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Acta Cryst. (2007). E63, m2516    [ doi:10.1107/S1600536807043504 ]

Bis(benzylammonium) tetraaqua[bis(sulfato)cadmate(II)]

M. M. Amini, G. S. Mohammadnezhad and H. R. Khavasi

Abstract top

In the crystal structure of the title compound, (C7H7NH3)2[Cd(SO4)2(H2O)4], the Cd atom of the complex anion is located on a center of inversion and exhibits a slightly distorted octahedral coordination by six O atoms which belong to four water molecules and two sulfate ligands. Intermolecular hydrogen bonding between the cations and the anions consolidates the monomeric units into a three-dimensional network structure. The title compound is isotypic with its CuII and MnII analogues.

Comment top

Tutton's salts with general formula MI2MII(SO4)2.6H2O, where MI is a monovalent metal or ammonium, and MII is a divalent transition metal, are a well know class of compounds (Mahadevan Pillai et al., 1997). Replacing ammonium with alkylammonium cations leads to different structures. In this communication we report on the crystal structure of the title compound, (I), where the ammonium cations are replaced with benzylammonium.

The molecular geometry and atom labelling of (I) are shown in Fig. 1. In the crystal structure, the Cd atom is located on a centre of inversion and shows a slightly distorted octahedral coordination of oxygen atoms belonging to four water molecules and to two sulfate ligands. Intermolecular hydrogen bonding between the complex anion and the cation leads to a formation of a tightly bonded 3-D network structure. The crystal structure of (I) is isotypic with the CuII (Rademeyer, 2004) and the MnII analogue (Naumov et al., 2005).

Related literature top

The formula of the title compound resembles the general formula of Tutton's salts, MI2MII(SO4)2.6H2O (Mahadevan Pillai et al., 1997), but with only four water molecules and benzylammonium instead of ammonium. For the isotypic Cu and Mn analogues, see Rademeyer (2004) and Naumov et al. (2005), respectively. The preparation of the title compound was described by Jordanovska et al. (2000).

Experimental top

(I) was crystallized as described previously (Jordanovska et al., 2000) by evaporation of an aqueous mixture of Cd(II) sulfate and benzylammonium sulfate in the molar ratio 1:2 at room temperature and in the presence of sulfuric acid. Suitable colorless crystals with block-like habit were obtained by slow evaporation.

Refinement top

The H atoms were located in a difference Fourier map and were refined freely.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The cation and anion of (I), displayed at the 30% probability level. [Symmetry operator: i) −x + 2, −y + 2, −z]. H atoms are given as spheres of arbitrary radius.
Bis(benzylammonium) tetraaqua[bis(sulfato)cadmate(II)] top
Crystal data top
(C7H10N)2[Cd(SO4)2(H2O)4]Z = 1
Mr = 592.93F000 = 302
Triclinic, P1Dx = 1.729 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.6361 (14) ÅCell parameters from 2000 reflections
b = 8.1378 (18) Åθ = 2.6–28.9º
c = 11.087 (3) ŵ = 1.20 mm−1
α = 81.246 (18)ºT = 120 (2) K
β = 80.320 (18)ºBlock, colorless
γ = 76.302 (18)º0.40 × 0.35 × 0.18 mm
V = 569.5 (2) Å3
Data collection top
Stoe IPDS II
diffractometer		Rint = 0.034
ω–scansθmax = 27.9º
Absorption correction: numerical
[X-RED and X-SHAPE (Stoe & Cie, 2005)]		θmin = 2.6º
Tmin = 0.620, Tmax = 0.840h = −8→8
5164 measured reflectionsk = −9→10
2502 independent reflectionsl = −13→14
2498 reflections with I > 2σ(I)
Refinement top
Refinement on F2All H-atom parameters refined
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0279P)2 + 0.2838P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.020(Δ/σ)max = 0.011
wR(F2) = 0.052Δρmax = 0.45 e Å−3
S = 1.09Δρmin = −0.55 e Å−3
2502 reflectionsExtinction correction: none
198 parameters
Crystal data top
(C7H10N)2[Cd(SO4)2(H2O)4]γ = 76.302 (18)º
Mr = 592.93V = 569.5 (2) Å3
Triclinic, P1Z = 1
a = 6.6361 (14) ÅMo Kα
b = 8.1378 (18) ŵ = 1.20 mm−1
c = 11.087 (3) ÅT = 120 (2) K
α = 81.246 (18)º0.40 × 0.35 × 0.18 mm
β = 80.320 (18)º
Data collection top
Stoe IPDS II
diffractometer		2502 independent reflections
Absorption correction: numerical
[X-RED and X-SHAPE (Stoe & Cie, 2005)]		2498 reflections with I > 2σ(I)
Tmin = 0.620, Tmax = 0.840Rint = 0.034
5164 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.020198 parameters
wR(F2) = 0.052All H-atom parameters refined
S = 1.09Δρmax = 0.45 e Å−3
2502 reflectionsΔρmin = −0.55 e Å−3
Special details top

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
xyzUiso*/Ueq
Cd11100.01113 (7)
C10.3326 (3)0.5167 (2)−0.30551 (14)0.0207 (3)
H1A0.479 (4)0.460 (3)−0.314 (2)0.026 (5)*
H1B0.237 (4)0.434 (3)−0.291 (2)0.026 (6)*
C20.2858 (3)0.64749 (19)−0.41469 (13)0.0183 (3)
C30.4280 (3)0.7478 (2)−0.46858 (14)0.0218 (3)
H30.556 (4)0.741 (3)−0.437 (2)0.034 (7)*
C40.3845 (3)0.8656 (2)−0.57095 (15)0.0267 (4)
H40.488 (4)0.929 (3)−0.609 (2)0.032 (6)*
C50.2018 (4)0.8822 (2)−0.62017 (15)0.0298 (4)
H50.174 (5)0.962 (4)−0.687 (3)0.049 (8)*
C60.0586 (3)0.7838 (3)−0.56597 (17)0.0322 (4)
H6−0.073 (5)0.794 (4)−0.605 (3)0.042 (7)*
C70.1004 (3)0.6673 (2)−0.46258 (16)0.0257 (3)
H70.003 (4)0.599 (3)−0.424 (2)0.037 (7)*
N10.2975 (2)0.59854 (16)−0.18991 (11)0.0142 (2)
H1C0.319 (4)0.523 (3)−0.136 (2)0.029 (6)*
H1D0.172 (4)0.667 (3)−0.179 (2)0.024 (5)*
H1E0.394 (4)0.665 (3)−0.193 (2)0.028 (6)*
S10.74925 (5)0.71887 (4)−0.10746 (3)0.01189 (8)
O1W1.22112 (19)0.76313 (15)0.06889 (12)0.0221 (2)
H1W1.351 (5)0.743 (4)0.056 (2)0.035 (7)*
H2W1.195 (5)0.665 (4)0.096 (2)0.041 (7)*
O2W1.25772 (18)1.06754 (15)−0.14851 (10)0.0184 (2)
H3W1.296 (4)1.136 (4)−0.119 (2)0.035 (7)*
H4W1.372 (5)0.988 (4)−0.161 (2)0.036 (7)*
O30.90400 (16)0.82761 (13)−0.11968 (9)0.01422 (19)
O40.85681 (18)0.55127 (14)−0.14329 (11)0.0212 (2)
O50.58598 (18)0.79984 (14)−0.18596 (10)0.0169 (2)
O60.64769 (17)0.70174 (14)0.02367 (9)0.0166 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.00982 (9)0.00915 (8)0.01465 (9)−0.00280 (5)−0.00174 (5)−0.00085 (5)
C10.0318 (9)0.0134 (7)0.0165 (7)−0.0041 (6)−0.0032 (6)−0.0017 (5)
C20.0272 (8)0.0137 (6)0.0142 (6)−0.0048 (6)−0.0021 (5)−0.0023 (5)
C30.0273 (8)0.0212 (7)0.0176 (7)−0.0077 (6)−0.0013 (6)−0.0027 (6)
C40.0413 (11)0.0203 (8)0.0185 (7)−0.0116 (8)0.0014 (7)−0.0005 (6)
C50.0511 (12)0.0194 (8)0.0170 (7)−0.0040 (8)−0.0082 (7)0.0022 (6)
C60.0389 (10)0.0311 (9)0.0281 (9)−0.0059 (8)−0.0154 (8)0.0005 (7)
C70.0315 (9)0.0243 (8)0.0241 (7)−0.0118 (7)−0.0069 (7)0.0009 (6)
N10.0138 (6)0.0141 (6)0.0146 (5)−0.0041 (5)−0.0023 (4)0.0006 (4)
S10.01048 (16)0.00978 (15)0.01586 (16)−0.00383 (12)−0.00262 (12)0.00054 (11)
O1W0.0127 (5)0.0132 (5)0.0374 (6)−0.0028 (4)−0.0045 (4)0.0070 (4)
O2W0.0158 (5)0.0188 (5)0.0204 (5)−0.0060 (4)0.0008 (4)−0.0019 (4)
O30.0130 (5)0.0143 (5)0.0171 (5)−0.0071 (4)−0.0018 (4)−0.0010 (4)
O40.0193 (5)0.0106 (5)0.0332 (6)−0.0040 (4)0.0004 (4)−0.0037 (4)
O50.0146 (5)0.0184 (5)0.0189 (5)−0.0048 (4)−0.0062 (4)0.0009 (4)
O60.0138 (5)0.0188 (5)0.0166 (5)−0.0063 (4)−0.0014 (4)0.0034 (4)
Geometric parameters (Å, °) top
Cd1—O1Wi2.2453 (13)C5—C61.388 (3)
Cd1—O1W2.2453 (13)C5—H50.92 (3)
Cd1—O2Wi2.2718 (12)C6—C71.393 (3)
Cd1—O2W2.2718 (12)C6—H61.02 (3)
Cd1—O3i2.3257 (11)C7—H70.96 (3)
Cd1—O32.3257 (11)N1—H1C0.80 (3)
C1—N11.4922 (19)N1—H1D0.89 (3)
C1—C21.507 (2)N1—H1E0.92 (3)
C1—H1A0.97 (3)S1—O41.4615 (12)
C1—H1B1.01 (2)S1—O51.4731 (12)
C2—C71.386 (2)S1—O31.4843 (10)
C2—C31.393 (2)S1—O61.4968 (11)
C3—C41.392 (2)O1W—H1W0.83 (3)
C3—H30.95 (3)O1W—H2W0.85 (3)
C4—C51.382 (3)O2W—H3W0.79 (3)
C4—H40.96 (3)O2W—H4W0.88 (3)
O1Wi—Cd1—O1W180.00 (6)C3—C4—H4118.3 (15)
O1Wi—Cd1—O2Wi90.41 (5)C4—C5—C6120.02 (16)
O1W—Cd1—O2Wi89.59 (5)C4—C5—H5119 (2)
O1Wi—Cd1—O2W89.59 (5)C6—C5—H5121 (2)
O1W—Cd1—O2W90.41 (5)C5—C6—C7119.90 (18)
O2Wi—Cd1—O2W180.00 (6)C5—C6—H6119.3 (17)
O1Wi—Cd1—O3i85.87 (5)C7—C6—H6120.8 (17)
O1W—Cd1—O3i94.13 (5)C2—C7—C6120.24 (17)
O2Wi—Cd1—O3i93.16 (4)C2—C7—H7118.6 (16)
O2W—Cd1—O3i86.84 (4)C6—C7—H7121.1 (16)
O1Wi—Cd1—O394.13 (5)C1—N1—H1C106.3 (18)
O1W—Cd1—O385.87 (5)C1—N1—H1D111.8 (14)
O2Wi—Cd1—O386.84 (4)H1C—N1—H1D114 (2)
O2W—Cd1—O393.16 (4)C1—N1—H1E110.1 (15)
O3i—Cd1—O3180.0000 (10)H1C—N1—H1E108 (2)
N1—C1—C2111.17 (13)H1D—N1—H1E107 (2)
N1—C1—H1A104.4 (14)O4—S1—O5110.57 (7)
C2—C1—H1A111.0 (14)O4—S1—O3109.17 (7)
N1—C1—H1B105.9 (13)O5—S1—O3109.64 (6)
C2—C1—H1B111.5 (13)O4—S1—O6110.00 (7)
H1A—C1—H1B113 (2)O5—S1—O6108.46 (7)
C7—C2—C3119.64 (15)O3—S1—O6108.97 (6)
C7—C2—C1119.73 (15)Cd1—O1W—H1W127 (2)
C3—C2—C1120.63 (15)Cd1—O1W—H2W128 (2)
C4—C3—C2119.93 (16)H1W—O1W—H2W103 (3)
C4—C3—H3117.5 (16)Cd1—O2W—H3W102.1 (19)
C2—C3—H3122.5 (16)Cd1—O2W—H4W117.0 (18)
C5—C4—C3120.25 (16)H3W—O2W—H4W103 (3)
C5—C4—H4121.3 (15)S1—O3—Cd1137.75 (6)
N1—C1—C2—C7−103.32 (17)C5—C6—C7—C2−0.9 (3)
N1—C1—C2—C377.17 (19)O4—S1—O3—Cd1−129.45 (9)
C7—C2—C3—C4−0.8 (2)O5—S1—O3—Cd1109.29 (10)
C1—C2—C3—C4178.68 (15)O6—S1—O3—Cd1−9.29 (11)
C2—C3—C4—C5−0.7 (3)O1Wi—Cd1—O3—S1−91.15 (10)
C3—C4—C5—C61.4 (3)O1W—Cd1—O3—S188.85 (10)
C4—C5—C6—C7−0.6 (3)O2Wi—Cd1—O3—S1−0.96 (9)
C3—C2—C7—C61.6 (3)O2W—Cd1—O3—S1179.04 (9)
C1—C2—C7—C6−177.88 (17)O3i—Cd1—O3—S112E1(10)
Symmetry codes: (i) −x+2, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O6ii0.79 (2)2.04 (2)2.817 (2)167 (3)
N1—H1D···O3iii0.89 (3)2.02 (3)2.890 (2)168 (2)
N1—H1D···O4iii0.89 (3)2.44 (3)2.990 (2)120 (3)
N1—H1E···O50.93 (3)1.89 (3)2.808 (2)175 (3)
O1W—H1W···O6iv0.83 (3)1.90 (3)2.728 (2)179 (3)
O1W—H2W···O4v0.86 (3)1.85 (3)2.708 (2)176 (3)
O2W—H3W···O6i0.80 (3)1.95 (3)2.734 (2)170 (3)
O2W—H4W···O5iv0.88 (3)1.85 (3)2.718 (2)172 (3)
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+2, −y+1, −z; (i) −x+2, −y+2, −z.
Selected geometric parameters (Å) top
Cd1—O1W2.2453 (13)S1—O51.4731 (12)
Cd1—O2W2.2718 (12)S1—O31.4843 (10)
Cd1—O32.3257 (11)S1—O61.4968 (11)
S1—O41.4615 (12)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O6i0.79 (2)2.04 (2)2.817 (2)167 (3)
N1—H1D···O3ii0.89 (3)2.02 (3)2.890 (2)168 (2)
N1—H1D···O4ii0.89 (3)2.44 (3)2.990 (2)120 (3)
N1—H1E···O50.93 (3)1.89 (3)2.808 (2)175 (3)
O1W—H1W···O6iii0.83 (3)1.90 (3)2.728 (2)179 (3)
O1W—H2W···O4iv0.86 (3)1.85 (3)2.708 (2)176 (3)
O2W—H3W···O6v0.80 (3)1.95 (3)2.734 (2)170 (3)
O2W—H4W···O5iii0.88 (3)1.85 (3)2.718 (2)172 (3)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+2, −y+1, −z; (v) −x+2, −y+2, −z.
Acknowledgements top

The authors acknowledge Shahid Beheshti University for financial support.

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Jordanovska, V., Boyanov, B. & Naumov, P. (2000). J. Therm. Anal. Calorim. 62, 267–275.

Mahadevan Pillai, V. P., Nayar, V. U. & Jordanovska, V. B. (1997). J. Solid State Chem. 133, 407–415.

Naumov, P., Jordanovska, V. & Ng, S. W. (2005). Acta Cryst. E61, m1970–m1971.

Rademeyer, M. (2004). Acta Cryst. E60, m993–m995.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Stoe & Cie (2005). X-AREA (Version 1.31), X-RED (Version 1.28b) and X-SHAPE (Version 2.05). Stoe & Cie, Darmstadt, Germany.