[Co(H2O)6]{[Co(C4H4N2)(H2O)2][V2O2(pmida)2]}·2H2O [H4pmida is N-(phosphono­meth­yl)imino­diacetic acid]: the first two-dimensional hybrid framework containing [V2O2(pmida)2]4− building blocks

Almeida Paz, F.A.; Shi, F.-N.; Mafra, L.; Makal, A.; Wozniak, K.; Trindade, T.; Klinowski, J.; Rocha, J.

doi:10.1107/S1600536805023263

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages m1628-m1632

https://doi.org/10.1107/S1600536805023263

[Co(H₂O)₆]{[Co(C₄H₄N₂)(H₂O)₂][V₂O₂(pmida)₂]}·2H₂O [H₄pmida is N-(phosphonomethyl)iminodiacetic acid]: the first two-dimensional hybrid framework containing [V₂O₂(pmida)₂]⁴⁻ building blocks

Filipe A. Almeida Paz,^a ^* Fa-Nian Shi,^a Luís Mafra,^a Anna Makal,^b Krzysztof Wozniak,^b Tito Trindade,^a Jacek Klinowski ^c and João Rocha ^a

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, ^bDepartment of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warszawa, Poland, and ^cDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England
^*Correspondence e-mail: fpaz@dq.ua.pt

(Received 11 July 2005; accepted 21 July 2005; online 27 July 2005)

The crystal structure of the title compound, polymeric hexaaquacobalt(II) diaquadioxodi-μ₂-pyrazine-bis[μ₃-N-(phosphonomethyl)iminodiacetato]cobalt(II)divanadate(IV) dihydrate, {[Co(H₂O)₆][CoV₂(C₃H₄O₈P)₂(C₄H₄N₂)₂(H₂O)₂]·2H₂O}_n, is the first example of a two-dimensional hybrid framework containing centrosymmetric dimeric [V₂O₂(pmida)₂]⁴⁻ anionic units [H₄pmida is N-(phosphonomethyl)iminodiacetic acid]. The structure contains two crystallographically unique cobalt(II) centres, both located at inversion centres and exhibiting Jahn–Teller-distorted octahedral coordination geometries. One Co²⁺ cation establishes physical links between adjacent [V₂O₂(pmida)₂]⁴⁻ anionic units, forming one-dimensional anionic ribbons which run along the [010] direction, {[Co(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻. Pyrazine ligands, with their centroids located at inversion centres, bridge the above-mentioned Co²⁺ centres, forming {[Co(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻ anionic layers which alternate along the [001] direction with [Co(H₂O)₆]²⁺ cations and the water molecules of crystallization. An extensive and highly directional hydrogen-bonded network interconnects the structural components.

Comment

The design of coordination-based materials in which the topology is extended from zero-dimensional (i.e. discrete complexes) into one-, two- or three-dimensional, is a topical and interesting field of research. Since the seminal paper by Hoskins & Robson (1990 ), where diamondoid-type hybrid frameworks were engineered based upon the simple structures of cadmium and zinc cyanides, the field has expanded rapidly. This was motivated by the unusual architectures and the potential applications of such frameworks (Batten & Robson, 1998 ; Janiak, 2003 ; Mori et al., 2004 ; Moulton & Zaworotko, 2001 ; Rowsell & Yaghi, 2004 ). In order to control, at least partially, the occurrence of `supramolecular isomerism' (Moulton & Zaworotko, 2001), these hydrid crystalline materials are now being constructed using a typical modular approach: rigid and highly robust coordination-based cores are used as secondary building units (SBUs) for the construction of multidimensional metal–organic frameworks (MOFs) (Yaghi et al., 1998 ).

During the course of our work on crystalline organic–inorganic hybrid materials (Paz et al., 2002 , 2002a ,b ,c ; Paz & Klinowski, 2003 , 2004a ,b ,c ; Paz, Shi et al., 2004 ), we came across N-(phosphonomethyl)iminodiacetic acid (H₄pmida), an organic molecule which, despite possessing several types of chelating functional groups, is relatively unexplored in the construction of MOFs (Fan et al., 2004 ; Gutschke et al., 1999 ; Mao et al., 2002 ; Pei et al., 2004 ; Song et al., 2004 ), as confirmed by a search in the Cambridge Structural Database (Version 5.25 of November 2003; Allen, 2002 ; Allen & Motherwell, 2002 ). This molecule forms with V⁴⁺ centres centrosymmetric dimeric [V₂O₂(pmida)₂]⁴⁻ anionic units, as originally reported by Crans et al. (1998 ); this anionic dimer is a rather convenient SBU owing, on the one hand, to its predictable self-assembly in aqueous media (particularly when hydrothermal synthetic approaches are employed) and, on the other, to the several terminal O atoms which can bound to a large variety of metal centres through various coordination modes. We recently reported the first three-dimensional frameworks containing [V₂O₂(pmida)₂]⁴⁻ anionic units, through their combination with transition metal centres (namely, Cd²⁺ and Co²⁺) and the bridging 4,4′-bipyridine organic ligand (Paz, Shi et al., 2004). We report here the first two-dimensional framework containing these anionic units: [Co(H₂O)₆]{[Co(pyr)(H₂O)₂][V₂O₂(pmida)₂]}·2(H₂O), (I) (where pyr is pyrazine).

The title compound, (I), crystallizes in the triclinic space group P $[\overline{1}]$ , with all its primary building blocks having inversion symmetry: the [V₂O₂(pmida)₂]⁴⁻ anionic unit has its centroid located at the inversion centre ( $[{1\over 2}]$ , 0, 0); both Co1 and Co2 are themselves located at inversion centres, with the former positioned in the middle of the ab plane, at ( $[{1\over 2}]$ , $[{1\over 2}]$ , 0), and the latter in the centre of the unit cell, at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ); the pyrazine bridging organic ligand, as for the [V₂O₂(pmida)₂]⁴⁻ anionic unit, is also centrosymmetric, with its centroid located at (0, $[1\over2]$ , 0).

The geometry of the [V₂O₂(pmida)₂]⁴⁻ anionic unit is very similar to that previously reported for related compounds (Crans et al., 1998; Paz, Shi et al., 2004), with the pmida⁴⁻ anionic ligands encapsulating the V⁴⁺ centres inside three five-membered chelate rings (average bite angle of ca 77°, Table 1). The coordination polyhedron of these metal centres resembles a highly distorted octahedron, {VNO₅}, with the oxo group [V=O = 1.593 (2) Å] markedly showing its trans influence in the rather long V—N distance [2.354 (2) Å]. The phosphonate groups establish the physical bridges between adjacent V⁴⁺ centres (Fig. 1a), leading to a V1⋯V1^v distance of 5.149 (2) Å [symmetry code: (v) 1 − x, −y, 1 − z].

Both cobalt(II) centres adopt Jahn–Teller-distorted octahedral cooordination geometries, as depicted in Fig. 1 and Table 1. For Co1, the equatorial plane is formed by two water molecules plus two O-donor atoms from phosphonate groups (Fig. 1a), with an average Co—O distance of ca 2.07 Å; pyr ligands, axially coordinated, complete the coordination, with Co—N bond lengths of 2.218 (2) Å (Table 1). Co2 is coordinated only by water molecules, with O3W and O4W forming the equatorial plane (the average Co—O bond length is 2.06 Å) and O2W located 2.144 (2) Å from the metal centre. The cis octahedral angles are within the ranges 88.04 (6)–91.96 (6) and 87.84 (6)–92.16 (6)° for Co1 and Co2, respectively (Table 1).

The centrosymmetric [V₂O₂(pmida)₂]⁴⁻ anionic unit is bound to two adjacent Co1 metal centres via the trans-uncoordinated P—O bonds, imposing a Co1⋯Co1^viii separation of 10.140 (2) Å [symmetry code: (viii) x, −1 + y, z] (Fig. 1a). The repetition of this bridging motif leads to the formation of a one-dimensional anionic ribbon (running along the [010] direction), {[Co(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻, as depicted in Fig. 2(a). Centrosymmetric bridging pyr ligands are axially coordinated to these Co1 centres (Fig. 2b), establishing physical connections between adjacent ribbons and further imposing a Co1⋯Co1^vii separation of 7.220 (1) Å [symmetry code: (vii) 1 + x, y, z]. Such an arrangement leads to the formation of a decorated two-dimensional {[Co(pyr)(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻ anionic layer with distances between Co1 atoms defined by the a- and b-axis lengths. The charge of this layer is compensated by the presence of hexaaquacobalt(II) cations, [Co(H₂O)₆]²⁺ (Fig. 1b), which also act as space-filling groups, located in the available spaces resulting from the parallel packing, along the [001] direction, of individual anionic layers (Fig. 3). Each {[Co(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻ layer is further interconnected to the [Co(H₂O)₆]²⁺ cations via a series of very strong and highly directional hydrogen-bond interactions, also involving the water molecules of crystallization (Fig. 4 and Table 2).

Figure 1
Schematic representation of (a) a portion of the anionic two-dimensional {[Co(pyr)(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻ layer and (b) the interlayer [Co(H₂O)₆]²⁺ cations, showing the labelling scheme for selected atoms in the asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Schematic representation of the construction of the anionic two-dimensional {[Co(pyr)(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻ layers, which lie in the ab plane of the unit cell.

Figure 3
Alternation along the [001] direction of anionic two-dimensional {[Co(pyr)(H₂O)₂][V₂O₂(pmida)₂]}_n²ⁿ⁻ layers (in green and orange), which are intercalated by [Co(H₂O)₆]²⁺ cations (in grey). H atoms have been omitted for clarity.

Figure 4
Perspective view of the crystal packing of the title compound, viewed along the (a) [100] and (b) [010] directions of the unit cell. Hydrogen bonds are represented as green dashed bonds and H atoms have been omitted for clarity.

Experimental

Chemicals were readily available from commercial sources and were used as received without further purification: N-(phosphonomethyl)iminodiacetic acid hydrate (H₄pmida, 97% Fluka), pyrazine (98% Fluka), vanadium(IV) oxide sulfate pentahydrate (99% Sigma–Aldrich) and cobalt acetate tetrahydrate (99.0% Fluka). Syntheses were typically carried out in PTFE-lined stainless steel reaction vessels (ca 40 cm³), under autogenous pressure and static conditions in a preheated oven at 373 K. Reactions took place over a period of 4 d, after which the vessels were removed from the oven and left to cool to ambient temperature before opening. The title compound proved to be air- and light-stable, and insoluble in water and common organic solvents such as methanol, ethanol, acetone, dichloromethane, toluene, dimethyl sulfoxide and chloroform. The title compound was synthesized from a mixture containing VOSO₄·5H₂O (0.40 g), CoC₄H₆O₄·4H₂O (0.34 g), H₄pmida (0.27 g), pyrazine (0.10 g) and NaOH (0.20 g) in distilled water (ca 10 g). The mixture was stirred at ambient temperature for 30 min, yielding a suspension with a molar composition of 2.1:1.2:1.0:1.1:4.2:467, which was transferred to the reaction vessel. After the reaction, a large quantity of light-blue single crystals of the title compound were isolated by vacuum filtration, washed with copious amounts of distilled water (ca 3 × 50 ml), and then air-dried at ambient temperature.

Crystal data

C₁₄H₂₀CoN₄O₁₈P₂V₂·CoH₁₂O₆·2H₂O
M_r = 958.15
Triclinic, $[P \overline 1]$
a = 7.2200 (14) Å
b = 10.140 (2) Å
c = 12.080 (2) Å
α = 93.79 (3)°
β = 103.21 (3)°
γ = 104.21 (3)°
V = 827.6 (3) Å³
Z = 1
D_x = 1.922 Mg m⁻³
Mo Kα radiation
Cell parameters from 5000 reflections
θ = 2–22.5°
μ = 1.73 mm⁻¹
T = 298 (2) K
Prism, blue
0.44 × 0.33 × 0.14 mm

Data collection

Kuma KM-4 CCD diffractometer
ω scans
Absorption correction: numerical(SADABS; Sheldrick, 1996 )T_min = 0.354, T_max = 0.724
14552 measured reflections
3994 independent reflections
3510 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 28.8°
h = −9 → 9
k = −13 → 13
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.068
S = 1.08
3994 reflections
260 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0369P)² + 0.2906P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.46 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0134 (13)

Table 1
Selected geometric parameters (Å, °)

Co1—O1ⁱ	2.044 (2)
Co1—O1W	2.093 (2)
Co1—N2	2.218 (2)
Co2—O2W	2.144 (2)
Co2—O3W	2.063 (2)
Co2—O4W	2.061 (2)
V1—O2ⁱⁱ	1.996 (2)
V1—O3	1.957 (2)
V1—O4	2.041 (2)
V1—O6	2.030 (2)
V1—O8	1.593 (2)
V1—N1	2.354 (2)
O1—P1	1.508 (2)
O2—P1	1.534 (2)
O3—P1	1.529 (2)
O1—Co1	2.044 (2)
P1—C1	1.829 (2)

O1—Co1—O1Wⁱ	89.40 (6)
O1—Co1—O1W	90.60 (6)
O1ⁱ—Co1—N2	91.96 (6)
O1—Co1—N2	88.04 (6)
O1Wⁱ—Co1—N2	88.11 (7)
O1W—Co1—N2	91.89 (7)
O3W—Co2—O2W	88.56 (6)
O3W—Co2—O2Wⁱⁱⁱ	91.44 (6)
O4W—Co2—O2Wⁱⁱⁱ	87.84 (6)
O4W—Co2—O2W	92.16 (6)
O4W—Co2—O3Wⁱⁱⁱ	91.43 (7)
O4W—Co2—O3W	88.57 (7)
O2ⁱⁱ—V1—O4	165.00 (5)
O2ⁱⁱ—V1—O6	84.32 (6)
O2ⁱⁱ—V1—N1	89.08 (6)
O3—V1—O2ⁱⁱ	91.38 (6)
O3—V1—O4	90.11 (6)
O3—V1—O6	154.21 (5)
O3—V1—N1	80.43 (6)
O4—V1—N1	76.45 (6)
O6—V1—O4	87.87 (6)
O6—V1—N1	74.10 (5)
O8—V1—O2ⁱⁱ	100.68 (8)
O8—V1—O3	105.45 (7)
O8—V1—O4	93.29 (8)
O8—V1—O6	100.33 (7)
O8—V1—N1	168.34 (7)
O1—P1—O3	112.77 (8)
O1—P1—O2	111.06 (7)
O3—P1—O2	110.17 (7)
O1—P1—C1	110.75 (8)
O3—P1—C1	104.04 (7)
O2—P1—C1	107.73 (8)
P1—O1—Co1	136.12 (7)
P1—O3—V1	126.89 (7)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y, -z+2; (iii) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1C⋯O2ⁱ	0.84 (2)	1.98 (1)	2.7489 (19)	154 (2)
O1W—H1D⋯O2W	0.84 (2)	2.09 (1)	2.878 (2)	160 (3)
O2W—H2C⋯O5	0.84 (2)	2.00 (1)	2.798 (2)	159 (2)
O2W—H2D⋯O7^iv	0.84 (2)	1.93 (1)	2.736 (2)	166 (2)
O3W—H3A⋯O5	0.84 (2)	1.87 (1)	2.672 (2)	159 (2)
O3W—H3B⋯O6^v	0.84 (2)	1.95 (2)	2.7801 (18)	173 (2)
O4W—H4C⋯O5Wⁱⁱⁱ	0.84 (2)	1.86 (1)	2.698 (2)	175 (3)
O4W—H4D⋯O7^vi	0.84 (2)	1.86 (1)	2.689 (2)	167 (2)
O5W—H5B⋯O4	0.84 (2)	2.14 (2)	2.893 (2)	151 (3)
O5W—H5A⋯O5^vii	0.84 (2)	2.54 (2)	3.311 (3)	157 (3)
Symmetry codes: (i) -x+1, -y+1, -z+2; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z; (v) -x+1, -y, -z+1; (vi) -x, -y, -z+1; (vii) x+1, y, z.

Non-H atoms were located from difference Fourier maps calculated in successive least-squares refinement cycles. The C-bound H atoms were placed in idealized positions and refined as riding with C—H = 0.93–0.97 Å and U_iso = 1.2U_eq(C). H atoms of water molecules were located in difference Fourier maps, and refined with the O—H and H⋯H distances restrained to 0.84 (1) and 1.37 (1) Å, respectively, to ensure chemically reasonable geometry, with U_iso fixed at 1.5U_eq(O).

Data collection: CrysAlis CCD (Kuma, 1999 $[Kuma (1999). CrysAlis CCD and CrysAlis RED. Kuma Diffraction, Wrocław, Poland.]$ ); cell refinement: CrysAlis RED (Kuma, 1999 $[Kuma (1999). CrysAlis CCD and CrysAlis RED. Kuma Diffraction, Wrocław, Poland.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Bruker, 2001 ); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805023263/cv6554sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805023263/cv6554Isup2.hkl

Computing details top

Data collection: CrysAlis CCD (Kuma, 1999); cell refinement: CrysAlis RED (Kuma, 1999); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL.

polymeric hexaaquacobalt(II) diaquadioxodi-µ₂-pyrazine- bis[µ₃-N-(phosphonomethyl)iminodiacetato]cobaltdivanadium dihydrate top

Crystal data top

C₁₄H₂₀CoN₄O₁₈P₂V₂·CoH₁₂O₆·2H₂O	Z = 1
M_r = 958.15	F(000) = 486
Triclinic, P1	D_x = 1.922 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2200 (14) Å	Cell parameters from 5000 reflections
b = 10.140 (2) Å	θ = 2–22.5°
c = 12.080 (2) Å	µ = 1.73 mm⁻¹
α = 93.79 (3)°	T = 298 K
β = 103.21 (3)°	Prism, blue
γ = 104.21 (3)°	0.44 × 0.33 × 0.14 mm
V = 827.6 (3) Å³

Data collection top

Kuma KM-4 CCD diffractometer	3994 independent reflections
Radiation source: fine-focus sealed tube	3510 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 1024x1024 pixels mm^-1	θ_max = 28.8°, θ_min = 3.8°
ω scans	h = −9→9
Absorption correction: numerical (SADABS; Sheldrick, 1996)	k = −13→13
T_min = 0.354, T_max = 0.724	l = −16→16
14552 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0369P)² + 0.2906P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
3994 reflections	Δρ_max = 0.62 e Å⁻³
260 parameters	Δρ_min = −0.46 e Å⁻³
15 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0134 (13)

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
V1	0.51181 (4)	−0.03887 (3)	0.78924 (2)	0.01748 (8)
O1	0.38825 (17)	0.29890 (12)	0.92992 (10)	0.0214 (2)
O2	0.48337 (19)	0.16776 (12)	1.09285 (10)	0.0245 (3)
O3	0.56779 (16)	0.11785 (12)	0.90678 (11)	0.0227 (3)
O4	0.42943 (19)	0.07725 (14)	0.66491 (12)	0.0313 (3)
O5	0.2021 (2)	0.16356 (15)	0.56053 (13)	0.0407 (4)
O6	0.33410 (17)	−0.20694 (12)	0.68114 (11)	0.0237 (3)
O7	0.0648 (2)	−0.37963 (14)	0.64107 (14)	0.0390 (4)
O8	0.71664 (19)	−0.03326 (15)	0.75874 (14)	0.0375 (3)
P1	0.41953 (6)	0.16339 (4)	0.96220 (4)	0.01682 (10)
N1	0.18692 (19)	−0.04201 (13)	0.79481 (11)	0.0163 (3)
C1	0.1916 (2)	0.02552 (16)	0.90872 (14)	0.0188 (3)
H1A	0.1839	−0.0415	0.9623	0.023*
H1B	0.0786	0.0628	0.9023	0.023*
C2	0.1096 (3)	0.03117 (19)	0.70046 (15)	0.0256 (4)
H2A	0.0596	0.1019	0.7317	0.031*
H2B	−0.0006	−0.0331	0.6460	0.031*
C3	0.2581 (3)	0.09627 (18)	0.63776 (16)	0.0257 (4)
C4	0.0813 (2)	−0.18895 (17)	0.77421 (16)	0.0223 (3)
H4A	−0.0585	−0.2002	0.7421	0.027*
H4B	0.0970	−0.2271	0.8462	0.027*
C5	0.1623 (2)	−0.26528 (17)	0.69158 (15)	0.0220 (3)
Co1	0.5000	0.5000	1.0000	0.01579 (9)
N2	0.1939 (2)	0.50640 (15)	0.99665 (13)	0.0230 (3)
O1W	0.4763 (3)	0.56113 (14)	0.83634 (12)	0.0373 (3)
H1C	0.502 (4)	0.6456 (10)	0.839 (2)	0.056*
H1D	0.448 (4)	0.522 (2)	0.7698 (11)	0.056*
C6	0.0397 (3)	0.4324 (2)	0.91448 (17)	0.0287 (4)
H6	0.0621	0.3836	0.8532	0.034*
C7	0.1526 (3)	0.57413 (19)	1.08241 (16)	0.0272 (4)
H7	0.2559	0.6271	1.1416	0.033*
Co2	0.5000	0.5000	0.5000	0.01874 (9)
O2W	0.28922 (19)	0.44976 (14)	0.60052 (12)	0.0289 (3)
H2C	0.234 (3)	0.3656 (10)	0.590 (2)	0.043*
H2D	0.208 (3)	0.4943 (18)	0.602 (2)	0.043*
O3W	0.4097 (2)	0.29797 (13)	0.42618 (12)	0.0294 (3)
H3A	0.355 (3)	0.2393 (19)	0.4626 (19)	0.044*
H3B	0.490 (3)	0.267 (2)	0.399 (2)	0.044*
O4W	0.2951 (2)	0.54223 (15)	0.36770 (13)	0.0344 (3)
H4C	0.276 (3)	0.6200 (12)	0.380 (2)	0.052*
H4D	0.187 (2)	0.4825 (16)	0.359 (2)	0.052*
O5W	0.7873 (3)	0.2140 (2)	0.6045 (2)	0.0671 (6)
H5A	0.866 (4)	0.188 (3)	0.575 (3)	0.101*
H5B	0.695 (4)	0.151 (2)	0.611 (3)	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.01399 (13)	0.01636 (14)	0.02252 (15)	0.00357 (10)	0.00684 (10)	−0.00046 (10)
O1	0.0248 (6)	0.0135 (5)	0.0242 (6)	0.0076 (5)	0.0011 (5)	−0.0004 (4)
O2	0.0305 (6)	0.0169 (6)	0.0221 (6)	0.0068 (5)	−0.0009 (5)	0.0004 (5)
O3	0.0156 (5)	0.0169 (6)	0.0336 (7)	0.0037 (4)	0.0051 (5)	−0.0042 (5)
O4	0.0261 (6)	0.0353 (7)	0.0352 (8)	0.0057 (6)	0.0130 (6)	0.0143 (6)
O5	0.0455 (9)	0.0369 (8)	0.0390 (8)	0.0092 (7)	0.0067 (7)	0.0209 (7)
O6	0.0204 (6)	0.0241 (6)	0.0254 (6)	0.0038 (5)	0.0083 (5)	−0.0060 (5)
O7	0.0240 (6)	0.0254 (7)	0.0595 (10)	0.0010 (5)	0.0078 (6)	−0.0198 (7)
O8	0.0232 (6)	0.0395 (8)	0.0533 (9)	0.0080 (6)	0.0188 (6)	0.0001 (7)
P1	0.01643 (19)	0.01190 (19)	0.0207 (2)	0.00478 (15)	0.00191 (15)	−0.00152 (15)
N1	0.0151 (6)	0.0149 (6)	0.0182 (6)	0.0037 (5)	0.0037 (5)	0.0002 (5)
C1	0.0163 (7)	0.0181 (7)	0.0219 (8)	0.0040 (6)	0.0062 (6)	−0.0009 (6)
C2	0.0232 (8)	0.0309 (9)	0.0260 (9)	0.0130 (7)	0.0050 (7)	0.0083 (7)
C3	0.0297 (9)	0.0204 (8)	0.0249 (9)	0.0053 (7)	0.0041 (7)	0.0042 (7)
C4	0.0177 (7)	0.0167 (8)	0.0309 (9)	0.0006 (6)	0.0090 (7)	−0.0031 (6)
C5	0.0181 (7)	0.0196 (8)	0.0259 (9)	0.0059 (6)	0.0017 (6)	−0.0040 (6)
Co1	0.01567 (15)	0.01301 (15)	0.01878 (16)	0.00569 (11)	0.00303 (11)	0.00031 (11)
N2	0.0173 (6)	0.0229 (7)	0.0295 (8)	0.0074 (6)	0.0053 (6)	0.0013 (6)
O1W	0.0689 (10)	0.0210 (7)	0.0209 (7)	0.0146 (7)	0.0068 (7)	0.0018 (5)
C6	0.0221 (8)	0.0324 (10)	0.0304 (10)	0.0085 (7)	0.0059 (7)	−0.0065 (7)
C7	0.0199 (8)	0.0290 (9)	0.0289 (9)	0.0050 (7)	0.0029 (7)	−0.0059 (7)
Co2	0.01870 (16)	0.01772 (16)	0.01970 (16)	0.00470 (12)	0.00555 (12)	0.00003 (12)
O2W	0.0292 (7)	0.0260 (7)	0.0354 (7)	0.0086 (5)	0.0151 (6)	0.0008 (6)
O3W	0.0349 (7)	0.0210 (6)	0.0350 (8)	0.0066 (5)	0.0170 (6)	−0.0016 (5)
O4W	0.0250 (6)	0.0337 (8)	0.0399 (8)	0.0056 (6)	0.0002 (6)	0.0097 (6)
O5W	0.0588 (12)	0.0496 (11)	0.1159 (19)	0.0278 (10)	0.0442 (12)	0.0441 (12)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.044 (2)	N1—C4	1.473 (2)
Co1—O1Wⁱ	2.093 (2)	N1—C2	1.478 (2)
Co1—O1W	2.093 (2)	N1—C1	1.485 (2)
Co1—N2	2.218 (2)	C1—H1A	0.9700
Co1—N2ⁱ	2.218 (2)	C1—H1B	0.9700
Co2—O2Wⁱⁱ	2.144 (2)	C2—C3	1.500 (3)
Co2—O2W	2.144 (2)	C2—H2A	0.9700
Co2—O3Wⁱⁱ	2.063 (2)	C2—H2B	0.9700
Co2—O3W	2.063 (2)	C4—C5	1.525 (2)
Co2—O4Wⁱⁱ	2.061 (2)	C4—H4A	0.9700
Co2—O4W	2.061 (2)	C4—H4B	0.9700
V1—O2ⁱⁱⁱ	1.996 (2)	N2—C6	1.332 (2)
V1—O3	1.957 (2)	N2—C7	1.334 (2)
V1—O4	2.041 (2)	O1W—H1C	0.828 (9)
V1—O6	2.030 (2)	O1W—H1D	0.829 (9)
V1—O8	1.593 (2)	C6—C7^iv	1.384 (2)
V1—N1	2.354 (2)	C6—H6	0.9300
O1—P1	1.508 (2)	C7—C6^iv	1.384 (2)
O2—P1	1.534 (2)	C7—H7	0.9300
O2—V1ⁱⁱⁱ	1.996 (2)	O2W—H2C	0.84 (2)
O3—P1	1.529 (2)	O2W—H2D	0.84 (2)
O1—Co1	2.044 (2)	O3W—H3A	0.84 (2)
O4—C3	1.271 (2)	O3W—H3B	0.84 (2)
O5—C3	1.244 (2)	O4W—H4C	0.84 (2)
O6—C5	1.275 (2)	O4W—H4D	0.84 (2)
O7—C5	1.234 (2)	O5W—H5A	0.84 (2)
P1—C1	1.829 (2)	O5W—H5B	0.84 (2)

O1ⁱ—Co1—O1	180.0	P1—O1—Co1	136.12 (7)
O1ⁱ—Co1—O1Wⁱ	90.60 (6)	P1—O3—V1	126.89 (7)
O1—Co1—O1Wⁱ	89.40 (6)	P1—O2—V1ⁱⁱⁱ	139.35 (8)
O1ⁱ—Co1—O1W	89.40 (6)	C3—O4—V1	123.11 (12)
O1—Co1—O1W	90.60 (6)	C5—O6—V1	121.69 (11)
O1ⁱ—Co1—N2	91.96 (6)	C4—N1—C2	111.32 (14)
O1—Co1—N2	88.04 (6)	C4—N1—C1	113.13 (13)
O1ⁱ—Co1—N2ⁱ	88.04 (6)	C2—N1—C1	112.01 (13)
O1—Co1—N2ⁱ	91.96 (6)	C4—N1—V1	104.02 (9)
O1Wⁱ—Co1—O1W	180.000 (1)	C2—N1—V1	107.11 (10)
O1Wⁱ—Co1—N2	88.11 (7)	C1—N1—V1	108.73 (9)
O1W—Co1—N2	91.89 (7)	N1—C1—P1	110.13 (11)
O1Wⁱ—Co1—N2ⁱ	91.89 (7)	N1—C1—H1A	109.6
O1W—Co1—N2ⁱ	88.11 (7)	P1—C1—H1A	109.6
N2—Co1—N2ⁱ	180.000 (1)	N1—C1—H1B	109.6
C6—N2—C7	116.30 (15)	P1—C1—H1B	109.6
C6—N2—Co1	121.70 (12)	H1A—C1—H1B	108.1
C7—N2—Co1	121.71 (12)	N1—C2—C3	114.49 (14)
O2Wⁱⁱ—Co2—O2W	180.0	N1—C2—H2A	108.6
O3W—Co2—O2W	88.56 (6)	C3—C2—H2A	108.6
O3Wⁱⁱ—Co2—O2W	91.44 (6)	N1—C2—H2B	108.6
O3W—Co2—O2Wⁱⁱ	91.44 (6)	C3—C2—H2B	108.6
O3Wⁱⁱ—Co2—O2Wⁱⁱ	88.56 (6)	H2A—C2—H2B	107.6
O3Wⁱⁱ—Co2—O3W	180.0	O5—C3—O4	124.57 (18)
O4Wⁱⁱ—Co2—O2Wⁱⁱ	92.16 (6)	O5—C3—C2	116.87 (17)
O4W—Co2—O2Wⁱⁱ	87.84 (6)	O4—C3—C2	118.55 (15)
O4Wⁱⁱ—Co2—O2W	87.84 (6)	N1—C4—C5	110.13 (14)
O4W—Co2—O2W	92.16 (6)	N1—C4—H4A	109.6
O4Wⁱⁱ—Co2—O3Wⁱⁱ	88.57 (7)	C5—C4—H4A	109.6
O4W—Co2—O3Wⁱⁱ	91.43 (7)	N1—C4—H4B	109.6
O4Wⁱⁱ—Co2—O3W	91.43 (7)	C5—C4—H4B	109.6
O4W—Co2—O3W	88.57 (7)	H4A—C4—H4B	108.1
O4Wⁱⁱ—Co2—O4W	180.000 (1)	O7—C5—O6	123.15 (16)
O2ⁱⁱⁱ—V1—O4	165.00 (5)	O7—C5—C4	120.01 (15)
O2ⁱⁱⁱ—V1—O6	84.32 (6)	O6—C5—C4	116.81 (14)
O2ⁱⁱⁱ—V1—N1	89.08 (6)	Co1—O1W—H1C	111.9 (16)
O3—V1—O2ⁱⁱⁱ	91.38 (6)	Co1—O1W—H1D	136.3 (16)
O3—V1—O4	90.11 (6)	H1C—O1W—H1D	111.8 (16)
O3—V1—O6	154.21 (5)	N2—C6—C7^iv	121.99 (17)
O3—V1—N1	80.43 (6)	N2—C6—H6	119.0
O4—V1—N1	76.45 (6)	C7^iv—C6—H6	119.0
O6—V1—O4	87.87 (6)	N2—C7—C6^iv	121.72 (17)
O6—V1—N1	74.10 (5)	N2—C7—H7	119.1
O8—V1—O2ⁱⁱⁱ	100.68 (8)	C6^iv—C7—H7	119.1
O8—V1—O3	105.45 (7)	Co2—O2W—H2C	111.1 (16)
O8—V1—O4	93.29 (8)	Co2—O2W—H2D	121.1 (17)
O8—V1—O6	100.33 (7)	H2C—O2W—H2D	110.5 (15)
O8—V1—N1	168.34 (7)	Co2—O3W—H3A	117.6 (16)
O1—P1—O3	112.77 (8)	Co2—O3W—H3B	117.6 (16)
O1—P1—O2	111.06 (7)	H3A—O3W—H3B	108.7 (14)
O3—P1—O2	110.17 (7)	Co2—O4W—H4C	113.2 (18)
O1—P1—C1	110.75 (8)	Co2—O4W—H4D	108.3 (18)
O3—P1—C1	104.04 (7)	H4C—O4W—H4D	108.0 (15)
O2—P1—C1	107.73 (8)	H5A—O5W—H5B	113.1 (18)

O8—V1—O3—P1	177.17 (10)	O4—V1—N1—C1	−116.81 (11)
O2ⁱⁱⁱ—V1—O3—P1	−81.35 (10)	C4—N1—C1—P1	148.25 (11)
O6—V1—O3—P1	−1.59 (19)	C2—N1—C1—P1	−84.94 (14)
O4—V1—O3—P1	83.73 (10)	V1—N1—C1—P1	33.23 (12)
N1—V1—O3—P1	7.49 (9)	O1—P1—C1—N1	93.41 (12)
O8—V1—O4—C3	171.55 (15)	O3—P1—C1—N1	−28.01 (13)
O3—V1—O4—C3	−82.97 (15)	O2—P1—C1—N1	−144.95 (10)
O2ⁱⁱⁱ—V1—O4—C3	12.8 (3)	C4—N1—C2—C3	−118.68 (16)
O6—V1—O4—C3	71.31 (15)	C1—N1—C2—C3	113.55 (16)
N1—V1—O4—C3	−2.84 (14)	V1—N1—C2—C3	−5.58 (17)
O8—V1—O6—C5	166.52 (14)	V1—O4—C3—O5	−178.12 (15)
O3—V1—O6—C5	−14.7 (2)	V1—O4—C3—C2	0.4 (2)
O2ⁱⁱⁱ—V1—O6—C5	66.66 (14)	N1—C2—C3—O5	−177.29 (16)
O4—V1—O6—C5	−100.52 (14)	N1—C2—C3—O4	4.1 (2)
N1—V1—O6—C5	−24.00 (13)	C2—N1—C4—C5	80.61 (17)
Co1—O1—P1—O3	−95.31 (12)	C1—N1—C4—C5	−152.22 (14)
Co1—O1—P1—O2	28.90 (13)	V1—N1—C4—C5	−34.42 (15)
Co1—O1—P1—C1	148.56 (10)	V1—O6—C5—O7	−167.08 (15)
V1—O3—P1—O1	−112.31 (10)	V1—O6—C5—C4	10.9 (2)
V1—O3—P1—O2	122.98 (10)	N1—C4—C5—O7	−161.79 (17)
V1—O3—P1—C1	7.75 (12)	N1—C4—C5—O6	20.2 (2)
V1ⁱⁱⁱ—O2—P1—O1	159.07 (11)	P1—O1—Co1—O1Wⁱ	−34.28 (12)
V1ⁱⁱⁱ—O2—P1—O3	−75.24 (13)	P1—O1—Co1—O1W	145.72 (12)
V1ⁱⁱⁱ—O2—P1—C1	37.63 (14)	P1—O1—Co1—N2	−122.41 (12)
O8—V1—N1—C4	93.5 (3)	P1—O1—Co1—N2ⁱ	57.59 (12)
O3—V1—N1—C4	−145.17 (11)	O1ⁱ—Co1—N2—C6	146.95 (15)
O2ⁱⁱⁱ—V1—N1—C4	−53.62 (11)	O1—Co1—N2—C6	−33.05 (15)
O6—V1—N1—C4	30.73 (10)	O1Wⁱ—Co1—N2—C6	−122.52 (16)
O4—V1—N1—C4	122.38 (11)	O1W—Co1—N2—C6	57.48 (16)
O8—V1—N1—C2	−24.5 (4)	O1ⁱ—Co1—N2—C7	−39.57 (15)
O3—V1—N1—C2	96.86 (11)	O1—Co1—N2—C7	140.43 (15)
O2ⁱⁱⁱ—V1—N1—C2	−171.59 (11)	O1Wⁱ—Co1—N2—C7	50.97 (15)
O6—V1—N1—C2	−87.24 (11)	O1W—Co1—N2—C7	−129.03 (15)
O4—V1—N1—C2	4.41 (11)	C7—N2—C6—C7^iv	0.0 (3)
O8—V1—N1—C1	−145.7 (3)	Co1—N2—C6—C7^iv	173.84 (15)
O3—V1—N1—C1	−24.37 (10)	C6—N2—C7—C6^iv	0.0 (3)
O2ⁱⁱⁱ—V1—N1—C1	67.19 (10)	Co1—N2—C7—C6^iv	−173.84 (15)
O6—V1—N1—C1	151.54 (11)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+2; (iv) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1C···O2ⁱ	0.84 (2)	1.98 (1)	2.7489 (19)	154 (2)
O1W—H1D···O2W	0.84 (2)	2.09 (1)	2.878 (2)	160 (3)
O2W—H2C···O5	0.84 (2)	2.00 (1)	2.798 (2)	159 (2)
O2W—H2D···O7^v	0.84 (2)	1.93 (1)	2.736 (2)	166 (2)
O3W—H3A···O5	0.84 (2)	1.87 (1)	2.672 (2)	159 (2)
O3W—H3B···O6^vi	0.84 (2)	1.95 (2)	2.7801 (18)	173 (2)
O4W—H4C···O5Wⁱⁱ	0.84 (2)	1.86 (1)	2.698 (2)	175 (3)
O4W—H4D···O7^vii	0.84 (2)	1.86 (1)	2.689 (2)	167 (2)
O5W—H5B···O4	0.84 (2)	2.14 (2)	2.893 (2)	151 (3)
O5W—H5A···O5^viii	0.84 (2)	2.54 (2)	3.311 (3)	157 (3)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (v) x, y+1, z; (vi) −x+1, −y, −z+1; (vii) −x, −y, −z+1; (viii) x+1, y, z.

Acknowledgements

We are grateful to FEDER, POCTI (Portugal), InTerreg IIIB and to Fundação para a Ciência e Tecnologia (FCT, Portugal) for their general financial support and the postdoctoral and PhD research grants Nos. SFRH/BPD/9309/2002 (to FNS) and SFRH/BD/13858/2003 (to LM).

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ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages m1628-m1632

https://doi.org/10.1107/S1600536805023263

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