Crystal structure of CdSO4(H2O): a redetermination

Theppitak, C.; Chainok, K.

doi:10.1107/S2056989015016904

inorganic compounds

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Crystal structure of CdSO₄(H₂O): a redetermination

Chatphorn Theppitak ^a and Kittipong Chainok ^b ^*

^aDepartment 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

Edited by M. Weil, Vienna University of Technology, Austria (Received 31 August 2015; accepted 9 September 2015; online 17 September 2015)

The crystal structure of the title compound, cadmium sulfate monohydrate or poly[(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.

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

CdSO₄(H₂O)
M_r = 226.48
Monoclinic, P 2₁ /c
a = 7.6195 (3) Å
b = 7.4517 (3) Å
c = 8.1457 (3) Å
β = 122.244 (1)°
V = 391.17 (3) Å³
Z = 4
Mo Kα radiation
μ = 6.01 mm⁻¹
T = 296 K
0.26 × 0.22 × 0.22 mm

2.2. Data collection

Bruker APEXII D8 QUEST CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ) T_min = 0.701, T_max = 0.746
17459 measured reflections
1004 independent reflections
958 reflections with I > 2σ(I)
R_int = 0.023

2.3. Refinement

R[F² > 2σ(F²)] = 0.012
wR(F²) = 0.026
S = 1.18
1004 reflections
72 parameters
2 restraints
All H-atom parameters refined
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O3ⁱ	0.82 (2)	1.88 (2)	2.6958 (17)	170 (3)
O5—H5B⋯O2ⁱⁱ	0.86 (2)	1.90 (2)	2.7530 (17)	173 (2)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z.

Table 2
Comparison of bond lengths (Å) in the current and the previous (Bregeault & Herpin, 1970) refinement of cadmium sulfate monohydrate

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 + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) −x, −y + 1, −z; (iii) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT; method used to solve structure: coordinates taken from previous refinement; 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

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015016904/wm5211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016904/wm5211Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016904/wm5211Isup3.cdx

checkCIF report

Synthesis and crystallization top

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.

Refinement top

The same cell setting and atom numbering scheme as in the previous refinement (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.

Related literature top

For the previous report on the structure of the title compound, see: Bregeault & Herpin (1970).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: coordinates taken from previous refinement; 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).

Figures top

	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.

Poly[(µ₂-aqua)(µ₄-sulfato)cadmium] top

Crystal data top

CdSO₄(H₂O)	F(000) = 424
M_r = 226.48	D_x = 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

Data collection top

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	R_int = 0.023
Detector resolution: 10.5 pixels mm^-1	θ_max = 28.7°, θ_min = 3.2°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −10→10
T_min = 0.701, T_max = 0.746	l = −10→10
17459 measured reflections

Refinement top

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(F_o²) + (0.0107P)² + 0.2955P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.001
1004 reflections	Δρ_max = 0.28 e Å⁻³
72 parameters	Δρ_min = −0.33 e Å⁻³
2 restraints

Crystal data top

CdSO₄(H₂O)	V = 391.17 (3) Å³
M_r = 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)°

Data collection top

Bruker APEXII D8 QUEST CMOS diffractometer	1004 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	958 reflections with I > 2σ(I)
T_min = 0.701, T_max = 0.746	R_int = 0.023
17459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.012	2 restraints
wR(F²) = 0.026	All H-atom parameters refined
S = 1.18	Δρ_max = 0.28 e Å⁻³
1004 reflections	Δρ_min = −0.33 e Å⁻³
72 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—Cd1^iv	2.2417 (12)
Cd1—O4ⁱⁱⁱ	2.3112 (12)	O2—Cd1ⁱⁱ	2.2530 (13)
Cd1—O5ⁱ	2.3210 (12)	O4—Cd1^v	2.3112 (12)
Cd1—O5	2.4024 (12)	O5—Cd1^iv	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—Cd1^iv	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—Cd1^v	140.91 (8)
O3—Cd1—O4ⁱⁱⁱ	86.05 (4)	Cd1^iv—O5—Cd1	119.27 (5)
O3—Cd1—O5	89.80 (4)	Cd1^iv—O5—H5A	109.7 (18)
O3—Cd1—O5ⁱ	87.54 (4)	Cd1—O5—H5A	99.9 (18)
O4ⁱⁱⁱ—Cd1—O5ⁱ	78.31 (4)	Cd1^iv—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—Cd1^iv	−54.81 (11)
O1—S1—O3—Cd1	−23.82 (12)	O3—S1—O2—Cd1ⁱⁱ	−116.29 (8)
O1—S1—O4—Cd1^v	−135.57 (12)	O3—S1—O4—Cd1^v	−13.61 (15)
O2—S1—O1—Cd1^iv	−173.39 (9)	O4—S1—O1—Cd1^iv	66.74 (12)
O2—S1—O3—Cd1	93.01 (11)	O4—S1—O2—Cd1ⁱⁱ	124.30 (8)
O2—S1—O4—Cd1^v	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.

Hydrogen-bond geometry (Å, º) top

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···O2^vi	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.

Hydrogen-bond geometry (Å, º) top

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.

Comparison of bond lengths (Å) in the current and the previous (Bregeault & Herpin, 1970) refinement of cadmium sulfate monohydrate top

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

Bregeault, J. M. & Herpin, P. (1970). Bull. Soc. Fr. Mineral. Cristallogr. 93, 37–42. CAS Google Scholar
Bruker (2014). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages i8-i9

doi:10.1107/S2056989015016904

Open

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