(1,4,7,10-Tetra­aza­cyclo­dodecane-κ4 N 1,N 4,N 7,N 10)(tetra­oxidomolybdato-κO)copper(II) monohydrate

Dorothea Rohde; Kurt Merzweiler

doi:10.1107/S1600536810026000

. 2010 Jul 7;66(Pt 8):m894. doi: 10.1107/S1600536810026000

(1,4,7,10-Tetraazacyclododecane-κ⁴ N ¹,N ⁴,N ⁷,N ¹⁰)(tetraoxidomolybdato-κO)copper(II) monohydrate

Dorothea Rohde ^a, Kurt Merzweiler ^a,^*

PMCID: PMC3007245 PMID: 21588138

Abstract

In the title compound, [CuMoO₄(C₈H₂₀N₄)]·H₂O, the Cu^II atom is coordinated by four N atoms of the 1,4,7,10-tetraazacyclododecane (cyclen) ligand and one O atom of the molybdate unit in a distorted square-pyramidal environment. The water molecules are linked to the complex unit to form centrosymmetric dimers [R ₄ ⁴(12) and R ₄ ⁴(16)] and discrete D ₃ ²(9), D ₃ ³(11) and D ₃ ³(13) chains by O—H⋯O and N—H⋯O interactions. Additionally, the complex molecules are linked into C ₄ ⁴(18) chain motifs by N—H⋯O interactions. As a result [(cyclen)CuMoO₄] units and water molecules are linked to layers that are oriented parallel to the ac plane. The stacking of the layers in the b-axis direction is supported by weak C—H⋯O hydrogen bridges.

Related literature

For inorganic–organic hybrid materials based on copper complexes with bridging molybdate ligands, see, for example: Rarig et al. (2002 ▶); Hagrman et al. (1998 ▶). For copper complexes with the cyclen ligand, see: Clay et al. (1979 ▶); Lu et al. (1997 ▶); Yeung et al. (2000 ▶); Guo et al. (2008 ▶). For related literature, see: Bernstein et al. (1995 ▶); Choi et al. (2004 ▶).

Experimental

Crystal data

[CuMoO₄(C₈H₂₀N₄)]·H₂O
M _r = 413.78
Triclinic,
a = 8.6985 (6) Å
b = 8.9784 (6) Å
c = 9.0055 (6) Å
α = 90.358 (6)°
β = 91.949 (6)°
γ = 100.742 (5)°
V = 690.54 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.47 mm⁻¹
T = 200 K
0.22 × 0.21 × 0.13 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: numerical (X-RED; Stoe & Cie, 2009 ▶) T _min = 0.612, T _max = 0.737
9700 measured reflections
3017 independent reflections
2788 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.063
S = 1.04
3017 reflections
196 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −1.05 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026000/bx2287sup1.cif

e-66-0m894-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026000/bx2287Isup2.hkl

e-66-0m894-Isup2.hkl^{(148.1KB, 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
O5—H5⋯O4ⁱ	0.83 (2)	1.95 (2)	2.770 (2)	169 (3)
N1—H1⋯O5ⁱⁱ	0.86 (2)	2.35 (2)	3.156 (3)	156 (3)
N2—H2⋯O1ⁱⁱ	0.89 (2)	2.19 (2)	2.949 (2)	143 (3)
N3—H3⋯O4ⁱ	0.88 (2)	2.28 (3)	2.955 (3)	133 (3)
N4—H4⋯O5ⁱⁱⁱ	0.88 (2)	2.10 (2)	2.928 (3)	157 (3)
O5—H6⋯O2^iv	0.84 (2)	1.85 (2)	2.666 (3)	163 (4)
C3—H3B⋯O3^v	0.99	2.36	3.345 (3)	175

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

supplementary crystallographic information

Comment

In the title compound (I) the central copper atom is coordinated by four nitrogen atoms of the cyclen ligand and one oxygen atom of the molydate group. This leads to a distorted square pyramidal coordination environment with the four N atoms in the basal positions and the molybdate oxygen atom at the apex. The arrangement of the four nitrogen atoms is nearly co-planar within a maximum deviation of 0.015 Å and the copper atom lies 0.569 Å above this plane. The Cu—N distances ranging from 2.033 (2) to 2.049 (2) Å which is comparable to the Cu—N bond lengths oberserved in other cyclen copper complexes, like [(cyclen)Cu(NO₃)]NO₃ (Clay et al., 1979), [(cyclen)Cu(SCN)]₂[Ca(NCS)₆] H₂O (Lu et al., 1997), [(cyclen)Cu(Ag(CN)₂)][Ag(CN)₂] (Yeung et al., 2000) and [(cyclen)Cu(MnN(CN)₅)] (Guo et al., 2008). The molybdate unit coordinates as a monodentate ligand with a Cu—O distance of 2.104 (2) Å. The Mo—O distances ranging from 1.749 to 1.765 Å for the terminal oxygen atoms. In the case of the µ-bridging O atom O1 the Mo—O distance is slightly enlarged to 1.796 (2) Å. A similar monodentate coordination of molybdate has been observed in the copper complex [LCuMoO₄]₂ 5H₂O (L = 1,3,10, 12,16,19-hexaazatetracyclo[17,3,1,1^12.16,0^4.9]tetracosane with Cu—O distances of 2.320 (12) and 2.418 (11) Å and Mo—O distances ranging from 1.621 to 1.849 Å (Choi et al., 2004).

Compound (I) contains a water molecule which is involved into two strong hydrogen bonds to the molybdate O2 and O4 oxygen atoms . This leads to [(cyclen)CuMoO₄]₂(H₂O)₂ dimers containing a centrosymmetric Mo₂O₆H₄ ring of the type R₄⁴(12) (Fig. 2) (Bernstein et al., 1995). Additionally the NH groups of the cyclen ligand are also involved in hydrogen bonds either to water molecules (N1H1 and N4H4) or to molybdate groups (N2H2 and N3H3). As a resuslt of these hydrogen bonds [(cyclen)CuMoO₄] units and water are interlinked to layers which are oriented parallel to the crystallographic a-c plane. The stacking of the layers in direction of the crystallographic b axis is supported by weak C—H···O hydrogen bonds (C···O 3.35 Å) between cyclen ligands and molydate units.

Experimental

To a stirred suspension of 0.440 mg (2.0 mmol) CuMoO₄ in 70 ml of aqueous methanol (90%) 0.350 mg (2.0 mmol) cyclen was added. After four hours the blue suspension was filtered and the filtrate evaporated to dryness.Yield. 420 mg (50%). The residue was dissolved in 3 ml of methanol and then the solution was layered with 2-propanol. After one week single crystals of (I) were formed at the methanol/2-propanol interface. IR(cm^-1): 3172(s), 2960(w), 2937(w), 2920(w), 2869(w), 1631(w), 1592(w), 824(s); Elemental Analysis [Cu(cyclen)MoO₄] H₂O (413.78), C 23.0 (calc. 23.2), H 5.4 (5.4), N 13.1 (13.5) %.