[N,N-Bis(2-pyridylmeth­yl)glycinato-κ4 N,N′,N′′,O]dichloridoiron(III)–[N,N-bis­(2-pyridylmeth­yl)glycine-κ4 N,N′,N′′,O]dichloridozinc(II) (1/1)

Anne Nielsen; Christine J McKenzie; Andrew D Bond

doi:10.1107/S1600536809051022

. 2009 Nov 28;65(Pt 12):m1706. doi: 10.1107/S1600536809051022

[N,N-Bis(2-pyridylmethyl)glycinato-κ⁴ N,N′,N′′,O]dichloridoiron(III)–[N,N-bis(2-pyridylmethyl)glycine-κ⁴ N,N′,N′′,O]dichloridozinc(II) (1/1)

Anne Nielsen ^a, Christine J McKenzie ^a, Andrew D Bond ^a,^*

PMCID: PMC2972039 PMID: 21578707

Abstract

The title compound, [Fe(C₁₄H₁₄N₃O₂)Cl₂]·[ZnCl₂(C₁₄H₁₅N₃O₂)], is formulated as [Fe^III(bpg)Cl₂][Zn^IICl₂(bpgH)], where bpg is the tetradentate ligand N,N-bis(2-pyridylmethyl)glycine. The structure contains one crystallographically distinct complex with Fe^III and Zn^II atoms present in a 50:50 ratio in a single-atom site. The non-coordinated O atoms of the carboxyl groups of bpg meet across crystallographic inversion centres, forming O—H⋯O hydrogen bonds that include only one H atom per two complexes, consistent with the 1:1 disorder of Fe^III and Zn^II.

Related literature

For related Fe^III structures of bpg, see: Mortensen et al. (2004 ▶). For details of the synthesis, see: Suzuki et al. (1988 ▶). graphic file with name e-65-m1706-scheme1.jpg

Experimental

Crystal data

[Fe(C₁₄H₁₄N₃O₂)Cl₂]·[ZnCl₂(C₁₄H₁₅N₃O₂)]
M _r = 776.59
Monoclinic,
a = 8.8710 (3) Å
b = 13.1898 (5) Å
c = 13.3983 (4) Å
β = 91.737 (2)°
V = 1566.97 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.62 mm⁻¹
T = 180 K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker–Nonius X8APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.701, T _max = 0.794
32580 measured reflections
4775 independent reflections
4248 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.132
S = 1.36
4775 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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 global, I. DOI: 10.1107/S1600536809051022/jh2118sup1.cif

e-65-m1706-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051022/jh2118Isup2.hkl

e-65-m1706-Isup2.hkl^{(233.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O2ⁱ	0.93	1.64	2.559 (6)	169

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to the Danish Natural Sciences Research Council and the Carlsberg Foundation for provision of the X-ray equipment.

supplementary crystallographic information

Comment

Crystallization of the title compound, [FeCl₂(bpg)][ZnCl₂(bpgH)] (where bpg denotes the tetradentate ligand N,N-bis(2-pyridylmethyl)glycine), was surprising given the presence of water in its preparation. In our hands, simple binary mixtures of bpgH and FeCl₃ in water-containing solutions do not yield the complex [FeCl₂(bpg)]. If only chloride ions but not Zn^II are present in equivalent reaction mixtures (i.e. aerobic conditions and containing water), oligomeric (hydr)oxo-bridged Fe^III complexes are formed, such as [Fe₂(O)(bpg)₂(H₂O)₂](ClO₄)₂ and [Fe₃(O)₂(OH)(bpg)₃](ClO₄) (Mortensen et al., 2004). Addition of Zn^II has in this case enabled isolation of [FeCl₂(bpg)] from water as one component of the co-crystal.

Experimental

N,N-Bis(2-pyridylmethyl)glycine (bpgH) was prepared according to a literature method (Suzuki et al., 1988). BpgH (125 mg, 49 mmol) was then dissolved in hot acetonitrile (5 ml) and water (0.5 ml), before Fe(NO₃)₃.9H₂O (99 mg, 24 mmol), ZnCl₂ (67 mg, 49 mmol) and NH₄Cl (78 mg, 15 mmol) were added. A few yellow crystals of the title compound were deposited overnight.