Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811030005/go2021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536811030005/go2021Isup2.hkl |
CCDC reference: 845200
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.030
- wR factor = 0.070
- Data-to-parameter ratio = 44.6
checkCIF/PLATON results
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Alert level C PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cd PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 16 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 42 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 12
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 6 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 5 PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cd (II) 2.22 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 5 ALERT level C = Check. Ensure it is not caused by an omission or oversight 7 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
Single-crystals of the title compound were grown by slow evaporation at room temperature of an aqueous solution of CdSO4.8(H2O)/C2H8N2 /H2SO4in a ratio 1:1:1. The product was filtered off and washed with a small amount of distilled water.
The aqua H atoms were located in difference map and refined with O—H distance restraints of 0.85 (2) Å and H—H distance restraints of 1.35 (2) Å. H atoms bonded to C and N atomswere positioned geometrically and allowed to ride on their parent atom, with C—H = 0.97 Å, N—H = 0.89 Å and Uiso = 1.2Ueq(C, N). The 1 1 3 reflection has been omitted, (Iobs/Ical)/sigma greater than 10.
Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
(C2H10N2)[Cd(SO4)2(H2O)4] | Z = 1 |
Mr = 438.70 | F(000) = 220 |
Triclinic, P1 | Dx = 2.166 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9114 (2) Å | Cell parameters from 8732 reflections |
b = 7.3056 (2) Å | θ = 2.9–42.2° |
c = 7.3629 (1) Å | µ = 1.99 mm−1 |
α = 74.013 (2)° | T = 293 K |
β = 71.731 (1)° | Prism, colourless |
γ = 78.043 (1)° | 0.12 × 0.11 × 0.07 mm |
V = 336.39 (1) Å3 |
Nonius KappaCCD diffractometer | 4684 independent reflections |
Radiation source: fine-focus sealed tube | 4352 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.040 |
Detector resolution: 9 pixels mm-1 | θmax = 42.2°, θmin = 2.9° |
CCD rotation images, thick slices scans | h = −13→13 |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | k = −9→13 |
Tmin = 0.817, Tmax = 0.885 | l = −9→13 |
8732 measured reflections |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0105P)2 + 0.0726P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
4684 reflections | Δρmax = 0.90 e Å−3 |
105 parameters | Δρmin = −1.49 e Å−3 |
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.242 (7) |
(C2H10N2)[Cd(SO4)2(H2O)4] | γ = 78.043 (1)° |
Mr = 438.70 | V = 336.39 (1) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.9114 (2) Å | Mo Kα radiation |
b = 7.3056 (2) Å | µ = 1.99 mm−1 |
c = 7.3629 (1) Å | T = 293 K |
α = 74.013 (2)° | 0.12 × 0.11 × 0.07 mm |
β = 71.731 (1)° |
Nonius KappaCCD diffractometer | 4684 independent reflections |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | 4352 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.885 | Rint = 0.040 |
8732 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 6 restraints |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.90 e Å−3 |
4684 reflections | Δρmin = −1.49 e Å−3 |
105 parameters |
Experimental. Data were corrected for Lorentz-polarization effects and an analytical absorption correction (de Meulenaer & Tompa, 1965) was applied. The structure was solved in the P -1 space group by the direct methods (Cd and S) and subsequent difference Fourier syntheses (all other atoms), with an exception for H atoms bonded to C and N atoms which are positioned geometrically. |
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 | ||
Cd | 0.5000 | 0.5000 | 1.0000 | 0.01899 (4) | |
OW1 | 0.5857 (3) | 0.24405 (19) | 1.22634 (18) | 0.0483 (4) | |
OW2 | 0.77475 (16) | 0.43008 (19) | 0.74717 (15) | 0.0293 (2) | |
S | 0.69724 (4) | 0.72895 (4) | 1.24802 (4) | 0.01654 (5) | |
O1 | 0.81539 (17) | 0.55801 (17) | 1.34097 (15) | 0.02945 (19) | |
O2 | 0.49364 (16) | 0.76868 (19) | 1.38281 (14) | 0.0302 (2) | |
O3 | 0.81079 (17) | 0.89591 (15) | 1.18806 (15) | 0.02517 (18) | |
O4 | 0.66952 (18) | 0.69978 (16) | 1.06591 (13) | 0.0285 (2) | |
N | 0.83624 (18) | 0.99858 (18) | 0.75717 (15) | 0.02352 (18) | |
H0A | 0.7789 | 0.9054 | 0.8533 | 0.035* | |
H0B | 0.7386 | 1.0923 | 0.7270 | 0.035* | |
H0C | 0.9219 | 1.0448 | 0.7964 | 0.035* | |
C | 0.9515 (2) | 0.92081 (19) | 0.58209 (17) | 0.0226 (2) | |
H1D | 0.8591 | 0.8685 | 0.5400 | 0.027* | |
H1E | 1.0575 | 0.8180 | 0.6145 | 0.027* | |
H21 | 0.765 (3) | 0.456 (4) | 0.633 (2) | 0.037 (6)* | |
H12 | 0.661 (4) | 0.140 (3) | 1.205 (4) | 0.066 (9)* | |
H11 | 0.561 (4) | 0.235 (4) | 1.347 (2) | 0.045 (7)* | |
H22 | 0.896 (3) | 0.439 (4) | 0.740 (3) | 0.044 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.02244 (6) | 0.01866 (6) | 0.01811 (6) | −0.00551 (4) | −0.00646 (4) | −0.00462 (4) |
OW1 | 0.0878 (12) | 0.0283 (6) | 0.0277 (5) | 0.0176 (7) | −0.0281 (6) | −0.0090 (4) |
OW2 | 0.0206 (4) | 0.0431 (6) | 0.0245 (4) | −0.0046 (4) | −0.0047 (3) | −0.0096 (4) |
S | 0.01696 (11) | 0.01998 (12) | 0.01439 (10) | −0.00478 (9) | −0.00561 (8) | −0.00337 (8) |
O1 | 0.0256 (5) | 0.0265 (5) | 0.0308 (4) | −0.0015 (4) | −0.0096 (4) | 0.0031 (4) |
O2 | 0.0200 (4) | 0.0437 (6) | 0.0221 (4) | −0.0006 (4) | −0.0016 (3) | −0.0069 (4) |
O3 | 0.0289 (5) | 0.0231 (4) | 0.0292 (4) | −0.0102 (4) | −0.0118 (3) | −0.0056 (3) |
O4 | 0.0410 (6) | 0.0350 (5) | 0.0168 (3) | −0.0214 (5) | −0.0087 (3) | −0.0045 (3) |
N | 0.0244 (5) | 0.0274 (5) | 0.0175 (4) | −0.0054 (4) | −0.0040 (3) | −0.0036 (3) |
C | 0.0275 (5) | 0.0220 (5) | 0.0178 (4) | −0.0080 (4) | −0.0036 (4) | −0.0032 (4) |
Cd—OW1i | 2.2511 (12) | S—O2 | 1.4708 (10) |
Cd—OW1 | 2.2511 (12) | S—O3 | 1.4770 (10) |
Cd—O4 | 2.2789 (9) | S—O4 | 1.4884 (8) |
Cd—O4i | 2.2789 (9) | N—C | 1.4803 (16) |
Cd—OW2i | 2.2887 (10) | N—H0A | 0.8900 |
Cd—OW2 | 2.2887 (10) | N—H0B | 0.8900 |
OW1—H12 | 0.846 (16) | N—H0C | 0.8900 |
OW1—H11 | 0.833 (15) | C—Cii | 1.514 (2) |
OW2—H21 | 0.833 (15) | C—H1D | 0.9700 |
OW2—H22 | 0.842 (15) | C—H1E | 0.9700 |
S—O1 | 1.4669 (11) | ||
OW1i—Cd—OW1 | 180.0 | H21—OW2—H22 | 107.2 (19) |
OW1i—Cd—O4 | 85.76 (5) | O1—S—O2 | 110.44 (7) |
OW1—Cd—O4 | 94.24 (5) | O1—S—O3 | 110.09 (7) |
OW1i—Cd—O4i | 94.24 (5) | O2—S—O3 | 110.47 (7) |
OW1—Cd—O4i | 85.76 (5) | O1—S—O4 | 110.31 (7) |
O4—Cd—O4i | 180.0 | O2—S—O4 | 108.81 (6) |
OW1i—Cd—OW2i | 95.02 (5) | O3—S—O4 | 106.63 (6) |
OW1—Cd—OW2i | 84.98 (5) | S—O4—Cd | 134.68 (6) |
O4—Cd—OW2i | 87.96 (4) | C—N—H0A | 109.5 |
O4i—Cd—OW2i | 92.04 (4) | C—N—H0B | 109.5 |
OW1i—Cd—OW2 | 84.98 (5) | H0A—N—H0B | 109.5 |
OW1—Cd—OW2 | 95.02 (5) | C—N—H0C | 109.5 |
O4—Cd—OW2 | 92.04 (4) | H0A—N—H0C | 109.5 |
O4i—Cd—OW2 | 87.96 (4) | H0B—N—H0C | 109.5 |
OW2i—Cd—OW2 | 180.000 (1) | N—C—Cii | 109.62 (13) |
Cd—OW1—H12 | 127.0 (18) | N—C—H1D | 109.7 |
Cd—OW1—H11 | 127.6 (18) | Cii—C—H1D | 109.7 |
H12—OW1—H11 | 105 (2) | N—C—H1E | 109.7 |
Cd—OW2—H21 | 121.2 (16) | Cii—C—H1E | 109.7 |
Cd—OW2—H22 | 123.0 (15) | H1D—C—H1E | 108.2 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···O4 | 0.89 | 1.93 | 2.8155 (15) | 177 |
N—H0B···O2iii | 0.89 | 1.99 | 2.8378 (16) | 160 |
N—H0C···O3iv | 0.89 | 2.03 | 2.8767 (15) | 160 |
OW1—H11···O2v | 0.83 (2) | 1.90 (2) | 2.7342 (15) | 176 (3) |
OW1—H12···O3vi | 0.85 (2) | 1.89 (2) | 2.7293 (17) | 173 (3) |
OW2—H21···O1vii | 0.83 (2) | 2.01 (2) | 2.8177 (14) | 163 (2) |
OW2—H22···O1viii | 0.84 (2) | 1.89 (2) | 2.7150 (15) | 165 (2) |
Symmetry codes: (iii) −x+1, −y+2, −z+2; (iv) −x+2, −y+2, −z+2; (v) −x+1, −y+1, −z+3; (vi) x, y−1, z; (vii) x, y, z−1; (viii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C2H10N2)[Cd(SO4)2(H2O)4] |
Mr | 438.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.9114 (2), 7.3056 (2), 7.3629 (1) |
α, β, γ (°) | 74.013 (2), 71.731 (1), 78.043 (1) |
V (Å3) | 336.39 (1) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.99 |
Crystal size (mm) | 0.12 × 0.11 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.817, 0.885 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8732, 4684, 4352 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.945 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.070, 1.04 |
No. of reflections | 4684 |
No. of parameters | 105 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.90, −1.49 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Berndt, 1999), WinGX (Farrugia, 1999).
Cd—OW1i | 2.2511 (12) | Cd—O4i | 2.2789 (9) |
Cd—OW1 | 2.2511 (12) | Cd—OW2i | 2.2887 (10) |
Cd—O4 | 2.2789 (9) | Cd—OW2 | 2.2887 (10) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···O4 | 0.89 | 1.93 | 2.8155 (15) | 176.7 |
N—H0B···O2ii | 0.89 | 1.99 | 2.8378 (16) | 159.5 |
N—H0C···O3iii | 0.89 | 2.03 | 2.8767 (15) | 159.5 |
OW1—H11···O2iv | 0.833 (15) | 1.902 (15) | 2.7342 (15) | 176 (3) |
OW1—H12···O3v | 0.846 (16) | 1.887 (17) | 2.7293 (17) | 173 (3) |
OW2—H21···O1vi | 0.833 (15) | 2.012 (17) | 2.8177 (14) | 163 (2) |
OW2—H22···O1vii | 0.842 (15) | 1.894 (17) | 2.7150 (15) | 165 (2) |
Symmetry codes: (ii) −x+1, −y+2, −z+2; (iii) −x+2, −y+2, −z+2; (iv) −x+1, −y+1, −z+3; (v) x, y−1, z; (vi) x, y, z−1; (vii) −x+2, −y+1, −z+2. |
The chemistry of organic-inorganic hybrid materials has received increasing attention over the last few years, mainly with the idea of using amines as templates and associating transition metals. A great interest has been shown in some organically templated metal sulfate because of their open-framework structure and ferroelastic and ferroelectric propreties. We note also that a previous work of synthesis and characterization of mixed metal sulfates and amines, leading to many important physical properties, has been realized in our laboratory (Rekik et al., 2005; Naïli, et al., 2006; Rekik et al., 2007; Yahyaoui et al., 2007; Rekik et al., 2008; Rekik et al., 2009a). In the course of our investigations on new sulfate materials having interesting properties, we report here the chemical preparation and the structural characterization of a new ethylenediammonium cadmium (II) teraaquadisulfato, [NH3(CH2)2NH3][Cd(SO4)2(H2O)4]. The title compound is isostructural with the manganese, iron, cobalt and magnesium related phases (Chaabouni et al., 1996; Held, 2003; Rekik et al., 2008; Rekik et al., 2009b). As it can be seen in figure 1, the crystal structure shows an alternate stacking of inorganic layers of tetraaquabis(sulfato-O)cadmium anions, [Cd(SO4)2(H2O)4]2-, and organic layers of [NH3(CH2)2NH3]2+ cations along the crystallographic b axis. Anions and cations are linked together through N—H···O hydrogen bonds to form a three-dimensional network. The asymmetric unit (Fig. 2) of the title compound contains only one cadmium atom located at a symmetry centre, only one sulfate tetrahedron and ethylendiammonium cation lying about inversion centre. The Cd(II) central atom is octahedrally coordinated by one oxygen atom of sulfate group, two water molecules and the corresponding centrosymmetrically located atoms. Each octahedron around Cd shares two oxygen atoms with two sulfate groups to form trimeric units. These latest are stabilized and linked via OW—H···O hydrogen bonds giving rise to a three-dimensional inorganic framework delimiting tunnels along the three crystallographic axes. The negative charge of the inorganic part is compensated by ethylediammonium cations which are located on inversion centres in the inorganic framework cavities. The structure cohesion and stability are assured by two types of hydrogen bonds, OW—H···O and N—H···O.