Deca­aqua­dioxobis[μ3-N-(phosphono­meth­yl)imino­diacetato]dimanganesedivanadium dihydrate

Cunha-Silva, L.; Shi, F.-N.; Klinowski, J.; Trindade, T.; Rocha, J.; Almeida Paz, F.A.

doi:10.1107/S1600536806054675

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 63| Part 2| February 2007| Pages m372-m375

https://doi.org/10.1107/S1600536806054675

Decaaquadioxobis[μ₃-N-(phosphonomethyl)iminodiacetato]dimanganesedivanadium dihydrate

Luís Cunha-Silva,^a Fa-Nian Shi,^a Jacek Klinowski,^b Tito Trindade,^a João Rocha ^a and Filipe A. Almeida Paz ^a ^*

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

(Received 13 December 2006; accepted 15 December 2006; online 10 January 2007)

The crystal structure of the title compound, [Mn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O, contains a centrosymmetric dimeric [V₂O₂(pmida)₂]⁴⁻ unit [where H₄pmida is N-(phosphonomethyl)iminodiacetic acid] connecting two neighbouring Mn²⁺ cations through the phosphonate groups. The crystal structure is characterized by the presence of an extensive network of strong and highly directional O—H⋯O hydrogen bonds, involving the water molecules (coordinated and uncoordinated) and the functional groups of pmida⁴⁻.

Comment

Since the report by Hoskins & Robson (1990 ), research focused on the structural design and synthesis of novel coordination-based materials, in which the topology is extended from discrete complexes to one, two or three dimensions, has seen a great and exponential growth (for recent reviews see Cheetham et al., 2006 ; Kitagawa & Uemura, 2005 ). During the course of our ongoing research on novel multi-dimensional hybrid crystalline materials incorporating N-(phosphonomethyl)iminodiacetic acid (H₄pmida) residues (Mafra et al., 2006 ; Almeida Paz et al., 2004 ; Almeida Paz, Shi, Trindade et al., 2005 ; Almeida Paz, Shi, Mafra et al., 2005 ; Almeida Paz, Rocha, Klinowski et al., 2005 ; Shi et al., 2005 ; Shi, Almeida Paz, Trindade & Rocha, 2006 ; Shi, Almeida Paz, Girginova, Amaral et al., 2006 ; Shi, Almeida Paz, Girginova, Rocha et al., 2006 ), we have isolated the crystalline material [Mn₂V₂O₂(pmida)₂(H₂O)₁₀]·2H₂O [where pmida⁴⁻ is (C₅H₆NO₇P)⁴⁻], (I), whose crystal structure at the temperature of 180 (2) K we report here.

The title compound, (I), contains two crystallographically unique metal centres, Mn1 and V1, both exhibiting octahedral coordination geometries, {MnO₆} and {VO₅N} (Fig. 1; Table 1). Mn1 is coordinated by five water molecules plus one O atom from the μ₃-bridging phosphonate group of pmida⁴⁻ (Fig. 1), with a coordination geometry resembling a quasi-regular octahedron [Mn—O bond lengths ranging from 2.092 (2) to 2.236 (2) Å; cis and trans O—Mn—O angles found in the 86.85 (10)–93.21 (11)° and 175.14 (10)–178.21 (9)° ranges, respectively; see Table 1]. The intermetallic Mn1⋯Mn1ⁱ distance between exo-coordinated manganese(II) centres (and across the unit depicted in Fig. 1) is of 10.175 (3) Å, while the shortest Mn1⋯V1ⁱ distance within the tetranuclear unit is 5.368 (1) Å [symmetry code: (i) 2 − x, −y, −z].

The core of the neutral tetranuclear [Mn₂V₂O₂(pmida)₂(H₂O)₁₀] molecule is composed of the anionic centrosymmetric [V₂O₂(pmida)₂]⁴⁻ dimeric unit, first described by Crans et al. (1998 ). The geometrical aspects of this unit, in particular the highly distorted octahedral coordination mode of V1 (Table 1) plus the coordination fashion of the pmida⁴⁻ ligand (which forms with V1 three five-membered chelate rings; see Fig. 1), are typical and in good agreement with those described in detail in our previous reports (Almeida Paz et al., 2004; Almeida Paz, Shi, Trindade et al., 2005; Almeida Paz, Shi, Mafra et al., 2005; Almeida Paz, Rocha, Klinowski et al., 2005; Shi et al., 2005; Shi, Almeida Paz, Trindade & Rocha, 2006; Shi, Almeida Paz, Girginova, Amaral et al., 2006; Shi, Almeida Paz, Girginova, Rocha et al., 2006).

In the extended solid-state [Mn₂V₂O₂(pmida)₂(H₂O)₁₀] molecular units pack closely in a typical brick-wall-like fashion along the crystallographic [010] direction (Fig. 2a), mediated by an extensive network of strong and highly directional O—H⋯O hydrogen-bonding interactions, which also involve the water molecule of crystallization (Fig. 2 and Table 3).

Figure 1
The structure of the tetranuclear centrosymmetric [Mn₂V₂O₂(pmida)₂(H₂O)₁₀] complex, showing the labelling scheme for all non-H atoms belonging to the asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres. The water molecule of crystallization, O6W, was omitted for clarity. Symmetry transformation used to generate non-labelled atoms: 2 − x, −y, −z.

Figure 2
Perspective views of the crystal packing of the title compound, viewed along the (a) [100] and (b) [001] directions of the unit cell. Hydrogen bonds are represented as light-blue dashed lines. H atoms have been omitted for clarity. For details on the hydrogen-bonding geometry see Table 2

Experimental

Chemicals were readily available from commercial sources and were used as received without further purification: N-(phosphonomethyl)iminodiacetic acid hydrate (H₄pmida, C₅H₁₀NO₇P, 97% Fluka), vanadium(IV) oxide sulfate pentahydrate (VOSO₄·5H₂O, 99% Sigma–Aldrich), manganese(II) acetate tetrahydrate (MnC₄H₆O₄·4H₂O, 99.0% Fluka), 4,4′-trimethylenedipyridine (TMD, C₁₃H₁₄N₂, 98%, Aldrich).

Synthesis was typically carried out in a PTFE-lined stainless steel reaction vessel (ca 40 ml), under autogeneous pressure and static conditions in a preheated oven at 393 K. The reaction took place over a period of 3 d, after which the vessel was removed from the oven and left to cool to ambient temperature before opening. The title compound proved to be air- and light-stable.

The title compound was synthesized from a mixture containing 0.40 g of VOSO₄·5H₂O, 0.61 g of MnC₄H₆O₄·4H₂O, and 0.40 g of H₄pmida, and 0.24 g of TMD in ca 15 g of distilled water. The mixture was stirred thoroughly at ambient temperature for 30 minutes, yielding a suspension with a molar composition of 1.4:1.4:1.0:0.7:473, which was transferred to the reaction vessel. After reacting, a small quantity of green/blue single crystals of the title compound were isolated as a pure phase by vacuum filtering, washed with copious amounts of distilled water (ca 3 × 50 ml), and then air-dried at ambient temperature. The same material can also be isolated as large single crystals by slow evaporation (in the open air) of the autoclave mother liquor over a period of one month. It is of considerable interest to note that similar reactions where TMD was not included in the starting reactive mixture failed to lead to the isolation of the title material.

Crystal data

[Mn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O
M_r = 906.11
Monoclinic, P 2₁ /c
a = 10.096 (2) Å
b = 14.934 (3) Å
c = 10.848 (2) Å
β = 110.52 (3)°
V = 1531.8 (6) Å³
Z = 2
D_x = 1.965 Mg m⁻³
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 180 (2) K
Prism, brown
0.15 × 0.10 × 0.09 mm

Data collection

Nonius KappaCCD diffractometer
Thin–slice ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.794, T_max = 0.869
17432 measured reflections
3502 independent reflections
2880 reflections with I > 2σ(I)
R_int = 0.059
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.05
3502 reflections
233 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0517P)² + 3.2528P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Mn1—O1	2.092 (2)
Mn1—O1W	2.164 (2)
Mn1—O2W	2.212 (2)
Mn1—O3W	2.152 (2)
Mn1—O4W	2.236 (2)
Mn1—O5W	2.187 (2)
V1—O2ⁱ	1.991 (2)
V1—O3	1.988 (2)
V1—O4	2.030 (2)
V1—O6	2.028 (2)
V1—O8	1.598 (2)
V1—N1	2.370 (3)

O1—Mn1—O1W	88.63 (9)
O1—Mn1—O2W	90.18 (9)
O1—Mn1—O3W	175.14 (10)
O1—Mn1—O4W	92.29 (8)
O1—Mn1—O5W	93.12 (9)
O1W—Mn1—O2W	93.21 (11)
O1W—Mn1—O4W	89.40 (9)
O1W—Mn1—O5W	178.21 (9)
O2W—Mn1—O4W	176.45 (9)
O3W—Mn1—O1W	87.68 (10)
O3W—Mn1—O2W	86.85 (10)
O3W—Mn1—O4W	90.85 (9)
O3W—Mn1—O5W	90.58 (9)
O5W—Mn1—O2W	87.12 (10)
O5W—Mn1—O4W	90.21 (9)
O2ⁱ—V1—O4	163.79 (9)
O2ⁱ—V1—O6	86.89 (9)
O2ⁱ—V1—N1	88.32 (9)
O3—V1—O2ⁱ	90.96 (9)
O3—V1—O4	87.04 (9)
O3—V1—O6	154.03 (9)
O3—V1—N1	79.41 (9)
O4—V1—N1	75.50 (9)
O6—V1—O4	87.90 (9)
O6—V1—N1	74.66 (9)
O8—V1—O2ⁱ	101.24 (11)
O8—V1—O3	103.95 (11)
O8—V1—O4	94.85 (11)
O8—V1—O6	101.86 (11)
O8—V1—N1	169.72 (10)
Symmetry code: (i) -x+2, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1C⋯O4Wⁱⁱ	0.845 (10)	1.982 (12)	2.813 (3)	167 (4)
O1W—H1D⋯O5ⁱⁱ	0.84 (3)	1.92 (3)	2.759 (3)	171 (3)
O2W—H2C⋯O2	0.83 (4)	2.15 (3)	2.847 (3)	142 (4)
O2W—H2D⋯O6Wⁱⁱⁱ	0.84 (4)	1.880 (17)	2.675 (6)	160 (4)
O3W—H3A⋯O4ⁱⁱ	0.84 (3)	1.920 (16)	2.735 (3)	163 (4)
O3W—H3B⋯O6^iv	0.84 (3)	1.93 (3)	2.745 (3)	166 (4)
O4W—H4C⋯O7^v	0.844 (10)	1.856 (11)	2.698 (3)	175 (3)
O4W—H4D⋯O3ⁱⁱ	0.85 (3)	1.94 (3)	2.778 (3)	173 (4)
O5W—H5A⋯O5^vi	0.84 (3)	1.996 (15)	2.803 (3)	161 (4)
O5W—H5B⋯O7^iv	0.841 (10)	1.989 (12)	2.823 (3)	171 (3)
Symmetry codes: (ii) -x+1, -y, -z; (iii) x, y, z-1; (iv) x-1, y, z-1; (v) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

H atoms bound to carbon were placed in idealized positions and allowed to ride on their parent atoms with U_iso fixed at 1.2 times U_eq(C) (C—H = 0.99 Å). H atoms associated with the five crystallographically unique coordinated water molecules were markedly visible in difference Fourier maps, and were included in subsequent least-squares refinement cycles with the O—H and H⋯H distances restrained to 0.84 (1) and 1.37 (1) Å, respectively, to ensure a chemically reasonable geometry of water molecules. These H atoms were also allowed to ride on their parent atoms with U_iso fixed at 1.5 times U_eq(O).

The crystallographically unique water molecule of crystallization was found to be severely affected by disorder, which prevented a sensible refinement using anisotropic displacement parameters. In fact, both the highest peak and deepest hole from the final difference Fourier synthesis were found close to this (0.01 and 0.64 Å, respectively). Therefore, the O atom from this molecule was refined assuming an isotropic displacement parameter. H atoms associated with this water molecule could not be located in difference Fourier maps, and attempts to place them in calculated positions did not lead to a reasonable model for the geometrical aspects of the resulting hydrogen-bonding interactions. Therefore, these H atoms were omitted from the present structural model but were included in the chemical formula of the compound.

Data collection: COLLECT (Nonius 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Bruker 2001 ); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806054675/gk2046sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806054675/gk2046Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Bruker 2001); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.

decaaquadioxobis[µ₃-N-(phosphonomethyl)iminodiacetato]dimanganesedivanadium dihydrate, [Mn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O top

Crystal data top

[Mn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O	F(000) = 920
M_r = 906.11	D_x = 1.965 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9712 reflections
a = 10.096 (2) Å	θ = 1.0–27.5°
b = 14.934 (3) Å	µ = 1.61 mm⁻¹
c = 10.848 (2) Å	T = 180 K
β = 110.52 (3)°	Prism, brown
V = 1531.8 (6) Å³	0.15 × 0.10 × 0.09 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	2880 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Thin–slice ω and φ scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −12→13
T_min = 0.794, T_max = 0.869	k = −19→19
17432 measured reflections	l = −14→14
3502 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0517P)² + 3.2528P] where P = (F_o² + 2F_c²)/3
3502 reflections	(Δ/σ)_max = 0.001
233 parameters	Δρ_max = 1.05 e Å⁻³
15 restraints	Δρ_min = −0.95 e Å⁻³

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
Mn1	0.47798 (5)	0.06629 (3)	−0.23812 (4)	0.01467 (14)
O1W	0.5014 (3)	−0.07031 (16)	−0.1672 (2)	0.0285 (6)
H1C	0.531 (4)	−0.082 (3)	−0.0859 (12)	0.043*
H1D	0.438 (3)	−0.108 (2)	−0.205 (3)	0.043*
O2W	0.5853 (3)	0.0392 (2)	−0.3804 (2)	0.0316 (6)
H2C	0.657 (3)	0.009 (3)	−0.343 (4)	0.047*
H2D	0.599 (4)	0.074 (2)	−0.435 (4)	0.047*
O3W	0.2854 (2)	0.02509 (18)	−0.3901 (2)	0.0255 (5)
H3A	0.239 (3)	−0.017 (2)	−0.374 (4)	0.038*
H3B	0.235 (3)	0.052 (2)	−0.458 (3)	0.038*
O4W	0.3596 (2)	0.09866 (15)	−0.1040 (2)	0.0180 (5)
H4C	0.339 (3)	0.1530 (8)	−0.098 (4)	0.027*
H4D	0.291 (3)	0.0673 (17)	−0.101 (4)	0.027*
O5W	0.4474 (2)	0.20346 (16)	−0.3136 (2)	0.0222 (5)
H5A	0.525 (2)	0.227 (3)	−0.308 (3)	0.033*
H5B	0.391 (3)	0.209 (3)	−0.3914 (16)	0.033*
V1	1.00944 (5)	0.02657 (3)	0.24106 (5)	0.01255 (14)
N1	0.9881 (2)	0.16751 (18)	0.1354 (2)	0.0144 (5)
P1	0.82006 (8)	0.05841 (5)	−0.05527 (7)	0.01277 (18)
O1	0.6728 (2)	0.09610 (15)	−0.0929 (2)	0.0169 (4)
O2	0.8417 (2)	0.00520 (15)	−0.1674 (2)	0.0171 (5)
O3	0.8583 (2)	−0.00015 (14)	0.0697 (2)	0.0158 (4)
O4	0.8598 (2)	0.09240 (15)	0.2912 (2)	0.0190 (5)
O5	0.7024 (2)	0.20093 (16)	0.2621 (2)	0.0236 (5)
O6	1.1562 (2)	0.10601 (15)	0.3703 (2)	0.0173 (4)
O7	1.2826 (3)	0.23093 (16)	0.4190 (2)	0.0264 (5)
O8	1.0113 (2)	−0.05963 (15)	0.3290 (2)	0.0222 (5)
C1	0.9495 (3)	0.1494 (2)	−0.0073 (3)	0.0150 (6)
H1A	1.0349	0.1325	−0.0267	0.018*
H1B	0.9088	0.2040	−0.0582	0.018*
C2	0.8752 (3)	0.2192 (2)	0.1622 (3)	0.0184 (6)
H2A	0.8017	0.2360	0.0774	0.022*
H2B	0.9164	0.2752	0.2089	0.022*
C3	0.8069 (3)	0.1677 (2)	0.2439 (3)	0.0162 (6)
C4	1.1288 (3)	0.2098 (2)	0.1951 (3)	0.0187 (6)
H4A	1.1192	0.2757	0.1890	0.022*
H4B	1.1912	0.1910	0.1469	0.022*
C5	1.1943 (3)	0.1818 (2)	0.3395 (3)	0.0159 (6)
O6W	0.5865 (6)	0.1765 (4)	0.4618 (6)	0.1092 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0117 (2)	0.0175 (3)	0.0126 (2)	−0.00012 (17)	0.00141 (18)	0.00099 (17)
O1W	0.0293 (14)	0.0205 (13)	0.0254 (13)	−0.0045 (10)	−0.0033 (11)	0.0034 (10)
O2W	0.0214 (12)	0.0543 (19)	0.0194 (13)	0.0064 (12)	0.0074 (10)	−0.0002 (11)
O3W	0.0173 (11)	0.0351 (15)	0.0179 (12)	−0.0091 (10)	−0.0015 (9)	0.0096 (10)
O4W	0.0173 (11)	0.0169 (11)	0.0210 (11)	−0.0006 (9)	0.0080 (9)	−0.0001 (9)
O5W	0.0189 (11)	0.0219 (12)	0.0221 (12)	−0.0027 (9)	0.0025 (10)	0.0047 (10)
V1	0.0118 (2)	0.0132 (3)	0.0118 (2)	−0.00010 (18)	0.00294 (19)	0.00108 (19)
N1	0.0120 (11)	0.0189 (13)	0.0108 (12)	−0.0015 (10)	0.0022 (10)	−0.0006 (10)
P1	0.0093 (3)	0.0163 (4)	0.0110 (4)	−0.0002 (3)	0.0015 (3)	−0.0009 (3)
O1	0.0106 (10)	0.0207 (12)	0.0172 (10)	0.0016 (8)	0.0022 (8)	−0.0026 (9)
O2	0.0109 (10)	0.0234 (12)	0.0154 (10)	−0.0003 (9)	0.0025 (8)	−0.0049 (9)
O3	0.0139 (10)	0.0179 (11)	0.0136 (10)	−0.0022 (8)	0.0021 (8)	−0.0001 (8)
O4	0.0199 (11)	0.0193 (12)	0.0221 (11)	0.0022 (9)	0.0125 (9)	0.0026 (9)
O5	0.0194 (11)	0.0220 (12)	0.0328 (13)	0.0016 (9)	0.0132 (10)	−0.0030 (10)
O6	0.0192 (11)	0.0168 (11)	0.0135 (10)	−0.0029 (9)	0.0026 (9)	0.0021 (8)
O7	0.0284 (13)	0.0232 (13)	0.0179 (11)	−0.0110 (10)	−0.0039 (10)	0.0012 (10)
O8	0.0244 (12)	0.0191 (12)	0.0237 (12)	0.0017 (9)	0.0091 (10)	0.0047 (9)
C1	0.0142 (13)	0.0177 (16)	0.0121 (14)	0.0006 (11)	0.0032 (11)	0.0003 (11)
C2	0.0220 (16)	0.0165 (16)	0.0181 (15)	0.0028 (12)	0.0088 (13)	0.0001 (12)
C3	0.0159 (14)	0.0154 (15)	0.0164 (15)	−0.0021 (12)	0.0043 (12)	−0.0047 (12)
C4	0.0160 (14)	0.0206 (16)	0.0160 (15)	−0.0064 (12)	0.0014 (12)	0.0034 (12)
C5	0.0121 (13)	0.0188 (16)	0.0153 (14)	0.0001 (11)	0.0029 (12)	0.0009 (12)

Geometric parameters (Å, º) top

Mn1—O1	2.092 (2)	V1—N1	2.370 (3)
Mn1—O1W	2.164 (2)	N1—C4	1.480 (4)
Mn1—O2W	2.212 (2)	N1—C1	1.482 (4)
Mn1—O3W	2.152 (2)	N1—C2	1.488 (4)
Mn1—O4W	2.236 (2)	P1—O1	1.506 (2)
Mn1—O5W	2.187 (2)	P1—O2	1.531 (2)
O1W—H1C	0.845 (10)	P1—O3	1.544 (2)
O1W—H1D	0.84 (3)	P1—C1	1.830 (3)
O2W—H2C	0.83 (4)	O2—V1ⁱ	1.991 (2)
O2W—H2D	0.84 (4)	O4—C3	1.273 (4)
O3W—H3A	0.84 (3)	O5—C3	1.243 (4)
O3W—H3B	0.84 (3)	O6—C5	1.277 (4)
O4W—H4C	0.844 (10)	O7—C5	1.240 (4)
O4W—H4D	0.85 (3)	C1—H1A	0.9900
O5W—H5A	0.84 (3)	C1—H1B	0.9900
O5W—H5B	0.841 (10)	C2—C3	1.512 (4)
V1—O2ⁱ	1.991 (2)	C2—H2A	0.9900
V1—O3	1.988 (2)	C2—H2B	0.9900
V1—O4	2.030 (2)	C4—C5	1.529 (4)
V1—O6	2.028 (2)	C4—H4A	0.9900
V1—O8	1.598 (2)	C4—H4B	0.9900

O1—Mn1—O1W	88.63 (9)	O8—V1—O6	101.86 (11)
O1—Mn1—O2W	90.18 (9)	O8—V1—N1	169.72 (10)
O1—Mn1—O3W	175.14 (10)	C4—N1—C1	113.3 (2)
O1—Mn1—O4W	92.29 (8)	C4—N1—C2	112.1 (2)
O1—Mn1—O5W	93.12 (9)	C1—N1—C2	111.1 (2)
O1W—Mn1—O2W	93.21 (11)	C4—N1—V1	104.84 (18)
O1W—Mn1—O4W	89.40 (9)	C1—N1—V1	106.81 (18)
O1W—Mn1—O5W	178.21 (9)	C2—N1—V1	108.21 (17)
O2W—Mn1—O4W	176.45 (9)	O1—P1—O2	112.38 (12)
O3W—Mn1—O1W	87.68 (10)	O1—P1—O3	111.64 (12)
O3W—Mn1—O2W	86.85 (10)	O2—P1—O3	110.01 (12)
O3W—Mn1—O4W	90.85 (9)	O1—P1—C1	109.77 (14)
O3W—Mn1—O5W	90.58 (9)	O2—P1—C1	108.96 (13)
O5W—Mn1—O2W	87.12 (10)	O3—P1—C1	103.71 (13)
O5W—Mn1—O4W	90.21 (9)	P1—O1—Mn1	134.66 (13)
Mn1—O1W—H1C	121 (3)	P1—O2—V1ⁱ	141.30 (13)
Mn1—O1W—H1D	119 (3)	P1—O3—V1	125.51 (13)
H1C—O1W—H1D	108 (4)	C3—O4—V1	124.53 (19)
Mn1—O2W—H2C	109 (3)	C5—O6—V1	123.48 (19)
Mn1—O2W—H2D	128 (3)	N1—C1—P1	109.4 (2)
H2C—O2W—H2D	111 (4)	N1—C1—H1A	109.8
Mn1—O3W—H3A	118 (2)	P1—C1—H1A	109.8
Mn1—O3W—H3B	130 (2)	N1—C1—H1B	109.8
H3A—O3W—H3B	109.7 (17)	P1—C1—H1B	109.8
Mn1—O4W—H4C	117 (2)	H1A—C1—H1B	108.2
Mn1—O4W—H4D	123 (2)	N1—C2—C3	112.9 (3)
H4C—O4W—H4D	108.0 (16)	N1—C2—H2A	109.0
Mn1—O5W—H5A	112 (3)	C3—C2—H2A	109.0
Mn1—O5W—H5B	115 (3)	N1—C2—H2B	109.0
H5A—O5W—H5B	108.4 (16)	C3—C2—H2B	109.0
O2ⁱ—V1—O4	163.79 (9)	H2A—C2—H2B	107.8
O2ⁱ—V1—O6	86.89 (9)	O5—C3—O4	123.3 (3)
O2ⁱ—V1—N1	88.32 (9)	O5—C3—C2	118.5 (3)
O3—V1—O2ⁱ	90.96 (9)	O4—C3—C2	118.2 (3)
O3—V1—O4	87.04 (9)	N1—C4—C5	109.6 (2)
O3—V1—O6	154.03 (9)	N1—C4—H4A	109.7
O3—V1—N1	79.41 (9)	C5—C4—H4A	109.7
O4—V1—N1	75.50 (9)	N1—C4—H4B	109.7
O6—V1—O4	87.90 (9)	C5—C4—H4B	109.7
O6—V1—N1	74.66 (9)	H4A—C4—H4B	108.2
O8—V1—O2ⁱ	101.24 (11)	O7—C5—O6	123.4 (3)
O8—V1—O3	103.95 (11)	O7—C5—C4	119.9 (3)
O8—V1—O4	94.85 (11)	O6—C5—C4	116.6 (3)

O8—V1—N1—C4	97.0 (6)	N1—V1—O3—P1	14.95 (15)
O3—V1—N1—C4	−152.95 (19)	O8—V1—O4—C3	−176.3 (2)
O2ⁱ—V1—N1—C4	−61.66 (18)	O3—V1—O4—C3	−72.6 (2)
O6—V1—N1—C4	25.58 (18)	O2ⁱ—V1—O4—C3	10.7 (5)
O4—V1—N1—C4	117.39 (19)	O6—V1—O4—C3	81.9 (2)
O8—V1—N1—C1	−142.5 (6)	N1—V1—O4—C3	7.2 (2)
O3—V1—N1—C1	−32.42 (17)	O8—V1—O6—C5	176.7 (2)
O2ⁱ—V1—N1—C1	58.87 (18)	O3—V1—O6—C5	−9.9 (4)
O6—V1—N1—C1	146.11 (18)	O2ⁱ—V1—O6—C5	75.9 (2)
O4—V1—N1—C1	−122.08 (18)	O4—V1—O6—C5	−88.7 (2)
O8—V1—N1—C2	−22.8 (7)	N1—V1—O6—C5	−13.2 (2)
O3—V1—N1—C2	87.24 (19)	C4—N1—C1—P1	155.7 (2)
O2ⁱ—V1—N1—C2	178.53 (19)	C2—N1—C1—P1	−77.0 (3)
O6—V1—N1—C2	−94.24 (19)	V1—N1—C1—P1	40.8 (2)
O4—V1—N1—C2	−2.42 (18)	O1—P1—C1—N1	88.4 (2)
O2—P1—O1—Mn1	20.0 (2)	O2—P1—C1—N1	−148.10 (19)
O3—P1—O1—Mn1	−104.11 (19)	O3—P1—C1—N1	−31.0 (2)
C1—P1—O1—Mn1	141.47 (18)	C4—N1—C2—C3	−116.4 (3)
O1W—Mn1—O1—P1	55.1 (2)	C1—N1—C2—C3	115.7 (3)
O5W—Mn1—O1—P1	−125.19 (19)	V1—N1—C2—C3	−1.3 (3)
O2W—Mn1—O1—P1	−38.1 (2)	V1—O4—C3—O5	169.9 (2)
O4W—Mn1—O1—P1	144.48 (19)	V1—O4—C3—C2	−10.5 (4)
O1—P1—O2—V1ⁱ	149.0 (2)	N1—C2—C3—O5	−173.4 (3)
O3—P1—O2—V1ⁱ	−86.0 (2)	N1—C2—C3—O4	6.9 (4)
C1—P1—O2—V1ⁱ	27.1 (3)	C1—N1—C4—C5	−149.8 (3)
O1—P1—O3—V1	−115.47 (16)	C2—N1—C4—C5	83.5 (3)
O2—P1—O3—V1	119.05 (15)	V1—N1—C4—C5	−33.7 (3)
C1—P1—O3—V1	2.65 (18)	V1—O6—C5—O7	179.0 (2)
O8—V1—O3—P1	−175.00 (15)	V1—O6—C5—C4	−3.1 (4)
O2ⁱ—V1—O3—P1	−73.17 (16)	N1—C4—C5—O7	−154.2 (3)
O6—V1—O3—P1	11.7 (3)	N1—C4—C5—O6	27.8 (4)
O4—V1—O3—P1	90.74 (16)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1C···O4Wⁱⁱ	0.85 (1)	1.98 (1)	2.813 (3)	167 (4)
O1W—H1D···O5ⁱⁱ	0.84 (3)	1.92 (3)	2.759 (3)	171 (3)
O2W—H2C···O2	0.83 (4)	2.15 (3)	2.847 (3)	142 (4)
O2W—H2D···O6Wⁱⁱⁱ	0.84 (4)	1.88 (2)	2.675 (6)	160 (4)
O3W—H3A···O4ⁱⁱ	0.84 (3)	1.92 (2)	2.735 (3)	163 (4)
O3W—H3B···O6^iv	0.84 (3)	1.93 (3)	2.745 (3)	166 (4)
O4W—H4C···O7^v	0.84 (1)	1.86 (1)	2.698 (3)	175 (3)
O4W—H4D···O3ⁱⁱ	0.85 (3)	1.94 (3)	2.778 (3)	173 (4)
O5W—H5A···O5^vi	0.84 (3)	2.00 (2)	2.803 (3)	161 (4)
O5W—H5B···O7^iv	0.84 (1)	1.99 (1)	2.823 (3)	171 (3)

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

Acknowledgements

We are grateful to Fundação para a Ciência e Tecnologia (FCT, Portugal) for their general financial support (POCI/QUI/58377/2004 supported by FEDER), and also for the postdoctoral research grants Nos. SFRH/BPD/9309/2002 (to FNS) and SFRH/BPD/14410/2003 (to LCS).

References

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Volume 63| Part 2| February 2007| Pages m372-m375

https://doi.org/10.1107/S1600536806054675

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