A new organically templated vanadium tellurite: (H₂dien)[(VO₂)(TeO₃)]₂·2H₂O (dien is diethyl­enetriamine)

A new organically templated vanadium tellurite, poly[2,2'-im­ino­diethanaminium [hexa-[mu]₂-oxido-tetra­oxidoditellurium(IV)di­vanadium(V)] dihydrate], {(C₄H₁₅N₃)[Te₂V₂O₁₀]·2H₂O}_n, features the inter­connection of distorted [VO₅] trigonal bipyramids by bridging [TeO₃] pyramids, leading to a two-dimensional corrugated anionic layer with an inter­layer distance of about 13.47 Å. The inter­layer space is occupied by doubly proton­ated diethyl­ene­triamine cations (H₂dien) and guest water mol­ecules. The two terminal amino groups of H₂dien are proton­ated, while the middle amino group, located on a twofold rotation axis, is not protonated. All the three amino groups and water mol­ecules are involved in hydrogen-bonding inter­actions. The compound represents a new member in the series (H₂am)[(VO₂)(TeO₃)]₂·xH₂O, where H₂am represents a doubly protonated diamine. Similarities and differences between the structures of members of the series are discussed.

S1. Comment

A large variety of inorganic open-framework compounds have been reported during the last decade, most of which are metal silicates, phosphates and carboxylates (Cheetham et al., 1999; Yu et al., 2006; Natarajan et al., 2008). Recently, the studies of such materials have extended to using the oxotellurites as anionic units. The stereochemically active lone-pair electrons of Te^IV can act as an invisible structure-directing agent, having a dramatic effect on the coordination geometries, as well as on the structures of the compounds formed with different metals (Rao et al., 2006; Kim et al., 2007; Mao et al., 2008). In addition to the usual [TeO₃] pyramid like sulphite or selenites, tellurites can also form [TeO₄] folded-square and [TeO₅] square-pyramidal geometries. Vanadium can also adopt various coordination geometries. The oxidation state of vanadium may vary among +3, +4 and +5, and the coordination polyhedron can be tetrahedral, square pyramidal, trigonal bipyramidal, or octahedral (Chiang et al., 2005). The variety in the coordination chemistry of tellurium(IV) and vanadium suggests a great deal of flexibility in any framework architecture and the potential for a variety of open-framework topologies.

Most inorganic open-framework materials are prepared under hydro/solvothermal conditions with the aid of organic amines. The protonated organic amines usually occupy the structural voids as charge compensation and contribute to the stability of the framework structure through hydrogen bonding (Cheetham et al., 1999; Yu et al., 2006; Natarajan et al., 2008). Reports of organically templated vanadium tellurites are still rare. Only four such materials, namely [H₂en][VTeO₅], [H₂en]₂[V₂Te₆O₁₈], [H₂en][(VO₂)(TeO₃)]₂.H₂O and [H₂pip][(VO₂)(TeO₃)]₂ (en = ethylenediamine, pip = piperazine), with two- or three-dimensional open frameworks, have been reported (Feng et al., 2005; Gao et al., 2005; Jung et al., 2006). Recent reports suggest that the use of a diamine or a triamine seems to be more effective than monoamines in the construction of open architecture of zinc phosphates (Choudhury et al., 2000). As an extension of our previous work on metal selenites and tellurites (Lian et al., 2004; Hou et al., 2005, 2006), we are examining the role of multiple amines in the V/Te/O system. In this paper, we describe the synthesis and crystal structure of a new organically templated vanadium tellurite, catena-(bis(2-ammonioethyl)-amine hexakis-(µ2-oxo)-tetraoxo-di-tellurium(iv)-di-vanadium(v) dihydrate), [H₂dien][(VO₂)(TeO₃)]₂.2H₂O (1, dien = diethylenetriamine), (I). (I) features two-dimensional anionic layers with the template cations located in the interlayer space.

(I) is built up from strictly alternating [VO₅] polyhedra and [TeO₃] pyramids linked through shared vertices (Fig. 1), giving rise to a corrugated inorganic anionic layer parallel to the bc plane that is like those observed in the previously reported compounds [H₂en][(VO₂)(TeO₃)]₂.H₂O (II) and [H₂pip][(VO₂)(TeO₃)]₂ (III) (Feng & Mao, 2005). Indeed, the three compounds represent a series with the same space group and similar b and c axis dimensions, with the length of the a axis dependent on the size of the templating cation. There are some notable differences between the structures. Although the M—O bond lengths and O—M—O bond angles of (I) are comparable with those of (II) and (III), the amplitude of the corrugated anionic layer [5.1596 (4) Å, equal to the b axis length] of (I) is shorter [less] than in (III) [5.858 (2) Å], and is close to that of (II) [5.081 (2) Å]. This dissimilarity might be derived from the different forms of the templating cations, i.e. the ring shape of piperazine versus the linear shapes of ethylenediamine and diethylenetriamine. Although the layers themselves are essentially the same among the three compounds, they stack differently. In (I) the layers stack with no offset in the c direction (Fig. 2), while in (II) and (III) there is a sizable offset of about 4.25Å (2) or 4.00 Å (3) between two adjacent layers along the equivalent direction. This offset is reflected in the β angle of (I) [90.06 (4)°] versus those of (II) and (III) which are both about 112°. In addition, the interlayer distance of (I) (one-half the a axis length, or about 13.47 Å) is significantly greater than those of (II) (circa 11.38 Å) and (III) (circa 10.50 Å) due to the different sizes of the templates and how they are positioned, as well as the different levels of hydration.

The interlayer space is occupied by templated H₂dien cations and the guest water molecules. In order to balance the negative charge of the anionic framework, the two terminal amino groups of the diethylenetriamine molecules are protonated, while the middle one is unprotonated. The protonated NH₃ group acts as the hydrogen donor to form hydrogen bonds with two O atoms from the anionic layers and one water molecule. The N2 atom is located on a twofold rotation axis and its attached H4 atom is statistically distributed on the two corners of the N2-centred polyhedron. One of the H atoms on the water molecule is also disordered across two positions. Thus, the hydrogen bonds involving the N2–H4 and OW1–H6 groups can readily be divided into two symmetrically related sets (Figs. 3a and 3b). N2–H4 serves as a hydrogen donor to form a hydrogen bond with OW1ⁱ [symmetry code: (i): 1 - x, y, 0.5 - z], and N2 simultaneously acts as a hydrogen acceptor with H6B on OW1 (Fig. 3a). The alternate arrangements of N2–H4ⁱ and OW1–H6A lead to the interactions N2–H4ⁱ···OW1, OW1ⁱ–H6Bⁱ···N2, and OW1–H6B···OW1^vi (Fig. 3b) [symmetry code: (vi): 1 - x, -y, 1 - z].

This study shows that the [(VO₂)(TeO₃)]₂ layer can be produced with a variety of amine templates of different shapes and sizes. The specific details of the stacking of the layers, as well as the degree of hydration of the material, depend on the template used.

Related literature

For related literature, see: Brown & Shannon (1973); Cheetham et al. (1999); Chiang & Chuang (2005); Choudhury et al. (2000); Feng & Mao (2005); Gao et al. (2005); Hou et al. (2005, 2006); Jung et al. (2006); Kim et al. (2007); Lian et al. (2004); Mao et al. (2008); Natarajan & Mandal (2008); Rao et al. (2006); Yu & Xu (2006).

S2. Experimental

NaVO₃.2H₂O (0.314 g, 2 mmol), Na₂TeO₃ (0.442 g, 2 mmol) and diethylenetriamine (0.21 ml, 2 mmol) were dissolved in 10 ml water. The mixture was adjusted to about pH 8 with 2.0 mol l^-1 HCl solution and stirred for about 10 min. Then, the resulting gel-like mixture was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 363 K for 48 h. After slow cooling to room temperature over 24 h, light yellow crystals were collected by filtration, washed with distilled water, and dried in air (yield: 19% on the basis of Te).

S3. Refinement

H atoms bonded to C and N atoms were positioned geometrically and were included in the refinement in the riding-model approximation with C—H = 0.97, N—H = 0.90 Å, and U_iso(H) = 1.2U_eq(C or N). Atom H4 is statistically distributed across two symmetry-related positions. The water H atoms were located in a difference Fourier map and were included with O—H distances constrained to 0.85 Å and U_iso(H) = 1.2U_eq(O). Atom H6 atom is statistically distributed across two positions, H6A and H6B, both of which have 50% occupancy.

Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the asymmetric unit and some symmetry-related atoms of compound (I), with the atom-numbering scheme (30% probability displacement ellipsoids). Only one of the disordered H6 positions is shown. Symmetry codes: (i) 1 - x, y, 0.5 - z; (ii) 0.5 - x, 0.5 - y, -z; (iii) 0.5 - x, 1/2 + y, 0.5 - z.
	Fig. 2. Crystal packing diagram for compound (I). All atoms are shown as isotropic spheres of arbitrary size. H atoms bonded to C atoms are omitted for clarity. The hydrogen-bonding interactions between the amine groups, water molecules and the anionic layers are shown as dashed lines.
	Fig. 3. The hydrogen-bonding interactions involving the disordered N2–H4 and OW1–H6 groups are divided into two symmetrically related sets (top and bottom). The diagram also shows the hydrogen-bonding interactions involving the protonated NH3 groups. Symmetry codes: (i) 1 - x, y, 0.5 - z; (ii) x, 1 - y, -1/2 + z; (iii) x, 1 + y, z; (iv) 0.5 - x, -1/2 + y, 0.5 - z; (v) x, 1 - y, 1/2 + z; (vi) 1 - x, -y, 1 - z; (vii) 1 - x, -1 + y, 0.5 - z; (viii) x, -y, 1/2 + z; (ix) 1 - x, 1 - y, 1 - z; (x) 1/2 + x, 0.5 - y, 1/2 + z.

poly[2,2'-iminodiethanaminium [hexa-µ₂-oxido-tetraoxidoditellurium(IV)divanadium(V)] dihydrate]

Crystal data

(C4H15N3)[Te2V2O10]·2H2O	F(000) = 1240
Mr = 658.30	Dx = 2.706 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7405 reflections
a = 26.939 (2) Å	θ = 3.0–27.5°
b = 5.1596 (4) Å	µ = 4.76 mm^−1
c = 11.6242 (12) Å	T = 293 K
β = 90.06 (4)°	Block, light yellow
V = 1615.7 (3) Å^3	0.20 × 0.18 × 0.12 mm
Z = 4

Data collection

Rigaku Mercury CCD area-detector diffractometer	1851 independent reflections
Radiation source: fine-focus sealed tube	1732 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (RAPID AUTO; Rigaku, 1998)	h = 0→34
Tmin = 0.450, Tmax = 0.599	k = 0→6
7405 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: mixed
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0328P)^2 + 0.3247P] where P = (Fo^2 + 2Fc^2)/3
1851 reflections	(Δ/σ)max = 0.001
105 parameters	Δρmax = 0.94 e Å^−3
0 restraints	Δρmin = −2.14 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Te1	0.271639 (7)	0.01536 (3)	0.109419 (14)	0.01485 (9)
V1	0.173187 (18)	0.40503 (10)	0.13978 (4)	0.01506 (12)
O1	0.30153 (7)	0.2588 (4)	0.00589 (15)	0.0182 (4)
O2	0.33087 (9)	−0.0062 (4)	0.19653 (19)	0.0199 (5)
O3	0.23748 (7)	0.2607 (4)	0.19831 (15)	0.0195 (4)
O4	0.11802 (7)	0.2734 (5)	0.13142 (16)	0.0250 (5)
O5	0.17181 (8)	0.6945 (4)	0.08473 (17)	0.0261 (5)
C1	0.41930 (12)	0.3910 (7)	0.1542 (3)	0.0287 (7)
H1A	0.4303	0.2464	0.1075	0.034*
H1B	0.4030	0.3220	0.2220	0.034*
C2	0.46342 (11)	0.5521 (7)	0.1900 (3)	0.0260 (7)
H2A	0.4786	0.6294	0.1225	0.031*
H2B	0.4526	0.6909	0.2403	0.031*
N1	0.38373 (11)	0.5524 (6)	0.0875 (2)	0.0265 (6)
H1	0.3583	0.4533	0.0632	0.032*
H2	0.3721	0.6813	0.1322	0.032*
H3	0.3992	0.6239	0.0267	0.032*
N2	0.5000	0.3907 (7)	0.2500	0.0242 (8)
H4	0.5157	0.2884	0.1989	0.029*	0.50
OW1	0.45648 (10)	0.1140 (6)	0.4433 (2)	0.0410 (6)
H5	0.4434	−0.0305	0.4255	0.049*
H6A	0.4799	0.0860	0.4907	0.049*	0.50
H6B	0.4677	0.1881	0.3835	0.049*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Te1	0.01434 (13)	0.01858 (13)	0.01163 (13)	0.00018 (6)	0.00017 (10)	−0.00110 (6)
V1	0.0134 (2)	0.0194 (3)	0.0124 (2)	0.00037 (19)	−0.00036 (18)	0.0005 (2)
O1	0.0195 (10)	0.0220 (9)	0.0129 (8)	−0.0014 (8)	0.0015 (8)	0.0020 (9)
O2	0.0151 (11)	0.0288 (12)	0.0157 (10)	0.0002 (8)	0.0000 (9)	0.0027 (8)
O3	0.0210 (10)	0.0256 (10)	0.0118 (8)	0.0068 (9)	−0.0019 (8)	−0.0031 (9)
O4	0.0178 (10)	0.0351 (12)	0.0220 (9)	−0.0047 (9)	0.0024 (8)	−0.0033 (10)
O5	0.0323 (12)	0.0223 (10)	0.0238 (10)	0.0037 (9)	−0.0007 (9)	0.0046 (9)
C1	0.0249 (16)	0.0274 (17)	0.0337 (16)	0.0018 (13)	−0.0110 (14)	0.0004 (15)
C2	0.0144 (14)	0.0314 (15)	0.0321 (17)	0.0001 (13)	−0.0064 (14)	0.0012 (15)
N1	0.0219 (14)	0.0311 (13)	0.0266 (14)	0.0041 (12)	−0.0047 (12)	−0.0040 (13)
N2	0.0183 (17)	0.0257 (19)	0.0287 (18)	0.000	−0.0068 (15)	0.000
OW1	0.0451 (16)	0.0450 (16)	0.0329 (12)	−0.0107 (14)	−0.0043 (12)	−0.0014 (13)

Geometric parameters (Å, º)

Te1—O3	1.876 (2)	C1—H1B	0.9700
Te1—O2	1.892 (2)	C2—N2	1.466 (4)
Te1—O1	1.9174 (19)	C2—H2A	0.9700
V1—O5	1.625 (2)	C2—H2B	0.9700
V1—O4	1.637 (2)	N1—H1	0.9002
V1—O2^i	1.960 (2)	N1—H2	0.9001
V1—O3	2.004 (2)	N1—H3	0.9000
V1—O1^ii	2.0120 (19)	N2—C2^iv	1.466 (4)
O1—V1^ii	2.0120 (19)	N2—H4	0.8999
O2—V1^iii	1.960 (2)	OW1—H5	0.8501
C1—N1	1.487 (4)	OW1—H6A	0.8499
C1—C2	1.508 (4)	OW1—H6B	0.8501
C1—H1A	0.9700
O3—Te1—O2	99.14 (9)	C2—C1—H1B	109.7
O3—Te1—O1	96.33 (10)	H1A—C1—H1B	108.2
O2—Te1—O1	91.14 (9)	N2—C2—C1	110.3 (3)
O5—V1—O4	109.73 (12)	N2—C2—H2A	109.6
O5—V1—O2^i	99.57 (10)	C1—C2—H2A	109.6
O4—V1—O2^i	95.92 (10)	N2—C2—H2B	109.6
O5—V1—O3	119.64 (11)	C1—C2—H2B	109.6
O4—V1—O3	130.58 (10)	H2A—C2—H2B	108.1
O2^i—V1—O3	78.82 (9)	C1—N1—H1	109.6
O5—V1—O1^ii	93.57 (10)	C1—N1—H2	109.7
O4—V1—O1^ii	94.81 (9)	H1—N1—H2	109.7
O2^i—V1—O1^ii	159.12 (9)	C1—N1—H3	109.9
O3—V1—O1^ii	80.59 (8)	H1—N1—H3	109.7
Te1—O1—V1^ii	113.31 (10)	H2—N1—H3	108.2
Te1—O2—V1^iii	119.04 (12)	C2^iv—N2—C2	110.8 (4)
Te1—O3—V1	119.22 (9)	C2^iv—N2—H4	109.4
N1—C1—C2	110.0 (3)	C2—N2—H4	109.5
N1—C1—H1A	109.7	H5—OW1—H6A	108.4
C2—C1—H1A	109.7	H5—OW1—H6B	110.0
N1—C1—H1B	109.7	H6A—OW1—H6B	110.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.90	1.95	2.845 (3)	176
N1—H2···O2^v	0.90	2.10	2.970 (4)	163
N1—H3···OW1^vi	0.90	2.27	3.101 (4)	153
N2—H4···OW1^iv	0.90	2.03	2.910 (3)	167
OW1—H5···O4^iii	0.85	2.05	2.805 (3)	148
OW1—H6A···OW1^vii	0.85	2.14	2.935 (5)	155
OW1—H6B···N2	0.85	2.06	2.910 (3)	174

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