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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043504/wm2138sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043504/wm2138Isup2.hkl
Contains datablock I

CCDC reference: 663587

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.020
  • wR factor = 0.052
  • Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 27.91 From the CIF: _diffrn_reflns_theta_full 27.91 From the CIF: _reflns_number_total 2502 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2730 Completeness (_total/calc) 91.65% PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 1800 Deg. PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 7 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cd1 - O2W .. 5.56 su PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 18 O3 -CD1 -O3 -S1 12.00 0.00 2.775 1.555 1.555 1.555 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C7 H10 N
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C14 H28 Cd1 N2 O12 S2 Atom count from _chemical_formula_moiety:C14 H20 N2 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 2.35
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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.

Structure description 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).

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).

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 = 592.93F(000) = 302
Triclinic, P1Dx = 1.729 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6361 (14) ÅCell parameters from 2000 reflections
b = 8.1378 (18) Åθ = 2.6–28.9°
c = 11.087 (3) ŵ = 1.20 mm1
α = 81.246 (18)°T = 120 K
β = 80.320 (18)°Block, colorless
γ = 76.302 (18)°0.40 × 0.35 × 0.18 mm
V = 569.5 (2) Å3
Data collection top
Stoe IPDS II
diffractometer
2498 reflections with I > 2σ(I)
ω–scansRint = 0.034
Absorption correction: numerical
[X-RED and X-SHAPE (Stoe & Cie, 2005)]
θmax = 27.9°, θmin = 2.6°
Tmin = 0.620, Tmax = 0.840h = 88
5164 measured reflectionsk = 910
2502 independent reflectionsl = 1314
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.020 w = 1/[σ2(Fo2) + (0.0279P)2 + 0.2838P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.052(Δ/σ)max = 0.011
S = 1.09Δρmax = 0.45 e Å3
2502 reflectionsΔρmin = 0.55 e Å3
198 parameters
Crystal data top
(C7H10N)2[Cd(SO4)2(H2O)4]γ = 76.302 (18)°
Mr = 592.93V = 569.5 (2) Å3
Triclinic, P1Z = 1
a = 6.6361 (14) ÅMo Kα radiation
b = 8.1378 (18) ŵ = 1.20 mm1
c = 11.087 (3) ÅT = 120 K
α = 81.246 (18)°0.40 × 0.35 × 0.18 mm
β = 80.320 (18)°
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)] = 0.0200 restraints
wR(F2) = 0.052All H-atom parameters refined
S = 1.09Δρmax = 0.45 e Å3
2502 reflectionsΔρmin = 0.55 e Å3
198 parameters
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)
H60.073 (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, º) 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—C7103.32 (17)C5—C6—C7—C20.9 (3)
N1—C1—C2—C377.17 (19)O4—S1—O3—Cd1129.45 (9)
C7—C2—C3—C40.8 (2)O5—S1—O3—Cd1109.29 (10)
C1—C2—C3—C4178.68 (15)O6—S1—O3—Cd19.29 (11)
C2—C3—C4—C50.7 (3)O1Wi—Cd1—O3—S191.15 (10)
C3—C4—C5—C61.4 (3)O1W—Cd1—O3—S188.85 (10)
C4—C5—C6—C70.6 (3)O2Wi—Cd1—O3—S10.96 (9)
C3—C2—C7—C61.6 (3)O2W—Cd1—O3—S1179.04 (9)
C1—C2—C7—C6177.88 (17)O3i—Cd1—O3—S112E1 (10)
Symmetry code: (i) x+2, y+2, z.
Hydrogen-bond geometry (Å, º) 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: (i) x+2, y+2, z; (ii) x+1, y+1, z; (iii) x1, y, z; (iv) x+1, y, z; (v) x+2, y+1, z.

Experimental details

Crystal data
Chemical formula(C7H10N)2[Cd(SO4)2(H2O)4]
Mr592.93
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)6.6361 (14), 8.1378 (18), 11.087 (3)
α, β, γ (°)81.246 (18), 80.320 (18), 76.302 (18)
V3)569.5 (2)
Z1
Radiation typeMo Kα
µ (mm1)1.20
Crystal size (mm)0.40 × 0.35 × 0.18
Data collection
DiffractometerStoe IPDS II
Absorption correctionNumerical
[X-RED and X-SHAPE (Stoe & Cie, 2005)]
Tmin, Tmax0.620, 0.840
No. of measured, independent and
observed [I > 2σ(I)] reflections
5164, 2502, 2498
Rint0.034
(sin θ/λ)max1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.052, 1.09
No. of reflections2502
No. of parameters198
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.45, 0.55

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (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, º) 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) x1, y, z; (iii) x+1, y, z; (iv) x+2, y+1, z; (v) x+2, y+2, z.
 

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