Literature DB >> 22259311

Redetermination of LaZn(5) based on single crystal X-ray diffraction data.

Igor Oshchapovsky, Oksana Zelinska, Beata Rozdzynska-Kielbik, Volodymyr Pavlyuk.

Abstract

The crystal structure of the already known binary title compound LaZn(5) (lanthanum penta-zinc) (space group P6/mmm, Pearson symbol hP6, CaCu(5) structure type) has been redetermined from single-crystal X-ray diffraction data. In contrast to previous determinations based on X-ray powder data [Nowotny (1942). Z. Metallkd.34, 247-253; de Negri et al. (2008). Inter-metallics, 16, 168-178], where unit-cell parameters and assignment of the structure type were reported, the present study reveals anisotropic displacement parameters for all atoms. The crystal structure consists of three crytallographically distinct atoms. The La atom (Wyckoff site 1a, site symmetry 6/mmm) is surrounded by 18 Zn atoms and two La atoms. The coordination polyhedron around one of the Zn atoms (Wyckoff site 2c, site symmetry -6m2) is an icosa-hedron made up from three La and nine Zn atoms. The other Zn atom (Wyckoff site 3g, site symmetry mmm) is surrounded by four La and eight Zn atoms. Bonding between atoms is explored by means of the TB-LMTO-ASA (tight-binding linear muffin-tin orbital atomic spheres approximation) program package. The positive charge density is localized around La atoms, and the negative charge density is around Zn atoms, with weak covalent bonding between the latter.

Entities: CellLine Chemical Disease Gene

Year: 2011 PMID： 22259311 PMCID： PMC3254268 DOI： 10.1107/S1600536811050987

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For previous structural studies of the title compound, see: de Negri et al. (2008 ▶); Nowotny (1942 ▶). For general background, see: Andersen et al. (1986 ▶); Berche et al. (2009 ▶); Oshchapovsky et al. (2011 ▶); Pavlyuk et al. (2009 ▶); Zelinska et al. (2004 ▶).

Experimental

Crystal data

LaZn5 M = 465.86 Hexagonal, a = 5.4654 (17) Å c = 4.2574 (15) Å V = 110.13 (6) Å3 Z = 1 Mo Kα radiation μ = 36.05 mm−1 T = 296 K 0.04 × 0.02 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.410, T max = 0.478 1123 measured reflections 73 independent reflections 62 reflections with I > 2σ(I) R int = 0.069

Refinement

R[F 2 > 2σ(F 2)] = 0.018 wR(F 2) = 0.037 S = 1.17 73 reflections 9 parameters Δρmax = 1.11 e Å−3 Δρmin = −0.71 e Å−3 Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶) and VESTA (Momma & Izumi, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811050987/wm2565sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050987/wm2565Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

LaZn₅	D_x = 7.024 Mg m⁻³
M_r = 465.86	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6/mmm	Cell parameters from 1123 reflections
Hall symbol: -P 6 2	θ = 4.3–27.5°
a = 5.4654 (17) Å	µ = 36.05 mm⁻¹
c = 4.2574 (15) Å	T = 296 K
V = 110.13 (6) Å³	Irregular shape, metallic grey
Z = 1	0.04 × 0.02 × 0.02 mm
F(000) = 207

Bruker APEXII CCD diffractometer	73 independent reflections
Radiation source: fine-focus sealed tube	62 reflections with I > 2σ(I)
graphite	R_int = 0.069
φ and ω scans	θ_max = 27.5°, θ_min = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→7
T_min = 0.410, T_max = 0.478	k = −6→7
1123 measured reflections	l = −5→5

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)] = 0.018	w = 1/[σ²(F_o²) + (0.P)² + 0.1413P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.037	(Δ/σ)_max < 0.001
S = 1.17	Δρ_max = 1.11 e Å⁻³
73 reflections	Δρ_min = −0.71 e Å⁻³
9 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.022 (4)
0 constraints

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	U_iso*/U_eq
La1	0.0000	0.0000	0.0000	0.0099 (4)
Zn1	0.3333	0.6667	0.0000	0.0124 (4)
Zn2	0.5000	1.0000	0.5000	0.0121 (4)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0106 (4)	0.0106 (4)	0.0085 (6)	0.0053 (2)	0.000	0.000
Zn1	0.0146 (5)	0.0146 (5)	0.0081 (8)	0.0073 (3)	0.000	0.000
Zn2	0.0162 (5)	0.0104 (6)	0.0079 (6)	0.0052 (3)	0.000	0.000

La1—Zn1ⁱ	3.1554 (10)	Zn1—Zn2^xiii	2.6496 (7)
La1—Zn1ⁱⁱ	3.1554 (10)	Zn1—Zn1ⁱ	3.1554 (10)
La1—Zn1ⁱⁱⁱ	3.1554 (10)	Zn1—La1^xiv	3.1555 (10)
La1—Zn1	3.1555 (10)	Zn1—La1^xv	3.1555 (10)
La1—Zn1^iv	3.1555 (10)	Zn1—Zn1^xvi	3.1555 (10)
La1—Zn1^v	3.1555 (10)	Zn1—Zn1^v	3.1555 (10)
La1—Zn2^vi	3.4640 (8)	Zn2—Zn1^xvii	2.6496 (7)
La1—Zn2^vii	3.4640 (8)	Zn2—Zn1^xvi	2.6496 (7)
La1—Zn2^viii	3.4640 (8)	Zn2—Zn1^xviii	2.6496 (7)
La1—Zn2^ix	3.4640 (8)	Zn2—Zn2^xix	2.7327 (8)
La1—Zn2^iv	3.4640 (8)	Zn2—Zn2^viii	2.7327 (8)
La1—Zn2^x	3.4640 (8)	Zn2—Zn2^xx	2.7327 (8)
Zn1—Zn2^xi	2.6496 (7)	Zn2—Zn2^vi	2.7327 (8)
Zn1—Zn2	2.6496 (7)	Zn2—La1^xxi	3.4640 (8)
Zn1—Zn2^viii	2.6496 (7)	Zn2—La1^xiv	3.4640 (8)
Zn1—Zn2^xii	2.6496 (7)	Zn2—La1^xv	3.4640 (8)
Zn1—Zn2^vi	2.6496 (7)	Zn2—La1^xxii	3.4640 (8)

Zn1ⁱ—La1—Zn1ⁱⁱ	120.0	Zn2^xiii—Zn1—La1^xv	72.679 (6)
Zn1ⁱ—La1—Zn1ⁱⁱⁱ	180.0	Zn1ⁱ—Zn1—La1^xv	60.0
Zn1ⁱⁱ—La1—Zn1ⁱⁱⁱ	60.0	La1^xiv—Zn1—La1^xv	120.0
Zn1ⁱ—La1—Zn1	60.0	Zn2^xi—Zn1—La1	72.679 (6)
Zn1ⁱⁱ—La1—Zn1	180.0	Zn2—Zn1—La1	126.545 (13)
Zn1ⁱⁱⁱ—La1—Zn1	120.0	Zn2^viii—Zn1—La1	72.679 (6)
Zn1ⁱ—La1—Zn1^iv	60.0	Zn2^xii—Zn1—La1	126.545 (13)
Zn1ⁱⁱ—La1—Zn1^iv	60.0	Zn2^vi—Zn1—La1	72.679 (5)
Zn1ⁱⁱⁱ—La1—Zn1^iv	120.0	Zn2^xiii—Zn1—La1	72.679 (6)
Zn1—La1—Zn1^iv	120.0	Zn1ⁱ—Zn1—La1	60.0
Zn1ⁱ—La1—Zn1^v	120.0	La1^xiv—Zn1—La1	120.0
Zn1ⁱⁱ—La1—Zn1^v	120.0	La1^xv—Zn1—La1	120.0
Zn1ⁱⁱⁱ—La1—Zn1^v	60.0	Zn2^xi—Zn1—Zn1^xvi	107.321 (5)
Zn1—La1—Zn1^v	60.0	Zn2—Zn1—Zn1^xvi	53.455 (13)
Zn1^iv—La1—Zn1^v	180.0	Zn2^viii—Zn1—Zn1^xvi	107.321 (6)
Zn1ⁱ—La1—Zn2^vi	46.905 (10)	Zn2^xii—Zn1—Zn1^xvi	53.455 (13)
Zn1ⁱⁱ—La1—Zn2^vi	133.095 (10)	Zn2^vi—Zn1—Zn1^xvi	107.321 (6)
Zn1ⁱⁱⁱ—La1—Zn2^vi	133.095 (10)	Zn2^xiii—Zn1—Zn1^xvi	107.321 (6)
Zn1—La1—Zn2^vi	46.906 (10)	Zn1ⁱ—Zn1—Zn1^xvi	120.0
Zn1^iv—La1—Zn2^vi	90.0	La1^xiv—Zn1—Zn1^xvi	60.0
Zn1^v—La1—Zn2^vi	90.0	La1^xv—Zn1—Zn1^xvi	60.0
Zn1ⁱ—La1—Zn2^vii	133.095 (10)	La1—Zn1—Zn1^xvi	180.0
Zn1ⁱⁱ—La1—Zn2^vii	46.905 (10)	Zn2^xi—Zn1—Zn1^v	53.455 (13)
Zn1ⁱⁱⁱ—La1—Zn2^vii	46.905 (10)	Zn2—Zn1—Zn1^v	107.321 (5)
Zn1—La1—Zn2^vii	133.094 (10)	Zn2^viii—Zn1—Zn1^v	53.455 (13)
Zn1^iv—La1—Zn2^vii	90.0	Zn2^xii—Zn1—Zn1^v	107.321 (6)
Zn1^v—La1—Zn2^vii	90.0	Zn2^vi—Zn1—Zn1^v	107.321 (6)
Zn2^vi—La1—Zn2^vii	180.0	Zn2^xiii—Zn1—Zn1^v	107.321 (6)
Zn1ⁱ—La1—Zn2^viii	90.0	Zn1ⁱ—Zn1—Zn1^v	120.0
Zn1ⁱⁱ—La1—Zn2^viii	133.094 (9)	La1^xiv—Zn1—Zn1^v	60.0
Zn1ⁱⁱⁱ—La1—Zn2^viii	90.0	La1^xv—Zn1—Zn1^v	180.0
Zn1—La1—Zn2^viii	46.906 (10)	La1—Zn1—Zn1^v	60.0
Zn1^iv—La1—Zn2^viii	133.094 (10)	Zn1^xvi—Zn1—Zn1^v	120.0
Zn1^v—La1—Zn2^viii	46.906 (10)	Zn1—Zn2—Zn1^xvii	180.0
Zn2^vi—La1—Zn2^viii	46.463 (8)	Zn1—Zn2—Zn1^xvi	73.09 (3)
Zn2^vii—La1—Zn2^viii	133.537 (8)	Zn1^xvii—Zn2—Zn1^xvi	106.91 (3)
Zn1ⁱ—La1—Zn2^ix	90.0	Zn1—Zn2—Zn1^xviii	106.91 (3)
Zn1ⁱⁱ—La1—Zn2^ix	46.906 (9)	Zn1^xvii—Zn2—Zn1^xviii	73.09 (3)
Zn1ⁱⁱⁱ—La1—Zn2^ix	90.0	Zn1^xvi—Zn2—Zn1^xviii	180.0
Zn1—La1—Zn2^ix	133.094 (10)	Zn1—Zn2—Zn2^xix	121.043 (10)
Zn1^iv—La1—Zn2^ix	46.906 (10)	Zn1^xvii—Zn2—Zn2^xix	58.958 (10)
Zn1^v—La1—Zn2^ix	133.094 (10)	Zn1^xvi—Zn2—Zn2^xix	58.958 (10)
Zn2^vi—La1—Zn2^ix	133.537 (8)	Zn1^xviii—Zn2—Zn2^xix	121.042 (10)
Zn2^vii—La1—Zn2^ix	46.463 (8)	Zn1—Zn2—Zn2^viii	58.957 (10)
Zn2^viii—La1—Zn2^ix	180.0	Zn1^xvii—Zn2—Zn2^viii	121.042 (11)
Zn1ⁱ—La1—Zn2^iv	46.906 (9)	Zn1^xvi—Zn2—Zn2^viii	121.042 (10)
Zn1ⁱⁱ—La1—Zn2^iv	90.0	Zn1^xviii—Zn2—Zn2^viii	58.958 (10)
Zn1ⁱⁱⁱ—La1—Zn2^iv	133.094 (9)	Zn2^xix—Zn2—Zn2^viii	180.0
Zn1—La1—Zn2^iv	90.0	Zn1—Zn2—Zn2^xx	121.043 (10)
Zn1^iv—La1—Zn2^iv	46.906 (10)	Zn1^xvii—Zn2—Zn2^xx	58.957 (10)
Zn1^v—La1—Zn2^iv	133.094 (10)	Zn1^xvi—Zn2—Zn2^xx	58.957 (10)
Zn2^vi—La1—Zn2^iv	46.463 (8)	Zn1^xviii—Zn2—Zn2^xx	121.043 (10)
Zn2^vii—La1—Zn2^iv	133.537 (8)	Zn2^xix—Zn2—Zn2^xx	60.0
Zn2^viii—La1—Zn2^iv	86.189 (19)	Zn2^viii—Zn2—Zn2^xx	120.0
Zn2^ix—La1—Zn2^iv	93.811 (19)	Zn1—Zn2—Zn2^vi	58.957 (10)
Zn1ⁱ—La1—Zn2^x	133.094 (9)	Zn1^xvii—Zn2—Zn2^vi	121.043 (10)
Zn1ⁱⁱ—La1—Zn2^x	90.0	Zn1^xvi—Zn2—Zn2^vi	121.043 (10)
Zn1ⁱⁱⁱ—La1—Zn2^x	46.906 (9)	Zn1^xviii—Zn2—Zn2^vi	58.957 (10)
Zn1—La1—Zn2^x	90.0	Zn2^xix—Zn2—Zn2^vi	120.0
Zn1^iv—La1—Zn2^x	133.094 (10)	Zn2^viii—Zn2—Zn2^vi	60.0
Zn1^v—La1—Zn2^x	46.906 (10)	Zn2^xx—Zn2—Zn2^vi	180.0
Zn2^vi—La1—Zn2^x	133.537 (8)	Zn1—Zn2—La1^xxi	119.585 (15)
Zn2^vii—La1—Zn2^x	46.463 (8)	Zn1^xvii—Zn2—La1^xxi	60.416 (15)
Zn2^viii—La1—Zn2^x	93.811 (19)	Zn1^xvi—Zn2—La1^xxi	119.585 (15)
Zn2^ix—La1—Zn2^x	86.189 (19)	Zn1^xviii—Zn2—La1^xxi	60.415 (15)
Zn2^iv—La1—Zn2^x	180.0	Zn2^xix—Zn2—La1^xxi	66.768 (4)
Zn2^xi—Zn1—Zn2	145.358 (11)	Zn2^viii—Zn2—La1^xxi	113.232 (4)
Zn2^xi—Zn1—Zn2^viii	106.91 (3)	Zn2^xx—Zn2—La1^xxi	113.232 (4)
Zn2—Zn1—Zn2^viii	62.09 (2)	Zn2^vi—Zn2—La1^xxi	66.768 (4)
Zn2^xi—Zn1—Zn2^xii	62.09 (2)	Zn1—Zn2—La1^xiv	60.415 (15)
Zn2—Zn1—Zn2^xii	106.91 (3)	Zn1^xvii—Zn2—La1^xiv	119.584 (15)
Zn2^viii—Zn1—Zn2^xii	145.358 (11)	Zn1^xvi—Zn2—La1^xiv	60.415 (15)
Zn2^xi—Zn1—Zn2^vi	145.358 (11)	Zn1^xviii—Zn2—La1^xiv	119.585 (15)
Zn2—Zn1—Zn2^vi	62.09 (2)	Zn2^xix—Zn2—La1^xiv	113.232 (5)
Zn2^viii—Zn1—Zn2^vi	62.09 (2)	Zn2^viii—Zn2—La1^xiv	66.768 (4)
Zn2^xii—Zn1—Zn2^vi	145.358 (11)	Zn2^xx—Zn2—La1^xiv	66.768 (5)
Zn2^xi—Zn1—Zn2^xiii	62.09 (2)	Zn2^vi—Zn2—La1^xiv	113.232 (4)
Zn2—Zn1—Zn2^xiii	145.358 (11)	La1^xxi—Zn2—La1^xiv	180.0
Zn2^viii—Zn1—Zn2^xiii	145.358 (11)	Zn1—Zn2—La1^xv	60.415 (15)
Zn2^xii—Zn1—Zn2^xiii	62.09 (2)	Zn1^xvii—Zn2—La1^xv	119.585 (15)
Zn2^vi—Zn1—Zn2^xiii	106.91 (3)	Zn1^xvi—Zn2—La1^xv	60.416 (15)
Zn2^xi—Zn1—Zn1ⁱ	107.321 (6)	Zn1^xviii—Zn2—La1^xv	119.584 (15)
Zn2—Zn1—Zn1ⁱ	107.321 (6)	Zn2^xix—Zn2—La1^xv	66.768 (4)
Zn2^viii—Zn1—Zn1ⁱ	107.321 (6)	Zn2^viii—Zn2—La1^xv	113.232 (4)
Zn2^xii—Zn1—Zn1ⁱ	107.321 (6)	Zn2^xx—Zn2—La1^xv	113.232 (4)
Zn2^vi—Zn1—Zn1ⁱ	53.455 (13)	Zn2^vi—Zn2—La1^xv	66.768 (4)
Zn2^xiii—Zn1—Zn1ⁱ	53.455 (13)	La1^xxi—Zn2—La1^xv	75.84 (3)
Zn2^xi—Zn1—La1^xiv	72.679 (6)	La1^xiv—Zn2—La1^xv	104.16 (3)
Zn2—Zn1—La1^xiv	72.679 (6)	Zn1—Zn2—La1^xxii	119.585 (15)
Zn2^viii—Zn1—La1^xiv	72.679 (6)	Zn1^xvii—Zn2—La1^xxii	60.415 (15)
Zn2^xii—Zn1—La1^xiv	72.679 (6)	Zn1^xvi—Zn2—La1^xxii	119.584 (15)
Zn2^vi—Zn1—La1^xiv	126.545 (13)	Zn1^xviii—Zn2—La1^xxii	60.416 (15)
Zn2^xiii—Zn1—La1^xiv	126.545 (13)	Zn2^xix—Zn2—La1^xxii	113.232 (4)
Zn1ⁱ—Zn1—La1^xiv	180.0	Zn2^viii—Zn2—La1^xxii	66.768 (4)
Zn2^xi—Zn1—La1^xv	126.545 (13)	Zn2^xx—Zn2—La1^xxii	66.768 (4)
Zn2—Zn1—La1^xv	72.679 (6)	Zn2^vi—Zn2—La1^xxii	113.232 (4)
Zn2^viii—Zn1—La1^xv	126.545 (13)	La1^xxi—Zn2—La1^xxii	104.16 (3)
Zn2^xii—Zn1—La1^xv	72.679 (6)	La1^xiv—Zn2—La1^xxii	75.84 (3)
Zn2^vi—Zn1—La1^xv	72.679 (6)	La1^xv—Zn2—La1^xxii	180.0

3 in total

1 in total

1. Penta-lanthanum zinc diplumbide, La5Zn1-x Pb2+x (x ≃ 0.6).

Authors: Igor Oshchapovsky; Volodymyr Pavlyuk; Grygoriy Dmytriv; Bernd Harbrecht
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2013-12-18