catena-Poly[[[bis­(1,10-phenanthroline-κ2N,N′)manganese(II)]-μ-9,10-dioxo­anthracene-1,5-disulfonato-κ2O1:O5] tetra­hydrate]

Jia, J.; Feng, W.; Zhao, H.-K.; Yang, E.-C.

doi:10.1107/S1600536809019503

catena-Poly[[[bis(1,10-phenanthroline-κ²N,N′)manganese(II)]-μ-9,10-dioxoanthracene-1,5-disulfonato-κ²O¹:O⁵] tetrahydrate]

J. Jia, W. Feng, H.-K. Zhao and E.-C. Yang

The title complex, {[Mn(C₁₄H₆O₈S₂)(C₁₂H₈N₂)₂]·4H₂O}_n, exhibits a chain-like polymeric structure with 9,10-dioxoanthracene-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 octahedral 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, interligand π–π stacking [centroid-to-centroid distances 3.532 (1) and 3.497 (3) Å] and intermolecular O—H

O hydrogen-bonding interactions assemble the chains into a three-dimensional supramolecular network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809019503/im2118sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809019503/im2118Isup2.hkl Contains datablock I

CCDC reference: 738110

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
R factor = 0.030
wR factor = 0.086
Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    --  N1      ..       5.18 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    --  N2      ..       5.67 su
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C8     -C19           1.41 Ang.
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          5
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          4
            O1  -MN1 -O1  -S1    163.00 13.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            N1  -MN1 -N1  -C9    -37.00  8.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N1  -MN1 -N1  -C8    146.00  8.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            N2  -MN1 -N2  -C18    36.00 17.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         26
            N2  -MN1 -N2  -C19  -146.00 17.00   2.666   1.555   1.555   1.555

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   8 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Recently, organosulfonate-based metal complexes have drawn intense interest due to their adjustable coordination ability and interesting applications as functional materials [Cai, 2004; Côté & Shimizu, 2003; Zhao et al., 2007]. By introducing popular nitrogen-containing functional organic molecules as coligands, a series of sulfonate-based complexes have successfully been synthesized, which exhibit diverse structures ranging from discrete zero-dimensional (0D) to infinite high-dimensional structures [Cai et al., 2001; Gándara et al., 2006; Du et al., 2006]. As part of our continuous investigation on the coordination chemistry of mixed-ligand systems [Dai et al., 2006; Cui et al., 2007; Wu et al., 2007], we herein report the crystal structure of a Mn^II complex with 1,10-phenanthroline and 9,10-dioxoanthracene-1,5-disulfonate ligands (I).

The local coordination environment of Mn^II atom in I is shown in Fig. 1. The unique Mn^II atom is situated on a crystallodraphic centre of inversion and is six-coordinated by four N atoms from two chelating 1,10-phenanthroline ligands and two sulfonate O atoms from two independent 9,10-dioxoanthracene-1,5-disulfonate anions, exhibiting a slightly distorted octahedral coordination mode. The centrosymmetric 9,10-dioxoanthracene-1,5-disulfonate anion adopts a bis-monodentate mode, linking the adjacent Mn^II atoms into a one-dimensional infinite chain along the c-axis (Fig. 2). Two interligand π–π stacking interactions between the intrachain 1,10-phenanthroline and anthraquinone ring as well as between the two interchain 1,10-phenanthroline rings were observed (Fig. 1 and 2), which stabilize the one-dimensional chain and further extend the chains into a two-dimensional plane. The centroid–centroid distance and the dihedral angle between the 1,10-phenanthroline and anthraquinone ring measures to 3.532 (1) Å and 2.704 (4)°. In contrast, the π-stacking parameters between the interchain 1,10-phenanthroline rings are 3.497 (3) Å and 0.0°, respectively.

Additionally, the adjacent two-dimensional planes are extended into a three-dimensional supramolecular network by fourfold O—H···O hydrogen-bonding interactions between the sulfonate O atoms and the lattice water molecules (Table 1 and Fig. 2).

Related literature top

For applications of organosulfonate-based metal complexes [Revised text OK?], 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 top

A mixture of disodium 9,10-dioxoanthracene-1,5-disulfonate (164.8 mg, 0.4 mmol), Mn(OAc)₂.4H₂O (98.0 mg, 0.4 mmol), 1,10-phenanthroline (79.3 mg, 0.4 mmol), and H₂O (20 ml) was sealed in a 23 ml teflon lined stainless steel vessel. The vessel was heated to 413 K for 2 d under autogenous pressure and then cooled to room temperature at a rate of 2.4 K/h. Yellow block-shaped crystals suitable for X-ray analysis were obtained in a 41% yield. Analysis calculated for C₁₉H₁₅Mn_0.50N₂O₆S: C 53.46, H 3.54, N 6.56%; found: C 53.56, H 3.50, N 6.70%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The local coordination environment of Mn^II in I) drawn with 30% probability displacement ellipsoids. H atoms were omitted for clarity. The short dashed lines indicate interligand π-π stacking interactions [Symmetry code: (A) 1 - x, 1 - y, 1 - z.]
	Fig. 2. The three-dimensional supramolecular network of (I) produced by hydrogen-bonding and π–π stacking interactions.

catena-Poly[[[bis(1,10-phenanthroline- κ²N,N')manganese(II)]-µ-9,10-dioxoanthracene-1,5- disulfonato-κ²O¹:\<i>O⁵] tetrahydrate] top

Crystal data top

[Mn(C₁₄H₆O₈S₂)(C₁₂H₈N₂)₂]·4H₂O	Z = 1
M_r = 853.74	F(000) = 439
Triclinic, P1	D_x = 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 = 0.58 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

Data collection top

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

Refinement top

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(F_o²) + (0.0505P)² + 0.3551P] where P = (F_o² + 2F_c²)/3
3042 reflections	(Δ/σ)_max < 0.001
259 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Mn(C₁₄H₆O₈S₂)(C₁₂H₈N₂)₂]·4H₂O	γ = 93.120 (1)°
M_r = 853.74	V = 871.5 (2) Å³
Triclinic, P1	Z = 1
a = 8.8882 (9) Å	Mo Kα radiation
b = 9.578 (1) Å	µ = 0.58 mm⁻¹
c = 11.016 (1) Å	T = 294 K
α = 105.962 (1)°	0.32 × 0.28 × 0.26 mm
β = 103.050 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3042 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2751 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.865	R_int = 0.011
4767 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	Δρ_max = 0.36 e Å⁻³
3042 reflections	Δρ_min = −0.32 e Å⁻³
259 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

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

Hydrogen-bond geometry (Å, º) top

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···O5W^iv	0.85	2.13	2.868 (3)	145
O6W—H6B···O3^v	0.85	2.12	2.922 (3)	157

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

Experimental details

Crystal data
Chemical formula	[Mn(C₁₄H₆O₈S₂)(C₁₂H₈N₂)₂]·4H₂O
M_r	853.74
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	8.8882 (9), 9.578 (1), 11.016 (1)
α, β, γ (°)	105.962 (1), 103.050 (1), 93.120 (1)
V (Å³)	871.5 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.32 × 0.28 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.838, 0.865
No. of measured, independent and observed [I > 2σ(I)] reflections	4767, 3042, 2751
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.086, 1.05
No. of reflections	3042
No. of parameters	259
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.32

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999), SHELXTL (Sheldrick, 2008).