Poly[[diaquabis(μ2-4,4′-bipyridyl)iron(II)] bis{2-[(3-carboxypyridin-2-yl)disulfanyl]nicotinate}]

Shan, J.-J.; Chai, S.-Y.; Feng, Y.-L.

doi:10.1107/S1600536811052287

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page m28

doi:10.1107/S1600536811052287

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Poly[[diaquabis(μ₂-4,4′-bipyridyl)iron(II)] bis{2-[(3-carboxypyridin-2-yl)disulfanyl]nicotinate}]

Jie-Jie Shan,^a Sheng-Yuan Chai ^a and Yun-Long Feng ^a ^*

^aDepartment of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China
^*Correspondence e-mail: sky37@zjnu.cn

(Received 9 November 2011; accepted 4 December 2011; online 10 December 2011)

In the title compound, {[Fe(C₁₀H₈N₂)₂(H₂O)₂](C₁₂H₇N₂O₄S₂)₂}_n, synthesized by hydrothermal reaction, the 4,4′-bipyridyl ligands (one with symmetry 2, one with symmetry $[\overline1]$ ) connect Fe²⁺ cations, forming a cationic layer parallel to (001). The coordination of the Fe²⁺ cation (site symmetry 2) is octahedral, with four N atoms from four 4,4′-bipyridyl ligands and O atoms from two trans water molecules. Adjacent layers are linked with each other by intermolecular O—H⋯O hydrogen bonds, forming a three-dimensional supramolecular structure. Parts of the nicotinic acid derivative are equally disordered over two sets of sites.

Related literature

For related structures, see: Smith & Sagatys (2003 ); Panagiotis et al. (2003 ); Wang et al. (2011 ).

Experimental

Crystal data

[Fe(C₁₀H₈N₂)₂(H₂O)₂](C₁₂H₇N₂O₄S₂)₂
M_r = 1018.92
Monoclinic, P 2/c
a = 11.5161 (2) Å
b = 11.6531 (2) Å
c = 16.3216 (3) Å
β = 102.403 (1)°
V = 2139.21 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 296 K
0.21 × 0.07 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.938, T_max = 0.957
32774 measured reflections
4930 independent reflections
3286 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.126
S = 1.05
4930 reflections
389 parameters
127 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3ⁱ	0.86 (2)	1.78 (2)	2.634 (3)	172 (3)
O1W—H1WB⋯O4ⁱⁱ	0.83 (2)	1.96 (2)	2.788 (3)	177 (3)
O2—H2⋯O4ⁱⁱⁱ	0.86 (2)	1.74 (4)	2.549 (6)	156 (8)
O2′—H2′⋯O4ⁱⁱⁱ	0.87 (2)	1.93 (3)	2.776 (10)	164 (9)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y, z-1; (iii) x, y-1, z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052287/rk2316sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052287/rk2316Isup2.hkl

checkCIF report

Comment top

The 2-mercaptopyridine-3-carboxylic acid is an interesting ligand because of its potential versatile coordinate behavior. It may act as a deprotonated ligand through either the carboxylate or the thiolate group, such as 2-mercaptopyridine-3-carboxylate hydrate (Smith et al., 2003) or 2-mercapto-nicotinic acid (Panagiotis et al., 2003). Meanwhile, 2-mercaptopyridine-3-carboxylic acid can produce its derivative, 2-(3-carboxy-pyridine-2-yl disulfanyl)-nicotinic acid under hydrothermal reaction (Wang et al., 2011). As shown in Fig. 1, the Fe atom is six-coordinated by four nitrogen atoms from four bipy ligand and two coordinated water molecules in an octahedral configuration. Fe centers are interconnected by neutral bipy ligands to form a two-dimensional cationic square-grid layer (Fig. 2). The layers are stacking along the crystallographic c axis and the free L ligands act as charge-compensating anions (Fig. 3). The intermolecular O–H···O hydrogen bonds between the coordinated water molecules and the uncoordinated carboxylate oxygen atoms play an important role in the formation of the three-dimensional network.

Related literature top

For related structures, see: Smith et al. (2003); Panagiotis et al. (2003); Wang et al. (2011).

Experimental top

All reagents were purchased commercially and used without further purification. The mixture of 2-mercaptopyridine-3-carboxylic acid (0.0465 g, 0.3 mmol), FeSO₄×7H₂O (0.0834 g, 0.3 mmol), bipy (0.0468 g, 0.3 mmol) and H₂O (16 ml) was placed into a 25 ml Teflon-leaned reactor and kept under autogenous pressure at 433 K for 3 days. The mixture was cooled to room temperature at a rate of 5 degrees per hour. The crystals were filtered and washed with water. Then the single crystals suitable for X-ray diffraction were obtained in the mother solution.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry codes: (i) -x+1, y, -z-1/2; (ii) x, y+1, z; (iv) -x, y, -z-1/2; (vii) 1+x, y, z.
	Fig. 2. A two-dimensional layered structure (anion molecules are omitted for clarity).
	Fig. 3. View of the three-dimensional network involving hydrogen bonds.

Poly[[diaquabis(µ₂-4,4'-bipyridyl)iron(II)] bis{2-[(3-carboxypyridin-2-yl)disulfanyl]nicotinate}] top

Crystal data top

[Fe(C₁₀H₈N₂)₂(H₂O)₂](C₁₂H₇N₂O₄S₂)₂	F(000) = 1048
M_r = 1018.92	D_x = 1.582 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 3520 reflections
a = 11.5161 (2) Å	θ = 1.8–27.6°
b = 11.6531 (2) Å	µ = 0.62 mm⁻¹
c = 16.3216 (3) Å	T = 296 K
β = 102.403 (1)°	Block, red
V = 2139.21 (7) Å³	0.21 × 0.07 × 0.05 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	4930 independent reflections
Radiation source: fine-focus sealed tube	3286 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ω scans	θ_max = 27.6°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.938, T_max = 0.957	k = −14→15
32774 measured reflections	l = −21→21

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0592P)² + 0.4305P] where P = (F_o² + 2F_c²)/3
4930 reflections	(Δ/σ)_max = 0.001
389 parameters	Δρ_max = 0.36 e Å⁻³
127 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Fe(C₁₀H₈N₂)₂(H₂O)₂](C₁₂H₇N₂O₄S₂)₂	V = 2139.21 (7) Å³
M_r = 1018.92	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 11.5161 (2) Å	µ = 0.62 mm⁻¹
b = 11.6531 (2) Å	T = 296 K
c = 16.3216 (3) Å	0.21 × 0.07 × 0.05 mm
β = 102.403 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4930 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3286 reflections with I > 2σ(I)
T_min = 0.938, T_max = 0.957	R_int = 0.064
32774 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	127 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.36 e Å⁻³
4930 reflections	Δρ_min = −0.58 e Å⁻³
389 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	Occ. (<1)
Fe1	0.5000	0.60631 (4)	−0.2500	0.02882 (15)
S1	0.30455 (9)	−0.03861 (10)	0.46412 (6)	0.0812 (3)
S2	0.33622 (7)	0.13250 (9)	0.46478 (5)	0.0673 (3)
O3	0.3830 (2)	0.3534 (3)	0.47678 (15)	0.0871 (9)
O4	0.2747 (2)	0.4971 (3)	0.51206 (17)	0.0838 (8)
O1W	0.46496 (16)	0.60454 (16)	−0.38083 (11)	0.0384 (4)
H1WA	0.5140 (18)	0.612 (2)	−0.4132 (14)	0.046*
H1WB	0.4066 (17)	0.574 (2)	−0.4120 (15)	0.046*
N1	0.5000	−0.1992 (2)	−0.2500	0.0320 (6)
N2	0.5000	0.4115 (2)	−0.2500	0.0322 (6)
N3	0.30520 (16)	0.60959 (17)	−0.25723 (13)	0.0339 (5)
N5	0.1051 (3)	0.1215 (3)	0.46728 (17)	0.0726 (9)
C1	0.4545 (2)	−0.1388 (2)	−0.31906 (16)	0.0403 (6)
H1A	0.4216	−0.1786	−0.3679	0.048*
C2	0.4538 (2)	−0.0207 (2)	−0.32156 (16)	0.0446 (7)
H2A	0.4222	0.0170	−0.3716	0.054*
C3	0.5000	0.0423 (3)	−0.2500	0.0348 (8)
C4	0.5000	0.1695 (3)	−0.2500	0.0322 (7)
C5	0.4950 (2)	0.2323 (2)	−0.17883 (16)	0.0404 (6)
H5A	0.4918	0.1947	−0.1291	0.048*
C6	0.4948 (2)	0.3499 (2)	−0.18169 (16)	0.0392 (6)
H6A	0.4908	0.3894	−0.1329	0.047*
C7	0.2323 (2)	0.5242 (2)	−0.28880 (18)	0.0444 (7)
H7A	0.2638	0.4626	−0.3129	0.053*
C8	0.1132 (2)	0.5219 (2)	−0.28784 (18)	0.0450 (7)
H8A	0.0665	0.4598	−0.3105	0.054*
C9	0.06347 (19)	0.6128 (2)	−0.25276 (15)	0.0347 (5)
C10	0.1365 (2)	0.7045 (2)	−0.22368 (16)	0.0400 (6)
H10A	0.1061	0.7693	−0.2026	0.048*
C11	0.2552 (2)	0.6987 (2)	−0.22625 (17)	0.0399 (6)
H11A	0.3035	0.7606	−0.2052	0.048*
C18	0.1968 (3)	0.1929 (3)	0.47415 (17)	0.0599 (9)
C19	0.1879 (3)	0.3118 (3)	0.48620 (18)	0.0618 (9)
C20	0.0773 (3)	0.3543 (4)	0.4883 (2)	0.0778 (11)
H20A	0.0675	0.4325	0.4960	0.093*
C21	−0.0196 (3)	0.2817 (5)	0.4791 (3)	0.0884 (13)
H21A	−0.0951	0.3100	0.4792	0.106*
C22	−0.0011 (3)	0.1677 (5)	0.4699 (2)	0.0822 (13)
H22A	−0.0658	0.1186	0.4650	0.099*
C23	0.2897 (3)	0.3938 (4)	0.4916 (2)	0.0703 (11)
O1	0.3004 (5)	−0.2480 (5)	0.4844 (3)	0.0697 (17)	0.50
O2	0.2225 (6)	−0.3746 (4)	0.3829 (3)	0.0763 (15)	0.50
H2	0.252 (7)	−0.427 (5)	0.418 (4)	0.092*	0.50
N4	0.2052 (17)	0.026 (3)	0.3020 (18)	0.055 (4)	0.50
C12	0.2344 (3)	−0.0670 (3)	0.3587 (2)	0.0575 (8)	0.50
C13	0.2216 (8)	−0.1758 (10)	0.3477 (6)	0.051 (3)	0.50
C14	0.1735 (11)	−0.2053 (13)	0.2620 (9)	0.072 (3)	0.50
H14A	0.1626	−0.2820	0.2466	0.087*	0.50
C15	0.1438 (13)	−0.1219 (14)	0.2032 (9)	0.071 (4)	0.50
H15A	0.1198	−0.1415	0.1468	0.085*	0.50
C16	0.150 (2)	0.005 (3)	0.230 (2)	0.085 (7)	0.50
H16A	0.1138	0.0622	0.1935	0.102*	0.50
C17	0.2512 (9)	−0.2712 (7)	0.4106 (5)	0.046 (2)	0.50
O1'	0.1141 (7)	−0.3593 (6)	0.3517 (4)	0.123 (2)	0.50
O2'	0.2801 (8)	−0.2910 (9)	0.4351 (7)	0.087 (3)	0.50
H2'	0.292 (8)	−0.353 (5)	0.465 (5)	0.105*	0.50
N4'	0.2197 (17)	0.014 (3)	0.3108 (19)	0.064 (6)	0.50
C12'	0.2344 (3)	−0.0670 (3)	0.3587 (2)	0.0575 (8)	0.50
C13'	0.1886 (9)	−0.1804 (8)	0.3196 (8)	0.054 (3)	0.50
C14'	0.1310 (11)	−0.1877 (13)	0.2374 (10)	0.081 (4)	0.50
H14B	0.1020	−0.2578	0.2144	0.097*	0.50
C15'	0.1163 (15)	−0.0891 (14)	0.1885 (12)	0.091 (5)	0.50
H15B	0.0703	−0.0859	0.1342	0.109*	0.50
C16'	0.1714 (18)	−0.006 (3)	0.2251 (16)	0.062 (4)	0.50
H16B	0.1827	0.0541	0.1898	0.074*	0.50
C17'	0.1925 (7)	−0.2874 (7)	0.3708 (5)	0.073 (2)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0244 (2)	0.0232 (3)	0.0404 (3)	0.000	0.01043 (18)	0.000
S1	0.0802 (6)	0.0940 (8)	0.0628 (6)	0.0049 (6)	0.0006 (5)	0.0307 (5)
S2	0.0547 (5)	0.0969 (8)	0.0490 (5)	−0.0114 (4)	0.0084 (4)	−0.0028 (4)
O3	0.0699 (16)	0.129 (2)	0.0725 (16)	−0.0343 (16)	0.0374 (13)	−0.0150 (15)
O4	0.0838 (18)	0.079 (2)	0.0859 (19)	−0.0177 (15)	0.0127 (14)	0.0126 (16)
O1W	0.0383 (9)	0.0388 (11)	0.0394 (10)	−0.0043 (8)	0.0108 (7)	−0.0009 (8)
N1	0.0319 (14)	0.0256 (16)	0.0392 (16)	0.000	0.0095 (12)	0.000
N2	0.0324 (14)	0.0258 (17)	0.0400 (16)	0.000	0.0108 (12)	0.000
N3	0.0261 (9)	0.0307 (12)	0.0467 (12)	−0.0017 (9)	0.0119 (8)	−0.0043 (9)
N5	0.0644 (18)	0.104 (3)	0.0502 (16)	−0.0275 (17)	0.0152 (13)	−0.0067 (16)
C1	0.0499 (15)	0.0267 (15)	0.0411 (15)	0.0011 (11)	0.0026 (12)	−0.0038 (11)
C2	0.0613 (17)	0.0296 (15)	0.0385 (15)	0.0019 (12)	0.0009 (12)	0.0020 (12)
C3	0.0365 (18)	0.027 (2)	0.040 (2)	0.000	0.0068 (14)	0.000
C4	0.0347 (17)	0.0203 (19)	0.041 (2)	0.000	0.0070 (14)	0.000
C5	0.0578 (16)	0.0274 (15)	0.0374 (14)	−0.0015 (12)	0.0134 (12)	0.0023 (11)
C6	0.0511 (15)	0.0272 (14)	0.0415 (15)	−0.0001 (12)	0.0147 (12)	−0.0033 (11)
C7	0.0354 (13)	0.0355 (16)	0.0649 (18)	0.0020 (11)	0.0168 (12)	−0.0106 (13)
C8	0.0319 (12)	0.0350 (16)	0.0682 (19)	−0.0046 (11)	0.0111 (12)	−0.0094 (13)
C9	0.0276 (11)	0.0350 (14)	0.0423 (14)	0.0026 (11)	0.0092 (10)	0.0020 (11)
C10	0.0325 (12)	0.0377 (16)	0.0515 (15)	0.0028 (11)	0.0128 (11)	−0.0074 (12)
C11	0.0291 (12)	0.0378 (16)	0.0541 (16)	−0.0038 (11)	0.0115 (11)	−0.0079 (13)
C18	0.0533 (17)	0.094 (3)	0.0345 (15)	−0.0192 (18)	0.0133 (12)	−0.0051 (16)
C19	0.0553 (18)	0.094 (3)	0.0382 (16)	−0.0185 (18)	0.0137 (13)	−0.0071 (17)
C20	0.066 (2)	0.102 (3)	0.070 (2)	−0.008 (2)	0.0246 (18)	−0.014 (2)
C21	0.057 (2)	0.135 (5)	0.077 (3)	−0.010 (3)	0.0231 (18)	−0.009 (3)
C22	0.062 (2)	0.128 (4)	0.059 (2)	−0.039 (3)	0.0182 (17)	−0.010 (2)
C23	0.068 (2)	0.100 (3)	0.0446 (18)	−0.024 (2)	0.0177 (16)	0.001 (2)
O1	0.089 (4)	0.056 (3)	0.053 (3)	−0.007 (3)	−0.010 (3)	−0.002 (3)
O2	0.113 (4)	0.039 (3)	0.066 (3)	−0.003 (3)	−0.003 (3)	0.000 (2)
N4	0.073 (7)	0.044 (6)	0.043 (6)	0.005 (6)	0.000 (6)	0.015 (5)
C12	0.0566 (18)	0.046 (2)	0.072 (2)	0.0075 (15)	0.0172 (15)	0.0074 (17)
C13	0.050 (5)	0.066 (6)	0.036 (5)	0.001 (4)	0.006 (4)	0.000 (4)
C14	0.078 (6)	0.073 (6)	0.061 (6)	0.003 (5)	0.003 (5)	−0.003 (5)
C15	0.088 (7)	0.069 (8)	0.048 (5)	0.003 (6)	−0.003 (5)	−0.012 (5)
C16	0.099 (11)	0.084 (9)	0.067 (8)	0.010 (8)	0.008 (7)	−0.012 (6)
C17	0.041 (4)	0.053 (5)	0.041 (4)	−0.008 (4)	−0.001 (3)	−0.017 (4)
O1'	0.149 (6)	0.102 (5)	0.116 (5)	−0.055 (5)	0.020 (4)	−0.003 (4)
O2'	0.064 (5)	0.088 (6)	0.108 (6)	−0.002 (4)	0.015 (4)	0.037 (5)
N4'	0.070 (6)	0.054 (9)	0.054 (8)	0.012 (5)	−0.014 (4)	0.005 (6)
C12'	0.0566 (18)	0.046 (2)	0.072 (2)	0.0075 (15)	0.0172 (15)	0.0074 (17)
C13'	0.055 (5)	0.043 (4)	0.063 (7)	−0.004 (4)	0.013 (5)	0.002 (5)
C14'	0.085 (7)	0.063 (7)	0.093 (8)	−0.025 (6)	0.015 (6)	−0.025 (6)
C15'	0.099 (8)	0.077 (8)	0.091 (8)	−0.005 (6)	0.006 (6)	−0.011 (6)
C16'	0.063 (6)	0.073 (8)	0.046 (6)	0.002 (6)	0.003 (5)	−0.001 (5)
C17'	0.074 (5)	0.077 (6)	0.069 (5)	−0.015 (5)	0.020 (4)	−0.020 (4)

Geometric parameters (Å, º) top

Fe1—O1Wⁱ	2.0863 (17)	C9—C10	1.379 (3)
Fe1—O1W	2.0863 (17)	C9—C9^iv	1.484 (4)
Fe1—N3	2.2213 (18)	C10—C11	1.378 (3)
Fe1—N3ⁱ	2.2213 (18)	C10—H10A	0.9300
Fe1—N1ⁱⁱ	2.267 (3)	C11—H11A	0.9300
Fe1—N2	2.270 (3)	C18—C19	1.406 (5)
S1—C12	1.768 (4)	C19—C20	1.374 (5)
S1—S2	2.0266 (16)	C19—C23	1.500 (5)
S2—C18	1.789 (3)	C20—C21	1.382 (5)
O3—C23	1.243 (4)	C20—H20A	0.9300
O4—C23	1.272 (5)	C21—C22	1.359 (6)
O1W—H1WA	0.857 (16)	C21—H21A	0.9300
O1W—H1WB	0.828 (16)	C22—H22A	0.9300
N1—C1ⁱ	1.337 (3)	O1—C17	1.246 (8)
N1—C1	1.337 (3)	O2—C17	1.304 (8)
N1—Fe1ⁱⁱⁱ	2.267 (3)	O2—H2	0.86 (2)
N2—C6	1.338 (3)	N4—C16	1.24 (4)
N2—C6ⁱ	1.338 (3)	N4—C12	1.42 (3)
N3—C7	1.332 (3)	C12—C13	1.284 (12)
N3—C11	1.338 (3)	C13—C14	1.431 (15)
N5—C18	1.330 (4)	C13—C17	1.503 (9)
N5—C22	1.346 (5)	C14—C15	1.36 (2)
C1—C2	1.377 (4)	C14—H14A	0.9300
C1—H1A	0.9300	C15—C16	1.54 (4)
C2—C3	1.385 (3)	C15—H15A	0.9300
C2—H2A	0.9300	C16—H16A	0.9300
C3—C2ⁱ	1.385 (3)	O1'—C17'	1.222 (8)
C3—C4	1.483 (5)	O2'—C17'	1.291 (8)
C4—C5ⁱ	1.384 (3)	O2'—H2'	0.87 (2)
C4—C5	1.384 (3)	N4'—C16'	1.41 (4)
C5—C6	1.371 (4)	C13'—C14'	1.367 (17)
C5—H5A	0.9300	C13'—C17'	1.496 (9)
C6—H6A	0.9300	C14'—C15'	1.39 (2)
C7—C8	1.375 (3)	C14'—H14B	0.9300
C7—H7A	0.9300	C15'—C16'	1.24 (3)
C8—C9	1.386 (4)	C15'—H15B	0.9300
C8—H8A	0.9300	C16'—H16B	0.9300

O1Wⁱ—Fe1—O1W	178.87 (10)	C10—C9—C9^iv	121.02 (17)
O1Wⁱ—Fe1—N3	91.47 (7)	C8—C9—C9^iv	121.68 (18)
O1W—Fe1—N3	88.55 (7)	C11—C10—C9	119.2 (2)
O1Wⁱ—Fe1—N3ⁱ	88.55 (7)	C11—C10—H10A	120.4
O1W—Fe1—N3ⁱ	91.47 (7)	C9—C10—H10A	120.4
N3—Fe1—N3ⁱ	178.03 (11)	N3—C11—C10	124.0 (2)
O1Wⁱ—Fe1—N1ⁱⁱ	90.57 (5)	N3—C11—H11A	118.0
O1W—Fe1—N1ⁱⁱ	90.57 (5)	C10—C11—H11A	118.0
N3—Fe1—N1ⁱⁱ	89.01 (5)	N5—C18—C19	123.2 (3)
N3ⁱ—Fe1—N1ⁱⁱ	89.01 (5)	N5—C18—S2	117.2 (3)
O1Wⁱ—Fe1—N2	89.43 (5)	C19—C18—S2	119.5 (2)
O1W—Fe1—N2	89.43 (5)	C20—C19—C18	117.0 (3)
N3—Fe1—N2	90.99 (5)	C20—C19—C23	119.1 (4)
N3ⁱ—Fe1—N2	90.99 (5)	C18—C19—C23	123.8 (3)
N1ⁱⁱ—Fe1—N2	180.0	C19—C20—C21	120.5 (4)
C12—S1—S2	103.51 (13)	C19—C20—H20A	119.7
C18—S2—S1	102.92 (13)	C21—C20—H20A	119.7
Fe1—O1W—H1WA	128.5 (17)	C22—C21—C20	117.9 (4)
Fe1—O1W—H1WB	125.8 (18)	C22—C21—H21A	121.1
H1WA—O1W—H1WB	103 (2)	C20—C21—H21A	121.1
C1ⁱ—N1—C1	116.5 (3)	N5—C22—C21	124.1 (4)
C1ⁱ—N1—Fe1ⁱⁱⁱ	121.77 (15)	N5—C22—H22A	117.9
C1—N1—Fe1ⁱⁱⁱ	121.77 (15)	C21—C22—H22A	117.9
C6—N2—C6ⁱ	115.1 (3)	O3—C23—O4	125.5 (3)
C6—N2—Fe1	122.47 (15)	O3—C23—C19	116.4 (4)
C6ⁱ—N2—Fe1	122.47 (15)	O4—C23—C19	118.1 (3)
C7—N3—C11	116.1 (2)	C17—O2—H2	113 (6)
C7—N3—Fe1	123.58 (16)	C16—N4—C12	118 (3)
C11—N3—Fe1	120.31 (16)	C13—C12—N4	131.3 (14)
C18—N5—C22	117.2 (4)	C13—C12—S1	109.6 (5)
N1—C1—C2	123.4 (2)	N4—C12—S1	119.0 (13)
N1—C1—H1A	118.3	C12—C13—C14	112.5 (9)
C2—C1—H1A	118.3	C12—C13—C17	129.2 (8)
C1—C2—C3	120.4 (3)	C14—C13—C17	118.2 (10)
C1—C2—H2A	119.8	C15—C14—C13	120.4 (14)
C3—C2—H2A	119.8	C15—C14—H14A	119.8
C2—C3—C2ⁱ	116.0 (3)	C13—C14—H14A	119.8
C2—C3—C4	122.01 (17)	C14—C15—C16	119.9 (16)
C2ⁱ—C3—C4	122.01 (17)	C14—C15—H15A	120.0
C5ⁱ—C4—C5	116.2 (3)	C16—C15—H15A	120.0
C5ⁱ—C4—C3	121.90 (16)	N4—C16—C15	117 (3)
C5—C4—C3	121.90 (16)	N4—C16—H16A	121.7
C6—C5—C4	120.0 (2)	C15—C16—H16A	121.7
C6—C5—H5A	120.0	O1—C17—O2	124.4 (8)
C4—C5—H5A	120.0	O1—C17—C13	119.3 (7)
N2—C6—C5	124.4 (2)	O2—C17—C13	116.3 (7)
N2—C6—H6A	117.8	C17'—O2'—H2'	119 (7)
C5—C6—H6A	117.8	C14'—C13'—C17'	116.5 (11)
N3—C7—C8	123.9 (2)	C13'—C14'—C15'	119.1 (13)
N3—C7—H7A	118.0	C16'—C15'—C14'	112.6 (18)
C8—C7—H7A	118.0	C15'—C16'—N4'	131 (3)
C7—C8—C9	119.4 (2)	O1'—C17'—O2'	126.2 (9)
C7—C8—H8A	120.3	O1'—C17'—C13'	119.8 (8)
C9—C8—H8A	120.3	O2'—C17'—C13'	113.9 (9)
C10—C9—C8	117.3 (2)

C12—S1—S2—C18	82.35 (14)	C9—C10—C11—N3	1.5 (4)
O1Wⁱ—Fe1—N2—C6	13.85 (14)	C22—N5—C18—C19	1.9 (4)
O1W—Fe1—N2—C6	−166.15 (14)	C22—N5—C18—S2	−176.6 (2)
N3—Fe1—N2—C6	−77.61 (14)	S1—S2—C18—N5	−8.6 (2)
N3ⁱ—Fe1—N2—C6	102.39 (14)	S1—S2—C18—C19	172.9 (2)
O1Wⁱ—Fe1—N2—C6ⁱ	−166.15 (14)	N5—C18—C19—C20	−1.9 (5)
O1W—Fe1—N2—C6ⁱ	13.85 (14)	S2—C18—C19—C20	176.5 (2)
N3—Fe1—N2—C6ⁱ	102.39 (14)	N5—C18—C19—C23	−178.2 (3)
N3ⁱ—Fe1—N2—C6ⁱ	−77.61 (14)	S2—C18—C19—C23	0.2 (4)
O1Wⁱ—Fe1—N3—C7	−114.2 (2)	C18—C19—C20—C21	0.1 (5)
O1W—Fe1—N3—C7	64.6 (2)	C23—C19—C20—C21	176.6 (3)
N1ⁱⁱ—Fe1—N3—C7	155.2 (2)	C19—C20—C21—C22	1.5 (6)
N2—Fe1—N3—C7	−24.8 (2)	C18—N5—C22—C21	−0.1 (5)
O1Wⁱ—Fe1—N3—C11	63.3 (2)	C20—C21—C22—N5	−1.6 (6)
O1W—Fe1—N3—C11	−117.8 (2)	C20—C19—C23—O3	−169.5 (3)
N1ⁱⁱ—Fe1—N3—C11	−27.23 (19)	C18—C19—C23—O3	6.8 (5)
N2—Fe1—N3—C11	152.77 (19)	C20—C19—C23—O4	11.6 (5)
C1ⁱ—N1—C1—C2	0.54 (19)	C18—C19—C23—O4	−172.2 (3)
Fe1ⁱⁱⁱ—N1—C1—C2	−179.46 (19)	C16—N4—C12—C13	6.0 (17)
N1—C1—C2—C3	−1.1 (4)	C16—N4—C12—S1	−175.9 (13)
C1—C2—C3—C2ⁱ	0.50 (18)	S2—S1—C12—C13	172.7 (5)
C1—C2—C3—C4	−179.50 (18)	S2—S1—C12—N4	−5.8 (7)
C2—C3—C4—C5ⁱ	−28.97 (19)	N4—C12—C13—C14	2.8 (12)
C2ⁱ—C3—C4—C5ⁱ	151.03 (19)	S1—C12—C13—C14	−175.5 (7)
C2—C3—C4—C5	151.03 (19)	N4—C12—C13—C17	−178.2 (12)
C2ⁱ—C3—C4—C5	−28.97 (19)	S1—C12—C13—C17	3.5 (12)
C5ⁱ—C4—C5—C6	0.22 (17)	C12—C13—C14—C15	−1.8 (16)
C3—C4—C5—C6	−179.78 (17)	C17—C13—C14—C15	179.0 (12)
C6ⁱ—N2—C6—C5	0.24 (19)	C13—C14—C15—C16	−6 (2)
Fe1—N2—C6—C5	−179.76 (19)	C12—N4—C16—C15	−14 (2)
C4—C5—C6—N2	−0.5 (4)	C14—C15—C16—N4	15 (3)
C11—N3—C7—C8	−2.7 (4)	C12—C13—C17—O1	−3.7 (16)
Fe1—N3—C7—C8	175.0 (2)	C14—C13—C17—O1	175.3 (10)
N3—C7—C8—C9	0.4 (4)	C12—C13—C17—O2	176.2 (9)
C7—C8—C9—C10	2.9 (4)	C14—C13—C17—O2	−4.7 (14)
C7—C8—C9—C9^iv	−177.7 (3)	C17'—C13'—C14'—C15'	175.0 (12)
C8—C9—C10—C11	−3.7 (4)	C13'—C14'—C15'—C16'	8 (2)
C9^iv—C9—C10—C11	176.9 (3)	C14'—C15'—C16'—N4'	−18 (3)
C7—N3—C11—C10	1.7 (4)	C14'—C13'—C17'—O1'	−27.1 (14)
Fe1—N3—C11—C10	−176.0 (2)	C14'—C13'—C17'—O2'	155.7 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3^v	0.86 (2)	1.78 (2)	2.634 (3)	172 (3)
O1W—H1WB···O4^vi	0.83 (2)	1.96 (2)	2.788 (3)	177 (3)
O2—H2···O4ⁱⁱⁱ	0.86 (2)	1.74 (4)	2.549 (6)	156 (8)
O2′—H2′···O4ⁱⁱⁱ	0.87 (2)	1.93 (3)	2.776 (10)	164 (9)

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

Experimental details

Crystal data
Chemical formula	[Fe(C₁₀H₈N₂)₂(H₂O)₂](C₁₂H₇N₂O₄S₂)₂
M_r	1018.92
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	296
a, b, c (Å)	11.5161 (2), 11.6531 (2), 16.3216 (3)
β (°)	102.403 (1)
V (Å³)	2139.21 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.21 × 0.07 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.938, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	32774, 4930, 3286
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.126, 1.05
No. of reflections	4930
No. of parameters	389
No. of restraints	127
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.58

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3ⁱ	0.857 (16)	1.782 (16)	2.634 (3)	172 (3)
O1W—H1WB···O4ⁱⁱ	0.828 (16)	1.962 (17)	2.788 (3)	177 (3)
O2—H2···O4ⁱⁱⁱ	0.86 (2)	1.74 (4)	2.549 (6)	156 (8)
O2'—H2'···O4ⁱⁱⁱ	0.87 (2)	1.93 (3)	2.776 (10)	164 (9)

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

References

Brandenburg, K. (2007). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Panagiotis, C. Z., Sotiris, K. H., Nick, H., Adonis, M., Stavroula, S., Yang, M. & Yu, X. L. (2003). Inorg. Chim. Acta, 343, 361–365. 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
Smith, G. & Sagatys, D. S. (2003). Acta Cryst. E59, o540–o541. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, X. J., Jiang, Z. G., Chen, J. & Feng, Y. L. (2011). Inorg. Chim. Acta, 373, 270–275. Web of Science CSD CrossRef CAS Google Scholar

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