Hexaaqua-aluminium(III) tris-(methane-sulfonate).

The title compound, [Al(H(2)O)(6)](CH(3)SO(3))(3) (common name: aluminium methane-sulfonate hexa-hydrate), was crystallized from an aqueous solution prepared by the precipitation reaction of aluminium sulfate and barium methane-sulfonate. Its crystal structure is the first of the boron group methane-sulfonates to be determined. The characteristic building block is a centrosymmetric unit containing two hexa-aqua-aluminium cations that are connected to each other by two O atoms of the -SO(3) groups in an O-H⋯O⋯H-O sequence. Further O-H⋯O hydrogen bonding links these blocks in orthogonal directions - along [010] forming a double chain array, along [10-1] forming a layered arrangement of parallel chains and along [101] forming a three-dimensional network. As indicated by the O⋯O distances of 2.600 (3)-2.715 (3) Å, the hydrogen bonds are from medium-strong to strong. A further structural feature is the arrangement of two and four methyl groups, respectively, establishing 'hydro-phobic islands' of different size, all positioned in a layer-like region perpendicular to [101]. The only other building block within this region is one of the -SO(3) groups giving a local connection between the hydro-philic structural regions on both sides of the 'hydro-phobic' one. Thermal analysis indicates that a stepwise dehydration process starts at about 413 K and proceeds via the respective penta- and dihydrate until the compound completely decomposes at about 688 K.

Related literature

For crystal structure determinations of hexa­aqua­aluminium salts, see: Andress & Carpenter (1934 ▶); Buchanan & Harris (1968 ▶); Cameron et al. (1990 ▶); Herpin & Sudarsanan (1965 ▶); Lazar et al. (1991 ▶); Lipson & Beevers (1935 ▶). For hexa­coordinated aluminium in compounds with chelating ligands, see: Hon & Pfluger (1973 ▶); McClelland (1975 ▶); Taylor (1978 ▶). For ligand properties of methane­sulfonate, see: Paul et al. (1974 ▶). For physical and chemical properties of methane­sulfonates in general, see: Aricó et al. (2001 ▶); Gernon et al. (1999 ▶); Trella et al. (2012 ▶); Wang, Song, Jiang & Gong (2009 ▶). For other metal(III) methane­sulfonates, see: Aricó et al. (1997 ▶); Aricó et al. (2001 ▶); Frank & Wallus (2006 ▶); Lindqvist-Reis et al. (2006 ▶); Wickleder (2001 ▶); Wickleder & Müller (2004 ▶). For spectroscopic data of other methane­sulfonates, see: Capwell et al. (1968 ▶); Reiss & Meyer (2011 ▶); Stahlberg et al. (1967 ▶). For methane­sulfonates in catalysis, see: Wang, Jiang, Gong & Wang (2003 ▶); Wang, Jiang, Gong, Wang & Liu (2003 ▶); Wang, Tian, Song & Jiang (2009 ▶); Zhang (2007 ▶). For graph-set analysis, see Etter et al. (1990 ▶).

Experimental

Crystal data

[Al(H2O)6](CH3O3S)3

M = 420.39

Monoclinic,

a = 16.4677 (9) Å

b = 6.4239 (4) Å

c = 17.4295 (8) Å

β = 117.035 (5)°

V = 1642.34 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.58 mm−1

T = 173 K

0.38 × 0.12 × 0.03 mm

Data collection

Stoe IPDS diffractometer

Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008 ▶) T min = 0.811, T max = 0.983

20432 measured reflections

2874 independent reflections

2076 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.073

S = 1.12

2874 reflections

262 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.29 e Å−3

Data collection: IPDS Software (Stoe & Cie, 2000 ▶); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2010 ▶) and SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812033235/gg2089sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033235/gg2089Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Al(H2O)6](CH3O3S)3	F(000) = 880
Mr = 420.39	-
Monoclinic, P21/n	Dx = 1.700 Mg m−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 16.4677 (9) Å	Cell parameters from 8000 reflections
b = 6.4239 (4) Å	θ = 4.7–23.2°
c = 17.4295 (8) Å	µ = 0.58 mm−1
β = 117.035 (5)°	T = 173 K
V = 1642.34 (17) Å3	Plate, colourless
Z = 4	0.38 × 0.12 × 0.03 mm

Stoe IPDS diffractometer	2874 independent reflections
Radiation source: fine-focus sealed tube	2076 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 6.67 pixels mm-1	θmax = 25.0°, θmin = 2.3°
φ–scans	h = −19→19
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008)	k = −7→7
Tmin = 0.811, Tmax = 0.983	l = −20→20
20432 measured reflections

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)] = 0.031	Hydrogen site location: difference Fourier map
wR(F2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.035P)2] where P = (Fo2 + 2Fc2)/3
2874 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.43 e Å−3
2 restraints	Δρmin = −0.29 e Å−3

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
S1	0.42486 (4)	0.07708 (9)	0.14732 (4)	0.02005 (16)
S2	0.65617 (4)	0.97454 (9)	0.60472 (4)	0.02049 (16)
S3	0.82913 (4)	0.04636 (9)	0.38082 (4)	0.02131 (16)
Al1	0.59239 (4)	0.50961 (11)	0.37580 (5)	0.01734 (17)
O1	0.47670 (12)	−0.0109 (3)	0.23435 (11)	0.0270 (4)
O2	0.40427 (12)	0.2956 (2)	0.15149 (11)	0.0267 (4)
O3	0.34515 (11)	−0.0492 (3)	0.09627 (12)	0.0278 (4)
O4	0.67367 (12)	1.0148 (3)	0.53116 (11)	0.0274 (4)
O5	0.59731 (12)	0.7901 (3)	0.58804 (12)	0.0309 (5)
O6	0.62196 (12)	1.1551 (3)	0.62981 (13)	0.0349 (5)
O7	0.82038 (12)	0.2633 (3)	0.40091 (12)	0.0297 (4)
O8	0.89366 (12)	0.0213 (3)	0.34588 (11)	0.0278 (4)
O9	0.74081 (12)	−0.0488 (3)	0.32608 (12)	0.0300 (4)
O10	0.65563 (13)	0.4196 (3)	0.31723 (13)	0.0235 (4)
H1	0.644 (2)	0.450 (5)	0.266 (2)	0.036 (9)*
H2	0.709 (3)	0.375 (5)	0.345 (2)	0.054 (11)*
O11	0.53554 (13)	0.2484 (3)	0.36416 (13)	0.0214 (4)
H3	0.5226 (19)	0.168 (5)	0.322 (2)	0.029 (8)*
H4	0.4966 (19)	0.230 (4)	0.3798 (18)	0.021 (8)*
O12	0.49533 (12)	0.5926 (3)	0.27037 (12)	0.0217 (4)
H5	0.489 (2)	0.707 (4)	0.254 (2)	0.037 (9)*
H6	0.471 (2)	0.496 (5)	0.234 (2)	0.035 (9)*
O13	0.68364 (12)	0.4112 (3)	0.48197 (12)	0.0231 (4)
H7	0.7314 (18)	0.462 (5)	0.511 (2)	0.048 (10)*
H8	0.678 (2)	0.282 (6)	0.498 (2)	0.056 (11)*
O14	0.64698 (13)	0.7730 (3)	0.39399 (14)	0.0236 (4)
H9	0.675 (2)	0.819 (6)	0.371 (3)	0.055 (12)*
H10	0.650 (2)	0.852 (5)	0.436 (2)	0.044 (10)*
O15	0.52616 (14)	0.6042 (3)	0.43396 (13)	0.0218 (4)
H11	0.481 (2)	0.666 (5)	0.411 (2)	0.046 (11)*
H12	0.554 (2)	0.651 (5)	0.487 (3)	0.053 (11)*
C1	0.4976 (2)	0.0604 (5)	0.0999 (2)	0.0355 (7)
H1A	0.4669 (7)	0.111 (3)	0.0418 (10)	0.051 (10)*
H1B	0.5151 (10)	−0.082 (2)	0.0997 (10)	0.034 (8)*
H1C	0.5510 (11)	0.143 (3)	0.1321 (8)	0.037 (8)*
C2	0.76073 (18)	0.9109 (4)	0.69268 (18)	0.0298 (6)
H2A	0.8019 (8)	1.022 (2)	0.7039 (8)	0.029 (7)*
H2B	0.7846 (7)	0.790 (3)	0.6798 (5)	0.039 (8)*
H2C	0.7517 (3)	0.886 (3)	0.7415 (9)	0.039 (9)*
C3	0.87409 (18)	−0.0882 (4)	0.47970 (17)	0.0296 (6)
H3A	0.9326 (10)	−0.0398 (19)	0.5152 (7)	0.032 (8)*
H3B	0.8764 (10)	−0.230 (2)	0.4698 (2)	0.037 (8)*
H3C	0.8370 (8)	−0.066 (2)	0.5063 (7)	0.022 (7)*

	U11	U22	U33	U12	U13	U23
S1	0.0225 (3)	0.0177 (3)	0.0182 (3)	0.0007 (2)	0.0077 (3)	−0.0005 (2)
S2	0.0203 (3)	0.0211 (3)	0.0199 (3)	0.0000 (2)	0.0089 (3)	−0.0015 (2)
S3	0.0220 (3)	0.0238 (3)	0.0200 (3)	0.0004 (2)	0.0111 (3)	0.0012 (2)
Al1	0.0179 (4)	0.0166 (4)	0.0179 (4)	−0.0005 (3)	0.0084 (3)	−0.0002 (3)
O1	0.0356 (10)	0.0181 (9)	0.0206 (9)	0.0014 (7)	0.0068 (8)	−0.0008 (7)
O2	0.0331 (10)	0.0183 (9)	0.0243 (10)	0.0036 (7)	0.0093 (8)	−0.0012 (7)
O3	0.0254 (9)	0.0235 (9)	0.0273 (10)	−0.0007 (7)	0.0058 (8)	−0.0025 (8)
O4	0.0362 (10)	0.0225 (9)	0.0250 (10)	−0.0050 (8)	0.0150 (8)	−0.0011 (8)
O5	0.0334 (10)	0.0349 (11)	0.0307 (11)	−0.0126 (8)	0.0200 (9)	−0.0100 (8)
O6	0.0296 (10)	0.0349 (11)	0.0329 (11)	0.0088 (8)	0.0079 (9)	−0.0100 (9)
O7	0.0287 (10)	0.0273 (10)	0.0322 (11)	0.0042 (8)	0.0132 (9)	−0.0020 (8)
O8	0.0279 (9)	0.0335 (10)	0.0247 (10)	0.0028 (8)	0.0145 (8)	0.0025 (8)
O9	0.0275 (9)	0.0356 (11)	0.0261 (10)	−0.0073 (8)	0.0114 (8)	0.0002 (8)
O10	0.0244 (10)	0.0282 (10)	0.0203 (11)	0.0064 (8)	0.0123 (9)	0.0036 (8)
O11	0.0248 (10)	0.0212 (9)	0.0211 (10)	−0.0032 (7)	0.0129 (9)	−0.0028 (8)
O12	0.0245 (9)	0.0148 (9)	0.0203 (10)	0.0005 (8)	0.0054 (8)	0.0009 (8)
O13	0.0216 (10)	0.0204 (10)	0.0225 (10)	−0.0023 (8)	0.0058 (8)	0.0028 (8)
O14	0.0287 (10)	0.0213 (9)	0.0248 (11)	−0.0058 (7)	0.0157 (9)	−0.0025 (8)
O15	0.0215 (9)	0.0245 (9)	0.0205 (10)	0.0019 (8)	0.0106 (8)	−0.0026 (8)
C1	0.0380 (16)	0.0380 (17)	0.0393 (18)	−0.0076 (13)	0.0253 (14)	−0.0083 (13)
C2	0.0254 (13)	0.0299 (14)	0.0294 (16)	0.0038 (12)	0.0084 (12)	0.0033 (12)
C3	0.0312 (15)	0.0337 (16)	0.0256 (15)	0.0034 (12)	0.0143 (13)	0.0060 (12)

S1—O1	1.4737 (18)	O11—H3	0.84 (3)
S1—O2	1.4535 (17)	O11—H4	0.81 (3)
S1—O3	1.4530 (18)	O12—H5	0.77 (2)
S1—C1	1.741 (3)	O12—H6	0.85 (3)
S2—O4	1.459 (2)	O13—H7	0.79 (2)
S2—O5	1.4737 (18)	O13—H8	0.89 (4)
S2—O6	1.4413 (19)	O14—H9	0.79 (4)
S2—C2	1.756 (3)	O14—H10	0.88 (4)
S3—O7	1.4599 (18)	O15—H11	0.78 (4)
S3—O8	1.4539 (19)	O15—H12	0.87 (4)
S3—O9	1.4623 (18)	C1—H1A	0.9599
S3—C3	1.762 (3)	C1—H1B	0.9599
Al1—O10	1.851 (2)	C1—H1C	0.9599
Al1—O11	1.8868 (19)	C2—H2A	0.9411
Al1—O12	1.8830 (18)	C2—H2B	0.9411
Al1—O13	1.8853 (18)	C2—H2C	0.9411
Al1—O14	1.8740 (19)	C3—H3A	0.9302
Al1—O15	1.895 (2)	C3—H3B	0.9302
O10—H1	0.85 (4)	C3—H3C	0.9302
O10—H2	0.83 (4)
O1—S1—O2	110.99 (10)	O12—Al1—O13	175.67 (9)
O1—S1—O3	110.83 (11)	O12—Al1—O14	92.21 (9)
O2—S1—O3	113.79 (10)	O12—Al1—O15	89.52 (9)
O1—S1—C1	105.26 (13)	O13—Al1—O14	91.69 (9)
O2—S1—C1	108.04 (13)	O13—Al1—O15	88.75 (9)
O3—S1—C1	107.47 (13)	O14—Al1—O15	88.20 (9)
O4—S2—O5	110.13 (11)	Al1—O10—H1	126 (2)
O4—S2—O6	112.60 (12)	Al1—O10—H2	119 (3)
O5—S2—O6	113.21 (12)	H1—O10—H2	112 (3)
O4—S2—C2	107.55 (13)	Al1—O11—H3	123 (2)
O5—S2—C2	106.32 (12)	Al1—O11—H4	121.4 (19)
O6—S2—C2	106.61 (12)	H3—O11—H4	106 (3)
O7—S3—O8	112.15 (11)	Al1—O12—H5	123 (2)
O7—S3—O9	112.23 (11)	Al1—O12—H6	115 (2)
O8—S3—O9	112.33 (11)	H5—O12—H6	119 (3)
O7—S3—C3	106.08 (13)	Al1—O13—H7	128 (3)
O8—S3—C3	107.04 (12)	Al1—O13—H8	118 (2)
O9—S3—C3	106.50 (12)	H7—O13—H8	114 (3)
O10—Al1—O11	92.23 (9)	Al1—O14—H9	127 (3)
O10—Al1—O12	89.49 (9)	Al1—O14—H10	120 (2)
O10—Al1—O13	92.26 (9)	H9—O14—H10	113 (3)
O10—Al1—O14	91.63 (9)	Al1—O15—H11	123 (3)
O10—Al1—O15	178.99 (10)	Al1—O15—H12	121 (2)
O11—Al1—O12	89.27 (8)	H11—O15—H12	107 (3)
O11—Al1—O13	86.71 (8)	S1—C1—H1A	109.5
O11—Al1—O14	175.87 (11)	H1A—C1—H1B	109.5
O11—Al1—O15	87.96 (9)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H1···O8i	0.85 (4)	1.81 (4)	2.659 (3)	174 (3)
O10—H2···O7	0.83 (4)	1.80 (4)	2.627 (3)	176 (4)
O11—H3···O1	0.84 (3)	1.78 (3)	2.615 (3)	169 (3)
O11—H4···O5ii	0.81 (3)	1.87 (3)	2.683 (3)	175 (3)
O12—H5···O1iii	0.77 (2)	1.84 (2)	2.608 (2)	171 (3)
O12—H6···O2	0.85 (3)	1.87 (3)	2.713 (2)	174 (3)
O13—H7···O3iv	0.79 (2)	1.87 (2)	2.648 (2)	169 (4)
O13—H8···O4v	0.89 (4)	1.82 (4)	2.715 (3)	177 (3)
O14—H9···O9iii	0.79 (4)	1.82 (4)	2.600 (3)	174 (4)
O14—H10···O4	0.88 (4)	1.84 (4)	2.714 (3)	172 (3)
O15—H11···O6vi	0.78 (4)	1.89 (4)	2.667 (3)	171 (4)
O15—H12···O5	0.87 (4)	1.81 (4)	2.674 (3)	169 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H1⋯O8i	0.85 (4)	1.81 (4)	2.659 (3)	174 (3)
O10—H2⋯O7	0.83 (4)	1.80 (4)	2.627 (3)	176 (4)
O11—H3⋯O1	0.84 (3)	1.78 (3)	2.615 (3)	169 (3)
O11—H4⋯O5ii	0.81 (3)	1.87 (3)	2.683 (3)	175 (3)
O12—H5⋯O1iii	0.77 (2)	1.84 (2)	2.608 (2)	171 (3)
O12—H6⋯O2	0.85 (3)	1.87 (3)	2.713 (2)	174 (3)
O13—H7⋯O3iv	0.79 (2)	1.87 (2)	2.648 (2)	169 (4)
O13—H8⋯O4v	0.89 (4)	1.82 (4)	2.715 (3)	177 (3)
O14—H9⋯O9iii	0.79 (4)	1.82 (4)	2.600 (3)	174 (4)
O14—H10⋯O4	0.88 (4)	1.84 (4)	2.714 (3)	172 (3)
O15—H11⋯O6vi	0.78 (4)	1.89 (4)	2.667 (3)	171 (4)
O15—H12⋯O5	0.87 (4)	1.81 (4)	2.674 (3)	169 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .