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Crystal structure of bis-[(phenyl-methanamine-κN)(phthalocyaninato-κ(4) N)zinc] phenyl-methan-amine tris-olvate.

Shamsudin N, Tan AL, Wimmer FL, Young DJ, Tiekink ER - Acta Crystallogr E Crystallogr Commun (2015)

Bottom Line: Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules.The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside.This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

View Article: PubMed Central - HTML - PubMed

Affiliation: Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link BE 1410, Negara Brunei Darussalam.

ABSTRACT
The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

No MeSH data available.


Related in: MedlinePlus

The unit-cell contents of (I), shown in projection down the a axis. Inter­molecular N—H⋯N, N—H⋯π and π–π inter­actions are shown as orange, purple and blue dashed lines, respectively. One supra­molecular layer sustained by N—H⋯N and N—H⋯π inter­actions has been highlighted in space-filling mode.
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fig4: The unit-cell contents of (I), shown in projection down the a axis. Inter­molecular N—H⋯N, N—H⋯π and π–π inter­actions are shown as orange, purple and blue dashed lines, respectively. One supra­molecular layer sustained by N—H⋯N and N—H⋯π inter­actions has been highlighted in space-filling mode.

Mentions: Based on the standard criteria incorporated within PLATON (Spek, 2009 ▸), the most notable directional inter­actions in the crystal packing of (I) are N—H⋯N hydrogen bonds, N—H⋯π inter­actions and face-to-face π–π inter­actions. These contacts involve six of the 10 available N—H atoms. The nature of the inter­actions involving amino-H atoms is highlighted in Fig. 3 ▸, and geometric parameters characterizing the inter­molecular inter­actions are given in Table 2 ▸. From the upper view of Fig. 3 ▸, it evident that the Zn1-bound benzyl­amine mol­ecule forms two N—H donor inter­actions, one being a conventional N—H⋯N hydrogen bond to the N19 atom of an uncoordinated benzyl­amine mol­ecule which is orientated to place one amine-H proximate to a five-membered NC4 ring, leading to a N—H⋯π(pyrrol­yl) inter­action. The second amine-H atom of the coordinating benzyl­amine mol­ecule forms an N—H⋯π(phen­yl) inter­action with a non-coordinating N21-benzyl­amine mol­ecule. For the Zn2-containing mol­ecule, the coordinating N18-benzyl­amine forms a donor N—H⋯N hydrogen bond to a non-coordinating N20-benzyl­amine mol­ecule which is folded to enable a donor N—H⋯N hydrogen bond to an exocyclic-N atom of the PC dianion. As seen from the lower view of Fig. 3 ▸, the second H atom of the N20-benzyl­amine mol­ecule does not form an inter­action within the standard distance criteria (Spek, 2009 ▸). The N21-benzyl­amine mol­ecule forms a donor N—H⋯N hydrogen bond to an exocyclic-N of the PC dianion. This mol­ecule functions as the bridge between the two complex mol­ecules and leads to the formation of supra­molecular layers in the ab plane. These have a zigzag topology and present the flat PC residues to the outside with the benzyl­amine mol­ecules, both coordinating and non-coordinating, in the inter-layer region. The layers stack along the c axis being connected by π–π inter­actions between pyrrolyl and fused-phenyl rings [inter-centroid (N6,C17, C18,C23,C24)⋯(C57–C62) distance = 3.593 (2) Å with an angle of inclination = 6.1 (2)°]. A view of the unit cell contents is shown in Fig. 4 ▸.


Crystal structure of bis-[(phenyl-methanamine-κN)(phthalocyaninato-κ(4) N)zinc] phenyl-methan-amine tris-olvate.

Shamsudin N, Tan AL, Wimmer FL, Young DJ, Tiekink ER - Acta Crystallogr E Crystallogr Commun (2015)

The unit-cell contents of (I), shown in projection down the a axis. Inter­molecular N—H⋯N, N—H⋯π and π–π inter­actions are shown as orange, purple and blue dashed lines, respectively. One supra­molecular layer sustained by N—H⋯N and N—H⋯π inter­actions has been highlighted in space-filling mode.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4555378&req=5

fig4: The unit-cell contents of (I), shown in projection down the a axis. Inter­molecular N—H⋯N, N—H⋯π and π–π inter­actions are shown as orange, purple and blue dashed lines, respectively. One supra­molecular layer sustained by N—H⋯N and N—H⋯π inter­actions has been highlighted in space-filling mode.
Mentions: Based on the standard criteria incorporated within PLATON (Spek, 2009 ▸), the most notable directional inter­actions in the crystal packing of (I) are N—H⋯N hydrogen bonds, N—H⋯π inter­actions and face-to-face π–π inter­actions. These contacts involve six of the 10 available N—H atoms. The nature of the inter­actions involving amino-H atoms is highlighted in Fig. 3 ▸, and geometric parameters characterizing the inter­molecular inter­actions are given in Table 2 ▸. From the upper view of Fig. 3 ▸, it evident that the Zn1-bound benzyl­amine mol­ecule forms two N—H donor inter­actions, one being a conventional N—H⋯N hydrogen bond to the N19 atom of an uncoordinated benzyl­amine mol­ecule which is orientated to place one amine-H proximate to a five-membered NC4 ring, leading to a N—H⋯π(pyrrol­yl) inter­action. The second amine-H atom of the coordinating benzyl­amine mol­ecule forms an N—H⋯π(phen­yl) inter­action with a non-coordinating N21-benzyl­amine mol­ecule. For the Zn2-containing mol­ecule, the coordinating N18-benzyl­amine forms a donor N—H⋯N hydrogen bond to a non-coordinating N20-benzyl­amine mol­ecule which is folded to enable a donor N—H⋯N hydrogen bond to an exocyclic-N atom of the PC dianion. As seen from the lower view of Fig. 3 ▸, the second H atom of the N20-benzyl­amine mol­ecule does not form an inter­action within the standard distance criteria (Spek, 2009 ▸). The N21-benzyl­amine mol­ecule forms a donor N—H⋯N hydrogen bond to an exocyclic-N of the PC dianion. This mol­ecule functions as the bridge between the two complex mol­ecules and leads to the formation of supra­molecular layers in the ab plane. These have a zigzag topology and present the flat PC residues to the outside with the benzyl­amine mol­ecules, both coordinating and non-coordinating, in the inter-layer region. The layers stack along the c axis being connected by π–π inter­actions between pyrrolyl and fused-phenyl rings [inter-centroid (N6,C17, C18,C23,C24)⋯(C57–C62) distance = 3.593 (2) Å with an angle of inclination = 6.1 (2)°]. A view of the unit cell contents is shown in Fig. 4 ▸.

Bottom Line: Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules.The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside.This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

View Article: PubMed Central - HTML - PubMed

Affiliation: Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link BE 1410, Negara Brunei Darussalam.

ABSTRACT
The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

No MeSH data available.


Related in: MedlinePlus