Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043504/wm2138sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043504/wm2138Isup2.hkl |
CCDC reference: 663587
(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.
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).
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).
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. |
(C7H10N)2[Cd(SO4)2(H2O)4] | Z = 1 |
Mr = 592.93 | F(000) = 302 |
Triclinic, P1 | Dx = 1.729 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6361 (14) Å | Cell parameters from 2000 reflections |
b = 8.1378 (18) Å | θ = 2.6–28.9° |
c = 11.087 (3) Å | µ = 1.20 mm−1 |
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 |
Stoe IPDS II diffractometer | 2498 reflections with I > 2σ(I) |
ω–scans | Rint = 0.034 |
Absorption correction: numerical [X-RED and X-SHAPE (Stoe & Cie, 2005)] | θmax = 27.9°, θmin = 2.6° |
Tmin = 0.620, Tmax = 0.840 | h = −8→8 |
5164 measured reflections | k = −9→10 |
2502 independent reflections | l = −13→14 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All 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 = 1.09 | Δρmax = 0.45 e Å−3 |
2502 reflections | Δρmin = −0.55 e Å−3 |
198 parameters |
(C7H10N)2[Cd(SO4)2(H2O)4] | γ = 76.302 (18)° |
Mr = 592.93 | V = 569.5 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.6361 (14) Å | Mo Kα radiation |
b = 8.1378 (18) Å | µ = 1.20 mm−1 |
c = 11.087 (3) Å | T = 120 K |
α = 81.246 (18)° | 0.40 × 0.35 × 0.18 mm |
β = 80.320 (18)° |
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 = 0.840 | Rint = 0.034 |
5164 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.052 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.45 e Å−3 |
2502 reflections | Δρmin = −0.55 e Å−3 |
198 parameters |
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 | 1 | 1 | 0 | 0.01113 (7) | |
C1 | 0.3326 (3) | 0.5167 (2) | −0.30551 (14) | 0.0207 (3) | |
H1A | 0.479 (4) | 0.460 (3) | −0.314 (2) | 0.026 (5)* | |
H1B | 0.237 (4) | 0.434 (3) | −0.291 (2) | 0.026 (6)* | |
C2 | 0.2858 (3) | 0.64749 (19) | −0.41469 (13) | 0.0183 (3) | |
C3 | 0.4280 (3) | 0.7478 (2) | −0.46858 (14) | 0.0218 (3) | |
H3 | 0.556 (4) | 0.741 (3) | −0.437 (2) | 0.034 (7)* | |
C4 | 0.3845 (3) | 0.8656 (2) | −0.57095 (15) | 0.0267 (4) | |
H4 | 0.488 (4) | 0.929 (3) | −0.609 (2) | 0.032 (6)* | |
C5 | 0.2018 (4) | 0.8822 (2) | −0.62017 (15) | 0.0298 (4) | |
H5 | 0.174 (5) | 0.962 (4) | −0.687 (3) | 0.049 (8)* | |
C6 | 0.0586 (3) | 0.7838 (3) | −0.56597 (17) | 0.0322 (4) | |
H6 | −0.073 (5) | 0.794 (4) | −0.605 (3) | 0.042 (7)* | |
C7 | 0.1004 (3) | 0.6673 (2) | −0.46258 (16) | 0.0257 (3) | |
H7 | 0.003 (4) | 0.599 (3) | −0.424 (2) | 0.037 (7)* | |
N1 | 0.2975 (2) | 0.59854 (16) | −0.18991 (11) | 0.0142 (2) | |
H1C | 0.319 (4) | 0.523 (3) | −0.136 (2) | 0.029 (6)* | |
H1D | 0.172 (4) | 0.667 (3) | −0.179 (2) | 0.024 (5)* | |
H1E | 0.394 (4) | 0.665 (3) | −0.193 (2) | 0.028 (6)* | |
S1 | 0.74925 (5) | 0.71887 (4) | −0.10746 (3) | 0.01189 (8) | |
O1W | 1.22112 (19) | 0.76313 (15) | 0.06889 (12) | 0.0221 (2) | |
H1W | 1.351 (5) | 0.743 (4) | 0.056 (2) | 0.035 (7)* | |
H2W | 1.195 (5) | 0.665 (4) | 0.096 (2) | 0.041 (7)* | |
O2W | 1.25772 (18) | 1.06754 (15) | −0.14851 (10) | 0.0184 (2) | |
H3W | 1.296 (4) | 1.136 (4) | −0.119 (2) | 0.035 (7)* | |
H4W | 1.372 (5) | 0.988 (4) | −0.161 (2) | 0.036 (7)* | |
O3 | 0.90400 (16) | 0.82761 (13) | −0.11968 (9) | 0.01422 (19) | |
O4 | 0.85681 (18) | 0.55127 (14) | −0.14329 (11) | 0.0212 (2) | |
O5 | 0.58598 (18) | 0.79984 (14) | −0.18596 (10) | 0.0169 (2) | |
O6 | 0.64769 (17) | 0.70174 (14) | 0.02367 (9) | 0.0166 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.00982 (9) | 0.00915 (8) | 0.01465 (9) | −0.00280 (5) | −0.00174 (5) | −0.00085 (5) |
C1 | 0.0318 (9) | 0.0134 (7) | 0.0165 (7) | −0.0041 (6) | −0.0032 (6) | −0.0017 (5) |
C2 | 0.0272 (8) | 0.0137 (6) | 0.0142 (6) | −0.0048 (6) | −0.0021 (5) | −0.0023 (5) |
C3 | 0.0273 (8) | 0.0212 (7) | 0.0176 (7) | −0.0077 (6) | −0.0013 (6) | −0.0027 (6) |
C4 | 0.0413 (11) | 0.0203 (8) | 0.0185 (7) | −0.0116 (8) | 0.0014 (7) | −0.0005 (6) |
C5 | 0.0511 (12) | 0.0194 (8) | 0.0170 (7) | −0.0040 (8) | −0.0082 (7) | 0.0022 (6) |
C6 | 0.0389 (10) | 0.0311 (9) | 0.0281 (9) | −0.0059 (8) | −0.0154 (8) | 0.0005 (7) |
C7 | 0.0315 (9) | 0.0243 (8) | 0.0241 (7) | −0.0118 (7) | −0.0069 (7) | 0.0009 (6) |
N1 | 0.0138 (6) | 0.0141 (6) | 0.0146 (5) | −0.0041 (5) | −0.0023 (4) | 0.0006 (4) |
S1 | 0.01048 (16) | 0.00978 (15) | 0.01586 (16) | −0.00383 (12) | −0.00262 (12) | 0.00054 (11) |
O1W | 0.0127 (5) | 0.0132 (5) | 0.0374 (6) | −0.0028 (4) | −0.0045 (4) | 0.0070 (4) |
O2W | 0.0158 (5) | 0.0188 (5) | 0.0204 (5) | −0.0060 (4) | 0.0008 (4) | −0.0019 (4) |
O3 | 0.0130 (5) | 0.0143 (5) | 0.0171 (5) | −0.0071 (4) | −0.0018 (4) | −0.0010 (4) |
O4 | 0.0193 (5) | 0.0106 (5) | 0.0332 (6) | −0.0040 (4) | 0.0004 (4) | −0.0037 (4) |
O5 | 0.0146 (5) | 0.0184 (5) | 0.0189 (5) | −0.0048 (4) | −0.0062 (4) | 0.0009 (4) |
O6 | 0.0138 (5) | 0.0188 (5) | 0.0166 (5) | −0.0063 (4) | −0.0014 (4) | 0.0034 (4) |
Cd1—O1Wi | 2.2453 (13) | C5—C6 | 1.388 (3) |
Cd1—O1W | 2.2453 (13) | C5—H5 | 0.92 (3) |
Cd1—O2Wi | 2.2718 (12) | C6—C7 | 1.393 (3) |
Cd1—O2W | 2.2718 (12) | C6—H6 | 1.02 (3) |
Cd1—O3i | 2.3257 (11) | C7—H7 | 0.96 (3) |
Cd1—O3 | 2.3257 (11) | N1—H1C | 0.80 (3) |
C1—N1 | 1.4922 (19) | N1—H1D | 0.89 (3) |
C1—C2 | 1.507 (2) | N1—H1E | 0.92 (3) |
C1—H1A | 0.97 (3) | S1—O4 | 1.4615 (12) |
C1—H1B | 1.01 (2) | S1—O5 | 1.4731 (12) |
C2—C7 | 1.386 (2) | S1—O3 | 1.4843 (10) |
C2—C3 | 1.393 (2) | S1—O6 | 1.4968 (11) |
C3—C4 | 1.392 (2) | O1W—H1W | 0.83 (3) |
C3—H3 | 0.95 (3) | O1W—H2W | 0.85 (3) |
C4—C5 | 1.382 (3) | O2W—H3W | 0.79 (3) |
C4—H4 | 0.96 (3) | O2W—H4W | 0.88 (3) |
O1Wi—Cd1—O1W | 180.00 (6) | C3—C4—H4 | 118.3 (15) |
O1Wi—Cd1—O2Wi | 90.41 (5) | C4—C5—C6 | 120.02 (16) |
O1W—Cd1—O2Wi | 89.59 (5) | C4—C5—H5 | 119 (2) |
O1Wi—Cd1—O2W | 89.59 (5) | C6—C5—H5 | 121 (2) |
O1W—Cd1—O2W | 90.41 (5) | C5—C6—C7 | 119.90 (18) |
O2Wi—Cd1—O2W | 180.00 (6) | C5—C6—H6 | 119.3 (17) |
O1Wi—Cd1—O3i | 85.87 (5) | C7—C6—H6 | 120.8 (17) |
O1W—Cd1—O3i | 94.13 (5) | C2—C7—C6 | 120.24 (17) |
O2Wi—Cd1—O3i | 93.16 (4) | C2—C7—H7 | 118.6 (16) |
O2W—Cd1—O3i | 86.84 (4) | C6—C7—H7 | 121.1 (16) |
O1Wi—Cd1—O3 | 94.13 (5) | C1—N1—H1C | 106.3 (18) |
O1W—Cd1—O3 | 85.87 (5) | C1—N1—H1D | 111.8 (14) |
O2Wi—Cd1—O3 | 86.84 (4) | H1C—N1—H1D | 114 (2) |
O2W—Cd1—O3 | 93.16 (4) | C1—N1—H1E | 110.1 (15) |
O3i—Cd1—O3 | 180.0000 (10) | H1C—N1—H1E | 108 (2) |
N1—C1—C2 | 111.17 (13) | H1D—N1—H1E | 107 (2) |
N1—C1—H1A | 104.4 (14) | O4—S1—O5 | 110.57 (7) |
C2—C1—H1A | 111.0 (14) | O4—S1—O3 | 109.17 (7) |
N1—C1—H1B | 105.9 (13) | O5—S1—O3 | 109.64 (6) |
C2—C1—H1B | 111.5 (13) | O4—S1—O6 | 110.00 (7) |
H1A—C1—H1B | 113 (2) | O5—S1—O6 | 108.46 (7) |
C7—C2—C3 | 119.64 (15) | O3—S1—O6 | 108.97 (6) |
C7—C2—C1 | 119.73 (15) | Cd1—O1W—H1W | 127 (2) |
C3—C2—C1 | 120.63 (15) | Cd1—O1W—H2W | 128 (2) |
C4—C3—C2 | 119.93 (16) | H1W—O1W—H2W | 103 (3) |
C4—C3—H3 | 117.5 (16) | Cd1—O2W—H3W | 102.1 (19) |
C2—C3—H3 | 122.5 (16) | Cd1—O2W—H4W | 117.0 (18) |
C5—C4—C3 | 120.25 (16) | H3W—O2W—H4W | 103 (3) |
C5—C4—H4 | 121.3 (15) | S1—O3—Cd1 | 137.75 (6) |
N1—C1—C2—C7 | −103.32 (17) | C5—C6—C7—C2 | −0.9 (3) |
N1—C1—C2—C3 | 77.17 (19) | O4—S1—O3—Cd1 | −129.45 (9) |
C7—C2—C3—C4 | −0.8 (2) | O5—S1—O3—Cd1 | 109.29 (10) |
C1—C2—C3—C4 | 178.68 (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—C6 | 1.4 (3) | O1W—Cd1—O3—S1 | 88.85 (10) |
C4—C5—C6—C7 | −0.6 (3) | O2Wi—Cd1—O3—S1 | −0.96 (9) |
C3—C2—C7—C6 | 1.6 (3) | O2W—Cd1—O3—S1 | 179.04 (9) |
C1—C2—C7—C6 | −177.88 (17) | O3i—Cd1—O3—S1 | 12E1 (10) |
Symmetry code: (i) −x+2, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O6ii | 0.79 (2) | 2.04 (2) | 2.817 (2) | 167 (3) |
N1—H1D···O3iii | 0.89 (3) | 2.02 (3) | 2.890 (2) | 168 (2) |
N1—H1D···O4iii | 0.89 (3) | 2.44 (3) | 2.990 (2) | 120 (3) |
N1—H1E···O5 | 0.93 (3) | 1.89 (3) | 2.808 (2) | 175 (3) |
O1W—H1W···O6iv | 0.83 (3) | 1.90 (3) | 2.728 (2) | 179 (3) |
O1W—H2W···O4v | 0.86 (3) | 1.85 (3) | 2.708 (2) | 176 (3) |
O2W—H3W···O6i | 0.80 (3) | 1.95 (3) | 2.734 (2) | 170 (3) |
O2W—H4W···O5iv | 0.88 (3) | 1.85 (3) | 2.718 (2) | 172 (3) |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+1, −z; (iii) x−1, 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] |
Mr | 592.93 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 569.5 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.20 |
Crystal size (mm) | 0.40 × 0.35 × 0.18 |
Data collection | |
Diffractometer | Stoe IPDS II |
Absorption correction | Numerical [X-RED and X-SHAPE (Stoe & Cie, 2005)] |
Tmin, Tmax | 0.620, 0.840 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5164, 2502, 2498 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.052, 1.09 |
No. of reflections | 2502 |
No. of parameters | 198 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
Cd1—O1W | 2.2453 (13) | S1—O5 | 1.4731 (12) |
Cd1—O2W | 2.2718 (12) | S1—O3 | 1.4843 (10) |
Cd1—O3 | 2.3257 (11) | S1—O6 | 1.4968 (11) |
S1—O4 | 1.4615 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O6i | 0.79 (2) | 2.04 (2) | 2.817 (2) | 167 (3) |
N1—H1D···O3ii | 0.89 (3) | 2.02 (3) | 2.890 (2) | 168 (2) |
N1—H1D···O4ii | 0.89 (3) | 2.44 (3) | 2.990 (2) | 120 (3) |
N1—H1E···O5 | 0.93 (3) | 1.89 (3) | 2.808 (2) | 175 (3) |
O1W—H1W···O6iii | 0.83 (3) | 1.90 (3) | 2.728 (2) | 179 (3) |
O1W—H2W···O4iv | 0.86 (3) | 1.85 (3) | 2.708 (2) | 176 (3) |
O2W—H3W···O6v | 0.80 (3) | 1.95 (3) | 2.734 (2) | 170 (3) |
O2W—H4W···O5iii | 0.88 (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. |
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).