catena-Poly­[[[di­aqua­lanthanum(III)]-tri-μ-glycinato] trichloride monohydrate]

The title complex, [La(C₂H₅NO₂)₃(H₂O)₂]Cl₃·H₂O or [La(gly)₃(H₂O)₂]Cl₃·H₂O, is a one-dimensional coordination polymer. Its basic repeat unit contains three glycine mol­ecules in the zwitterion form and two coordinated water mol­ecules. Three carboxyl moieties of the three glycine mol­ecules serve as bridging groups, which connect the neighbouring La^III ions. The coordination number of lanthanum is nine. Intermolecular hydrogen bonds, involving water mol­ecules and chloride ions, form a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.032
• wR factor = 0.086
• Data-to-parameter ratio = 16.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               3168
         Count of symmetry unique reflns         1895
         Completeness (_total/calc)            167.18%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1273
         Fraction of Friedel pairs measured     0.672
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

S1. Comment

Lanthanide ions are often used as spectroscopic probes of Ca²⁺ in studies of biological systems, as well as dyeing promoters in the wool dyeing industry, and diagnostic agents in clinical medicine (Brittain et al., 1978; Brittain, 1979; Fang et al., 1987; Lauffer et al., 1987). In order to obtain a deeper understanding of the interactions between lanthanide ions and biological tissue, studies of the bonding modes and structures of lanthanide complexes with some amino acids have been carried out. Studies on the coordination behaviour of rare-earth salts with some amino acids in water have been carried out using the semimicro method of phase-equilibrium study. Many studies on these complexes in the solid state have also appeared (Gao et al., 1993; Dang et al., 1995; Jiang et al., 1993; Chen et al., 1886). The present paper reports the crystal structure of the title compound, (I).

Compound (I) is a one-dimensional chain complex of infinite length along the a axis (Figs. 2 and 3). Its basic repeat unit, [La(gly)₃(H₂O)₂]Cl₃·H₂O, consist of three glycine molecules in the zwitterion form, two coordinated water molecules, three free chloride ions and one water molecule of crystallization (Fig. 1). The three carboxyl groups from the three glycine molecules serve as bridging groups, which connect neighboring La atoms. The La···La distance is 4.798 (4) Å, showing that there is no direct metal–metal bond between the La atoms. The coordination number of La is nine and the coordination polyhedron can be approximated by a distorted trigonal prism (Fig. 2). The La—O bond lengths are in the range 2.419 (4)–2.908 (4) Å, and the average bond length is 2.576 (4) Å (Table 1).

There are two intramolecular hydrogen bonds and 14 intermolecular hydrogen bonds (Table 2). The three free Cl^- anions are located in the neighborhood of the –NH³⁺ groups of the coordinated glycine molecules and form N—H···Cl hydrogen bonds with an average N···O distance of 3.123 (4) Å. The average hydrogen-bond length for water–water (O—H···O) is 2.805 (4) Å. The average hydrogen bond lengths for O—H···Cl and N—H···Cl are 3.147 (4) and 2.757 (4) Å, respectively. These hydrogen bonds produce a three-dimensional network in the crystal (Fig. 3).

S2. Experimental

All chemicals were of reagent grade and were used without further purification. The title complex was prepared based on phase equilibrium data. LaCl₃·6H₂O and glycinic acid are dissolved in water (molar ratio 1: 3), the colourless crystals of (I) were obtained by slow evaporation of the above aqueous solution (pH = 4–5) at room temperature. Its metal composition was determined by titration with edta using xylenol orange as the end point indicator.

S3. Refinement

The achiral title compound crystallizes in a chiral space group. All the H atoms were placed in geometrically calculated positions, with N—H = 0.89 Å and C—H = 0.97 Å (except for the water H atoms, which were found in difference maps) and refined as riding atoms, with U_iso(H) = 1.2–1.5U_eq(parent atom).

Computing details

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

Figures

	Fig. 1. View of the basic repeating unit of (I).
	Fig. 2. View of the one-dimensional chain complex of infinite length in (I).
	Fig. 3. View of the packing form along a axis and the hydrogen-bond network for (I).

catena-Poly[[[diaqualanthanum(III)]-tri-µ-glycinato] trichloride monohydrate]

Crystal data

[La(C2H5NO2)3(H2O)2]Cl3·H2O	F(000) = 1032
Mr = 524.52	Dx = 1.938 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 4.798 (1) Å	θ = 2.2–12.8°
b = 12.094 (1) Å	µ = 2.86 mm^−1
c = 30.974 (2) Å	T = 293 K
V = 1797.3 (4) Å^3	Prism, colourless
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection

Siemens P4 diffractometer	3145 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.074
Graphite monochromator	θmax = 25.0°, θmin = 1.3°
ω scans	h = −5→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
Tmin = 0.509, Tmax = 0.566	l = 0→36
3172 measured reflections	3 standard reflections every 100 reflections
3168 independent reflections	intensity decay: 2.2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.01P)^2 + 0.35P] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
3172 reflections	Δρmax = 0.60 e Å^−3
196 parameters	Δρmin = −0.74 e Å^−3
0 restraints	Absolute structure: (Flack, 1983), 1274 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.0012 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
La1	0.51428 (5)	0.836846 (18)	0.621733 (7)	0.01291 (5)
C1	0.0107 (12)	0.7847 (4)	0.70260 (14)	0.0221 (2)
C2	−0.0368 (12)	0.7659 (4)	0.75082 (14)	0.0222 (3)
H2A	0.0762	0.7046	0.7609	0.027*
H2B	0.0147	0.8315	0.7670	0.027*
C3	0.0098 (11)	0.6395 (3)	0.60684 (13)	0.0199 (2)
C4	−0.1170 (10)	0.5296 (4)	0.61807 (16)	0.0205 (3)
H4A	−0.1963	0.4970	0.5922	0.025*
H4B	−0.2671	0.5409	0.6386	0.025*
C5	−0.0753 (10)	1.0132 (4)	0.58891 (15)	0.0194 (2)
C6	0.0924 (11)	1.1141 (4)	0.57406 (15)	0.0219 (2)
H6A	0.1985	1.1433	0.5982	0.026*
H6B	0.2229	1.0921	0.5517	0.026*
N1	−0.3374 (9)	0.7410 (3)	0.75718 (14)	0.0219 (2)
H1A	−0.4102	0.7892	0.7757	0.033*
H1B	−0.3560	0.6728	0.7676	0.033*
H1C	−0.4260	0.7460	0.7320	0.033*
N2	0.0925 (9)	0.4503 (3)	0.63720 (12)	0.0209 (4)
H2C	0.2535	0.4563	0.6231	0.031*
H2D	0.0288	0.3814	0.6348	0.031*
H2E	0.1186	0.4664	0.6649	0.031*
N3	−0.0928 (9)	1.2001 (3)	0.55727 (14)	0.0232 (4)
H3A	−0.2072	1.1708	0.5378	0.035*
H3B	0.0083	1.2532	0.5450	0.035*
H3C	−0.1922	1.2285	0.5788	0.035*
O1	0.2602 (8)	0.8109 (3)	0.69456 (11)	0.0222 (3)
O2	−0.1720 (8)	0.7656 (3)	0.67616 (10)	0.0233 (4)
O3	0.2616 (7)	0.6563 (3)	0.61453 (10)	0.0199 (3)
O4	−0.1519 (7)	0.7054 (3)	0.58806 (11)	0.0207 (4)
O5	0.0567 (7)	0.9367 (3)	0.60643 (10)	0.0215 (3)
O6	−0.3329 (7)	1.0120 (3)	0.58153 (10)	0.0190 (4)
O7	0.5703 (9)	1.0023 (3)	0.67305 (11)	0.0376 (6)
H7A	0.5982	0.9791	0.6986	0.045*
H7B	0.7089	1.0408	0.6649	0.045*
O8	0.4215 (7)	0.8183 (3)	0.53953 (10)	0.0191 (6)
H8A	0.5122	0.7531	0.5288	0.023*
H8B	0.4936	0.8821	0.5249	0.023*
Cl3	0.3642 (3)	0.75681 (10)	0.85047 (4)	0.0288 (3)
Cl2	0.8645 (3)	0.12101 (11)	0.45879 (4)	0.0327 (3)
O9	0.9272 (7)	0.8869 (3)	0.49882 (11)	0.0243 (9)
H9A	1.0286	0.9393	0.5082	0.029*
H9B	0.8343	0.9137	0.4779	0.029*
Cl1	0.5663 (4)	0.00902 (12)	0.77496 (5)	0.0504 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.01268 (10)	0.01056 (10)	0.01550 (11)	−0.00064 (11)	−0.00011 (11)	0.00245 (9)
C1	0.0260 (4)	0.0237 (5)	0.0165 (4)	−0.0015 (4)	0.0004 (3)	0.0023 (4)
C2	0.0271 (5)	0.0216 (5)	0.0180 (4)	−0.0004 (5)	0.0010 (4)	0.0028 (5)
C3	0.0237 (4)	0.0156 (4)	0.0205 (5)	−0.0039 (4)	−0.0036 (4)	0.0003 (4)
C4	0.0222 (5)	0.0169 (4)	0.0224 (6)	−0.0039 (4)	−0.0043 (5)	0.0007 (5)
C5	0.0232 (4)	0.0148 (4)	0.0201 (5)	0.0061 (4)	0.0021 (4)	0.0027 (4)
C6	0.0266 (4)	0.0167 (4)	0.0223 (4)	0.0027 (4)	0.0021 (4)	0.0033 (4)
N1	0.0266 (4)	0.0167 (4)	0.0223 (4)	0.0027 (4)	0.0021 (4)	0.0033 (4)
N2	0.0222 (8)	0.0168 (6)	0.0237 (8)	−0.0037 (6)	−0.0037 (7)	0.0012 (6)
N3	0.0284 (7)	0.0152 (6)	0.0260 (8)	0.0027 (6)	0.0019 (7)	0.0034 (6)
O1	0.0254 (5)	0.0233 (6)	0.0179 (4)	−0.0006 (6)	0.0019 (4)	0.0027 (5)
O2	0.0266 (6)	0.0243 (8)	0.0190 (6)	−0.0006 (7)	−0.0012 (5)	0.0013 (7)
O3	0.0249 (5)	0.0133 (4)	0.0214 (6)	−0.0044 (4)	−0.0041 (6)	0.0023 (4)
O4	0.0246 (6)	0.0181 (6)	0.0196 (7)	−0.0023 (6)	−0.0022 (6)	0.0017 (6)
O5	0.0242 (5)	0.0179 (5)	0.0224 (6)	0.0076 (5)	0.0024 (5)	0.0051 (5)
O6	0.0227 (5)	0.0143 (7)	0.0198 (7)	0.0059 (5)	0.0025 (6)	0.0009 (7)
O7	0.0650 (14)	0.0302 (8)	0.0177 (9)	−0.0239 (10)	−0.0025 (10)	−0.0059 (6)
O8	0.0310 (15)	0.0085 (11)	0.0179 (5)	−0.0022 (11)	−0.0008 (8)	−0.0019 (6)
O9	0.024 (2)	0.0201 (16)	0.0292 (17)	−0.0022 (14)	−0.0053 (16)	−0.0011 (15)
Cl1	0.0898 (13)	0.0291 (7)	0.0323 (7)	0.0129 (9)	−0.0126 (9)	−0.0039 (6)
Cl2	0.0433 (8)	0.0222 (6)	0.0325 (6)	0.0103 (6)	−0.0069 (7)	−0.0009 (6)
Cl3	0.0473 (8)	0.0216 (6)	0.0175 (5)	0.0080 (6)	0.0056 (6)	0.0015 (5)

Geometric parameters (Å, º)

La1—O3	2.507 (3)	C5—O5	1.246 (6)
La1—O5	2.550 (3)	C5—O6	1.257 (6)
La1—O7	2.570 (4)	C5—C6	1.533 (7)
La1—O1	2.583 (3)	C6—N3	1.463 (6)
La1—O8	2.594 (3)	C6—H6A	0.9700
La1—O6^i	2.565 (3)	C6—H6B	0.9700
La1—O2^i	2.419 (4)	N1—H1A	0.8900
La1—O4^i	2.486 (3)	N1—H1B	0.8900
La1—O5^i	2.908 (4)	N1—H1C	0.8900
C1—O2	1.222 (6)	N2—H2C	0.8900
C1—O1	1.263 (7)	N2—H2D	0.8900
C1—C2	1.528 (6)	N2—H2E	0.8900
C2—N1	1.486 (7)	N3—H3A	0.8900
C2—H2A	0.9700	N3—H3B	0.8900
C2—H2B	0.9700	N3—H3C	0.8900
C3—O3	1.248 (6)	O7—H7A	0.8497
C3—O4	1.255 (6)	O7—H7B	0.8501
C3—C4	1.503 (6)	O8—H8A	0.9600
C4—N2	1.510 (6)	O8—H8B	0.9600
C4—H4A	0.9700	O9—H9A	0.8499
C4—H4B	0.9700	O9—H9B	0.8499
O2^i—La1—O4^i	70.35 (12)	N1—C2—H2B	110.2
O2^i—La1—O3	93.03 (12)	C1—C2—H2B	110.2
O4^i—La1—O3	73.59 (11)	H2A—C2—H2B	108.5
O2^i—La1—O5	146.51 (11)	O3—C3—O4	125.7 (4)
O4^i—La1—O5	141.22 (10)	O3—C3—C4	119.4 (4)
O3—La1—O5	88.82 (11)	O4—C3—C4	114.7 (4)
O2^i—La1—O6^i	117.05 (12)	C3—C4—N2	112.5 (4)
O4^i—La1—O6^i	98.06 (11)	C3—C4—H4A	109.1
O3—La1—O6^i	144.53 (10)	N2—C4—H4A	109.1
O5—La1—O6^i	76.40 (10)	C3—C4—H4B	109.1
O2^i—La1—O7	77.35 (13)	N2—C4—H4B	109.1
O4^i—La1—O7	133.63 (13)	H4A—C4—H4B	107.8
O3—La1—O7	141.60 (12)	O5—C5—O6	124.8 (5)
O5—La1—O7	80.58 (12)	O5—C5—C6	117.1 (4)
O6^i—La1—O7	68.11 (11)	O6—C5—C6	118.0 (4)
O2^i—La1—O1	69.01 (12)	N3—C6—C5	110.7 (4)
O4^i—La1—O1	126.36 (11)	N3—C6—H6A	109.5
O3—La1—O1	75.17 (11)	C5—C6—H6A	109.5
O5—La1—O1	79.25 (11)	N3—C6—H6B	109.5
O6^i—La1—O1	131.23 (11)	C5—C6—H6B	109.5
O7—La1—O1	66.64 (12)	H6A—C6—H6B	108.1
O2^i—La1—O8	139.47 (11)	C2—N1—H1A	109.5
O4^i—La1—O8	69.12 (11)	C2—N1—H1B	109.5
O3—La1—O8	75.78 (10)	H1A—N1—H1B	109.5
O5—La1—O8	73.19 (10)	C2—N1—H1C	109.5
O6^i—La1—O8	69.14 (10)	H1A—N1—H1C	109.5
O7—La1—O8	133.81 (11)	H1B—N1—H1C	109.5
O1—La1—O8	139.96 (11)	C4—N2—H2C	109.5
O2^i—La1—O5^i	72.80 (11)	C4—N2—H2D	109.5
O4^i—La1—O5^i	67.69 (10)	H2C—N2—H2D	109.5
O3—La1—O5^i	141.24 (10)	C4—N2—H2E	109.5
O5—La1—O5^i	122.94 (12)	H2C—N2—H2E	109.5
O6^i—La1—O5^i	47.31 (10)	H2D—N2—H2E	109.5
O7—La1—O5^i	71.58 (12)	C6—N3—H3A	109.5
O1—La1—O5^i	127.95 (10)	C6—N3—H3B	109.5
O8—La1—O5^i	91.69 (10)	H3A—N3—H3B	109.5
O2^i—La1—C5^i	94.52 (13)	C6—N3—H3C	109.5
O4^i—La1—C5^i	83.80 (12)	H3A—N3—H3C	109.5
O3—La1—C5^i	152.12 (11)	H3B—N3—H3C	109.5
O5—La1—C5^i	99.30 (11)	C1—O1—La1	130.5 (3)
O6^i—La1—C5^i	23.60 (12)	C3—O3—La1	128.8 (3)
O7—La1—C5^i	66.27 (12)	H8A—O8—H8B	109.5
O1—La1—C5^i	132.44 (12)	H9A—O9—H9B	106.0
O8—La1—C5^i	81.11 (11)	La1—O7—H7A	109.6
O5^i—La1—C5^i	23.82 (11)	La1—O7—H7B	109.0
O2—C1—O1	126.5 (4)	La1—O8—H8A	109.4
O2—C1—C2	121.3 (5)	La1—O8—H8B	109.5
O1—C1—C2	111.8 (4)	H7A—O7—H7B	109.5
N1—C2—C1	107.7 (4)	H8A—O8—H8B	109.5
N1—C2—H2A	110.2	H9A—O9—H9B	106.0
C1—C2—H2A	110.2

Symmetry code: (i) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl3^ii	0.89	2.59	3.231 (4)	130
N1—H1A···Cl1^iii	0.89	2.66	3.320 (4)	132
N1—H1B···Cl1^iv	0.89	2.59	3.173 (5)	124
N1—H1C···O1^ii	0.89	2.06	2.864 (6)	150
N1—H1C···O2	0.89	2.13	2.649 (5)	117
N2—H2C···Cl2^v	0.89	2.76	3.360 (4)	126
N2—H2D···Cl3^vi	0.89	2.46	3.228 (4)	145
N2—H2E···Cl1^vii	0.89	2.45	3.254 (4)	150
N3—H3A···Cl2^iii	0.89	2.54	3.203 (4)	132
N3—H3B···Cl2^viii	0.89	2.29	3.122 (5)	155
N3—H3C···Cl3^iv	0.89	2.36	3.214 (4)	160
O7—H7A···Cl1^ix	0.85	2.40	3.158 (4)	149
O7—H7B···Cl3^vii	0.85	2.68	3.179 (4)	119
O8—H8A···O9^viii	0.96	1.94	2.752 (5)	141
O8—H8B···O9	0.96	2.23	2.858 (5)	122
O9—H9B···Cl2^ix	0.85	2.58	3.105 (4)	121

Symmetry codes: (ii) x−1, y, z; (iii) x−1, y+1, z; (iv) −x, y+1/2, −z+3/2; (v) x−1/2, −y+1/2, −z+1; (vi) −x, y−1/2, −z+3/2; (vii) −x+1, y+1/2, −z+3/2; (viii) x−1/2, −y+3/2, −z+1; (ix) x, y+1, z.