Literature DB >> 22090807

LaZn(12.37 (1)), a zinc-deficient variant of the NaZn(13) structure type.

Igor Oshchapovsky, Volodymyr Pavlyuk, Grygoriy Dmytriv, Fraser White.

Abstract

The title compound (lanthanum dodecazinc), LaZn(12.37 (1)), is confirmed to be a nonstoichiometric (zinc-deficient) modification of the NaZn(13) structure type, in which one Zn atom (Wyckoff site 8b, site symmetry m[Formula: see text]) has a fractional site occupancy of 0.372 (11). The other Zn atom (96i, m) and the La atom (8a, 432) are fully occupied. The coordination polyhedra of the Zn atoms are distorted icosa-hedra, whereas the La atoms are surrounded by 24 Zn atoms, forming pseudo-Frank-Kasper polyhedra. Electronic structure calculations indicate that Zn-Zn bonding is much stronger than La-Zn bonding.

Entities: CellLine Chemical Disease Gene

Year: 2011 PMID： 22090807 PMCID： PMC3212105 DOI： 10.1107/S1600536811028893

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

Related literature

For general background to intermetallics, see: Berche et al. (2009 ▶); Oshchapovsky et al. (2010 ▶); Pavlyuk et al. (2009 ▶); Rolla & Iandelli (1941 ▶). For isotypic structures, see: Iandelli & Palenzona (1967 ▶); Kuz’ma et al. (1966 ▶); Veleckis et al. (1967 ▶). For electronic structure calculations with the TB-LMTO-ASA package, see: Andersen et al. (1986 ▶).

Experimental

Crystal data

LaZn12.37 M = 947.00 Cubic, a = 12.0940 (9) Å V = 1768.9 (2) Å3 Z = 8 Mo Kα radiation μ = 37.49 mm−1 T = 293 K 0.05 × 0.03 × 0.01 mm

Data collection

Agilent Gemini Ultra diffractometer with Eos CCD detector Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.368, T max = 1.0 1543 measured reflections 110 independent reflections 108 reflections with I > 2σ(I) R int = 0.122

Refinement

R[F 2 > 2σ(F 2)] = 0.024 wR(F 2) = 0.052 S = 1.22 110 reflections 12 parameters Δρmax = 0.81 e Å−3 Δρmin = −1.08 e Å−3 Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, New_Global_Publ_Block. DOI: 10.1107/S1600536811028893/hb5947sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028893/hb5947Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

LaZn_12.37	D_x = 7.113 Mg m⁻³
M_r = 947.00	Mo Kα radiation, λ = 0.71073 Å
Cubic, Fm3c	Cell parameters from 811 reflections
Hall symbol: -F 4c 2 3	θ = 3.4–28.9°
a = 12.0940 (9) Å	µ = 37.49 mm⁻¹
V = 1768.9 (2) Å³	T = 293 K
Z = 8	Irregular platelet, grey
F(000) = 3426.0	0.05 × 0.03 × 0.01 mm

Agilent Gemini Ultra diffractometer with Eos CCD detector	110 independent reflections
Radiation source: Enhance (Mo) X-ray Source	108 reflections with I > 2σ(I)
graphite	R_int = 0.122
ω scans	θ_max = 28.3°, θ_min = 3.4°
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2011)	h = −14→16
T_min = 0.368, T_max = 1.0	k = −16→16
1543 measured reflections	l = −9→16

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)] = 0.024	w = 1/[σ²(F_o²) + (0.0097P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.052	(Δ/σ)_max < 0.001
S = 1.22	Δρ_max = 0.81 e Å⁻³
110 reflections	Δρ_min = −1.08 e Å⁻³
12 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00058 (8)

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	Occ. (<1)
La1	0.2500	0.2500	0.2500	0.0081 (5)
Zn2	0.0000	0.17786 (6)	0.11938 (6)	0.0113 (4)
Zn3	0.0000	0.0000	0.0000	0.006 (2)	0.372 (11)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0081 (5)	0.0081 (5)	0.0081 (5)	0.000	0.000	0.000
Zn2	0.0120 (5)	0.0097 (5)	0.0123 (5)	0.000	0.000	0.0031 (3)
Zn3	0.006 (2)	0.006 (2)	0.006 (2)	0.000	0.000	0.000

La1—Zn2ⁱ	3.5211 (4)	Zn2—Zn2ⁱⁱ	2.6854 (8)
La1—Zn2ⁱⁱ	3.5211 (4)	Zn2—Zn2ⁱ	2.6854 (8)
La1—Zn2	3.5211 (4)	Zn2—Zn2^ix	2.6859 (12)
La1—Zn2ⁱⁱⁱ	3.5211 (4)	Zn2—Zn2^xv	2.6859 (12)
La1—Zn2^iv	3.5211 (4)	Zn2—Zn2^xvi	2.8875 (15)
La1—Zn2^v	3.5211 (4)	Zn2—La1^xvii	3.5211 (4)
La1—Zn2^vi	3.5211 (4)	Zn3—Zn2^xviii	2.5906 (7)
La1—Zn2^vii	3.5211 (4)	Zn3—Zn2^xix	2.5906 (7)
La1—Zn2^viii	3.5211 (4)	Zn3—Zn2^xx	2.5906 (7)
La1—Zn2^ix	3.5211 (4)	Zn3—Zn2ⁱ	2.5906 (7)
La1—Zn2^x	3.5211 (4)	Zn3—Zn2ⁱⁱ	2.5906 (7)
La1—Zn2^xi	3.5211 (4)	Zn3—Zn2^xiii	2.5906 (7)
Zn2—Zn2^xii	2.5522 (10)	Zn3—Zn2^xxi	2.5906 (7)
Zn2—Zn2^x	2.5522 (10)	Zn3—Zn2^xxii	2.5906 (7)
Zn2—Zn3	2.5906 (7)	Zn3—Zn2^xxiii	2.5906 (7)
Zn2—Zn2^xiii	2.6854 (8)	Zn3—Zn2^xvi	2.5906 (7)
Zn2—Zn2^xiv	2.6854 (8)	Zn3—Zn2^xiv	2.5906 (7)

Zn2ⁱ—La1—Zn2ⁱⁱ	44.832 (17)	Zn2ⁱⁱ—Zn2—Zn2^xv	161.98 (3)
Zn2ⁱ—La1—Zn2	44.832 (17)	Zn2ⁱ—Zn2—Zn2^xv	108.22 (3)
Zn2ⁱⁱ—La1—Zn2	44.832 (17)	Zn2^ix—Zn2—Zn2^xv	65.03 (3)
Zn2ⁱ—La1—Zn2ⁱⁱⁱ	163.67 (2)	Zn2^xii—Zn2—Zn2^xvi	106.09 (2)
Zn2ⁱⁱ—La1—Zn2ⁱⁱⁱ	128.82 (2)	Zn2^x—Zn2—Zn2^xvi	163.91 (2)
Zn2—La1—Zn2ⁱⁱⁱ	146.29 (2)	Zn3—Zn2—Zn2^xvi	56.130 (16)
Zn2ⁱ—La1—Zn2^iv	128.82 (2)	Zn2^xiii—Zn2—Zn2^xvi	57.477 (19)
Zn2ⁱⁱ—La1—Zn2^iv	146.29 (2)	Zn2^xiv—Zn2—Zn2^xvi	105.27 (2)
Zn2—La1—Zn2^iv	163.67 (2)	Zn2ⁱⁱ—Zn2—Zn2^xvi	105.27 (2)
Zn2ⁱⁱⁱ—La1—Zn2^iv	44.832 (17)	Zn2ⁱ—Zn2—Zn2^xvi	57.477 (19)
Zn2ⁱ—La1—Zn2^v	146.29 (2)	Zn2^ix—Zn2—Zn2^xvi	57.484 (14)
Zn2ⁱⁱ—La1—Zn2^v	163.67 (2)	Zn2^xv—Zn2—Zn2^xvi	57.484 (14)
Zn2—La1—Zn2^v	128.82 (2)	Zn2^xii—Zn2—La1	68.752 (6)
Zn2ⁱⁱⁱ—La1—Zn2^v	44.832 (17)	Zn2^x—Zn2—La1	68.752 (6)
Zn2^iv—La1—Zn2^v	44.832 (17)	Zn3—Zn2—La1	117.115 (12)
Zn2ⁱ—La1—Zn2^vi	119.133 (3)	Zn2^xiii—Zn2—La1	173.86 (2)
Zn2ⁱⁱ—La1—Zn2^vi	106.477 (13)	Zn2^xiv—Zn2—La1	122.82 (4)
Zn2—La1—Zn2^vi	151.31 (2)	Zn2ⁱⁱ—Zn2—La1	67.584 (9)
Zn2ⁱⁱⁱ—La1—Zn2^vi	44.84 (2)	Zn2ⁱ—Zn2—La1	67.584 (9)
Zn2^iv—La1—Zn2^vi	42.496 (13)	Zn2^ix—Zn2—La1	67.580 (12)
Zn2^v—La1—Zn2^vi	78.388 (9)	Zn2^xv—Zn2—La1	122.80 (3)
Zn2ⁱ—La1—Zn2^vii	151.31 (2)	Zn2^xvi—Zn2—La1	116.657 (11)
Zn2ⁱⁱ—La1—Zn2^vii	119.133 (3)	Zn2^xii—Zn2—La1^xvii	68.752 (6)
Zn2—La1—Zn2^vii	106.477 (13)	Zn2^x—Zn2—La1^xvii	68.752 (6)
Zn2ⁱⁱⁱ—La1—Zn2^vii	42.496 (13)	Zn3—Zn2—La1^xvii	117.115 (12)
Zn2^iv—La1—Zn2^vii	78.388 (9)	Zn2^xiii—Zn2—La1^xvii	67.584 (9)
Zn2^v—La1—Zn2^vii	44.84 (2)	Zn2^xiv—Zn2—La1^xvii	67.584 (9)
Zn2^vi—La1—Zn2^vii	86.486 (17)	Zn2ⁱⁱ—Zn2—La1^xvii	122.82 (4)
Zn2ⁱ—La1—Zn2^viii	106.477 (13)	Zn2ⁱ—Zn2—La1^xvii	173.86 (2)
Zn2ⁱⁱ—La1—Zn2^viii	151.31 (2)	Zn2^ix—Zn2—La1^xvii	122.80 (3)
Zn2—La1—Zn2^viii	119.133 (3)	Zn2^xv—Zn2—La1^xvii	67.580 (12)
Zn2ⁱⁱⁱ—La1—Zn2^viii	78.388 (9)	Zn2^xvi—Zn2—La1^xvii	116.657 (11)
Zn2^iv—La1—Zn2^viii	44.84 (2)	La1—Zn2—La1^xvii	118.34 (2)
Zn2^v—La1—Zn2^viii	42.496 (13)	Zn2^xviii—Zn3—Zn2^xix	62.436 (7)
Zn2^vi—La1—Zn2^viii	86.486 (17)	Zn2^xviii—Zn3—Zn2^xx	62.436 (7)
Zn2^vii—La1—Zn2^viii	86.486 (17)	Zn2^xix—Zn3—Zn2^xx	62.436 (7)
Zn2ⁱ—La1—Zn2^ix	42.496 (13)	Zn2^xviii—Zn3—Zn2	117.564 (7)
Zn2ⁱⁱ—La1—Zn2^ix	78.388 (9)	Zn2^xix—Zn3—Zn2	117.564 (7)
Zn2—La1—Zn2^ix	44.84 (2)	Zn2^xx—Zn3—Zn2	180.00 (3)
Zn2ⁱⁱⁱ—La1—Zn2^ix	151.31 (2)	Zn2^xviii—Zn3—Zn2ⁱ	180.00 (3)
Zn2^iv—La1—Zn2^ix	119.133 (3)	Zn2^xix—Zn3—Zn2ⁱ	117.564 (7)
Zn2^v—La1—Zn2^ix	106.477 (13)	Zn2^xx—Zn3—Zn2ⁱ	117.564 (7)
Zn2^vi—La1—Zn2^ix	146.29 (2)	Zn2—Zn3—Zn2ⁱ	62.436 (7)
Zn2^vii—La1—Zn2^ix	121.00 (2)	Zn2^xviii—Zn3—Zn2ⁱⁱ	117.564 (7)
Zn2^viii—La1—Zn2^ix	77.04 (2)	Zn2^xix—Zn3—Zn2ⁱⁱ	180.00 (3)
Zn2ⁱ—La1—Zn2^x	78.388 (9)	Zn2^xx—Zn3—Zn2ⁱⁱ	117.564 (7)
Zn2ⁱⁱ—La1—Zn2^x	44.84 (2)	Zn2—Zn3—Zn2ⁱⁱ	62.436 (7)
Zn2—La1—Zn2^x	42.496 (13)	Zn2ⁱ—Zn3—Zn2ⁱⁱ	62.436 (7)
Zn2ⁱⁱⁱ—La1—Zn2^x	106.477 (13)	Zn2^xviii—Zn3—Zn2^xiii	67.74 (3)
Zn2^iv—La1—Zn2^x	151.31 (2)	Zn2^xix—Zn3—Zn2^xiii	62.436 (7)
Zn2^v—La1—Zn2^x	119.133 (3)	Zn2^xx—Zn3—Zn2^xiii	117.564 (7)
Zn2^vi—La1—Zn2^x	121.00 (2)	Zn2—Zn3—Zn2^xiii	62.436 (7)
Zn2^vii—La1—Zn2^x	77.04 (2)	Zn2ⁱ—Zn3—Zn2^xiii	112.26 (3)
Zn2^viii—La1—Zn2^x	146.29 (2)	Zn2ⁱⁱ—Zn3—Zn2^xiii	117.564 (7)
Zn2^ix—La1—Zn2^x	86.486 (17)	Zn2^xviii—Zn3—Zn2^xxi	117.564 (7)
Zn2ⁱ—La1—Zn2^xi	44.84 (2)	Zn2^xix—Zn3—Zn2^xxi	67.74 (3)
Zn2ⁱⁱ—La1—Zn2^xi	42.496 (13)	Zn2^xx—Zn3—Zn2^xxi	62.436 (7)
Zn2—La1—Zn2^xi	78.388 (9)	Zn2—Zn3—Zn2^xxi	117.564 (7)
Zn2ⁱⁱⁱ—La1—Zn2^xi	119.133 (3)	Zn2ⁱ—Zn3—Zn2^xxi	62.436 (7)
Zn2^iv—La1—Zn2^xi	106.477 (13)	Zn2ⁱⁱ—Zn3—Zn2^xxi	112.26 (3)
Zn2^v—La1—Zn2^xi	151.31 (2)	Zn2^xiii—Zn3—Zn2^xxi	117.564 (7)
Zn2^vi—La1—Zn2^xi	77.04 (2)	Zn2^xviii—Zn3—Zn2^xxii	62.436 (7)
Zn2^vii—La1—Zn2^xi	146.29 (2)	Zn2^xix—Zn3—Zn2^xxii	117.564 (7)
Zn2^viii—La1—Zn2^xi	121.00 (2)	Zn2^xx—Zn3—Zn2^xxii	67.74 (3)
Zn2^ix—La1—Zn2^xi	86.486 (17)	Zn2—Zn3—Zn2^xxii	112.26 (3)
Zn2^x—La1—Zn2^xi	86.486 (17)	Zn2ⁱ—Zn3—Zn2^xxii	117.564 (7)
Zn2^xii—Zn2—Zn2^x	90.0	Zn2ⁱⁱ—Zn3—Zn2^xxii	62.436 (7)
Zn2^xii—Zn2—Zn3	162.22 (4)	Zn2^xiii—Zn3—Zn2^xxii	117.564 (7)
Zn2^x—Zn2—Zn3	107.78 (4)	Zn2^xxi—Zn3—Zn2^xxii	117.564 (7)
Zn2^xii—Zn2—Zn2^xiii	113.70 (3)	Zn2^xviii—Zn3—Zn2^xxiii	112.26 (3)
Zn2^x—Zn2—Zn2^xiii	116.33 (3)	Zn2^xix—Zn3—Zn2^xxiii	117.564 (7)
Zn3—Zn2—Zn2^xiii	58.782 (3)	Zn2^xx—Zn3—Zn2^xxiii	62.436 (7)
Zn2^xii—Zn2—Zn2^xiv	134.159 (17)	Zn2—Zn3—Zn2^xxiii	117.564 (7)
Zn2^x—Zn2—Zn2^xiv	61.64 (4)	Zn2ⁱ—Zn3—Zn2^xxiii	67.74 (3)
Zn3—Zn2—Zn2^xiv	58.782 (3)	Zn2ⁱⁱ—Zn3—Zn2^xxiii	62.436 (7)
Zn2^xiii—Zn2—Zn2^xiv	60.0	Zn2^xiii—Zn3—Zn2^xxiii	180.0
Zn2^xii—Zn2—Zn2ⁱⁱ	134.159 (17)	Zn2^xxi—Zn3—Zn2^xxiii	62.436 (7)
Zn2^x—Zn2—Zn2ⁱⁱ	61.64 (4)	Zn2^xxii—Zn3—Zn2^xxiii	62.436 (7)
Zn3—Zn2—Zn2ⁱⁱ	58.782 (3)	Zn2^xviii—Zn3—Zn2^xvi	117.564 (7)
Zn2^xiii—Zn2—Zn2ⁱⁱ	111.18 (2)	Zn2^xix—Zn3—Zn2^xvi	62.436 (7)
Zn2^xiv—Zn2—Zn2ⁱⁱ	65.05 (4)	Zn2^xx—Zn3—Zn2^xvi	112.26 (3)
Zn2^xii—Zn2—Zn2ⁱ	113.70 (3)	Zn2—Zn3—Zn2^xvi	67.74 (3)
Zn2^x—Zn2—Zn2ⁱ	116.33 (3)	Zn2ⁱ—Zn3—Zn2^xvi	62.436 (7)
Zn3—Zn2—Zn2ⁱ	58.782 (3)	Zn2ⁱⁱ—Zn3—Zn2^xvi	117.564 (7)
Zn2^xiii—Zn2—Zn2ⁱ	106.450 (14)	Zn2^xiii—Zn3—Zn2^xvi	62.436 (7)
Zn2^xiv—Zn2—Zn2ⁱ	111.18 (2)	Zn2^xxi—Zn3—Zn2^xvi	62.436 (7)
Zn2ⁱⁱ—Zn2—Zn2ⁱ	60.0	Zn2^xxii—Zn3—Zn2^xvi	180.0
Zn2^xii—Zn2—Zn2^ix	61.62 (4)	Zn2^xxiii—Zn3—Zn2^xvi	117.564 (7)
Zn2^x—Zn2—Zn2^ix	134.15 (2)	Zn2^xviii—Zn3—Zn2^xiv	62.436 (7)
Zn3—Zn2—Zn2^ix	103.88 (3)	Zn2^xix—Zn3—Zn2^xiv	112.26 (3)
Zn2^xiii—Zn2—Zn2^ix	108.22 (3)	Zn2^xx—Zn3—Zn2^xiv	117.564 (7)
Zn2^xiv—Zn2—Zn2^ix	161.98 (3)	Zn2—Zn3—Zn2^xiv	62.436 (7)
Zn2ⁱⁱ—Zn2—Zn2^ix	111.90 (3)	Zn2ⁱ—Zn3—Zn2^xiv	117.564 (7)
Zn2ⁱ—Zn2—Zn2^ix	56.74 (3)	Zn2ⁱⁱ—Zn3—Zn2^xiv	67.74 (3)
Zn2^xii—Zn2—Zn2^xv	61.62 (4)	Zn2^xiii—Zn3—Zn2^xiv	62.436 (7)
Zn2^x—Zn2—Zn2^xv	134.15 (2)	Zn2^xxi—Zn3—Zn2^xiv	180.00 (3)
Zn3—Zn2—Zn2^xv	103.88 (3)	Zn2^xxii—Zn3—Zn2^xiv	62.436 (7)
Zn2^xiii—Zn2—Zn2^xv	56.74 (3)	Zn2^xxiii—Zn3—Zn2^xiv	117.564 (7)
Zn2^xiv—Zn2—Zn2^xv	111.90 (3)	Zn2^xvi—Zn3—Zn2^xiv	117.564 (7)

1 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

1 in total

3 in total