Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010501317X/ta1492sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010501317X/ta1492Isup2.hkl |
CCDC reference: 275511
Compound (I) was synthesized hydrothermally under autogenous pressure. A mixture of (NH4)6Mo7O24, ZnCl2, H2C2O4, ethylenediamine and water in the molar ratio 1:4:4:34.8:833 was sealed in a 17 ml Teflon-lined autoclave and heated at 393 K for 72 h. The reaction mixture was cooled slowly to room temperature at a rate of 12 K h−1 and green plate-like crystals of (I) were obtained. The resultant crystals were filtered off, washed with distilled water and dried in air (75% yield, based on molybdenum). The pH of the medium decreased from 10.2 before heating to 9.3 at the end of the reaction. The strong features at 934, 909, 861 and 653 cm−1 in the IR spectrum of (I) are attributed to Mo—O stretching vibrations, and the bands at 1407, 1223, 1199, 1118 and 1046 cm−1 are related to the C—C and C—N stretchings. The weight loss of (I) in the range 457–689 K is 44.77%, in agreement with the calculated removal of the en molecules associated with the Zn2+ cations (44.45%). Analysis, calculated for C6H24MoN6O4Zn: C 17.76, H 5.96, N 20.72, Zn 16.12, Mo 23.65%; found: C 17.82, H 6.05, N 20.64, Zn 16.29, Mo 23.73%.
All H atoms were fixed geometrically and allowed to ride on their parent C and N atoms, at C—H distances of 0.97 Å and N—H distances of 0.90 Å, with Uiso(H) = 1.2 Ueq(parent stom).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1987); cell refinement: TEXSAN (Molecular Structure Corporation, 1987); data reduction: TEXSAN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
[Zn(C2H8N2)3][MoO4] | Dx = 1.868 Mg m−3 |
Mr = 405.62 | Mo Kα radiation, λ = 0.71069 Å |
Trigonal, P3c1 | Cell parameters from 100 reflections |
Hall symbol: -P 3 2"c | θ = 10–15° |
a = 15.8791 (19) Å | µ = 2.55 mm−1 |
c = 9.905 (2) Å | T = 293 K |
V = 2163.0 (6) Å3 | Needle, colourless |
Z = 6 | 0.42 × 0.17 × 0.09 mm |
F(000) = 1236 |
Rigaku AFC-5R diffractometer | 1361 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 27.5°, θmin = 1.5° |
ω/2θ scans | h = −20→17 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→20 |
Tmin = 0.414, Tmax = 0.803 | l = −12→12 |
11127 measured reflections | 3 standard reflections every 150 reflections |
1658 independent reflections | intensity decay: 0.2% |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0496P)2 + 0.578P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
1658 reflections | Δρmax = 0.57 e Å−3 |
84 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0037 (3) |
[Zn(C2H8N2)3][MoO4] | Z = 6 |
Mr = 405.62 | Mo Kα radiation |
Trigonal, P3c1 | µ = 2.55 mm−1 |
a = 15.8791 (19) Å | T = 293 K |
c = 9.905 (2) Å | 0.42 × 0.17 × 0.09 mm |
V = 2163.0 (6) Å3 |
Rigaku AFC-5R diffractometer | 1361 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.052 |
Tmin = 0.414, Tmax = 0.803 | 3 standard reflections every 150 reflections |
11127 measured reflections | intensity decay: 0.2% |
1658 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.57 e Å−3 |
1658 reflections | Δρmin = −0.41 e Å−3 |
84 parameters |
Experimental. crystal coated in epoxy glue |
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. |
x | y | z | Uiso*/Ueq | ||
Mo | 0.336864 (12) | 0.0000 | 0.2500 | 0.02717 (15) | |
Zn | 0.334045 (15) | 0.334045 (15) | 0.2500 | 0.02814 (17) | |
O1 | 0.31279 (16) | 0.07523 (13) | 0.34805 (17) | 0.0799 (6) | |
O2 | 0.43416 (11) | 0.06868 (14) | 0.14315 (16) | 0.0702 (6) | |
N1 | 0.41471 (13) | 0.28664 (13) | 0.37294 (17) | 0.0371 (4) | |
H1A | 0.4164 | 0.3056 | 0.4590 | 0.045* | |
H1B | 0.3858 | 0.2213 | 0.3713 | 0.045* | |
N2 | 0.46062 (12) | 0.37720 (13) | 0.12070 (17) | 0.0402 (4) | |
H2A | 0.4417 | 0.3611 | 0.0344 | 0.048* | |
H2B | 0.5007 | 0.4420 | 0.1252 | 0.048* | |
N3 | 0.25697 (12) | 0.19519 (12) | 0.13877 (18) | 0.0398 (4) | |
H3A | 0.2637 | 0.2067 | 0.0493 | 0.048* | |
H3B | 0.2827 | 0.1576 | 0.1597 | 0.048* | |
C1 | 0.51343 (16) | 0.32962 (17) | 0.3195 (2) | 0.0468 (5) | |
H1C | 0.5439 | 0.2938 | 0.3525 | 0.056* | |
H1D | 0.5517 | 0.3964 | 0.3500 | 0.056* | |
C2 | 0.51038 (16) | 0.32677 (16) | 0.1679 (2) | 0.0449 (5) | |
H2C | 0.5760 | 0.3580 | 0.1320 | 0.054* | |
H2D | 0.4762 | 0.2598 | 0.1369 | 0.054* | |
C3 | 0.15401 (16) | 0.14513 (16) | 0.1749 (2) | 0.0495 (6) | |
H3C | 0.1237 | 0.0771 | 0.1497 | 0.059* | |
H3D | 0.1213 | 0.1740 | 0.1270 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo | 0.02956 (18) | 0.02852 (19) | 0.0231 (2) | 0.01426 (10) | 0.00038 (3) | 0.00076 (7) |
Zn | 0.0282 (2) | 0.0282 (2) | 0.0262 (3) | 0.01275 (14) | −0.00018 (5) | 0.00018 (5) |
O1 | 0.1329 (18) | 0.0629 (11) | 0.0655 (11) | 0.0652 (12) | 0.0300 (11) | 0.0026 (9) |
O2 | 0.0442 (9) | 0.1009 (14) | 0.0514 (10) | 0.0258 (9) | 0.0109 (7) | 0.0288 (9) |
N1 | 0.0453 (10) | 0.0383 (9) | 0.0313 (9) | 0.0235 (8) | −0.0039 (7) | −0.0002 (7) |
N2 | 0.0348 (9) | 0.0458 (10) | 0.0351 (9) | 0.0164 (8) | 0.0028 (7) | 0.0046 (7) |
N3 | 0.0451 (10) | 0.0344 (9) | 0.0362 (9) | 0.0172 (8) | −0.0019 (7) | −0.0042 (7) |
C1 | 0.0427 (12) | 0.0547 (14) | 0.0497 (14) | 0.0294 (11) | −0.0083 (10) | −0.0006 (10) |
C2 | 0.0394 (11) | 0.0488 (12) | 0.0497 (13) | 0.0244 (10) | 0.0073 (9) | −0.0027 (10) |
C3 | 0.0407 (12) | 0.0405 (12) | 0.0486 (13) | 0.0062 (9) | −0.0063 (10) | −0.0073 (10) |
Mo—O1i | 1.7243 (15) | N2—H2A | 0.9000 |
Mo—O1 | 1.7243 (15) | N2—H2B | 0.9000 |
Mo—O2 | 1.7354 (15) | N3—C3 | 1.461 (3) |
Mo—O2i | 1.7354 (15) | N3—H3A | 0.9000 |
Zn—N1 | 2.1573 (16) | N3—H3B | 0.9000 |
Zn—N1ii | 2.1573 (16) | C1—C2 | 1.503 (3) |
Zn—N2ii | 2.1845 (16) | C1—H1C | 0.9700 |
Zn—N2 | 2.1845 (16) | C1—H1D | 0.9700 |
Zn—N3 | 2.2079 (16) | C2—H2C | 0.9700 |
Zn—N3ii | 2.2079 (16) | C2—H2D | 0.9700 |
N1—C1 | 1.461 (3) | C3—C3ii | 1.508 (4) |
N1—H1A | 0.9000 | C3—H3C | 0.9700 |
N1—H1B | 0.9000 | C3—H3D | 0.9700 |
N2—C2 | 1.455 (3) | ||
O1i—Mo—O1 | 110.76 (15) | Zn—N2—H2A | 110.1 |
O1i—Mo—O2 | 108.08 (9) | C2—N2—H2B | 110.1 |
O1—Mo—O2 | 110.14 (9) | Zn—N2—H2B | 110.1 |
O1i—Mo—O2i | 110.14 (9) | H2A—N2—H2B | 108.4 |
O1—Mo—O2i | 108.08 (9) | C3—N3—Zn | 109.39 (13) |
O2—Mo—O2i | 109.65 (11) | C3—N3—H3A | 109.8 |
N1—Zn—N1ii | 165.94 (10) | Zn—N3—H3A | 109.8 |
N1—Zn—N2ii | 91.27 (7) | C3—N3—H3B | 109.8 |
N1ii—Zn—N2ii | 80.02 (8) | Zn—N3—H3B | 109.8 |
N1—Zn—N2 | 80.02 (8) | H3A—N3—H3B | 108.2 |
N1ii—Zn—N2 | 91.27 (7) | N1—C1—C2 | 109.71 (16) |
N2ii—Zn—N2 | 103.83 (10) | N1—C1—H1C | 109.7 |
N1—Zn—N3 | 93.59 (7) | C2—C1—H1C | 109.7 |
N1ii—Zn—N3 | 97.33 (7) | N1—C1—H1D | 109.7 |
N2ii—Zn—N3 | 166.81 (7) | C2—C1—H1D | 109.7 |
N2—Zn—N3 | 89.10 (6) | H1C—C1—H1D | 108.2 |
N1—Zn—N3ii | 97.33 (7) | N2—C2—C1 | 108.81 (16) |
N1ii—Zn—N3ii | 93.59 (7) | N2—C2—H2C | 109.9 |
N2ii—Zn—N3ii | 89.10 (6) | C1—C2—H2C | 109.9 |
N2—Zn—N3ii | 166.81 (7) | N2—C2—H2D | 109.9 |
N3—Zn—N3ii | 78.12 (9) | C1—C2—H2D | 109.9 |
C1—N1—Zn | 108.55 (12) | H2C—C2—H2D | 108.3 |
C1—N1—H1A | 110.0 | N3—C3—C3ii | 108.81 (15) |
Zn—N1—H1A | 110.0 | N3—C3—H3C | 109.9 |
C1—N1—H1B | 110.0 | C3ii—C3—H3C | 109.9 |
Zn—N1—H1B | 110.0 | N3—C3—H3D | 109.9 |
H1A—N1—H1B | 108.4 | C3ii—C3—H3D | 109.9 |
C2—N2—Zn | 107.87 (12) | H3C—C3—H3D | 108.3 |
C2—N2—H2A | 110.1 | ||
N1ii—Zn—N1—C1 | −39.00 (13) | N1—Zn—N3—C3 | 111.78 (15) |
N2ii—Zn—N1—C1 | −90.35 (15) | N1ii—Zn—N3—C3 | −77.10 (15) |
N2—Zn—N1—C1 | 13.46 (13) | N2ii—Zn—N3—C3 | 0.4 (3) |
N3—Zn—N1—C1 | 101.91 (14) | N2—Zn—N3—C3 | −168.27 (14) |
N3ii—Zn—N1—C1 | −179.61 (14) | N3ii—Zn—N3—C3 | 15.04 (11) |
N1—Zn—N2—C2 | 16.07 (12) | Zn—N1—C1—C2 | −40.7 (2) |
N1ii—Zn—N2—C2 | −175.04 (14) | Zn—N2—C2—C1 | −42.4 (2) |
N2ii—Zn—N2—C2 | 104.92 (14) | N1—C1—C2—N2 | 56.9 (3) |
N3—Zn—N2—C2 | −77.73 (14) | Zn—N3—C3—C3ii | −42.2 (3) |
N3ii—Zn—N2—C2 | −63.4 (3) |
Symmetry codes: (i) −x, −x+y, −z+1/2; (ii) y, x, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.90 | 2.01 | 2.905 (2) | 172 |
N1—H1B···O1 | 0.90 | 2.02 | 2.918 (3) | 173 |
N2—H2B···O2iv | 0.90 | 2.06 | 2.894 (2) | 154 |
N3—H3A···O1v | 0.90 | 2.11 | 2.989 (2) | 166 |
N3—H3B···O1 | 0.90 | 2.46 | 3.225 (3) | 143 |
Symmetry codes: (iii) −x+y, y, z+1/2; (iv) −x+y+1, −x+1, z; (v) −x+y, y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2H8N2)3][MoO4] |
Mr | 405.62 |
Crystal system, space group | Trigonal, P3c1 |
Temperature (K) | 293 |
a, c (Å) | 15.8791 (19), 9.905 (2) |
V (Å3) | 2163.0 (6) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 2.55 |
Crystal size (mm) | 0.42 × 0.17 × 0.09 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.414, 0.803 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11127, 1658, 1361 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.099, 1.03 |
No. of reflections | 1658 |
No. of parameters | 84 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.41 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1987), TEXSAN (Molecular Structure Corporation, 1987), TEXSAN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990), SHELXL97.
Mo—O1 | 1.7243 (15) | Zn—N2 | 2.1845 (16) |
Mo—O2 | 1.7354 (15) | Zn—N3 | 2.2079 (16) |
Zn—N1 | 2.1573 (16) | ||
O1i—Mo—O1 | 110.76 (15) | N2ii—Zn—N2 | 103.83 (10) |
O1—Mo—O2 | 110.14 (9) | N1—Zn—N3 | 93.59 (7) |
O1—Mo—O2i | 108.08 (9) | N2—Zn—N3 | 89.10 (6) |
O2—Mo—O2i | 109.65 (11) | N1—Zn—N3ii | 97.33 (7) |
N1—Zn—N1ii | 165.94 (10) | N2—Zn—N3ii | 166.81 (7) |
N1—Zn—N2ii | 91.27 (7) | N3—Zn—N3ii | 78.12 (9) |
N1—Zn—N2 | 80.02 (8) |
Symmetry codes: (i) −x, −x+y, −z+1/2; (ii) y, x, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.90 | 2.01 | 2.905 (2) | 172.3 |
N1—H1B···O1 | 0.90 | 2.02 | 2.918 (3) | 173.4 |
N2—H2B···O2iv | 0.90 | 2.06 | 2.894 (2) | 154.0 |
N3—H3A···O1v | 0.90 | 2.11 | 2.989 (2) | 166.2 |
N3—H3B···O1 | 0.90 | 2.46 | 3.225 (3) | 143.2 |
Symmetry codes: (iii) −x+y, y, z+1/2; (iv) −x+y+1, −x+1, z; (v) −x+y, y, z−1/2. |
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There has been extensive interest in organic–inorganic hybrid materials in the past few years, reflecting their potential application in catalysis, conductivity and photochemistry, as well as their interesting structural features (Braun et al., 1999). Exploitation of hydrothermal techniques, combined with amine-ligated transition metal complex cations, has been demonstrated as an effective strategy to obtain such materials, for example, [Co(dien)2](VO3)3·H2O (dien is diethylenetriamine; Lin, Li et al., 2003), [Co(bpy)Mo3O10] (bpy is 2,2'-bipyridine; Zapf et al., 1997), [Cu(en)2]2[Mo8O26] (en is ethylenediamine; DeBord et al., 1997) and [Cu(en)2]3[{Cu(en)2}2(H2W12O42)] (Lin, Chen & Liu, 2003). More recently, several metal oxides including M(en)3n+ complex cations have been synthesized, including [Ni(en)3](VO3)2 (Liu et al., 2000) and [Co(en)3][C4H12N2]0.5[(Mo5O15)(HPO4)2] (He et al., 2004), but hybrids including Zn(en)32+ complex cations are yet to be studied. This paper presents the hydrothermal synthesis and crystal structure of the title novel organic–inorganic hybrid [Zn(en)3]MoO4, (I).
As shown in Fig. 1, the molecular structure of (I) is made up of an MoO42− anion and a [Zn(en)3]2+ complex cation. The Mo atom, on a twofold axis, is in an almost regular MoO4 tetrahedral environment, with Mo—O bond distances ranging from 1.7240 (15) to 1.7354 (14) Å (Table 1), which are in accordance with those observed in [Co(en)MoO4] (Lin, 2002). The Zn atom, on the same twofold axis, exhibits a distorted octahedral coordination geometry defined by six N atoms from three ethylenediamine ligands, with Zn—N distances ranging from 2.1575 (16) to 2.2081 (16) Å, which are in agreement with those observed in [Zn(en)3]2(Sn2Te6) (Li et al., 1998).
The MoO42− anions and [Zn(en)3]2+ complex cations in the crystal structure of (I) mainly interact with each other through electrostatic interactions. The packing arrangement of (I) along the c axis is depicted in Fig. 2. There is extensive hydrogen bonding between the N—H groups of the [Zn(en)3]2+ complex cations and the O atoms of the MoO42− anions, with N···O interatomic distances ranging from 2.894 (2) to 3.225 (3) Å (Table 2). These hydrogen-bonding interactions hold MoO42− anions and [Zn(en)3]2+ complex cations together in a three-dimensional network.
A noteworthy feature of (I) is that the [Zn(en)3]2+ cations in the crystal structure exhibit two configurations, Λ(δδδ) and Δ(λλλ), as a pair of enantiomers due to the D3d symmetry. Similar cases have been reported by other authors when [Co(en)3]2+ is used as a template in the synthesis of phosphates (He et al., 2004; Morgan et al., 1995). As shown in Fig. 2, the MoO42− anions and [Zn(en)3]2+ cations in the crystal structure of (I) are arranged alternately along the c axis into one-dimensional linear chains via hydrogen-bonding interactions. Adjacent one-dimensional chains are further held together via other N—H···O hydrogen bonds into a three-dimensional network, in which six adjacent linear chains are linked together resulting in the formation of a one-dimensional tunnel. All [Zn(en)3]2+ complex cations in a linear chain have a uniform configuration, and those in its adjacent chains have the other configuration. If the one-dimensional linear chains including Λ(δδδ) and Δ(λλλ) [Zn(en)3]2+ cations are denoted Λ-chains and Δ-chains, respectively, the one-dimensional tunnel mentioned above is constructed from three Λ-chains and three Δ-chains.