Acta Cryst. (2008). E64, m79 [ doi:10.1107/S1600536807062836 ]
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3N,N',N'')iron(II) dinitrate dihydrateThe title complex, [Fe(C15H10ClN3)2](NO3)2·2H2O, has a six-coordinate iron(II) center balanced by two nitrate anions. The Fe atom lies on a twofold rotation axis. The complex exhibits an octahedral coordination configuration, where the dihedral angle between the two planar tridentate ligands is 92.4 (1)°. The crystal structure involves O-H
O hydrogen bonds.
The treatment of Fe(NO3)2.6H2O (0.072 g, 0.25 mmol) and 4'-chloro-2,2':6',2'-terpyridine (0.134 g, 0.50 mmol) in 30 cm3 me thanol under reflux condition for 1 h produced deep red microcrystals in a yield of 83% (0.156 g). Anal. Calcd. for FeC30H24N8Cl2O8: C: 47.96, H: 3.22, N: 14.91. Found: C: 47.88; H: 3.24; N: 14.98. Main FT—IR (KBr pellets, cm-1): 3447 (s), 1663 (s), 1560 (s), 1545 (s), 1466 (m) and 1368 (s). Single crystals of the title complex suitable for X-ray diffraction measurement were obtained from the mixture of ethanol and water solutions at a ratio of 3:1 by slow evaporation in air at ambient temperature.
The two H atoms bonded to the water oxygen atom were located in the difference synthesis and were refined isotropically, whereas the other H atoms were placed in geometrically idealized positions (C—H = 0.93 Å) and refined as riding atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
![[Figure 1]](./at2511fig1thm.gif)
| Fig. 1. A drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| [Fe(C15H10ClN3)2](NO3)2·2H2O | F000 = 1536 |
| Mr = 751.32 | Dx = 1.541 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2481 reflections |
| a = 18.049 (2) Å | θ = 2.3–25.0º |
| b = 18.255 (3) Å | µ = 0.70 mm−1 |
| c = 10.0741 (14) Å | T = 291 (2) K |
| β = 102.668 (2)º | Block, red |
| V = 3238.5 (8) Å3 | 0.12 × 0.10 × 0.10 mm |
| Z = 4 |
| Bruker SMART 1K CCD area-detector diffractometer | 3192 independent reflections |
| Radiation source: fine-focus sealed tube | 2120 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.042 |
| T = 291(2) K | θmax = 26.0º |
| φ and ω scans | θmin = 1.6º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −21→22 |
| Tmin = 0.922, Tmax = 0.931 | k = −15→22 |
| 8547 measured reflections | l = −12→11 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0635P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.97 | (Δ/σ)max < 0.001 |
| 3192 reflections | Δρmax = 0.43 e Å−3 |
| 233 parameters | Δρmin = −0.41 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Fe(C15H10ClN3)2](NO3)2·2H2O | V = 3238.5 (8) Å3 |
| Mr = 751.32 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 18.049 (2) Å | µ = 0.70 mm−1 |
| b = 18.255 (3) Å | T = 291 (2) K |
| c = 10.0741 (14) Å | 0.12 × 0.10 × 0.10 mm |
| β = 102.668 (2)º |
| Bruker SMART 1K CCD area-detector diffractometer | 3192 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2120 reflections with I > 2σ(I) |
| Tmin = 0.922, Tmax = 0.931 | Rint = 0.042 |
| 8547 measured reflections |
| R[F2 > 2σ(F2)] = 0.042 | 233 parameters |
| wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.97 | Δρmax = 0.43 e Å−3 |
| 3192 reflections | Δρmin = −0.41 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 | 1.0000 | 0.25347 (2) | 0.2500 | 0.04349 (18) | |
| C1 | 0.89844 (14) | 0.28704 (15) | 0.4385 (3) | 0.0581 (7) | |
| H1 | 0.9074 | 0.3364 | 0.4250 | 0.070* | |
| C2 | 0.85298 (17) | 0.26824 (18) | 0.5259 (3) | 0.0733 (9) | |
| H2 | 0.8330 | 0.3045 | 0.5727 | 0.088* | |
| C3 | 0.83702 (17) | 0.19608 (19) | 0.5445 (3) | 0.0737 (9) | |
| H3 | 0.8058 | 0.1829 | 0.6027 | 0.088* | |
| C4 | 0.86806 (14) | 0.14357 (16) | 0.4753 (3) | 0.0609 (7) | |
| H4 | 0.8569 | 0.0943 | 0.4844 | 0.073* | |
| C5 | 0.91552 (13) | 0.16424 (13) | 0.3929 (2) | 0.0484 (6) | |
| C6 | 0.95684 (13) | 0.11401 (13) | 0.3214 (2) | 0.0490 (6) | |
| C7 | 0.95566 (15) | 0.03835 (13) | 0.3241 (3) | 0.0566 (7) | |
| H7 | 0.9262 | 0.0130 | 0.3739 | 0.068* | |
| C8 | 1.0000 | 0.00191 (19) | 0.2500 | 0.0569 (10) | |
| C9 | 0.87358 (14) | 0.22036 (15) | 0.0110 (3) | 0.0552 (7) | |
| H9 | 0.8832 | 0.1710 | 0.0305 | 0.066* | |
| C10 | 0.81690 (16) | 0.23907 (17) | −0.0981 (3) | 0.0652 (8) | |
| H10 | 0.7888 | 0.2028 | −0.1514 | 0.078* | |
| C11 | 0.80185 (16) | 0.31174 (18) | −0.1283 (3) | 0.0674 (8) | |
| H11 | 0.7634 | 0.3251 | −0.2019 | 0.081* | |
| C12 | 0.84469 (14) | 0.36479 (15) | −0.0478 (3) | 0.0582 (7) | |
| H12 | 0.8358 | 0.4143 | −0.0666 | 0.070* | |
| C13 | 0.90054 (12) | 0.34274 (13) | 0.0603 (2) | 0.0459 (6) | |
| C14 | 0.94967 (13) | 0.39307 (13) | 0.1540 (2) | 0.0461 (6) | |
| C15 | 0.94826 (14) | 0.46877 (13) | 0.1511 (3) | 0.0554 (7) | |
| H15 | 0.9137 | 0.4941 | 0.0849 | 0.066* | |
| C16 | 1.0000 | 0.50551 (19) | 0.2500 | 0.0563 (9) | |
| Cl1 | 1.0000 | −0.09281 (5) | 0.2500 | 0.0883 (4) | |
| Cl2 | 1.0000 | 0.60025 (6) | 0.2500 | 0.0908 (4) | |
| H4A | 0.8087 (18) | 0.0502 (17) | −0.052 (3) | 0.069 (11)* | |
| H4B | 0.809 (3) | 0.036 (3) | 0.071 (5) | 0.16 (2)* | |
| N1 | 0.93034 (11) | 0.23672 (10) | 0.3718 (2) | 0.0483 (5) | |
| N2 | 1.0000 | 0.15050 (14) | 0.2500 | 0.0450 (7) | |
| N3 | 0.91592 (11) | 0.27102 (10) | 0.0912 (2) | 0.0462 (5) | |
| N4 | 1.0000 | 0.35651 (14) | 0.2500 | 0.0421 (6) | |
| N5 | 0.72096 (17) | 0.05138 (16) | 0.6869 (3) | 0.0819 (8) | |
| O1 | 0.7680 (2) | 0.0029 (2) | 0.7212 (3) | 0.1692 (17) | |
| O2 | 0.6813 (2) | 0.05091 (14) | 0.5761 (4) | 0.1604 (16) | |
| O3 | 0.71662 (18) | 0.09870 (17) | 0.7664 (3) | 0.1287 (11) | |
| O4 | 0.84123 (15) | 0.04554 (14) | 0.0124 (3) | 0.0804 (7) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.0474 (3) | 0.0321 (3) | 0.0510 (3) | 0.000 | 0.0108 (2) | 0.000 |
| C1 | 0.0563 (16) | 0.0513 (16) | 0.0695 (18) | −0.0025 (13) | 0.0201 (14) | −0.0072 (14) |
| C2 | 0.075 (2) | 0.075 (2) | 0.078 (2) | −0.0025 (17) | 0.0355 (17) | −0.0120 (17) |
| C3 | 0.0697 (19) | 0.087 (2) | 0.072 (2) | −0.0072 (17) | 0.0318 (16) | 0.0073 (18) |
| C4 | 0.0575 (16) | 0.0599 (17) | 0.0656 (17) | −0.0099 (14) | 0.0140 (14) | 0.0088 (15) |
| C5 | 0.0479 (14) | 0.0449 (14) | 0.0500 (14) | −0.0026 (12) | 0.0059 (11) | 0.0047 (12) |
| C6 | 0.0509 (14) | 0.0398 (14) | 0.0520 (15) | −0.0021 (12) | 0.0020 (12) | 0.0048 (12) |
| C7 | 0.0576 (16) | 0.0429 (15) | 0.0612 (17) | −0.0068 (13) | −0.0043 (13) | 0.0098 (13) |
| C8 | 0.062 (2) | 0.0336 (19) | 0.063 (2) | 0.000 | −0.013 (2) | 0.000 |
| C9 | 0.0576 (16) | 0.0470 (14) | 0.0608 (17) | −0.0072 (12) | 0.0128 (13) | −0.0106 (13) |
| C10 | 0.0645 (18) | 0.071 (2) | 0.0578 (17) | −0.0130 (16) | 0.0088 (14) | −0.0152 (15) |
| C11 | 0.0615 (17) | 0.082 (2) | 0.0537 (17) | −0.0016 (16) | 0.0021 (13) | −0.0035 (16) |
| C12 | 0.0598 (16) | 0.0551 (16) | 0.0566 (16) | 0.0010 (13) | 0.0058 (13) | 0.0016 (13) |
| C13 | 0.0450 (13) | 0.0427 (14) | 0.0497 (14) | 0.0014 (11) | 0.0094 (11) | 0.0014 (11) |
| C14 | 0.0468 (14) | 0.0388 (13) | 0.0506 (14) | 0.0008 (11) | 0.0060 (11) | 0.0008 (11) |
| C15 | 0.0576 (16) | 0.0406 (14) | 0.0635 (17) | 0.0034 (12) | 0.0035 (13) | 0.0068 (12) |
| C16 | 0.066 (2) | 0.0329 (18) | 0.068 (2) | 0.000 | 0.011 (2) | 0.000 |
| Cl1 | 0.1096 (9) | 0.0342 (5) | 0.1052 (9) | 0.000 | −0.0113 (7) | 0.000 |
| Cl2 | 0.1091 (9) | 0.0332 (5) | 0.1170 (10) | 0.000 | −0.0033 (8) | 0.000 |
| N1 | 0.0486 (12) | 0.0416 (12) | 0.0539 (12) | 0.0015 (9) | 0.0095 (10) | 0.0020 (9) |
| N2 | 0.0479 (16) | 0.0347 (15) | 0.0522 (17) | 0.000 | 0.0107 (13) | 0.000 |
| N3 | 0.0512 (12) | 0.0390 (11) | 0.0501 (12) | −0.0044 (9) | 0.0147 (9) | −0.0042 (9) |
| N4 | 0.0444 (15) | 0.0335 (14) | 0.0480 (16) | 0.000 | 0.0096 (13) | 0.000 |
| N5 | 0.083 (2) | 0.0703 (19) | 0.082 (2) | −0.0056 (15) | −0.0041 (17) | −0.0227 (16) |
| O1 | 0.159 (3) | 0.232 (5) | 0.097 (2) | 0.093 (3) | −0.015 (2) | −0.032 (2) |
| O2 | 0.204 (3) | 0.0771 (18) | 0.142 (3) | 0.033 (2) | −0.089 (3) | −0.0424 (18) |
| O3 | 0.154 (3) | 0.114 (2) | 0.116 (2) | −0.015 (2) | 0.025 (2) | −0.0545 (19) |
| O4 | 0.0779 (16) | 0.0696 (15) | 0.0858 (18) | 0.0044 (12) | 0.0011 (16) | −0.0029 (13) |
| Fe1—N2 | 1.880 (3) | C9—C10 | 1.371 (4) |
| Fe1—N4 | 1.881 (3) | C9—H9 | 0.9300 |
| Fe1—N1 | 1.964 (2) | C10—C11 | 1.375 (4) |
| Fe1—N1i | 1.964 (2) | C10—H10 | 0.9300 |
| Fe1—N3 | 1.975 (2) | C11—C12 | 1.385 (4) |
| Fe1—N3i | 1.975 (2) | C11—H11 | 0.9300 |
| C1—N1 | 1.340 (3) | C12—C13 | 1.372 (3) |
| C1—C2 | 1.373 (4) | C12—H12 | 0.9300 |
| C1—H1 | 0.9300 | C13—N3 | 1.360 (3) |
| C2—C3 | 1.370 (4) | C13—C14 | 1.468 (3) |
| C2—H2 | 0.9300 | C14—N4 | 1.349 (3) |
| C3—C4 | 1.374 (4) | C14—C15 | 1.382 (3) |
| C3—H3 | 0.9300 | C15—C16 | 1.381 (3) |
| C4—C5 | 1.370 (3) | C15—H15 | 0.9300 |
| C4—H4 | 0.9300 | C16—C15i | 1.381 (3) |
| C5—N1 | 1.375 (3) | C16—Cl2 | 1.729 (4) |
| C5—C6 | 1.467 (3) | N2—C6i | 1.346 (3) |
| C6—N2 | 1.346 (3) | N4—C14i | 1.349 (3) |
| C6—C7 | 1.382 (3) | N5—O2 | 1.187 (3) |
| C7—C8 | 1.379 (3) | N5—O3 | 1.193 (3) |
| C7—H7 | 0.9300 | N5—O1 | 1.223 (4) |
| C8—C7i | 1.379 (3) | O4—H4A | 0.78 (3) |
| C8—Cl1 | 1.729 (4) | O4—H4B | 0.93 (5) |
| C9—N3 | 1.349 (3) | ||
| N2—Fe1—N4 | 180.000 (1) | N3—C9—H9 | 118.8 |
| N2—Fe1—N1 | 81.04 (6) | C10—C9—H9 | 118.8 |
| N4—Fe1—N1 | 98.96 (6) | C9—C10—C11 | 119.6 (3) |
| N2—Fe1—N1i | 81.04 (6) | C9—C10—H10 | 120.2 |
| N4—Fe1—N1i | 98.96 (6) | C11—C10—H10 | 120.2 |
| N1—Fe1—N1i | 162.09 (11) | C10—C11—C12 | 119.1 (3) |
| N2—Fe1—N3 | 99.34 (6) | C10—C11—H11 | 120.4 |
| N4—Fe1—N3 | 80.66 (6) | C12—C11—H11 | 120.4 |
| N1—Fe1—N3 | 92.75 (8) | C13—C12—C11 | 118.6 (3) |
| N1i—Fe1—N3 | 90.14 (8) | C13—C12—H12 | 120.7 |
| N2—Fe1—N3i | 99.34 (6) | C11—C12—H12 | 120.7 |
| N4—Fe1—N3i | 80.66 (6) | N3—C13—C12 | 122.8 (2) |
| N1—Fe1—N3i | 90.14 (8) | N3—C13—C14 | 113.0 (2) |
| N1i—Fe1—N3i | 92.75 (8) | C12—C13—C14 | 124.2 (2) |
| N3—Fe1—N3i | 161.33 (11) | N4—C14—C15 | 121.1 (2) |
| N1—C1—C2 | 122.2 (3) | N4—C14—C13 | 111.6 (2) |
| N1—C1—H1 | 118.9 | C15—C14—C13 | 127.3 (2) |
| C2—C1—H1 | 118.9 | C16—C15—C14 | 117.6 (2) |
| C3—C2—C1 | 120.1 (3) | C16—C15—H15 | 121.2 |
| C3—C2—H2 | 120.0 | C14—C15—H15 | 121.2 |
| C1—C2—H2 | 120.0 | C15—C16—C15i | 121.9 (3) |
| C2—C3—C4 | 118.7 (3) | C15—C16—Cl2 | 119.06 (16) |
| C2—C3—H3 | 120.6 | C15i—C16—Cl2 | 119.06 (16) |
| C4—C3—H3 | 120.6 | C1—N1—C5 | 117.6 (2) |
| C5—C4—C3 | 119.6 (3) | C1—N1—Fe1 | 127.63 (18) |
| C5—C4—H4 | 120.2 | C5—N1—Fe1 | 114.76 (16) |
| C3—C4—H4 | 120.2 | C6i—N2—C6 | 120.7 (3) |
| C4—C5—N1 | 121.8 (2) | C6i—N2—Fe1 | 119.65 (14) |
| C4—C5—C6 | 125.3 (2) | C6—N2—Fe1 | 119.65 (14) |
| N1—C5—C6 | 112.9 (2) | C9—N3—C13 | 117.5 (2) |
| N2—C6—C7 | 121.2 (2) | C9—N3—Fe1 | 127.40 (18) |
| N2—C6—C5 | 111.7 (2) | C13—N3—Fe1 | 115.06 (15) |
| C7—C6—C5 | 127.1 (2) | C14i—N4—C14 | 120.7 (3) |
| C8—C7—C6 | 117.3 (3) | C14i—N4—Fe1 | 119.65 (13) |
| C8—C7—H7 | 121.4 | C14—N4—Fe1 | 119.65 (13) |
| C6—C7—H7 | 121.4 | O2—N5—O3 | 121.5 (4) |
| C7—C8—C7i | 122.3 (3) | O2—N5—O1 | 119.9 (3) |
| C7—C8—Cl1 | 118.84 (17) | O3—N5—O1 | 118.6 (3) |
| C7i—C8—Cl1 | 118.84 (17) | H4A—O4—H4B | 95 (3) |
| N3—C9—C10 | 122.3 (3) |
| Symmetry codes: (i) −x+2, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4B···O1ii | 0.93 (5) | 1.96 (5) | 2.859 (5) | 162 (4) |
| O4—H4A···O3iii | 0.78 (3) | 2.36 (3) | 3.114 (4) | 164 (3) |
| O4—H4A···O1iii | 0.78 (3) | 2.40 (3) | 3.042 (4) | 140 (3) |
| Symmetry codes: (ii) x, −y, z−1/2; (iii) x, y, z−1. |
| Fe1—N2 | 1.880 (3) | Fe1—N1i | 1.964 (2) |
| Fe1—N4 | 1.881 (3) | Fe1—N3 | 1.975 (2) |
| Fe1—N1 | 1.964 (2) | Fe1—N3i | 1.975 (2) |
| N2—Fe1—N4 | 180.000 (1) | N4—Fe1—N3 | 80.66 (6) |
| N2—Fe1—N1 | 81.04 (6) | N1—Fe1—N3 | 92.75 (8) |
| N4—Fe1—N1 | 98.96 (6) | N1i—Fe1—N3 | 90.14 (8) |
| N1—Fe1—N1i | 162.09 (11) | N3—Fe1—N3i | 161.33 (11) |
| N2—Fe1—N3 | 99.34 (6) |
| Symmetry codes: (i) −x+2, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4B···O1ii | 0.93 (5) | 1.96 (5) | 2.859 (5) | 162 (4) |
| O4—H4A···O3iii | 0.78 (3) | 2.36 (3) | 3.114 (4) | 164 (3) |
| O4—H4A···O1iii | 0.78 (3) | 2.40 (3) | 3.042 (4) | 140 (3) |
| Symmetry codes: (ii) x, −y, z−1/2; (iii) x, y, z−1. |
WH acknowledge the Major State Basic Research Development Programs (No. 2006CB806104 and No. 2007CB925101), the National Natural Science Foundation of China (No. 20301009) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry, for financial aid.
Bruker (2000). SMART (Version 5.622), SAINT (Version 6.02a), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.
Huang, W. & Qian, H. F. (2007a). J. Mol. Struct. 832, 108–106.
Huang, W. & Qian, H. F. (2007b). J. Mol. Struct. In the press.. doi:10.1016/j.molstruc.2007.03.038. Any update?
We have newly reported the hydrochlorate tetrafluoroborate and hydrochlorate hexafluorophosphorate of 4'-chloro-2,2':6',2''-terpyridine (Huang & Qian, 2007a), and Ru(II), Cu(II), Zn(II), Ni(II) and Fe(II) complexes of 4'-chloro-2,2':6',2''-terpyridine with the metal/ligand ratios of 1:1 and 1:2. In this paper, we report the structure of a ferrous nitrate complex bearing the same 4'-chloro-2,2':6',2''-terpyridine ligand with the 1:2 metal/ligand ratio.
The atom-numbering scheme of the title compound (I) is shown in Fig. 1, while selected bond distances and bond angles are given in Table 1. The iron(II) center displays a six-coordinate octahedral configuration where each 4'-chloro-2,2':6',2'-terpyridine molecule serves as a 3 N tridentate ligand. The six Fe—N bond lengths fall with the normal ranges of 1.880 (3)—1.975 (2) Å (Huang & Qian, 2007b), where the two central Fe—N bond lengths are somewhat shorter than the side ones. The two terpyridine ligands are planar and the dihedral angle between them is 92.4 (1)°. In addition, O—H···O hydrogen bonds are observed between the hydrogen atoms of water molecule and the oxygen atoms of nitrate anions (Table 2).