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The novel Zintl phase dibarium zinc diphosphide (Ba2ZnP2) was synthesized for the first time. This was accomplished using the Pb flux technique, which allowed for the growth of crystals of adequate size for structural determination via single-crystal X-ray diffraction methods. The Ba2ZnP2 compound was determined to crystallize in a body-centered orthorhombic space group, Ibam (No. 72). Formally, this crystallographic arrangement belongs to the K2SiP2 structure type. Therefore, the structure can be best described as infinite [ZnP2]4− polyanionic chains with divalent Ba2+ cations located between the chains. All valence electrons are partitioned, which conforms to the Zintl–Klemm concept and suggests that Ba2ZnP2 is a valence-precise composition. The electronic band structure of this new compound, computed with the aid of the TB–LMTO–ASA code, shows that Ba2ZnP2 is an intrinsic semiconductor with a band gap of ca 0.6 eV.
Supporting information
CCDC reference: 2021633
Data collection: SMART (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2014) and OLEX2 (Dolomanov et al.,
2009); software used to prepare material for publication: publCIF (Westrip, 2010).
Dibarium zinc diphosphide
top
Crystal data top
Ba2ZnP2 | Dx = 4.722 Mg m−3 |
Mr = 401.99 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Ibam | Cell parameters from 995 reflections |
a = 6.756 (4) Å | θ = 3.1–29.2° |
b = 13.108 (8) Å | µ = 18.38 mm−1 |
c = 6.385 (4) Å | T = 200 K |
V = 565.4 (6) Å3 | Block, black |
Z = 4 | 0.05 × 0.04 × 0.03 mm |
F(000) = 688 | |
Data collection top
Bruker APEXII CCD diffractometer | 396 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.046 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | θmax = 29.6°, θmin = 3.1° |
Tmin = 0.249, Tmax = 0.336 | h = −9→9 |
3529 measured reflections | k = −18→18 |
437 independent reflections | l = −8→8 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0163P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.018 | (Δ/σ)max < 0.001 |
wR(F2) = 0.037 | Δρmax = 1.12 e Å−3 |
S = 1.04 | Δρmin = −0.86 e Å−3 |
437 reflections | Extinction correction: SHELXL2018 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
17 parameters | Extinction coefficient: 0.00142 (12) |
0 restraints | |
Special details top
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. The collected data were integrated with the Bruker-supplied software
(Bruker, 2014), and absorption correction was applied using the
SADABS software (Bruker, 2014). The crystal structure was solved
using the ShelXT code (Sheldrick, 2015a), using Olex2 as the graphical
interface (Dolomanov et al., 2009). Structural parameters were
refined using the full-matrix least squares method on F2 with
SHELXL (Sheldrick 2015b). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ba | 0.19118 (4) | 0.35970 (2) | 0.000000 | 0.01146 (12) | |
Zn | 0.000000 | 0.000000 | 0.250000 | 0.01103 (19) | |
P | 0.20008 (18) | 0.10649 (10) | 0.000000 | 0.0107 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ba | 0.01154 (17) | 0.01068 (17) | 0.01215 (17) | −0.00097 (11) | 0.000 | 0.000 |
Zn | 0.0105 (4) | 0.0117 (4) | 0.0109 (4) | 0.000 | 0.000 | 0.000 |
P | 0.0117 (6) | 0.0100 (6) | 0.0105 (6) | −0.0018 (5) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Ba—Bai | 4.1067 (19) | Ba—P | 3.320 (2) |
Ba—Baii | 4.370 (2) | Ba—Piii | 3.306 (2) |
Ba—Baiii | 4.3698 (19) | Ba—Pviii | 3.317 (2) |
Ba—Baiv | 4.1067 (19) | Ba—Pii | 3.306 (2) |
Ba—Znv | 3.2066 (12) | Zn—P | 2.5147 (14) |
Ba—Zniii | 3.2066 (12) | Zn—Pi | 2.5147 (14) |
Ba—Pvi | 3.347 (2) | Zn—Pix | 2.5147 (14) |
Ba—Pvii | 3.466 (2) | Zn—Px | 2.5147 (14) |
| | | |
Baiv—Ba—Baiii | 133.03 (3) | P—Ba—Pvi | 98.64 (3) |
Bai—Ba—Baiii | 63.03 (3) | Piii—Ba—Pvii | 76.26 (2) |
Baii—Ba—Baiii | 93.87 (5) | Pii—Ba—Pviii | 79.64 (3) |
Bai—Ba—Baii | 133.03 (3) | Pii—Ba—P | 97.47 (3) |
Baiv—Ba—Baii | 63.03 (3) | Pviii—Ba—Pvii | 69.86 (4) |
Baiv—Ba—Bai | 102.05 (5) | Baiii—Zn—Bavi | 110.01 (4) |
Zniii—Ba—Bai | 91.28 (4) | Baiii—Zn—Baxi | 98.82 (4) |
Zniii—Ba—Baiii | 84.00 (4) | Bavi—Zn—Baxi | 120.29 (4) |
Znv—Ba—Baii | 84.00 (4) | Baiii—Zn—Baxii | 120.29 (4) |
Znv—Ba—Baiv | 91.28 (4) | Baxii—Zn—Baxi | 110.01 (4) |
Znv—Ba—Bai | 142.77 (2) | Baxii—Zn—Bavi | 98.82 (4) |
Zniii—Ba—Baiv | 142.77 (2) | Pi—Zn—Baxi | 169.75 (2) |
Znv—Ba—Baiii | 128.52 (3) | Pi—Zn—Bavi | 69.39 (5) |
Zniii—Ba—Baii | 128.52 (3) | Px—Zn—Baxii | 73.46 (5) |
Zniii—Ba—Znv | 59.71 (4) | P—Zn—Baxii | 169.75 (2) |
Zniii—Ba—Pviii | 45.31 (2) | Px—Zn—Baiii | 69.67 (5) |
Znv—Ba—Pvii | 44.06 (2) | Pix—Zn—Baxii | 69.39 (4) |
Zniii—Ba—Piii | 45.40 (2) | Pix—Zn—Bavi | 69.67 (5) |
Znv—Ba—Pii | 45.40 (2) | P—Zn—Baiii | 69.39 (5) |
Znv—Ba—Pvi | 124.68 (3) | P—Zn—Baxi | 69.67 (5) |
Znv—Ba—Piii | 105.03 (4) | P—Zn—Bavi | 73.46 (5) |
Zniii—Ba—Pvi | 124.68 (3) | Px—Zn—Baxi | 69.39 (5) |
Zniii—Ba—Pii | 105.03 (4) | Pix—Zn—Baxi | 73.46 (5) |
Zniii—Ba—P | 124.17 (3) | Pi—Zn—Baxii | 69.67 (5) |
Znv—Ba—Pviii | 45.31 (2) | Pix—Zn—Baiii | 169.75 (2) |
Zniii—Ba—Pvii | 44.06 (2) | Px—Zn—Bavi | 169.75 (2) |
Znv—Ba—P | 124.17 (3) | Pi—Zn—Baiii | 73.46 (5) |
Pii—Ba—Baiv | 52.34 (4) | Px—Zn—Pi | 101.19 (6) |
Pvi—Ba—Baiii | 105.509 (19) | P—Zn—Px | 114.97 (7) |
Piii—Ba—Baiii | 48.87 (4) | P—Zn—Pix | 101.19 (6) |
P—Ba—Baii | 48.60 (3) | P—Zn—Pi | 112.56 (7) |
Pvi—Ba—Baii | 105.509 (19) | Pix—Zn—Px | 112.56 (7) |
Pviii—Ba—Baiii | 126.98 (3) | Pix—Zn—Pi | 114.97 (7) |
Pii—Ba—Baiii | 138.88 (3) | Baxi—P—Ba | 168.24 (4) |
Pviii—Ba—Baiv | 98.006 (17) | Baxi—P—Bavii | 84.81 (4) |
Pviii—Ba—Baii | 126.98 (3) | Baxi—P—Bavi | 110.14 (4) |
Piii—Ba—Baiv | 152.94 (3) | Baiii—P—Ba | 82.53 (2) |
P—Ba—Baiii | 48.60 (3) | Baiii—P—Bavi | 101.73 (3) |
Pvii—Ba—Baiii | 84.48 (2) | Baii—P—Bavi | 101.73 (3) |
Pvi—Ba—Bai | 51.43 (3) | Baiii—P—Baii | 149.92 (5) |
Pvii—Ba—Baii | 84.48 (2) | Baii—P—Bavii | 76.23 (2) |
Pvii—Ba—Bai | 128.60 (3) | Baiii—P—Baxi | 94.67 (3) |
Pviii—Ba—Bai | 98.006 (17) | Baii—P—Ba | 82.53 (3) |
Pii—Ba—Baii | 48.87 (4) | Baii—P—Baxi | 94.67 (3) |
Pvi—Ba—Baiv | 51.43 (3) | Ba—P—Bavii | 83.43 (3) |
Piii—Ba—Bai | 52.34 (4) | Bavii—P—Bavi | 165.05 (5) |
Piii—Ba—Baii | 138.88 (3) | Baiii—P—Bavii | 76.23 (2) |
Pii—Ba—Bai | 152.94 (3) | Ba—P—Bavi | 81.62 (3) |
Pvii—Ba—Baiv | 128.60 (3) | Zn—P—Bavii | 127.32 (4) |
P—Ba—Bai | 90.653 (14) | Zn—P—Ba | 123.04 (4) |
P—Ba—Baiv | 90.653 (14) | Zn—P—Baii | 143.79 (4) |
Piii—Ba—Pviii | 79.64 (3) | Znix—P—Baxi | 65.02 (4) |
Piii—Ba—Pii | 149.92 (5) | Znix—P—Ba | 123.04 (4) |
Pvi—Ba—Pvii | 165.05 (5) | Zn—P—Bavi | 62.47 (3) |
Pviii—Ba—P | 166.169 (16) | Zn—P—Baxi | 65.02 (4) |
P—Ba—Pvii | 96.31 (3) | Zn—P—Baiii | 65.22 (3) |
Pviii—Ba—Pvi | 95.19 (4) | Znix—P—Bavi | 62.47 (3) |
Pii—Ba—Pvii | 76.26 (2) | Znix—P—Bavii | 127.32 (4) |
Piii—Ba—P | 97.47 (3) | Znix—P—Baii | 65.22 (3) |
Pii—Ba—Pvi | 101.68 (3) | Znix—P—Baiii | 143.79 (4) |
Piii—Ba—Pvi | 101.68 (3) | Znix—P—Zn | 78.81 (6) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, −y+1/2, −z−1/2; (iii) −x+1/2, −y+1/2, −z+1/2; (iv) −x, y, −z−1/2; (v) x+1/2, y+1/2, z−1/2; (vi) x−1/2, −y+1/2, z; (vii) x+1/2, −y+1/2, z; (viii) −x+1/2, y+1/2, −z; (ix) −x, −y, −z; (x) x, −y, z+1/2; (xi) −x+1/2, y−1/2, −z; (xii) x−1/2, y−1/2, z+1/2. |
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