(Dicyanamido)[tris­(2-pyridylmeth­yl)amine]zinc(II) perchlorate

Hong Li; Hong Yan Zhao; Shi Guo Zhang

doi:10.1107/S1600536808004741

. 2008 Feb 27;64(Pt 3):m495. doi: 10.1107/S1600536808004741

(Dicyanamido)[tris(2-pyridylmethyl)amine]zinc(II) perchlorate

Hong Li ^a,^*, Hong Yan Zhao ^b, Shi Guo Zhang ^a

PMCID: PMC2960752 PMID: 21201877

Abstract

In the title complex, [Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄, the Zn^II ion has a slightly distorted trigonal–bipyramidal ZnN₅ coordination geometry. The crystal structure is stabilized by weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds. In addition, there are relatively close contacts between the O atoms of the perchlorate anion and symmetry-related pyridine rings [O⋯Cg = 3.179 (3) and 3.236 (3) Å, where Cg is the centroid of a pyridine ring], and between the terminal N atom of the dicyanamide ligand and pyridine rings [N⋯Cg = 3.381 (4)–3.761 (3) Å]. The central N atom of the dicyanamide ligand is disordered over two sites in an approximately 0.6:0.4 ratio.

Related literature

For related literature, see: Makowska-Grzyska et al. (2003 ▶); Sun et al. (2003 ▶); Martin et al. (2001 ▶).

Experimental

Crystal data

[Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄
M _r = 521.23
Monoclinic,
a = 13.931 (2) Å
b = 10.8578 (18) Å
c = 14.653 (2) Å
β = 91.590 (3)°
V = 2215.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.702, T _max = 0.803
12346 measured reflections
4800 independent reflections
3352 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.106
S = 0.99
4800 reflections
308 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004741/lh2594sup1.cif

e-64-0m495-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004741/lh2594Isup2.hkl

e-64-0m495-Isup2.hkl^{(235.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

N1—Zn1	2.053 (2)
N2—Zn1	2.048 (2)
N3—Zn1	2.059 (2)
N4—Zn1	2.215 (2)
N5—Zn1	2.021 (3)

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N5—Zn1—N2	101.94 (10)
N5—Zn1—N1	100.96 (11)
N2—Zn1—N1	118.19 (9)
N5—Zn1—N3	100.98 (10)
N2—Zn1—N3	117.58 (9)
N1—Zn1—N3	112.99 (9)
N5—Zn1—N4	179.41 (10)
N2—Zn1—N4	78.60 (9)
N1—Zn1—N4	78.95 (9)
N3—Zn1—N4	78.55 (9)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O4ⁱ	0.93	2.53	3.272 (4)	138
C7—H7B⋯O2ⁱⁱ	0.97	2.59	3.455 (4)	148
C10—H10⋯O1ⁱⁱⁱ	0.93	2.58	3.511 (5)	179
C13—H13A⋯N6^iv	0.97	2.61	3.457 (5)	146
C16—H16⋯N7′^v	0.93	2.48	3.412 (18)	178

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank the Natural Science Foundation of Shandong Province of China (grant No. Y2007B26).

supplementary crystallographic information

Comment

Tris[(2-pyridyl)methylene)amine is a very common terminal ligand and many complexes containing this ligand have been reported, including some Zn(II) complexes with perchlorate anions (e.g. Makowska-Grzyska et al., 2003) such as in the title compound. The dicyanamide anion can play a role as bridging ligand to form multi-nuclear complexes (e.g. Sun et al., 2003; Martin et al., 2001). As part of our work we wanted to prepare a coordination polymer with dicyanamide group acting as a bridging ligand and tris[(2-pyridyl)methylene)amine as terminal ligand, but instead we obtained the title mononuclear five-coordinated Zn(II) complex (I) and its crystal structure is reported herein. At this time there appears to be no other published examples of crystal structures of complexes of the two above mentioned ligands both coordinated to a transition metal.

The title complex is shown in Fig. 1. The Zn^II ion is in a slightly distorted trigonal-bipyramidal coordination geometry. In the crystal structure, there are weak hydrogen bonds formed between complex cations and perchlorate anions, and between symmetry related complex cations (Fig. 2). In addition there also exists interactions between Cl—O bonds and π-rings systems and between C—N bonds and π-ring systems, and the relevant distances (Å) are as follows: Cl1—O2···Cg1ⁱ = 3.236 (3), Cl1—O2···Cg1ⁱ_perp = 3.120; Cl1—O4···Cg2ⁱ = 3.179 (3), Cl1—O4···Cg2ⁱ_perp = 3.111; C20—N6···Cg2ⁱⁱ = 3.381 (4), C20—N6···Cg2ⁱⁱ_perp = 3.360; C20—N6···Cg1ⁱⁱⁱ = 3.453 (4), C20—N6···Cg1ⁱⁱⁱ_perp = 3.156; C20—N6···Cg3ⁱⁱⁱ = 3.761 (3), C20—N6···Cg3ⁱⁱⁱ_perp = 3.365; (Cg1, Cg2 and Cg3 are the centroids of N2/C1—C5 ring, N1/C8—C12 ring and N3/C14—C18 ring, respectively; A—B···Cgj_perp is the perpendicular distance from B atom to ring j; symmetry codes: (i) x,-1 + y,z; (ii) 1 - x,2 - y,-z; (iii) 1 - x,1/2 + y,1/2 - z).

Experimental

A 10 ml me thanol solution of tris[(2-pyridyl)methylene]amine (0.2103 g, 0.72 mmol) was added into 20 ml H₂O solution containing Zn(ClO₄)6H₂O (0.2621 g, 0.70 mmol) and sodium dicyanamide (0.0645 g, 0.72 mmol), and the mixture was stirred for a few minutes. Colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for 10 d.