Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027675/hb2425sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027675/hb2425Isup2.hkl |
CCDC reference: 654734
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).
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).
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).
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).
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.
[Fe(SO4)(C18H10N4)2]·H2O | F(000) = 1504 |
Mr = 734.53 | Dx = 1.657 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1263 reflections |
a = 17.527 (2) Å | θ = 2.3–26.0° |
b = 7.2674 (10) Å | µ = 0.65 mm−1 |
c = 23.203 (3) Å | T = 292 K |
β = 94.826 (2)° | Slab, brown |
V = 2944.9 (7) Å3 | 0.32 × 0.14 × 0.09 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 2908 independent reflections |
Radiation source: fine-focus sealed tube | 2041 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ω scans | θmax = 26.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −21→21 |
Tmin = 0.895, Tmax = 0.939 | k = −8→8 |
12199 measured reflections | l = −28→28 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0651P)2 + 4.1225P] where P = (Fo2 + 2Fc2)/3 |
2908 reflections | (Δ/σ)max < 0.001 |
242 parameters | Δρmax = 0.55 e Å−3 |
3 restraints | Δρmin = −0.39 e Å−3 |
[Fe(SO4)(C18H10N4)2]·H2O | V = 2944.9 (7) Å3 |
Mr = 734.53 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.527 (2) Å | µ = 0.65 mm−1 |
b = 7.2674 (10) Å | T = 292 K |
c = 23.203 (3) Å | 0.32 × 0.14 × 0.09 mm |
β = 94.826 (2)° |
Bruker SMART CCD diffractometer | 2908 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2041 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.939 | Rint = 0.061 |
12199 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 3 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.55 e Å−3 |
2908 reflections | Δρmin = −0.39 e Å−3 |
242 parameters |
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 | Occ. (<1) | |
O1W | 0.4209 (3) | 0.1304 (8) | 0.3969 (3) | 0.0561 (17) | 0.50 |
C1 | 0.4474 (2) | 0.5284 (5) | 0.35121 (16) | 0.0351 (9) | |
H1 | 0.3998 | 0.5299 | 0.3303 | 0.042* | |
C2 | 0.4539 (2) | 0.6080 (5) | 0.40550 (16) | 0.0374 (9) | |
H2 | 0.4117 | 0.6633 | 0.4201 | 0.045* | |
C3 | 0.52355 (19) | 0.6044 (5) | 0.43763 (15) | 0.0335 (8) | |
H3 | 0.5292 | 0.6546 | 0.4746 | 0.040* | |
C4 | 0.58578 (19) | 0.5231 (4) | 0.41324 (15) | 0.0291 (8) | |
C5 | 0.66145 (19) | 0.5085 (5) | 0.44494 (14) | 0.0296 (8) | |
C6 | 0.7382 (2) | 0.5424 (5) | 0.52866 (15) | 0.0335 (8) | |
C7 | 0.7487 (2) | 0.5916 (5) | 0.58783 (16) | 0.0432 (10) | |
H7 | 0.7077 | 0.6361 | 0.6067 | 0.052* | |
C8 | 0.8191 (3) | 0.5735 (6) | 0.61717 (18) | 0.0490 (11) | |
H8 | 0.8259 | 0.6076 | 0.6559 | 0.059* | |
C9 | 0.8811 (2) | 0.5045 (5) | 0.58975 (17) | 0.0467 (10) | |
H9 | 0.9284 | 0.4921 | 0.6108 | 0.056* | |
C10 | 0.8739 (2) | 0.4551 (5) | 0.53300 (17) | 0.0436 (10) | |
H10 | 0.9159 | 0.4105 | 0.5154 | 0.052* | |
C11 | 0.8013 (2) | 0.4723 (5) | 0.50083 (16) | 0.0343 (8) | |
C12 | 0.72472 (19) | 0.4395 (4) | 0.41675 (15) | 0.0292 (8) | |
C13 | 0.71308 (19) | 0.3818 (4) | 0.35639 (14) | 0.0284 (8) | |
C14 | 0.77242 (19) | 0.3215 (5) | 0.32452 (15) | 0.0341 (8) | |
H14 | 0.8228 | 0.3274 | 0.3405 | 0.041* | |
C15 | 0.7563 (2) | 0.2534 (5) | 0.26961 (15) | 0.0353 (8) | |
H15 | 0.7953 | 0.2125 | 0.2479 | 0.042* | |
C16 | 0.6803 (2) | 0.2471 (5) | 0.24735 (16) | 0.0362 (9) | |
H16 | 0.6692 | 0.1956 | 0.2109 | 0.043* | |
C17 | 0.63881 (18) | 0.3793 (4) | 0.32890 (14) | 0.0281 (7) | |
C18 | 0.57456 (18) | 0.4516 (4) | 0.35795 (14) | 0.0266 (7) | |
N1 | 0.50531 (15) | 0.4501 (4) | 0.32740 (12) | 0.0297 (7) | |
N2 | 0.62257 (15) | 0.3105 (4) | 0.27515 (12) | 0.0307 (7) | |
N3 | 0.66826 (17) | 0.5592 (4) | 0.50016 (12) | 0.0339 (7) | |
N4 | 0.79357 (16) | 0.4221 (4) | 0.44431 (13) | 0.0329 (7) | |
O1 | 0.48704 (15) | 0.0364 (3) | 0.29847 (10) | 0.0432 (7) | |
O2 | 0.43230 (14) | −0.2049 (4) | 0.23570 (12) | 0.0496 (7) | |
S | 0.5000 | −0.09498 (18) | 0.2500 | 0.0333 (3) | |
Fe | 0.5000 | 0.28602 (10) | 0.2500 | 0.0322 (2) | |
HW11 | 0.431 (4) | 0.077 (10) | 0.3686 (18) | 0.048* | 0.50 |
HW12 | 0.453 (3) | 0.123 (12) | 0.423 (2) | 0.048* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.071 (4) | 0.044 (3) | 0.060 (4) | −0.009 (3) | 0.051 (3) | −0.010 (3) |
C1 | 0.0228 (18) | 0.042 (2) | 0.040 (2) | 0.0028 (16) | 0.0006 (16) | 0.0013 (17) |
C2 | 0.029 (2) | 0.040 (2) | 0.044 (2) | 0.0051 (16) | 0.0048 (16) | −0.0009 (17) |
C3 | 0.032 (2) | 0.037 (2) | 0.0314 (19) | 0.0018 (16) | 0.0037 (15) | −0.0036 (16) |
C4 | 0.0275 (18) | 0.0286 (18) | 0.0309 (19) | −0.0020 (14) | 0.0014 (15) | 0.0025 (15) |
C5 | 0.0313 (19) | 0.0279 (18) | 0.0291 (19) | −0.0007 (15) | 0.0001 (15) | 0.0025 (15) |
C6 | 0.039 (2) | 0.0312 (19) | 0.029 (2) | −0.0063 (16) | −0.0053 (16) | 0.0051 (15) |
C7 | 0.053 (3) | 0.043 (2) | 0.033 (2) | −0.0086 (19) | −0.0005 (18) | 0.0003 (17) |
C8 | 0.064 (3) | 0.046 (2) | 0.035 (2) | −0.012 (2) | −0.010 (2) | 0.0043 (18) |
C9 | 0.051 (3) | 0.043 (2) | 0.043 (2) | −0.008 (2) | −0.018 (2) | 0.0045 (19) |
C10 | 0.040 (2) | 0.040 (2) | 0.048 (3) | −0.0026 (18) | −0.0105 (19) | 0.0044 (18) |
C11 | 0.034 (2) | 0.0282 (18) | 0.038 (2) | −0.0047 (15) | −0.0089 (17) | 0.0030 (15) |
C12 | 0.0266 (18) | 0.0287 (19) | 0.0316 (19) | 0.0002 (14) | −0.0027 (14) | 0.0033 (14) |
C13 | 0.0253 (18) | 0.0291 (18) | 0.0303 (18) | 0.0019 (14) | −0.0004 (14) | 0.0025 (14) |
C14 | 0.0212 (18) | 0.040 (2) | 0.039 (2) | 0.0000 (15) | −0.0042 (15) | 0.0029 (17) |
C15 | 0.0297 (19) | 0.042 (2) | 0.034 (2) | 0.0035 (16) | 0.0033 (15) | −0.0022 (16) |
C16 | 0.033 (2) | 0.046 (2) | 0.030 (2) | 0.0032 (17) | 0.0012 (15) | −0.0040 (16) |
C17 | 0.0257 (17) | 0.0286 (18) | 0.0300 (18) | 0.0018 (14) | 0.0012 (14) | 0.0032 (14) |
C18 | 0.0246 (17) | 0.0288 (18) | 0.0256 (18) | 0.0003 (14) | −0.0018 (14) | 0.0041 (14) |
N1 | 0.0219 (15) | 0.0324 (16) | 0.0343 (16) | 0.0004 (12) | −0.0008 (12) | 0.0039 (12) |
N2 | 0.0269 (15) | 0.0392 (17) | 0.0256 (15) | 0.0010 (13) | 0.0006 (12) | −0.0016 (13) |
N3 | 0.0358 (17) | 0.0357 (17) | 0.0297 (16) | −0.0034 (13) | −0.0005 (13) | −0.0005 (13) |
N4 | 0.0270 (16) | 0.0347 (17) | 0.0359 (17) | −0.0026 (13) | −0.0043 (13) | −0.0007 (13) |
O1 | 0.0521 (17) | 0.0475 (16) | 0.0298 (14) | 0.0019 (13) | 0.0023 (12) | −0.0019 (12) |
O2 | 0.0301 (15) | 0.0503 (17) | 0.0663 (19) | −0.0089 (13) | −0.0086 (13) | −0.0017 (14) |
S | 0.0253 (6) | 0.0395 (7) | 0.0341 (7) | 0.000 | −0.0036 (5) | 0.000 |
Fe | 0.0237 (4) | 0.0425 (5) | 0.0294 (4) | 0.000 | −0.0037 (3) | 0.000 |
O1W—HW11 | 0.79 (2) | C11—N4 | 1.357 (4) |
O1W—HW12 | 0.80 (2) | C12—N4 | 1.323 (4) |
C1—N1 | 1.324 (4) | C12—C13 | 1.460 (5) |
C1—C2 | 1.382 (5) | C13—C14 | 1.396 (5) |
C1—H1 | 0.9300 | C13—C17 | 1.401 (4) |
C2—C3 | 1.377 (5) | C14—C15 | 1.374 (5) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.401 (5) | C15—C16 | 1.389 (5) |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
C4—C18 | 1.383 (5) | C16—N2 | 1.327 (4) |
C4—C5 | 1.465 (5) | C16—H16 | 0.9300 |
C5—N3 | 1.329 (4) | C17—N2 | 1.352 (4) |
C5—C12 | 1.425 (5) | C17—C18 | 1.458 (4) |
C6—N3 | 1.348 (4) | C18—N1 | 1.353 (4) |
C6—C7 | 1.416 (5) | O1—S | 1.507 (3) |
C6—C11 | 1.422 (5) | O2—S | 1.446 (2) |
C7—C8 | 1.364 (5) | S—O2i | 1.446 (3) |
C7—H7 | 0.9300 | S—O1i | 1.507 (3) |
C8—C9 | 1.399 (6) | Fe—N1 | 2.151 (3) |
C8—H8 | 0.9300 | Fe—N2 | 2.185 (3) |
C9—C10 | 1.361 (5) | Fe—O1 | 2.156 (3) |
C9—H9 | 0.9300 | Fe—N1i | 2.151 (3) |
C10—C11 | 1.425 (5) | Fe—O1i | 2.156 (3) |
C10—H10 | 0.9300 | Fe—N2i | 2.185 (3) |
HW11—O1W—HW12 | 114 (4) | C14—C15—C16 | 118.2 (3) |
N1—C1—C2 | 123.6 (3) | C14—C15—H15 | 120.9 |
N1—C1—H1 | 118.2 | C16—C15—H15 | 120.9 |
C2—C1—H1 | 118.2 | N2—C16—C15 | 123.7 (3) |
C3—C2—C1 | 119.1 (3) | N2—C16—H16 | 118.2 |
C3—C2—H2 | 120.5 | C15—C16—H16 | 118.2 |
C1—C2—H2 | 120.5 | N2—C17—C13 | 122.7 (3) |
C2—C3—C4 | 118.3 (3) | N2—C17—C18 | 116.7 (3) |
C2—C3—H3 | 120.8 | C13—C17—C18 | 120.6 (3) |
C4—C3—H3 | 120.8 | N1—C18—C4 | 122.7 (3) |
C18—C4—C3 | 118.6 (3) | N1—C18—C17 | 116.6 (3) |
C18—C4—C5 | 119.4 (3) | C4—C18—C17 | 120.6 (3) |
C3—C4—C5 | 122.0 (3) | C1—N1—C18 | 117.6 (3) |
N3—C5—C12 | 122.0 (3) | C1—N1—Fe | 127.3 (2) |
N3—C5—C4 | 117.9 (3) | C18—N1—Fe | 114.6 (2) |
C12—C5—C4 | 120.1 (3) | C16—N2—C17 | 117.8 (3) |
N3—C6—C7 | 119.4 (4) | C16—N2—Fe | 127.9 (2) |
N3—C6—C11 | 121.3 (3) | C17—N2—Fe | 113.7 (2) |
C7—C6—C11 | 119.2 (3) | C5—N3—C6 | 116.9 (3) |
C8—C7—C6 | 119.9 (4) | C12—N4—C11 | 117.0 (3) |
C8—C7—H7 | 120.1 | S—O1—Fe | 96.58 (13) |
C6—C7—H7 | 120.1 | O2—S—O2i | 112.9 (2) |
C7—C8—C9 | 120.8 (4) | O2—S—O1 | 110.43 (15) |
C7—C8—H8 | 119.6 | O2i—S—O1 | 110.55 (15) |
C9—C8—H8 | 119.6 | O2—S—O1i | 110.55 (15) |
C10—C9—C8 | 121.5 (4) | O2i—S—O1i | 110.43 (15) |
C10—C9—H9 | 119.3 | O1—S—O1i | 101.4 (2) |
C8—C9—H9 | 119.3 | N1—Fe—N1i | 112.66 (15) |
C9—C10—C11 | 119.4 (4) | N1—Fe—O1i | 154.52 (10) |
C9—C10—H10 | 120.3 | N1i—Fe—O1i | 91.72 (10) |
C11—C10—H10 | 120.3 | N1—Fe—O1 | 91.72 (10) |
N4—C11—C6 | 121.1 (3) | N1i—Fe—O1 | 154.52 (10) |
N4—C11—C10 | 119.7 (4) | O1i—Fe—O1 | 65.47 (13) |
C6—C11—C10 | 119.2 (3) | N1—Fe—N2i | 98.64 (10) |
N4—C12—C5 | 121.7 (3) | N1i—Fe—N2i | 76.08 (10) |
N4—C12—C13 | 119.0 (3) | O1i—Fe—N2i | 94.22 (10) |
C5—C12—C13 | 119.3 (3) | O1—Fe—N2i | 93.64 (10) |
C14—C13—C17 | 117.4 (3) | N1—Fe—N2 | 76.08 (10) |
C14—C13—C12 | 123.2 (3) | N1i—Fe—N2 | 98.64 (10) |
C17—C13—C12 | 119.3 (3) | O1i—Fe—N2 | 93.64 (10) |
C15—C14—C13 | 120.0 (3) | O1—Fe—N2 | 94.22 (10) |
C15—C14—H14 | 120.0 | N2i—Fe—N2 | 170.66 (15) |
C13—C14—H14 | 120.0 |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW11···O1 | 0.80 (5) | 1.99 (5) | 2.734 (7) | 155 (7) |
Experimental details
Crystal data | |
Chemical formula | [Fe(SO4)(C18H10N4)2]·H2O |
Mr | 734.53 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 292 |
a, b, c (Å) | 17.527 (2), 7.2674 (10), 23.203 (3) |
β (°) | 94.826 (2) |
V (Å3) | 2944.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.32 × 0.14 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.895, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12199, 2908, 2041 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.139, 1.03 |
No. of reflections | 2908 |
No. of parameters | 242 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.39 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXTL.
Fe—N1 | 2.151 (3) | Fe—O1 | 2.156 (3) |
Fe—N2 | 2.185 (3) | ||
N1—Fe—N2 | 76.08 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW11···O1 | 0.80 (5) | 1.99 (5) | 2.734 (7) | 155 (7) |
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).