metal-organic compounds
Bis(ethylenediammonium) μ-ethylenediaminetetraacetato-1κ3O,N,O′:2κ3O′′,N′,O′′′-bis[trioxidomolybdate(VI)] tetrahydrate
aLaboratoire de Chimie Minérale et Analytique (LACHIMIA), Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, bDepartment of Physics-Chemistry, UFR Science and Technology, Iba Der THIAM University of THIES, Senegal, and cUniversité Alioune Diop de Bambey, UFR Sciences Appliquées et Technologies de l'Information et de la Communication (SATIC), Équipe Chimie des Matériaux Inorganiques et Organiques (ECMIO), Senegal
*Correspondence e-mail: lamine.yaffa@ucad.edu.sn
This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.
The title compound, (C2H10N2)2[(C10H12N2O8)(MoO3)2]·4H2O, which crystallizes in the monoclinic C2/c was obtained by mixing molybdenum oxide, ethylenediamine and ethylenediaminetetraacetic acid (H4edta) in a 2:4:1 ratio. The complex anion contains two MoO3 units bridged by an edta4− anion. The midpoint of the central C—C bond of the edta4− anion is located on a crystallographic inversion centre. The independent Mo atom is tridentately coordinated by a nitrogen atom and two carboxylate groups of the edta4− ligand, together with the three oxo ligands, producing a distorted octahedral coordination environment. In the three-dimensional supramolecular the dinuclear anions, the organoammonium counter-ions and the solvent water molecules are linked by N—H⋯Ow, N—H⋯Oedta and O—H⋯O hydrogen bonds.
CCDC reference: 2368916
Structure description
The advancement of materials science has meant that many well-established materials, such as metals, ceramics or plastics, cannot meet the demand for new applications (photovoltaic cells, field-effect transistors, etc.). This desire to design new functional materials demands enormous research effort. In order to overcome this challenge, scientists quickly understood that mixtures of materials could have properties superior to those of their pure counterparts, and thus meet this demand. Hybrid framework materials research is one of the fastest growing research fields.
Their unique hybrid nature enables the combination of properties from both inorganic and organic materials (Cheetham & Rao, 2007). As organic ligands, polycarboxylates are multidentate chelating agents, widespread in nature and industry, due to their ability to coordinate to various transition metals in different ratios. In this field, the study of molybdenum polycarboxylate complexes has led to thorough investigation over the past three decades. Some well-characterized mono-, bi- and polynuclear molybdenum and tungsten complexes have been reported, for example [(H2TEMED)Mo2O6(H2edta)]·H2O (TMED = tetramethylethylenediamine; Kumar et al., 2012), Mo2(O2CCH2OH)4, M2[MoO3(C2O4)] (M = Na, K, Rb, Cs) and Na2[MO2(C6H6O7)2]·3H2O (M = Mo, W; Cotton et al., 2002; Cindrić et al., 2000; Zhou et al., 1999), Na2K2[Mo2O6(edta)]·10H2O and Na4[W2O6(edta)]·8H2O (Lin et al., 2006). In our study, the reaction of H4edta (ethylenediaminetetraacetic acid) with molybdenum oxide has been investigated, and a new binuclear 2:1 Mo–edta complex, (C2H10N2)2[(C10H12N2O8)(MoO3)2]·4H2O, including edta4− as ligand has been isolated and structurally characterized.
The single-crystal structure shows that the 2:1 Mo–edta complex anion of the title compound is discrete (Fig. 1). All of the carboxylic groups of H4edta are deprotonated, coordinating the molybdenum oxide groups by nitrogen and two oxygen atoms. The edta4− ligand itself is a bridge between the two MoO3 units, and the midpoint of the central C—C bond is situated on an inversion centre. In the 2:1 Mo–edta complex, the edta4− ligand thus chelates a pair of MoVI centres, in a tridentate fashion, giving a trans configuration to the complex. Each MoVI ion is chelated by the edta4− ligand, simultaneously forming two glycinato rings occupying contiguous vertices that define one face of the The other three vertices of the opposite face are occupied by three terminal oxo atoms of the MoO3 unit, completing the octahedral geometry. In the complex, the Mo—O bond lengths are in the range 1.7195 (16) to 1.7686 (15) Å for Mo=Ot groups (Ot are terminal oxygen atoms: O5, O6 and O7). The resulting bond angles Ot—Mo—Ot are 107.27 (7), 103.83 (7) and 106.75 (7)°, considerably larger than the expected value of 90° for a regular octahedron, confirming the distortion from octahedral geometry.
The crystal packing can be rationalized in terms of non-bonding interactions between the three tectons: the Mo–edta complex anion, two (C2H10N2)+ cations and four lattice water molecules. These units are linked through hydrogen bonds of the type N—H⋯Owater, N—H⋯Oedta and O—H⋯O (Table 1). This interconnection leads to the supramolecular structure, as shown in Fig. 2.
Synthesis and crystallization
Solid molybdenum oxide (4 mmol) and ethylenediamine (4 mmol) were mixed in 30 ml of distilled water. To this mixture were slowly added 2 mmol of ethylenediamminetetraacetic acid (H4edta) under vigorous stirring. The solution was then stirred for 2 h at room temperature. The colourless solution thus obtained was left at room temperature for slow evaporation of water. After a few days, colourless crystals (yield 13.6% based on Mo) were obtained.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 2368916
https://doi.org/10.1107/S2414314624006679/bh4085sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624006679/bh4085Isup2.hkl
(C2H10N2)2[Mo2(C10H12N2O8)O6]·4H2O | F(000) = 1576 |
Mr = 772.40 | Dx = 1.853 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.5897 (14) Å | Cell parameters from 9873 reflections |
b = 7.5100 (4) Å | θ = 2.9–27.5° |
c = 16.3743 (10) Å | µ = 1.00 mm−1 |
β = 94.716 (2)° | T = 150 K |
V = 2768.5 (3) Å3 | Block, colourless |
Z = 4 | 0.17 × 0.17 × 0.13 mm |
Bruker APEXII CCD diffractometer | 2946 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.032 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 27.5°, θmin = 1.8° |
Tmin = 0.691, Tmax = 0.746 | h = −29→29 |
24031 measured reflections | k = −9→9 |
3192 independent reflections | l = −20→21 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0247P)2 + 9.3382P] where P = (Fo2 + 2Fc2)/3 |
3192 reflections | (Δ/σ)max = 0.001 |
189 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −1.06 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Mo1 | 0.34131 (2) | 0.30046 (2) | 0.43898 (2) | 0.01140 (6) | |
O2 | 0.38304 (7) | 0.07064 (19) | 0.38526 (10) | 0.0184 (3) | |
O3 | 0.34930 (6) | 0.3750 (2) | 0.31149 (9) | 0.0153 (3) | |
O5 | 0.32695 (7) | 0.5278 (2) | 0.45742 (9) | 0.0167 (3) | |
O6 | 0.27328 (7) | 0.1984 (2) | 0.41260 (10) | 0.0192 (3) | |
O7 | 0.36649 (7) | 0.2195 (2) | 0.53376 (10) | 0.0199 (3) | |
O8 | 0.46292 (8) | −0.0988 (2) | 0.38094 (12) | 0.0305 (4) | |
O9 | 0.40393 (8) | 0.4592 (3) | 0.21238 (10) | 0.0313 (4) | |
N1 | 0.44444 (7) | 0.3699 (2) | 0.42662 (10) | 0.0110 (3) | |
N2 | 0.68095 (9) | −0.1480 (2) | 0.31790 (11) | 0.0180 (4) | |
H2C | 0.682765 | −0.194661 | 0.266874 | 0.022* | |
H2D | 0.644495 | −0.169814 | 0.335592 | 0.022* | |
H2E | 0.709362 | −0.199255 | 0.352923 | 0.022* | |
N3 | 0.68986 (8) | 0.3285 (2) | 0.39152 (11) | 0.0166 (4) | |
H3C | 0.662370 | 0.374203 | 0.353458 | 0.020* | |
H3D | 0.726961 | 0.352136 | 0.376498 | 0.020* | |
H3E | 0.685339 | 0.379149 | 0.441115 | 0.020* | |
C1 | 0.43883 (10) | 0.0440 (3) | 0.39471 (13) | 0.0165 (4) | |
C2 | 0.46667 (9) | 0.4795 (3) | 0.49874 (12) | 0.0136 (4) | |
H2A | 0.458550 | 0.415662 | 0.549512 | 0.016* | |
H2B | 0.444417 | 0.593202 | 0.497625 | 0.016* | |
C3 | 0.44903 (9) | 0.4682 (3) | 0.34868 (12) | 0.0158 (4) | |
H3A | 0.486764 | 0.435686 | 0.325738 | 0.019* | |
H3B | 0.450105 | 0.597629 | 0.360192 | 0.019* | |
C4 | 0.68156 (10) | 0.1326 (3) | 0.39721 (13) | 0.0181 (4) | |
H4A | 0.640934 | 0.106237 | 0.412324 | 0.022* | |
H4B | 0.710243 | 0.083077 | 0.440266 | 0.022* | |
C5 | 0.39759 (10) | 0.4287 (3) | 0.28535 (13) | 0.0159 (4) | |
C6 | 0.47677 (9) | 0.1985 (3) | 0.42775 (15) | 0.0184 (4) | |
H6A | 0.492092 | 0.171560 | 0.484797 | 0.022* | |
H6B | 0.511335 | 0.210675 | 0.394705 | 0.022* | |
C7 | 0.69112 (12) | 0.0470 (3) | 0.31517 (13) | 0.0225 (5) | |
H7A | 0.663501 | 0.100557 | 0.271922 | 0.027* | |
H7B | 0.732207 | 0.070407 | 0.301180 | 0.027* | |
O1 | 0.30869 (7) | −0.2039 (2) | 0.34909 (9) | 0.0180 (3) | |
H1A | 0.317459 | −0.290614 | 0.383210 | 0.027* | |
H1B | 0.333866 | −0.120160 | 0.364109 | 0.027* | |
O10 | 0.56206 (14) | −0.0882 (7) | 0.30040 (19) | 0.1003 (14) | |
H10A | 0.533675 | −0.115649 | 0.330976 | 0.151* | |
H10B | 0.549760 | −0.103261 | 0.249098 | 0.151* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01159 (9) | 0.01140 (9) | 0.01128 (9) | −0.00124 (6) | 0.00129 (6) | −0.00028 (6) |
O2 | 0.0146 (7) | 0.0131 (7) | 0.0272 (8) | −0.0018 (6) | −0.0006 (6) | −0.0051 (6) |
O3 | 0.0139 (7) | 0.0207 (7) | 0.0113 (7) | −0.0022 (6) | −0.0005 (5) | 0.0000 (6) |
O5 | 0.0197 (8) | 0.0149 (7) | 0.0157 (7) | 0.0013 (6) | 0.0031 (6) | −0.0022 (6) |
O6 | 0.0142 (7) | 0.0206 (8) | 0.0229 (8) | −0.0029 (6) | 0.0024 (6) | −0.0023 (6) |
O7 | 0.0201 (8) | 0.0226 (8) | 0.0172 (7) | −0.0033 (6) | 0.0021 (6) | 0.0059 (6) |
O8 | 0.0238 (9) | 0.0153 (8) | 0.0507 (12) | 0.0053 (7) | −0.0067 (8) | −0.0107 (8) |
O9 | 0.0263 (9) | 0.0548 (12) | 0.0123 (7) | −0.0165 (8) | −0.0016 (7) | 0.0047 (8) |
N1 | 0.0129 (8) | 0.0100 (7) | 0.0097 (7) | −0.0009 (6) | −0.0016 (6) | −0.0013 (6) |
N2 | 0.0225 (9) | 0.0163 (9) | 0.0152 (8) | 0.0008 (7) | 0.0019 (7) | 0.0001 (7) |
N3 | 0.0183 (9) | 0.0176 (9) | 0.0137 (8) | 0.0017 (7) | −0.0007 (7) | −0.0025 (7) |
C1 | 0.0174 (10) | 0.0132 (9) | 0.0185 (10) | 0.0003 (8) | −0.0018 (8) | −0.0013 (8) |
C2 | 0.0133 (10) | 0.0156 (9) | 0.0115 (9) | −0.0025 (7) | −0.0017 (7) | −0.0027 (7) |
C3 | 0.0150 (10) | 0.0198 (10) | 0.0125 (9) | −0.0062 (8) | 0.0001 (7) | 0.0020 (8) |
C4 | 0.0234 (11) | 0.0170 (10) | 0.0138 (9) | 0.0003 (8) | 0.0019 (8) | −0.0002 (8) |
C5 | 0.0190 (10) | 0.0160 (10) | 0.0125 (9) | −0.0031 (8) | −0.0002 (8) | 0.0000 (8) |
C6 | 0.0130 (10) | 0.0141 (10) | 0.0273 (11) | 0.0015 (8) | −0.0038 (8) | −0.0038 (8) |
C7 | 0.0376 (13) | 0.0159 (10) | 0.0138 (10) | −0.0012 (9) | 0.0013 (9) | −0.0001 (8) |
O1 | 0.0207 (8) | 0.0152 (7) | 0.0175 (7) | −0.0052 (6) | −0.0025 (6) | 0.0023 (6) |
O10 | 0.0533 (18) | 0.200 (4) | 0.0469 (16) | 0.015 (2) | 0.0000 (14) | 0.007 (2) |
Mo1—O2 | 2.1858 (15) | N3—C4 | 1.487 (3) |
Mo1—O3 | 2.1831 (14) | C1—C6 | 1.516 (3) |
Mo1—O5 | 1.7686 (15) | C2—C2i | 1.534 (4) |
Mo1—O6 | 1.7397 (15) | C2—H2A | 0.9900 |
Mo1—O7 | 1.7195 (16) | C2—H2B | 0.9900 |
Mo1—N1 | 2.4121 (17) | C3—H3A | 0.9900 |
O2—C1 | 1.273 (3) | C3—H3B | 0.9900 |
O3—C5 | 1.270 (3) | C3—C5 | 1.521 (3) |
O8—C1 | 1.232 (3) | C4—H4A | 0.9900 |
O9—C5 | 1.236 (3) | C4—H4B | 0.9900 |
N1—C2 | 1.492 (2) | C4—C7 | 1.521 (3) |
N1—C3 | 1.485 (3) | C6—H6A | 0.9900 |
N1—C6 | 1.479 (3) | C6—H6B | 0.9900 |
N2—H2C | 0.9100 | C7—H7A | 0.9900 |
N2—H2D | 0.9100 | C7—H7B | 0.9900 |
N2—H2E | 0.9100 | O1—H1A | 0.8703 |
N2—C7 | 1.484 (3) | O1—H1B | 0.8697 |
N3—H3C | 0.9100 | O10—H10A | 0.8701 |
N3—H3D | 0.9100 | O10—H10B | 0.8702 |
N3—H3E | 0.9100 | ||
O2—Mo1—N1 | 71.68 (6) | O8—C1—C6 | 119.11 (19) |
O3—Mo1—O2 | 75.25 (6) | N1—C2—C2i | 113.4 (2) |
O3—Mo1—N1 | 73.02 (5) | N1—C2—H2A | 108.9 |
O5—Mo1—O2 | 157.26 (6) | N1—C2—H2B | 108.9 |
O5—Mo1—O3 | 86.93 (6) | C2i—C2—H2A | 108.9 |
O5—Mo1—N1 | 89.85 (6) | C2i—C2—H2B | 108.9 |
O6—Mo1—O2 | 87.34 (6) | H2A—C2—H2B | 107.7 |
O6—Mo1—O3 | 90.94 (7) | N1—C3—H3A | 109.1 |
O6—Mo1—O5 | 107.27 (7) | N1—C3—H3B | 109.1 |
O6—Mo1—N1 | 156.07 (6) | N1—C3—C5 | 112.68 (16) |
O7—Mo1—O2 | 87.85 (7) | H3A—C3—H3B | 107.8 |
O7—Mo1—O3 | 155.03 (7) | C5—C3—H3A | 109.1 |
O7—Mo1—O5 | 103.83 (7) | C5—C3—H3B | 109.1 |
O7—Mo1—O6 | 106.75 (7) | N3—C4—H4A | 109.8 |
O7—Mo1—N1 | 84.38 (7) | N3—C4—H4B | 109.8 |
C1—O2—Mo1 | 122.03 (13) | N3—C4—C7 | 109.60 (17) |
C5—O3—Mo1 | 123.00 (13) | H4A—C4—H4B | 108.2 |
C2—N1—Mo1 | 108.51 (11) | C7—C4—H4A | 109.8 |
C3—N1—Mo1 | 108.40 (12) | C7—C4—H4B | 109.8 |
C3—N1—C2 | 111.30 (15) | O3—C5—C3 | 117.47 (18) |
C6—N1—Mo1 | 106.85 (12) | O9—C5—O3 | 123.7 (2) |
C6—N1—C2 | 109.66 (16) | O9—C5—C3 | 118.68 (19) |
C6—N1—C3 | 111.95 (16) | N1—C6—C1 | 113.43 (17) |
H2C—N2—H2D | 109.5 | N1—C6—H6A | 108.9 |
H2C—N2—H2E | 109.5 | N1—C6—H6B | 108.9 |
H2D—N2—H2E | 109.5 | C1—C6—H6A | 108.9 |
C7—N2—H2C | 109.5 | C1—C6—H6B | 108.9 |
C7—N2—H2D | 109.5 | H6A—C6—H6B | 107.7 |
C7—N2—H2E | 109.5 | N2—C7—C4 | 110.94 (18) |
H3C—N3—H3D | 109.5 | N2—C7—H7A | 109.5 |
H3C—N3—H3E | 109.5 | N2—C7—H7B | 109.5 |
H3D—N3—H3E | 109.5 | C4—C7—H7A | 109.5 |
C4—N3—H3C | 109.5 | C4—C7—H7B | 109.5 |
C4—N3—H3D | 109.5 | H7A—C7—H7B | 108.0 |
C4—N3—H3E | 109.5 | H1A—O1—H1B | 104.5 |
O2—C1—C6 | 116.65 (18) | H10A—O10—H10B | 109.4 |
O8—C1—O2 | 124.2 (2) | ||
Mo1—O2—C1—O8 | 164.21 (18) | N1—C3—C5—O3 | 24.0 (3) |
Mo1—O2—C1—C6 | −13.7 (3) | N1—C3—C5—O9 | −159.7 (2) |
Mo1—O3—C5—O9 | 174.61 (18) | N3—C4—C7—N2 | −177.90 (18) |
Mo1—O3—C5—C3 | −9.3 (3) | C2—N1—C3—C5 | −143.96 (17) |
Mo1—N1—C2—C2i | 175.59 (18) | C2—N1—C6—C1 | 145.79 (18) |
Mo1—N1—C3—C5 | −24.7 (2) | C3—N1—C2—C2i | −65.2 (3) |
Mo1—N1—C6—C1 | 28.4 (2) | C3—N1—C6—C1 | −90.2 (2) |
O2—C1—C6—N1 | −13.0 (3) | C6—N1—C2—C2i | 59.2 (3) |
O8—C1—C6—N1 | 169.0 (2) | C6—N1—C3—C5 | 92.9 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O1ii | 0.91 | 1.93 | 2.795 (2) | 159 |
N2—H2D···O10 | 0.91 | 2.00 | 2.715 (4) | 134 |
N2—H2D···O7iii | 0.91 | 2.21 | 2.786 (2) | 121 |
N2—H2E···O6iv | 0.91 | 1.84 | 2.748 (2) | 172 |
N3—H3C···O9ii | 0.91 | 1.88 | 2.785 (3) | 170 |
N3—H3D···O1v | 0.91 | 1.98 | 2.838 (2) | 156 |
N3—H3E···O5i | 0.91 | 1.84 | 2.753 (2) | 177 |
O1—H1A···O5vi | 0.87 | 1.83 | 2.694 (2) | 173 |
O1—H1B···O2 | 0.87 | 1.83 | 2.694 (2) | 173 |
O10—H10A···O8 | 0.87 | 1.86 | 2.692 (4) | 160 |
O10—H10B···O8ii | 0.87 | 2.13 | 2.978 (4) | 166 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y, −z+1; (iv) x+1/2, y−1/2, z; (v) x+1/2, y+1/2, z; (vi) x, y−1, z. |
Acknowledgements
The authors acknowledge the Cheikh Anta Diop University of Dakar (Senegal) for financial support.
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