μ-Oxido-bis­[bis­(phenanthroline-κ2N,N′)(sulfato-κO)iron(III)] octa­hydrate

Zhang, J.Y.; Wang, L.; Liu, Y.

doi:10.1107/S1600536811042723

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1568-m1569

doi:10.1107/S1600536811042723

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μ-Oxido-bis[bis(phenanthroline-κ²N,N′)(sulfato-κO)iron(III)] octahydrate

JingYa Zhang,^a Ling Wang ^b and Yanju Liu ^a ^*

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China, and ^bChemistry Department, Zheng Zhou Normal University, Zhengzhou 450044, People's Republic of China
^*Correspondence e-mail: liuyanju886@163.com

(Received 6 September 2011; accepted 15 October 2011; online 22 October 2011)

The title complex, [Fe₂O(SO₄)₂(C₁₂H₈N₂)₄]·8H₂O, contains two unique Fe^III cations, one oxide anion, four 1,10-phenanthroline (phen) ligands, two coordinated sulfate anions and eight lattice water molecules. Each Fe^III ion has an approximate octahedral geometry, coordinated by four N atoms from two phen molecules, two O atoms from oxide and sulfate anions, respectively. The parallel phen molecules form two-dimensional supermolecules through π–π stacking interactions [centroid–centroid distances = 3.684 (3), 3.711 (3), 3.790 (3), 3.847 (3), 3.746 (3), 3.732 (3) and 3.729 (3) Å]. This architecture is further stabilized by O—H⋯O hydrogen bonds involving the lattice water molecules and sulfate O atoms.

Related literature

For transition metal complexes containing organic ligands with nitrogen heteroatoms, see: Manson et al. (2001 ); Wu et al. (2009 ); Accorsi et al. (2009 ); Xie & Huang (2011 ); Feng et al. (2006 ); Yu et al. (2010 ); Weyhermüller et al. (2005 ). For phen (1,10-phenanthroline) ligands, see: Gu et al. (2006 ); Hu et al. (2009 ). For related bond lengths and angles, see: Yang et al. (2010 ).

Experimental

Crystal data

[Fe₂O(SO₄)₂(C₁₂H₈N₂)₄]·8H₂O
M_r = 1184.76
Monoclinic, C 2/c
a = 21.589 (15) Å
b = 14.181 (10) Å
c = 16.500 (12) Å
β = 97.289 (9)°
V = 5010 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 273 K
0.20 × 0.10 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ) T_min = 0.865, T_max = 0.971
11655 measured reflections
4398 independent reflections
3506 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.107
S = 1.05
4398 reflections
372 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—O1	1.7804 (10)
Fe1—O2	1.936 (2)
Fe1—N4	2.125 (2)
Fe1—N1	2.151 (2)
Fe1—N3	2.237 (3)
Fe1—N2	2.243 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3W—H3WA⋯O3ⁱ	0.85 (1)	2.14 (3)	2.872 (4)	144 (4)
O2W—H2WB⋯O4ⁱⁱ	0.85 (1)	1.89 (2)	2.713 (4)	163 (4)
O4W—H4WB⋯O5	0.85 (1)	1.98 (2)	2.756 (4)	151 (4)
O1W—H1WB⋯O3Wⁱⁱⁱ	0.86 (1)	2.06 (1)	2.909 (5)	171 (4)
O1W—H1WA⋯O4W^iv	0.86 (1)	1.97 (2)	2.811 (5)	165 (5)
O3W—H3WB⋯O4W^v	0.85 (1)	2.28 (3)	2.964 (5)	138 (3)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z; (iii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-1]$ ; (iv) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811042723/jj2103sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042723/jj2103Isup2.hkl

checkCIF report

Comment top

Organic ligands containing nitrogen heteroatoms play an important role in the assembling process of transition-metal complexes (Manson et al., 2001; Wu et al., 2009; Accorsi et al., 2009; Xie et al., 2011; Feng et al., 2006; Yu et al., 2010; Weyhermuller et al., 2005). Phen (1,10-phenanthroline) ligands fit together to form transition-metal complexes (Gu et al., 2006; Hu et al., 2009). In order to study the coordination behavior of this ligand to Fe, we have synthesized herein the title complex [(Fe₂O)(phen)₄(SO₄)₂).8H₂O], (I). The asymmetric unit contains one Fe^III atom, one half of an O^2- atom, two phen ligands, one coordinated SO₄ anion and four lattice water molecules (Fig. 1). The phen ligands lie parallel to each other in the structure and form two-dimensional supermolecules through π–π stacking inteactions [centroid–centroid distances = 3.684 (3)Å (Cg1—Cg1)ⁱ; 3.711 (3)Å (Cg3—Cg4)ⁱ, 3.790 (3)Å; (Cg4—Cg4)ⁱ, 3.847 (3)Å (Cg4—Cg7)ⁱ; 3.746 (3)Å (Cg6—Cg6)ⁱⁱ; 3.732(3(Å (Cg7—Cg7)ⁱ and 3.729(30Å Cg8—Cg6)ⁱⁱ where i = 1-x, y, 1/2-z; ii = 1-x, -y, -z and Cg1 = Fe/N1/C5/C10/N2; Cg3 = Fe1/N3/C17/C22/N4; Cg4 = N2/C6–C10; Cg6 = N4/C18–C22; Cg7 = C4/C5/C9–C12; Cg8 = C16/C17/C21–C24]. This architecture is further stabilized by O—H···O hydrogen bonds involving the lattice water molecules and oxygen atoms from the SO₄ anions (Table 1). The bond distances for Fe—N vary from 2.125 (2)Å to 2.243 (2)Å, and the angles for N—Fe—N and N—Fe—O are between 75.21 (10)° and 168.95 (6)°, respectively. The Fe—O bond lengths are 1.7804 (10)Å, 1.936 (2)Å and the bond angle for O1—Fe—O2 is 97.99 (10)°, respectively. These bond distances and bondangles are in agreement with those found in the reported iron phen compounds (Yang et al. 2010).

Related literature top

For transition metal complexes containing organic ligands with nitrogen heteroatoms, see: Manson et al., (2001); Wu et al. (2009); Accorsi et al. (2009); Xie & Huang (2011); Feng et al. (2006); Yu et al. (2010); Weyhermuller et al. (2005). For phen (1,10-phenanthroline) ligands, see: Gu et al. (2006); Hu et al. (2009). For related bond distances and angles, see: Yang et al. (2010).

Experimental top

0.151 g of 1,10-phenanthroline hydrate was dissolved in methanol (5 ml). To the solution, 5 ml of H₂O was added, then layered with 5 ml of a methanol solution of Fe₂(SO₄)₃ (0.020 g). The resulting solution was allowed to stand at room temperature for several days and black block crystals were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. The molecular structure for title compound. Displacement ellipsoids at the 30% probability level. Hydrogen atoms have been deleated for clarity.

µ-Oxido-bis[bis(phenanthroline-κ²N,N')(sulfato- κO)iron(III)] octahydrate top

Crystal data top

[Fe₂O(SO₄)₂(C₁₂H₈N₂)₄]·8H₂O	F(000) = 2448
M_r = 1184.76	D_x = 1.571 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5306 reflections
a = 21.589 (15) Å	θ = 2.2–27.3°
b = 14.181 (10) Å	µ = 0.75 mm⁻¹
c = 16.500 (12) Å	T = 273 K
β = 97.289 (9)°	Block, black
V = 5010 (6) Å³	0.20 × 0.10 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	4398 independent reflections
Radiation source: fine-focus sealed tube	3506 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −25→24
T_min = 0.865, T_max = 0.971	k = −15→16
11655 measured reflections	l = −10→19

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.059P)² + 4.8592P] where P = (F_o² + 2F_c²)/3
4398 reflections	(Δ/σ)_max < 0.001
372 parameters	Δρ_max = 0.66 e Å⁻³
15 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Fe₂O(SO₄)₂(C₁₂H₈N₂)₄]·8H₂O	V = 5010 (6) Å³
M_r = 1184.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.589 (15) Å	µ = 0.75 mm⁻¹
b = 14.181 (10) Å	T = 273 K
c = 16.500 (12) Å	0.20 × 0.10 × 0.04 mm
β = 97.289 (9)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4398 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	3506 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.971	R_int = 0.029
11655 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	15 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.66 e Å⁻³
4398 reflections	Δρ_min = −0.34 e Å⁻³
372 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
Fe1	0.448260 (15)	0.23530 (3)	0.15718 (2)	0.02377 (13)
S1	0.33448 (3)	0.07600 (5)	0.16883 (4)	0.03358 (19)
N1	0.38927 (10)	0.34694 (15)	0.19124 (14)	0.0311 (5)
N2	0.49425 (10)	0.36835 (15)	0.12194 (13)	0.0300 (5)
N3	0.40007 (10)	0.24313 (16)	0.02909 (14)	0.0324 (5)
N4	0.50712 (9)	0.15827 (15)	0.08713 (13)	0.0280 (5)
C1	0.33823 (14)	0.3357 (2)	0.2267 (2)	0.0451 (8)
H1A	0.3242	0.2749	0.2350	0.054*
C2	0.30476 (15)	0.4114 (2)	0.2520 (2)	0.0542 (9)
H2A	0.2688	0.4007	0.2762	0.065*
C3	0.32438 (15)	0.5010 (2)	0.2414 (2)	0.0529 (9)
H3A	0.3023	0.5518	0.2591	0.063*
C4	0.37800 (14)	0.5163 (2)	0.20385 (19)	0.0405 (7)
C5	0.40939 (12)	0.43659 (18)	0.18015 (16)	0.0299 (6)
C6	0.54657 (13)	0.3774 (2)	0.08885 (18)	0.0374 (7)
H6A	0.5667	0.3232	0.0742	0.045*
C7	0.57287 (14)	0.4650 (2)	0.0749 (2)	0.0468 (8)
H7A	0.6100	0.4688	0.0519	0.056*
C8	0.54351 (15)	0.5446 (2)	0.0954 (2)	0.0481 (8)
H8A	0.5603	0.6034	0.0859	0.058*
C9	0.48812 (14)	0.5384 (2)	0.13080 (18)	0.0390 (7)
C10	0.46545 (12)	0.44758 (18)	0.14267 (16)	0.0294 (6)
C11	0.40202 (17)	0.6080 (2)	0.1890 (2)	0.0527 (9)
H11A	0.3810	0.6612	0.2037	0.063*
C12	0.45421 (17)	0.6181 (2)	0.1542 (2)	0.0536 (9)
H12A	0.4687	0.6784	0.1450	0.064*
C13	0.34567 (14)	0.2827 (2)	0.0008 (2)	0.0483 (8)
H13A	0.3242	0.3157	0.0372	0.058*
C14	0.31937 (16)	0.2773 (3)	−0.0807 (2)	0.0602 (10)
H14A	0.2809	0.3053	−0.0975	0.072*
C15	0.35054 (17)	0.2305 (3)	−0.1358 (2)	0.0566 (9)
H15A	0.3335	0.2263	−0.1904	0.068*
C16	0.40840 (15)	0.1890 (2)	−0.10906 (18)	0.0440 (7)
C17	0.43098 (13)	0.1969 (2)	−0.02581 (16)	0.0327 (6)
C18	0.56001 (12)	0.1158 (2)	0.11755 (19)	0.0368 (7)
H18A	0.5726	0.1188	0.1735	0.044*
C19	0.59695 (14)	0.0673 (2)	0.0685 (2)	0.0440 (8)
H19A	0.6337	0.0387	0.0917	0.053*
C20	0.57940 (15)	0.0616 (2)	−0.0132 (2)	0.0456 (8)
H20A	0.6040	0.0289	−0.0460	0.055*
C21	0.52383 (14)	0.1052 (2)	−0.04818 (18)	0.0384 (7)
C22	0.48900 (12)	0.15288 (18)	0.00512 (16)	0.0308 (6)
C23	0.44517 (19)	0.1396 (3)	−0.1616 (2)	0.0552 (9)
H23A	0.4306	0.1343	−0.2169	0.066*
C24	0.50066 (18)	0.1005 (2)	−0.1325 (2)	0.0524 (9)
H24A	0.5240	0.0701	−0.1683	0.063*
O1	0.5000	0.22796 (18)	0.2500	0.0307 (6)
O1W	0.65938 (13)	0.2776 (2)	0.01141 (19)	0.0760 (8)
O2	0.39311 (9)	0.13274 (15)	0.17760 (13)	0.0445 (5)
O2W	0.32992 (16)	0.80292 (19)	0.14393 (18)	0.0765 (8)
O3	0.31002 (12)	0.0750 (2)	0.08246 (15)	0.0694 (7)
O3W	0.21915 (15)	0.9578 (3)	0.9884 (2)	0.1018 (11)
O4	0.35088 (12)	−0.01746 (17)	0.19715 (18)	0.0709 (8)
O4W	0.26638 (15)	0.1716 (2)	0.36928 (17)	0.0777 (8)
O5	0.29116 (11)	0.12164 (18)	0.21519 (16)	0.0640 (7)
H2WA	0.334 (2)	0.792 (3)	0.0943 (11)	0.096*
H4WA	0.2455 (19)	0.220 (2)	0.352 (2)	0.096*
H2WB	0.333 (2)	0.8619 (9)	0.151 (2)	0.096*
H1WA	0.6784 (19)	0.250 (3)	0.0541 (19)	0.096*
H4WB	0.2867 (18)	0.153 (3)	0.3310 (18)	0.096*
H1WB	0.6807 (17)	0.3280 (18)	0.008 (3)	0.096*
H3WB	0.2496 (13)	0.936 (3)	0.966 (3)	0.096*
H3WA	0.2316 (17)	1.0085 (18)	1.013 (3)	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0213 (2)	0.0267 (2)	0.0239 (2)	0.00157 (14)	0.00528 (14)	−0.00084 (15)
S1	0.0288 (4)	0.0339 (4)	0.0391 (4)	−0.0059 (3)	0.0086 (3)	−0.0057 (3)
N1	0.0267 (11)	0.0321 (13)	0.0356 (13)	0.0037 (9)	0.0089 (10)	−0.0025 (10)
N2	0.0285 (12)	0.0313 (12)	0.0305 (12)	0.0006 (9)	0.0054 (9)	0.0018 (10)
N3	0.0249 (12)	0.0375 (13)	0.0338 (13)	−0.0004 (9)	−0.0003 (10)	0.0025 (10)
N4	0.0270 (11)	0.0290 (12)	0.0285 (12)	0.0002 (9)	0.0057 (9)	−0.0043 (9)
C1	0.0353 (16)	0.0445 (18)	0.059 (2)	−0.0010 (13)	0.0179 (15)	−0.0051 (15)
C2	0.0362 (17)	0.061 (2)	0.070 (2)	0.0075 (15)	0.0244 (17)	−0.0127 (19)
C3	0.0414 (18)	0.055 (2)	0.062 (2)	0.0223 (15)	0.0065 (16)	−0.0137 (17)
C4	0.0385 (16)	0.0369 (17)	0.0448 (18)	0.0129 (13)	−0.0001 (14)	−0.0047 (14)
C5	0.0280 (13)	0.0315 (15)	0.0288 (15)	0.0064 (11)	−0.0014 (11)	−0.0006 (11)
C6	0.0326 (15)	0.0409 (17)	0.0402 (17)	−0.0023 (12)	0.0101 (13)	0.0034 (13)
C7	0.0376 (17)	0.055 (2)	0.049 (2)	−0.0118 (15)	0.0106 (14)	0.0064 (16)
C8	0.0517 (19)	0.0401 (18)	0.051 (2)	−0.0160 (15)	0.0028 (16)	0.0063 (15)
C9	0.0460 (17)	0.0319 (15)	0.0370 (16)	−0.0044 (13)	−0.0021 (13)	0.0050 (13)
C10	0.0312 (14)	0.0285 (14)	0.0270 (14)	0.0011 (11)	−0.0021 (11)	0.0011 (11)
C11	0.065 (2)	0.0285 (16)	0.063 (2)	0.0141 (15)	0.0031 (18)	−0.0055 (15)
C12	0.070 (2)	0.0262 (16)	0.063 (2)	−0.0002 (15)	0.0034 (19)	0.0021 (15)
C13	0.0364 (17)	0.060 (2)	0.0479 (19)	0.0023 (15)	0.0028 (14)	0.0070 (16)
C14	0.0385 (18)	0.079 (3)	0.057 (2)	−0.0018 (17)	−0.0150 (17)	0.023 (2)
C15	0.057 (2)	0.071 (2)	0.0373 (18)	−0.0160 (18)	−0.0108 (16)	0.0111 (17)
C16	0.0529 (19)	0.0467 (18)	0.0312 (16)	−0.0169 (15)	0.0009 (14)	0.0044 (14)
C17	0.0367 (15)	0.0324 (14)	0.0291 (15)	−0.0084 (12)	0.0049 (12)	0.0015 (12)
C18	0.0297 (14)	0.0370 (16)	0.0441 (17)	0.0026 (12)	0.0057 (12)	−0.0030 (13)
C19	0.0305 (15)	0.0391 (17)	0.064 (2)	0.0040 (12)	0.0138 (15)	−0.0052 (15)
C20	0.0472 (18)	0.0387 (17)	0.057 (2)	−0.0020 (14)	0.0297 (16)	−0.0101 (15)
C21	0.0473 (17)	0.0331 (15)	0.0386 (17)	−0.0110 (13)	0.0206 (14)	−0.0049 (13)
C22	0.0366 (15)	0.0283 (14)	0.0285 (14)	−0.0067 (11)	0.0083 (12)	−0.0002 (11)
C23	0.081 (3)	0.058 (2)	0.0278 (17)	−0.0188 (19)	0.0112 (17)	−0.0084 (15)
C24	0.074 (2)	0.051 (2)	0.0370 (18)	−0.0136 (18)	0.0265 (17)	−0.0101 (15)
O1	0.0298 (14)	0.0383 (15)	0.0241 (13)	0.000	0.0038 (11)	0.000
O1W	0.0698 (19)	0.077 (2)	0.084 (2)	0.0032 (15)	0.0218 (16)	0.0093 (16)
O2	0.0327 (11)	0.0473 (12)	0.0547 (14)	−0.0119 (9)	0.0102 (10)	−0.0007 (10)
O2W	0.109 (2)	0.0455 (15)	0.076 (2)	−0.0050 (16)	0.0158 (18)	−0.0005 (14)
O3	0.0637 (16)	0.089 (2)	0.0500 (15)	−0.0046 (14)	−0.0119 (12)	−0.0159 (14)
O3W	0.081 (2)	0.119 (3)	0.104 (3)	−0.027 (2)	0.005 (2)	−0.030 (2)
O4	0.0770 (18)	0.0403 (14)	0.094 (2)	−0.0042 (12)	0.0056 (15)	0.0135 (13)
O4W	0.078 (2)	0.096 (2)	0.0598 (18)	0.0219 (16)	0.0127 (15)	−0.0060 (16)
O5	0.0531 (14)	0.0703 (17)	0.0763 (18)	−0.0122 (12)	0.0377 (13)	−0.0198 (14)

Geometric parameters (Å, º) top

Fe1—O1	1.7804 (10)	C9—C12	1.427 (4)
Fe1—O2	1.936 (2)	C11—C12	1.335 (5)
Fe1—N4	2.125 (2)	C11—H11A	0.9300
Fe1—N1	2.151 (2)	C12—H12A	0.9300
Fe1—N3	2.237 (3)	C13—C14	1.393 (5)
Fe1—N2	2.243 (2)	C13—H13A	0.9300
S1—O4	1.435 (3)	C14—C15	1.370 (5)
S1—O5	1.435 (2)	C14—H14A	0.9300
S1—O3	1.456 (3)	C15—C16	1.401 (5)
S1—O2	1.491 (2)	C15—H15A	0.9300
N1—C1	1.321 (4)	C16—C17	1.403 (4)
N1—C5	1.363 (3)	C16—C23	1.431 (5)
N2—C6	1.322 (3)	C17—C22	1.434 (4)
N2—C10	1.349 (3)	C18—C19	1.389 (4)
N3—C13	1.332 (4)	C18—H18A	0.9300
N3—C17	1.360 (4)	C19—C20	1.355 (5)
N4—C18	1.331 (3)	C19—H19A	0.9300
N4—C22	1.362 (3)	C20—C21	1.407 (5)
C1—C2	1.387 (4)	C20—H20A	0.9300
C1—H1A	0.9300	C21—C22	1.401 (4)
C2—C3	1.358 (5)	C21—C24	1.419 (4)
C2—H2A	0.9300	C23—C24	1.351 (5)
C3—C4	1.398 (4)	C23—H23A	0.9300
C3—H3A	0.9300	C24—H24A	0.9300
C4—C5	1.399 (4)	O1—Fe1ⁱ	1.7804 (10)
C4—C11	1.432 (5)	O1W—H1WA	0.861 (10)
C5—C10	1.436 (4)	O1W—H1WB	0.856 (10)
C6—C7	1.397 (4)	O2W—H2WA	0.849 (10)
C6—H6A	0.9300	O2W—H2WB	0.845 (10)
C7—C8	1.358 (5)	O3W—H3WB	0.848 (7)
C7—H7A	0.9300	O3W—H3WA	0.849 (7)
C8—C9	1.399 (4)	O4W—H4WA	0.851 (10)
C8—H8A	0.9300	O4W—H4WB	0.854 (10)
C9—C10	1.400 (4)

O1—Fe1—O2	97.99 (10)	C9—C8—H8A	119.9
O1—Fe1—N4	94.85 (9)	C8—C9—C10	116.7 (3)
O2—Fe1—N4	97.58 (10)	C8—C9—C12	123.9 (3)
O1—Fe1—N1	98.39 (9)	C10—C9—C12	119.4 (3)
O2—Fe1—N1	96.31 (10)	N2—C10—C9	123.4 (3)
N4—Fe1—N1	159.26 (9)	N2—C10—C5	117.4 (2)
O1—Fe1—N3	168.95 (6)	C9—C10—C5	119.3 (2)
O2—Fe1—N3	88.80 (9)	C12—C11—C4	121.0 (3)
N4—Fe1—N3	75.53 (9)	C12—C11—H11A	119.5
N1—Fe1—N3	89.46 (9)	C4—C11—H11A	119.5
O1—Fe1—N2	91.27 (9)	C11—C12—C9	121.4 (3)
O2—Fe1—N2	168.33 (8)	C11—C12—H12A	119.3
N4—Fe1—N2	88.65 (9)	C9—C12—H12A	119.3
N1—Fe1—N2	75.21 (10)	N3—C13—C14	123.3 (3)
N3—Fe1—N2	83.19 (8)	N3—C13—H13A	118.4
O4—S1—O5	113.16 (17)	C14—C13—H13A	118.4
O4—S1—O3	110.74 (17)	C15—C14—C13	119.5 (3)
O5—S1—O3	110.24 (16)	C15—C14—H14A	120.2
O4—S1—O2	107.19 (15)	C13—C14—H14A	120.2
O5—S1—O2	107.91 (14)	C14—C15—C16	119.2 (3)
O3—S1—O2	107.35 (14)	C14—C15—H15A	120.4
C1—N1—C5	118.0 (2)	C16—C15—H15A	120.4
C1—N1—Fe1	125.6 (2)	C15—C16—C17	117.4 (3)
C5—N1—Fe1	116.24 (17)	C15—C16—C23	123.8 (3)
C6—N2—C10	118.0 (2)	C17—C16—C23	118.8 (3)
C6—N2—Fe1	128.21 (19)	N3—C17—C16	123.5 (3)
C10—N2—Fe1	113.67 (18)	N3—C17—C22	116.9 (2)
C13—N3—C17	117.1 (3)	C16—C17—C22	119.5 (3)
C13—N3—Fe1	129.5 (2)	N4—C18—C19	122.2 (3)
C17—N3—Fe1	113.38 (17)	N4—C18—H18A	118.9
C18—N4—C22	118.3 (2)	C19—C18—H18A	118.9
C18—N4—Fe1	124.80 (19)	C20—C19—C18	120.0 (3)
C22—N4—Fe1	116.94 (17)	C20—C19—H19A	120.0
N1—C1—C2	122.4 (3)	C18—C19—H19A	120.0
N1—C1—H1A	118.8	C19—C20—C21	119.9 (3)
C2—C1—H1A	118.8	C19—C20—H20A	120.1
C3—C2—C1	120.2 (3)	C21—C20—H20A	120.1
C3—C2—H2A	119.9	C22—C21—C20	116.9 (3)
C1—C2—H2A	119.9	C22—C21—C24	119.2 (3)
C2—C3—C4	119.4 (3)	C20—C21—C24	123.9 (3)
C2—C3—H3A	120.3	N4—C22—C21	122.8 (3)
C4—C3—H3A	120.3	N4—C22—C17	117.2 (2)
C3—C4—C5	117.2 (3)	C21—C22—C17	120.0 (3)
C3—C4—C11	123.7 (3)	C24—C23—C16	121.4 (3)
C5—C4—C11	119.1 (3)	C24—C23—H23A	119.3
N1—C5—C4	122.8 (3)	C16—C23—H23A	119.3
N1—C5—C10	117.3 (2)	C23—C24—C21	121.0 (3)
C4—C5—C10	119.8 (3)	C23—C24—H24A	119.5
N2—C6—C7	122.8 (3)	C21—C24—H24A	119.5
N2—C6—H6A	118.6	Fe1ⁱ—O1—Fe1	173.30 (17)
C7—C6—H6A	118.6	H1WA—O1W—H1WB	103 (2)
C8—C7—C6	119.1 (3)	S1—O2—Fe1	157.16 (15)
C8—C7—H7A	120.5	H2WA—O2W—H2WB	107 (2)
C6—C7—H7A	120.5	H3WB—O3W—H3WA	107.4
C7—C8—C9	120.1 (3)	H4WA—O4W—H4WB	107 (2)
C7—C8—H8A	119.9

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O3ⁱⁱ	0.85 (1)	2.14 (3)	2.872 (4)	144 (4)
O2W—H2WB···O4ⁱⁱⁱ	0.85 (1)	1.89 (2)	2.713 (4)	163 (4)
O4W—H4WB···O5	0.85 (1)	1.98 (2)	2.756 (4)	151 (4)
O1W—H1WB···O3W^iv	0.86 (1)	2.06 (1)	2.909 (5)	171 (4)
O1W—H1WA···O4Wⁱ	0.86 (1)	1.97 (2)	2.811 (5)	165 (5)
O3W—H3WB···O4W^v	0.85 (1)	2.28 (3)	2.964 (5)	138 (3)

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

Experimental details

Crystal data
Chemical formula	[Fe₂O(SO₄)₂(C₁₂H₈N₂)₄]·8H₂O
M_r	1184.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	21.589 (15), 14.181 (10), 16.500 (12)
β (°)	97.289 (9)
V (Å³)	5010 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.20 × 0.10 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1995)
T_min, T_max	0.865, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	11655, 4398, 3506
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.107, 1.05
No. of reflections	4398
No. of parameters	372
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.34

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Fe1—O1	1.7804 (10)	S1—O2	1.491 (2)
Fe1—O2	1.936 (2)	N1—C1	1.321 (4)
Fe1—N4	2.125 (2)	N1—C5	1.363 (3)
Fe1—N1	2.151 (2)	N2—C6	1.322 (3)
Fe1—N3	2.237 (3)	N2—C10	1.349 (3)
Fe1—N2	2.243 (2)	N3—C13	1.332 (4)
S1—O4	1.435 (3)	N3—C17	1.360 (4)
S1—O5	1.435 (2)	N4—C18	1.331 (3)
S1—O3	1.456 (3)	N4—C22	1.362 (3)

O1—Fe1—O2	97.99 (10)	O2—Fe1—N2	168.33 (8)
O1—Fe1—N4	94.85 (9)	N4—Fe1—N2	88.65 (9)
O2—Fe1—N4	97.58 (10)	N1—Fe1—N2	75.21 (10)
O1—Fe1—N1	98.39 (9)	N3—Fe1—N2	83.19 (8)
O2—Fe1—N1	96.31 (10)	O4—S1—O5	113.16 (17)
N4—Fe1—N1	159.26 (9)	O4—S1—O3	110.74 (17)
O1—Fe1—N3	168.95 (6)	O5—S1—O3	110.24 (16)
O2—Fe1—N3	88.80 (9)	O4—S1—O2	107.19 (15)
N4—Fe1—N3	75.53 (9)	O5—S1—O2	107.91 (14)
N1—Fe1—N3	89.46 (9)	O3—S1—O2	107.35 (14)
O1—Fe1—N2	91.27 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O3ⁱ	0.849 (7)	2.14 (3)	2.872 (4)	144 (4)
O2W—H2WB···O4ⁱⁱ	0.845 (10)	1.894 (15)	2.713 (4)	163 (4)
O4W—H4WB···O5	0.854 (10)	1.98 (2)	2.756 (4)	151 (4)
O1W—H1WB···O3Wⁱⁱⁱ	0.856 (10)	2.061 (12)	2.909 (5)	171 (4)
O1W—H1WA···O4W^iv	0.861 (10)	1.970 (17)	2.811 (5)	165 (5)
O3W—H3WB···O4W^v	0.848 (7)	2.28 (3)	2.964 (5)	138 (3)

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

Acknowledgements

This study was supported by the Science and Technology Department of Henan Province (grant No. 102102310321) and the Doctoral Research Fund of Henan Chinese Medicine (grant No. BSJJ2009–38).

References

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