Crystal structure characterization and electronic structure of a rare-earth-containing Zintl phase in the Yb–Al–Sb family: Yb₃AlSb₃

A rare-earth-containing com­pound, ytterbium aluminium anti­monide, Yb₃AlSb₃ (Ca₃AlAs₃-type structure), has been successfully synthesized within the Yb–Al–Sb system through flux methods. According to the Zintl formalism, this structure is nominally made up of (Yb²⁺)₃[(Al¹⁻)(1b – Sb²⁻)₂(2b – Sb¹⁻)], where 1b and 2b indicate 1-bonded and 2-bonded, respectively, and Al is treated as part of the covalent anionic network. The crystal structure features infinite corner-sharing AlSb₄ tetra­hedra, [AlSb₂Sb_2/2]⁶⁻, with Yb²⁺ cations residing between the tetra­hedra to provide charge balance. Herein, the synthetic con­ditions, the crystal structure determined from single-crystal X-ray diffraction data, and electronic structure calculations are reported.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker, 2016); software used to prepare material for publication: SHELXTL (Bruker, 2016) and XPREP (Sheldrick, 2008).

Ytterbium aluminium antimonide

Crystal data

AlSb3Yb3	Dx = 7.468 Mg m^−3
Mr = 911.35	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 9949 reflections
a = 12.803 (3) Å	θ = 2.9–30.6°
b = 4.4751 (9) Å	µ = 44.11 mm^−1
c = 14.148 (3) Å	T = 100 K
V = 810.6 (3) Å^3	Needle, black
Z = 4	0.06 × 0.05 × 0.03 mm
F(000) = 1504

Data collection

Bruker APEXII CCD diffractometer	1283 reflections with I > 2σ(I)
Radiation source: microsource	Rint = 0.038
φ and ω scans	θmax = 30.6°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −18→18
Tmin = 0.100, Tmax = 0.201	k = −6→6
16634 measured reflections	l = −20→20
1395 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0144P)^2 + 1.4011P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max = 0.002
wR(F^2) = 0.034	Δρmax = 1.39 e Å^−3
S = 1.17	Δρmin = −1.38 e Å^−3
1395 reflections	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
44 parameters	Extinction coefficient: 0.00046 (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. Single-crystal X-ray diffraction data were collected from a Bruker X-ray diffractometer with Mo radiation and processed by APEX 3 and SADABS (see Table 1) (Bruker, 2016). The black needle crystals were selected and cut to appropriate dimensions in Paratone-N oil. The space group Pnma was determined by XPREP automatically (Sheldrick, 2008). The structure was solved by direct methods in the SHELXTL suite of programs (Sheldrick, 2008). During the refinement cycles, unphysical atomic positions based on van der Waals radius were ignored manually, with the final refinement cycles obtained a highest residue peak 2.725 e^-/ų and a deepest hole of -1.784 e^-/ų. The absorption correction was further employed in the refinement using SADABS (Bruker, 2016) resulting in a drop in the R₁ factor to 1.58 % with highest residue peak 1.389 e^-/ų and the deepest hole -1.378 e^-/ų. Atomic coordinates were standardized using the STRUCTURE TIDY program (Gelato & Parthé, 1987).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Yb1	0.55940 (2)	0.250000	0.61179 (2)	0.00583 (6)
Yb2	0.27262 (2)	0.250000	0.72127 (2)	0.00586 (6)
Yb3	0.35004 (2)	0.250000	0.00587 (2)	0.00623 (6)
Sb1	0.25645 (3)	0.250000	0.38116 (2)	0.00527 (7)
Sb2	0.11386 (3)	0.250000	0.10925 (2)	0.00517 (7)
Sb3	0.04007 (3)	0.250000	0.64920 (2)	0.00543 (8)
Al1	0.06670 (12)	0.250000	0.29703 (12)	0.0061 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Yb1	0.00605 (10)	0.00642 (11)	0.00503 (11)	0.000	−0.00007 (8)	0.000
Yb2	0.00642 (10)	0.00572 (11)	0.00543 (11)	0.000	0.00049 (8)	0.000
Yb3	0.00714 (10)	0.00650 (11)	0.00505 (11)	0.000	−0.00028 (8)	0.000
Sb1	0.00581 (15)	0.00496 (15)	0.00504 (16)	0.000	−0.00015 (12)	0.000
Sb2	0.00593 (15)	0.00540 (16)	0.00418 (16)	0.000	−0.00035 (12)	0.000
Sb3	0.00601 (15)	0.00547 (15)	0.00480 (16)	0.000	0.00029 (12)	0.000
Al1	0.0072 (7)	0.0050 (7)	0.0061 (7)	0.000	0.0010 (6)	0.000

Geometric parameters (Å, º)

Yb1—Sb2^i	3.1509 (5)	Yb2—Al1^ii	3.2230 (12)
Yb1—Sb2^ii	3.1509 (5)	Yb2—Al1^i	3.2230 (12)
Yb1—Sb2^iii	3.2039 (7)	Yb2—Yb3^i	4.0939 (6)
Yb1—Sb1^iv	3.2520 (5)	Yb2—Yb3^ii	4.0939 (6)
Yb1—Sb1^v	3.2520 (5)	Yb2—Yb3^vii	4.1466 (8)
Yb1—Sb3^vi	3.3906 (8)	Yb3—Sb1^viii	3.1589 (5)
Yb1—Yb2^vi	3.6097 (6)	Yb3—Sb1^ix	3.1589 (5)
Yb1—Yb2	3.9849 (8)	Yb3—Sb3^iii	3.2760 (6)
Yb1—Yb3^iii	4.0764 (8)	Yb3—Sb3^ix	3.3313 (5)
Yb1—Yb1^v	4.1623 (7)	Yb3—Sb3^viii	3.3313 (5)
Yb1—Yb1^iv	4.1623 (7)	Yb3—Sb2	3.3590 (7)
Yb2—Sb2^i	3.1034 (5)	Sb1—Al1	2.7053 (17)
Yb2—Sb2^ii	3.1034 (5)	Sb2—Al1	2.7245 (18)
Yb2—Sb3	3.1470 (7)	Sb3—Al1^x	2.7302 (10)
Yb2—Sb1^ii	3.2034 (5)	Sb3—Al1^xi	2.7302 (10)
Yb2—Sb1^i	3.2034 (5)
Sb2^i—Yb1—Sb2^ii	90.493 (19)	Sb1^viii—Yb3—Sb3^iii	86.932 (15)
Sb2^i—Yb1—Sb2^iii	98.168 (9)	Sb1^ix—Yb3—Sb3^iii	86.932 (14)
Sb2^ii—Yb1—Sb2^iii	98.168 (9)	Sb1^viii—Yb3—Sb3^ix	176.402 (9)
Sb2^i—Yb1—Sb1^iv	177.931 (9)	Sb1^ix—Yb3—Sb3^ix	92.665 (16)
Sb2^ii—Yb1—Sb1^iv	91.267 (18)	Sb3^iii—Yb3—Sb3^ix	95.394 (15)
Sb2^iii—Yb1—Sb1^iv	82.658 (9)	Sb1^viii—Yb3—Sb3^viii	92.665 (16)
Sb2^i—Yb1—Sb1^v	91.267 (17)	Sb1^ix—Yb3—Sb3^viii	176.402 (9)
Sb2^ii—Yb1—Sb1^v	177.931 (9)	Sb3^iii—Yb3—Sb3^viii	95.394 (15)
Sb2^iii—Yb1—Sb1^v	82.658 (9)	Sb3^ix—Yb3—Sb3^viii	84.393 (17)
Sb1^iv—Yb1—Sb1^v	86.954 (19)	Sb1^viii—Yb3—Sb2	81.643 (13)
Sb2^i—Yb1—Sb3^vi	87.708 (9)	Sb1^ix—Yb3—Sb2	81.643 (13)
Sb2^ii—Yb1—Sb3^vi	87.708 (9)	Sb3^iii—Yb3—Sb2	163.769 (12)
Sb2^iii—Yb1—Sb3^vi	171.614 (12)	Sb3^ix—Yb3—Sb2	96.612 (14)
Sb1^iv—Yb1—Sb3^vi	91.275 (9)	Sb3^viii—Yb3—Sb2	96.612 (14)
Sb1^v—Yb1—Sb3^vi	91.275 (9)	Sb1^viii—Yb3—Yb1^xiii	51.533 (8)
Sb2^i—Yb1—Yb2^vi	122.672 (11)	Sb1^ix—Yb3—Yb1^xiii	51.533 (8)
Sb2^ii—Yb1—Yb2^vi	122.672 (10)	Sb3^iii—Yb3—Yb1^xiii	113.857 (16)
Sb2^iii—Yb1—Yb2^vi	118.297 (14)	Sb3^ix—Yb3—Yb1^xiii	129.349 (8)
Sb1^iv—Yb1—Yb2^vi	55.363 (11)	Sb3^viii—Yb3—Yb1^xiii	129.349 (8)
Sb1^v—Yb1—Yb2^vi	55.363 (10)	Sb2—Yb3—Yb1^xiii	49.912 (14)
Sb3^vi—Yb1—Yb2^vi	53.317 (12)	Sb1^viii—Yb3—Yb2^ix	129.596 (14)
Sb2^i—Yb1—Yb2	49.896 (10)	Sb1^ix—Yb3—Yb2^ix	82.131 (16)
Sb2^ii—Yb1—Yb2	49.896 (10)	Sb3^iii—Yb3—Yb2^ix	141.571 (8)
Sb2^iii—Yb1—Yb2	125.444 (10)	Sb3^ix—Yb3—Yb2^ix	48.834 (12)
Sb1^iv—Yb1—Yb2	130.999 (11)	Sb3^viii—Yb3—Yb2^ix	94.358 (16)
Sb1^v—Yb1—Yb2	130.999 (11)	Sb2—Yb3—Yb2^ix	47.977 (7)
Sb3^vi—Yb1—Yb2	62.942 (8)	Yb1^xiii—Yb3—Yb2^ix	87.353 (12)
Yb2^vi—Yb1—Yb2	116.259 (15)	Sb1^viii—Yb3—Yb2^viii	82.131 (15)
Sb2^i—Yb1—Yb3^iii	129.639 (10)	Sb1^ix—Yb3—Yb2^viii	129.596 (14)
Sb2^ii—Yb1—Yb3^iii	129.639 (10)	Sb3^iii—Yb3—Yb2^viii	141.571 (8)
Sb2^iii—Yb1—Yb3^iii	53.330 (8)	Sb3^ix—Yb3—Yb2^viii	94.358 (16)
Sb1^iv—Yb1—Yb3^iii	49.514 (10)	Sb3^viii—Yb3—Yb2^viii	48.834 (12)
Sb1^v—Yb1—Yb3^iii	49.514 (10)	Sb2—Yb3—Yb2^viii	47.977 (7)
Sb3^vi—Yb1—Yb3^iii	118.284 (10)	Yb1^xiii—Yb3—Yb2^viii	87.353 (12)
Yb2^vi—Yb1—Yb3^iii	64.967 (15)	Yb2^ix—Yb3—Yb2^viii	66.263 (15)
Yb2—Yb1—Yb3^iii	178.774 (8)	Sb1^viii—Yb3—Yb2^xiv	49.793 (9)
Sb2^i—Yb1—Yb1^v	49.636 (9)	Sb1^ix—Yb3—Yb2^xiv	49.793 (9)
Sb2^ii—Yb1—Yb1^v	96.654 (14)	Sb3^iii—Yb3—Yb2^xiv	61.789 (14)
Sb2^iii—Yb1—Yb1^v	48.532 (11)	Sb3^ix—Yb3—Yb2^xiv	133.789 (9)
Sb1^iv—Yb1—Yb1^v	131.158 (12)	Sb3^viii—Yb3—Yb2^xiv	133.789 (9)
Sb1^v—Yb1—Yb1^v	85.317 (12)	Sb2—Yb3—Yb2^xiv	101.980 (13)
Sb3^vi—Yb1—Yb1^v	136.991 (10)	Yb1^xiii—Yb3—Yb2^xiv	52.068 (6)
Yb2^vi—Yb1—Yb1^v	140.673 (8)	Yb2^ix—Yb3—Yb2^xiv	129.133 (11)
Yb2—Yb1—Yb1^v	87.635 (12)	Yb2^viii—Yb3—Yb2^xiv	129.133 (11)
Yb3^iii—Yb1—Yb1^v	91.331 (13)	Al1—Sb1—Yb3^ii	81.84 (3)
Sb2^i—Yb1—Yb1^iv	96.654 (14)	Al1—Sb1—Yb3^i	81.84 (3)
Sb2^ii—Yb1—Yb1^iv	49.636 (9)	Yb3^ii—Sb1—Yb3^i	90.199 (17)
Sb2^iii—Yb1—Yb1^iv	48.532 (11)	Al1—Sb1—Yb2^viii	65.48 (2)
Sb1^iv—Yb1—Yb1^iv	85.317 (12)	Yb3^ii—Sb1—Yb2^viii	147.037 (15)
Sb1^v—Yb1—Yb1^iv	131.158 (13)	Yb3^i—Sb1—Yb2^viii	81.343 (15)
Sb3^vi—Yb1—Yb1^iv	136.991 (10)	Al1—Sb1—Yb2^ix	65.48 (2)
Yb2^vi—Yb1—Yb1^iv	140.673 (8)	Yb3^ii—Sb1—Yb2^ix	81.343 (15)
Yb2—Yb1—Yb1^iv	87.635 (12)	Yb3^i—Sb1—Yb2^ix	147.037 (15)
Yb3^iii—Yb1—Yb1^iv	91.331 (13)	Yb2^viii—Sb1—Yb2^ix	88.613 (19)
Yb1^v—Yb1—Yb1^iv	65.038 (15)	Al1—Sb1—Yb1^iv	131.650 (17)
Sb2^i—Yb2—Sb2^ii	92.274 (18)	Yb3^ii—Sb1—Yb1^iv	78.953 (14)
Sb2^i—Yb2—Sb3	106.117 (12)	Yb3^i—Sb1—Yb1^iv	141.550 (14)
Sb2^ii—Yb2—Sb3	106.117 (12)	Yb2^viii—Sb1—Yb1^iv	125.910 (14)
Sb2^i—Yb2—Sb1^ii	156.728 (12)	Yb2^ix—Sb1—Yb1^iv	67.994 (11)
Sb2^ii—Yb2—Sb1^ii	84.917 (16)	Al1—Sb1—Yb1^v	131.650 (17)
Sb3—Yb2—Sb1^ii	96.828 (11)	Yb3^ii—Sb1—Yb1^v	141.550 (14)
Sb2^i—Yb2—Sb1^i	84.917 (16)	Yb3^i—Sb1—Yb1^v	78.953 (14)
Sb2^ii—Yb2—Sb1^i	156.728 (12)	Yb2^viii—Sb1—Yb1^v	67.994 (11)
Sb3—Yb2—Sb1^i	96.828 (11)	Yb2^ix—Sb1—Yb1^v	125.910 (14)
Sb1^ii—Yb2—Sb1^i	88.613 (19)	Yb1^iv—Sb1—Yb1^v	86.955 (19)
Sb2^i—Yb2—Al1^ii	111.80 (3)	Al1—Sb2—Yb2^ix	66.78 (2)
Sb2^ii—Yb2—Al1^ii	50.97 (3)	Al1—Sb2—Yb2^viii	66.78 (2)
Sb3—Yb2—Al1^ii	135.37 (2)	Yb2^ix—Sb2—Yb2^viii	92.272 (18)
Sb1^ii—Yb2—Al1^ii	49.79 (3)	Al1—Sb2—Yb1^viii	80.38 (3)
Sb1^i—Yb2—Al1^ii	108.92 (3)	Yb2^ix—Sb2—Yb1^viii	146.707 (14)
Sb2^i—Yb2—Al1^i	50.97 (3)	Yb2^viii—Sb2—Yb1^viii	79.157 (14)
Sb2^ii—Yb2—Al1^i	111.80 (3)	Al1—Sb2—Yb1^ix	80.38 (3)
Sb3—Yb2—Al1^i	135.37 (2)	Yb2^ix—Sb2—Yb1^ix	79.157 (14)
Sb1^ii—Yb2—Al1^i	108.92 (3)	Yb2^viii—Sb2—Yb1^ix	146.707 (14)
Sb1^i—Yb2—Al1^i	49.79 (3)	Yb1^viii—Sb2—Yb1^ix	90.493 (19)
Al1^ii—Yb2—Al1^i	87.93 (4)	Al1—Sb2—Yb1^xiii	154.63 (4)
Sb2^i—Yb2—Yb1^xii	133.498 (8)	Yb2^ix—Sb2—Yb1^xiii	126.898 (9)
Sb2^ii—Yb2—Yb1^xii	133.498 (8)	Yb2^viii—Sb2—Yb1^xiii	126.898 (9)
Sb3—Yb2—Yb1^xii	59.773 (15)	Yb1^viii—Sb2—Yb1^xiii	81.833 (9)
Sb1^ii—Yb2—Yb1^xii	56.642 (10)	Yb1^ix—Sb2—Yb1^xiii	81.833 (9)
Sb1^i—Yb2—Yb1^xii	56.642 (10)	Al1—Sb2—Yb3	128.61 (4)
Al1^ii—Yb2—Yb1^xii	105.37 (3)	Yb2^ix—Sb2—Yb3	78.506 (13)
Al1^i—Yb2—Yb1^xii	105.37 (3)	Yb2^viii—Sb2—Yb3	78.506 (13)
Sb2^i—Yb2—Yb1	50.948 (9)	Yb1^viii—Sb2—Yb3	129.695 (11)
Sb2^ii—Yb2—Yb1	50.948 (9)	Yb1^ix—Sb2—Yb3	129.695 (11)
Sb3—Yb2—Yb1	138.219 (14)	Yb1^xiii—Sb2—Yb3	76.758 (13)
Sb1^ii—Yb2—Yb1	112.428 (9)	Al1^x—Sb3—Al1^xi	110.08 (6)
Sb1^i—Yb2—Yb1	112.428 (9)	Al1^x—Sb3—Yb2	112.54 (3)
Al1^ii—Yb2—Yb1	62.69 (3)	Al1^xi—Sb3—Yb2	112.54 (3)
Al1^i—Yb2—Yb1	62.69 (3)	Al1^x—Sb3—Yb3^xiii	79.33 (4)
Yb1^xii—Yb2—Yb1	162.008 (8)	Al1^xi—Sb3—Yb3^xiii	79.33 (4)
Sb2^i—Yb2—Yb3^i	53.517 (12)	Yb2—Sb3—Yb3^xiii	156.866 (14)
Sb2^ii—Yb2—Yb3^i	101.160 (15)	Al1^x—Sb3—Yb3^i	80.25 (3)
Sb3—Yb2—Yb3^i	52.836 (7)	Al1^xi—Sb3—Yb3^i	158.67 (4)
Sb1^ii—Yb2—Yb3^i	149.637 (11)	Yb2—Sb3—Yb3^i	78.329 (12)
Sb1^i—Yb2—Yb3^i	95.699 (16)	Yb3^xiii—Sb3—Yb3^i	84.607 (15)
Al1^ii—Yb2—Yb3^i	150.67 (3)	Al1^x—Sb3—Yb3^ii	158.67 (4)
Al1^i—Yb2—Yb3^i	96.49 (3)	Al1^xi—Sb3—Yb3^ii	80.25 (3)
Yb1^xii—Yb2—Yb3^i	101.360 (15)	Yb2—Sb3—Yb3^ii	78.329 (12)
Yb1—Yb2—Yb3^i	93.673 (12)	Yb3^xiii—Sb3—Yb3^ii	84.607 (15)
Sb2^i—Yb2—Yb3^ii	101.160 (15)	Yb3^i—Sb3—Yb3^ii	84.392 (17)
Sb2^ii—Yb2—Yb3^ii	53.517 (12)	Al1^x—Sb3—Yb1^xii	76.03 (4)
Sb3—Yb2—Yb3^ii	52.836 (7)	Al1^xi—Sb3—Yb1^xii	76.03 (4)
Sb1^ii—Yb2—Yb3^ii	95.699 (16)	Yb2—Sb3—Yb1^xii	66.909 (9)
Sb1^i—Yb2—Yb3^ii	149.637 (11)	Yb3^xiii—Sb3—Yb1^xii	136.224 (14)
Al1^ii—Yb2—Yb3^ii	96.49 (3)	Yb3^i—Sb3—Yb1^xii	125.189 (10)
Al1^i—Yb2—Yb3^ii	150.67 (3)	Yb3^ii—Sb3—Yb1^xii	125.189 (11)
Yb1^xii—Yb2—Yb3^ii	101.360 (14)	Sb1—Al1—Sb2	103.30 (5)
Yb1—Yb2—Yb3^ii	93.673 (11)	Sb1—Al1—Sb3^x	109.09 (4)
Yb3^i—Yb2—Yb3^ii	66.263 (14)	Sb2—Al1—Sb3^x	112.50 (4)
Sb2^i—Yb2—Yb3^vii	112.578 (11)	Sb1—Al1—Sb3^xi	109.09 (4)
Sb2^ii—Yb2—Yb3^vii	112.578 (11)	Sb2—Al1—Sb3^xi	112.50 (4)
Sb3—Yb2—Yb3^vii	122.737 (9)	Sb3^x—Al1—Sb3^xi	110.08 (6)
Sb1^ii—Yb2—Yb3^vii	48.862 (10)	Sb1—Al1—Yb2^ix	64.73 (3)
Sb1^i—Yb2—Yb3^vii	48.862 (10)	Sb2—Al1—Yb2^ix	62.24 (3)
Al1^ii—Yb2—Yb3^vii	61.61 (3)	Sb3^x—Al1—Yb2^ix	168.88 (5)
Al1^i—Yb2—Yb3^vii	61.61 (3)	Sb3^xi—Al1—Yb2^ix	80.983 (17)
Yb1^xii—Yb2—Yb3^vii	62.964 (14)	Sb1—Al1—Yb2^viii	64.73 (3)
Yb1—Yb2—Yb3^vii	99.044 (12)	Sb2—Al1—Yb2^viii	62.24 (3)
Yb3^i—Yb2—Yb3^vii	144.539 (8)	Sb3^x—Al1—Yb2^viii	80.983 (17)
Yb3^ii—Yb2—Yb3^vii	144.539 (8)	Sb3^xi—Al1—Yb2^viii	168.88 (5)
Sb1^viii—Yb3—Sb1^ix	90.197 (17)	Yb2^ix—Al1—Yb2^viii	87.93 (4)

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