Lücke, Jan

Schnick, Wolfgang

English

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Zn7[P12N24]Cl2—A Sodalite with a Phosphorus–Nitrogen Framework

Universität München: Elektronischen Publikationen

i
Z n 7 [ P 1 2 N 2 4 l C l 2 — A Sodalite with a Phosphorus-
Nitrogen Framework** 
By Wolfgang Schnick* and Jan Lücke 
Dedicated to Professor Karl-Heinz Büchel 
on the occasion of his 60th birthday 
Zeolites have increasingly found application as catalysts, 
molecular sieves, adsorbents, or ion exchangers in recent 
[*] Dr. W Schnick, Dipl.-Chem. J. Lücke 
Institut für Anorganische Chemie der Universität 
Gerhard-Domagk-Strasse 1, D-W-5300 Bonn 1 (FRG) 
[**] This work was supported by the Minister für Wissenschaft und Forschung 
des Landes Nordrhein-Westfalen, the Deutsche Forschungsgemeinschaft, 
and the Fonds der Chemischen Industrie. 
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2 © VCH Verlagsgesellschaft mbH, W-6940 Weinheim. 1992 0570-0833(9210202-0213 $ 3.50+ .25/0 213 
years. The useful properties of these aluminosilicates are 
based particularly on the characteristic topology of the tetra-
hedral skeletal structures, which have the general composi­
tion T 0 2 (T = A l , Si) . 1 1 1 Instead o f aluminum and silicon, 
many other elements such as Β, P, Fe, Cr, Sb, As, Ga, Ge, T i , 
Zr, and H f can be incorporated as central atoms o f the tetra­
hedrons in the zeolite la t t ice . 1 1 , 2 1 These modifications suc­
ceed in tailoring the catalytic properties o f zeolites for certain 
reactions. 1 2 1 However, hardly any proven facts on the ex­
change of elements of the anionic part of the lattice are 
known. Yet the replacement of oxygen by other electronega­
tive elements such as nitrogen should be a promising method 
of modifying the properties and potential applications o f this 
class of substances. 
Recently we prepared pure, crystalline H P N 2 through the 
ammonolysis of P 3 N 5 in thick-walled quartz ampules under 
pressure [Eq. (a)]. The required N H 3 was formed in situ in 
another compartment o f the apparatus by treatment o f 
M g 3 N 2 with N H 4 C I [Eq. ( b ) ] . f 3 J 
sso°c f . 
P 3 N 5 + N H 3 > 3 H P N 2 (a) 
6d, 30 bar 
400 °C 
Mg 3 N 2 + 6NH 4C1 • 3 MgCl 2 + 8 N H 3 (b) 
The structural investigation [ 3 1 shows a [PNJ] skeleton 
isosteric with ß-cristobalite, as has been found in L i P N 2 . f 4 ] 
Since these phosphorus(v) nitrides have structural similari-
ties with silicates, the possibility of constructing zeolite-like 
P - N structures occurred to us. In fact, we succeeded in re-
placing M g 3 N 2 by Z n 3 N 2 in the H P N 2 preparation and 
we obtained a new compound with composition 
Z n 5 H 4 [ P I 2 N 2 4 ] C l 2 in quantitative y ie ld 1 5 1 . Analogously to 
H P N 2 , a phosphorus(v) nitride had formed with molar ratio 
P : N = 1:2, while zinc from Z n C l 2 , which is volatile under 
the given conditions, was incorporated into the solid while it 
forms. A complete exchange of the hydrogen atoms in the 
product was achieved afterwards through treatment wi th 
Z n C l 2 accompanied by evolution of H C l [Eq. (c)]. 
700°C,3d 
Zn 5 H 4 [P I 2 N 2 4 ]C l 2 + 2ZnCl 2 • Z n 7 [ P 1 2 N 2 4 ] C l 2 + 4HC1 (c) 
Surprisingly however, the title compound Z n 7 [ P 1 2 N 2 4 ] C l 2 
can also be prepared by reaction of the inexpensive starting 
materials N H 4 C 1 , Z n C l 2 , and (PNC1 2 ) 3 [Eq. (d)]. 
700 °C, 3d 
7ZnCi 2 + 12NH4C1 + 4(PNCI 2 ) 3 > 
Zn.tPj 2 N 2 4 ] C 1 2 + 48 HCl (d) 
In all preparations Z n 7 [ P 1 2 N 2 4 ] C l 2 forms as a fine crys-
talline and colorless powder insoluble in water and acid. 
Only in a special autoclave system 1 6 1 does Z n 7 [ P 1 2 N 2 4 ] C i 2 
decompose in dilute sulfuric acid (190°C, 10 bar, 2 d ; the 
phosphorus(v) nitride hydrolyses to ammonium hydrogen 
phosphate). 
The powder diagram o f the title compound indicates a 
cubic structure; the similarity to the powder diagram of so-
dalite N a 8 [ A l 6 S i 6 0 2 4 ] C l 2 is evident. 1 7 1 The Rietveld refine-
ment of the crystal structure of Z n 7 [ P 1 2 N 2 4 ] C l 2 on the basis 
of the powder diffraction data 1 8 1 confirmed the suspected 
analogy. 1 9 1 I t shows that phosphorus and nitrogen form a 
sodalite-like framework of corner-sharing P N 4 tetrahedrons 
(Fig. 1). The P - N distance of 163.6(7) pm is comparable 
with that in L i P N 2 (164.5(7) pm) . 1 4 1 Also the experimentally 
determined P-N-P bond angle (125.8(4)°) agrees with the 
corresponding angle in L i P N 2 (123.6(8)°) . f 4 i This result is in 
Fig. 1. Section of the crystal structure of Zn 7 [P 1 2 N 2 4 JCl 2 . The [P t 2 N 2 4 J frame-
work of the sodalite type is constructed from [P 4 N 4 ] and [P 6 N 6 ] rings (P-N 
163.6(7) pm). In the center of each β cage is a CI" ion, surrounded by tetrahe-
drally arranged Zn 2 + ions (Zn-CI 259.6(2) pm). The Zn 2 + ions are coordinated 
in a distorted tetrahedral manner by one C I i o n and three Ν atoms (Zn-N 
196.0(8) pm). Size of Zn and CI correspond to the respective ionic radii. P. 
black, N : white, CI: gray, Zn: striped. 
accord with the topological similarity between the P - N part 
of the structure in L i P N 2 (analogous to ß-cristobalite) and 
the P - N structure found here: in both cases the network 
skeletons include P N 4 tetrahedrons linked through all four 
apexes by corner-sharing. However, whereas three-dimension-
ally bonded [ P 6 N 6 ] rings occur exclusively in the ß-cristo-
balite variant ( L i P N 2 ) , in the sodalite framework [P 4 N 4 J 
rings are also found. The two types of rings together form 
capped octahedrons (β cages), which are typical building 
units of the sodalite type structure (Fig. 1). Situated at the 
center of each β cage is a C I " ion, in a tetrahedral environ­
ment of Z n 2 + ions. Every metal cation has, besides the Z n -
Cl contact (259.6(2) pm), three contacts to nitrogen atoms of 
the P - N framework ( Z - N 196.0(8) pm) forming a distorted 
tetrahedron. In each case the contact distances correspond to 
the sum of the ionic r a d i i . 1 1 0 1 Comparison of the composition 
of Z n 7 [ P 1 2 N 2 4 ] C l 2 [ 5 1 with that of N a 8 ( S i 6 A l 6 0 2 4 ] C l 2 reveals 
a statistical occupation o f the Zn positions (occupancy fac­
tor 7/8). However, a part o f the Z n 2 + ions may be replaced 
by two protons each. The P - N sodalite described here has a 
phase width of Z n ( 7 _ x ) H 2 x [ P 1 2 N 2 4 ] C l 2 (0 < χ < 2). A contin­
uous increase in the lattice constant is observed with increas­
ing zinc content. Other metals such as Co, N i , and Y b were 
also built into the P - N sodalite in place o f zinc, as described 
by Equation (d). 
Received: July 11, 1991 [Z4789 IE] 
Publication delayed at the authors* request 
German version: Angew. Chem. 1992, 104, 208 
CAS Registry numbers: 
P 3 N 5 , 12136-91-3; NH4C1,12125-02-9; Zn 3 N 2 , 128579-03-3; Zn 5 H 4 [P 1 2 N 2 4 ] -
Cl 2 , 136952-78-8; ZnCl 2 , 7646-85-7; Zn,[P l 2 N 2 4 ]Cl 2 , 136952-79-9; (PNCl 2) 3, 
940-71-6. 
[1] J. V. Smith, Chem. Rev. 1988. 8, 149. 
[2] W Hölderich, Μ. Hesse, F. Naumann, Angew. Chem. 1988, 100, 232; 
Angew. Chem. Int. Ed. Engl. 1988, 27, 226. 
214 © VCH Verlagsgesellschaft mbH, W-6940 Weinheim. 1992 0570-0833f92f0202O2I4$ 3.50+.25J0 Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2 
[3] W. Schnick, J. Lücke, Z. Anorg. Allg. Chem., in press. 
[4] W. Schnick, J. Lücke, Z. Anorg. Allg. Chem. 1990, 588, 19. 
[5] For the elemental analyses the products were hydrolyzed. Zinc was then 
determined complexometrically with EDTA, phosphorus photometrically 
as molybdovanadatophosphate, nitrogen photometrically as indophenol, 
and chloride argentometrically. In a parallel study the composition in the 
solid was checked by energy and wavelength dispersive X-ray microanaly-
sis (EDX: Zn, P, CI; WDX: absence of O). The presence of hydrogen (as 
N-H groups) was ascertained by IR spectroscopy. 
[6] Cf. O. Buresch, H. G. von Schnering, Fresenius Ζ. Anal. Chem. 1984, 319, 
418. 
[7] I . Hassan, H. D. Grundy, Acta Crystallogr. Sect. Β 1984, 40, 6. 
[8] Zn 7(P 1 2N 2 ,JCl 2: /43m, a = 824.21(1) pm, Z = 1, Stoe-Stadi-P transmis­
sion powder diffractometer, Cu K e l radiation, germanium monochromator, 
linear position-sensitive counter (Stoe Mini-PSD), Lindemann capillary, 
5451 data points, measurement range 10° <,29 < 119°, duration of mea­
surement 12 h, 57 observed reflections, 3 refined site parameters, 4 temper­
ature parameters. Rietveld refinement: R^ « 0.0848, Ä, = 0.076, GOF = 
4.0. Further details of the crystal structure investigation may be obtained 
from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissen-
schaftlich-technische Information mbH, D-W-7514 Eggenstein-Leopolds-
hafen 2 (FRG) on quoting the depository number CSD-55611, the names 
of the authors, and the journal citation. 
[9] The Ρ atoms in Zn 7 [P I 2 N 2 4 ]Cl 2 occupy positions identical to those of Al 
and Si in Na 8 [Al 6 Si e 0 2 4 ]Cl 2 . The structure of the P-N sodalite described 
in the space group /53m, a Klassengleich supergroup (k2) of 7*43/1, which 
is the space group of Na sodalite. Z n 7 [ P 1 2 N 2 4 ] C l 2 thus crystallizes in a 
defect variant of the Ca 8 [Al 6 Si 6 0 1 4 ]0 2 type; cf. V. I . Ponomarev, D. M . 
Kheiker, Ν. V. Belov, Kristallograßya 1970, 15, 918. 
[10] a) W. H. Baur, Crystallogr. Rev. 1987, 1, 59; b) A. F. Wells: Structural 
Inorganic Chemistry, 5. ed., Clarendon, Oxford 1987, p. 313. 
 
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2 © VCH Verlagsgesellschaft mbH, W-6940 Weinheim, 1992 0570-0833/92/0202-0215 $ 3.50+ .25/0 2 1 5 


German

Zn7[P12N24]Cl2 - A Sodalite with a Phosphorus-Nitrogen Framework

Open Access LMU ( Ludwig-Maximilians-Univ. München)

iZ n 7 [ P 1 2 N 2 4 l C l 2 — A Sodalite with a Phosphorus-Nitrogen Framework** By Wolfgang Schnick* and Jan Lücke Dedicated to Professor Karl-Heinz Büchel on the occasion of his 60th birthday Zeolites have increasingly found application as catalysts, molecular sieves, adsorbents, or ion exchangers in recent [*] Dr. W Schnick, Dipl.-Chem. J. Lücke Institut für Anorganische Chemie der Universität Gerhard-Domagk-Strasse 1, D-W-5300 Bonn 1 (FRG) [**] This work was supported by the Minister für Wissenschaft und Forschung des Landes Nordrhein-Westfalen, the Deutsche Forschungsgemeinschaft, and the Fonds der Chemischen Industrie. Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2 © VCH Verlagsgesellschaft mbH, W-6940 Weinheim. 1992 0570-0833(9210202-0213 $ 3.50+ .25/0 213 years. The useful properties of these aluminosilicates are based particularly on the characteristic topology of the tetra-hedral skeletal structures, which have the general composi­tion T 0 2 (T = A l , Si) . 1 1 1 Instead o f aluminum and silicon, many other elements such as Β, P, Fe, Cr, Sb, As, Ga, Ge, T i , Zr, and H f can be incorporated as central atoms o f the tetra­hedrons in the zeolite la t t ice . 1 1 , 2 1 These modifications suc­ceed in tailoring the catalytic properties o f zeolites for certain reactions. 1 2 1 However, hardly any proven facts on the ex­change of elements of the anionic part of the lattice are known. Yet the replacement of oxygen by other electronega­tive elements such as nitrogen should be a promising method of modifying the properties and potential applications o f this class of substances. Recently we prepared pure, crystalline H P N 2 through the ammonolysis of P 3 N 5 in thick-walled quartz ampules under pressure [Eq. (a)]. The required N H 3 was formed in situ in another compartment o f the apparatus by treatment o f M g 3 N 2 with N H 4 C I [Eq. ( b ) ] . f 3 J sso°c f . P 3 N 5 + N H 3 > 3 H P N 2 (a) 6d, 30 bar 400 °C Mg 3 N 2 + 6NH 4C1 • 3 MgCl 2 + 8 N H 3 (b) The structural investigation [ 3 1 shows a [PNJ] skeleton isosteric with ß-cristobalite, as has been found in L i P N 2 . f 4 ] Since these phosphorus(v) nitrides have structural similari-ties with silicates, the possibility of constructing zeolite-like P - N structures occurred to us. In fact, we succeeded in re-placing M g 3 N 2 by Z n 3 N 2 in the H P N 2 preparation and we obtained a new compound with composition Z n 5 H 4 [ P I 2 N 2 4 ] C l 2 in quantitative y ie ld 1 5 1 . Analogously to H P N 2 , a phosphorus(v) nitride had formed with molar ratio P : N = 1:2, while zinc from Z n C l 2 , which is volatile under the given conditions, was incorporated into the solid while it forms. A complete exchange of the hydrogen atoms in the product was achieved afterwards through treatment wi th Z n C l 2 accompanied by evolution of H C l [Eq. (c)]. 700°C,3d Zn 5 H 4 [P I 2 N 2 4 ]C l 2 + 2ZnCl 2 • Z n 7 [ P 1 2 N 2 4 ] C l 2 + 4HC1 (c) Surprisingly however, the title compound Z n 7 [ P 1 2 N 2 4 ] C l 2 can also be prepared by reaction of the inexpensive starting materials N H 4 C 1 , Z n C l 2 , and (PNC1 2 ) 3 [Eq. (d)]. 700 °C, 3d 7ZnCi 2 + 12NH4C1 + 4(PNCI 2 ) 3 > Zn.tPj 2 N 2 4 ] C 1 2 + 48 HCl (d) In all preparations Z n 7 [ P 1 2 N 2 4 ] C l 2 forms as a fine crys-talline and colorless powder insoluble in water and acid. Only in a special autoclave system 1 6 1 does Z n 7 [ P 1 2 N 2 4 ] C i 2 decompose in dilute sulfuric acid (190°C, 10 bar, 2 d ; the phosphorus(v) nitride hydrolyses to ammonium hydrogen phosphate). The powder diagram o f the title compound indicates a cubic structure; the similarity to the powder diagram of so-dalite N a 8 [ A l 6 S i 6 0 2 4 ] C l 2 is evident. 1 7 1 The Rietveld refine-ment of the crystal structure of Z n 7 [ P 1 2 N 2 4 ] C l 2 on the basis of the powder diffraction data 1 8 1 confirmed the suspected analogy. 1 9 1 I t shows that phosphorus and nitrogen form a sodalite-like framework of corner-sharing P N 4 tetrahedrons (Fig. 1). The P - N distance of 163.6(7) pm is comparable with that in L i P N 2 (164.5(7) pm) . 1 4 1 Also the experimentally determined P-N-P bond angle (125.8(4)°) agrees with the corresponding angle in L i P N 2 (123.6(8)°) . f 4 i This result is in Fig. 1. Section of the crystal structure of Zn 7 [P 1 2 N 2 4 JCl 2 . The [P t 2 N 2 4 J frame-work of the sodalite type is constructed from [P 4 N 4 ] and [P 6 N 6 ] rings (P-N 163.6(7) pm). In the center of each β cage is a CI" ion, surrounded by tetrahe-drally arranged Zn 2 + ions (Zn-CI 259.6(2) pm). The Zn 2 + ions are coordinated in a distorted tetrahedral manner by one C I i o n and three Ν atoms (Zn-N 196.0(8) pm). Size of Zn and CI correspond to the respective ionic radii. P. black, N : white, CI: gray, Zn: striped. accord with the topological similarity between the P - N part of the structure in L i P N 2 (analogous to ß-cristobalite) and the P - N structure found here: in both cases the network skeletons include P N 4 tetrahedrons linked through all four apexes by corner-sharing. However, whereas three-dimension-ally bonded [ P 6 N 6 ] rings occur exclusively in the ß-cristo-balite variant ( L i P N 2 ) , in the sodalite framework [P 4 N 4 J rings are also found. The two types of rings together form capped octahedrons (β cages), which are typical building units of the sodalite type structure (Fig. 1). Situated at the center of each β cage is a C I " ion, in a tetrahedral environ­ment of Z n 2 + ions. Every metal cation has, besides the Z n -Cl contact (259.6(2) pm), three contacts to nitrogen atoms of the P - N framework ( Z - N 196.0(8) pm) forming a distorted tetrahedron. In each case the contact distances correspond to the sum of the ionic r a d i i . 1 1 0 1 Comparison of the composition of Z n 7 [ P 1 2 N 2 4 ] C l 2 [ 5 1 with that of N a 8 ( S i 6 A l 6 0 2 4 ] C l 2 reveals a statistical occupation o f the Zn positions (occupancy fac­tor 7/8). However, a part o f the Z n 2 + ions may be replaced by two protons each. The P - N sodalite described here has a phase width of Z n ( 7 _ x ) H 2 x [ P 1 2 N 2 4 ] C l 2 (0 < χ < 2). A contin­uous increase in the lattice constant is observed with increas­ing zinc content. Other metals such as Co, N i , and Y b were also built into the P - N sodalite in place o f zinc, as described by Equation (d). Received: July 11, 1991 [Z4789 IE] Publication delayed at the authors* request German version: Angew. Chem. 1992, 104, 208 CAS Registry numbers: P 3 N 5 , 12136-91-3; NH4C1,12125-02-9; Zn 3 N 2 , 128579-03-3; Zn 5 H 4 [P 1 2 N 2 4 ] -Cl 2 , 136952-78-8; ZnCl 2 , 7646-85-7; Zn,[P l 2 N 2 4 ]Cl 2 , 136952-79-9; (PNCl 2) 3, 940-71-6. [1] J. V. Smith, Chem. Rev. 1988. 8, 149. [2] W Hölderich, Μ. Hesse, F. Naumann, Angew. Chem. 1988, 100, 232; Angew. Chem. Int. Ed. Engl. 1988, 27, 226. 214 © VCH Verlagsgesellschaft mbH, W-6940 Weinheim. 1992 0570-0833f92f0202O2I4$ 3.50+.25J0 Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2 [3] W. Schnick, J. Lücke, Z. Anorg. Allg. Chem., in press. [4] W. Schnick, J. Lücke, Z. Anorg. Allg. Chem. 1990, 588, 19. [5] For the elemental analyses the products were hydrolyzed. Zinc was then determined complexometrically with EDTA, phosphorus photometrically as molybdovanadatophosphate, nitrogen photometrically as indophenol, and chloride argentometrically. In a parallel study the composition in the solid was checked by energy and wavelength dispersive X-ray microanaly-sis (EDX: Zn, P, CI; WDX: absence of O). The presence of hydrogen (as N-H groups) was ascertained by IR spectroscopy. [6] Cf. O. Buresch, H. G. von Schnering, Fresenius Ζ. Anal. Chem. 1984, 319, 418. [7] I . Hassan, H. D. Grundy, Acta Crystallogr. Sect. Β 1984, 40, 6. [8] Zn 7(P 1 2N 2 ,JCl 2: /43m, a = 824.21(1) pm, Z = 1, Stoe-Stadi-P transmis­sion powder diffractometer, Cu K e l radiation, germanium monochromator, linear position-sensitive counter (Stoe Mini-PSD), Lindemann capillary, 5451 data points, measurement range 10° <,29 < 119°, duration of mea­surement 12 h, 57 observed reflections, 3 refined site parameters, 4 temper­ature parameters. Rietveld refinement: R^ « 0.0848, Ä, = 0.076, GOF = 4.0. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissen-schaftlich-technische Information mbH, D-W-7514 Eggenstein-Leopolds-hafen 2 (FRG) on quoting the depository number CSD-55611, the names of the authors, and the journal citation. [9] The Ρ atoms in Zn 7 [P I 2 N 2 4 ]Cl 2 occupy positions identical to those of Al and Si in Na 8 [Al 6 Si e 0 2 4 ]Cl 2 . The structure of the P-N sodalite described in the space group /53m, a Klassengleich supergroup (k2) of 7*43/1, which is the space group of Na sodalite. Z n 7 [ P 1 2 N 2 4 ] C l 2 thus crystallizes in a defect variant of the Ca 8 [Al 6 Si 6 0 1 4 ]0 2 type; cf. V. I . Ponomarev, D. M . Kheiker, Ν. V. Belov, Kristallograßya 1970, 15, 918. [10] a) W. H. Baur, Crystallogr. Rev. 1987, 1, 59; b) A. F. Wells: Structural Inorganic Chemistry, 5. ed., Clarendon, Oxford 1987, p. 313.  Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2 © VCH Verlagsgesellschaft mbH, W-6940 Weinheim, 1992 0570-0833/92/0202-0215 $ 3.50+ .25/0 2 1 5 

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Zn7[P12N24]Cl2 - A Sodalite with a Phosphorus-Nitrogen Framework

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