Di-μ-sulfato-bis-[diaqua-(1H-imidazo[4,5-f][1,10]phenanthroline)iron(II)] dihydrate.

The title dinuclear Fe(II) complex, [Fe(2)(SO(4))(2)(C(13)H(8)N(4))(2)(H(2)O)(4)]·2H(2)O, is centrosymmetric. Two sulfate anions bridge two Fe(II) cations to form the binuclear complex. Each Fe(II) cation is coordinated by two N atoms from a 1H-imidazo[4,5-f][1,10]phenanthroline (IP) ligand, two O atoms from two sulfate anions and two water mol-ecules in a distorted octa-hedral geometry. Extensive O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonding is present in the crystal structure. Weak π-π stacking is observed between parallel IP ring systems, the face-to-face separation being 3.428 (14) Å.

Related literature

For metal complexes with the 1H-imidazo[4,5-f][1,10]phenanthroline (IP) ligand, see: Liu et al. (2009 ▶); Stephenson et al. (2008 ▶); Wu et al. (1997 ▶); Yang et al. (2010 ▶); Yu (2009 ▶). For the synthesis of IP, see: Wu et al. (1997 ▶).

Experimental

Crystal data

[Fe2(SO4)2(C13H8N4)2(H2O)4]·2H2O

M = 852.38

Monoclinic,

a = 10.2879 (9) Å

b = 9.0738 (8) Å

c = 17.0089 (16) Å

β = 98.892 (5)°

V = 1568.7 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.14 mm−1

T = 293 K

0.20 × 0.20 × 0.10 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ▶) T min = 0.673, T max = 1.000

11834 measured reflections

3500 independent reflections

2884 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.099

S = 1.05

3500 reflections

259 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.47 e Å−3

Data collection: CrystalClear (Rigaku, 2002 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032496/xu5012sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032496/xu5012Isup2.hkl

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

[Fe2(SO4)2(C13H8N4)2(H2O)4]·2H2O	F(000) = 872
Mr = 852.38	Dx = 1.805 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3717 reflections
a = 10.2879 (9) Å	θ = 3.0–27.5°
b = 9.0738 (8) Å	µ = 1.14 mm−1
c = 17.0089 (16) Å	T = 293 K
β = 98.892 (5)°	Prism, yellow
V = 1568.7 (2) Å3	0.20 × 0.20 × 0.10 mm
Z = 2

Rigaku Mercury CCD diffractometer	3500 independent reflections
Radiation source: fine-focus sealed tube	2884 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 14.6306 pixels mm-1	θmax = 27.5°, θmin = 2.6°
ω scan	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	k = −11→11
Tmin = 0.673, Tmax = 1.000	l = −22→21
11834 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0483P)2 + 0.6512P] where P = (Fo2 + 2Fc2)/3
3500 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.44 e Å−3
9 restraints	Δρmin = −0.47 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Fe1	0.31610 (3)	0.68065 (4)	−0.03898 (2)	0.02489 (13)
S1	0.53353 (6)	0.60216 (6)	0.11438 (4)	0.02472 (16)
O1	0.46200 (17)	0.71051 (18)	0.05947 (11)	0.0298 (4)
O2	0.63573 (18)	0.53106 (19)	0.07634 (12)	0.0348 (4)
O3	0.44027 (17)	0.48994 (19)	0.13588 (11)	0.0314 (4)
O4	0.5938 (2)	0.6791 (2)	0.18664 (12)	0.0402 (5)
O5	0.20448 (19)	0.5633 (2)	0.04180 (11)	0.0347 (4)
O6	0.4329 (2)	0.7669 (2)	−0.11949 (14)	0.0465 (5)
O7	0.4090 (4)	1.0134 (3)	−0.20216 (16)	0.0697 (8)
N1	0.2437 (2)	0.9048 (2)	−0.03242 (12)	0.0256 (5)
N2	0.1277 (2)	0.6775 (2)	−0.11677 (12)	0.0261 (5)
N3	−0.1442 (2)	1.2057 (2)	−0.13981 (14)	0.0339 (5)
N4	−0.2454 (2)	1.0126 (2)	−0.20243 (13)	0.0329 (5)
H4B	−0.3055	0.9614	−0.2308	0.040*
C1	0.3070 (2)	1.0173 (3)	0.00618 (16)	0.0297 (6)
H1A	0.3891	1.0002	0.0362	0.036*
C2	0.2562 (3)	1.1597 (3)	0.00372 (17)	0.0333 (6)
H2B	0.3047	1.2358	0.0307	0.040*
C3	0.1336 (3)	1.1870 (3)	−0.03888 (16)	0.0301 (6)
H3C	0.0971	1.2809	−0.0399	0.036*
C4	0.0648 (2)	1.0710 (3)	−0.08061 (15)	0.0252 (5)
C5	−0.0639 (2)	1.0827 (3)	−0.12661 (15)	0.0265 (5)
C6	−0.1251 (2)	0.9628 (3)	−0.16564 (14)	0.0264 (5)
C7	−0.0665 (2)	0.8197 (3)	−0.16491 (14)	0.0244 (5)
C8	−0.1246 (3)	0.6951 (3)	−0.20433 (16)	0.0324 (6)
H8A	−0.2079	0.7007	−0.2345	0.039*
C9	−0.0566 (3)	0.5653 (3)	−0.19772 (17)	0.0339 (6)
H9A	−0.0940	0.4804	−0.2222	0.041*
C10	0.0698 (3)	0.5616 (3)	−0.15377 (16)	0.0307 (6)
H10A	0.1156	0.4728	−0.1504	0.037*
C11	0.0604 (2)	0.8071 (3)	−0.12085 (14)	0.0235 (5)
C12	0.1247 (2)	0.9309 (2)	−0.07685 (14)	0.0225 (5)
C13	−0.2508 (3)	1.1563 (3)	−0.18553 (17)	0.0373 (7)
H13A	−0.3226	1.2156	−0.2042	0.045*
H2	0.266 (2)	0.521 (3)	0.0720 (16)	0.061 (11)*
H3	0.484 (3)	0.705 (2)	−0.1358 (18)	0.045 (9)*
H1	0.165 (4)	0.631 (4)	0.064 (2)	0.113 (19)*
H5	0.410 (4)	1.1018 (18)	−0.187 (2)	0.087 (15)*
H4	0.425 (4)	0.847 (2)	−0.145 (2)	0.085 (14)*
H6	0.413 (4)	1.001 (4)	−0.2509 (9)	0.080 (14)*

	U11	U22	U33	U12	U13	U23
Fe1	0.0230 (2)	0.02412 (19)	0.0261 (2)	0.00472 (14)	−0.00072 (15)	0.00128 (14)
S1	0.0243 (3)	0.0228 (3)	0.0247 (3)	0.0051 (2)	−0.0034 (2)	−0.0018 (2)
O1	0.0280 (9)	0.0261 (8)	0.0323 (10)	0.0032 (7)	−0.0052 (8)	0.0037 (7)
O2	0.0306 (10)	0.0254 (8)	0.0496 (12)	0.0044 (8)	0.0099 (9)	−0.0017 (9)
O3	0.0305 (9)	0.0295 (9)	0.0342 (10)	0.0033 (8)	0.0046 (8)	0.0048 (8)
O4	0.0499 (12)	0.0330 (10)	0.0315 (10)	0.0058 (9)	−0.0135 (9)	−0.0075 (8)
O5	0.0322 (10)	0.0370 (10)	0.0345 (11)	0.0040 (9)	0.0038 (9)	0.0017 (9)
O6	0.0586 (14)	0.0318 (10)	0.0556 (14)	0.0146 (10)	0.0291 (12)	0.0116 (10)
O7	0.137 (3)	0.0325 (12)	0.0432 (15)	0.0165 (15)	0.0272 (17)	0.0078 (11)
N1	0.0226 (10)	0.0277 (10)	0.0254 (11)	0.0019 (8)	0.0008 (9)	−0.0009 (9)
N2	0.0263 (10)	0.0248 (10)	0.0258 (11)	0.0028 (8)	0.0000 (9)	−0.0003 (9)
N3	0.0335 (12)	0.0325 (11)	0.0342 (13)	0.0094 (10)	0.0004 (10)	0.0014 (10)
N4	0.0255 (11)	0.0399 (12)	0.0304 (12)	0.0024 (10)	−0.0050 (9)	−0.0004 (10)
C1	0.0215 (12)	0.0322 (13)	0.0331 (14)	−0.0005 (10)	−0.0023 (11)	−0.0029 (11)
C2	0.0327 (14)	0.0277 (12)	0.0380 (15)	−0.0059 (11)	0.0006 (12)	−0.0045 (12)
C3	0.0341 (14)	0.0225 (11)	0.0332 (14)	0.0016 (10)	0.0037 (12)	−0.0001 (10)
C4	0.0258 (12)	0.0255 (11)	0.0241 (12)	0.0031 (10)	0.0035 (10)	0.0017 (10)
C5	0.0278 (12)	0.0257 (12)	0.0254 (13)	0.0066 (10)	0.0020 (10)	0.0020 (10)
C6	0.0227 (12)	0.0337 (13)	0.0220 (12)	0.0049 (10)	0.0013 (10)	0.0013 (10)
C7	0.0231 (12)	0.0268 (12)	0.0230 (12)	0.0024 (10)	0.0027 (10)	0.0000 (10)
C8	0.0245 (12)	0.0376 (14)	0.0330 (15)	−0.0006 (11)	−0.0020 (11)	−0.0037 (11)
C9	0.0359 (14)	0.0303 (13)	0.0349 (15)	−0.0052 (12)	0.0034 (12)	−0.0071 (11)
C10	0.0336 (14)	0.0247 (11)	0.0333 (14)	0.0024 (11)	0.0037 (12)	−0.0009 (11)
C11	0.0227 (11)	0.0260 (11)	0.0219 (12)	0.0025 (10)	0.0036 (10)	0.0003 (9)
C12	0.0219 (11)	0.0229 (11)	0.0225 (12)	0.0031 (9)	0.0027 (10)	−0.0004 (9)
C13	0.0344 (15)	0.0424 (15)	0.0325 (15)	0.0172 (12)	−0.0027 (12)	0.0040 (12)

Fe1—N1	2.175 (2)	N4—C13	1.338 (4)
Fe1—N2	2.172 (2)	N4—C6	1.373 (3)
Fe1—O1	2.0865 (17)	N4—H4B	0.8600
Fe1—O2i	2.1065 (18)	C1—C2	1.392 (4)
Fe1—O5	2.197 (2)	C1—H1A	0.9300
Fe1—O6	2.108 (2)	C2—C3	1.377 (4)
S1—O4	1.4649 (18)	C2—H2B	0.9300
S1—O2	1.4665 (19)	C3—C4	1.399 (3)
S1—O1	1.4723 (17)	C3—H3C	0.9300
S1—O3	1.4831 (19)	C4—C12	1.411 (3)
O5—H2	0.84 (2)	C4—C5	1.433 (3)
O5—H1	0.86 (4)	C5—C6	1.375 (3)
O6—H3	0.84 (3)	C6—C7	1.431 (3)
O6—H4	0.84 (2)	C7—C8	1.400 (3)
O7—H5	0.842 (19)	C7—C11	1.405 (3)
O7—H6	0.844 (18)	C8—C9	1.366 (4)
N1—C1	1.329 (3)	C8—H8A	0.9300
N1—C12	1.356 (3)	C9—C10	1.397 (4)
N2—C10	1.320 (3)	C9—H9A	0.9300
N2—C11	1.361 (3)	C10—H10A	0.9300
N3—C13	1.320 (4)	C11—C12	1.452 (3)
N3—C5	1.387 (3)	C13—H13A	0.9300
O1—Fe1—O2i	100.77 (7)	N1—C1—C2	123.0 (2)
O1—Fe1—O6	93.52 (9)	N1—C1—H1A	118.5
O2i—Fe1—O6	87.60 (8)	C2—C1—H1A	118.5
O1—Fe1—N2	162.62 (8)	C3—C2—C1	119.5 (2)
O2i—Fe1—N2	91.93 (7)	C3—C2—H2B	120.3
O6—Fe1—N2	98.86 (9)	C1—C2—H2B	120.3
O1—Fe1—N1	92.70 (7)	C2—C3—C4	118.8 (2)
O2i—Fe1—N1	165.19 (8)	C2—C3—H3C	120.6
O6—Fe1—N1	85.43 (8)	C4—C3—H3C	120.6
N2—Fe1—N1	76.29 (7)	C3—C4—C12	118.1 (2)
O1—Fe1—O5	86.66 (7)	C3—C4—C5	125.0 (2)
O2i—Fe1—O5	85.22 (8)	C12—C4—C5	116.9 (2)
O6—Fe1—O5	172.72 (8)	C6—C5—N3	110.0 (2)
N2—Fe1—O5	82.59 (8)	C6—C5—C4	121.4 (2)
N1—Fe1—O5	101.83 (8)	N3—C5—C4	128.7 (2)
O4—S1—O2	109.92 (12)	N4—C6—C5	105.8 (2)
O4—S1—O1	108.61 (10)	N4—C6—C7	130.6 (2)
O2—S1—O1	109.63 (11)	C5—C6—C7	123.5 (2)
O4—S1—O3	109.03 (12)	C8—C7—C11	118.8 (2)
O2—S1—O3	110.00 (11)	C8—C7—C6	125.5 (2)
O1—S1—O3	109.62 (10)	C11—C7—C6	115.7 (2)
S1—O1—Fe1	130.50 (11)	C9—C8—C7	118.8 (2)
S1—O2—Fe1i	138.81 (12)	C9—C8—H8A	120.6
Fe1—O5—H2	100 (2)	C7—C8—H8A	120.6
Fe1—O5—H1	105 (3)	C8—C9—C10	119.2 (2)
H2—O5—H1	114.9 (18)	C8—C9—H9A	120.4
Fe1—O6—H3	114.5 (19)	C10—C9—H9A	120.4
Fe1—O6—H4	129 (2)	N2—C10—C9	123.4 (2)
H3—O6—H4	114.8 (17)	N2—C10—H10A	118.3
H5—O7—H6	115.9 (18)	C9—C10—H10A	118.3
C1—N1—C12	118.2 (2)	N2—C11—C7	121.4 (2)
C1—N1—Fe1	126.73 (16)	N2—C11—C12	117.0 (2)
C12—N1—Fe1	114.93 (15)	C7—C11—C12	121.6 (2)
C10—N2—C11	118.4 (2)	N1—C12—C4	122.2 (2)
C10—N2—Fe1	126.54 (16)	N1—C12—C11	116.9 (2)
C11—N2—Fe1	114.76 (15)	C4—C12—C11	120.8 (2)
C13—N3—C5	104.0 (2)	N3—C13—N4	113.5 (2)
C13—N4—C6	106.7 (2)	N3—C13—H13A	123.2
C13—N4—H4B	126.7	N4—C13—H13A	123.2
C6—N4—H4B	126.7
O4—S1—O1—Fe1	−162.26 (14)	C3—C4—C5—N3	0.5 (4)
O2—S1—O1—Fe1	77.62 (16)	C12—C4—C5—N3	179.7 (3)
O3—S1—O1—Fe1	−43.22 (18)	C13—N4—C6—C5	0.8 (3)
O2i—Fe1—O1—S1	−28.46 (16)	C13—N4—C6—C7	−178.7 (3)
O6—Fe1—O1—S1	−116.68 (15)	N3—C5—C6—N4	−0.8 (3)
N2—Fe1—O1—S1	107.8 (2)	C4—C5—C6—N4	179.4 (2)
N1—Fe1—O1—S1	157.73 (15)	N3—C5—C6—C7	178.8 (2)
O5—Fe1—O1—S1	56.03 (15)	C4—C5—C6—C7	−1.0 (4)
O4—S1—O2—Fe1i	123.58 (18)	N4—C6—C7—C8	0.1 (5)
O1—S1—O2—Fe1i	−117.10 (18)	C5—C6—C7—C8	−179.4 (3)
O3—S1—O2—Fe1i	3.5 (2)	N4—C6—C7—C11	179.6 (3)
O1—Fe1—N1—C1	18.0 (2)	C5—C6—C7—C11	0.2 (4)
O2i—Fe1—N1—C1	−137.6 (3)	C11—C7—C8—C9	0.8 (4)
O6—Fe1—N1—C1	−75.3 (2)	C6—C7—C8—C9	−179.6 (3)
N2—Fe1—N1—C1	−175.6 (2)	C7—C8—C9—C10	−1.7 (4)
O5—Fe1—N1—C1	105.1 (2)	C11—N2—C10—C9	0.7 (4)
O1—Fe1—N1—C12	−166.31 (17)	Fe1—N2—C10—C9	174.5 (2)
O2i—Fe1—N1—C12	38.2 (4)	C8—C9—C10—N2	1.0 (4)
O6—Fe1—N1—C12	100.37 (18)	C10—N2—C11—C7	−1.6 (4)
N2—Fe1—N1—C12	0.08 (17)	Fe1—N2—C11—C7	−176.12 (19)
O5—Fe1—N1—C12	−79.15 (18)	C10—N2—C11—C12	177.6 (2)
O1—Fe1—N2—C10	−123.8 (3)	Fe1—N2—C11—C12	3.1 (3)
O2i—Fe1—N2—C10	13.4 (2)	C8—C7—C11—N2	0.9 (4)
O6—Fe1—N2—C10	101.3 (2)	C6—C7—C11—N2	−178.7 (2)
N1—Fe1—N2—C10	−175.7 (2)	C8—C7—C11—C12	−178.3 (2)
O5—Fe1—N2—C10	−71.5 (2)	C6—C7—C11—C12	2.1 (4)
O1—Fe1—N2—C11	50.2 (3)	C1—N1—C12—C4	−2.6 (4)
O2i—Fe1—N2—C11	−172.64 (18)	Fe1—N1—C12—C4	−178.72 (19)
O6—Fe1—N2—C11	−84.77 (19)	C1—N1—C12—C11	177.6 (2)
N1—Fe1—N2—C11	−1.72 (17)	Fe1—N1—C12—C11	1.5 (3)
O5—Fe1—N2—C11	102.43 (18)	C3—C4—C12—N1	2.2 (4)
C12—N1—C1—C2	0.8 (4)	C5—C4—C12—N1	−177.0 (2)
Fe1—N1—C1—C2	176.3 (2)	C3—C4—C12—C11	−178.0 (2)
N1—C1—C2—C3	1.5 (4)	C5—C4—C12—C11	2.7 (4)
C1—C2—C3—C4	−1.8 (4)	N2—C11—C12—N1	−3.1 (3)
C2—C3—C4—C12	0.1 (4)	C7—C11—C12—N1	176.1 (2)
C2—C3—C4—C5	179.3 (3)	N2—C11—C12—C4	177.1 (2)
C13—N3—C5—C6	0.4 (3)	C7—C11—C12—C4	−3.7 (4)
C13—N3—C5—C4	−179.8 (3)	C5—N3—C13—N4	0.1 (3)
C3—C4—C5—C6	−179.7 (3)	C6—N4—C13—N3	−0.6 (3)
C12—C4—C5—C6	−0.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O4ii	0.86	2.05	2.891 (3)	164
O5—H1···N3iii	0.86 (4)	2.00 (4)	2.807 (3)	157 (4)
O5—H2···O3	0.84 (2)	1.97 (2)	2.773 (3)	159 (2)
O6—H3···O3i	0.84 (3)	1.93 (2)	2.706 (3)	152 (3)
O6—H4···O7	0.84 (2)	1.79 (2)	2.633 (3)	178 (4)
O7—H5···O4iv	0.84 (2)	1.99 (2)	2.803 (3)	163 (3)
O7—H6···O3v	0.84 (2)	1.99 (2)	2.823 (3)	169 (3)

Table 1

Selected bond lengths (Å)

Fe1—N1	2.175 (2)
Fe1—N2	2.172 (2)
Fe1—O1	2.0865 (17)
Fe1—O2i	2.1065 (18)
Fe1—O5	2.197 (2)
Fe1—O6	2.108 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O4ii	0.86	2.05	2.891 (3)	164
O5—H1⋯N3iii	0.86 (4)	2.00 (4)	2.807 (3)	157 (4)
O5—H2⋯O3	0.84 (2)	1.97 (2)	2.773 (3)	159 (2)
O6—H3⋯O3i	0.84 (3)	1.93 (2)	2.706 (3)	152 (3)
O6—H4⋯O7	0.84 (2)	1.79 (2)	2.633 (3)	178 (4)
O7—H5⋯O4iv	0.84 (2)	1.99 (2)	2.803 (3)	163 (3)
O7—H6⋯O3v	0.84 (2)	1.99 (2)	2.823 (3)	169 (3)

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