Chloridobis(1,10-phenanthroline-κ2 N,N′)copper(II) tetra­kis­(nitrato-κ2 O,O′)(1,10-phenanthroline-κ2 N,N′)terbate(III)

Guo-Ran Gao; Hong-Xue Man; Zhi-Chang Xiao; Yu-Heng Deng

doi:10.1107/S160053681101837X

. 2011 May 25;67(Pt 6):m787–m788. doi: 10.1107/S160053681101837X

Chloridobis(1,10-phenanthroline-κ² N,N′)copper(II) tetrakis(nitrato-κ² O,O′)(1,10-phenanthroline-κ² N,N′)terbate(III)

Guo-Ran Gao ^a, Hong-Xue Man ^a, Zhi-Chang Xiao ^a, Yu-Heng Deng ^a,^*

PMCID: PMC3120589 PMID: 21754668

Abstract

The title complex salt, [CuCl(C₁₂H₈N₂)₂][Tb(NO₃)₄(C₁₂H₈N₂)], consists of discrete [CuCl(phen))₂]⁺ cations and [Tb(NO₃)₄(phen)]⁻ anions (phen is 1,10-phenanthroline). The [CuCl(phen))₂]⁺ cation contains a five-coordinate Cu²⁺ ion, ligated by two bidentate phen ligands and one Cl⁻ ion, exhibiting a distorted CuN₄Cl trigonal–bipyramidal geometry. In the [Tb(NO₃)₄(phen)]⁻ anion, the Tb³⁺ ion is coordinated by one chelating phen ligand and four chelating nitrates, forming a distorted TbN₂O₈ bicapped dodecahedral configuration. The anions and cations are assembled into a three-dimensional network by weak C—H⋯Cl and C—H⋯O hydrogen bonds. There is also a significant π–π stacking interaction, with a centroid–centroid distance of 3.635 (2) Å.

Related literature

For studies on mixed-metal ionic adducts with [CuCl(phen)₂]⁺, see: Beznischenko et al. (2009 ▶); Draper et al. (2004 ▶); Yang et al. (2004 ▶). For related structures, see: Frechette et al. (1992 ▶); Kepert et al. (1996 ▶); Niu et al. (1997 ▶); Wei et al. (2002 ▶).

Experimental

Crystal data

[CuCl(C₁₂H₈N₂)₂][Tb(NO₃)₄(C₁₂H₈N₂)]
M _r = 1046.56
Triclinic,
a = 10.1556 (1) Å
b = 13.4799 (2) Å
c = 14.7710 (2) Å
α = 81.103 (1)°
β = 75.631 (1)°
γ = 84.465 (1)°
V = 1931.71 (4) Å³
Z = 2
Mo Kα radiation
μ = 2.51 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.12 mm

Data collection

Brucker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.620, T _max = 0.753
25145 measured reflections
8895 independent reflections
6625 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.078
S = 1.03
8895 reflections
550 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101837X/fj2415sup1.cif

e-67-0m787-sup1.cif^{(36.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101837X/fj2415Isup2.hkl

e-67-0m787-Isup2.hkl^{(435KB, 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
C5—H5⋯Cl1ⁱ	0.93	2.64	3.551 (5)	167
C33—H33⋯O1ⁱⁱ	0.93	2.62	3.287 (5)	130
C2—H2⋯O2	0.93	2.47	3.302 (5)	149
C14—H14⋯O3ⁱⁱⁱ	0.93	2.67	3.350 (5)	131
C26—H26⋯O4ⁱⁱⁱ	0.93	2.57	3.468 (5)	162
C6—H6⋯O5^iv	0.93	2.53	3.261 (5)	136
C9—H9⋯O6^v	0.93	2.66	3.228 (6)	120
C22—H22⋯O9^v	0.93	2.67	3.342 (6)	130
C1—H1⋯O10	0.93	2.58	3.377 (5)	144
C29—H29⋯O11^vi	0.93	2.69	3.314 (4)	126

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

Acknowledgments

We are grateful for support by the Scientific Research Common Program of Beijing Municipal Commission of Education (grant No. KM201010028008).

supplementary crystallographic information

Comment

The title compound [CuCl(phen)₂][Tb(NO₃)₄(phen)] is an unexpected product isolated from the reaction system of Tb(NO₃)₃.6H₂O, Cu(ClO₄)₂.6H₂O, 2-(Carboxymethylthio)benzoic acid and 1,10-phenanthroline in methanol solution.

There are few of mixed-metal ionic adducts similar to the title compound containing [CuCl(phen))₂]⁺ ion reported now (Beznischenko, et al., 2009; Draper, et al., 2004; Yang, et al., 2004]. Herein, we report a new ion adduct of Cu(II) complexcation and Tb(III) complexanion, [CuCl(phen)₂][Tb(NO₃)₄(phen)]. The center Cu²⁺ ion of [CuCl(phen))₂]⁺ is coordinated by two bidentate phen ligands and one Cl^- ion, exhibiting a distorted five-coordinated CuN₄Cl trigonalbipyramidal geometry. However, the [Tb(NO₃)₄(phen)]^- anion is a distinct structure which is unique to the other lanthanide complexes with phen and NO^3-. The center Tb³⁺ ion is coordinated by one phen and four nitrates, forming a conventional ten-coordinated dicapped dodecahedral configuration. But in the previous literatures, all the ten-coordinated mononuclear lanthanide complex containing phen and nitrate ligands had a universal RE(NO₃)₃(phen)₂ (RE = La, Ce, Pr, Nd, Lu, Gd, Tb) structure (Frechette et al., 1992; Kepert et al., 1996; Niu et al., 1997; Wei et al., 2002). However, the title [Tb(NO₃)₄(phen)]^- anion is the first example of ten-coordinated mononuclear lanthanide complex with one phen and four nitrate ligands. (Fig. 1)

There are several weak nontraditional C—H···O interactions which are significant in the crystal packing. The O(1), O(2), O(3), O(4), O(5), O(6), O(8), O(9), O(10) and O(11) atoms of the nitrates take part in constructing of C—H···O hydrogen bonds. The C(5)—H(5)···Cl(1) and C(26)—H(26)···O(4) hydrogen bonds link the [CuCl(phen))₂]⁺ and [Tb(NO₃)₄(phen)]^- to form infinite cation and anion chains along the a direction, respectively.

Two cation chains join together to generate a double chain by obvious π–π stacking interaction between the 10-member rings of the [CuCl(phen))₂]⁺ from the adjacent cation chains (Cg(1)···Cg(1)^a = 3.635 (2) Å: Cg(1) [N(4)—C(22)—C(21)—C(20)—C(19)—C(18)—C(17)—C(16)—C(24)—C(23)]; symmetry code a: -x + 2, -y + 1, -z). Two anion chains attach each other also to generate a double chain similarly by C(33)—H(33)···O(1), C(29)—H(29)···O(11) hydrogen bonds and π–π stacking force between the adjacent anion chains (Cg(2)···Cg(2)^b = 3.574 (2) Å: Cg(2) [C(28)—C(29)—C(30)—C(31)—C(35)— C(36)]; symmetry code b: -x + 1, -y, -z + 1). (Fig. 2)

Between the neighboring cation and anion chains, there are six weak intramolecular hydrogen bonds, i.e. C(2)—H(2)···O(2), C(14)—H(14)···O(3), C(6)—H(6)···O(5), C(9)—H(9)···O(6), C(22)—H(22)···O(9) and C(1)—H(1)···O(10), to assemble the cation and anion chains to a three-dimensional network. The 10-member rings of the phen in the [CuCl(phen))₂]⁺ and [Tb(NO₃)₄(phen)]^- from the neighboring cation and anion chains are too close to result in π–π stacking effect (Cg(3)···Cg(4)^b = 3.543 (2) Å: Cg(3) [N(2)—C(10)—C(9)— C(8)—C(7)—C(6)—C(5)—C(4)—C(12)—C(11)], Cg(4) [N(5)—C(25)—C(26)—C(27)—C(28)—C(29)—C(30)—C(31)—C(35)—C(36)]) (Fig. 3)

Experimental

All the solvents and reagents were of analytical reagent grade and were used without further purification.2-(Carboxymethylthio) benzoic acid (2.0 mmol, 0.424 g)and phen (1.0 mmol, 0.198 g) were mixed in 30 ml me thanol and stirred for half an hour. Then Tb(NO₃)₃.6H₂O (1.0 mmol, 0.453 g) and Cu(ClO)₂.6H₂O (1.0 mmol, 0.371 g) in 20 ml me thanol solution was added dropwise into the above solution and the mixture was carefully adjusted to pH = 5.5 by adding 0.1 mol/L NaOH methanol solution. The resulting mixture was left to react by stirring for 6 h at 80°C. The filtrate was slowly evaporated at ambient temperature for 3 days and block crystals were crystallized and isolated.