Jessica
Lichte
,
Christian
Näther
and
Wolfgang
Bensch
*
Christian-Albrechts Universität, Institut für Anorganische Chemie, D-24118 Kiel, Germany. E-mail: wbensch@ac.uni-kiel.de; Fax: +49 431 880 1520; Tel: +49 431 880 2091
First published on 2nd May 2014
Four compounds of composition [dienH2][Co(dien)2][Ge2S6] (dien = diethylenetriamine) were obtained under solvothermal conditions changing the reaction time and educt ratio in the reaction slurries. In three compounds the [Co(dien)2]2+ complexes adopt the s-fac and in one the u-fac configuration. The main differences between the samples are found in the number and type of protonated dien molecules. In one distinct cation of compound 1 as well as in compound 2 the terminal N atoms are protonated, whereas in the second cation of 1 as well as in 3 and 4, one terminal and the central N atom are protonated. Therefore, the compounds with different protonated cations are tautomers, whereas compounds 3 and 4 represent polymorphic modifications. The occurrence of tautomerism and polymorphism for compounds with identical chemical composition is unprecedented in the chemistry of thiometallates and was never reported until now. In the crystal structure of all compounds the (dienH2)2+ cations and the [Ge2S6]4− anions are linked by intermolecular N–H⋯S hydrogen bonding into different supramolecular networks.
The situation is different for As and Sb, especially if these atoms are in the oxidation state +3 forming [AsS3]3− resp. [SbS3]3− trigonal pyramids as primary building units which often undergo condensation reactions to form more complex anions.22,23 Combination of the tetrahedral [GeS4]4− group with the [SbS3]3− pyramid should generate new compounds exhibiting unique structures. Indeed there are some examples for such combinations reported in literature like [Co(dien)2]2[GeSb4S10] (dien = diethylenetriamine) or [Mn(en)3][GeSb2S6] (en = ethylenediamine). In the former compound semi-cube like [GeSb2S7] clusters and chain-like Sb4S10 tetramers are observed being interconnected into a double layer with composition [GeSb4S10]. In the latter compound a GeS4 tetrahedron, one SbS3 pyramid and a SbS4 moiety are joined to form a [GeSb2S8] group and each of these groups is interconnected to three adjacent units via their four terminal S atoms to generate a 2-D anionic network with composition [GeSb2S6].24 A semi-cube like moiety [GeSb2S7] is also the main structural motif in [Ni(dien)2]3[Ge3Sb8S21]·0.5H2O. Alternating [GeSb2S7] units and SbS3 pyramids sharing a common S atom lead to the formation of a layered anion [Ge3Sb8S21] containing large pores with dimensions of about 13·13 Å.25 Remarkable ion exchange properties were reported for the three-dimensional network compound [(Me)2NH2]2[Sb2GeS6] ([(Me)2NH2]2 = dimethylammonium). Two different left-handed helices generated by corner-sharing of SbS4 and GeS4 units are joined to form channels hosting the cations.26 In the compound [(Me)2NH2]6[Ge2Sb2S7][Ge4S10] the adamantane-like [Ge4S10]4− anion coexists with the [GeSb2S7]2− anion. In the latter anion a Sb–Sb bond is observed which is very rare in thioantimonates. The structure of [dabcoH]2[Ge2Sb3S10] (dabco = 1,4-diazabicyclo[2.2.2]octane) features a [Ge2Sb3S10]n3n− ribbon constructed by two [GeSbS5] chains interconnected by a SbS4 moiety.27 A one-dimensional anionic ribbon [GeSb2S6]n2n− containing the unique {GeSb3S11} building unit was observed in the structure of [AEPH2][GeSb2S6]·CH3OH (AEP = N-(2-aminoethyl)piperazine). This compound exhibits photocatalytic activity in the degradation of rhodamine B.28
In the past few years we demonstrated that transition metal complexes are suitable structure directing molecules forcing the formation of new thiometallate compounds exhibiting unusual and unique crystal structures.29–33 During further explorative syntheses to combine thioantimonates with thiogermanates and using an in situ generated Co2+ transition metal complex to prepare new compounds exhibiting new structural motifs, we obtained three compounds with composition [dienH2][Co(dien)2][Ge2S6] by increasing the amount of Sb in the reaction mixture. Another compound with identical composition was isolated using slightly different educt ratios and increasing the reaction time. The appearance of tautomeric and polymorphic forms of a thiometalate is unique and was never reported before. Here we report the solvothermal syntheses and the crystal structures of these new compounds exhibiting dienH2 molecules being protonated at different N atoms.
Compound | 1 | 2 | 3 | 4 |
---|---|---|---|---|
Formula | C12H41CoGe2N9S6 | C12H41CoGe2N9S6 | C12H41CoGe2N9S6 | C12H41CoGe2N9S6 |
MW/g mol−1 | 708.01 | 708.01 | 708.01 | 708.01 |
Crystal system | Triclinic | Triclinic | Orthorhombic | Orthorhombic |
Space group | P | P | Pbca | Pca21 |
a/Å | 11.3224(3) | 7.2034(5) | 15.2110(3) | 14.7043(3) |
b/Å | 14.6492(4) | 9.2773(6) | 16.7025(4) | 9.0099(2) |
c/Å | 18.3710(5) | 11.4365(8) | 21.8821(4) | 21.4540(5) |
α/° | 71.000(2) | 74.107(5) | 90 | 90 |
β/° | 78.352(2) | 73.402(5) | 90 | 90 |
γ/° | 73.441(2) | 71.293(5) | 90 | 90 |
V/Å3 | 2741.5(2) | 679.62(8) | 5559.4(2) | 2842.3(2) |
T/K | 293 | 293 | 293 | 293 |
Z | 4 | 1 | 8 | 4 |
D calc/g cm−3 | 1.715 | 1.730 | 1.692 | 1.655 |
μ/mm−1 | 3.254 | 3.282 | 3.209 | 3.139 |
θ max/deg | 28.0 | 28.0 | 28.0 | 26.0 |
Measured refl. | 38362 | 7633 | 42958 | 38098 |
R int | 0.0462 | 0.0198 | 0.0704 | 0.0404 |
T min/max | 0.5285/0.6177 | 0.5423/0.6735 | 0.5149/0.7110 | 0.5386/0.7204 |
Unique refl. | 13102 | 3205 | 6648 | 5573 |
Refl. [F0 > 4σ(F0)] | 10537 | 2933 | 5672 | 5486 |
Parameters | 552 | 148 | 273 | 283 |
R 1 [F0 > 4σ(F0)] | 0.0388 | 0.0295 | 0.0474 | 0.0199 |
wR2 [all data] | 0.0908 | 0.0744 | 0.0832 | 0.0482 |
GOF | 1.043 | 1.110 | 1.142 | 1.042 |
Δρmax/min/e Å−3 | 0.851/−0.606 | 0.818/−0.701 | 0.503/−0.537 | 0.284/−0.249 |
CCDC – 985614 (1), CCDC – 985615 (2), CCDC – 985616 (3) and CCDC – 985617 (4) contain the supplementary crystallographic data for this paper.
The role of antimony for the formation of the samples is not understood. But there are examples reported in literature that an element or a compound which were not in the final product was a necessary ingredient for the formation of the material.35,36
All four compounds contain the well known [Ge2S6]4− anion composed of two edge-sharing GeS4 tetrahedra (Fig. 1), [Co(dien)2]2+ complexes and diprotonated dien molecules (see Scheme 1). In all [Ge2S6]4− anions of the title compounds the Ge–S bonds exhibit the typical pattern of two long Ge–Sbr–Ge bonds (range in the four compounds: 2.2658(9)–2.2973(7) Å) and two shorter Ge–Sterm bonds (range in the four compounds: 2.1416(8)–2.1714(10) Å) (see tables in ESI†).
Fig. 1 The Co1 centred [Co(dien)2]2+ complex in 1 with numbering of selected atoms. Note that the other two [Co(dien)2]2+ complexes have the same configuration. H atoms are not displayed. |
Surprisingly, the dien molecules in these compounds are differently protonated. In compound 2 only the terminal N atoms are protonated, whereas in 3 and 4 only cations are observed, in which one terminal and the central N atom is protonated, leading to two different polymorphic modifications. In compound 1 both tautomeric dien cations are found.
Compounds 1 and 2 crystallize in the triclinic space group P (Table 1) but with different number of molecules in the unit cell. In the structure of 1 three crystallographically independent Co2+ ions are present of which two occupy special positions. The four unique Ge atoms and all other atoms in 1 are located on general positions. The three independent Co2+ ions are each surrounded by two dien molecules yielding distorted CoN6 octahedra in s-fac configuration (Fig. 1).
The Co–N bond lengths in the three complexes (Co1: 2.159(3)–2.188(3) Å; Co2: 2.140(3)–2.184(3) Å; Co3: 2.141(3)–2.197(3) Å, Table S1†) are typical for [Co(dien)2]2+ with the s-fac configuration.
A remarkable structural detail of 1 is the occurrence of both tautomeric dien cations (see Scheme 1). In the structure of 1 anions and Co2+ centred cations alternate along [100] while along [001] the sequence is ⋯[Ge2S6]4−–[dienH2]2+–[Ge2S6]4−⋯ (Fig. 2). Along [010] the different constituents form rods. Alternatively, the arrangement of the constituents may be described as alternating layers composed of [dienH2]2+–[Ge2S6]4− and of Co2+ centred complexes. The H atoms of the [dienH2]2+ bound to the N atoms are involved in S⋯H–N bonding interactions and a layer-like arrangement of cations and anions is realized within the (010) plane (Fig. 3). The two unique [dienH2]2+ cations each join three [Ge2S6]4− anions via their terminal S atoms generating different types of ring-like motifs (Fig. 3). All three H atoms of the terminal NH3 group and both H atoms of the central NH2 moiety of molecule 1 are involved in S⋯H interactions while only one H atom of the terminal NH2 unit has such an interaction. In the second protonated dien molecule containing two terminal NH3 groups five H atoms are engaged in S⋯H bonding and also the H atom of the central NH unit. Hence, in both molecules six out of seven H atoms bonded to N have S⋯H bonds (Table S2†). Taking into account the hydrogen bonding interactions between S atoms of the anions and the H atoms of the Co2+ centred complexes a very complex N–H⋯S bonding pattern is generated yielding a 3D supramolecular assembly.
Fig. 3 Layers in the structure of 1 generated by intermolecular S⋯H–N bonding interactions. Only H atoms bonded to N atoms are displayed. |
In the structure of compound 2 with one formula unit in the cell the unique Co2+ ion is located on a special position while all remaining independent atoms are located on general positions. Like in compound 2 the [Co(dien)2]2+ complex adopts the s-fac configuration with comparable Co–N bond lengths as observed in 1 (Co–N: 2.153(2)–2.188(2) Å, Table S3†). In contrast to 1 only one type of protonated dien molecule is observed (Scheme 1) with two terminal NH3 groups. In the structure of 2 a similar arrangement of the anions and cations like in 1 is found with [Ge2S6]4− anions and [Co(dien)2]2+ complexes alternating along [001] and the protonated amine molecules and the anions along [010] (Fig. 4).
The two NH3 groups of the dien molecule and the terminal S atoms of the anion exhibit N–H⋯S bonding interactions leading to formation of a two dimensional supramolecular layer-like arrangement within the (001) plane being characterized by rings composed of two dienH2 cations and two [Ge2S6]4− anions (Fig. 5). We note that all H atoms of the NH3 groups are engaged in S⋯H–N bonding to two different anions (Table S4†) while the H atom of the central NH group does not show S⋯H interactions. Along [100] adjacent [Ge2S6]4− anions are interconnected into rods by the [dienH2]2+ ions.
Fig. 5 N–H⋯S hydrogen bonding network in the structure of compound 2 involving [Ge2S6]4− anions and [dienH2]2+ cations. Note that not all H atoms are displayed. |
The [Co(dien)2]2+ complexes are located between the layers composed of [dienH2]2+ cations and [Ge2S6]4− and including the S⋯H–N interactions between the anions and the [Co(dien)2]2+ complex a three-dimensional array of the cations and anions is generated.
Compound 3 crystallizing in the orthorhombic space group Pbca (Table 1) contains eight formula units and all unique atoms sit on general positions. The unique Co2+ ion is surrounded by two dien ligands (Co–N bond lengths: 2.139(3)–2.210(3) Å, Table S5†) and adopts the u-fac configuration (Fig. 6). In this compound charge neutrality is achieved by the presence of one dien molecule with one protonated terminal N atom and the protonated central N atom (Scheme 1).
Fig. 6 The [Co(dien)2]2+ cation with u-fac configuration (left) and the arrangement of the cations and anions in the structure of compound 3 (right). |
The arrangement of the cations and anions follows the same pattern as observed for 1 and 2 where cations and anions alternate along two directions (here: [010] and [001]) and individual ions are arranged to form rods along the third direction.
The N–H⋯S bonding interactions (Table S6†) generate a layer-like arrangement within the (001) plane containing rings composed of three cations and anions (Fig. 7). Two H atoms of the terminal NH3 group and both H atoms of the central and terminal NH2 units exhibit such interactions (Table S6†). In contrast to compounds 1 and 2, one bridging S atom of the [Ge2S6]4− anion has a short S⋯H–N contact besides the four terminal S atoms. The N–H atoms of the [Co(dien)2]2+ complex exhibit also hydrogen bonds to S atoms to form a three-dimensional supramolecular network.
Fig. 7 The S⋯H–N bonding network in the structure of compound 3. The C–H H atoms are omitted for clarity. |
Compound 4 crystallizes in the non-centrosymmetric space group Pca21 (Table 1) with four formula units and all atoms being located on general positions. The unique [Co(dien)2]2+ complex adopts the s-fac configuration with Co–N bond length very similar to those observed for the other three compounds (Co–N: 2.139(3)–2.210(3) Å, Table S7†). The charge compensating protonated dien molecule contains a terminal NH3 group and a central NH2 unit (Scheme 1). In the structure rows composed of [Co(dien)2]2+ complexes and [Ge2S6]4− ions are arranged along [001] and along [010] columns consisting of either only [Co(dien)2]2+ complexes or [Ge2S6]4−/[dienH2]2+ ions alternate (Fig. 8).
Fig. 8 Arrangement of the constituents in the structure of compound 4. Note that H atoms are not drawn for clarity. |
The N–H⋯S bonding pattern between [dienH2]2+ cations and [Ge2S6]4− anions leads to the formation of chains being directed along [010] (Fig. 9). In contrast to compounds 1–3 only five of the seven H atoms bound to N atoms are involved in the hydrogen bonding interactions (Table S8†).
Fig. 9 The N–H⋯S bonding pattern between [dienH2]2+ ions and [Ge2S6]4− anions. Only the H atoms bonded to the N atoms are shown. |
Like for the other three compounds the S atoms have also hydrogen bonding interactions to H atoms of the [Co(dien)2]2+ complex.
As mentioned above, in all compounds a completely different topology of the hydrogen-bonded network between [Ge2S6]4− anions and dienH2 cations is observed. The topology not only depends on the position where the nitrogen atoms of the dien ligands – central or terminal – are protonated. It also depends on the number of hydrogen bonds formed by the different amine and ammonium groups. This is schematically shown in Fig. 10, displaying the numbers of hydrogen bonds formed by the different H atoms. From this representation it is obvious that e.g. despite the fact that both terminal N atoms of the dien molecules in compounds 1 and 2 are protonated not all H atoms are equally involved in hydrogen bonding interactions even if the overall number of the H-bonds is identical. Consequently a different H-bonding pattern must result in the structures.
Fig. 10 The [dienH2]2+ cations in the four compounds. The numbers of N–H⋯S interactions to the [Ge2S6]4− anions is indicated. Only N–H H atoms are shown. |
Footnote |
† Electronic supplementary information (ESI) available: Tables with interatomic distances and angles. CCDC 985614–985617. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4ce00312h |
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