Poly[[diaqua­bis(μ2-4,4′-bipyridine)­manganese(II)] bis­[2-(2-carboxy­phenyl­di­sulfanyl)benzoate]]

Hu, M.; Ma, S.-T.; Guo, L.-Q.; Fang, S.-M.

doi:10.1107/S1600536809013646

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m538-m539

doi:10.1107/S1600536809013646

Open

access

Poly[[diaquabis(μ₂-4,4′-bipyridine)manganese(II)] bis[2-(2-carboxyphenyldisulfanyl)benzoate]]

Min Hu,^a Song-Tao Ma,^a Liang-Qi Guo ^a and Shao-Ming Fang ^a ^*

^aZhengzhou University of Light Industry, Henan Provincial Key Laboratory of Surface and Interface Science, Henan, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: humin@zzuli.edu.cn

(Received 9 March 2009; accepted 10 April 2009; online 22 April 2009)

The title complex, {[Mn(C₁₀H₈N₂)₂(H₂O)₂](C₁₄H₉O₄S₂)₂}_n, contains an octahedrally coordinated Mn^II cation and 2-(2-carboxyphenyldisulfanyl)benzoate anions. The Mn^II center is situated on a crystallographic center of inversion and is coordinated by four 4,4′-bipyridine (4,4′-bipy) ligands and two water molecules. The 4,4′-bipy ligands act as bridging ligands, producing a fishing-net-like two-dimensional framework. In the crystal structure, this positively charged framework is charge balanced by 2-(2-carboxyphenyldisulfanyl)benzoate anions that form a separate anionic two-dimensional framework via intermolecular O—H⋯O hydrogen bonds and C—H⋯π stacking interactions. Additional intermolecular O—H⋯O hydrogen bonds link the cationic and anionic frameworks to form the three-dimensional crystal structure.

Related literature

For general background on the design and synthesis of coordination polymers, see: James (2003 ); Kitagawa et al. (2004 ); Steel (2005 ); Ye et al. (2005 ). For the crystal structures of related complexes with 4,4′-bipyridine ligands, see: Biradha et al. (2006 ); Denning et al. (2008 ); Hoffart et al. (2007 ); Noro et al. (2002 ); Qin et al. (2007 ); Zhang et al. (2007 ). For metal–organic framework materials containing 2,2′-dithiodibenzoic acid, see: Humphrey et al. (2004 ); Murugavel et al. (2001 ); Wang et al. (2004 ); Zhao et al. (2004 ).

Experimental

Crystal data

[Mn(C₁₀H₈N₂)₂(H₂O)₂](C₁₄H₉O₄S₂)₂
M_r = 1014.00
Triclinic, $[P \overline 1]$
a = 8.260 (5) Å
b = 11.771 (7) Å
c = 11.917 (7) Å
α = 94.334 (6)°
β = 102.339 (7)°
γ = 96.217 (7)°
V = 1119 (1) Å³
Z = 1
Mo Kα radiation
μ = 0.55 mm⁻¹
T = 293 K
0.41 × 0.13 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.807, T_max = 0.952
8248 measured reflections
3921 independent reflections
3242 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 1.03
3921 reflections
304 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11⋯O2	0.85	1.92	2.761 (3)	173
O1—H12⋯O3ⁱ	0.85	1.82	2.667 (3)	174
O5—H51⋯O2ⁱⁱ	0.82	1.83	2.637 (3)	169
C4—H4⋯S1ⁱⁱⁱ	0.93	2.86	3.562 (3)	133
C23—H23⋯S2	0.93	2.66	3.191 (3)	117
C22—H22⋯Cg1^iv	0.93	2.94	3.79 (2)	153
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y, z-1; (iii) -x, -y, -z; (iv) x+1, y, z. Cg1 is the centroid of the C12–C17 ring.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809013646/im2106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013646/im2106Isup2.hkl

checkCIF report

Comment top

Rational design and synthesis of novel coordination polymers have achieved considerable progress in the field of supramolecular chemistry and crystal engineering. (James, 2003; Kitagawa et al., 2004; Steel, 2005; Ye et al., 2005). Particularly classical ligands are represented such as 4,4' -bipy. Numerous polymeric transition metal complexes with 4,4'-bipy have been synthesized and structurally characterized to date. 4,4'-bipyridine is an ideal connector between transition metal atoms for the propagation of coordination networks due to its two potential binding sites (Denning et al., 2008; Hoffart et al., 2007; Zhang et al., 2007; Qin et al., 2007; Noro et al., 2002; Biradha et al., 2006). During our investigation of the assembly of metal ions and mixed ligands (4,4'-bipyridine and 2,2'-dithiodibenzoic acid), we did not obtain the expected compound. The title complex,{[Mn(C₁₀H₈N₂)₂(H₂O)₂] (C₁₄H₉O₄S₂)₂}_n, (I) was synthesized. In contrast to many metal-organic framework materials containing 2,2'-dithiodibenzoic acid, the anions in I do not act as bridging ligands, but rather as extraframework guest molecules (Murugavel et al., 2001; Zhao et al., 2004; Humphrey et al., 2004; Wang et al., 2004). In the title crystal structure, each Mn^II center is separated by 4,4'-bipy spacers to give a large rhombic arrangement with each metal ion adopting an octahedral environment by binding to four 4,4' -bipy ligands and two water molecules (Fig. 1). All of the 4,4'-bipy molecules act as doubly bridging ligands. Mn^II centers are bridged by 4,4'-bipy ligands to form a fishing-net like, two-dimensional framework (Fig.2). In the crystal structure, the positively charged framework of I is charge balanced by 2-o-benzoato-disulfanyl-benzoic acid anions. Intermolecular O—H···O hydrogen bonds and C—H··· π stacking interactions (Table 1) (Fig.3) between anions link them to form a two-dimensional framework. Intermolecular O—H···O hydrogen bonds link the cationic and anionic frameworks (Fig.1, Table 1) to form the observed crystal structure.

Related literature top

For general background on the design and synthesis of coordination polymers, see: James (2003); Kitagawa et al. (2004); Steel (2005); Ye et al. (2005). For the crystal structures of related complexes with 4,4'-bipyridine ligands, see: Biradha et al. (2006); Denning et al. (2008); Hoffart et al. (2007); Noro et al. (2002); Qin et al. (2007); Zhang et al. (2007). For metal–organic framework materials containing 2,2'-dithiodibenzoic acid, see: Humphrey et al. (2004); Murugavel et al. (2001); Wang et al. (2004); Zhao et al. (2004).

Experimental top

A solution of 4,4'-bipy (0.05 mmol) and 2,2'-dithiodibenzoic acid (0.05 mmol) in CH₃OH (10 ml) in the presence of excess 2,6-dimethylpyridine (ca. 0.05 ml for adjusting the pH value of the reaction system to basic conditions) was carefully layered on top of an aqueous solution (15 ml) of Mn(ClO₄)₂(0.1 mmol) in a test tube. Yellow single crystals suitable for X-ray analysis appeared at the tube wall after ca. one month at room temperature (yield ~30% based on 4,4'-bipy). Elemental analysis calculated for (C₄₈H₃₈MnN₄O₁₀S₄): H 3.78 C 56.86 N 5.53%; found: H 3.52, C 56.62, N 5.34%. IR (KBr pellet, cm^-1): 3094br, 1690m, 1594vs, 1540 s, 1457m, 1412m, 1377 s, 1306w, 1258 s, 1232m, 1171w, 1144m, 1037m,1000w, 903w, 806m, 742 s, 689m, 649w, 622m, 542w, 468w.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and the intermolecular O–H···O hydrogen-bonding interactions. Displacement ellipsoids are drawn at the 30% probability level. The atoms labelled with the suffixes A, B, C, D, and E are generated by the symmetry operations (–x, –y, 1 –z), (–x, –y + 1, –z + 1), (–x, y - 1, z), (x, y, z + 1), and (–x, –y, –z), respectively.
	Fig. 2. Cationic two-dimensional network, parallel to the (001) plane, formed by [Mn(4,4'-bipy)₄(H₂O)₂] units.
	Fig. 3. Anionic two-dimensional network, parallel to the (100) plane, formed by intermolecular O—H···O hydrogen bonds and C—H···π stacking interactions between 2-o-benzoato-disulfanyl-benzoic acid anions.

Poly[[diaquabis(µ₂-4,4'-bipyridine)manganese(II)] bis[2-(2-carboxyphenyldisulfanyl)benzoate]] top

Crystal data top

[Mn(C₁₀H₈N₂)₂(H₂O)₂](C₁₄H₉O₄S₂)₂	Z = 1
M_r = 1014.00	F(000) = 523
Triclinic, P1	D_x = 1.504 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.260 (5) Å	Cell parameters from 3063 reflections
b = 11.771 (7) Å	θ = 2.6–27.3°
c = 11.917 (7) Å	µ = 0.55 mm⁻¹
α = 94.334 (6)°	T = 293 K
β = 102.339 (7)°	Prism, yellow
γ = 96.217 (7)°	0.41 × 0.13 × 0.09 mm
V = 1119 (1) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3921 independent reflections
Radiation source: fine-focus sealed tube	3242 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.807, T_max = 0.952	k = −14→14
8248 measured reflections	l = −14→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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0338P)² + 0.4902P] where P = (F_o² + 2F_c²)/3
3921 reflections	(Δ/σ)_max = 0.001
304 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

[Mn(C₁₀H₈N₂)₂(H₂O)₂](C₁₄H₉O₄S₂)₂	γ = 96.217 (7)°
M_r = 1014.00	V = 1119 (1) Å³
Triclinic, P1	Z = 1
a = 8.260 (5) Å	Mo Kα radiation
b = 11.771 (7) Å	µ = 0.55 mm⁻¹
c = 11.917 (7) Å	T = 293 K
α = 94.334 (6)°	0.41 × 0.13 × 0.09 mm
β = 102.339 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3921 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3242 reflections with I > 2σ(I)
T_min = 0.807, T_max = 0.952	R_int = 0.018
8248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.03	Δρ_max = 0.24 e Å⁻³
3921 reflections	Δρ_min = −0.21 e Å⁻³
304 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	0.0000	0.0000	0.5000	0.02618 (12)
C1	0.1323 (3)	0.0099 (2)	0.26331 (18)	0.0413 (5)
H1	0.2313	0.0235	0.3195	0.050*
C2	0.1417 (3)	0.0171 (2)	0.14994 (18)	0.0426 (6)
H2	0.2450	0.0358	0.1321	0.051*
C3	−0.0016 (2)	−0.00339 (17)	0.06212 (16)	0.0288 (4)
C4	−0.1492 (3)	−0.03266 (19)	0.09752 (17)	0.0367 (5)
H4	−0.2496	−0.0490	0.0428	0.044*
C5	−0.1486 (3)	−0.03779 (19)	0.21322 (17)	0.0365 (5)
H5	−0.2499	−0.0580	0.2333	0.044*
C6	−0.0798 (3)	0.24339 (19)	0.4099 (2)	0.0470 (6)
H6	−0.1457	0.1943	0.3484	0.056*
C7	−0.0917 (3)	0.35907 (19)	0.4094 (2)	0.0499 (6)
H7	−0.1659	0.3853	0.3497	0.060*
C8	0.0067 (3)	0.43706 (17)	0.49789 (18)	0.0329 (5)
C9	0.1167 (3)	0.38947 (19)	0.58152 (19)	0.0420 (5)
H9	0.1880	0.4370	0.6419	0.050*
C10	0.1207 (3)	0.27247 (19)	0.57538 (19)	0.0418 (5)
H10	0.1977	0.2441	0.6318	0.050*
C11	0.4897 (3)	0.19836 (19)	0.37959 (18)	0.0366 (5)
C12	0.4734 (3)	0.29917 (18)	0.30933 (17)	0.0344 (5)
C13	0.4283 (3)	0.3990 (2)	0.3568 (2)	0.0488 (6)
H13	0.3984	0.3993	0.4278	0.059*
C14	0.4264 (4)	0.4974 (2)	0.3015 (2)	0.0626 (8)
H14	0.3949	0.5633	0.3344	0.075*
C15	0.4719 (4)	0.4971 (2)	0.1964 (2)	0.0560 (7)
H15	0.4741	0.5639	0.1595	0.067*
C16	0.5139 (3)	0.3989 (2)	0.14617 (19)	0.0429 (6)
H16	0.5428	0.3998	0.0749	0.051*
C17	0.5139 (2)	0.29761 (18)	0.20047 (17)	0.0330 (5)
C18	0.6650 (3)	0.2313 (2)	−0.25469 (19)	0.0427 (6)
C19	0.7963 (3)	0.26720 (19)	−0.14760 (19)	0.0400 (5)
C20	0.9572 (3)	0.3118 (2)	−0.1525 (2)	0.0571 (7)
H20	0.9828	0.3190	−0.2241	0.069*
C21	1.0794 (3)	0.3457 (3)	−0.0539 (3)	0.0704 (9)
H21	1.1863	0.3754	−0.0590	0.084*
C22	1.0418 (3)	0.3351 (3)	0.0525 (2)	0.0638 (8)
H22	1.1237	0.3575	0.1195	0.077*
C23	0.8834 (3)	0.2913 (2)	0.0595 (2)	0.0488 (6)
H23	0.8592	0.2850	0.1317	0.059*
C24	0.7592 (3)	0.25648 (18)	−0.03888 (18)	0.0369 (5)
N1	0.0201 (2)	0.19659 (14)	0.49270 (14)	0.0338 (4)
N2	−0.0105 (2)	−0.01530 (14)	0.29787 (14)	0.0309 (4)
O1	0.26802 (17)	0.02247 (12)	0.53842 (12)	0.0354 (3)
H11	0.3286	0.0809	0.5256	0.042*
H12	0.3335	−0.0201	0.5745	0.042*
O2	0.4542 (2)	0.20761 (14)	0.47789 (13)	0.0493 (4)
O3	0.5396 (2)	0.11191 (14)	0.33731 (13)	0.0466 (4)
O4	0.5199 (2)	0.20487 (17)	−0.25451 (14)	0.0602 (5)
O5	0.7208 (2)	0.23484 (17)	−0.35055 (14)	0.0606 (5)
H51	0.6376	0.2168	−0.4033	0.073*
S1	0.55261 (7)	0.19603 (5)	−0.03290 (5)	0.04397 (16)
S2	0.56728 (7)	0.16800 (5)	0.13681 (5)	0.03939 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0335 (2)	0.0252 (2)	0.0210 (2)	0.00591 (17)	0.00676 (18)	0.00459 (17)
C1	0.0358 (12)	0.0617 (15)	0.0222 (11)	−0.0030 (11)	0.0030 (9)	0.0019 (10)
C2	0.0351 (12)	0.0648 (16)	0.0268 (11)	−0.0044 (11)	0.0104 (9)	0.0038 (11)
C3	0.0363 (11)	0.0293 (11)	0.0213 (10)	0.0047 (9)	0.0078 (8)	0.0014 (8)
C4	0.0318 (11)	0.0534 (14)	0.0227 (11)	0.0015 (10)	0.0037 (9)	0.0031 (9)
C5	0.0346 (12)	0.0489 (13)	0.0267 (11)	0.0024 (10)	0.0097 (9)	0.0042 (9)
C6	0.0566 (15)	0.0302 (12)	0.0442 (14)	0.0031 (11)	−0.0087 (11)	0.0018 (10)
C7	0.0539 (15)	0.0344 (13)	0.0501 (15)	0.0061 (11)	−0.0135 (12)	0.0054 (11)
C8	0.0329 (11)	0.0299 (11)	0.0357 (11)	0.0025 (9)	0.0080 (9)	0.0038 (9)
C9	0.0481 (14)	0.0352 (12)	0.0362 (12)	0.0066 (10)	−0.0035 (10)	−0.0016 (10)
C10	0.0500 (14)	0.0375 (13)	0.0361 (12)	0.0132 (10)	0.0007 (11)	0.0069 (10)
C11	0.0350 (12)	0.0436 (13)	0.0301 (12)	0.0033 (10)	0.0040 (9)	0.0091 (10)
C12	0.0338 (11)	0.0401 (12)	0.0293 (11)	0.0053 (9)	0.0055 (9)	0.0079 (9)
C13	0.0643 (16)	0.0508 (15)	0.0367 (13)	0.0151 (12)	0.0183 (12)	0.0072 (11)
C14	0.095 (2)	0.0449 (15)	0.0562 (17)	0.0262 (14)	0.0249 (16)	0.0083 (13)
C15	0.0811 (19)	0.0419 (14)	0.0492 (16)	0.0164 (13)	0.0145 (14)	0.0188 (12)
C16	0.0522 (14)	0.0476 (14)	0.0323 (12)	0.0096 (11)	0.0125 (11)	0.0129 (10)
C17	0.0298 (11)	0.0399 (12)	0.0282 (11)	0.0061 (9)	0.0019 (9)	0.0069 (9)
C18	0.0582 (16)	0.0414 (13)	0.0326 (12)	0.0110 (11)	0.0155 (11)	0.0073 (10)
C19	0.0455 (13)	0.0426 (13)	0.0353 (12)	0.0120 (10)	0.0124 (10)	0.0068 (10)
C20	0.0574 (17)	0.0724 (19)	0.0480 (15)	0.0075 (14)	0.0245 (13)	0.0110 (13)
C21	0.0445 (16)	0.098 (2)	0.068 (2)	−0.0070 (15)	0.0194 (15)	0.0086 (17)
C22	0.0462 (16)	0.086 (2)	0.0505 (16)	−0.0066 (14)	0.0019 (13)	0.0022 (15)
C23	0.0469 (14)	0.0637 (16)	0.0328 (12)	0.0006 (12)	0.0069 (11)	0.0014 (11)
C24	0.0404 (12)	0.0382 (12)	0.0326 (12)	0.0045 (10)	0.0099 (10)	0.0015 (9)
N1	0.0400 (10)	0.0308 (9)	0.0303 (9)	0.0072 (8)	0.0059 (8)	0.0032 (7)
N2	0.0366 (10)	0.0330 (9)	0.0242 (9)	0.0039 (7)	0.0091 (8)	0.0032 (7)
O1	0.0333 (8)	0.0389 (8)	0.0353 (8)	0.0072 (6)	0.0059 (6)	0.0141 (6)
O2	0.0654 (11)	0.0569 (11)	0.0292 (8)	0.0068 (8)	0.0160 (8)	0.0132 (7)
O3	0.0575 (10)	0.0477 (10)	0.0425 (9)	0.0208 (8)	0.0162 (8)	0.0204 (8)
O4	0.0569 (12)	0.0838 (14)	0.0348 (9)	−0.0073 (10)	0.0084 (8)	0.0034 (9)
O5	0.0658 (12)	0.0897 (14)	0.0305 (9)	0.0164 (10)	0.0168 (8)	0.0068 (9)
S1	0.0428 (3)	0.0576 (4)	0.0289 (3)	−0.0034 (3)	0.0082 (2)	0.0014 (3)
S2	0.0464 (3)	0.0420 (3)	0.0326 (3)	0.0074 (3)	0.0131 (2)	0.0070 (2)

Geometric parameters (Å, º) top

Mn1—O1	2.1453 (18)	C11—C12	1.505 (3)
Mn1—O1ⁱ	2.1453 (18)	C12—C13	1.387 (3)
Mn1—N1ⁱ	2.312 (2)	C12—C17	1.407 (3)
Mn1—N1	2.312 (2)	C13—C14	1.376 (3)
Mn1—N2	2.384 (2)	C13—H13	0.9300
Mn1—N2ⁱ	2.384 (2)	C14—C15	1.381 (4)
C1—N2	1.341 (3)	C14—H14	0.9300
C1—C2	1.378 (3)	C15—C16	1.374 (3)
C1—H1	0.9300	C15—H15	0.9300
C2—C3	1.388 (3)	C16—C17	1.399 (3)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.391 (3)	C17—S2	1.792 (2)
C3—C3ⁱⁱ	1.495 (4)	C18—O4	1.206 (3)
C4—C5	1.384 (3)	C18—O5	1.322 (3)
C4—H4	0.9300	C18—C19	1.487 (3)
C5—N2	1.338 (3)	C19—C20	1.390 (3)
C5—H5	0.9300	C19—C24	1.405 (3)
C6—N1	1.338 (3)	C20—C21	1.376 (4)
C6—C7	1.376 (3)	C20—H20	0.9300
C6—H6	0.9300	C21—C22	1.380 (4)
C7—C8	1.393 (3)	C21—H21	0.9300
C7—H7	0.9300	C22—C23	1.376 (4)
C8—C9	1.393 (3)	C22—H22	0.9300
C8—C8ⁱⁱⁱ	1.495 (4)	C23—C24	1.385 (3)
C9—C10	1.378 (3)	C23—H23	0.9300
C9—H9	0.9300	C24—S1	1.794 (2)
C10—N1	1.347 (3)	O1—H11	0.8488
C10—H10	0.9300	O1—H12	0.8488
C11—O3	1.249 (3)	O5—H51	0.8220
C11—O2	1.267 (3)	S1—S2	2.0539 (14)

O1—Mn1—O1ⁱ	180.0	C17—C12—C11	121.76 (19)
O1—Mn1—N1ⁱ	93.78 (6)	C14—C13—C12	121.6 (2)
O1ⁱ—Mn1—N1ⁱ	86.22 (6)	C14—C13—H13	119.2
O1—Mn1—N1	86.22 (6)	C12—C13—H13	119.2
O1ⁱ—Mn1—N1	93.78 (6)	C13—C14—C15	119.2 (2)
N1ⁱ—Mn1—N1	180.0	C13—C14—H14	120.4
O1—Mn1—N2	91.06 (5)	C15—C14—H14	120.4
O1ⁱ—Mn1—N2	88.94 (5)	C16—C15—C14	120.5 (2)
N1ⁱ—Mn1—N2	93.20 (6)	C16—C15—H15	119.8
N1—Mn1—N2	86.80 (6)	C14—C15—H15	119.8
O1—Mn1—N2ⁱ	88.94 (5)	C15—C16—C17	121.0 (2)
O1ⁱ—Mn1—N2ⁱ	91.06 (5)	C15—C16—H16	119.5
N1ⁱ—Mn1—N2ⁱ	86.80 (6)	C17—C16—H16	119.5
N1—Mn1—N2ⁱ	93.20 (6)	C16—C17—C12	118.4 (2)
N2—Mn1—N2ⁱ	180.0	C16—C17—S2	122.06 (17)
N2—C1—C2	124.3 (2)	C12—C17—S2	119.51 (16)
N2—C1—H1	117.9	O4—C18—O5	122.9 (2)
C2—C1—H1	117.9	O4—C18—C19	123.2 (2)
C1—C2—C3	120.5 (2)	O5—C18—C19	113.9 (2)
C1—C2—H2	119.7	C20—C19—C24	118.7 (2)
C3—C2—H2	119.7	C20—C19—C18	121.1 (2)
C2—C3—C4	115.27 (18)	C24—C19—C18	120.2 (2)
C2—C3—C3ⁱⁱ	122.7 (2)	C21—C20—C19	121.6 (2)
C4—C3—C3ⁱⁱ	122.0 (2)	C21—C20—H20	119.2
C5—C4—C3	120.80 (19)	C19—C20—H20	119.2
C5—C4—H4	119.6	C20—C21—C22	119.3 (3)
C3—C4—H4	119.6	C20—C21—H21	120.3
N2—C5—C4	123.71 (19)	C22—C21—H21	120.3
N2—C5—H5	118.1	C23—C22—C21	120.1 (3)
C4—C5—H5	118.1	C23—C22—H22	119.9
N1—C6—C7	124.6 (2)	C21—C22—H22	119.9
N1—C6—H6	117.7	C22—C23—C24	121.2 (2)
C7—C6—H6	117.7	C22—C23—H23	119.4
C6—C7—C8	120.3 (2)	C24—C23—H23	119.4
C6—C7—H7	119.8	C23—C24—C19	119.0 (2)
C8—C7—H7	119.8	C23—C24—S1	122.39 (17)
C7—C8—C9	115.4 (2)	C19—C24—S1	118.59 (17)
C7—C8—C8ⁱⁱⁱ	121.8 (2)	C6—N1—C10	114.97 (18)
C9—C8—C8ⁱⁱⁱ	122.8 (2)	C6—N1—Mn1	121.51 (14)
C10—C9—C8	120.5 (2)	C10—N1—Mn1	123.27 (14)
C10—C9—H9	119.8	C5—N2—C1	115.39 (17)
C8—C9—H9	119.8	C5—N2—Mn1	126.19 (13)
N1—C10—C9	124.1 (2)	C1—N2—Mn1	118.17 (13)
N1—C10—H10	118.0	Mn1—O1—H11	124.9
C9—C10—H10	118.0	Mn1—O1—H12	127.9
O3—C11—O2	124.6 (2)	H11—O1—H12	106.9
O3—C11—C12	117.53 (19)	C18—O5—H51	105.1
O2—C11—C12	117.8 (2)	C24—S1—S2	105.21 (8)
C13—C12—C17	119.2 (2)	C17—S2—S1	104.13 (8)
C13—C12—C11	118.9 (2)

N2—C1—C2—C3	−0.7 (4)	C20—C19—C24—C23	0.4 (3)
C1—C2—C3—C4	−1.1 (3)	C18—C19—C24—C23	−179.5 (2)
C1—C2—C3—C3ⁱⁱ	179.9 (2)	C20—C19—C24—S1	−178.70 (18)
C2—C3—C4—C5	1.3 (3)	C18—C19—C24—S1	1.4 (3)
C3ⁱⁱ—C3—C4—C5	−179.7 (2)	C7—C6—N1—C10	−4.3 (4)
C3—C4—C5—N2	0.3 (3)	C7—C6—N1—Mn1	170.2 (2)
N1—C6—C7—C8	1.4 (4)	C9—C10—N1—C6	4.3 (3)
C6—C7—C8—C9	1.6 (4)	C9—C10—N1—Mn1	−170.04 (18)
C6—C7—C8—C8ⁱⁱⁱ	−178.1 (3)	O1—Mn1—N1—C6	137.19 (18)
C7—C8—C9—C10	−1.6 (3)	O1ⁱ—Mn1—N1—C6	−42.81 (18)
C8ⁱⁱⁱ—C8—C9—C10	178.1 (2)	N1ⁱ—Mn1—N1—C6	−123 (100)
C8—C9—C10—N1	−1.5 (4)	N2—Mn1—N1—C6	45.92 (18)
O3—C11—C12—C13	−176.1 (2)	N2ⁱ—Mn1—N1—C6	−134.08 (18)
O2—C11—C12—C13	3.0 (3)	O1—Mn1—N1—C10	−48.84 (17)
O3—C11—C12—C17	−0.6 (3)	O1ⁱ—Mn1—N1—C10	131.16 (17)
O2—C11—C12—C17	178.5 (2)	N1ⁱ—Mn1—N1—C10	51 (100)
C17—C12—C13—C14	−1.8 (4)	N2—Mn1—N1—C10	−140.12 (18)
C11—C12—C13—C14	173.8 (2)	N2ⁱ—Mn1—N1—C10	39.88 (18)
C12—C13—C14—C15	−0.5 (4)	C4—C5—N2—C1	−2.0 (3)
C13—C14—C15—C16	1.8 (4)	C4—C5—N2—Mn1	172.24 (16)
C14—C15—C16—C17	−0.9 (4)	C2—C1—N2—C5	2.2 (3)
C15—C16—C17—C12	−1.4 (3)	C2—C1—N2—Mn1	−172.51 (19)
C15—C16—C17—S2	179.74 (19)	O1—Mn1—N2—C5	176.09 (17)
C13—C12—C17—C16	2.7 (3)	O1ⁱ—Mn1—N2—C5	−3.91 (17)
C11—C12—C17—C16	−172.80 (19)	N1ⁱ—Mn1—N2—C5	82.25 (17)
C13—C12—C17—S2	−178.41 (17)	N1—Mn1—N2—C5	−97.75 (17)
C11—C12—C17—S2	6.1 (3)	N2ⁱ—Mn1—N2—C5	−142 (100)
O4—C18—C19—C20	−171.1 (2)	O1—Mn1—N2—C1	−9.86 (16)
O5—C18—C19—C20	6.7 (3)	O1ⁱ—Mn1—N2—C1	170.14 (16)
O4—C18—C19—C24	8.8 (4)	N1ⁱ—Mn1—N2—C1	−103.70 (16)
O5—C18—C19—C24	−173.4 (2)	N1—Mn1—N2—C1	76.30 (16)
C24—C19—C20—C21	−0.2 (4)	N2ⁱ—Mn1—N2—C1	33 (100)
C18—C19—C20—C21	179.8 (3)	C23—C24—S1—S2	−9.7 (2)
C19—C20—C21—C22	0.1 (5)	C19—C24—S1—S2	169.35 (16)
C20—C21—C22—C23	−0.2 (5)	C16—C17—S2—S1	−15.88 (19)
C21—C22—C23—C24	0.4 (4)	C12—C17—S2—S1	165.29 (15)
C22—C23—C24—C19	−0.5 (4)	C24—S1—S2—C17	91.50 (11)
C22—C23—C24—S1	178.6 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O2	0.85	1.92	2.761 (3)	173
O1—H12···O3^iv	0.85	1.82	2.667 (3)	174
O5—H51···O2^v	0.82	1.83	2.637 (3)	169
C4—H4···S1ⁱⁱ	0.93	2.86	3.562 (3)	133
C23—H23···S2	0.93	2.66	3.191 (3)	117
C22—H22···Cg1^vi	0.93	2.94	3.79 (2)	153

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

Experimental details

Crystal data
Chemical formula	[Mn(C₁₀H₈N₂)₂(H₂O)₂](C₁₄H₉O₄S₂)₂
M_r	1014.00
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.260 (5), 11.771 (7), 11.917 (7)
α, β, γ (°)	94.334 (6), 102.339 (7), 96.217 (7)
V (Å³)	1119 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.41 × 0.13 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.807, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	8248, 3921, 3242
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 1.03
No. of reflections	3921
No. of parameters	304
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O2	0.85	1.92	2.761 (3)	173
O1—H12···O3ⁱ	0.85	1.82	2.667 (3)	174
O5—H51···O2ⁱⁱ	0.82	1.83	2.637 (3)	169
C4—H4···S1ⁱⁱⁱ	0.93	2.86	3.562 (3)	133
C23—H23···S2	0.93	2.66	3.191 (3)	117
C22—H22···Cg1^iv	0.93	2.94	3.79 (2)	153

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

Acknowledgements

This work was supported by the Startup Fund for PhDs of Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 2006BSJJ001 to S-MF). We also thank Dr Chun-Sen Liu for helpful discussions and valuable suggestions.

References

Biradha, K., Sarkar, M. & Rajput, L. (2006). Chem. Commun. pp. 4169–4179. Web of Science CrossRef Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Denning, M. S., Irwin, M. & Goicoechea, J. M. (2008). Inorg. Chem. 47, 6118–6120. Web of Science CSD CrossRef PubMed CAS Google Scholar
Hoffart, D. J., Habermehl, N. C. & Loeb, S. J. (2007). Dalton Trans. pp. 2870–2875. Web of Science CSD CrossRef Google Scholar
Humphrey, S. M., Mole, R. A., Rawson, J. M. & Wood, P. T. (2004). Dalton Trans. pp. 1670–1678. Web of Science CSD CrossRef PubMed Google Scholar
James, S. L. (2003). Chem. Soc. Rev. 32, 276–288. Web of Science CrossRef PubMed CAS Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375. Web of Science CrossRef CAS Google Scholar
Murugavel, R., Baheti, K. & Anantharaman, G. (2001). Inorg. Chem. 40, 6870–6878. Web of Science CSD CrossRef PubMed CAS Google Scholar
Noro, S.-I., Kitaura, R., Kondo, M., Kitagawa, S., Ishii, T., Matsuzaka, H. & Yamashita, M. (2002). J. Am. Chem. Soc. 124, 2568–2583. Web of Science CSD CrossRef PubMed CAS Google Scholar
Qin, J.-H., Li, X.-L. & Guo, H. (2007). Z. Kristallogr. New Cryst. Struct. 222, 318–320. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steel, P. J. (2005). Acc. Chem. Res. 38, 243–250. Web of Science CrossRef PubMed CAS Google Scholar
Wang, S., Mao-Lin, H. & Chen, F. (2004). Acta Cryst. E60, m413–m415. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ye, B.-H., Tong, M.-L. & Chen, X.-M. (2005). Coord. Chem. Rev. 249, 545–565. Web of Science CrossRef CAS Google Scholar
Zhang, J., Liu, R., Feng, P. & Bu, X. (2007). Angew. Chem. Int. Ed. 46, 8388 –8391. Google Scholar
Zhao, W.-N., Zou, J.-W. & Yu, Q.-S. (2004). Acta Cryst. C60, m443–m444. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.