catena-Poly[[tetra­aqua­manganese(II)]-[mu]-4-(carboxyl­ato­methyl­sulfanyl)­phenoxy­acetato]

The title compound, [Mn(C₁₀H₈O₅S)(H₂O)₄]_n, a one-dimensional manganese(II) complex comprising helical chains bridged by 4-(carboxylatomethylsulfanyl)phenoxyacetate ligands has been characterized by single-crystal X-ray diffraction analysis. Hydrogen-bonding inter­actions between adjacent chains extend the complex into a three-dimensional supra­molecular architecture.

S1. Comment

The crystal engineering and synthesis of discrete metallohelicates and infinite metal-containing helical coordination polymers have received much attention from chemists, because helicity is an essential feature of living systems and is important in advanced materials, such as optical devices, enantiomer separation, chiral synthesis, ligand exchange and selective catalysis (Chen & Suslick, 1993; Woods et al., 1996; Piguet et al., 1997; Qi et al., 2003). Most of the recent studies in this area have been involved with the construction of compounds from d¹⁰ transition metal ions and functional ligands (Psillakes et al., 1997; Tong et al., 1998; Nomiya et al., 2000). In this context, the fine-tuning of organic ligands and the careful selection of metal ions are especially crucial to the construction of desirable helical frameworks (Nishida et al., 2001; Gao et al., 2003; Barnett & Champness, 2003). We are interested in the solid-state coordination chemistry of p-(carboxylmethoxyl)phenylthioacetic acid (p-CMPTH₂), which remains largely unexplored. Although this is a rather simple molecule, it has the potential for coordinative interaction and hydrogen bonding. Firstly, it has two carboxyl groups, one ether O atom and one ether S atom, which induce multiple coordination modes with transition metal ions. Secondly, it can act not only as a hydrogen-bond donor but also as hydrogen-bond acceptor, owing to the existence of deprotonated and/or protonated carboxyl groups. Therefore, it is regarded as an excellent candidate for the construction of different kinds of coordination polymers, including infinite one-dimensional chain compounds, two-dimensional layer compounds and three-dimensional netlike compounds (Gao, Huo et al., 2005; Gao, Su et al., 2005). Here, we report the title novel one-dimensional manganese(II) complex, (I), comprising helical chains bridged by p-(carboxylmethoxyl)phenylthioacetate (p-CMPT²⁻).

The present X-ray diffraction analysis shows that complex (I) possesses a one-dimensional single-helical structure. The fundamental unit of the crystal structure is illustrated in Fig. 1. Each Mn^II ion is six-coordinated in a distorted octahedral geometry. Its equatorial plane is defined by atoms O1, O1W, O3W and O4ⁱ [symmetry code: (i) −x + 1, y − 1/2, −z + 1], with an r.m.s. deviation of 0.075 (2) Å; the deviation of the Mn^II atom from this plane is 0.0116 (2) Å. The axial positions are occupied by atoms O2W and O4W, with an angle of 170.53 (6)°. It is interesting to note that each ligand, L, serves as a bridging ligand to link two Mn^II atoms, forming a single-strand helical coordination polymer. Both carboxylate anions in one L are mono-coordinated to the adjacent metal atom, with Mn—O distances of 2.1599 (15) and 2.1528 (16) Å (Fig. 2). In this way, each L acts as a bidentate group to link two metal atoms and yields a half-turn unit of the helical structure. The distance between neighbouring Mn atoms is 11.377 Å. Extension of the structure in one dimension along the b axis gives a one-dimensional helical Mn–L network (Fig. 2), resulting from the unique coordination feature of the L ligands. Each helical cycle contains three Mn atoms and two bridging L ligands.

The structure of (I) also contains intermolecular hydrogen bonds, which are formed between the free water molecules and uncoordinated carboxylate O atoms [O···O = 2.676 (2) and 2.744 (2) Å], resulting in a two-dimensional layer structure parallel to the bc plane. Adjacent two-dimensional layers form a three-dimensional framework linked by further intermolecular hydrogen bonds formed between the water molecules, coordinated carboxylate O atoms and water molecules of an adjacent layer [O···O = 2.972 (3) and 2.878 (2) Å] (Fig. 3).

In summary, employing the flexibility and unique coordination feature of L, we have successfully prepared a one-dimensional chain coordination polymer consisting of helical chains bridged by L. Knowledge of the chemistry of well defined helical coordination polymers is necessary for the understanding of the detection and amplification of chirality. There is increasing interest in dynamic helical coordination polymers (Yamada et al., 2004; Matsuda et al., 2004), the most important feature of which is high sensitivity to a chiral environment, and therefore such systems might provide the basis to construct a novel chirality-sensing probe. This work has demonstrated that extended structural motifs can be constructed through L ligands bridging neutral one-dimensional helical chains.

S2. Experimental

p-(Carboxylmethoxyl)phenylthioacetic acid was prepared following the method described for the synthesis of benzene-1,2-dioxyacetic acid by Mirci (1990). MnCl₂·6H₂O (0.099 g, 0.5 mmol) and p-(carboxylmethoxyl)phenylthioacetic acid (0.224 g, 1 mmol) were dissolved separately in water (25 ml) and the two solutions mixed slowly with stirring for about 15 min at room temperature. The pH value was adjusted to 6 with 0.1 M sodium hydroxide. Colourless crystals of (I) separated from the filtered solution after several days (yield ca 56%). Elementary analysis, calculated for C₁₀H₁₆O₉SMn (367.23): C 32.70, H 4.39%; found: C 33.02, H 4.41%.

S3. Refinement

C-bound H atoms were placed in calculated positions, with C—H = 0.93 Å (aromatic) or 0.97 Å (aliphatic) and U_iso(H) = 1.2U_eq(C), and treated using the riding-model approximation. The H atoms of the water molecules were located in a difference Fourier map and refined with O—H distance restraints of 0.85 (1) Å and with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the title compound, showing the atom-numbering scheme. Non-water H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1 − x, y − 1/2, 1 − z.] [Please check added symmetry code]
	Fig. 2. Ball-and-stick and space-filling plots of (I), showing the one-dimensional helical Mn–L network along the b axis. H atoms have been omitted. [H atoms are shown in the key - please revise]
	Fig. 3. A packing diagram for (I). Hydrogen bonds are depicted as dashed lines.

catena-Poly[[tetraaquamanganese(II)]-µ-4- (carboxylatomethylsulfanyl)phenoxyacetato]

Crystal data

[Mn(C10H8O5S)(H2O)4]	F(000) = 378
Mr = 367.24	Dx = 1.724 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6619 reflections
a = 5.0977 (10) Å	θ = 3.4–27.5°
b = 11.444 (2) Å	µ = 1.12 mm^−1
c = 12.183 (2) Å	T = 295 K
β = 95.58 (3)°	Prism, colourless
V = 707.4 (2) Å^3	0.37 × 0.25 × 0.16 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	3164 independent reflections
Radiation source: fine-focus sealed tube	2967 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 10.000 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ω scans	h = −6→5
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
Tmin = 0.709, Tmax = 0.840	l = −15→15
6919 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0264P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3164 reflections	Δρmax = 0.29 e Å^−3
214 parameters	Δρmin = −0.18 e Å^−3
13 restraints	Absolute structure: Flack (1983), with 1457 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (11)

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	0.57346 (5)	0.22290 (2)	0.90542 (2)	0.02444 (8)
S1	−0.07105 (9)	0.44281 (5)	0.63645 (4)	0.03256 (12)
O1W	0.8489 (3)	0.36610 (14)	0.96036 (14)	0.0344 (4)
H10	0.985 (3)	0.348 (2)	0.9282 (19)	0.052*
H11	0.778 (4)	0.4260 (16)	0.9273 (19)	0.052*
O2W	0.8179 (3)	0.19439 (13)	0.76427 (13)	0.0363 (4)
H12	0.959 (3)	0.1549 (18)	0.773 (2)	0.054*
H13	0.848 (5)	0.2597 (14)	0.736 (2)	0.054*
O3W	0.8603 (3)	0.11184 (13)	1.00137 (13)	0.0326 (3)
H14	0.850 (4)	0.0485 (14)	0.966 (2)	0.049*
H15	1.008 (3)	0.1433 (18)	1.000 (2)	0.049*
O4W	0.3616 (2)	0.22385 (16)	1.05590 (10)	0.0286 (3)
H16	0.361 (5)	0.2882 (11)	1.0907 (17)	0.043*
H17	0.407 (5)	0.1686 (13)	1.1003 (16)	0.043*
O1	0.3120 (3)	0.35505 (13)	0.83019 (14)	0.0315 (3)
O2	0.5573 (2)	0.51541 (13)	0.83481 (12)	0.0332 (3)
O3	0.6315 (3)	0.31153 (13)	0.29508 (12)	0.0331 (3)
O4	0.6867 (3)	0.58507 (14)	0.15736 (13)	0.0312 (3)
O5	0.3842 (3)	0.44466 (14)	0.12859 (12)	0.0334 (3)
C1	0.3536 (3)	0.45932 (18)	0.80449 (16)	0.0245 (4)
C2	0.1383 (4)	0.52629 (18)	0.73539 (16)	0.0290 (4)
H2A	0.2214	0.5875	0.6960	0.035*
H2B	0.0273	0.5640	0.7852	0.035*
C3	0.1481 (4)	0.40705 (18)	0.53770 (16)	0.0300 (4)
C4	0.1804 (4)	0.29063 (18)	0.50549 (19)	0.0373 (5)
H4	0.0943	0.2313	0.5399	0.045*
C5	0.3374 (4)	0.2630 (2)	0.42371 (19)	0.0381 (5)
H5	0.3522	0.1857	0.4015	0.046*
C6	0.4739 (4)	0.35008 (18)	0.37413 (16)	0.0302 (4)
C7	0.4455 (4)	0.46576 (18)	0.40495 (16)	0.0307 (4)
H7	0.5366	0.5246	0.3721	0.037*
C8	0.2800 (4)	0.49277 (18)	0.48513 (16)	0.0317 (4)
H8	0.2572	0.5706	0.5040	0.038*
C9	0.7775 (4)	0.40147 (19)	0.24398 (18)	0.0313 (4)
H9A	0.9036	0.3649	0.2001	0.038*
H9B	0.8754	0.4473	0.3011	0.038*
C10	0.6010 (4)	0.48206 (18)	0.17092 (16)	0.0254 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01891 (12)	0.02570 (13)	0.02851 (14)	−0.00052 (12)	0.00124 (10)	0.00161 (13)
S1	0.0263 (2)	0.0406 (3)	0.0303 (2)	−0.0005 (2)	0.0003 (2)	0.0039 (2)
O1W	0.0235 (7)	0.0335 (9)	0.0454 (9)	−0.0016 (6)	−0.0004 (7)	−0.0016 (7)
O2W	0.0345 (7)	0.0369 (11)	0.0383 (8)	−0.0017 (6)	0.0085 (7)	0.0026 (6)
O3W	0.0253 (7)	0.0342 (9)	0.0382 (8)	0.0007 (6)	0.0020 (7)	0.0061 (7)
O4W	0.0284 (6)	0.0266 (6)	0.0305 (6)	0.0026 (8)	0.0019 (5)	−0.0002 (7)
O1	0.0252 (7)	0.0283 (8)	0.0398 (8)	−0.0016 (6)	−0.0023 (7)	0.0076 (6)
O2	0.0254 (7)	0.0284 (8)	0.0451 (9)	−0.0024 (6)	0.0004 (7)	−0.0006 (7)
O3	0.0377 (7)	0.0303 (7)	0.0322 (7)	0.0061 (6)	0.0076 (7)	0.0019 (6)
O4	0.0267 (7)	0.0277 (8)	0.0391 (8)	0.0021 (6)	0.0027 (7)	0.0032 (7)
O5	0.0300 (7)	0.0314 (8)	0.0372 (8)	−0.0007 (6)	−0.0054 (6)	0.0009 (7)
C1	0.0237 (8)	0.0282 (11)	0.0226 (9)	0.0003 (8)	0.0074 (7)	−0.0030 (8)
C2	0.0312 (10)	0.0283 (10)	0.0277 (10)	0.0020 (8)	0.0037 (9)	0.0016 (8)
C3	0.0263 (9)	0.0326 (11)	0.0302 (10)	−0.0008 (8)	−0.0021 (9)	0.0039 (8)
C4	0.0401 (12)	0.0272 (11)	0.0451 (12)	−0.0065 (9)	0.0063 (11)	0.0076 (9)
C5	0.0425 (11)	0.0231 (9)	0.0482 (13)	−0.0006 (8)	0.0011 (11)	−0.0010 (9)
C6	0.0290 (9)	0.0310 (11)	0.0293 (10)	0.0039 (8)	−0.0045 (9)	0.0031 (8)
C7	0.0356 (10)	0.0286 (11)	0.0279 (10)	−0.0042 (8)	0.0028 (9)	0.0033 (8)
C8	0.0380 (10)	0.0252 (10)	0.0306 (10)	−0.0006 (8)	−0.0024 (9)	0.0002 (8)
C9	0.0267 (9)	0.0332 (11)	0.0343 (11)	0.0036 (8)	0.0053 (9)	0.0035 (9)
C10	0.0252 (9)	0.0265 (10)	0.0253 (9)	0.0037 (7)	0.0063 (8)	−0.0023 (8)

Geometric parameters (Å, º)

Mn1—O4^i	2.1528 (16)	O4—C10	1.274 (3)
Mn1—O1	2.1599 (15)	O4—Mn1^ii	2.1528 (15)
Mn1—O3W	2.1881 (15)	O5—C10	1.249 (2)
Mn1—O4W	2.2164 (14)	C1—C2	1.524 (3)
Mn1—O1W	2.2185 (15)	C2—H2A	0.9700
Mn1—O2W	2.2435 (17)	C2—H2B	0.9700
S1—C3	1.768 (2)	C3—C8	1.381 (3)
S1—C2	1.804 (2)	C3—C4	1.403 (3)
O1W—H10	0.85 (3)	C4—C5	1.374 (3)
O1W—H11	0.86 (2)	C4—H4	0.9300
O2W—H12	0.85 (2)	C5—C6	1.387 (3)
O2W—H13	0.85 (2)	C5—H5	0.9300
O3W—H14	0.85 (2)	C6—C7	1.388 (3)
O3W—H15	0.84 (2)	C7—C8	1.386 (3)
O4W—H16	0.85 (2)	C7—H7	0.9300
O4W—H17	0.85 (2)	C8—H8	0.9300
O1—C1	1.257 (3)	C9—C10	1.516 (3)
O2—C1	1.246 (2)	C9—H9A	0.9700
O3—C6	1.385 (3)	C9—H9B	0.9700
O3—C9	1.446 (3)
O4^i—Mn1—O1	91.66 (5)	C1—C2—S1	116.77 (14)
O4^i—Mn1—O3W	96.94 (6)	C1—C2—H2A	108.1
O1—Mn1—O3W	170.43 (6)	S1—C2—H2A	108.1
O4^i—Mn1—O4W	87.97 (6)	C1—C2—H2B	108.1
O1—Mn1—O4W	91.00 (6)	S1—C2—H2B	108.1
O3W—Mn1—O4W	85.13 (6)	H2A—C2—H2B	107.3
O4^i—Mn1—O1W	176.68 (7)	C8—C3—C4	118.0 (2)
O1—Mn1—O1W	87.54 (6)	C8—C3—S1	121.29 (16)
O3W—Mn1—O1W	84.11 (6)	C4—C3—S1	120.60 (16)
O4W—Mn1—O1W	95.27 (6)	C5—C4—C3	120.9 (2)
O4^i—Mn1—O2W	89.43 (6)	C5—C4—H4	119.6
O1—Mn1—O2W	98.19 (6)	C3—C4—H4	119.6
O3W—Mn1—O2W	86.15 (6)	C4—C5—C6	120.2 (2)
O4W—Mn1—O2W	170.53 (6)	C4—C5—H5	119.9
O1W—Mn1—O2W	87.49 (6)	C6—C5—H5	119.9
C3—S1—C2	101.86 (9)	O3—C6—C7	125.09 (19)
Mn1—O1W—H10	101.8 (19)	O3—C6—C5	115.06 (18)
Mn1—O1W—H11	102.9 (18)	C7—C6—C5	119.8 (2)
H10—O1W—H11	107.5 (14)	C8—C7—C6	119.35 (19)
Mn1—O2W—H12	120.3 (18)	C8—C7—H7	120.3
Mn1—O2W—H13	108.9 (19)	C6—C7—H7	120.3
H12—O2W—H13	109.9 (15)	C3—C8—C7	121.69 (19)
Mn1—O3W—H14	102.5 (18)	C3—C8—H8	119.2
Mn1—O3W—H15	107.0 (18)	C7—C8—H8	119.2
H14—O3W—H15	111.6 (16)	O3—C9—C10	112.64 (16)
Mn1—O4W—H16	116.2 (17)	O3—C9—H9A	109.1
Mn1—O4W—H17	113.6 (17)	C10—C9—H9A	109.1
H16—O4W—H17	109.9 (14)	O3—C9—H9B	109.1
C1—O1—Mn1	131.18 (13)	C10—C9—H9B	109.1
C6—O3—C9	115.49 (16)	H9A—C9—H9B	107.8
C10—O4—Mn1^ii	121.13 (12)	O5—C10—O4	124.39 (18)
O2—C1—O1	124.83 (18)	O5—C10—C9	119.01 (18)
O2—C1—C2	116.08 (18)	O4—C10—C9	116.60 (17)
O1—C1—C2	119.04 (17)
O4^i—Mn1—O1—C1	−158.7 (2)	C9—O3—C6—C7	1.0 (3)
O4W—Mn1—O1—C1	113.28 (19)	C9—O3—C6—C5	−179.18 (17)
O1W—Mn1—O1—C1	18.05 (19)	C4—C5—C6—O3	178.25 (17)
O2W—Mn1—O1—C1	−69.06 (19)	C4—C5—C6—C7	−1.9 (3)
Mn1—O1—C1—O2	−12.5 (3)	O3—C6—C7—C8	179.73 (17)
Mn1—O1—C1—C2	170.33 (13)	C5—C6—C7—C8	−0.1 (3)
O2—C1—C2—S1	150.04 (15)	C4—C3—C8—C7	−1.7 (3)
O1—C1—C2—S1	−32.5 (2)	S1—C3—C8—C7	−177.82 (14)
C3—S1—C2—C1	−69.78 (16)	C6—C7—C8—C3	1.9 (3)
C2—S1—C3—C8	−56.96 (17)	C6—O3—C9—C10	−68.7 (2)
C2—S1—C3—C4	127.05 (17)	Mn1^ii—O4—C10—O5	16.5 (3)
C8—C3—C4—C5	−0.3 (3)	Mn1^ii—O4—C10—C9	−163.30 (13)
S1—C3—C4—C5	175.80 (15)	O3—C9—C10—O5	−26.1 (3)
C3—C4—C5—C6	2.1 (3)	O3—C9—C10—O4	153.70 (18)

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H10···O1^iii	0.85 (3)	2.15 (3)	2.972 (3)	163 (2)
O1W—H11···O2	0.86 (2)	1.83 (3)	2.651 (2)	161 (3)
O2W—H12···O4^iv	0.85 (2)	2.08 (3)	2.896 (2)	162 (3)
O2W—H13···S1^iii	0.85 (2)	2.47 (3)	3.316 (2)	175 (3)
O3W—H14···O5^i	0.85 (2)	1.97 (3)	2.709 (2)	145 (2)
O3W—H15···O4W^iii	0.84 (2)	2.08 (3)	2.878 (2)	159 (2)
O4W—H16···O5^v	0.85 (2)	1.85 (2)	2.676 (2)	164 (2)
O4W—H17···O2^vi	0.85 (2)	1.93 (3)	2.744 (2)	162 (2)

Symmetry codes: (i) −x+1, y−1/2, −z+1; (iii) x+1, y, z; (iv) −x+2, y−1/2, −z+1; (v) x, y, z+1; (vi) −x+1, y−1/2, −z+2.