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Acta Cryst. (2007). E63, m1861    [ doi:10.1107/S1600536807027675 ]

Bis(dipyrido[3,2-a:2',3'-c]phenazine)sulfatoiron(II) monohydrate

Q.-W. Wang, X.-H. Zhao, Z.-X. Yu and J. Wang

Abstract top

In the title compound, [Fe(SO4)(C18H10N4)2]·H2O, the FeII atom (site symmetry 2) is six-coodinated by four N atoms from two dipyrido[3,2-a:2',3'-c]phenazine ligands and two O atoms from the SO42- dianion in a distorted cis-FeO2N4 octahedral geometry. Numerous aromatic [pi]-[pi] stacking interactions [centroid separation = 3.671 (2)-4.090 (2) Å] and O-H...O hydrogen bonds help to stabilize the structure. The water molecule is disordered with a site-occupancy factor of 0.5.

Comment top

Heteroaromatic N-donor chelating ligands such as 1,10-phenanthroline (phen) and its derivatives have been widely used in the construction of metal-organic complexes (Che, Liu et al.,2006; Li et al., 2006). As a continuation of our studies, we have prepared the title compound, FeSO4(L)2·H2O, using the phen derivative dipyrido[3,2 − a:2',3'-c]phenazine (L) ligand.

In compound (I), (Fig. 1, Table 1), the Fe2+ atom (site symmetry 2) is six coordinated by four N atoms from two L ligands and two O atoms from the same SO42− dianion in a distorted octahedral geometry. Neighbouring complexes are connected through π-π interactions between L ligands with a stacking distance of 3.671 (2) Å, leading to layers propagating in [101] (Fig. 2).

Related literature top

For related complexes containing phenanthroline-derived lgands, see: Che, Liu et al. (2006); Che (2006); Li et al. (2006). For the ligand synthesis, see: Che, Li et al. (2006).

Experimental top

Ligand L was synthesized according to the literature method of Che, Li et al. (2006). An ethanol solution (12 ml) of L (0.5 mmol) was added slowly to an aqueous solution (10 ml) of FeSO4 (0.5 mmol). The mixture was sealed in a Teflon-lined autoclave and heated to 433 K for 4 d. Brown blocks and slabs of (I) were obtained upon cooling and opening the autoclave (65% yield based on Fe).

Refinement top

The water O atom showed a large displacement parameter. Its site occupancy refined to close to 0.5 and the fit improved. Its occupancy was then fixed at 0.5. The water H atoms were located in a difference map and their positions were freely refined.

All C-bound H atoms were generated geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the asymmetric unit of (I), together with further atoms to complete the FeII coordination sphere. Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms). [Symmetry code: 1 − x, y, 1/2 − z.]
[Figure 2] Fig. 2. View of the π-π stacking in the structure of (I) leading to chains of molecules.
Bis(dipyrido[3,2 − a:2',3'-c]phenazine)sulfatoiron(II) monohydrate top
Crystal data top
[Fe(SO4)(C18H10N4)2]·H2OF000 = 1504
Mr = 734.53Dx = 1.657 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1263 reflections
a = 17.527 (2) Åθ = 2.3–26.0º
b = 7.2674 (10) ŵ = 0.65 mm−1
c = 23.203 (3) ÅT = 292 (2) K
β = 94.826 (2)ºSlab, brown
V = 2944.9 (7) Å30.32 × 0.14 × 0.09 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2908 independent reflections
Radiation source: fine-focus sealed tube2041 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.061
T = 292(2) Kθmax = 26.1º
ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −21→21
Tmin = 0.895, Tmax = 0.939k = −8→8
12199 measured reflectionsl = −28→28
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.139  w = 1/[σ2(Fo2) + (0.0651P)2 + 4.1225P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2908 reflectionsΔρmax = 0.55 e Å−3
242 parametersΔρmin = −0.39 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Fe(SO4)(C18H10N4)2]·H2OV = 2944.9 (7) Å3
Mr = 734.53Z = 4
Monoclinic, C2/cMo Kα
a = 17.527 (2) ŵ = 0.65 mm−1
b = 7.2674 (10) ÅT = 292 (2) K
c = 23.203 (3) Å0.32 × 0.14 × 0.09 mm
β = 94.826 (2)º
Data collection top
Bruker SMART CCD
diffractometer		2908 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		2041 reflections with I > 2σ(I)
Tmin = 0.895, Tmax = 0.939Rint = 0.061
12199 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0493 restraints
wR(F2) = 0.139H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 0.55 e Å−3
2908 reflectionsΔρmin = −0.39 e Å−3
242 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 > 2sigma(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
xyzUiso*/UeqOcc. (<1)
O1W0.4209 (3)0.1304 (8)0.3969 (3)0.0561 (17)0.50
C10.4474 (2)0.5284 (5)0.35121 (16)0.0351 (9)
H10.39980.52990.33030.042*
C20.4539 (2)0.6080 (5)0.40550 (16)0.0374 (9)
H20.41170.66330.42010.045*
C30.52355 (19)0.6044 (5)0.43763 (15)0.0335 (8)
H30.52920.65460.47460.040*
C40.58578 (19)0.5231 (4)0.41324 (15)0.0291 (8)
C50.66145 (19)0.5085 (5)0.44494 (14)0.0296 (8)
C60.7382 (2)0.5424 (5)0.52866 (15)0.0335 (8)
C70.7487 (2)0.5916 (5)0.58783 (16)0.0432 (10)
H70.70770.63610.60670.052*
C80.8191 (3)0.5735 (6)0.61717 (18)0.0490 (11)
H80.82590.60760.65590.059*
C90.8811 (2)0.5045 (5)0.58975 (17)0.0467 (10)
H90.92840.49210.61080.056*
C100.8739 (2)0.4551 (5)0.53300 (17)0.0436 (10)
H100.91590.41050.51540.052*
C110.8013 (2)0.4723 (5)0.50083 (16)0.0343 (8)
C120.72472 (19)0.4395 (4)0.41675 (15)0.0292 (8)
C130.71308 (19)0.3818 (4)0.35639 (14)0.0284 (8)
C140.77242 (19)0.3215 (5)0.32452 (15)0.0341 (8)
H140.82280.32740.34050.041*
C150.7563 (2)0.2534 (5)0.26961 (15)0.0353 (8)
H150.79530.21250.24790.042*
C160.6803 (2)0.2471 (5)0.24735 (16)0.0362 (9)
H160.66920.19560.21090.043*
C170.63881 (18)0.3793 (4)0.32890 (14)0.0281 (7)
C180.57456 (18)0.4516 (4)0.35795 (14)0.0266 (7)
N10.50531 (15)0.4501 (4)0.32740 (12)0.0297 (7)
N20.62257 (15)0.3105 (4)0.27515 (12)0.0307 (7)
N30.66826 (17)0.5592 (4)0.50016 (12)0.0339 (7)
N40.79357 (16)0.4221 (4)0.44431 (13)0.0329 (7)
O10.48704 (15)0.0364 (3)0.29847 (10)0.0432 (7)
O20.43230 (14)−0.2049 (4)0.23570 (12)0.0496 (7)
S0.5000−0.09498 (18)0.25000.0333 (3)
Fe0.50000.28602 (10)0.25000.0322 (2)
HW110.431 (4)0.077 (10)0.3686 (18)0.048*0.50
HW120.453 (3)0.123 (12)0.423 (2)0.048*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1W0.071 (4)0.044 (3)0.060 (4)−0.009 (3)0.051 (3)−0.010 (3)
C10.0228 (18)0.042 (2)0.040 (2)0.0028 (16)0.0006 (16)0.0013 (17)
C20.029 (2)0.040 (2)0.044 (2)0.0051 (16)0.0048 (16)−0.0009 (17)
C30.032 (2)0.037 (2)0.0314 (19)0.0018 (16)0.0037 (15)−0.0036 (16)
C40.0275 (18)0.0286 (18)0.0309 (19)−0.0020 (14)0.0014 (15)0.0025 (15)
C50.0313 (19)0.0279 (18)0.0291 (19)−0.0007 (15)0.0001 (15)0.0025 (15)
C60.039 (2)0.0312 (19)0.029 (2)−0.0063 (16)−0.0053 (16)0.0051 (15)
C70.053 (3)0.043 (2)0.033 (2)−0.0086 (19)−0.0005 (18)0.0003 (17)
C80.064 (3)0.046 (2)0.035 (2)−0.012 (2)−0.010 (2)0.0043 (18)
C90.051 (3)0.043 (2)0.043 (2)−0.008 (2)−0.018 (2)0.0045 (19)
C100.040 (2)0.040 (2)0.048 (3)−0.0026 (18)−0.0105 (19)0.0044 (18)
C110.034 (2)0.0282 (18)0.038 (2)−0.0047 (15)−0.0089 (17)0.0030 (15)
C120.0266 (18)0.0287 (19)0.0316 (19)0.0002 (14)−0.0027 (14)0.0033 (14)
C130.0253 (18)0.0291 (18)0.0303 (18)0.0019 (14)−0.0004 (14)0.0025 (14)
C140.0212 (18)0.040 (2)0.039 (2)0.0000 (15)−0.0042 (15)0.0029 (17)
C150.0297 (19)0.042 (2)0.034 (2)0.0035 (16)0.0033 (15)−0.0022 (16)
C160.033 (2)0.046 (2)0.030 (2)0.0032 (17)0.0012 (15)−0.0040 (16)
C170.0257 (17)0.0286 (18)0.0300 (18)0.0018 (14)0.0012 (14)0.0032 (14)
C180.0246 (17)0.0288 (18)0.0256 (18)0.0003 (14)−0.0018 (14)0.0041 (14)
N10.0219 (15)0.0324 (16)0.0343 (16)0.0004 (12)−0.0008 (12)0.0039 (12)
N20.0269 (15)0.0392 (17)0.0256 (15)0.0010 (13)0.0006 (12)−0.0016 (13)
N30.0358 (17)0.0357 (17)0.0297 (16)−0.0034 (13)−0.0005 (13)−0.0005 (13)
N40.0270 (16)0.0347 (17)0.0359 (17)−0.0026 (13)−0.0043 (13)−0.0007 (13)
O10.0521 (17)0.0475 (16)0.0298 (14)0.0019 (13)0.0023 (12)−0.0019 (12)
O20.0301 (15)0.0503 (17)0.0663 (19)−0.0089 (13)−0.0086 (13)−0.0017 (14)
S0.0253 (6)0.0395 (7)0.0341 (7)0.000−0.0036 (5)0.000
Fe0.0237 (4)0.0425 (5)0.0294 (4)0.000−0.0037 (3)0.000
Geometric parameters (Å, °) top
O1W—HW110.79 (2)C11—N41.357 (4)
O1W—HW120.80 (2)C12—N41.323 (4)
C1—N11.324 (4)C12—C131.460 (5)
C1—C21.382 (5)C13—C141.396 (5)
C1—H10.9300C13—C171.401 (4)
C2—C31.377 (5)C14—C151.374 (5)
C2—H20.9300C14—H140.9300
C3—C41.401 (5)C15—C161.389 (5)
C3—H30.9300C15—H150.9300
C4—C181.383 (5)C16—N21.327 (4)
C4—C51.465 (5)C16—H160.9300
C5—N31.329 (4)C17—N21.352 (4)
C5—C121.425 (5)C17—C181.458 (4)
C6—N31.348 (4)C18—N11.353 (4)
C6—C71.416 (5)O1—S1.507 (3)
C6—C111.422 (5)O2—S1.446 (2)
C7—C81.364 (5)S—O2i1.446 (3)
C7—H70.9300S—O1i1.507 (3)
C8—C91.399 (6)Fe—N12.151 (3)
C8—H80.9300Fe—N22.185 (3)
C9—C101.361 (5)Fe—O12.156 (3)
C9—H90.9300Fe—N1i2.151 (3)
C10—C111.425 (5)Fe—O1i2.156 (3)
C10—H100.9300Fe—N2i2.185 (3)
HW11—O1W—HW12114 (4)C14—C15—C16118.2 (3)
N1—C1—C2123.6 (3)C14—C15—H15120.9
N1—C1—H1118.2C16—C15—H15120.9
C2—C1—H1118.2N2—C16—C15123.7 (3)
C3—C2—C1119.1 (3)N2—C16—H16118.2
C3—C2—H2120.5C15—C16—H16118.2
C1—C2—H2120.5N2—C17—C13122.7 (3)
C2—C3—C4118.3 (3)N2—C17—C18116.7 (3)
C2—C3—H3120.8C13—C17—C18120.6 (3)
C4—C3—H3120.8N1—C18—C4122.7 (3)
C18—C4—C3118.6 (3)N1—C18—C17116.6 (3)
C18—C4—C5119.4 (3)C4—C18—C17120.6 (3)
C3—C4—C5122.0 (3)C1—N1—C18117.6 (3)
N3—C5—C12122.0 (3)C1—N1—Fe127.3 (2)
N3—C5—C4117.9 (3)C18—N1—Fe114.6 (2)
C12—C5—C4120.1 (3)C16—N2—C17117.8 (3)
N3—C6—C7119.4 (4)C16—N2—Fe127.9 (2)
N3—C6—C11121.3 (3)C17—N2—Fe113.7 (2)
C7—C6—C11119.2 (3)C5—N3—C6116.9 (3)
C8—C7—C6119.9 (4)C12—N4—C11117.0 (3)
C8—C7—H7120.1S—O1—Fe96.58 (13)
C6—C7—H7120.1O2—S—O2i112.9 (2)
C7—C8—C9120.8 (4)O2—S—O1110.43 (15)
C7—C8—H8119.6O2i—S—O1110.55 (15)
C9—C8—H8119.6O2—S—O1i110.55 (15)
C10—C9—C8121.5 (4)O2i—S—O1i110.43 (15)
C10—C9—H9119.3O1—S—O1i101.4 (2)
C8—C9—H9119.3N1—Fe—N1i112.66 (15)
C9—C10—C11119.4 (4)N1—Fe—O1i154.52 (10)
C9—C10—H10120.3N1i—Fe—O1i91.72 (10)
C11—C10—H10120.3N1—Fe—O191.72 (10)
N4—C11—C6121.1 (3)N1i—Fe—O1154.52 (10)
N4—C11—C10119.7 (4)O1i—Fe—O165.47 (13)
C6—C11—C10119.2 (3)N1—Fe—N2i98.64 (10)
N4—C12—C5121.7 (3)N1i—Fe—N2i76.08 (10)
N4—C12—C13119.0 (3)O1i—Fe—N2i94.22 (10)
C5—C12—C13119.3 (3)O1—Fe—N2i93.64 (10)
C14—C13—C17117.4 (3)N1—Fe—N276.08 (10)
C14—C13—C12123.2 (3)N1i—Fe—N298.64 (10)
C17—C13—C12119.3 (3)O1i—Fe—N293.64 (10)
C15—C14—C13120.0 (3)O1—Fe—N294.22 (10)
C15—C14—H14120.0N2i—Fe—N2170.66 (15)
C13—C14—H14120.0
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O10.80 (5)1.99 (5)2.734 (7)155 (7)
Selected geometric parameters (Å, °) top
Fe—N12.151 (3)Fe—O12.156 (3)
Fe—N22.185 (3)
N1—Fe—N276.08 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O10.80 (5)1.99 (5)2.734 (7)155 (7)
Acknowledgements top

The authors thank Dr Guangbo Che of Jilin Normal University for supporting this work.

references
References top

Bruker (2002). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Che, G.-B. (2006). Acta Cryst. E62, m1686–m1688.

Che, G.-B., Liu, C.-B., Cui, Y.-C. & Li, C.-B. (2006). Acta Cryst. E62, m1362–m1364.

Che, G.-B., Li, W.-L., Kong, Z.-G., Su, Z.-S., Chu, B., Li, B., Zhang, Z.-Q., Hu, Z.-Z. & Chi, H.-J. (2006). Synth. Commun. 36, 2519–2524.

Li, C.-B., Dong, E.-J., Fang, W., Liu, B. & Li, Y.-W. (2006). Acta Cryst. E62, m3122–m3124.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.