Poly[[bis(μ₂-4-amino­benzene­sul­fon­ato-κ² N:O)diaqua­manganese(II)] dihydrate]

Abstract

The title compound, {[Mn(NH₂C₆H₄SO₃)₂(H₂O)₂]·2H₂O}_n, was prepared under mild hydro­thermal conditions. The unique Mn^II ion is located on a crystallographic inversion center and is coordinated by two –NH₂ and two –SO₃ groups from four 4-amino­benzene­sulfonate ligands and by two water mol­ecules in the axial positions, forming a slightly distorted octa­hedral coordination environment. The 4-amino­benzene­sulfonate anions behave as μ₂-bridging ligands to produce a two-dimensional structure. In the crystal structure, inter­molecular N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the layers into a three-dimensional network.

Related literature

For the isostructural Zn and Co compounds, see: Shakeri & Haussuhl (1992 ▶). For a similar layered structure, see: Cai et al. (2003 ▶).

Experimental

Crystal data

• [Mn(C₆H₆NO₃S)₂(H₂O)₂]·2H₂O

• M _r = 471.36

• Monoclinic,

• a = 7.4485 (8) Å

• b = 17.4102 (19) Å

• c = 7.6509 (9) Å

• β = 116.688 (1)°

• V = 886.47 (17) ų

• Z = 2

• Mo Kα radiation

• μ = 1.04 mm⁻¹

• T = 295 (2) K

• 0.49 × 0.45 × 0.45 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.547, T _max = 0.625

• 6604 measured reflections

• 1637 independent reflections

• 1585 reflections with I > 2σ(I)

• R _int = 0.015

Refinement

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.149

• S = 1.11

• 1637 reflections

• 124 parameters

• H-atom parameters constrained

• Δρ_max = 1.19 e Å⁻³

• Δρ_min = −1.03 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected geometric parameters (Å, °).

Mn1—O4	1.993 (3)
Mn1—N1i	2.058 (3)
Mn1—O1	2.425 (3)

O4—Mn1—O4ii	180
O4—Mn1—N1i	92.95 (13)
O4—Mn1—N1iii	87.05 (13)
N1i—Mn1—N1iii	180
O4—Mn1—O1ii	84.94 (12)
O4—Mn1—O1	95.06 (12)
N1i—Mn1—O1	86.66 (11)
N1iii—Mn1—O1	93.34 (11)
O1ii—Mn1—O1	180

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2iv	0.90	2.46	2.980 (4)	117
O5—H3W⋯O1	0.82	2.06	2.855 (5)	164
C2—H2⋯O2	0.93	2.54	2.920 (5)	105
N1—H1B⋯O2iii	0.90	2.41	3.217 (4)	149
O4—H2W⋯O5v	0.83	1.83	2.651 (5)	175
C2—H2⋯O5v	0.93	2.53	3.431 (6)	164
O4—H1W⋯O3vi	0.82	2.02	2.795 (4)	157
N1—H1A⋯O3vii	0.90	2.24	3.070 (5)	153
C3—H3⋯O3vii	0.93	2.55	3.300 (5)	138
O5—H4W⋯O2viii	0.82	2.00	2.815 (5)	175

Symmetry codes: (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

supplementary crystallographic information

Comment

The asymmetric unit of the title compound (I) is illustrated in Fig.1. This consists of one half of Mn^II ion, one 4-aminobenzenesulfonate ligand, one coordinated water molecule and one solvent water molecule. The title compound is isostructural with the Cobalt and Zinc analogs (Shakeri & Haussuhl, 1992). It is interesting to note that the title compound has very similar layered structure as that observed in [Cd(1,5 nds)-(H₂O)₂]_n (Cai et al., 2003) (1,5-nds = 1,5-naphthalenedisulfonate) in which the Cd^II ion is also coordinated octahedrally by two water molecules occupying the axial positions and the layers are connected by hydrogen bonds formed between the coordinated water molecules and the sulfonate O atoms. In the crystal structure of (I) inter-layered hydrogen bonds formed between the coordinated water molecules and the –NH₂ groups with the free –SO₃^- oxygen atoms generate an extended 3-D structure (Fig.2)

Experimental

All the reagents were of AR grade and used without further purification. p-anilinesulfonic acid (0.8690 g, 5 mmol) were dissolved in 50 ml H₂O solution, the mixed solution was basified with 1 mol.L^-1 KOH to pH =7.5. Then the resultant solution was added in 10 ml double-distilled water containing MnCl₂.4H₂O (0.3950 g, 2 mmol), the resulting solution was heated at 423 K for 96 h. After cooling to room temperature, block crystals were obtained in a yield up to 37.6%.

Refinement

H atoms bonded to O atoms were included in 'as found' positions and refined with U_iso(H)=1.5U_eq(O). Other H atoms were positioned geometrically and refined using a riding model, with C-H = 0.97 Å ; N-H = 0.90 Å and with U_iso(H)=1.2 times U_eq(C,N).

Figures

Fig. 1.

The asymmetric unit of the title compound showing 30% probability ellipsoids.

Fig. 2.

Part of the crystal structure of the title compound showing hydrogen bonds as dashed lines.

Crystal data

[Mn(C6H6NO3S)2(H2O)2]·2H2O	F000 = 486
Mr = 471.36	Dx = 1.766 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2041 reflections
a = 7.4485 (8) Å	θ = 2.5–26.2º
b = 17.4102 (19) Å	µ = 1.04 mm−1
c = 7.6509 (9) Å	T = 295 (2) K
β = 116.688 (1)º	Block, yellow
V = 886.47 (17) Å3	0.49 × 0.45 × 0.45 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer	1637 independent reflections
Radiation source: fine-focus sealed tube	1585 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.015
Detector resolution: 0 pixels mm-1	θmax = 25.5º
T = 295(2) K	θmin = 2.3º
φ and ω scans	h = −9→9
Absorption correction: multi-scan(SADABS; Bruker, 2002)	k = −19→20
Tmin = 0.547, Tmax = 0.625	l = −9→9
6604 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.149	w = 1/[σ2(Fo2) + (0.0902P)2 + 2.4519P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max < 0.001
1637 reflections	Δρmax = 1.19 e Å−3
124 parameters	Δρmin = −1.03 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	1.0000	0.5000	0.0103 (3)
S1	0.65941 (14)	0.89771 (5)	0.94564 (13)	0.0222 (3)
O1	0.4931 (4)	0.92302 (17)	0.7611 (4)	0.0299 (7)
O2	0.8422 (4)	0.94184 (16)	0.9916 (4)	0.0315 (7)
O3	0.6018 (5)	0.89731 (17)	1.1046 (4)	0.0333 (7)
O4	0.7291 (5)	0.9436 (2)	0.4921 (4)	0.0376 (8)
H1W	0.7114	0.9406	0.3785	0.056*
H2W	0.8495	0.9411	0.5706	0.056*
N1	0.8133 (5)	0.57368 (19)	0.7847 (5)	0.0265 (7)
H1A	0.8601	0.5771	0.6950	0.032*
H1B	0.6918	0.5512	0.7253	0.032*
C1	0.7134 (6)	0.8009 (2)	0.9110 (5)	0.0238 (8)
C2	0.8724 (6)	0.7854 (2)	0.8697 (6)	0.0307 (9)
H2	0.9547	0.8250	0.8669	0.037*
C3	0.9088 (6)	0.7106 (2)	0.8325 (6)	0.0309 (9)
H3	1.0167	0.6997	0.8065	0.037*
C4	0.7828 (6)	0.6515 (2)	0.8344 (5)	0.0236 (8)
C5	0.6261 (6)	0.6673 (2)	0.8804 (6)	0.0289 (9)
H5	0.5452	0.6276	0.8857	0.035*
C6	0.5900 (6)	0.7421 (2)	0.9184 (6)	0.0288 (9)
H6	0.4847	0.7529	0.9485	0.035*
O5	0.1093 (5)	0.9329 (2)	0.7587 (5)	0.0484 (9)
H3W	0.2066	0.9285	0.7362	0.073*
H4W	0.1188	0.9679	0.8342	0.073*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Mn1	0.0192 (4)	0.0266 (4)	0.0139 (4)	−0.0005 (2)	0.0062 (3)	−0.0015 (2)
S1	0.0264 (5)	0.0180 (5)	0.0240 (5)	0.0012 (3)	0.0129 (4)	−0.0003 (3)
O1	0.0309 (15)	0.0283 (15)	0.0302 (15)	0.0046 (12)	0.0134 (12)	0.0053 (12)
O2	0.0311 (15)	0.0227 (15)	0.0398 (16)	−0.0025 (12)	0.0153 (13)	−0.0021 (12)
O3	0.0452 (18)	0.0300 (16)	0.0328 (15)	0.0003 (13)	0.0246 (14)	−0.0025 (12)
O4	0.0328 (16)	0.050 (2)	0.0276 (15)	0.0088 (14)	0.0110 (13)	−0.0041 (14)
N1	0.0320 (18)	0.0209 (17)	0.0281 (17)	−0.0011 (13)	0.0147 (15)	−0.0042 (13)
C1	0.0269 (19)	0.0205 (18)	0.0237 (18)	0.0017 (15)	0.0110 (15)	−0.0006 (14)
C2	0.036 (2)	0.021 (2)	0.042 (2)	−0.0019 (16)	0.023 (2)	−0.0006 (17)
C3	0.031 (2)	0.027 (2)	0.042 (2)	0.0011 (17)	0.0226 (19)	−0.0010 (17)
C4	0.028 (2)	0.0185 (18)	0.0210 (18)	0.0038 (14)	0.0081 (15)	0.0015 (14)
C5	0.031 (2)	0.025 (2)	0.032 (2)	−0.0039 (16)	0.0153 (17)	0.0010 (16)
C6	0.032 (2)	0.025 (2)	0.035 (2)	0.0006 (16)	0.0199 (18)	−0.0024 (16)
O5	0.0323 (17)	0.064 (2)	0.051 (2)	−0.0065 (16)	0.0208 (16)	−0.0216 (18)

Geometric parameters (Å, °)

Mn1—O4	1.993 (3)	N1—H1A	0.9000
Mn1—O4i	1.993 (3)	N1—H1B	0.9000
Mn1—N1ii	2.058 (3)	C1—C2	1.383 (6)
Mn1—N1iii	2.058 (3)	C1—C6	1.393 (6)
Mn1—O1i	2.425 (3)	C2—C3	1.385 (6)
Mn1—O1	2.425 (3)	C2—H2	0.9300
S1—O3	1.460 (3)	C3—C4	1.396 (6)
S1—O2	1.462 (3)	C3—H3	0.9300
S1—O1	1.467 (3)	C4—C5	1.390 (6)
S1—C1	1.780 (4)	C5—C6	1.387 (6)
O4—H1W	0.8200	C5—H5	0.9300
O4—H2W	0.8267	C6—H6	0.9300
N1—C4	1.453 (5)	O5—H3W	0.8197
N1—Mn1iv	2.058 (3)	O5—H4W	0.8216
O4—Mn1—O4i	180	C4—N1—Mn1iv	120.1 (2)
O4—Mn1—N1ii	92.95 (13)	C4—N1—H1A	107.3
O4i—Mn1—N1ii	87.05 (13)	Mn1iv—N1—H1A	107.3
O4—Mn1—N1iii	87.05 (13)	C4—N1—H1B	107.3
O4i—Mn1—N1iii	92.95 (13)	Mn1iv—N1—H1B	107.3
N1ii—Mn1—N1iii	180	H1A—N1—H1B	106.9
O4—Mn1—O1i	84.94 (12)	C2—C1—C6	121.0 (4)
O4i—Mn1—O1i	95.06 (12)	C2—C1—S1	119.5 (3)
N1ii—Mn1—O1i	93.34 (11)	C6—C1—S1	119.5 (3)
N1iii—Mn1—O1i	86.66 (11)	C1—C2—C3	119.8 (4)
O4—Mn1—O1	95.06 (12)	C1—C2—H2	120.1
O4i—Mn1—O1	84.94 (12)	C3—C2—H2	120.1
N1ii—Mn1—O1	86.66 (11)	C2—C3—C4	119.7 (4)
N1iii—Mn1—O1	93.34 (11)	C2—C3—H3	120.1
O1i—Mn1—O1	180	C4—C3—H3	120.1
O3—S1—O2	113.12 (18)	C5—C4—C3	120.1 (4)
O3—S1—O1	111.46 (18)	C5—C4—N1	119.9 (4)
O2—S1—O1	111.50 (18)	C3—C4—N1	119.9 (4)
O3—S1—C1	106.85 (18)	C6—C5—C4	120.2 (4)
O2—S1—C1	106.57 (18)	C6—C5—H5	119.9
O1—S1—C1	106.90 (18)	C4—C5—H5	119.9
S1—O1—Mn1	129.61 (17)	C5—C6—C1	119.2 (4)
Mn1—O4—H1W	109.4	C5—C6—H6	120.4
Mn1—O4—H2W	132.0	C1—C6—H6	120.4
H1W—O4—H2W	111.8	H3W—O5—H4W	114.3
O3—S1—O1—Mn1	143.8 (2)	C6—C1—C2—C3	0.8 (6)
O2—S1—O1—Mn1	16.3 (3)	S1—C1—C2—C3	−176.6 (3)
C1—S1—O1—Mn1	−99.8 (2)	C1—C2—C3—C4	0.9 (6)
O4—Mn1—O1—S1	45.3 (2)	C2—C3—C4—C5	−2.4 (6)
O4i—Mn1—O1—S1	−134.7 (2)	C2—C3—C4—N1	176.5 (4)
N1ii—Mn1—O1—S1	−47.3 (2)	Mn1iv—N1—C4—C5	−91.0 (4)
N1iii—Mn1—O1—S1	132.7 (2)	Mn1iv—N1—C4—C3	90.1 (4)
O3—S1—C1—C2	−141.2 (3)	C3—C4—C5—C6	2.1 (6)
O2—S1—C1—C2	−20.0 (4)	N1—C4—C5—C6	−176.8 (4)
O1—S1—C1—C2	99.4 (3)	C4—C5—C6—C1	−0.4 (6)
O3—S1—C1—C6	41.3 (4)	C2—C1—C6—C5	−1.1 (6)
O2—S1—C1—C6	162.5 (3)	S1—C1—C6—C5	176.4 (3)
O1—S1—C1—C6	−78.2 (4)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) −x+3/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2iv	0.90	2.46	2.980 (4)	117
O5—H3W···O1	0.82	2.06	2.855 (5)	164
C2—H2···O2	0.93	2.54	2.920 (5)	105
N1—H1B···O2iii	0.90	2.41	3.217 (4)	149
O4—H2W···O5v	0.83	1.83	2.651 (5)	175
C2—H2···O5v	0.93	2.53	3.431 (6)	164
O4—H1W···O3vi	0.82	2.02	2.795 (4)	157
N1—H1A···O3vii	0.90	2.24	3.070 (5)	153
C3—H3···O3vii	0.93	2.55	3.300 (5)	138
O5—H4W···O2viii	0.82	2.00	2.815 (5)	175

Symmetry codes: (iv) −x+3/2, y−1/2, −z+3/2; (iii) x−1/2, −y+3/2, z−1/2; (v) x+1, y, z; (vi) x, y, z−1; (vii) x+1/2, −y+3/2, z−1/2; (viii) −x+1, −y+2, −z+2.