Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052051/hk2348sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052051/hk2348Isup2.hkl |
CCDC reference: 1245644
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.006 Å
- R factor = 0.041
- wR factor = 0.117
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for Mn1
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - O1 .. 6.53 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - O2 .. 9.03 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - O3 .. 7.33 su PLAT245_ALERT_2_C U(iso) H1A Smaller than U(eq) O1 by ... 0.02 AngSq PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C1 -C6 1.35 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A .. S1 .. 3.00 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1B .. S1 .. 2.98 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (3) 3.11 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 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 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Lanthanum (III) nitrate hexahydrate (216.4 mg, 0.5 mmol), manganous nitrate hexahydrate (143.5 mg, 0.5 mmol), 4-methylbenzene- sulfonic acid (344.4 mg, 2 mmol), ammonia (0.5 mol/l, 4 ml) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 453 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H atoms (for H2O) were located in difference syntheses and refined isotropically [O—H = 0.814 (18)–0.877 (19) Å and Uiso(H) = 0.065 (10) -0.11 (2) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93 and 0.96 Å, for aromatic and methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.2 for aromatic H and x = 1.5 for methyl H atoms.
The crystal structure of hexaaquacopper(II) bis(4-methylbenzenesulfonate), (II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).
The asymmetric unit of the title compound, (I), (Fig. 1) contains one half -cation and one anion; the Mn atom lies on an inversion centre, as in (II). The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).
In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Fig. 2 and Table 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present, as in (II).
The both compounds, (I) and (II), are isostructural.
For a related structure, see: Zhong et al. (2007). For bond-length data, see: Allen et al. (1987).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996.
[Mn(H2O)6](C7H7O3S)2 | F(000) = 526 |
Mr = 505.41 | Dx = 1.601 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5239 reflections |
a = 7.002 (2) Å | θ = 2.5–27.8° |
b = 6.0153 (17) Å | µ = 0.89 mm−1 |
c = 24.9011 (11) Å | T = 273 K |
β = 90.997 (5)° | Prism, colorless |
V = 1048.7 (4) Å3 | 0.48 × 0.37 × 0.20 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2110 independent reflections |
Radiation source: fine-focus sealed tube | 1829 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 26.5°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.673, Tmax = 0.845 | k = −6→7 |
6632 measured reflections | l = −31→30 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0673P)2 + 0.7242P] where P = (Fo2 + 2Fc2)/3 |
2110 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.41 e Å−3 |
9 restraints | Δρmin = −0.46 e Å−3 |
[Mn(H2O)6](C7H7O3S)2 | V = 1048.7 (4) Å3 |
Mr = 505.41 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.002 (2) Å | µ = 0.89 mm−1 |
b = 6.0153 (17) Å | T = 273 K |
c = 24.9011 (11) Å | 0.48 × 0.37 × 0.20 mm |
β = 90.997 (5)° |
Bruker SMART CCD area-detector diffractometer | 2110 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1829 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.845 | Rint = 0.024 |
6632 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 9 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.41 e Å−3 |
2110 reflections | Δρmin = −0.46 e Å−3 |
158 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.5000 | 0.0000 | 0.0000 | 0.03519 (19) | |
S1 | −0.01448 (10) | 0.60823 (11) | 0.90523 (3) | 0.0493 (2) | |
O1 | 0.7232 (4) | −0.1027 (4) | 0.04798 (13) | 0.0811 (8) | |
O2 | 0.5084 (3) | 0.2890 (4) | 0.03489 (11) | 0.0634 (6) | |
O3 | 0.3032 (4) | −0.1043 (4) | 0.05314 (13) | 0.0820 (8) | |
O4 | 0.1537 (4) | 0.5144 (3) | 0.93043 (10) | 0.0625 (6) | |
O5 | −0.0142 (3) | 0.8389 (4) | 0.90908 (9) | 0.0620 (6) | |
O6 | −0.1915 (4) | 0.5171 (3) | 0.92383 (10) | 0.0633 (6) | |
C1 | 0.0132 (6) | 0.4349 (8) | 0.72946 (15) | 0.0735 (10) | |
C2 | −0.0456 (6) | 0.6327 (8) | 0.74479 (16) | 0.0821 (11) | |
H2 | −0.0830 | 0.7356 | 0.7188 | 0.099* | |
C3 | −0.0533 (6) | 0.6926 (7) | 0.79872 (15) | 0.0717 (9) | |
H3 | −0.0932 | 0.8344 | 0.8083 | 0.086* | |
C4 | −0.0031 (4) | 0.5457 (5) | 0.83685 (13) | 0.0539 (7) | |
C5 | 0.0530 (6) | 0.3421 (6) | 0.82199 (14) | 0.0675 (9) | |
H5 | 0.0860 | 0.2363 | 0.8478 | 0.081* | |
C6 | 0.0614 (6) | 0.2917 (8) | 0.76891 (16) | 0.0795 (11) | |
H6 | 0.1027 | 0.1505 | 0.7593 | 0.095* | |
C7 | 0.0320 (8) | 0.3697 (11) | 0.67176 (17) | 0.1042 (16) | |
H7A | −0.0156 | 0.4874 | 0.6492 | 0.156* | |
H7B | −0.0403 | 0.2368 | 0.6649 | 0.156* | |
H7C | 0.1640 | 0.3432 | 0.6642 | 0.156* | |
H1A | 0.762 (5) | −0.228 (3) | 0.0533 (13) | 0.065 (10)* | |
H2A | 0.616 (4) | 0.343 (7) | 0.0478 (17) | 0.088 (13)* | |
H3A | 0.258 (5) | −0.236 (3) | 0.0545 (18) | 0.100 (15)* | |
H1B | 0.804 (5) | −0.022 (5) | 0.0643 (17) | 0.088 (14)* | |
H2B | 0.432 (5) | 0.385 (8) | 0.049 (2) | 0.11 (2)* | |
H3B | 0.204 (4) | −0.030 (5) | 0.0628 (19) | 0.093 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0354 (3) | 0.0223 (3) | 0.0479 (3) | 0.00068 (18) | 0.0018 (2) | 0.00160 (19) |
S1 | 0.0511 (4) | 0.0356 (4) | 0.0614 (4) | 0.0005 (3) | 0.0032 (3) | −0.0004 (3) |
O1 | 0.0832 (17) | 0.0386 (13) | 0.120 (2) | 0.0051 (12) | −0.0439 (16) | 0.0007 (13) |
O2 | 0.0578 (13) | 0.0417 (12) | 0.0908 (17) | −0.0012 (10) | 0.0045 (12) | −0.0127 (11) |
O3 | 0.0897 (18) | 0.0395 (13) | 0.119 (2) | 0.0000 (12) | 0.0508 (16) | 0.0046 (13) |
O4 | 0.0699 (14) | 0.0449 (12) | 0.0722 (14) | 0.0046 (10) | −0.0104 (11) | −0.0025 (10) |
O5 | 0.0668 (13) | 0.0354 (10) | 0.0839 (15) | −0.0008 (9) | 0.0060 (11) | −0.0021 (10) |
O6 | 0.0673 (14) | 0.0443 (12) | 0.0788 (15) | −0.0044 (9) | 0.0176 (11) | −0.0028 (10) |
C1 | 0.065 (2) | 0.094 (3) | 0.061 (2) | −0.008 (2) | 0.0023 (16) | 0.0021 (19) |
C2 | 0.083 (3) | 0.095 (3) | 0.069 (2) | 0.008 (2) | 0.0002 (19) | 0.022 (2) |
C3 | 0.076 (2) | 0.066 (2) | 0.074 (2) | 0.0121 (17) | 0.0065 (17) | 0.0151 (18) |
C4 | 0.0478 (15) | 0.0483 (16) | 0.0657 (18) | −0.0001 (12) | 0.0015 (13) | 0.0049 (13) |
C5 | 0.087 (2) | 0.0522 (19) | 0.0629 (18) | 0.0116 (17) | −0.0012 (16) | −0.0034 (15) |
C6 | 0.086 (3) | 0.077 (3) | 0.076 (2) | 0.008 (2) | 0.0029 (19) | −0.017 (2) |
C7 | 0.097 (3) | 0.146 (5) | 0.069 (2) | −0.005 (3) | 0.008 (2) | −0.007 (3) |
Mn1—O1 | 2.046 (2) | O3—H3B | 0.865 (19) |
Mn1—O2 | 1.944 (2) | C1—C2 | 1.318 (6) |
Mn1—O3 | 2.027 (2) | C1—C6 | 1.345 (6) |
Mn1—O2i | 1.944 (2) | C1—C7 | 1.497 (6) |
Mn1—O3i | 2.026 (2) | C2—C3 | 1.392 (6) |
Mn1—O1i | 2.046 (2) | C2—H2 | 0.9300 |
S1—O5 | 1.391 (2) | C3—C4 | 1.339 (5) |
S1—O6 | 1.439 (2) | C3—H3 | 0.9300 |
S1—O4 | 1.440 (2) | C4—C5 | 1.341 (5) |
S1—C4 | 1.747 (3) | C5—C6 | 1.358 (5) |
O1—H1A | 0.814 (18) | C5—H5 | 0.9300 |
O1—H1B | 0.84 (4) | C6—H6 | 0.9300 |
O2—H2A | 0.877 (19) | C7—H7A | 0.9600 |
O2—H2B | 0.87 (4) | C7—H7B | 0.9600 |
O3—H3A | 0.853 (19) | C7—H7C | 0.9600 |
O1i—Mn1—O1 | 180 | H3A—O3—H3B | 100 (2) |
O1—Mn1—O2 | 89.54 (11) | C2—C1—C6 | 116.2 (4) |
O1i—Mn1—O2 | 90.46 (11) | C2—C1—C7 | 123.2 (4) |
O1i—Mn1—O3 | 87.34 (14) | C6—C1—C7 | 120.5 (5) |
O1—Mn1—O3 | 92.66 (14) | C1—C2—C3 | 122.0 (4) |
O2—Mn1—O2i | 180 | C1—C2—H2 | 119.0 |
O2—Mn1—O3i | 89.97 (11) | C3—C2—H2 | 119.0 |
O2—Mn1—O3 | 90.03 (11) | C4—C3—C2 | 119.9 (4) |
O3i—Mn1—O3 | 180 | C4—C3—H3 | 120.0 |
O2i—Mn1—O3i | 90.03 (11) | C2—C3—H3 | 120.0 |
O1i—Mn1—O2i | 89.54 (11) | C3—C4—C5 | 118.8 (3) |
O1i—Mn1—O3i | 92.66 (14) | C3—C4—S1 | 122.2 (3) |
O5—S1—O6 | 110.95 (14) | C5—C4—S1 | 119.0 (3) |
O5—S1—O4 | 111.15 (14) | C4—C5—C6 | 119.3 (3) |
O6—S1—O4 | 114.40 (15) | C4—C5—H5 | 120.3 |
O5—S1—C4 | 106.39 (15) | C6—C5—H5 | 120.3 |
O6—S1—C4 | 106.60 (15) | C1—C6—C5 | 123.6 (4) |
O4—S1—C4 | 106.84 (15) | C1—C6—H6 | 118.2 |
Mn1—O1—H1A | 129 (2) | C5—C6—H6 | 118.2 |
Mn1—O1—H1B | 127 (3) | C1—C7—H7A | 109.5 |
H1A—O1—H1B | 104 (3) | C1—C7—H7B | 109.5 |
Mn1—O2—H2A | 121 (3) | H7A—C7—H7B | 109.5 |
Mn1—O2—H2B | 140 (3) | C1—C7—H7C | 109.5 |
H2A—O2—H2B | 98 (3) | H7A—C7—H7C | 109.5 |
Mn1—O3—H3A | 125 (3) | H7B—C7—H7C | 109.5 |
Mn1—O3—H3B | 125 (3) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O5 | 0.93 | 2.56 | 2.894 (5) | 102 |
O3—H3A···S1ii | 0.85 (2) | 3.00 (3) | 3.798 (3) | 157 (3) |
O1—H1B···O5iii | 0.84 (4) | 1.95 (2) | 2.781 (3) | 170 (5) |
O1—H1B···S1iii | 0.84 (4) | 2.98 (2) | 3.779 (3) | 158 (3) |
O2—H2B···O6iv | 0.87 (4) | 1.92 (3) | 2.724 (3) | 154 (5) |
O3—H3B···O5iv | 0.87 (2) | 1.90 (2) | 2.756 (3) | 171 (4) |
O1—H1A···O4v | 0.81 (2) | 1.86 (2) | 2.674 (3) | 177 (4) |
O2—H2A···O4iii | 0.88 (2) | 1.90 (2) | 2.770 (3) | 173 (4) |
O3—H3A···O6ii | 0.85 (2) | 1.84 (2) | 2.669 (3) | 164 (4) |
Symmetry codes: (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(H2O)6](C7H7O3S)2 |
Mr | 505.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 7.002 (2), 6.0153 (17), 24.9011 (11) |
β (°) | 90.997 (5) |
V (Å3) | 1048.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.48 × 0.37 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.673, 0.845 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6632, 2110, 1829 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.118, 1.01 |
No. of reflections | 2110 |
No. of parameters | 158 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.46 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL (Siemens, 1996.
Mn1—O1 | 2.046 (2) | Mn1—O3 | 2.027 (2) |
Mn1—O2 | 1.944 (2) | ||
O1i—Mn1—O1 | 180 | O2—Mn1—O2i | 180 |
O1—Mn1—O2 | 89.54 (11) | O2—Mn1—O3i | 89.97 (11) |
O1i—Mn1—O2 | 90.46 (11) | O2—Mn1—O3 | 90.03 (11) |
O1i—Mn1—O3 | 87.34 (14) | O3i—Mn1—O3 | 180 |
O1—Mn1—O3 | 92.66 (14) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O5 | 0.93 | 2.56 | 2.894 (5) | 102 |
O3—H3A···S1ii | 0.853 (19) | 3.00 (3) | 3.798 (3) | 157 (3) |
O1—H1B···O5iii | 0.84 (4) | 1.95 (2) | 2.781 (3) | 170 (5) |
O1—H1B···S1iii | 0.84 (4) | 2.98 (2) | 3.779 (3) | 158 (3) |
O2—H2B···O6iv | 0.87 (4) | 1.92 (3) | 2.724 (3) | 154 (5) |
O3—H3B···O5iv | 0.865 (19) | 1.90 (2) | 2.756 (3) | 171 (4) |
O1—H1A···O4v | 0.814 (18) | 1.861 (18) | 2.674 (3) | 177 (4) |
O2—H2A···O4iii | 0.877 (19) | 1.90 (2) | 2.770 (3) | 173 (4) |
O3—H3A···O6ii | 0.853 (19) | 1.84 (2) | 2.669 (3) | 164 (4) |
Symmetry codes: (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1. |
The crystal structure of hexaaquacopper(II) bis(4-methylbenzenesulfonate), (II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).
The asymmetric unit of the title compound, (I), (Fig. 1) contains one half -cation and one anion; the Mn atom lies on an inversion centre, as in (II). The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).
In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Fig. 2 and Table 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present, as in (II).
The both compounds, (I) and (II), are isostructural.