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Article

The A-Type Ln4N2S3 Series: New Nitride Sulfides of the Light Lanthanoids (Ln = Ce–Nd)

by
Falk Lissner
and
Thomas Schleid
*
Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
*
Author to whom correspondence should be addressed.
Inorganics 2017, 5(1), 2; https://doi.org/10.3390/inorganics5010002
Submission received: 11 November 2016 / Revised: 13 December 2016 / Accepted: 14 December 2016 / Published: 23 December 2016
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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Abstract

:
The reaction of lanthanoid metal powders (Ln) with sulfur and cesium azide (CsN3) as a nitrogen source in the presence of lanthanoid tribromides (LnBr3) yields lanthanoid nitride sulfides with the composition Ln4N2S3 (Ln = Ce–Nd) when appropriate molar ratios of the starting material are used. Additional cesium bromide (CsBr) as a flux secures quantitative conversion (7 days) at 900 °C in evacuated silica tubes as well as the formation of black single crystals. All compounds crystallize isotypically with the orthorhombic crystal structure of La4N2S3 (Pnnm, Z = 2) and their structures were determined from single-crystal X-ray diffraction data (Ce4N2S3: a = 644.31(4), b = 1554.13(9), c = 404.20(3) pm; Pr4N2S3: a = 641.23(4), b = 1542.37(9), c = 400.18(3) pm; Nd4N2S3: a = 635.19(4), b = 1536.98(9), c = 397.85(3) pm). Compared to La4N2S3 the a-axes do not fulfill the expectation of the lanthanide contraction. The main feature of the crystal structure comprises N3−-centered (Ln3+)4 tetrahedra arranging as pairs [N2Ln6]12+ of edge-shared [NLn4]9+ units, which are further connected via four vertices to form double chains ∞ 1 {([NLn4/2]2)6+}. Bundled along [001] like a hexagonal rod packing, they are held together by two crystallographically different S2− anions. Two compounds of a second modification (B-type La4N2S3 and Pr4N2S3) will also be presented and discussed for comparison.

1. Introduction

The crystal structures of all ternary lanthanide(III) nitride chalcogenides known so far (Ln3NCh3, Ln4N2Ch3, Ln5NCh6, Ln23N5Ch27, and Ln13N5Ch12) and their halide derivatives (Ln3N2ChX, Ln4NCh3X3, Ln5N2Ch4X, Ln5N3Ch2X2, and Ln6N3Ch4X; Ln = La–Nd, Sm, Gd–Ho; Ch = S, Se, Te; X = Cl, Br) are dominated by N3− anions in a tetrahedral coordination of Ln3+ cations [1,2,3]. A very interesting structural behavior is exhibited by the nitride chalcogenides with the composition Ln4N2Ch3, which occur in seven different crystal structure types. Depending upon the size of both the lanthanide cation (Ln3+) and the chalcogenide anion (Ch2−), some of them differ fundamentally in the linkage of the structure-governing N3−-centered (Ln3+)4 tetrahedra. The representatives of the Sm4N2S3-type structure [4] crystallize in the monoclinic space group C2/m with Z = 4 and consist of [NLn4]9+ tetrahedra, which share cis-oriented edges to form linear strands ∞ 1 {[NLn2]3+}. In contrast, the linkage via trans-oriented edges of [NLn4]9+ tetrahedra builds up undulated chains in the orthorhombic Ce4N2Te3-type structure [5] (Ln = La–Nd; Pnma, Z = 4), the orthorhombic Tb4N2Te3-type structure [6] (Ln = Gd, Tb; Pnna, Z = 4), and the monoclinic Dy4N2Te3-type structure [6] (P21/c, Z = 4). As the main structural feature of the orthorhombic A-La4N2S3-type structure [7] (Pnnm, Z = 2), N3−-centered (Ln3+)4 tetrahedra, which first arrange as pairs [N2Ln6]12+ of two edge-shared [NLn4]9+ units, occur. These are further connected via their four free vertices to form double chains ∞ 1 {([NLn2]2)6+}. For the first time, an arrangement of interconnected [NLn4]9+ tetrahedra fused to layers is observed in the monoclinic Nd4N2Se3-type structure [8,9,10,11] (Ln = La–Nd; C2/c, Z = 4). In these compounds the [NLn4]9+ units are first edge-linked to congonial bitetrahedra [N2Ln6]12+ again, and they then become cross-connected to ∞ 2 {[NLn2]3+} layers via their remaining four free vertices. Finally, a second layered arrangement is found in the monoclinic B-Pr4N2S3-type structure [9] (Ln = La, Pr; C2/c, Z = 8). In this case, the [NLn4]9+ tetrahedra are first edge-linked to bitetrahedra [N2Ln6]12+ just like in A-type La4N2S3 and Nd4N2Se3, but then connected via two vertices to quadruples [N4Ln10]18+, which eventually build up layers ∞ 2 {[NLn2]3+} via their four remaining free corners. In addition, there are only two compounds crystallizing dimorphously so far. La4N2S3 [7,12] is found in the A-La4N2S3- and in the B-Pr4N2S3-type structures, while Ce4N2Se3 is observed either with the Nd4N2Se3- or with the Ce4N2Te3-type arrangement.

2. Results and Discussion

The members of the short Ln4N2S3 series (Ln = Ce–Nd) crystallize orthorhombically in the space group Pnnm with two formula units (Z = 2) per unit cell (Table 1, Table 2 and Table 3) and are therefore isotypical with the A-type structure of La4N2S3 [7]. Each of the two crystallographically independent Ln3+ cations is firstly surrounded by two N3− anions. For (Ln1)3+ another four, for (Ln2)3+ even four plus one S2− anions appear in their coordination spheres, thus resulting in overall coordination numbers (C.N.) of 6 and 6+1. The polyhedron around (Ln1)3+ having the site symmetry (..m) can be described as a trigonal prism (Figure 1, left), in which both a prism edge (N···N′) as well as the center (Ln1) reside on a mirror plane. (Ln2)3+, likewise with the site symmetry (..m), shows a trigonal prism or octahedron as a coordination polyhedron, which again proves to be very distorted, since it exhibits, in addition, another extra sulfur ligand (S2″) as a cap (Figure 1, right). The distances d(Ln3+–S2−) for Ln = Ce–Nd start at 283 pm and increase continuously up to a value of 308 pm. For A-type La4N2S3 (a = 641.98(4), b = 1581.42(9), c = 409.87(3) pm) [7], the following ligand provides an abrupt increase of distance (d(La2–S2″) = 341 pm), but shows an ECoN = 0.26 (effective coordination number [13]); nevertheless, it is a sound contribution to be considered for the whole coordination sphere of (La2)3+. In spite of the lanthanide contraction as anticipated, the compounds Ln4N2S3 (Ln = Ce–Nd) investigated in this work show a remarkable devolution of this mentioned distance d(Ln2–S2″). First an increase happens from 341 to 351 pm during the transition from the lanthanum to the cerium compound, accompanied by a decreasing ECoN value of 0.13. With the subsequent compounds Pr4N2S3 and Nd4N2S3, this distance stagnates and finally decreases again to values of 350 and 343 pm (Table 4 and Figure 2, yellow graph), so one can at most speak of a 6+1-fold but never of a real seven-fold coordination for (Ln2)3+ (Ln = Ce–Nd). This behavior is also repeated in the lattice constants (Table 1 and Figure 2), where in the extreme case an unusual increase of the a-axis from the lanthanum to the cerium compound can be observed. The molar volumes Vm monotonically decrease with the increasing atomic number of Ln, which finally reflects the lanthanide contraction again.
In analogy to all the rare-earth metal(III) nitride chalcogenides and their halide derivatives known to date [1,2,3], the N3− anions are again surrounded by a more or less distorted tetrahedron of Ln3+ cations, in which the four N3−–Ln3+ distances (228–241 pm) differ by a maximum of 13 pm and the angles range between 97° and 114° (Table 4). In fact, the typical characteristic of the structural construction is actually created by the individual linkage of these [NLn4]9+ tetrahedra. As shown in Figure 3, the [NLn4]9+ units initially occur as dimers [N2Ln6]12+ by sharing a common edge (Ln1···Ln1), and they are then condensed to one-dimensional infinite strands along [001] by corner-linkage (via Ln2) with two similar neighboring units corresponding to ∞ 1 {[N(Ln1) 2 / 2 e (Ln2) 2 / 2 v ]3+} (e = edge-linking, v = vertex-linking). This type of [NLn4]9+-tetrahedral linkage is also found in the crystal structures of the nitride chlorides β-Y2NCl3 and β-Gd2NCl3 [18] and in those of nitride sulfide halides Ln6N3S4X (Ln = La–Nd; X = Cl, Br) [19,20]. In the latter, however, the crystal structure is made up of two kinds of strands that are commensurable with each other along their propagation axis. Figure 4 shows a projection of the crystal structure of the new Ln4N2S3 representatives with an A-type La4N2S3 structure with a view along the c-axis. The ∞ 1 {([NLn2]2)6+} double strands are separated by two crystallographically different S2− anions with almost octahedral Ln3+-coordination spheres (Table 5). The neighboring cationic chain units in the a-direction are similarly oriented per se, but compared to their adjacent chains in the b-direction, they get mirrored by a diagonal glide plane n that runs vertical to the b-axis at heights of one-fourth and three-fourths and are shifted by one-half in the a- and c-directions, respectively. Thus, a single strand is surrounded by a total of six more in the manner of a hexagonal rod packing.
Apart from the nitride sulfides Ln4N2S3 (Ln = Ce–Nd) and La4N2S3 [7] of the orthorhombic A-type modification presented here, a monoclinic form (B-type) for La4N2S3 [12] and Pr4N2S3 [9] has been reported for each with a crystal structure quite different from the orthorhombic one. Unlike the crystal structure of the A-type Ln4N2S3 members (Ln = La, Pr), in which linear chains are built by linkage of [N2Ln6]12+ bitetrahedra, in the B-type structure layers are produced by their cross-linkage via common vertices according to ∞ 2 {[N(Ln3/4) 2 / 2 e (Ln1/2) 2 / 2 v ]3+} with four- and eight-fold pores (Figure 5). Accompanied by a quadruplication of the cell volume for the B-type (Z = 8) as compared to the A-type (Z = 2), the unit cell of the B-Ln4N2S3 representatives contains four times the total number of cations and anions, but only twice the number of crystallographically different unkind particles owing to the doubling of the respective Wyckoff positions (8f and 4c or 4e as compared to 4g and 2a). With the exception of the already-mentioned distance Ln2–S2″ which loses its coordinative influence upon the transition from A-La4N2S3 to A-Ce4N2S3, both kinds of anions (N3− and S2−) as well as the cations can analogously be assigned to each other in their respective modifications as shown in Table 5.
In addition to La4N2S3 [7,12] crystallizing dimorphously in the A-La4N2S3- and in the B-Pr4N2S3-type structures and Ce4N2Se3, which is observed either with the Nd4N2Se3- or with the Ce4N2Te3-type arrangement, now the next nitride sulfide of the lanthanoids with the composition Pr4N2S3 can represent both the A- and B-type structures. In order to determine the respective high-pressure and/or high-temperature phases, the theoretically calculated densities using X-ray diffraction (Dx) give at least uniform indications, even though they are not strong. With values of 5.426 [7] and 5.772 g/cm3 (Table 1) the A-type Ln4N2S3 members (Ln = La, Pr) show somewhat larger densities as compared to 5.363 [12] and 5.740 g/cm3 [9], respectively, which are available for the possible low-pressure and/or high-temperature phases of the B-type representatives. To what extent these differences of 1.2% and 0.6% could be significant is left to the reader to determine. As the physical parts of the preparation methods for members of both modifications are identical (seven days at 900 °C in evacuated fused silica ampoules, see Experimental), only the chemical conditions can provide an explanation. If for the synthesis of the A-type Ln4N2S3 representatives (Ln = La–Nd), in addition to the lanthanoid metal and sulfur, cesium azide (CsN3) and the corresponding lanthanide bromide (LnBr3, Ln = La–Nd) with CsBr as a fluxing agent were used (see Experimental), the alkali metal and the halides in the form of the triiodides LnI3 (Ln = La, Pr), sodium azide (NaN3) and fluxing NaI varied for the preparation of the B-type Ln4N2S3 ones. Whether, in this case, the intermediates formed, such as elemental iodine (causing changes in pressure or chemical transport) or ternary halides (such as Cs3LnBr6 [21] in the first or Na3LnI6 [22] in the second case) play a role can only be speculated.

3. Experimental

As adapted from the standard methodology reported in [1], the new lanthanoid nitride sulfides Ln4N2S3 (Ln = Ce–Nd) are obtained by the reaction of lanthanoid metal (Ln; ChemPur: 99.9%) with sulfur (S; ChemPur: 99.9999%) and lanthanoid tribromide (LnBr3; prepared from CeO2, Pr6O11 and Nd2O3 (all: Johnson-Matthey: 99.999%) by the ammonium-bromide method [23]) and cesium azide (CsN3; Ferak: 99.9%). On adding cesium bromide (CsBr; ChemPur: 99.9%) as flux almost black, rod-shaped single crystals of the target compounds Ln4N2S3 (Ln = Ce–Nd) that reflect strongly in the incident light under a microscope are obtained after seven days at 900 °C in evacuated torch-sealed fused silica tubes.
Nonetheless, the process of the reaction according to
34 Ln + 27 S + 6 CsN3 + 2 LnBr3 → 9 Ln4N2S3 + 6 CsBr (Ln = Ce–Nd),
which can be classified as redox metathesis with the formation of CsBr as driving force, is not complete. Besides some white amorphous parts, which are presumably produced by undesired reactions with the silica-ampoule walls, mostly brown rods that could be characterized as Ln3NS3 representatives (Ln = Ce–Nd) [24] were also obtained. As in addition to this the whole product mixture in excess of CsBr is stable to hydrolysis, so the fluxing agent and by-product can easily be rinsed off with water. A largest possible black rod (0.02 × 0.03 × 0.20 mm3) of each of the new Ln4N2S3 members was selected from the mixture under paraffin oil and transferred into a mark-tube capillary to subsequently record the intensity data sets of X-ray diffraction experiments with the help of a plate detector (four-circle diffractometer Kappa-CCD, Bruker AXS). In Table 1, Table 2 and Table 3 the crystallographic data for the three new nitride sulfides Ln4N2S3 (Ln = Ce–Nd) are summarized.

4. Conclusions

The new series of lanthanoid(III) nitride sulfides with the composition Ln4N2S3 (Ln = Ce–Nd) adopting the A-type structure of La4N2S3 [7] expands the knowledge about the constitution of lanthanoid(III) nitride chalcogenides in general. Just like for all members of the formula types Ln3NCh3 [2,24] and Ln4N2Ch3 [4,5,6,7,8,9,10,11,12], nitride-centered lanthanoid tetrahedra [NLn4]9+ display the fundamental building units, which are here connected by one edge (e) and two vertices (v) each to form ∞ 1 {([N(Ln1) 2 / 2 e (Ln2) 2 / 2 v ]3+)2} chains. Bundled like hexagonal rod packing, they are held together by S2− anions taking care of the charge compensation. Whereas the coordination numbers (C.N. = 5–6) of these compare well with those in the binary sesquisulfides Ln2S3 with A- or C-type crystal structures (C.N. = 5–6) [25,26,27,28,29], the presence of tetrahedrally coordinated N3− anions baffles a little, since all binary lanthanoid(III) mononitrides LnN [30,31] exhibit octahedrally coordinated N3− anions in their rocksalt-type crystal structures.

Supplementary Materials

The following are available online at www.mdpi.com/2304-6740/5/1/2/s1, cif and checkcif files of Ce4N2S3, Nd4N2S3, and Pr4N2S3.

Acknowledgments

At this point the authors gratefully acknowledge the State of Baden-Württemberg (Stuttgart, Germany), the Deutsche Forschungsgemeinschaft (Bonn, Germany) and the Fonds der Chemischen Industrie (Frankfurt am Main, Germany) for considerable financial support.

Author Contributions

Falk Lissner conceived and performed the experiments; Falk Lissner recorded the intensity data sets of X-ray diffraction experiments and analyzed the data; Falk Lissner and Thomas Schleid wrote the paper.

Conflicts of Interest

The authors declare no conflict of interest.

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Inorganics 05 00002 g001 550
Figure 1. Coordination polyhedra around (Ln1)3+ and (Ln2)3+ in the A-type crystal structure of the Ln4N2S3 series (Ln = Ce–Nd).
Figure 1. Coordination polyhedra around (Ln1)3+ and (Ln2)3+ in the A-type crystal structure of the Ln4N2S3 series (Ln = Ce–Nd).
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Inorganics 05 00002 g002 550
Figure 2. Lattice parameters (a, b, and c), selected distances (d(Ln2–S″)), and molar volumes (Vm) of the complete A-type Ln4N2S3 series (Ln = La–Nd, error bars with a percentage of 0.5%) versus the ionic radii (ri) of the trivalent lanthanide cations [17].
Figure 2. Lattice parameters (a, b, and c), selected distances (d(Ln2–S″)), and molar volumes (Vm) of the complete A-type Ln4N2S3 series (Ln = La–Nd, error bars with a percentage of 0.5%) versus the ionic radii (ri) of the trivalent lanthanide cations [17].
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Inorganics 05 00002 g003 550
Figure 3. Linkage of tetrahedral [NLn4]9+ units via edges to dimers [N2Ln6]12+ and their linear vertex connection to ∞ 1 {[N(Ln1) 2 / 2 e (Ln2) 2 / 2 v ]3+} strands along [001] in the crystal structure of the A-type Ln4N2S3 series (Ln = La–Nd).
Figure 3. Linkage of tetrahedral [NLn4]9+ units via edges to dimers [N2Ln6]12+ and their linear vertex connection to ∞ 1 {[N(Ln1) 2 / 2 e (Ln2) 2 / 2 v ]3+} strands along [001] in the crystal structure of the A-type Ln4N2S3 series (Ln = La–Nd).
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Figure 4. Projection of the crystal structure of the A-type Ln4N2S3 series (Ln = La–Nd) on the [001] plane.
Figure 4. Projection of the crystal structure of the A-type Ln4N2S3 series (Ln = La–Nd) on the [001] plane.
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Figure 5. Linkage of tetrahedral [NLn4]9+ units via edges to dimers [N2Ln6]12+, their initial linear vertex connection to quadruples [N4Ln10]18+ and their final vertex fusion to porous sheets ∞ 2 {[NLn4/2]3+} perpendicular to [001] consisting of four- and eight-membered rings in the crystal structure of the B-type Ln4N2S3 series (Ln = La, Pr).
Figure 5. Linkage of tetrahedral [NLn4]9+ units via edges to dimers [N2Ln6]12+, their initial linear vertex connection to quadruples [N4Ln10]18+ and their final vertex fusion to porous sheets ∞ 2 {[NLn4/2]3+} perpendicular to [001] consisting of four- and eight-membered rings in the crystal structure of the B-type Ln4N2S3 series (Ln = La, Pr).
Inorganics 05 00002 g005
Table
Table 1. Crystallographic data for the three members of the Ln4N2S3 series (Ln = Ce–Nd).
Table 1. Crystallographic data for the three members of the Ln4N2S3 series (Ln = Ce–Nd).
CompoundCe4N2S3Pr4N2S3Nd4N2S3
Crystal systemorthorhombic
Space groupPnnm (no. 58)
a/pm644.31(4)641.23(4)635.19(4)
b/pm1554.13(9)1542.37(9)1536.98(9)
c/pm404.20(3)400.18(3)397.85(3)
Z2
Vm/cm3·mol−1121.87(2)119.17(2)116.95(2)
Dx/g·cm−35.6185.7725.995
DeviceNonius Kappa-CCD (Bruker AXS)
RadiationMo-Kα (λ = 71.07 pm)
±h, ±k, ±l8, 20, 58, 20, 58, 20, 5
2θmax/°56.5456.6056.39
F(000)588596604
Absorption correctionnumerically (X-SHAPE [14])
μ/mm−122.7524.8827.00
Extinction (g)0.00530.00080.0007
Measured reflections907173866968
Independent reflections575552546
Refl. with |Fo| ≥ 4σ(Fo)538457494
Rint, Rσ0.048, 0.0160.058, 0.0220.067, 0.025
Structure solution and refinementSHELX-97 [15]
Scattering factorsInternational Tables, Vol. C [16]
R1, R1 with |Fo| ≥ 4α(Fo)0.021, 0.0180.041, 0.0290.035, 0.028
wR2, GooF0.036, 1.1740.064, 1.1000.049, 1.166
Resid. electron density ρmax, ρmin/10−6 pm−31.02, −1.031.56, −1.321.11, −1.11
CSD numbers 1431115431117431116
1 Details of the structure refinements are available at the Fachinformationszentrum Karlsruhe (FIZ), 76344 Eggenstein-Leopoldshafen, Germany ([email protected]), on quoting the CSD numbers.
Table
Table 2. Fractional atomic coordinates for the three members of the Ln4N2S3 series (Ln = Ce–Nd).
Table 2. Fractional atomic coordinates for the three members of the Ln4N2S3 series (Ln = Ce–Nd).
AtomSite 1Ce4N2S3Pr4N2S3Nd4N2S3
x/ay/bx/ay/bx/ay/b
Ln14g0.22375(5)0.56460(2)0.22392(9)0.56451(3)0.22374(7)0.56437(3)
Ln24g0.26571(5)0.84323(2)0.26709(9)0.84333(3)0.26598(8)0.84315(3)
N4g0.1313(7)0.4154(3)0.1312(13)0.4164(6)0.1312(12)0.4154(5)
S12a000000
S24g0.2680(2)0.20004(8)0.2683(5)0.20011(16)0.2636(4)0.19985(14)
1 z/c = 0 for all positions.
Table
Table 3. Anisotropic displacement parameters (Uij 1/pm2) for the three members of the Ln4N2S3 series (Ln = Ce–Nd).
Table 3. Anisotropic displacement parameters (Uij 1/pm2) for the three members of the Ln4N2S3 series (Ln = Ce–Nd).
CompoundAtomU11U22U33U23U13U12
Ce4N2S3Ce171(2)51(2)50(2)00−4(1)
Ce2103(2)45(2)46(2)00−6(1)
N96(22)57(20)69(20)00−6(17)
S161(8)105(9)69(8)00−2(7)
S2178(7)55(6)57(6)0011(5)
Pr4N2S3Pr197(3)91(3)59(3)00−3(2)
Pr2140(3)84(3)55(3)00−8(2)
N58(38)138(42)74(42)00−5(33)
S1119(17)136(18)66(16)00−14(13)
S2208(13)71(11)81(12)0029(9)
Nd4N2S3Nd1111(3)58(3)72(3)00−8(2)
Nd2145(3)54(3)72(3)00−9(2)
N111(37)126(40)93(37)00−48(31)
S1100(14)95(15)102(15)00−11(11)
S2223(12)50(9)86(10)009(8)
1 Given in the expression exp[−2π2(a*2h2U11 + b*2k2U22 + c*2l2U33 + 2b*c*klU23 + 2a*c*hlU13 + 2a*b*hkU12)].
Table
Table 4. Selected interatomic distances (d/pm) and angles (∡/°) for the three members of the Ln4N2S3 series (Ln = Ce–Nd) compared to A-type La4N2S3.
Table 4. Selected interatomic distances (d/pm) and angles (∡/°) for the three members of the Ln4N2S3 series (Ln = Ce–Nd) compared to A-type La4N2S3.
La [7]CePrNd
Ln1–N(1×)233.8(6)230.9(5)229.6(9)227.6(8)
–N’(1×)243.2(6)239.4(4)236.1(9)236.4(8)
–S1(2×)287.8(1)287.4(1)285.1(1)283.1(1)
–S2(2×)296.9(1)291.9(1)289.5(2)288.1(2)
Ln2–N(2×)243.8(3)240.5(3)238.7(5)237.0(5)
–S1(1×)299.8(1)297.8(1)296.2(1)294.4(1)
–S2(2×)306.1(1)301.4(1)298.9(2)297.4(2)
–S2’(1×)315.1(2)307.9(2)305.4(3)306.0(3)
–S2″(1×)341.1(2)350.5(2)349.8(3)342.8(3)
N–Ln1(1×)233.8(6)230.9(5)229.6(9)227.6(8)
–Ln1’(1×)243.2(6)239.4(4)236.1(9)236.4(8)
–Ln2(2×)243.8(3)240.5(3)238.7(5)237.0(5)
Ln1–N–Ln1(1×)96.3(2)96.7(2)97.2(3)96.5(3)
Ln1–N–Ln2(2×)109.8(2)109.6(1)109.4(2)109.7(2)
Ln1−N–Ln2’(2×)112.5(2)112.5(1)112.8(2)112.7(2)
Ln2–N–Ln2(1×)114.4(2)114.4(2)113.9(4)114.1(3)
Table
Table 5. Motifs of mutual adjunction for the A- and B-type Ln4N2S3 structures (Ln = La–Nd).
Table 5. Motifs of mutual adjunction for the A- and B-type Ln4N2S3 structures (Ln = La–Nd).
Ln1Ln2Ln3Ln4C.N.
A-type Ln4N2S3
N2/22/2 4
S12/41/2 6
S22/23+1/3+1 5+1
C.N.66+1
B-type Ln4N2S3
N11/11/11/11/14
N21/11/11/11/14
S11/21/21/20/06
S21/20/01/21/26
S31/11/11/13/36
S41/13/31/11/16
C.N.6767

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Lissner, F.; Schleid, T. The A-Type Ln4N2S3 Series: New Nitride Sulfides of the Light Lanthanoids (Ln = Ce–Nd). Inorganics 2017, 5, 2. https://doi.org/10.3390/inorganics5010002

AMA Style

Lissner F, Schleid T. The A-Type Ln4N2S3 Series: New Nitride Sulfides of the Light Lanthanoids (Ln = Ce–Nd). Inorganics. 2017; 5(1):2. https://doi.org/10.3390/inorganics5010002

Chicago/Turabian Style

Lissner, Falk, and Thomas Schleid. 2017. "The A-Type Ln4N2S3 Series: New Nitride Sulfides of the Light Lanthanoids (Ln = Ce–Nd)" Inorganics 5, no. 1: 2. https://doi.org/10.3390/inorganics5010002

APA Style

Lissner, F., & Schleid, T. (2017). The A-Type Ln4N2S3 Series: New Nitride Sulfides of the Light Lanthanoids (Ln = Ce–Nd). Inorganics, 5(1), 2. https://doi.org/10.3390/inorganics5010002

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