Retracted: Hexaaqua­manganese(II) bis­(4-methyl­benzene­sulfonate)

The asymmetric unit of the title compound, [Mn(H₂O)₆](C₇H₇O₃S)₂, contains one half-cation and one anion; the Mn atom lies on an inversion centre. In the crystal structure, inter­molecular O—H...O and O—H...S hydrogen bonds result in the formation of a supra­molecular network structure; an intra­molecular C—H...O hydrogen bond is also present.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

For a related structure, see: Zhong et al. (2007). For bond-length data, see: Allen et al. (1987).

S2. Experimental

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.

S3. Refinement

H atoms (for H₂O) were located in difference syntheses and refined isotropically [O—H = 0.814 (18)–0.877 (19) Å and U_iso(H) = 0.065 (10) -0.11 (2) Ų]. 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 U_iso(H) = xU_eq(C), where x = 1.2 for aromatic H and x = 1.5 for methyl H atoms.

Computing details

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.

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 3/2 - x, 1/2 - y, 1/2 - z].
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Hexaaquamanganese(II) bis(4-methylbenzenesulfonate)

Crystal data

[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) Å^3	0.48 × 0.37 × 0.20 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0673P)^2 + 0.7242P] where P = (Fo^2 + 2Fc^2)/3
2110 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.41 e Å^−3
9 restraints	Δρmin = −0.46 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—O2^i	1.944 (2)	C1—C7	1.497 (6)
Mn1—O3^i	2.026 (2)	C2—C3	1.392 (6)
Mn1—O1^i	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
O1^i—Mn1—O1	180	H3A—O3—H3B	100 (2)
O1—Mn1—O2	89.54 (11)	C2—C1—C6	116.2 (4)
O1^i—Mn1—O2	90.46 (11)	C2—C1—C7	123.2 (4)
O1^i—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—O2^i	180	C1—C2—H2	119.0
O2—Mn1—O3^i	89.97 (11)	C3—C2—H2	119.0
O2—Mn1—O3	90.03 (11)	C4—C3—C2	119.9 (4)
O3^i—Mn1—O3	180	C4—C3—H3	120.0
O2^i—Mn1—O3^i	90.03 (11)	C2—C3—H3	120.0
O1^i—Mn1—O2^i	89.54 (11)	C3—C4—C5	118.8 (3)
O1^i—Mn1—O3^i	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.

Hydrogen-bond geometry (Å, º)

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···S1^ii	0.85 (2)	3.00 (3)	3.798 (3)	157 (3)
O1—H1B···O5^iii	0.84 (4)	1.95 (2)	2.781 (3)	170 (5)
O1—H1B···S1^iii	0.84 (4)	2.98 (2)	3.779 (3)	158 (3)
O2—H2B···O6^iv	0.87 (4)	1.92 (3)	2.724 (3)	154 (5)
O3—H3B···O5^iv	0.87 (2)	1.90 (2)	2.756 (3)	171 (4)
O1—H1A···O4^v	0.81 (2)	1.86 (2)	2.674 (3)	177 (4)
O2—H2A···O4^iii	0.88 (2)	1.90 (2)	2.770 (3)	173 (4)
O3—H3A···O6^ii	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.