Bis(4′-chloro-2,2′:6′,2′′-terpyridine-κ3 N,N′,N′′)iron(II) dinitrate dihydrate

Wei You; Xue-Yun Yang; Cheng Yao; Wei Huang

doi:10.1107/S1600536807062836

. 2007 Dec 6;64(Pt 1):m79. doi: 10.1107/S1600536807062836

Bis(4′-chloro-2,2′:6′,2′′-terpyridine-κ³ N,N′,N′′)iron(II) dinitrate dihydrate

Wei You ^a, Xue-Yun Yang ^a, Cheng Yao ^a,^*, Wei Huang ^b,^*

PMCID: PMC2914957 PMID: 21200647

Abstract

The title complex, [Fe(C₁₅H₁₀ClN₃)₂](NO₃)₂·2H₂O, has a six-coordinate iron(II) center balanced by two nitrate anions. The Fe atom lies on a twofold rotation axis. The complex exhibits an octahedral coordination configuration, where the dihedral angle between the two planar tridentate ligands is 92.4 (1)°. The crystal structure involves O—H⋯O hydrogen bonds.

Related literature

For the related hydrochloride tetrafluoridoborate and hydrochloride hexafluorophosphate of 4′-chloro-2,2′:6′,2′′-terpyridine, see: Huang & Qian (2007a ▶). For the related Ru^II, Cu^II, Zn^II, Ni^II and Fe^II complexes of 4′-chloro-2,2′:6′,2′′-terpyridine, see: Huang & Qian 2007b ▶).

Experimental

Crystal data

[Fe(C₁₅H₁₀ClN₃)₂](NO₃)₂·2H₂O
M _r = 751.32
Monoclinic,
a = 18.049 (2) Å
b = 18.255 (3) Å
c = 10.0741 (14) Å
β = 102.668 (2)°
V = 3238.5 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 291 (2) K
0.12 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.922, T _max = 0.931
8547 measured reflections
3192 independent reflections
2120 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 0.97
3192 reflections
233 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000 ▶); 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/S1600536807062836/at2511sup1.cif

e-64-00m79-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062836/at2511Isup2.hkl

e-64-00m79-Isup2.hkl^{(156.7KB, hkl)}

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

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

Fe1—N2	1.880 (3)
Fe1—N4	1.881 (3)
Fe1—N1	1.964 (2)
Fe1—N1ⁱ	1.964 (2)
Fe1—N3	1.975 (2)
Fe1—N3ⁱ	1.975 (2)

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N2—Fe1—N4	180
N2—Fe1—N1	81.04 (6)
N4—Fe1—N1	98.96 (6)
N1—Fe1—N1ⁱ	162.09 (11)
N2—Fe1—N3	99.34 (6)
N4—Fe1—N3	80.66 (6)
N1—Fe1—N3	92.75 (8)
N1ⁱ—Fe1—N3	90.14 (8)
N3—Fe1—N3ⁱ	161.33 (11)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O1ⁱⁱ	0.93 (5)	1.96 (5)	2.859 (5)	162 (4)
O4—H4A⋯O3ⁱⁱⁱ	0.78 (3)	2.36 (3)	3.114 (4)	164 (3)
O4—H4A⋯O1ⁱⁱⁱ	0.78 (3)	2.40 (3)	3.042 (4)	140 (3)

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Symmetry codes: (ii) Inline graphic ; (iii) .

Acknowledgments

WH acknowledges the Major State Basic Research Development Programs (No. 2006CB806104 and No. 2007CB925101), the National Natural Science Foundation of China (No. 20301009) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for financial aid.

supplementary crystallographic information

Comment

We have newly reported the hydrochlorate tetrafluoroborate and hydrochlorate hexafluorophosphorate of 4'-chloro-2,2':6',2''-terpyridine (Huang & Qian, 2007a), and Ru(II), Cu(II), Zn(II), Ni(II) and Fe(II) complexes of 4'-chloro-2,2':6',2''-terpyridine with the metal/ligand ratios of 1:1 and 1:2. In this paper, we report the structure of a ferrous nitrate complex bearing the same 4'-chloro-2,2':6',2''-terpyridine ligand with the 1:2 metal/ligand ratio.

The atom-numbering scheme of the title compound (I) is shown in Fig. 1, while selected bond distances and bond angles are given in Table 1. The iron(II) center displays a six-coordinate octahedral configuration where each 4'-chloro-2,2':6',2'-terpyridine molecule serves as a 3 N tridentate ligand. The six Fe—N bond lengths fall with the normal ranges of 1.880 (3)—1.975 (2) Å (Huang & Qian, 2007b), where the two central Fe—N bond lengths are somewhat shorter than the side ones. The two terpyridine ligands are planar and the dihedral angle between them is 92.4 (1)°. In addition, O—H···O hydrogen bonds are observed between the hydrogen atoms of water molecule and the oxygen atoms of nitrate anions (Table 2).

Experimental

The treatment of Fe(NO₃)₂.6H₂O (0.072 g, 0.25 mmol) and 4'-chloro-2,2':6',2'-terpyridine (0.134 g, 0.50 mmol) in 30 cm³ me thanol under reflux condition for 1 h produced deep red microcrystals in a yield of 83% (0.156 g). Anal. Calcd. for FeC₃₀H₂₄N₈Cl₂O₈: C: 47.96, H: 3.22, N: 14.91. Found: C: 47.88; H: 3.24; N: 14.98. Main FT—IR (KBr pellets, cm^-1): 3447 (s), 1663 (s), 1560 (s), 1545 (s), 1466 (m) and 1368 (s). Single crystals of the title complex suitable for X-ray diffraction measurement were obtained from the mixture of ethanol and water solutions at a ratio of 3:1 by slow evaporation in air at ambient temperature.