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
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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
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).
(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. |
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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).