catena-Poly[[[tetra­aqua­neodymium(III)]-di-μ-isonicotinato] chloride]

Abstract

In the title complex, {[Nd(C₆H₄NO₂)₂(H₂O)₄]Cl}_n, the Nd^III cation is located on a twofold rotation axis and coordinated by four isonicotiniate anions and four water mol­ecules in a distorted square-anti­prismatic geometry. The carboxyl­ate groups of the isonicotinate anions bridge the Nd^III cations, forming polymeric chains running along the c axis. The Cl⁻ anion is located on a twofold rotation axis and is linked to the polymeric chains via O—H⋯Cl hydrogen bonding. Inter­molecular O—H⋯O and O—H⋯N hydrogen bonds are also present in the crystal structure.

Related literature

For some crystal structures of related lanthanide-isonicotinic acid complexes, see: Chen & Fukuzumi (2009 ▶); Ma et al. (1999 ▶); Han et al. (2010 ▶); Kay et al. (1972 ▶); Duan et al. (2010 ▶); Jia et al. (2008 ▶); Cheng et al. (2007 ▶); Liu et al. (2006 ▶); Chai et al. (2010 ▶).

Experimental

Crystal data

• [Nd(C₆H₄NO₂)₂(H₂O)₄]Cl

• M _r = 495.96

• Orthorhombic,

• a = 8.9223 (18) Å

• b = 19.684 (4) Å

• c = 10.151 (2) Å

• V = 1782.9 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 3.10 mm⁻¹

• T = 173 K

• 0.18 × 0.17 × 0.15 mm

Data collection

• Rigaku Saturn724+ CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.49, T _max = 0.63

• 9085 measured reflections

• 2056 independent reflections

• 1764 reflections with I > 2σ(I)

• R _int = 0.071

Refinement

• R[F ² > 2σ(F ²)] = 0.063

• wR(F ²) = 0.190

• S = 1.33

• 2056 reflections

• 122 parameters

• 6 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.12 e Å⁻³

• Δρ_min = −1.06 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811055619/xu5361Isup5.cdx

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

Table 1. Selected bond lengths (Å).

Nd1—O1i	2.425 (6)
Nd1—O2	2.385 (5)
Nd1—O3	2.544 (6)
Nd1—O4	2.480 (6)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H6⋯Cl2ii	0.95 (6)	2.29 (6)	3.211 (7)	163 (6)
O3—H7⋯N1iii	0.97 (4)	1.72 (4)	2.685 (10)	174 (9)
O4—H8⋯Cl2i	0.96 (4)	2.15 (5)	3.041 (6)	155 (6)
O4—H9⋯O3iv	0.95 (2)	1.93 (3)	2.841 (8)	160 (8)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

In the synthesis of prepare a lanthanide-isonicotinamide complex, the isonicotinamide changed to isonicotinic acid, resulting in the title complex.

Among aromatic carboxylic acids, isonicotinic acid has a conjugated structural motif and can be used to construct extended structures because it is unsymmetrical divergent ligand. Isonicotinic acid with metal ions may have various coordination modes (Chen et al., 2009). The molecular structure of the title compound is shown in Fig. 1. Nd(III) is 8-coordinated to four oxygen atoms from four isonicotinic acid molecules and four water molecules. Each ligand is coordinated to two metal ions as bidentate ligands via two oxygen atoms of carboxyl group. One metal ion is connected to four ligands, thus an extensive network form. Nd(III) is located at the center of a slightly distorted square antiprism. Nd-O distances are from 2.385 to 2.544 Å. The mean Nd-O bond lengths, 2.4585 Å is larger than the mean Sm-O bond lengths (2.426 Å), which is consistent with the lanthanide contraction. The O—H···Cl, O—H···O and O—H···N hydrogen bonds form a three-dimensional network.

For lanthanide-isonicotinate complexes, several structures have been observed. For example, Ln(III) ions can coordinate to six carboxylate oxygen atoms of bridging isonicotinate groups and to two water molecules (Ma et al., 1999); or may coordinate to four carboxylate oxygen atoms of bridging isonicotinate groups, two carboxylate oxygen atoms of the chelating isonicotinate group, and two water molecules (Ma et al., 1999; Han et al., 2010; Kay et al., 1972); or have structure similar to the NdCl-isonicotinic acid complex reported here (Chen et al., 2009). Because Cl^- or NO₃^- does not coordinate to lanthanide ions, so Nd(III) chloride or nitrate ion-isonicotinic acid complexes have the similar coordination sphere (Duan et al., 2010; Jia et al., 2008). When oxalate ligands, chromate ions or other ligands are involved, the coordination situations are a little different (Cheng et al., 2007; Liu et al., 2006; Chai et al., 2010) because oxalate ligand, chromate ions or other ligands also coordinate to metal ions.

Experimental

NdCl₃ (1 mmol) and isonicotinamide (3 mmol) were dissolved in 3ml water and 6 ml ethanol. The solution was put on a water bath, temperature was raised to 80°C. Small aliquots of EtOH were periodically added to the solution during the heating process to prolong the reaction time. The resulting mixtures were filtered and left for crystallization in room temperature, the suitable crystals for X-ray diffraction measuraments were obtained in two weeks.

Refinement

The C-bound H-atoms were placed in calculated positions (C—H 0.930 Å) and were included in the refinement in the riding model approximation, U_iso(H) = 1.2U_eq(C). The O-bound H atoms were located in a difference Fourier map and were refined with U_iso(H) = 1.2U_eq(O).

Figures

Fig. 1.

The molecular structure of the title compound, displacement ellipsoids drawn at 30% probability level. The Hydrogen atoms have been omitted for clarity.

Crystal data

[Nd(C6H4NO2)2(H2O)4]Cl	F(000) = 972
Mr = 495.96	Dx = 1.848 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4581 reflections
a = 8.9223 (18) Å	θ = 2.0–27.5°
b = 19.684 (4) Å	µ = 3.10 mm−1
c = 10.151 (2) Å	T = 173 K
V = 1782.9 (6) Å3	Block, blue
Z = 4	0.18 × 0.17 × 0.15 mm

Data collection

Rigaku Saturn724+ CCD diffractometer	2056 independent reflections
Radiation source: fine-focus sealed tube	1764 reflections with I > 2σ(I)
graphite	Rint = 0.071
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 2.1°
ω scans at fixed χ = 45°	h = −11→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	k = −25→23
Tmin = 0.49, Tmax = 0.63	l = −12→13
9085 measured reflections

Refinement

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190	H atoms treated by a mixture of independent and constrained refinement
S = 1.33	w = 1/[σ2(Fo2) + (0.0763P)2 + 8.5206P] where P = (Fo2 + 2Fc2)/3
2056 reflections	(Δ/σ)max = 0.004
122 parameters	Δρmax = 1.12 e Å−3
6 restraints	Δρmin = −1.06 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Nd1	0.5000	0.51140 (3)	0.2500	0.0166 (3)
Cl2	0.0000	0.55946 (19)	0.7500	0.0334 (8)
O4	0.6995 (7)	0.4591 (3)	0.1133 (5)	0.0263 (13)
H8	0.802 (4)	0.448 (5)	0.131 (7)	0.032*
H9	0.694 (9)	0.459 (5)	0.020 (2)	0.032*
O1	0.5450 (7)	0.3957 (3)	0.5981 (6)	0.0250 (13)
O2	0.6051 (7)	0.4301 (3)	0.3977 (5)	0.0225 (12)
O3	0.2471 (7)	0.5501 (3)	0.1620 (6)	0.0242 (13)
H6	0.163 (6)	0.526 (3)	0.195 (10)	0.029*
H7	0.211 (8)	0.5964 (15)	0.157 (9)	0.029*
C6	0.5817 (8)	0.3855 (4)	0.4827 (8)	0.0164 (15)
C3	0.6021 (10)	0.3129 (4)	0.4415 (8)	0.0217 (17)
C2	0.6744 (10)	0.2956 (4)	0.3247 (8)	0.0261 (19)
H2	0.7100	0.3295	0.2691	0.031*
C4	0.5480 (12)	0.2591 (4)	0.5189 (10)	0.030 (2)
H4	0.4971	0.2678	0.5970	0.035*
N1	0.6459 (9)	0.1776 (4)	0.3683 (7)	0.0286 (17)
C5	0.5713 (12)	0.1933 (4)	0.4775 (9)	0.030 (2)
H5	0.5329	0.1581	0.5285	0.036*
C1	0.6936 (11)	0.2279 (4)	0.2911 (10)	0.030 (2)
H1	0.7412	0.2173	0.2123	0.036*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Nd1	0.0210 (4)	0.0139 (4)	0.0148 (4)	0.000	−0.0010 (2)	0.000
Cl2	0.0240 (15)	0.0327 (18)	0.043 (2)	0.000	−0.0092 (13)	0.000
O4	0.025 (3)	0.040 (4)	0.014 (3)	0.008 (3)	0.001 (2)	−0.002 (3)
O1	0.034 (3)	0.019 (3)	0.022 (3)	−0.002 (3)	0.007 (3)	−0.005 (2)
O2	0.025 (3)	0.016 (3)	0.026 (3)	−0.001 (2)	−0.006 (3)	0.007 (2)
O3	0.022 (3)	0.015 (3)	0.035 (3)	0.005 (2)	0.005 (3)	0.005 (2)
C6	0.006 (4)	0.018 (4)	0.025 (4)	0.000 (3)	−0.008 (3)	0.000 (3)
C3	0.023 (4)	0.022 (4)	0.021 (4)	0.000 (3)	0.002 (3)	0.001 (3)
C2	0.026 (5)	0.026 (4)	0.027 (4)	−0.003 (4)	0.006 (4)	0.002 (4)
C4	0.037 (5)	0.020 (4)	0.032 (5)	−0.005 (4)	0.003 (4)	0.002 (4)
N1	0.040 (4)	0.021 (4)	0.025 (4)	0.002 (3)	−0.009 (3)	−0.009 (3)
C5	0.040 (6)	0.015 (4)	0.035 (5)	0.000 (4)	0.006 (4)	0.004 (3)
C1	0.035 (5)	0.023 (5)	0.031 (5)	0.005 (4)	−0.003 (4)	−0.008 (4)

Geometric parameters (Å, °)

Nd1—O1i	2.425 (6)	O3—H6	0.95 (2)
Nd1—O1ii	2.425 (6)	O3—H7	0.97 (2)
Nd1—O2iii	2.385 (5)	C6—C3	1.501 (10)
Nd1—O2	2.385 (5)	C3—C2	1.392 (11)
Nd1—O3iii	2.544 (6)	C3—C4	1.404 (12)
Nd1—O3	2.544 (6)	C2—C1	1.385 (12)
Nd1—O4iii	2.480 (6)	C2—H2	0.9300
Nd1—O4	2.480 (6)	C4—C5	1.377 (12)
O4—H8	0.96 (2)	C4—H4	0.9300
O4—H9	0.95 (2)	N1—C5	1.330 (12)
O1—C6	1.234 (9)	N1—C1	1.332 (12)
O1—Nd1i	2.425 (6)	C5—H5	0.9300
O2—C6	1.248 (9)	C1—H1	0.9300
O2iii—Nd1—O2	95.7 (3)	Nd1—O4—H8	132 (5)
O2iii—Nd1—O1i	147.2 (2)	Nd1—O4—H9	121 (5)
O2—Nd1—O1i	99.8 (2)	H8—O4—H9	104 (3)
O2iii—Nd1—O1ii	99.8 (2)	C6—O1—Nd1i	140.4 (5)
O2—Nd1—O1ii	147.2 (2)	C6—O2—Nd1	147.2 (5)
O1i—Nd1—O1ii	82.1 (3)	Nd1—O3—H6	115 (5)
O2iii—Nd1—O4iii	78.0 (2)	Nd1—O3—H7	127 (5)
O2—Nd1—O4iii	69.63 (19)	H6—O3—H7	103 (3)
O1i—Nd1—O4iii	80.7 (2)	O1—C6—O2	125.9 (7)
O1ii—Nd1—O4iii	141.9 (2)	O1—C6—C3	116.9 (7)
O2iii—Nd1—O4	69.63 (19)	O2—C6—C3	117.2 (7)
O2—Nd1—O4	78.0 (2)	C2—C3—C4	116.8 (8)
O1i—Nd1—O4	141.9 (2)	C2—C3—C6	121.8 (7)
O1ii—Nd1—O4	80.7 (2)	C4—C3—C6	121.4 (7)
O4iii—Nd1—O4	131.0 (3)	C1—C2—C3	120.2 (8)
O2iii—Nd1—O3iii	140.41 (19)	C1—C2—H2	119.9
O2—Nd1—O3iii	68.36 (19)	C3—C2—H2	119.9
O1i—Nd1—O3iii	72.4 (2)	C5—C4—C3	119.1 (9)
O1ii—Nd1—O3iii	81.4 (2)	C5—C4—H4	120.4
O4iii—Nd1—O3iii	124.35 (18)	C3—C4—H4	120.4
O4—Nd1—O3iii	71.60 (19)	C5—N1—C1	118.5 (7)
O2iii—Nd1—O3	68.36 (19)	N1—C5—C4	123.2 (8)
O2—Nd1—O3	140.41 (19)	N1—C5—H5	118.4
O1i—Nd1—O3	81.4 (2)	C4—C5—H5	118.4
O1ii—Nd1—O3	72.4 (2)	N1—C1—C2	122.0 (9)
O4iii—Nd1—O3	71.60 (19)	N1—C1—H1	119.0
O4—Nd1—O3	124.35 (18)	C2—C1—H1	119.0
O3iii—Nd1—O3	145.1 (3)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H6···Cl2iv	0.95 (6)	2.29 (6)	3.211 (7)	163 (6)
O3—H7···N1v	0.97 (4)	1.72 (4)	2.685 (10)	174 (9)
O4—H8···Cl2i	0.96 (4)	2.15 (5)	3.041 (6)	155 (6)
O4—H9···O3vi	0.95 (2)	1.93 (3)	2.841 (8)	160 (8)

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