Ethyl­enedi­ammonium aqua­bis­(malonato)­oxovanadate(IV)

In the anion of the title compound, (C₂H₁₀N₂)[VO(H₂O)(C₃H₂O₄)₂] or H₂en­[VO(mal)₂H₂O], vanadium(IV) is distorted-octahedrally coordinated by six donor O atoms. The two malonate ligands are situated in the equatorial plane, whereas the oxo and the water ligand occupy axial positions. The apical V=O bond exhibits a strong trans influence. The anion possesses crystallographically imposed C₂ symmetry, with the central V atom, the oxo and the water ligand lying on the twofold axis.

Key indicators

• Single-crystal X-ray study
• T = 210 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.025
• wR factor = 0.066
• Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_213  Alert C Atom O6      has ADP max/min Ratio .............       3.40 prolat


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

There are only few crystal structures of bis(dicarboxylato)oxovanadate(IV) complexes described in the literature, namely sodium bis(oxalato)fluorooxovanadate(IV) hexahydrate (Rieskamp & Mattes, 1976),diammonium aquabis(oxalato)oxovanadate(IV) monohydrate (Hazell, 1968; Oughtred et al., 1976), diammonium aquabis(malonato)oxovanadate(IV) monohydrate (Piro & Baran, 1997) and N,N,N',N'-tetramethylethylenediammonium aquabis(malonato)oxovanadate(IV) dihydrate (Pajunen & Pajunen, 1980).

For this type of complex, two different coordination modes are observed regarding the dicarboxylate ligand, which can either be arranged cis or trans to each other. It was noted that the oxovanadate(IV) complexes containing oxalate ligands prefer a cis configuration while the corresponding malonate complexes prefer a trans configuration. This suggests, that the size of the chelation ring has a profound effect on the distribution of geometric isomers. The conformation of the chelation ring is boat. As we expected in the ethylenediammonium aquabis(malonato)oxovanadate(IV) complex, (I), arrangement of malonate ligands are trans (Fig. 1), as in the described structure of N,N,N',N'-tetramethylethylenediammonium aquabis(malonato)oxovanadate(IV) dihydrate, (II) (Pajunen & Pajunen, 1980). Comparing apical V—O bond distances of these two complexes we can see that they are equivalent. Hence, for complex (I) in the equatorial plane, V—O bond distances [V—O1 = 2.012 (1) Å and V—O3 = 2.000 (1) Å] are longer than in complex (II) [V—O1 = 1.981 (2) Å and V—O3 = 1.995 (2) Å]. Atoms V1, O5 and O6 lie on twofold axis of symmetry.

Ethylenediammonium ion participates in five strong intermolecular bonds with five O atoms (Table 1). Moreover, water atom O6 also participates as a hydrogen-bond donor with atom O2. Structural units are exclusively connected over hydrogen bonds, which extend in three dimensions. Between atoms N4 and O4 cyclic hydrogen bonds are formed (Table 1) around the inversion centre at (1/2, 1/2, 1/2). Comparing differences in the same intermolecular hydrogen-bond distance in (I) (Table 1) and complex 2 [N(H)···O = 1.89 (1) Å], we found an unexpected result.

The more bulky cation of (II) has shorter hydrogen-bond distance. Conformation of cation in (I) is closer to eclipsed with torsion angle (N4—C4—C4b—N4b) of −54.8°. Probably the intermolecular interactions stabilize the conformation of the cation.

S2. Experimental

The title complex was obtained by the reaction of aqeous solution of ammonium monovanadate(V), malonate acid and ethylenediamine-N-acetic acid in a 1:1:1 molar ratio at pH 4.5. Reaction solution was filtered off, in order to remove yellow solid, which precipitated during the reaction. After a few days, from mother liquor crystallized a blue complex. Some reduction occurs and the obtained complex was of vanadium(IV).

S3. Refinement

The positions of all H atom were located in difference Fourier syntheses. All H atoms have been refined with individual isotropic displacement parameters.

Computing details

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the molecular structure showing H2en[VO(mal)2H2O] cation with the atom labels. Displacement ellipsoids are shown at the 50% probability level.

(I)

Crystal data

(C2H10N2)[VO(C3H2O4)2(H2O)]	F(000) = 724
Mr = 351.17	Dx = 1.838 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 48 reflections
a = 14.579 (2) Å	θ = 4.4–13.6°
b = 11.866 (1) Å	µ = 0.84 mm^−1
c = 8.758 (2) Å	T = 210 K
β = 123.13 (1)°	Prism, blue
V = 1268.8 (4) Å^3	0.52 × 0.34 × 0.26 mm
Z = 4

Data collection

Siemens P4 diffractometer	1568 reflections with I > 2σ(I)'
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 29.0°, θmin = 2.4°
profile data from ω scans	h = −19→19
Absorption correction: ψ scan (North et al., 1968)	k = −16→16
Tmin = 0.717, Tmax = 0.804	l = −11→11
3486 measured reflections	3 standard reflections every 100 reflections
1689 independent reflections	intensity decay: 5.4%

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)] = 0.025	Hydrogen site location: difference Fourier map
wR(F^2) = 0.066	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 1.3358P] where P = (Fo^2 + 2Fc^2)/3
1689 reflections	(Δ/σ)max = 0.001
129 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.47 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
V1	0.5000	0.10767 (2)	0.2500	0.01114 (9)
C1	0.25952 (10)	0.10589 (10)	0.06517 (16)	0.0137 (2)
C2	0.25885 (10)	0.06216 (11)	−0.09858 (16)	0.0165 (2)
C3	0.33219 (9)	0.12403 (10)	−0.14319 (16)	0.0130 (2)
O1	0.35173 (7)	0.13205 (8)	0.20988 (12)	0.01808 (19)
O2	0.17143 (8)	0.11267 (9)	0.05393 (13)	0.0203 (2)
O3	0.43277 (7)	0.13849 (8)	−0.01520 (12)	0.01585 (18)
O4	0.29336 (7)	0.15626 (8)	−0.30166 (12)	0.01790 (19)
O5	0.5000	−0.02680 (11)	0.2500	0.0182 (3)
O6	0.5000	0.29590 (13)	0.2500	0.0420 (5)
C4	0.02449 (12)	0.15068 (12)	0.3512 (2)	0.0244 (3)
N4	0.09058 (9)	0.25406 (10)	0.44152 (15)	0.0175 (2)
H2A	0.2872 (17)	−0.0146 (17)	−0.070 (3)	0.031 (5)*
H2B	0.1851 (16)	0.0612 (16)	−0.199 (3)	0.024 (4)*
H4A	0.1215 (18)	0.280 (2)	0.386 (3)	0.045 (6)*
H4B	0.1403 (18)	0.2405 (18)	0.545 (3)	0.033 (5)*
H4C	0.0481 (19)	0.3031 (19)	0.439 (3)	0.037 (6)*
H4D	−0.0347 (17)	0.1498 (17)	0.379 (3)	0.032 (5)*
H4E	0.0728 (17)	0.0823 (19)	0.407 (3)	0.034 (5)*
H6	0.4538 (18)	0.3316 (19)	0.167 (3)	0.037 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.00901 (13)	0.01337 (14)	0.00899 (14)	0.000	0.00359 (11)	0.000
C1	0.0126 (5)	0.0158 (5)	0.0118 (5)	0.0024 (4)	0.0060 (4)	0.0025 (4)
C2	0.0137 (5)	0.0236 (6)	0.0120 (5)	−0.0058 (4)	0.0070 (5)	−0.0039 (4)
C3	0.0116 (5)	0.0154 (5)	0.0116 (5)	0.0010 (4)	0.0062 (4)	−0.0003 (4)
O1	0.0115 (4)	0.0285 (5)	0.0122 (4)	0.0018 (3)	0.0052 (3)	−0.0040 (3)
O2	0.0122 (4)	0.0312 (5)	0.0179 (5)	0.0044 (3)	0.0086 (4)	0.0035 (4)
O3	0.0112 (4)	0.0234 (4)	0.0111 (4)	−0.0018 (3)	0.0049 (3)	0.0018 (3)
O4	0.0146 (4)	0.0262 (5)	0.0112 (4)	0.0026 (3)	0.0060 (3)	0.0038 (3)
O5	0.0189 (6)	0.0162 (6)	0.0191 (6)	0.000	0.0101 (5)	0.000
O6	0.0294 (8)	0.0153 (7)	0.0302 (9)	0.000	−0.0164 (7)	0.000
C4	0.0267 (7)	0.0211 (6)	0.0265 (7)	0.0019 (5)	0.0153 (6)	0.0043 (5)
N4	0.0129 (5)	0.0254 (6)	0.0126 (5)	0.0025 (4)	0.0060 (4)	0.0024 (4)

Geometric parameters (Å, º)

V1—O5	1.5957 (13)	C2—H2B	0.948 (19)
V1—O3	2.0002 (10)	C3—O4	1.2386 (15)
V1—O3^i	2.0002 (10)	C3—O3	1.2804 (14)
V1—O1^i	2.0123 (9)	O6—H6	0.79 (2)
V1—O1	2.0123 (9)	C4—N4	1.4920 (19)
V1—O6	2.2335 (16)	C4—C4^ii	1.505 (3)
C1—O2	1.2358 (15)	C4—H4D	1.01 (2)
C1—O1	1.2835 (15)	C4—H4E	1.01 (2)
C1—C2	1.5201 (17)	N4—H4A	0.88 (3)
C2—C3	1.5138 (16)	N4—H4B	0.81 (2)
C2—H2A	0.97 (2)	N4—H4C	0.84 (2)
O5—V1—O3	100.53 (3)	C3—C2—H2B	111.6 (11)
O5—V1—O3^i	100.53 (3)	C1—C2—H2B	107.5 (11)
O3—V1—O3^i	158.93 (6)	H2A—C2—H2B	109.6 (17)
O5—V1—O1^i	98.26 (3)	O4—C3—O3	122.88 (11)
O3—V1—O1^i	88.53 (4)	O4—C3—C2	118.96 (11)
O3^i—V1—O1^i	88.46 (4)	O3—C3—C2	118.14 (10)
O5—V1—O1	98.26 (3)	C1—O1—V1	125.66 (8)
O3—V1—O1	88.46 (4)	C3—O3—V1	126.29 (8)
O3^i—V1—O1	88.53 (4)	V1—O6—H6	122.3 (16)
O1^i—V1—O1	163.47 (6)	N4—C4—C4^ii	112.19 (9)
O5—V1—O6	180.0	N4—C4—H4D	105.6 (12)
O3—V1—O6	79.47 (3)	C4^ii—C4—H4D	111.2 (12)
O3^i—V1—O6	79.47 (3)	N4—C4—H4E	109.1 (13)
O1^i—V1—O6	81.74 (3)	C4^ii—C4—H4E	109.0 (12)
O1—V1—O6	81.74 (3)	H4D—C4—H4E	109.7 (16)
O2—C1—O1	123.02 (12)	C4—N4—H4A	111.8 (15)
O2—C1—C2	118.45 (11)	C4—N4—H4B	110.7 (15)
O1—C1—C2	118.52 (10)	H4A—N4—H4B	106 (2)
C3—C2—C1	115.89 (10)	C4—N4—H4C	107.5 (15)
C3—C2—H2A	105.1 (12)	H4A—N4—H4C	110 (2)
C1—C2—H2A	106.9 (12)	H4B—N4—H4C	111 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O4^iii	0.88 (3)	1.91 (3)	2.7859 (15)	171 (2)
N4—H4B···O4^iv	0.81 (2)	2.12 (2)	2.8067 (15)	142.3 (19)
N4—H4B···O1^v	0.81 (2)	2.58 (2)	3.0080 (16)	114.9 (17)
N4—H4C···O3^vi	0.84 (2)	2.05 (2)	2.8312 (15)	154 (2)
N4—H4C···O5^vii	0.84 (2)	2.46 (2)	2.9829 (17)	121.5 (18)
O6—H6···O2^iii	0.79 (2)	1.91 (2)	2.6902 (12)	168 (2)

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