inorganic compounds
4(H2O): a redetermination
of CdSOaDepartment of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok, 65000, Thailand, and bDepartment of Physics, Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani, 12120, Thailand
*Correspondence e-mail: kc@tu.ac.th
The μ2-aqua)(μ4-sulfato)cadmium], was redetermined based on modern CMOS (complementary metal oxide silicon) data. In comparison with the previous study [Bregeault & Herpin (1970). Bull. Soc. Fr. Mineral. Cristallogr. 93, 37–42], all non-H atoms were refined with anisotropic displacement parameters and the hydrogen-bonding pattern unambiguously established due to location of the hydrogen atoms. In addition, a significant improvement in terms of precision and accuracy was achieved. In the crystal, the Cd2+ cation is coordinated by four O atoms of four sulfate anions and two O atoms of water molecules, forming a distorted octahedral trans-[CdO6] polyhedron. Each sulfate anion bridges four Cd2+ cations and each water molecule bridges two Cd2+ cations, leading to the formation of a three-dimensional framework, with Cd⋯Cd separations in the range 4.0757 (2)–6.4462 (3) Å. O—H⋯O hydrogen-bonding interactions of medium strength between the coordinating water molecules and sulfate anions consolidate the crystal packing.
of the title compound, cadmium sulfate monohydrate or poly[(Keywords: crystal structure; redetermination; cadmium sulfate monohydrate; hydrothermal synthesis; hydrogen bonding.
CCDC reference: 1423357
1. Related literature
For the previous report on the structure of the title compound, see: Bregeault & Herpin (1970).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2014); cell SAINT (Bruker, 2014); data reduction: SAINT; method used to solve structure: coordinates taken from previous program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 1423357
10.1107/S2056989015016904/wm5211sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016904/wm5211Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016904/wm5211Isup3.cdx
The title compound was obtained serendipitously. CdSO4·8/3H2O (0.256 g, 1 mmol) and 3,6-di-2-pyridyl-1,2,4,5-tetrazine (0.236 g, 1 mmol) dissolved in water (5 ml) were added to a 23 ml Teflon-lined autoclave and heated at 356 K for 5 days. The product was collected by filtration, washed with water and air-dried. Colourless block-shaped crystals of the title compound suitable for X-ray analysis were isolated.
The same cell setting and atom numbering scheme as in the previous
(Bregeault & Herpin, 1970) were used. Starting coordinates for the atoms were also taken from the previous model. Hydrogen atoms of the water molecules were located from difference Fourier maps and were refined with an O—H distance restraint of 0.85 (2) Å.Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: coordinates taken from previous program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).Fig. 1. The coordination sphere around the Cd2+ cation with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, 1/2 – y, 1/2 + z; (ii) –x, 1 – y, –z; (iii) 1 – x, -1/2 + y, 1/2 – z]. | |
Fig. 2. The three-dimensional framework structure of the title compound in a view along the b axis. Dashed lines indicate intermolecular O—H···O hydrogen-bonding interactions. |
CdSO4(H2O) | F(000) = 424 |
Mr = 226.48 | Dx = 3.846 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6195 (3) Å | Cell parameters from 9894 reflections |
b = 7.4517 (3) Å | θ = 3.2–30.5° |
c = 8.1457 (3) Å | µ = 6.01 mm−1 |
β = 122.244 (1)° | T = 296 K |
V = 391.17 (3) Å3 | Block, colourless |
Z = 4 | 0.26 × 0.22 × 0.22 mm |
Bruker APEXII D8 QUEST CMOS diffractometer | 1004 independent reflections |
Radiation source: microfocus sealed x-ray tube, Incoatec Iµus | 958 reflections with I > 2σ(I) |
GraphiteDouble Bounce Multilayer Mirror monochromator | Rint = 0.023 |
Detector resolution: 10.5 pixels mm-1 | θmax = 28.7°, θmin = 3.2° |
ω and φ scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −10→10 |
Tmin = 0.701, Tmax = 0.746 | l = −10→10 |
17459 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.012 | All H-atom parameters refined |
wR(F2) = 0.026 | w = 1/[σ2(Fo2) + (0.0107P)2 + 0.2955P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | (Δ/σ)max = 0.001 |
1004 reflections | Δρmax = 0.28 e Å−3 |
72 parameters | Δρmin = −0.33 e Å−3 |
2 restraints |
CdSO4(H2O) | V = 391.17 (3) Å3 |
Mr = 226.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6195 (3) Å | µ = 6.01 mm−1 |
b = 7.4517 (3) Å | T = 296 K |
c = 8.1457 (3) Å | 0.26 × 0.22 × 0.22 mm |
β = 122.244 (1)° |
Bruker APEXII D8 QUEST CMOS diffractometer | 1004 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 958 reflections with I > 2σ(I) |
Tmin = 0.701, Tmax = 0.746 | Rint = 0.023 |
17459 measured reflections |
R[F2 > 2σ(F2)] = 0.012 | 2 restraints |
wR(F2) = 0.026 | All H-atom parameters refined |
S = 1.18 | Δρmax = 0.28 e Å−3 |
1004 reflections | Δρmin = −0.33 e Å−3 |
72 parameters |
Experimental. SADABS was used for absorption correction. wR2(int) was 0.0449 before and 0.0357 after correction. The Ratio of minimum to maximum transmission is 0.9396. The λ/2 correction factor is 0.00150. |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.21887 (2) | 0.26013 (2) | 0.26053 (2) | 0.01330 (5) | |
S1 | 0.25524 (6) | 0.61729 (5) | 0.01217 (5) | 0.01018 (8) | |
O1 | 0.13754 (18) | 0.50022 (16) | −0.15811 (17) | 0.0183 (2) | |
O2 | 0.1103 (2) | 0.75977 (15) | −0.00480 (19) | 0.0169 (3) | |
O3 | 0.32756 (18) | 0.51255 (16) | 0.19211 (17) | 0.0168 (2) | |
O4 | 0.43393 (18) | 0.69973 (18) | 0.02148 (18) | 0.0184 (2) | |
O5 | 0.27603 (19) | 0.09752 (16) | 0.03844 (17) | 0.0140 (2) | |
H5A | 0.400 (3) | 0.074 (4) | 0.110 (3) | 0.038 (7)* | |
H5B | 0.216 (3) | −0.005 (2) | 0.016 (3) | 0.023 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01176 (7) | 0.01373 (7) | 0.01200 (7) | −0.00165 (4) | 0.00472 (5) | 0.00087 (4) |
S1 | 0.00809 (16) | 0.00898 (17) | 0.01063 (17) | 0.00001 (13) | 0.00310 (14) | 0.00041 (13) |
O1 | 0.0156 (6) | 0.0170 (6) | 0.0158 (6) | −0.0004 (5) | 0.0041 (5) | −0.0054 (5) |
O2 | 0.0122 (6) | 0.0134 (6) | 0.0206 (6) | 0.0027 (4) | 0.0058 (5) | −0.0018 (4) |
O3 | 0.0155 (6) | 0.0153 (6) | 0.0147 (5) | −0.0019 (5) | 0.0048 (5) | 0.0046 (4) |
O4 | 0.0101 (5) | 0.0224 (6) | 0.0198 (6) | −0.0022 (5) | 0.0061 (5) | 0.0047 (5) |
O5 | 0.0120 (5) | 0.0133 (5) | 0.0145 (5) | −0.0008 (4) | 0.0055 (5) | −0.0001 (4) |
Cd1—O1i | 2.2417 (12) | S1—O3 | 1.4831 (12) |
Cd1—O2ii | 2.2530 (13) | S1—O4 | 1.4584 (12) |
Cd1—O3 | 2.2421 (12) | O1—Cd1iv | 2.2417 (12) |
Cd1—O4iii | 2.3112 (12) | O2—Cd1ii | 2.2530 (13) |
Cd1—O5i | 2.3210 (12) | O4—Cd1v | 2.3112 (12) |
Cd1—O5 | 2.4024 (12) | O5—Cd1iv | 2.3211 (12) |
S1—O1 | 1.4703 (12) | O5—H5A | 0.822 (17) |
S1—O2 | 1.4845 (12) | O5—H5B | 0.859 (16) |
O1i—Cd1—O2ii | 82.50 (4) | O1—S1—O3 | 109.76 (7) |
O1i—Cd1—O3 | 175.24 (4) | O3—S1—O2 | 109.52 (8) |
O1i—Cd1—O4iii | 89.31 (5) | O4—S1—O1 | 112.43 (8) |
O1i—Cd1—O5i | 92.57 (4) | O4—S1—O2 | 109.35 (7) |
O1i—Cd1—O5 | 88.62 (4) | O4—S1—O3 | 109.03 (7) |
O2ii—Cd1—O4iii | 161.94 (4) | S1—O1—Cd1iv | 131.81 (7) |
O2ii—Cd1—O5 | 80.22 (4) | S1—O2—Cd1ii | 116.42 (7) |
O2ii—Cd1—O5i | 117.97 (4) | S1—O3—Cd1 | 134.06 (7) |
O3—Cd1—O2ii | 101.65 (4) | S1—O4—Cd1v | 140.91 (8) |
O3—Cd1—O4iii | 86.05 (4) | Cd1iv—O5—Cd1 | 119.27 (5) |
O3—Cd1—O5 | 89.80 (4) | Cd1iv—O5—H5A | 109.7 (18) |
O3—Cd1—O5i | 87.54 (4) | Cd1—O5—H5A | 99.9 (18) |
O4iii—Cd1—O5i | 78.31 (4) | Cd1iv—O5—H5B | 113.3 (14) |
O4iii—Cd1—O5 | 83.53 (4) | Cd1—O5—H5B | 108.6 (14) |
O5i—Cd1—O5 | 161.78 (6) | H5A—O5—H5B | 104 (2) |
O1—S1—O2 | 106.70 (7) | ||
O1—S1—O2—Cd1ii | 2.46 (10) | O3—S1—O1—Cd1iv | −54.81 (11) |
O1—S1—O3—Cd1 | −23.82 (12) | O3—S1—O2—Cd1ii | −116.29 (8) |
O1—S1—O4—Cd1v | −135.57 (12) | O3—S1—O4—Cd1v | −13.61 (15) |
O2—S1—O1—Cd1iv | −173.39 (9) | O4—S1—O1—Cd1iv | 66.74 (12) |
O2—S1—O3—Cd1 | 93.01 (11) | O4—S1—O2—Cd1ii | 124.30 (8) |
O2—S1—O4—Cd1v | 106.10 (13) | O4—S1—O3—Cd1 | −147.38 (10) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2; (v) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3iii | 0.82 (2) | 1.88 (2) | 2.6958 (17) | 170 (3) |
O5—H5B···O2vi | 0.86 (2) | 1.90 (2) | 2.7530 (17) | 173 (2) |
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (vi) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3i | 0.822 (17) | 1.883 (17) | 2.6958 (17) | 170 (3) |
O5—H5B···O2ii | 0.859 (16) | 1.899 (17) | 2.7530 (17) | 173 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z. |
For the previous refinement: a = 7.607, b = 7.541, c = 8.186 Å, β = 121.86° and reliability index R = 0.12. |
Bond | Current refinement | Previous refinement |
Cd1—O1i | 2.2417 (12) | 2.21 (5) |
Cd1—O2ii | 2.2530 (13) | 2.27 (3) |
Cd1—O3 | 2.2421 (12) | 2.36 (5) |
Cd1—O4iii | 2.3112 (12) | 2.33 (3) |
Cd1—O5i | 2.3210 (12) | 2.24 (3) |
Cd1—O5 | 2.4024 (12) | 2.33 (3) |
S1—O1 | 1.4703 (12) | 1.50 (4) |
S1—O2 | 1.4845 (12) | 1.62 (6) |
S1—O3 | 1.4831 (12) | 1.45 (3) |
S1—O4 | 1.4584 (12) | 1.42 (4) |
Symmetry codes: (i) x, -y+1/2, z+1/2; (ii) -x, -y+1, -z; (iii) -x+1, y-1/2, -z+1/2. |
Acknowledgements
The authors gratefully acknowledge the financial support provided by Thammasat University Research Fund under the TU Research Scholar.
References
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