Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615023165/fp3019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023165/fp3019Isup2.hkl |
CCDC reference: 1440044
A first preliminary report on the crystal structure of a hydrated salt formulated as [Ge(taci)2]Cl4.13H2O (taci = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol) appeared more than 20 years ago (Ghisletta, 1994). However, at that time, structure elucidation remained unsatisfactory. It was not possible to discriminate unambiguously between the positions of some of the chloride ions and water O atoms. As a consequence, a disorder was postulated, with an occupation of these positions by the two atom types at random. This artifact is particularly regrettable, because a conclusive scheme of hydrogen bonding, which is – as we shall show in this contribution – a particularly appealing aspect of the structure, could not be elucidated. We therefore regrew single crystals of this complex, following Ghisletta's protocol, and repeated the structure elucidation at low temperature. In agreement with Ghisletta's description, the structure could again be solved and refined in the triclinic centrosymmetric space group P1. However, in contrast to the previous investigation, where only one position for the [Ge(taci)2]4+ cation has been considered, we encountered two crystallographically independent Ge-atom positions, both located on a centre of inversion. In addition, the amount of hydration appeared to be smaller and we formulate the new structure as [Ge(taci)2]2Cl8.12H2O. The new attempt now allowed an unambiguous discrimination between O atom and chloride anion positions. Consequently, a complete resolution of the structure without any disorder proved possible.
1,3,5-Triamino-1,3,5-trideoxy-cis-inositol (taci) was prepared as described by Hegetschweiler et al. (1990). The title compound, i.e. [Ge(taci)2]2Cl8.12H2O, was prepared by combining solutions of GeCl4 (0.50 g, 2.33 mmol in 5 ml of MeOH) and taci (0.82 g, 4.63 mmol in 25 ml of MeOH) following the protocol given by Ghisletta (1994). Colourless single crystals suitable for X-ray analysis were grown from an aqueous solution by slow evaporation at ambient temperature. 1H NMR (D2O): δ 4.53, 3.53; 13C NMR (D2O): δ 75.3, 54.7.
The crystals effloresce under ambient conditions when exposed to the air and lose two of the six equivalents of water, forming the terahydrate [Ge(taci)2]Cl4.4H2O. Elemental analysis calculated (%) for C12H38Cl4GeN6O10: C 22.49, H 5.98, Cl 22.13, Ge 11.33, N, 13.11; found: C 22.52, H 5.69, Cl 22.62, Ge 11.25, N, 12.80. Ge was determined by ICP–MS (inductively coupled plasma mass spectrometry) and Cl was determined by argentometric titrations.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in a difference Fourier map and were treated as recommended by Müller et al. (2006). A riding model was used for the C-bonded H atoms. The positional parameters of the O- and N-bonded H atoms were refined using isotropic displacement parameters which were set at 1.5×Ueq of the pivot atom. In addition, restraints of 0.84 and 0.88 Å were used for the O—H and N—H bond lengths, respectively.
In general, no significant difference in geometry has been noted for the two crystallographically independent [Ge(taci)2]4+ units of the title compound, (I). In agreement with Ghisletta's findings, the two ligand moieties coordinate exclusively via O-atom donors, forming a double-adamantane-type skeleton with approximate D3d symmetry. The hydroxy H atoms were all transferred to the amino groups, which act as internal bases. It has frequently been proposed that the adoption of such a zwitterionic form contributes in particular to a high stability: It allows binding of the GeIV centre to six highly nucleophilic alkoxo groups without any necessity for a deprotonation of the complex as a whole by an external base (Hegetschweiler, 1999).
Only two examples of complexes with a tetravalent centre, exhibiting such a zwitterionic bis-taci-type skeleton have structurally been characterized: [V(taci)2]4+ and [V(tdci)2]4+ (Morgenstern et al., 2004; tdci = 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol). The molecular structure of these complexes resembles the [Ge(taci)2]4+ cations of the title compound quite closely. A similar double-adamantane skeleton with exclusive O-atom coordination has also been observed for [Al(taci)2]3+, [Cr(taci)2]3+ and a series of corresponding tdci complexes with Al3+, Fe3+, Ga3+ and In3+ (Hegetschweiler, 1999). The two GeO6 polyhedra of (I) revealed, however, some structural peculiarities, which have not been mentioned in any of the previous reports. In the Ge complex, the mean intraligand O···O separation [2.707(?) Å for Ge1 and 2.686(?) Å for Ge2] is slightly larger than the mean interligand separation [2.638(?) Å for Ge1 and 2.643(?) Å for Ge2]. In addition, close inspection of the individual O···O distances exhibits the presence of a pseudo-mirror plane within error limits (Fig. 1). Together with the crystallographically imposed centre of inversion, the molecular symmetry of the two complexes adds up to C2h. Although small, the deviation from the expected D3d symmetry is significant. It is observed for both cations, although they are embedded in different environments. Therefore, it is not conclusive to explain this distortion simply by a specific packing. It is noteworthy that the O···O distances are all substantially shorter than the sum of the van der Waals radii of two O atoms (3.14 Å). Moreover, the intramolecular distances are also significantly shorter than in the free ligand or in its protonation products Hntacin+ (Neis & Hegetschweiler, 2014), where the O···O separations range from 2.9 to 3.1 Å, or from 2.7 to 2.8 Å if an intramolecular hydrogen bond is formed. In terms of simple VSEPR (valence shell electron pair repulsion) considerations, one would expect strict Oh symmetry for an unstrained GeO6 moiety. Regarding some negative charges on the alkoxo donors, enhanced ligand–ligand repulsion should result in an increase of interligand O···O distances (Hegetschweiler et al., 1995). As a matter of fact, in all our previous investigations, interligand O···O separations have been found to be larger than corresponding intraligand distances throughout. It appears thus that the GeIV centre might be too small to fit unconstrainedly in the cavity, formed by the six O atoms of two taci molecules. Such an assumption is further supported by a strong puckering of the cyclohexane rings. Puckering parameters were calculated according to Cremer & Pople, 1975): Q = 0.627 Å, θ = 1.62 ° and φ = 274.74 ° (for Ge1), and Q = 0.641 Å, θ = 1.20 ° and φ = 306.73 ° (for Ge2). These values confirm a pure chair conformation for both cations, however, the value of the total puckering amplitude Q is significantly larger in comparison to the free taci, its protonation products or metal complexes (Neis & Hegetschweiler, 2014; Neis et al., 2014). Interestingly, the Ge—O bonds appear, however, not to be widened. The Cambridge Structural Database (CSD, Version ???; Groom & Allen 2014) contains only one entry for GeIV bonded to six alkoxo donors for comparison. It is a complex of a deprotonated β-cyclodextrine reported by Benner et al. (2006), with a mean Ge—O bond length of 1.914 Å.
In recent times, we spent particular attention to the hydrogen-bonding properties of taci, its protonation products and its metal complexes (Neis & Hegetschweiler, 2014). These studies have shown that R—O—H···NH2—R' interactions are observed quite frequently and, the pairing of two OH—CH—CH—NH2-groups appears to be a particularly favoured motif. In terms of graph-set analysis (Bernstein et al., 1995), such a pattern receives the descriptor R22(10). In (I), the chloride anions and the alkoxo groups are potential acceptors and the ammonium groups potential donors, whereas the water molecules may undergo both donating and accepting interactions. Among them, the ammonium group represents the strongest donor and the coordinated alkoxo group the strongest acceptor. However, no N—H···Oalkoxo interactions have been observed in the structure of (I). Instead, interconnection of [Ge(taci)2]4+ cations is mediated via water molecules and chloride counter-ions. With respect to the approximate D3d symmetry of the [Ge(taci)2]4+ cation, the ammonium groups all adopt an orientation with one N—H bond in an axial orientation and the other two in equatorial orientations. The two equatorial N—H bonds point to the outside of the molecule (Fig. 2). The axial N—H protons point, however, towards an alkoxo O atom. Despite an N···O distance of 2.8–2.9 Å between such a vicinal ammonium–alkoxo group, the small N—H···O angle (<110 °) precludes an interpretation as intramolecular hydrogen bonding.
Both cations are surrounded by six water molecules. In cations of Ge2, all these water molecules accept an axial N—H hydrogen and donate an H atom to a coordinated alkoxo group of the opposite ligand. This interaction (denoted type-A) results in the formation of a nine-membered N—H···O(H)—H···O—Ge—O—C—C ring. The cations of Ge1, however, exhibit only four such type-A interactions. The remaining two water molecules (O5W) also accept an axial N2—H hydrogen but donate an H atom to a coordinated alkoxo group (O1) of the same ligand moiety. This interaction (denoted type-B) results in the formation of a seven-membered N—H···O(H)—H···O—C—C ring. Moreover, the axial N—H hydrogen of the type-B interaction is bifurcated, forming an additional hydrogen bond to O4W, which in turn represents again a type-A interaction (Fig. 2a). As a consequence, the remaining axial N—H hydrogen at atom N4 is not involved in this particular hydration scheme. Type-A interactions have been observed previously in other taci complexes with such a zwitterionic form (Hegetschweiler et al., 1995), whereas type-B interactions have not been reported yet. The specific structure of the taci ligand together with the characteristic hydration shell of the cations resulted in a strongly dipolar shape of the entire aggregate with two hydrophobic poles (the C6H6 frames) and a hydrophilic belt. Interconnection of these hydrated cations emerges mainly via intermolecular hydrogen bonding (Table 2) between the hydrophilic belts of neighbouring complex molecules either with or without participation of the chloride counter-ions. The following interactions are observed:
(i): N—H···Cl···H—N;
(ii): N—H···O(H)2···H—N, together with Oalkoxo···H(OH)···H—N;
(iii): N—H···O(H)—H···Cl···H—N, together with Oalkoxo···H—O—H···Cl···H—N;
(iv): N—H···O(H)—H···Cl···H—(H)O···H—N, together with Oalkoxo···H—O—H···Cl···H—(H)O···H—N and Oalkoxo···H—O—H···Cl···H—O—H···Oalkoxo.
Cations of Ge1 are interconnected via interaction types (i), (ii) and (iii), forming chains along the crystallographic a axis. Additional type (i) interlinking along the b axis generates layers, which are oriented parallel to the ab plane (Fig. 3a). Similarly, the cations of Ge2 form chains along the a axis via interaction types (i), (ii) and (iv). Further interlinking by type (i) hydrogen bonds along b results again in the formation of layers parallel to the ab plane (Fig. 3b). Finally, interlinking of the two different cationic species (Ge1 and Ge2) by all four interaction types constitutes layers oriented parallel to the bc plane (Fig. 3c). The four interaction types give rise to the formation of a variety of different cyclic patterns. Some of them are displayed in Fig. 4. The first example (Fig. 4a) shows the direct interlinking of [Ge1(taci)2](H2O)64+ aggregates via type-B-bonded H2O molecules. In terms of a graph-set description, the type-B binding comprises two individual finite hydrogen bonds and the corresponding first-level (N1) descriptor is DD. The cyclic nature of this arrangement becomes evident from the second level (N2) analysis with the descriptor R22(7). This pattern is further extended to chains of the type C12(9) along the a axis considering the additional hydrogen bond from O3W to O7, and the combination of two symmetry-related C12(9) patterns finally constitute large rings of the type R42(24). The interlinking of type-A-bonded water molecules, as observed for Ge2, takes place by a somewhat different mechanism (Fig. 4b). Again, the type-A binding comprises two finite hydrogen bonds (N1: DD). The emerging ring pattern (N2) is, however, R22(9). The formation of C12(9) chains follows again from the additional hydrogen bonding (O3W···O7) to a neighbouring cation, and the combination of symmetry-related C12(9) chains generates R42(8) and (more complex) R44(24) rings. It has been pointed out by Bernstein et al. that the R42(8) pattern is quite common for hydrogen bonding and is observed in a variety of different structures. The archetypal nature of the R42(8) pattern is also evident in the title compound. It is not only found for the abovementioned Ge2-cation···water interlinking along [100] (Fig. 4b), but also for the cation–chloride interactions of Ge1 along [110] (Fig. 4c). Further cyclic patterns containing ammonium groups and chloride anions with larger rings are obtained as some parts of the ligand skeleton is included within the loop. Fig. 4(d) shows the alignment of Ge1 along the b axis, forming R42(16)-rings, whereas connection of the Ge1 cations along the a axis is not only mediated via water molecules (Fig. 4a), but also via chloride anions (Fig. 4e), forming R42(12) and large R43(24) patterns. The latter are again obtained by combining two symmetry-related R42(12) motifs within the Ge1···Ge1 chain. Finally, even more complex structures evolve, if both H2O and Cl- are included within the cycle. Such an example, comprising two chloride anions and four water molecules, adding up to R86(22) (for a loop via N—H···OH2) or R86(20) (for a loop via H—O—H···Oalkoxo) is shown for the Ge2···Ge2 interaction along the b axis in Fig. 4(f).
With regard to the counter-ions (Fig. 5), Cl1 accepts one N—H and four H—O (water) hydrogens, thus having a coordination number of five. It is engaged by the interconnection from three cations (two Ge2 and one Ge1). Cl2 accepts three N—H hydrogens from three cations (two Ge1 and one Ge2), Cl3 accepts four N—H hydrogens from four cations (three Ge2 and one Ge1) and Cl4 accepts three N—H hydrogens and one water H atom, interlinking three cations of Ge1. As can be seen in Fig. 5, the geometry of the corresponding Cl1H5, Cl2H3, Cl3H4 and Cl4H4 polyhedra is strongly irregular throughout.
The title compound exhibits a remarkably complex three-dimensional network of hydrogen bonds. Although a waste variety of different types of interactions are formed, direct taci–taci contacts, such as N—H···Oalkoxo, are not observed. It is obvious that bis-taci complexes with a zwitterionic form of the ligand display a completely different behaviour than the free ligand, its protonation products and metal complexes with the ligand in a nonzwitterionic form (Neis et al., 2014). In addition, no direct interactions between the hydrophobic poles of the [Ge(taci)2]4+ cations in the form of C—H···H—C van der Waals contacts are observed. As can be seen in Figs. 3(b) and 3(c), the nearest neighbours of the hydrophobic poles are either water molecules or chloride ions, with H···O distances around 2.5 Å and H···Cl distances in the range from 2.6–2.8 Å. It remains questionable whether these interactions could be regarded as additional weak C—H···X hydrogen bonds. Inspection of this structure also supports the conclusion that simple electrostatic interactions contribute extensively to its stability. The non-observance of direct N—H···Oalkoxo interactions could be explained by the considerable Coulombic repulsion between the fourfold cations. On the other hand, cation–anion attraction, which of course results in a general Madelung-type stabilization, is directly visible (Fig. 5d), displaying a `salt bridge' with an ammonium group (N8) where all three H atoms (N8) are directed towards Cl4 [N8···Cl4 separation = 3.2(?) Å]. It is also noteworthy that in contrast to the well balanced pairing of vicinal HO—CH—CH—NH2 groups mentioned above, the hydrogen-bonding scheme in the title compound remains unbalanced. One of the water H atoms (H3W—O2W), as an example, remains without an acceptor (Fig. 3c).
A first preliminary report on the crystal structure of a hydrated salt formulated as [Ge(taci)2]Cl4.13H2O (taci = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol) appeared more than 20 years ago (Ghisletta, 1994). However, at that time, structure elucidation remained unsatisfactory. It was not possible to discriminate unambiguously between the positions of some of the chloride ions and water O atoms. As a consequence, a disorder was postulated, with an occupation of these positions by the two atom types at random. This artifact is particularly regrettable, because a conclusive scheme of hydrogen bonding, which is – as we shall show in this contribution – a particularly appealing aspect of the structure, could not be elucidated. We therefore regrew single crystals of this complex, following Ghisletta's protocol, and repeated the structure elucidation at low temperature. In agreement with Ghisletta's description, the structure could again be solved and refined in the triclinic centrosymmetric space group P1. However, in contrast to the previous investigation, where only one position for the [Ge(taci)2]4+ cation has been considered, we encountered two crystallographically independent Ge-atom positions, both located on a centre of inversion. In addition, the amount of hydration appeared to be smaller and we formulate the new structure as [Ge(taci)2]2Cl8.12H2O. The new attempt now allowed an unambiguous discrimination between O atom and chloride anion positions. Consequently, a complete resolution of the structure without any disorder proved possible.
In general, no significant difference in geometry has been noted for the two crystallographically independent [Ge(taci)2]4+ units of the title compound, (I). In agreement with Ghisletta's findings, the two ligand moieties coordinate exclusively via O-atom donors, forming a double-adamantane-type skeleton with approximate D3d symmetry. The hydroxy H atoms were all transferred to the amino groups, which act as internal bases. It has frequently been proposed that the adoption of such a zwitterionic form contributes in particular to a high stability: It allows binding of the GeIV centre to six highly nucleophilic alkoxo groups without any necessity for a deprotonation of the complex as a whole by an external base (Hegetschweiler, 1999).
Only two examples of complexes with a tetravalent centre, exhibiting such a zwitterionic bis-taci-type skeleton have structurally been characterized: [V(taci)2]4+ and [V(tdci)2]4+ (Morgenstern et al., 2004; tdci = 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol). The molecular structure of these complexes resembles the [Ge(taci)2]4+ cations of the title compound quite closely. A similar double-adamantane skeleton with exclusive O-atom coordination has also been observed for [Al(taci)2]3+, [Cr(taci)2]3+ and a series of corresponding tdci complexes with Al3+, Fe3+, Ga3+ and In3+ (Hegetschweiler, 1999). The two GeO6 polyhedra of (I) revealed, however, some structural peculiarities, which have not been mentioned in any of the previous reports. In the Ge complex, the mean intraligand O···O separation [2.707(?) Å for Ge1 and 2.686(?) Å for Ge2] is slightly larger than the mean interligand separation [2.638(?) Å for Ge1 and 2.643(?) Å for Ge2]. In addition, close inspection of the individual O···O distances exhibits the presence of a pseudo-mirror plane within error limits (Fig. 1). Together with the crystallographically imposed centre of inversion, the molecular symmetry of the two complexes adds up to C2h. Although small, the deviation from the expected D3d symmetry is significant. It is observed for both cations, although they are embedded in different environments. Therefore, it is not conclusive to explain this distortion simply by a specific packing. It is noteworthy that the O···O distances are all substantially shorter than the sum of the van der Waals radii of two O atoms (3.14 Å). Moreover, the intramolecular distances are also significantly shorter than in the free ligand or in its protonation products Hntacin+ (Neis & Hegetschweiler, 2014), where the O···O separations range from 2.9 to 3.1 Å, or from 2.7 to 2.8 Å if an intramolecular hydrogen bond is formed. In terms of simple VSEPR (valence shell electron pair repulsion) considerations, one would expect strict Oh symmetry for an unstrained GeO6 moiety. Regarding some negative charges on the alkoxo donors, enhanced ligand–ligand repulsion should result in an increase of interligand O···O distances (Hegetschweiler et al., 1995). As a matter of fact, in all our previous investigations, interligand O···O separations have been found to be larger than corresponding intraligand distances throughout. It appears thus that the GeIV centre might be too small to fit unconstrainedly in the cavity, formed by the six O atoms of two taci molecules. Such an assumption is further supported by a strong puckering of the cyclohexane rings. Puckering parameters were calculated according to Cremer & Pople, 1975): Q = 0.627 Å, θ = 1.62 ° and φ = 274.74 ° (for Ge1), and Q = 0.641 Å, θ = 1.20 ° and φ = 306.73 ° (for Ge2). These values confirm a pure chair conformation for both cations, however, the value of the total puckering amplitude Q is significantly larger in comparison to the free taci, its protonation products or metal complexes (Neis & Hegetschweiler, 2014; Neis et al., 2014). Interestingly, the Ge—O bonds appear, however, not to be widened. The Cambridge Structural Database (CSD, Version ???; Groom & Allen 2014) contains only one entry for GeIV bonded to six alkoxo donors for comparison. It is a complex of a deprotonated β-cyclodextrine reported by Benner et al. (2006), with a mean Ge—O bond length of 1.914 Å.
In recent times, we spent particular attention to the hydrogen-bonding properties of taci, its protonation products and its metal complexes (Neis & Hegetschweiler, 2014). These studies have shown that R—O—H···NH2—R' interactions are observed quite frequently and, the pairing of two OH—CH—CH—NH2-groups appears to be a particularly favoured motif. In terms of graph-set analysis (Bernstein et al., 1995), such a pattern receives the descriptor R22(10). In (I), the chloride anions and the alkoxo groups are potential acceptors and the ammonium groups potential donors, whereas the water molecules may undergo both donating and accepting interactions. Among them, the ammonium group represents the strongest donor and the coordinated alkoxo group the strongest acceptor. However, no N—H···Oalkoxo interactions have been observed in the structure of (I). Instead, interconnection of [Ge(taci)2]4+ cations is mediated via water molecules and chloride counter-ions. With respect to the approximate D3d symmetry of the [Ge(taci)2]4+ cation, the ammonium groups all adopt an orientation with one N—H bond in an axial orientation and the other two in equatorial orientations. The two equatorial N—H bonds point to the outside of the molecule (Fig. 2). The axial N—H protons point, however, towards an alkoxo O atom. Despite an N···O distance of 2.8–2.9 Å between such a vicinal ammonium–alkoxo group, the small N—H···O angle (<110 °) precludes an interpretation as intramolecular hydrogen bonding.
Both cations are surrounded by six water molecules. In cations of Ge2, all these water molecules accept an axial N—H hydrogen and donate an H atom to a coordinated alkoxo group of the opposite ligand. This interaction (denoted type-A) results in the formation of a nine-membered N—H···O(H)—H···O—Ge—O—C—C ring. The cations of Ge1, however, exhibit only four such type-A interactions. The remaining two water molecules (O5W) also accept an axial N2—H hydrogen but donate an H atom to a coordinated alkoxo group (O1) of the same ligand moiety. This interaction (denoted type-B) results in the formation of a seven-membered N—H···O(H)—H···O—C—C ring. Moreover, the axial N—H hydrogen of the type-B interaction is bifurcated, forming an additional hydrogen bond to O4W, which in turn represents again a type-A interaction (Fig. 2a). As a consequence, the remaining axial N—H hydrogen at atom N4 is not involved in this particular hydration scheme. Type-A interactions have been observed previously in other taci complexes with such a zwitterionic form (Hegetschweiler et al., 1995), whereas type-B interactions have not been reported yet. The specific structure of the taci ligand together with the characteristic hydration shell of the cations resulted in a strongly dipolar shape of the entire aggregate with two hydrophobic poles (the C6H6 frames) and a hydrophilic belt. Interconnection of these hydrated cations emerges mainly via intermolecular hydrogen bonding (Table 2) between the hydrophilic belts of neighbouring complex molecules either with or without participation of the chloride counter-ions. The following interactions are observed:
(i): N—H···Cl···H—N;
(ii): N—H···O(H)2···H—N, together with Oalkoxo···H(OH)···H—N;
(iii): N—H···O(H)—H···Cl···H—N, together with Oalkoxo···H—O—H···Cl···H—N;
(iv): N—H···O(H)—H···Cl···H—(H)O···H—N, together with Oalkoxo···H—O—H···Cl···H—(H)O···H—N and Oalkoxo···H—O—H···Cl···H—O—H···Oalkoxo.
Cations of Ge1 are interconnected via interaction types (i), (ii) and (iii), forming chains along the crystallographic a axis. Additional type (i) interlinking along the b axis generates layers, which are oriented parallel to the ab plane (Fig. 3a). Similarly, the cations of Ge2 form chains along the a axis via interaction types (i), (ii) and (iv). Further interlinking by type (i) hydrogen bonds along b results again in the formation of layers parallel to the ab plane (Fig. 3b). Finally, interlinking of the two different cationic species (Ge1 and Ge2) by all four interaction types constitutes layers oriented parallel to the bc plane (Fig. 3c). The four interaction types give rise to the formation of a variety of different cyclic patterns. Some of them are displayed in Fig. 4. The first example (Fig. 4a) shows the direct interlinking of [Ge1(taci)2](H2O)64+ aggregates via type-B-bonded H2O molecules. In terms of a graph-set description, the type-B binding comprises two individual finite hydrogen bonds and the corresponding first-level (N1) descriptor is DD. The cyclic nature of this arrangement becomes evident from the second level (N2) analysis with the descriptor R22(7). This pattern is further extended to chains of the type C12(9) along the a axis considering the additional hydrogen bond from O3W to O7, and the combination of two symmetry-related C12(9) patterns finally constitute large rings of the type R42(24). The interlinking of type-A-bonded water molecules, as observed for Ge2, takes place by a somewhat different mechanism (Fig. 4b). Again, the type-A binding comprises two finite hydrogen bonds (N1: DD). The emerging ring pattern (N2) is, however, R22(9). The formation of C12(9) chains follows again from the additional hydrogen bonding (O3W···O7) to a neighbouring cation, and the combination of symmetry-related C12(9) chains generates R42(8) and (more complex) R44(24) rings. It has been pointed out by Bernstein et al. that the R42(8) pattern is quite common for hydrogen bonding and is observed in a variety of different structures. The archetypal nature of the R42(8) pattern is also evident in the title compound. It is not only found for the abovementioned Ge2-cation···water interlinking along [100] (Fig. 4b), but also for the cation–chloride interactions of Ge1 along [110] (Fig. 4c). Further cyclic patterns containing ammonium groups and chloride anions with larger rings are obtained as some parts of the ligand skeleton is included within the loop. Fig. 4(d) shows the alignment of Ge1 along the b axis, forming R42(16)-rings, whereas connection of the Ge1 cations along the a axis is not only mediated via water molecules (Fig. 4a), but also via chloride anions (Fig. 4e), forming R42(12) and large R43(24) patterns. The latter are again obtained by combining two symmetry-related R42(12) motifs within the Ge1···Ge1 chain. Finally, even more complex structures evolve, if both H2O and Cl- are included within the cycle. Such an example, comprising two chloride anions and four water molecules, adding up to R86(22) (for a loop via N—H···OH2) or R86(20) (for a loop via H—O—H···Oalkoxo) is shown for the Ge2···Ge2 interaction along the b axis in Fig. 4(f).
With regard to the counter-ions (Fig. 5), Cl1 accepts one N—H and four H—O (water) hydrogens, thus having a coordination number of five. It is engaged by the interconnection from three cations (two Ge2 and one Ge1). Cl2 accepts three N—H hydrogens from three cations (two Ge1 and one Ge2), Cl3 accepts four N—H hydrogens from four cations (three Ge2 and one Ge1) and Cl4 accepts three N—H hydrogens and one water H atom, interlinking three cations of Ge1. As can be seen in Fig. 5, the geometry of the corresponding Cl1H5, Cl2H3, Cl3H4 and Cl4H4 polyhedra is strongly irregular throughout.
The title compound exhibits a remarkably complex three-dimensional network of hydrogen bonds. Although a waste variety of different types of interactions are formed, direct taci–taci contacts, such as N—H···Oalkoxo, are not observed. It is obvious that bis-taci complexes with a zwitterionic form of the ligand display a completely different behaviour than the free ligand, its protonation products and metal complexes with the ligand in a nonzwitterionic form (Neis et al., 2014). In addition, no direct interactions between the hydrophobic poles of the [Ge(taci)2]4+ cations in the form of C—H···H—C van der Waals contacts are observed. As can be seen in Figs. 3(b) and 3(c), the nearest neighbours of the hydrophobic poles are either water molecules or chloride ions, with H···O distances around 2.5 Å and H···Cl distances in the range from 2.6–2.8 Å. It remains questionable whether these interactions could be regarded as additional weak C—H···X hydrogen bonds. Inspection of this structure also supports the conclusion that simple electrostatic interactions contribute extensively to its stability. The non-observance of direct N—H···Oalkoxo interactions could be explained by the considerable Coulombic repulsion between the fourfold cations. On the other hand, cation–anion attraction, which of course results in a general Madelung-type stabilization, is directly visible (Fig. 5d), displaying a `salt bridge' with an ammonium group (N8) where all three H atoms (N8) are directed towards Cl4 [N8···Cl4 separation = 3.2(?) Å]. It is also noteworthy that in contrast to the well balanced pairing of vicinal HO—CH—CH—NH2 groups mentioned above, the hydrogen-bonding scheme in the title compound remains unbalanced. One of the water H atoms (H3W—O2W), as an example, remains without an acceptor (Fig. 3c).
1,3,5-Triamino-1,3,5-trideoxy-cis-inositol (taci) was prepared as described by Hegetschweiler et al. (1990). The title compound, i.e. [Ge(taci)2]2Cl8.12H2O, was prepared by combining solutions of GeCl4 (0.50 g, 2.33 mmol in 5 ml of MeOH) and taci (0.82 g, 4.63 mmol in 25 ml of MeOH) following the protocol given by Ghisletta (1994). Colourless single crystals suitable for X-ray analysis were grown from an aqueous solution by slow evaporation at ambient temperature. 1H NMR (D2O): δ 4.53, 3.53; 13C NMR (D2O): δ 75.3, 54.7.
The crystals effloresce under ambient conditions when exposed to the air and lose two of the six equivalents of water, forming the terahydrate [Ge(taci)2]Cl4.4H2O. Elemental analysis calculated (%) for C12H38Cl4GeN6O10: C 22.49, H 5.98, Cl 22.13, Ge 11.33, N, 13.11; found: C 22.52, H 5.69, Cl 22.62, Ge 11.25, N, 12.80. Ge was determined by ICP–MS (inductively coupled plasma mass spectrometry) and Cl was determined by argentometric titrations.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in a difference Fourier map and were treated as recommended by Müller et al. (2006). A riding model was used for the C-bonded H atoms. The positional parameters of the O- and N-bonded H atoms were refined using isotropic displacement parameters which were set at 1.5×Ueq of the pivot atom. In addition, restraints of 0.84 and 0.88 Å were used for the O—H and N—H bond lengths, respectively.
Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
C12H30GeN6O64+·4Cl−·6H2O | Z = 2 |
Mr = 676.90 | F(000) = 704 |
Triclinic, P1 | Dx = 1.730 Mg m−3 |
a = 8.5247 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.9152 (6) Å | Cell parameters from 9303 reflections |
c = 15.1592 (8) Å | θ = 2.5–33.3° |
α = 82.980 (2)° | µ = 1.66 mm−1 |
β = 79.248 (2)° | T = 123 K |
γ = 70.022 (2)° | Block, colourless |
V = 1299.78 (13) Å3 | 0.55 × 0.45 × 0.45 mm |
Bruker X8 APEX/Nonius KappaCCD diffractometer | 5520 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.021 |
Absorption correction: multi-scan (SADABS; Bruker, 2010) | θmax = 27.0°, θmin = 2.0° |
Tmin = 0.620, Tmax = 0.747 | h = −10→10 |
29040 measured reflections | k = −13→13 |
5652 independent reflections | l = −15→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.020P)2 + 1.016P] where P = (Fo2 + 2Fc2)/3 |
5652 reflections | (Δ/σ)max = 0.001 |
411 parameters | Δρmax = 0.60 e Å−3 |
30 restraints | Δρmin = −0.53 e Å−3 |
C12H30GeN6O64+·4Cl−·6H2O | γ = 70.022 (2)° |
Mr = 676.90 | V = 1299.78 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.5247 (5) Å | Mo Kα radiation |
b = 10.9152 (6) Å | µ = 1.66 mm−1 |
c = 15.1592 (8) Å | T = 123 K |
α = 82.980 (2)° | 0.55 × 0.45 × 0.45 mm |
β = 79.248 (2)° |
Bruker X8 APEX/Nonius KappaCCD diffractometer | 5652 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2010) | 5520 reflections with I > 2σ(I) |
Tmin = 0.620, Tmax = 0.747 | Rint = 0.021 |
29040 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 30 restraints |
wR(F2) = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.60 e Å−3 |
5652 reflections | Δρmin = −0.53 e Å−3 |
411 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ge1 | 0.5000 | 0.0000 | 0.5000 | 0.00507 (5) | |
Cl1 | 0.34505 (5) | 0.53186 (4) | 0.29724 (2) | 0.01918 (8) | |
O1 | 0.26716 (11) | 0.08331 (9) | 0.53532 (6) | 0.00782 (17) | |
C1 | 0.21252 (16) | 0.18593 (12) | 0.59443 (8) | 0.0079 (2) | |
H1 | 0.0862 | 0.2185 | 0.6053 | 0.009* | |
Ge2 | 0.0000 | 0.5000 | 1.0000 | 0.00523 (5) | |
Cl2 | 0.16658 (4) | 0.89804 (3) | 0.18156 (2) | 0.01299 (7) | |
N2 | 0.21771 (15) | 0.02494 (11) | 0.72309 (8) | 0.0104 (2) | |
H2C | 0.1080 (12) | 0.0512 (17) | 0.7434 (11) | 0.016* | |
H2B | 0.273 (2) | −0.0190 (16) | 0.7674 (9) | 0.016* | |
H2A | 0.235 (2) | −0.0291 (15) | 0.6808 (10) | 0.016* | |
C2 | 0.27454 (16) | 0.13831 (12) | 0.68518 (9) | 0.0086 (2) | |
H2 | 0.2248 | 0.2103 | 0.7273 | 0.010* | |
Cl3 | 0.58198 (4) | 0.09882 (3) | 0.11571 (2) | 0.01123 (7) | |
O3 | 0.54265 (11) | −0.01265 (9) | 0.61961 (6) | 0.00764 (17) | |
C3 | 0.46737 (16) | 0.09543 (12) | 0.67402 (8) | 0.0078 (2) | |
H3 | 0.5028 | 0.0695 | 0.7347 | 0.009* | |
Cl4 | 0.15020 (4) | 0.64858 (3) | 0.53102 (2) | 0.01232 (7) | |
C4 | 0.52395 (16) | 0.21148 (12) | 0.63282 (9) | 0.0083 (2) | |
H4 | 0.4726 | 0.2846 | 0.6740 | 0.010* | |
N4 | 0.71145 (14) | 0.17095 (11) | 0.62418 (8) | 0.0103 (2) | |
H4C | 0.741 (2) | 0.1627 (17) | 0.6779 (8) | 0.015* | |
H4B | 0.751 (2) | 0.2279 (14) | 0.5878 (10) | 0.015* | |
H4A | 0.761 (2) | 0.0953 (12) | 0.5987 (11) | 0.015* | |
O5 | 0.54073 (11) | 0.16181 (9) | 0.47733 (6) | 0.00759 (17) | |
C5 | 0.46765 (16) | 0.25862 (12) | 0.54107 (9) | 0.0080 (2) | |
H5 | 0.5026 | 0.3367 | 0.5178 | 0.010* | |
C7 | −0.14445 (16) | 0.74172 (12) | 0.89916 (8) | 0.0082 (2) | |
H7 | −0.2369 | 0.7875 | 0.8628 | 0.010* | |
O7 | −0.15275 (11) | 0.61525 (9) | 0.92760 (6) | 0.00795 (18) | |
C8 | 0.02392 (16) | 0.73851 (12) | 0.84157 (8) | 0.0084 (2) | |
H8 | 0.0216 | 0.8307 | 0.8258 | 0.010* | |
N8 | 0.04825 (15) | 0.67499 (11) | 0.75618 (8) | 0.0101 (2) | |
H8A | −0.0396 (17) | 0.7159 (16) | 0.7290 (11) | 0.015* | |
H8C | 0.1404 (16) | 0.6826 (17) | 0.7210 (10) | 0.015* | |
H8B | 0.057 (2) | 0.5923 (10) | 0.7650 (12) | 0.015* | |
C9 | 0.16852 (16) | 0.67069 (12) | 0.89530 (8) | 0.0079 (2) | |
H9 | 0.2772 | 0.6711 | 0.8567 | 0.010* | |
O9 | 0.18025 (11) | 0.53983 (9) | 0.92401 (6) | 0.00786 (18) | |
C12 | −0.16892 (16) | 0.82192 (12) | 0.97956 (9) | 0.0086 (2) | |
H12 | −0.1657 | 0.9111 | 0.9567 | 0.010* | |
O1W | −0.02517 (14) | 0.57481 (10) | 0.25090 (7) | 0.0154 (2) | |
H1W | 0.0704 (15) | 0.5636 (19) | 0.2642 (13) | 0.023* | |
H2W | −0.020 (2) | 0.5953 (18) | 0.1955 (7) | 0.023* | |
O2W | 0.27293 (13) | 0.22936 (10) | 0.30544 (7) | 0.0152 (2) | |
H3W | 0.343 (2) | 0.2516 (18) | 0.2675 (11) | 0.023* | |
H4W | 0.328 (2) | 0.1569 (12) | 0.3276 (12) | 0.023* | |
O3W | 0.41176 (13) | 0.44012 (10) | 0.09881 (7) | 0.0164 (2) | |
H5W | 0.3296 (18) | 0.4169 (19) | 0.0941 (13) | 0.025* | |
H6W | 0.402 (3) | 0.4533 (19) | 0.1530 (7) | 0.025* | |
O5W | 0.97249 (14) | 0.05039 (11) | 0.40190 (7) | 0.0188 (2) | |
H9W | 0.903 (2) | 0.0194 (19) | 0.4347 (12) | 0.028* | |
H10W | 0.952 (3) | 0.1225 (12) | 0.4217 (13) | 0.028* | |
O4W | 0.64995 (14) | 0.26799 (11) | 0.31329 (7) | 0.0164 (2) | |
H7W | 0.5723 (19) | 0.3392 (13) | 0.3084 (13) | 0.025* | |
H8W | 0.623 (2) | 0.2403 (18) | 0.3652 (8) | 0.025* | |
O6W | 0.59307 (17) | 0.65553 (12) | 0.16287 (9) | 0.0345 (3) | |
H11W | 0.658 (3) | 0.5880 (16) | 0.1386 (16) | 0.052* | |
H12W | 0.509 (2) | 0.636 (2) | 0.1882 (16) | 0.052* | |
N12 | −0.33744 (14) | 0.83462 (11) | 1.03432 (8) | 0.0099 (2) | |
H12A | −0.4124 (18) | 0.8493 (17) | 0.9983 (10) | 0.015* | |
H12B | −0.342 (2) | 0.7663 (13) | 1.0710 (10) | 0.015* | |
H12C | −0.371 (2) | 0.9038 (13) | 1.0660 (11) | 0.015* | |
C11 | −0.02864 (16) | 0.75855 (12) | 1.03694 (9) | 0.0082 (2) | |
H11 | −0.0456 | 0.8162 | 1.0868 | 0.010* | |
O11 | −0.02991 (11) | 0.63406 (9) | 1.07497 (6) | 0.00779 (17) | |
C10 | 0.13823 (16) | 0.75255 (12) | 0.97592 (9) | 0.0084 (2) | |
H10 | 0.1332 | 0.8434 | 0.9529 | 0.010* | |
H10B | 0.270 (2) | 0.7446 (16) | 1.0706 (9) | 0.018 (4)* | |
N10 | 0.28346 (14) | 0.69589 (11) | 1.02618 (8) | 0.0102 (2) | |
H10C | 0.3764 (16) | 0.6924 (17) | 0.9882 (10) | 0.015* | |
H10A | 0.298 (2) | 0.6147 (10) | 1.0483 (11) | 0.015* | |
C6 | 0.27445 (16) | 0.30084 (12) | 0.55631 (8) | 0.0086 (2) | |
H6 | 0.2287 | 0.3709 | 0.6000 | 0.010* | |
N6 | 0.21305 (15) | 0.35440 (11) | 0.46944 (8) | 0.0100 (2) | |
H6A | 0.264 (2) | 0.3019 (15) | 0.4259 (9) | 0.015* | |
H6B | 0.1050 (13) | 0.3638 (17) | 0.4739 (12) | 0.015* | |
H6C | 0.225 (2) | 0.4310 (11) | 0.4543 (12) | 0.015* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ge1 | 0.00563 (9) | 0.00489 (9) | 0.00471 (9) | −0.00180 (7) | −0.00080 (6) | −0.00011 (6) |
Cl1 | 0.02134 (18) | 0.02079 (18) | 0.01659 (16) | −0.01033 (14) | −0.00246 (13) | 0.00375 (13) |
O1 | 0.0070 (4) | 0.0074 (4) | 0.0088 (4) | −0.0018 (3) | −0.0006 (3) | −0.0022 (3) |
C1 | 0.0070 (6) | 0.0072 (6) | 0.0087 (6) | −0.0015 (5) | −0.0005 (4) | −0.0010 (5) |
Ge2 | 0.00552 (9) | 0.00493 (9) | 0.00533 (9) | −0.00180 (7) | −0.00099 (6) | −0.00017 (6) |
Cl2 | 0.01460 (16) | 0.01298 (15) | 0.01089 (14) | −0.00306 (12) | −0.00292 (12) | −0.00167 (11) |
N2 | 0.0105 (5) | 0.0116 (5) | 0.0092 (5) | −0.0048 (4) | −0.0009 (4) | 0.0012 (4) |
C2 | 0.0097 (6) | 0.0083 (6) | 0.0080 (6) | −0.0036 (5) | 0.0000 (5) | −0.0008 (4) |
Cl3 | 0.01186 (15) | 0.01079 (15) | 0.01166 (14) | −0.00423 (12) | −0.00366 (11) | 0.00135 (11) |
O3 | 0.0095 (4) | 0.0066 (4) | 0.0063 (4) | −0.0012 (3) | −0.0019 (3) | −0.0014 (3) |
C3 | 0.0088 (6) | 0.0085 (6) | 0.0062 (5) | −0.0028 (5) | −0.0009 (4) | −0.0015 (4) |
Cl4 | 0.01222 (15) | 0.01241 (15) | 0.01334 (15) | −0.00581 (12) | −0.00138 (11) | −0.00031 (11) |
C4 | 0.0076 (6) | 0.0086 (6) | 0.0089 (6) | −0.0026 (5) | −0.0013 (5) | −0.0019 (5) |
N4 | 0.0099 (5) | 0.0118 (6) | 0.0104 (5) | −0.0048 (4) | −0.0030 (4) | 0.0008 (4) |
O5 | 0.0094 (4) | 0.0063 (4) | 0.0071 (4) | −0.0030 (3) | −0.0001 (3) | −0.0012 (3) |
C5 | 0.0095 (6) | 0.0061 (6) | 0.0088 (6) | −0.0028 (5) | −0.0016 (5) | −0.0009 (4) |
C7 | 0.0090 (6) | 0.0069 (6) | 0.0081 (6) | −0.0019 (5) | −0.0021 (5) | 0.0008 (4) |
O7 | 0.0084 (4) | 0.0064 (4) | 0.0095 (4) | −0.0029 (3) | −0.0027 (3) | 0.0010 (3) |
C8 | 0.0103 (6) | 0.0078 (6) | 0.0071 (6) | −0.0032 (5) | −0.0012 (5) | 0.0001 (4) |
N8 | 0.0109 (5) | 0.0114 (5) | 0.0074 (5) | −0.0032 (4) | −0.0014 (4) | 0.0002 (4) |
C9 | 0.0088 (6) | 0.0073 (6) | 0.0079 (6) | −0.0034 (5) | −0.0010 (5) | 0.0008 (4) |
O9 | 0.0077 (4) | 0.0061 (4) | 0.0090 (4) | −0.0025 (3) | 0.0004 (3) | 0.0002 (3) |
C12 | 0.0088 (6) | 0.0068 (6) | 0.0090 (6) | −0.0019 (5) | −0.0004 (5) | −0.0002 (5) |
O1W | 0.0191 (5) | 0.0162 (5) | 0.0094 (5) | −0.0040 (4) | −0.0017 (4) | −0.0007 (4) |
O2W | 0.0148 (5) | 0.0134 (5) | 0.0148 (5) | −0.0015 (4) | −0.0050 (4) | 0.0036 (4) |
O3W | 0.0125 (5) | 0.0173 (5) | 0.0223 (5) | −0.0072 (4) | −0.0056 (4) | −0.0010 (4) |
O5W | 0.0194 (5) | 0.0169 (5) | 0.0207 (5) | −0.0076 (4) | 0.0015 (4) | −0.0057 (4) |
O4W | 0.0171 (5) | 0.0199 (5) | 0.0114 (5) | −0.0076 (4) | 0.0015 (4) | 0.0006 (4) |
O6W | 0.0347 (7) | 0.0131 (6) | 0.0414 (8) | −0.0053 (5) | 0.0264 (6) | −0.0047 (5) |
N12 | 0.0087 (5) | 0.0096 (5) | 0.0100 (5) | −0.0011 (4) | −0.0011 (4) | −0.0013 (4) |
C11 | 0.0100 (6) | 0.0067 (6) | 0.0084 (6) | −0.0032 (5) | −0.0017 (5) | −0.0010 (4) |
O11 | 0.0104 (4) | 0.0062 (4) | 0.0073 (4) | −0.0036 (3) | −0.0013 (3) | −0.0001 (3) |
C10 | 0.0086 (6) | 0.0078 (6) | 0.0098 (6) | −0.0032 (5) | −0.0030 (5) | 0.0004 (5) |
N10 | 0.0097 (5) | 0.0110 (5) | 0.0108 (5) | −0.0038 (4) | −0.0026 (4) | −0.0012 (4) |
C6 | 0.0102 (6) | 0.0072 (6) | 0.0082 (6) | −0.0020 (5) | −0.0027 (5) | 0.0000 (5) |
N6 | 0.0104 (5) | 0.0081 (5) | 0.0114 (5) | −0.0027 (4) | −0.0035 (4) | 0.0013 (4) |
Ge1—O1 | 1.8822 (9) | C8—C9 | 1.5280 (17) |
Ge1—O3 | 1.8946 (9) | C8—H8 | 1.0000 |
Ge1—O5 | 1.8933 (9) | N8—H8A | 0.878 (9) |
Ge1—O1i | 1.8822 (9) | N8—H8C | 0.886 (9) |
Ge1—O3i | 1.8946 (9) | N8—H8B | 0.876 (9) |
Ge1—O5i | 1.8932 (9) | C9—O9 | 1.4165 (15) |
O1—C1 | 1.4169 (15) | C9—C10 | 1.5330 (17) |
C1—C6 | 1.5321 (17) | C9—H9 | 1.0000 |
C1—C2 | 1.5333 (17) | C12—N12 | 1.4897 (17) |
C1—H1 | 1.0000 | C12—C11 | 1.5300 (17) |
Ge2—O7 | 1.8866 (9) | C12—H12 | 1.0000 |
Ge2—O9 | 1.8843 (9) | O1W—H1W | 0.841 (9) |
Ge2—O11 | 1.8818 (9) | O1W—H2W | 0.839 (9) |
Ge2—O7ii | 1.8866 (9) | O2W—H3W | 0.827 (9) |
Ge2—O9ii | 1.8844 (9) | O2W—H4W | 0.837 (9) |
Ge2—O11ii | 1.8817 (9) | O3W—H5W | 0.839 (9) |
N2—C2 | 1.4927 (16) | O3W—H6W | 0.835 (9) |
N2—H2C | 0.884 (9) | O5W—H9W | 0.833 (9) |
N2—H2B | 0.887 (9) | O5W—H10W | 0.828 (9) |
N2—H2A | 0.882 (9) | O4W—H7W | 0.837 (9) |
C2—C3 | 1.5296 (17) | O4W—H8W | 0.828 (9) |
C2—H2 | 1.0000 | O6W—H11W | 0.834 (10) |
O3—C3 | 1.4166 (15) | O6W—H12W | 0.832 (10) |
C3—C4 | 1.5293 (17) | N12—H12A | 0.879 (9) |
C3—H3 | 1.0000 | N12—H12B | 0.882 (9) |
C4—N4 | 1.4902 (16) | N12—H12C | 0.879 (9) |
C4—C5 | 1.5281 (17) | C11—O11 | 1.4125 (15) |
C4—H4 | 1.0000 | C11—C10 | 1.5310 (18) |
N4—H4C | 0.880 (9) | C11—H11 | 1.0000 |
N4—H4B | 0.891 (9) | C10—N10 | 1.4864 (16) |
N4—H4A | 0.888 (9) | C10—H10 | 1.0000 |
O5—C5 | 1.4190 (15) | N10—H10B | 0.877 (9) |
C5—C6 | 1.5309 (17) | N10—H10C | 0.881 (9) |
C5—H5 | 1.0000 | N10—H10A | 0.884 (9) |
C7—O7 | 1.4165 (15) | C6—N6 | 1.4865 (16) |
C7—C8 | 1.5261 (18) | C6—H6 | 1.0000 |
C7—C12 | 1.5286 (17) | N6—H6A | 0.877 (9) |
C7—H7 | 1.0000 | N6—H6B | 0.882 (9) |
C8—N8 | 1.4900 (16) | N6—H6C | 0.875 (9) |
O1—Ge1—O3 | 91.81 (4) | O5—C5—H5 | 108.5 |
O1—Ge1—O3i | 88.19 (4) | C4—C5—H5 | 108.5 |
O1—Ge1—O5 | 91.89 (4) | C6—C5—H5 | 108.5 |
O1—Ge1—O5i | 88.11 (4) | O7—C7—C8 | 112.67 (10) |
O5—Ge1—O3 | 90.74 (4) | O7—C7—C12 | 111.21 (10) |
O5—Ge1—O3i | 89.26 (4) | C8—C7—C12 | 107.48 (10) |
O9—Ge2—O7 | 89.88 (4) | O7—C7—H7 | 108.5 |
O9ii—Ge2—O7 | 90.12 (4) | C8—C7—H7 | 108.5 |
O11—Ge2—O7 | 91.30 (4) | C12—C7—H7 | 108.5 |
O11ii—Ge2—O7 | 88.70 (4) | N8—C8—C7 | 110.83 (10) |
O11—Ge2—O9 | 91.61 (4) | N8—C8—C9 | 111.87 (10) |
O11ii—Ge2—O9 | 88.39 (4) | C7—C8—C9 | 110.04 (10) |
C1—O1—Ge1 | 119.50 (8) | N8—C8—H8 | 108.0 |
C3—O3—Ge1 | 120.50 (7) | C7—C8—H8 | 108.0 |
C5—O5—Ge1 | 119.77 (7) | C9—C8—H8 | 108.0 |
C7—O7—Ge2 | 120.91 (8) | C8—N8—H8A | 108.1 (12) |
C9—O9—Ge2 | 121.04 (8) | C8—N8—H8C | 109.3 (12) |
C11—O11—Ge2 | 120.10 (8) | H8A—N8—H8C | 108.9 (16) |
O1i—Ge1—O1 | 180.0 | C8—N8—H8B | 112.8 (12) |
O1i—Ge1—O5i | 91.89 (4) | H8A—N8—H8B | 108.2 (16) |
O1i—Ge1—O5 | 88.11 (4) | H8C—N8—H8B | 109.4 (16) |
O5i—Ge1—O5 | 180.000 (13) | O9—C9—C8 | 112.89 (10) |
O1i—Ge1—O3i | 91.81 (4) | O9—C9—C10 | 110.99 (10) |
O5i—Ge1—O3i | 90.74 (4) | C8—C9—C10 | 106.82 (10) |
O1i—Ge1—O3 | 88.19 (4) | O9—C9—H9 | 108.7 |
O5i—Ge1—O3 | 89.26 (4) | C8—C9—H9 | 108.7 |
O3i—Ge1—O3 | 180.0 | C10—C9—H9 | 108.7 |
O1—C1—C6 | 112.77 (10) | N12—C12—C7 | 109.07 (10) |
O1—C1—C2 | 111.31 (10) | N12—C12—C11 | 110.52 (10) |
C6—C1—C2 | 107.57 (10) | C7—C12—C11 | 111.06 (10) |
O1—C1—H1 | 108.4 | N12—C12—H12 | 108.7 |
C6—C1—H1 | 108.4 | C7—C12—H12 | 108.7 |
C2—C1—H1 | 108.4 | C11—C12—H12 | 108.7 |
O11ii—Ge2—O11 | 180.00 (3) | H1W—O1W—H2W | 106.9 (19) |
O11ii—Ge2—O9ii | 91.61 (4) | H3W—O2W—H4W | 104.4 (19) |
O11—Ge2—O9ii | 88.39 (4) | H5W—O3W—H6W | 106.1 (19) |
O9—Ge2—O9ii | 180.0 | H9W—O5W—H10W | 104 (2) |
O11ii—Ge2—O7ii | 91.30 (4) | H7W—O4W—H8W | 102.5 (19) |
O11—Ge2—O7ii | 88.70 (4) | H11W—O6W—H12W | 105 (2) |
O9—Ge2—O7ii | 90.12 (4) | C12—N12—H12A | 109.3 (12) |
O9ii—Ge2—O7ii | 89.88 (4) | C12—N12—H12B | 115.1 (12) |
O7—Ge2—O7ii | 180.0 | H12A—N12—H12B | 107.9 (16) |
C2—N2—H2C | 110.8 (12) | C12—N12—H12C | 109.6 (12) |
C2—N2—H2B | 111.6 (12) | H12A—N12—H12C | 105.8 (16) |
H2C—N2—H2B | 109.0 (16) | H12B—N12—H12C | 108.7 (16) |
C2—N2—H2A | 110.3 (12) | O11—C11—C12 | 111.99 (10) |
H2C—N2—H2A | 106.7 (16) | O11—C11—C10 | 112.17 (10) |
H2B—N2—H2A | 108.3 (16) | C12—C11—C10 | 106.74 (10) |
N2—C2—C3 | 109.12 (10) | O11—C11—H11 | 108.6 |
N2—C2—C1 | 108.55 (10) | C12—C11—H11 | 108.6 |
C3—C2—C1 | 110.99 (10) | C10—C11—H11 | 108.6 |
N2—C2—H2 | 109.4 | N10—C10—C11 | 111.14 (10) |
C3—C2—H2 | 109.4 | N10—C10—C9 | 108.63 (10) |
C1—C2—H2 | 109.4 | C11—C10—C9 | 111.45 (10) |
O3—C3—C4 | 110.91 (10) | N10—C10—H10 | 108.5 |
O3—C3—C2 | 111.09 (10) | C11—C10—H10 | 108.5 |
C4—C3—C2 | 108.52 (10) | C9—C10—H10 | 108.5 |
O3—C3—H3 | 108.8 | C10—N10—H10B | 109.4 (12) |
C4—C3—H3 | 108.8 | C10—N10—H10C | 107.9 (12) |
C2—C3—H3 | 108.8 | H10B—N10—H10C | 111.3 (17) |
N4—C4—C5 | 110.44 (10) | C10—N10—H10A | 114.4 (12) |
N4—C4—C3 | 108.59 (10) | H10B—N10—H10A | 108.5 (16) |
C5—C4—C3 | 111.12 (10) | H10C—N10—H10A | 105.3 (16) |
N4—C4—H4 | 108.9 | N6—C6—C5 | 108.99 (10) |
C5—C4—H4 | 108.9 | N6—C6—C1 | 110.10 (10) |
C3—C4—H4 | 108.9 | C5—C6—C1 | 111.10 (10) |
C4—N4—H4C | 109.5 (12) | N6—C6—H6 | 108.9 |
C4—N4—H4B | 110.7 (12) | C5—C6—H6 | 108.9 |
H4C—N4—H4B | 111.4 (16) | C1—C6—H6 | 108.9 |
C4—N4—H4A | 111.5 (12) | C6—N6—H6A | 112.6 (12) |
H4C—N4—H4A | 108.6 (16) | C6—N6—H6B | 110.5 (12) |
H4B—N4—H4A | 105.0 (16) | H6A—N6—H6B | 104.9 (16) |
O5—C5—C4 | 112.44 (10) | C6—N6—H6C | 110.5 (12) |
O5—C5—C6 | 111.73 (10) | H6A—N6—H6C | 110.0 (16) |
C4—C5—C6 | 107.00 (10) | H6B—N6—H6C | 108.0 (16) |
O5i—Ge1—O1—C1 | 134.59 (9) | O7—C7—C8—C9 | −60.63 (13) |
O5—Ge1—O1—C1 | −45.41 (9) | C12—C7—C8—C9 | 62.23 (13) |
O3i—Ge1—O1—C1 | −134.60 (9) | N8—C8—C9—O9 | −63.31 (14) |
O3—Ge1—O1—C1 | 45.40 (9) | C7—C8—C9—O9 | 60.36 (13) |
Ge1—O1—C1—C6 | 59.68 (12) | N8—C8—C9—C10 | 174.43 (10) |
Ge1—O1—C1—C2 | −61.33 (12) | C7—C8—C9—C10 | −61.90 (13) |
O1—C1—C2—N2 | −55.20 (13) | C8—C9—O9—Ge2 | −60.42 (12) |
C6—C1—C2—N2 | −179.21 (10) | C10—C9—O9—Ge2 | 59.47 (12) |
O1—C1—C2—C3 | 64.72 (13) | O11ii—Ge2—O9—C9 | 134.69 (9) |
C6—C1—C2—C3 | −59.29 (13) | O11—Ge2—O9—C9 | −45.31 (9) |
O1i—Ge1—O3—C3 | 135.26 (9) | O7—Ge2—O9—C9 | 45.98 (9) |
O1—Ge1—O3—C3 | −44.74 (9) | O7ii—Ge2—O9—C9 | −134.02 (9) |
O5i—Ge1—O3—C3 | −132.83 (9) | O7—C7—C12—N12 | −59.90 (13) |
O5—Ge1—O3—C3 | 47.17 (9) | C8—C7—C12—N12 | 176.34 (10) |
Ge1—O3—C3—C4 | −61.58 (12) | O7—C7—C12—C11 | 62.13 (13) |
Ge1—O3—C3—C2 | 59.20 (12) | C8—C7—C12—C11 | −61.62 (13) |
N2—C2—C3—O3 | 56.33 (13) | N12—C12—C11—O11 | 58.16 (14) |
C1—C2—C3—O3 | −63.25 (13) | C7—C12—C11—O11 | −63.03 (13) |
N2—C2—C3—C4 | 178.51 (10) | N12—C12—C11—C10 | −178.72 (10) |
C1—C2—C3—C4 | 58.93 (13) | C7—C12—C11—C10 | 60.09 (13) |
O3—C3—C4—N4 | −59.22 (13) | C12—C11—O11—Ge2 | 60.37 (12) |
C2—C3—C4—N4 | 178.49 (10) | C10—C11—O11—Ge2 | −59.63 (12) |
O3—C3—C4—C5 | 62.44 (13) | O9—Ge2—O11—C11 | 44.76 (9) |
C2—C3—C4—C5 | −59.85 (13) | O9ii—Ge2—O11—C11 | −135.24 (9) |
O1i—Ge1—O5—C5 | −133.85 (9) | O7—Ge2—O11—C11 | −45.16 (9) |
O1—Ge1—O5—C5 | 46.15 (9) | O7ii—Ge2—O11—C11 | 134.84 (9) |
O3i—Ge1—O5—C5 | 134.32 (9) | O11—C11—C10—N10 | −58.74 (14) |
O3—Ge1—O5—C5 | −45.68 (9) | C12—C11—C10—N10 | 178.25 (10) |
Ge1—O5—C5—C4 | 60.05 (12) | O11—C11—C10—C9 | 62.59 (13) |
Ge1—O5—C5—C6 | −60.29 (12) | C12—C11—C10—C9 | −60.43 (13) |
N4—C4—C5—O5 | 58.15 (13) | O9—C9—C10—N10 | 61.00 (13) |
C3—C4—C5—O5 | −62.43 (13) | C8—C9—C10—N10 | −175.56 (10) |
N4—C4—C5—C6 | −178.81 (10) | O9—C9—C10—C11 | −61.78 (13) |
C3—C4—C5—C6 | 60.60 (13) | C8—C9—C10—C11 | 61.66 (13) |
C8—C7—O7—Ge2 | 61.04 (12) | O5—C5—C6—N6 | −59.57 (13) |
C12—C7—O7—Ge2 | −59.71 (12) | C4—C5—C6—N6 | 176.95 (10) |
O11ii—Ge2—O7—C7 | −134.70 (9) | O5—C5—C6—C1 | 61.91 (13) |
O11—Ge2—O7—C7 | 45.30 (9) | C4—C5—C6—C1 | −61.56 (13) |
O9—Ge2—O7—C7 | −46.31 (9) | O1—C1—C6—N6 | 58.82 (13) |
O9ii—Ge2—O7—C7 | 133.69 (9) | C2—C1—C6—N6 | −178.07 (10) |
O7—C7—C8—N8 | 63.64 (13) | O1—C1—C6—C5 | −62.01 (13) |
C12—C7—C8—N8 | −173.50 (10) | C2—C1—C6—C5 | 61.10 (13) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···Cl2iii | 0.88 | 2.31 | 3.1900 (12) | 171 |
N2—H2B···Cl3i | 0.89 | 2.27 | 3.1443 (12) | 170 |
N2—H2A···O5Wi | 0.88 | 2.44 | 3.0550 (16) | 128 |
N2—H2A···O4Wi | 0.88 | 2.45 | 3.088 (16) | 130 |
N4—H4C···Cl2iv | 0.88 | 2.35 | 3.2225 (12) | 170 |
N4—H4B···Cl4iv | 0.89 | 2.32 | 3.1978 (12) | 168 |
N4—H4A···O5Wv | 0.89 | 2.28 | 2.9395 (16) | 131 |
N8—H8A···O2Wiii | 0.88 | 2.02 | 2.8674 (16) | 161 |
N8—H8C···O4Wiv | 0.89 | 2.00 | 2.8352 (16) | 157 |
N8—H8C···Cl4 | 0.89 | 2.93 | 3.3840 (12) | 114 |
N8—H8B···O1Wiii | 0.88 | 1.98 | 2.8161 (16) | 159 |
O1W—H1W···Cl1 | 0.84 | 2.39 | 3.2264 (12) | 178 |
O1W—H2W···O11vi | 0.84 | 1.84 | 2.6708 (14) | 173 |
O2W—H4W···O3i | 0.84 | 1.78 | 2.6126 (13) | 173 |
O3W—H5W···O7iii | 0.84 | 1.76 | 2.5888 (14) | 172 |
O3W—H6W···Cl1 | 0.84 | 2.35 | 3.1755 (12) | 169 |
O5W—H9W···O1i | 0.83 | 2.08 | 2.8603 (14) | 156 |
O5W—H10W···Cl4iv | 0.83 | 2.50 | 3.3160 (11) | 171 |
O4W—H7W···Cl1 | 0.84 | 2.34 | 3.1716 (12) | 177 |
O4W—H8W···O5 | 0.83 | 1.93 | 2.7501 (14) | 171 |
O6W—H11W···O9iv | 0.83 | 1.81 | 2.6338 (15) | 170 |
O6W—H12W···Cl1 | 0.83 | 2.39 | 3.1801 (12) | 158 |
N12—H12A···Cl3iii | 0.88 | 2.35 | 3.2212 (12) | 171 |
N12—H12B···O6Wvii | 0.88 | 1.86 | 2.7202 (17) | 164 |
N12—H12C···Cl3viii | 0.88 | 2.23 | 3.0838 (12) | 165 |
N10—H10B···Cl2ix | 0.88 | 2.35 | 3.2097 (12) | 166 |
N10—H10C···O3Wiv | 0.88 | 2.21 | 2.9597 (16) | 143 |
N10—H10C···Cl3iv | 0.88 | 2.70 | 3.2591 (12) | 123 |
N10—H10A···O3Wix | 0.88 | 1.95 | 2.7953 (16) | 159 |
N6—H6A···O2W | 0.88 | 2.05 | 2.8606 (16) | 153 |
N6—H6B···Cl4iii | 0.88 | 2.24 | 3.1091 (12) | 168 |
N6—H6C···Cl4 | 0.88 | 2.60 | 3.2924 (12) | 137 |
N6—H6C···Cl1 | 0.88 | 2.67 | 3.3150 (12) | 131 |
Symmetry codes: (i) −x+1, −y, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y, −z+1; (vi) x, y, z−1; (vii) x−1, y, z+1; (viii) x−1, y+1, z+1; (ix) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H30GeN6O64+·4Cl−·6H2O |
Mr | 676.90 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 8.5247 (5), 10.9152 (6), 15.1592 (8) |
α, β, γ (°) | 82.980 (2), 79.248 (2), 70.022 (2) |
V (Å3) | 1299.78 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.66 |
Crystal size (mm) | 0.55 × 0.45 × 0.45 |
Data collection | |
Diffractometer | Bruker X8 APEX/Nonius KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2010) |
Tmin, Tmax | 0.620, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29040, 5652, 5520 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.048, 1.07 |
No. of reflections | 5652 |
No. of parameters | 411 |
No. of restraints | 30 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.53 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···Cl2iii | 0.88 | 2.31 | 3.1900 (12) | 171 |
N2—H2B···Cl3i | 0.89 | 2.27 | 3.1443 (12) | 170 |
N2—H2A···O5Wi | 0.88 | 2.44 | 3.0550 (16) | 128 |
N2—H2A···O4Wi | 0.88 | 2.45 | 3.088 (16) | 130 |
N4—H4C···Cl2iv | 0.88 | 2.35 | 3.2225 (12) | 170 |
N4—H4B···Cl4iv | 0.89 | 2.32 | 3.1978 (12) | 168 |
N4—H4A···O5Wv | 0.89 | 2.28 | 2.9395 (16) | 131 |
N8—H8A···O2Wiii | 0.88 | 2.02 | 2.8674 (16) | 161 |
N8—H8C···O4Wiv | 0.89 | 2.00 | 2.8352 (16) | 157 |
N8—H8C···Cl4 | 0.89 | 2.93 | 3.3840 (12) | 114 |
N8—H8B···O1Wiii | 0.88 | 1.98 | 2.8161 (16) | 159 |
O1W—H1W···Cl1 | 0.84 | 2.39 | 3.2264 (12) | 178 |
O1W—H2W···O11vi | 0.84 | 1.84 | 2.6708 (14) | 173 |
O2W—H4W···O3i | 0.84 | 1.78 | 2.6126 (13) | 173 |
O3W—H5W···O7iii | 0.84 | 1.76 | 2.5888 (14) | 172 |
O3W—H6W···Cl1 | 0.84 | 2.35 | 3.1755 (12) | 169 |
O5W—H9W···O1i | 0.83 | 2.08 | 2.8603 (14) | 156 |
O5W—H10W···Cl4iv | 0.83 | 2.50 | 3.3160 (11) | 171 |
O4W—H7W···Cl1 | 0.84 | 2.34 | 3.1716 (12) | 177 |
O4W—H8W···O5 | 0.83 | 1.93 | 2.7501 (14) | 171 |
O6W—H11W···O9iv | 0.83 | 1.81 | 2.6338 (15) | 170 |
O6W—H12W···Cl1 | 0.83 | 2.39 | 3.1801 (12) | 158 |
N12—H12A···Cl3iii | 0.88 | 2.35 | 3.2212 (12) | 171 |
N12—H12B···O6Wvii | 0.88 | 1.86 | 2.7202 (17) | 164 |
N12—H12C···Cl3viii | 0.88 | 2.23 | 3.0838 (12) | 165 |
N10—H10B···Cl2ix | 0.88 | 2.35 | 3.2097 (12) | 166 |
N10—H10C···O3Wiv | 0.88 | 2.21 | 2.9597 (16) | 143 |
N10—H10C···Cl3iv | 0.88 | 2.70 | 3.2591 (12) | 123 |
N10—H10A···O3Wix | 0.88 | 1.95 | 2.7953 (16) | 159 |
N6—H6A···O2W | 0.88 | 2.05 | 2.8606 (16) | 153 |
N6—H6B···Cl4iii | 0.88 | 2.24 | 3.1091 (12) | 168 |
N6—H6C···Cl4 | 0.88 | 2.60 | 3.2924 (12) | 137 |
N6—H6C···Cl1 | 0.88 | 2.67 | 3.3150 (12) | 131 |
Symmetry codes: (i) −x+1, −y, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y, −z+1; (vi) x, y, z−1; (vii) x−1, y, z+1; (viii) x−1, y+1, z+1; (ix) x, y, z+1. |