catena-Poly[[[bis-(1,10-phenanthroline-κN,N')manganese(II)]-μ-9,10-dioxo-anthracene-1,5-disulfonato-κO:O] tetra-hydrate].

The title complex, {[Mn(C(14)H(6)O(8)S(2))(C(12)H(8)N(2))(2)]·4H(2)O}(n), exhibits a chain-like polymeric structure with 9,10-dioxo-anthracene-1,5-disulfonate anions bridging Mn(II) atoms in a bis-monodentate mode. The unique Mn(II) atom is located on a crystallographic centre of inversion. Four N atoms from two chelating 1,10-phenanthroline ligands and two sulfonate O atoms from two symmetry-related 9,10-dioxoanthracene-1,5-disulfonate anions give rise to a slightly distorted octa-hedral coordination environment around the Mn(II) centre. The centroid of the central ring of the anthraquinone ligand represents another crystallographic centre of inversion. In the crystal structure, inter-ligand π-π stacking [centroid-to-centroid distances 3.532 (1) and 3.497 (3) Å] and inter-molecular O-H⋯O hydrogen-bonding inter-actions assemble the chains into a three-dimensional supra-molecular network.

Related literature

For applications of organosulfonate-based metal complexes, see: Côté & Shimizu (2003 ▶); Cai (2004 ▶). For synthetic procedure, see: Cui et al. (2007 ▶); Dai et al. (2006 ▶); Zhao et al. (2007 ▶). For related structures, see: Cai et al. (2001 ▶); Du et al. (2006 ▶); Gándara et al. (2006 ▶); Wu et al. (2007 ▶).

Experimental

Crystal data

[Mn(C14H6O8S2)(C12H8N2)2]·4H2O

M = 853.74

Triclinic,

a = 8.8882 (9) Å

b = 9.578 (1) Å

c = 11.016 (1) Å

α = 105.962 (1)°

β = 103.050 (1)°

γ = 93.120 (1)°

V = 871.5 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.58 mm−1

T = 294 K

0.32 × 0.28 × 0.26 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.838, T max = 0.865

4767 measured reflections

3042 independent reflections

2751 reflections with I > 2σ(I)

R int = 0.011

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.086

S = 1.05

3042 reflections

259 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019503/im2118sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019503/im2118Isup2.hkl

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

[Mn(C14H6O8S2)(C12H8N2)2]·4H2O	Z = 1
Mr = 853.74	F(000) = 439
Triclinic, P1	Dx = 1.627 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8882 (9) Å	Cell parameters from 3691 reflections
b = 9.578 (1) Å	θ = 2.2–27.9°
c = 11.016 (1) Å	µ = 0.57 mm−1
α = 105.962 (1)°	T = 294 K
β = 103.050 (1)°	Block, yellow
γ = 93.120 (1)°	0.32 × 0.28 × 0.26 mm
V = 871.5 (2) Å3

Bruker APEXII CCD area-detector diffractometer	3042 independent reflections
Radiation source: fine-focus sealed tube	2751 reflections with I > 2σ(I)
graphite	Rint = 0.011
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.838, Tmax = 0.865	k = −11→8
4767 measured reflections	l = −13→13

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0505P)2 + 0.3551P] where P = (Fo2 + 2Fc2)/3
3042 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.32 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
Mn1	0.5000	0.5000	0.5000	0.02553 (13)
S1	0.34382 (5)	0.24029 (5)	0.21379 (4)	0.03110 (14)
O1	0.34939 (15)	0.38120 (14)	0.30894 (12)	0.0344 (3)
O2	0.19137 (17)	0.18841 (18)	0.12816 (15)	0.0506 (4)
O3	0.40672 (19)	0.13426 (17)	0.27693 (17)	0.0532 (4)
O4	0.2494 (2)	0.4691 (2)	0.0881 (2)	0.0710 (6)
N1	0.59998 (18)	0.65125 (17)	0.40181 (15)	0.0323 (3)
N2	0.71074 (17)	0.40323 (16)	0.44201 (15)	0.0294 (3)
C1	0.3690 (2)	0.4857 (2)	0.05604 (19)	0.0388 (5)
C2	0.4839 (2)	0.3789 (2)	0.05903 (17)	0.0307 (4)
C3	0.4760 (2)	0.2649 (2)	0.11671 (17)	0.0306 (4)
C4	0.5807 (2)	0.1633 (2)	0.1047 (2)	0.0389 (5)
H4	0.5756	0.0884	0.1429	0.047*
C5	0.6932 (3)	0.1712 (2)	0.0368 (2)	0.0448 (5)
H5	0.7597	0.0995	0.0264	0.054*
C6	0.7061 (2)	0.2844 (2)	−0.0148 (2)	0.0425 (5)
H6	0.7838	0.2916	−0.0576	0.051*
C7	0.6032 (2)	0.3891 (2)	−0.00353 (18)	0.0338 (4)
C8	0.7230 (2)	0.60542 (19)	0.35365 (17)	0.0284 (4)
C9	0.5491 (3)	0.7727 (2)	0.3818 (2)	0.0454 (5)
H9	0.4652	0.8050	0.4142	0.055*
C10	0.6133 (3)	0.8547 (2)	0.3155 (2)	0.0486 (5)
H10	0.5727	0.9391	0.3041	0.058*
C11	0.7358 (3)	0.8100 (2)	0.2677 (2)	0.0448 (5)
H11	0.7806	0.8639	0.2235	0.054*
C12	0.7950 (2)	0.6821 (2)	0.28506 (19)	0.0351 (4)
C13	0.9234 (2)	0.6277 (2)	0.2369 (2)	0.0436 (5)
H13	0.9702	0.6779	0.1911	0.052*
C14	0.9780 (2)	0.5056 (2)	0.2565 (2)	0.0435 (5)
H14	1.0616	0.4724	0.2239	0.052*
C15	0.9090 (2)	0.4258 (2)	0.32685 (19)	0.0345 (4)
C16	0.9640 (2)	0.2989 (2)	0.3505 (2)	0.0419 (5)
H16	1.0480	0.2634	0.3200	0.050*
C17	0.8938 (2)	0.2278 (2)	0.4183 (2)	0.0431 (5)
H17	0.9290	0.1436	0.4348	0.052*
C18	0.7684 (2)	0.2839 (2)	0.4623 (2)	0.0383 (5)
H18	0.7217	0.2349	0.5090	0.046*
C19	0.7815 (2)	0.47471 (19)	0.37489 (17)	0.0281 (4)
O5W	0.9995 (2)	0.9273 (2)	0.12804 (18)	0.0708 (5)
H5A	0.9520	0.8694	0.0539	0.106*
H5B	1.0469	1.0073	0.1289	0.106*
O6W	0.7867 (3)	0.0448 (3)	0.6265 (2)	0.0998 (8)
H6A	0.8658	0.0844	0.6892	0.150*
H6B	0.7305	−0.0255	0.6340	0.150*

	U11	U22	U33	U12	U13	U23
Mn1	0.0264 (2)	0.0268 (2)	0.0277 (2)	0.00381 (15)	0.01252 (15)	0.01015 (15)
S1	0.0332 (3)	0.0287 (2)	0.0334 (3)	−0.00064 (18)	0.0137 (2)	0.00874 (19)
O1	0.0354 (7)	0.0363 (7)	0.0301 (7)	0.0033 (5)	0.0105 (6)	0.0061 (5)
O2	0.0369 (8)	0.0589 (10)	0.0456 (9)	−0.0125 (7)	0.0110 (7)	0.0018 (7)
O3	0.0627 (10)	0.0451 (9)	0.0749 (11)	0.0172 (7)	0.0383 (9)	0.0358 (8)
O4	0.0518 (10)	0.1099 (15)	0.1036 (15)	0.0435 (10)	0.0535 (10)	0.0824 (13)
N1	0.0336 (8)	0.0312 (8)	0.0380 (9)	0.0052 (6)	0.0160 (7)	0.0138 (7)
N2	0.0286 (8)	0.0310 (8)	0.0330 (8)	0.0038 (6)	0.0120 (6)	0.0128 (6)
C1	0.0334 (10)	0.0589 (13)	0.0369 (11)	0.0142 (9)	0.0180 (8)	0.0259 (10)
C2	0.0282 (9)	0.0396 (10)	0.0251 (9)	0.0035 (8)	0.0082 (7)	0.0095 (8)
C3	0.0305 (9)	0.0329 (9)	0.0269 (9)	0.0003 (7)	0.0098 (7)	0.0046 (7)
C4	0.0430 (11)	0.0329 (10)	0.0435 (11)	0.0057 (8)	0.0177 (9)	0.0100 (9)
C5	0.0461 (12)	0.0413 (11)	0.0546 (13)	0.0159 (9)	0.0245 (10)	0.0148 (10)
C6	0.0395 (11)	0.0510 (12)	0.0467 (12)	0.0136 (9)	0.0250 (10)	0.0171 (10)
C7	0.0304 (9)	0.0446 (11)	0.0308 (10)	0.0083 (8)	0.0123 (8)	0.0137 (8)
C8	0.0267 (9)	0.0315 (9)	0.0269 (9)	−0.0024 (7)	0.0092 (7)	0.0074 (7)
C9	0.0479 (12)	0.0411 (11)	0.0634 (14)	0.0145 (9)	0.0302 (11)	0.0265 (10)
C10	0.0555 (14)	0.0404 (11)	0.0653 (15)	0.0115 (10)	0.0261 (12)	0.0304 (11)
C11	0.0519 (13)	0.0416 (11)	0.0509 (12)	−0.0002 (10)	0.0215 (10)	0.0240 (10)
C12	0.0357 (10)	0.0366 (10)	0.0346 (10)	−0.0039 (8)	0.0121 (8)	0.0120 (8)
C13	0.0407 (11)	0.0512 (12)	0.0470 (12)	−0.0032 (9)	0.0247 (10)	0.0180 (10)
C14	0.0362 (11)	0.0507 (12)	0.0494 (12)	0.0034 (9)	0.0246 (10)	0.0132 (10)
C15	0.0284 (9)	0.0385 (10)	0.0359 (10)	0.0016 (8)	0.0132 (8)	0.0062 (8)
C16	0.0315 (10)	0.0453 (12)	0.0501 (12)	0.0103 (9)	0.0180 (9)	0.0089 (10)
C17	0.0405 (11)	0.0395 (11)	0.0550 (13)	0.0138 (9)	0.0162 (10)	0.0182 (10)
C18	0.0366 (10)	0.0396 (11)	0.0482 (12)	0.0095 (8)	0.0182 (9)	0.0211 (9)
C19	0.0248 (9)	0.0314 (9)	0.0261 (9)	−0.0012 (7)	0.0075 (7)	0.0055 (7)
O5W	0.0725 (12)	0.0829 (13)	0.0555 (10)	−0.0218 (10)	0.0079 (9)	0.0305 (10)
O6W	0.1002 (17)	0.1057 (18)	0.0955 (16)	−0.0265 (14)	−0.0050 (13)	0.0642 (14)

Mn1—O1i	2.1820 (12)	C7—C1ii	1.499 (3)
Mn1—O1	2.1820 (12)	C8—C12	1.412 (3)
Mn1—N2	2.2758 (15)	C8—C19	1.438 (3)
Mn1—N2i	2.2758 (15)	C9—C10	1.390 (3)
Mn1—N1i	2.2834 (15)	C9—H9	0.9300
Mn1—N1	2.2834 (15)	C10—C11	1.353 (3)
S1—O2	1.4368 (15)	C10—H10	0.9300
S1—O3	1.4499 (16)	C11—C12	1.403 (3)
S1—O1	1.4539 (13)	C11—H11	0.9300
S1—C3	1.8042 (18)	C12—C13	1.429 (3)
O4—C1	1.210 (2)	C13—C14	1.343 (3)
N1—C9	1.326 (3)	C13—H13	0.9300
N1—C8	1.362 (2)	C14—C15	1.432 (3)
N2—C18	1.331 (2)	C14—H14	0.9300
N2—C19	1.361 (2)	C15—C16	1.402 (3)
C1—C2	1.485 (3)	C15—C19	1.406 (3)
C1—C7ii	1.499 (3)	C16—C17	1.362 (3)
C2—C7	1.401 (2)	C16—H16	0.9300
C2—C3	1.412 (3)	C17—C18	1.390 (3)
C3—C4	1.383 (3)	C17—H17	0.9300
C4—C5	1.388 (3)	C18—H18	0.9300
C4—H4	0.9300	O5W—H5A	0.8502
C5—C6	1.366 (3)	O5W—H5B	0.8502
C5—H5	0.9300	O6W—H6A	0.8503
C6—C7	1.393 (3)	O6W—H6B	0.8500
C6—H6	0.9300
O1i—Mn1—O1	180.0	C5—C6—H6	119.9
O1i—Mn1—N2	88.86 (5)	C7—C6—H6	119.9
O1—Mn1—N2	91.14 (5)	C6—C7—C2	120.69 (18)
O1i—Mn1—N2i	91.14 (5)	C6—C7—C1ii	116.82 (17)
O1—Mn1—N2i	88.86 (5)	C2—C7—C1ii	122.43 (17)
N2—Mn1—N2i	180.00 (7)	N1—C8—C12	122.37 (17)
O1i—Mn1—N1i	87.76 (5)	N1—C8—C19	118.36 (15)
O1—Mn1—N1i	92.24 (5)	C12—C8—C19	119.27 (16)
N2—Mn1—N1i	106.48 (5)	N1—C9—C10	124.2 (2)
N2i—Mn1—N1i	73.52 (5)	N1—C9—H9	117.9
O1i—Mn1—N1	92.24 (5)	C10—C9—H9	117.9
O1—Mn1—N1	87.76 (5)	C11—C10—C9	119.0 (2)
N2—Mn1—N1	73.52 (5)	C11—C10—H10	120.5
N2i—Mn1—N1	106.48 (5)	C9—C10—H10	120.5
N1i—Mn1—N1	179.999 (2)	C10—C11—C12	119.77 (19)
O2—S1—O3	112.74 (10)	C10—C11—H11	120.1
O2—S1—O1	112.54 (9)	C12—C11—H11	120.1
O3—S1—O1	111.06 (9)	C11—C12—C8	117.56 (18)
O2—S1—C3	108.28 (9)	C11—C12—C13	122.97 (18)
O3—S1—C3	104.66 (9)	C8—C12—C13	119.46 (19)
O1—S1—C3	107.04 (8)	C14—C13—C12	121.33 (19)
S1—O1—Mn1	135.36 (8)	C14—C13—H13	119.3
C9—N1—C8	117.14 (16)	C12—C13—H13	119.3
C9—N1—Mn1	128.11 (13)	C13—C14—C15	120.80 (19)
C8—N1—Mn1	114.68 (12)	C13—C14—H14	119.6
C18—N2—C19	117.16 (16)	C15—C14—H14	119.6
C18—N2—Mn1	127.72 (12)	C16—C15—C19	117.87 (18)
C19—N2—Mn1	115.07 (12)	C16—C15—C14	122.40 (18)
O4—C1—C2	121.34 (19)	C19—C15—C14	119.73 (19)
O4—C1—C7ii	119.27 (19)	C17—C16—C15	119.72 (18)
C2—C1—C7ii	119.26 (16)	C17—C16—H16	120.1
C7—C2—C3	118.43 (17)	C15—C16—H16	120.1
C7—C2—C1	117.76 (17)	C16—C17—C18	118.60 (19)
C3—C2—C1	123.77 (16)	C16—C17—H17	120.7
C4—C3—C2	119.42 (17)	C18—C17—H17	120.7
C4—C3—S1	114.57 (15)	N2—C18—C17	124.23 (18)
C2—C3—S1	125.96 (14)	N2—C18—H18	117.9
C3—C4—C5	121.22 (19)	C17—C18—H18	117.9
C3—C4—H4	119.4	N2—C19—C15	122.41 (17)
C5—C4—H4	119.4	N2—C19—C8	118.19 (15)
C6—C5—C4	119.86 (19)	C15—C19—C8	119.40 (16)
C6—C5—H5	120.1	H5A—O5W—H5B	117.0
C4—C5—H5	120.1	H6A—O6W—H6B	117.0
C5—C6—C7	120.25 (18)
O2—S1—O1—Mn1	157.33 (11)	C4—C5—C6—C7	−2.3 (3)
O3—S1—O1—Mn1	29.85 (14)	C5—C6—C7—C2	−0.9 (3)
C3—S1—O1—Mn1	−83.83 (12)	C5—C6—C7—C1ii	176.6 (2)
O1i—Mn1—O1—S1	163 (13)	C3—C2—C7—C6	3.5 (3)
N2—Mn1—O1—S1	33.35 (11)	C1—C2—C7—C6	−174.07 (19)
N2i—Mn1—O1—S1	−146.65 (11)	C3—C2—C7—C1ii	−173.82 (17)
N1i—Mn1—O1—S1	−73.20 (11)	C1—C2—C7—C1ii	8.6 (3)
N1—Mn1—O1—S1	106.81 (11)	C9—N1—C8—C12	0.0 (3)
O1i—Mn1—N1—C9	−91.40 (18)	Mn1—N1—C8—C12	177.27 (14)
O1—Mn1—N1—C9	88.60 (18)	C9—N1—C8—C19	179.47 (18)
N2—Mn1—N1—C9	−179.54 (19)	Mn1—N1—C8—C19	−3.2 (2)
N2i—Mn1—N1—C9	0.45 (19)	C8—N1—C9—C10	0.0 (3)
N1i—Mn1—N1—C9	−37 (8)	Mn1—N1—C9—C10	−176.90 (18)
O1i—Mn1—N1—C8	91.68 (13)	N1—C9—C10—C11	−0.1 (4)
O1—Mn1—N1—C8	−88.32 (13)	C9—C10—C11—C12	0.4 (4)
N2—Mn1—N1—C8	3.53 (12)	C10—C11—C12—C8	−0.4 (3)
N2i—Mn1—N1—C8	−176.47 (12)	C10—C11—C12—C13	179.7 (2)
N1i—Mn1—N1—C8	146 (8)	N1—C8—C12—C11	0.2 (3)
O1i—Mn1—N2—C18	86.18 (16)	C19—C8—C12—C11	−179.24 (17)
O1—Mn1—N2—C18	−93.82 (16)	N1—C8—C12—C13	−179.86 (18)
N2i—Mn1—N2—C18	36 (17)	C19—C8—C12—C13	0.7 (3)
N1i—Mn1—N2—C18	−1.15 (17)	C11—C12—C13—C14	179.3 (2)
N1—Mn1—N2—C18	178.85 (17)	C8—C12—C13—C14	−0.6 (3)
O1i—Mn1—N2—C19	−96.18 (12)	C12—C13—C14—C15	−0.2 (3)
O1—Mn1—N2—C19	83.82 (12)	C13—C14—C15—C16	−179.2 (2)
N2i—Mn1—N2—C19	−146 (17)	C13—C14—C15—C19	0.8 (3)
N1i—Mn1—N2—C19	176.49 (12)	C19—C15—C16—C17	−0.1 (3)
N1—Mn1—N2—C19	−3.51 (12)	C14—C15—C16—C17	179.9 (2)
O4—C1—C2—C7	167.4 (2)	C15—C16—C17—C18	0.1 (3)
C7ii—C1—C2—C7	−8.3 (3)	C19—N2—C18—C17	−0.8 (3)
O4—C1—C2—C3	−10.0 (3)	Mn1—N2—C18—C17	176.82 (16)
C7ii—C1—C2—C3	174.24 (17)	C16—C17—C18—N2	0.4 (3)
C7—C2—C3—C4	−3.0 (3)	C18—N2—C19—C15	0.7 (3)
C1—C2—C3—C4	174.46 (18)	Mn1—N2—C19—C15	−177.20 (13)
C7—C2—C3—S1	174.29 (14)	C18—N2—C19—C8	−178.94 (17)
C1—C2—C3—S1	−8.3 (3)	Mn1—N2—C19—C8	3.2 (2)
O2—S1—C3—C4	−108.81 (16)	C16—C15—C19—N2	−0.3 (3)
O3—S1—C3—C4	11.67 (17)	C14—C15—C19—N2	179.75 (18)
O1—S1—C3—C4	129.62 (14)	C16—C15—C19—C8	179.36 (17)
O2—S1—C3—C2	73.81 (18)	C14—C15—C19—C8	−0.6 (3)
O3—S1—C3—C2	−165.72 (16)	N1—C8—C19—N2	0.1 (2)
O1—S1—C3—C2	−47.77 (18)	C12—C8—C19—N2	179.57 (16)
C2—C3—C4—C5	−0.2 (3)	N1—C8—C19—C15	−179.58 (16)
S1—C3—C4—C5	−177.72 (16)	C12—C8—C19—C15	−0.1 (3)
C3—C4—C5—C6	2.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O5W—H5A···O2ii	0.85	2.03	2.826 (2)	156
O5W—H5B···O2iii	0.85	2.10	2.948 (2)	172
O6W—H6A···O5Wiv	0.85	2.13	2.868 (3)	145
O6W—H6B···O3v	0.85	2.12	2.922 (3)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5W—H5A⋯O2i	0.85	2.03	2.826 (2)	156
O5W—H5B⋯O2ii	0.85	2.10	2.948 (2)	172
O6W—H6A⋯O5Wiii	0.85	2.13	2.868 (3)	145
O6W—H6B⋯O3iv	0.85	2.12	2.922 (3)	157

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