 2.423 (3) | La1—O1Wiii | 2.602 (3) |
La1—O2ii | 2.423 (3) | La1—O2W | 2.608 (3) |
La1—O1 | 2.460 (3) | La1—O2Wiii | 2.608 (3) |
La1—O1iii | 2.460 (3) | O2—La1ii | 2.423 (3) |
La1—O1W | 2.602 (3) | ||
O2i—La1—O2ii | 96.94 (14) | O1W—La1—O1Wiii | 128.39 (14) |
O2i—La1—O1 | 145.17 (10) | O2i—La1—O2W | 70.14 (9) |
O2ii—La1—O1 | 100.71 (10) | O2ii—La1—O2W | 143.36 (8) |
O2i—La1—O1iii | 100.71 (10) | O1—La1—O2W | 77.87 (10) |
O2ii—La1—O1iii | 145.17 (10) | O1iii—La1—O2W | 71.36 (9) |
O1—La1—O1iii | 81.22 (13) | O1W—La1—O2W | 127.16 (9) |
O2i—La1—O1W | 71.02 (9) | O1Wiii—La1—O2W | 72.53 (9) |
O2ii—La1—O1W | 75.40 (9) | O2i—La1—O2Wiii | 143.36 (8) |
O1—La1—O1W | 142.66 (10) | O2ii—La1—O2Wiii | 70.14 (9) |
O1iii—La1—O1W | 82.30 (9) | O1—La1—O2Wiii | 71.36 (9) |
O2i—La1—O1Wiii | 75.40 (9) | O1iii—La1—O2Wiii | 77.87 (10) |
O2ii—La1—O1Wiii | 71.02 (9) | O1W—La1—O2Wiii | 72.53 (9) |
O1—La1—O1Wiii | 82.30 (9) | O1Wiii—La1—O2Wiii | 127.16 (9) |
O1iii—La1—O1Wiii | 142.66 (10) | O2W—La1—O2Wiii | 139.15 (12) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y, −z+3/2. |
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.