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The title compound, [Fe(C
10H
8N
2)
3]Br
2·4.5H
2O, contains discrete tris(2,2′-bipyridyl)iron(II) cations, bromide anions and water molecules. The Fe atom (site symmetry 3) is octahedrally coordinated by six N atoms of the three bidentate bipyridyl ligands. One bromide ion occupies a site of symmetry
m; the other one is located on a site of symmetry 32. All the water O atoms are also located on special positions of site symmetries 3,
m (×2) and
.
Supporting information
CCDC reference: 615286
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.017 Å
- H-atom completeness 73%
- Disorder in solvent or counterion
- R factor = 0.101
- wR factor = 0.283
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O1
| Author Response: The water H atom could not be found and were excluded from
refinement.
|
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O2
| Author Response: The water H atom could not be found and were excluded from
refinement.
|
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O3
| Author Response: The water H atom could not be found and were excluded from
refinement.
|
PLAT430_ALERT_2_A Short Inter D...A Contact O2 .. O4' .. 1.97 Ang.
| Author Response: O4' is one site of a disordered water O atom.
|
Alert level B
PLAT341_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ... 17
PLAT431_ALERT_2_B Short Inter HL..A Contact Br2 .. O1 .. 2.98 Ang.
PLAT431_ALERT_2_B Short Inter HL..A Contact Br2 .. O1 .. 2.98 Ang.
Alert level C
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
calculated from the _atom_site* data lies outside
the range 0.99 <> 1.01
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_weight 765.29
TEST: Calculate formula weight from _atom_site_*
atom mass num sum
C 12.01 30.00 360.33
H 1.01 24.00 24.19
Br 79.90 2.00 159.81
Fe 55.85 1.00 55.85
N 14.01 6.00 84.04
O 16.00 4.50 72.00
Calculated formula weight 756.21
RFACG01_ALERT_3_C The value of the R factor is > 0.10
R factor given 0.101
RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25
Weighted R factor given 0.283
STRVA01_ALERT_4_C Flack test results are ambiguous.
From the CIF: _refine_ls_abs_structure_Flack 0.560
From the CIF: _refine_ls_abs_structure_Flack_su 0.050
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero ....... 0.56
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................ 765.29
PLAT044_ALERT_1_C Calculated and Reported Dx Differ .............. ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT084_ALERT_2_C High R2 Value .................................. 0.28
PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... 1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.16
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 14.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O4'
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <O4
PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O3 .. 3.22 Ang.
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C30 H33 Br2 Fe1 N6 O4.5
Atom count from the _atom_site data: C30 H24 Br2 Fe1 N6 O4.5
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C30 H33 Br2 Fe N6 O4.50
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 120.00 120.00 0.00
H 132.00 96.00 36.00
Br 8.00 8.00 0.00
Fe 4.00 4.00 0.00
N 24.00 24.00 0.00
O 18.00 18.00 0.00
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.57
From the CIF: _reflns_number_total 2071
Count of symmetry unique reflns 1193
Completeness (_total/calc) 173.60%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 878
Fraction of Friedel pairs measured 0.736
Are heavy atom types Z>Si present yes
4 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
18 ALERT level C = Check and explain
4 ALERT level G = General alerts; check
8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
14 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
Crystal data top
[Fe(C10H8N2)3]Br2·4.5H2O | Dx = 1.572 Mg m−3 |
Mr = 765.29 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P62c | Cell parameters from 12085 reflections |
Hall symbol: P -6c -2c | θ = 2.6–25.7° |
a = 13.1386 (12) Å | µ = 2.98 mm−1 |
c = 21.630 (3) Å | T = 173 K |
V = 3233.6 (6) Å3 | Plate, red |
Z = 4 | 0.26 × 0.24 × 0.08 mm |
F(000) = 1548 | |
Data collection top
STOE IPDSII two-circle diffractometer | 2071 independent reflections |
Radiation source: fine-focus sealed tube | 1569 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
ω scans | θmax = 25.6°, θmin = 2.6° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −15→15 |
Tmin = 0.511, Tmax = 0.796 | k = −15→15 |
25866 measured reflections | l = −25→26 |
Refinement top
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)] = 0.101 | H-atom parameters constrained |
wR(F2) = 0.283 | w = 1/[σ2(Fo2) + (0.188P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.033 |
2071 reflections | Δρmax = 2.19 e Å−3 |
139 parameters | Δρmin = −1.17 e Å−3 |
6 restraints | Absolute structure: Flack (1983), 892 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.56 (5) |
Special details top
Experimental. ; |
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 | Uiso*/Ueq | Occ. (<1) |
Fe1 | 0.3333 | 0.6667 | 0.51370 (11) | 0.0237 (6) | |
N1 | 0.3245 (7) | 0.5370 (8) | 0.5638 (5) | 0.030 (2) | |
C2 | 0.2488 (8) | 0.4271 (8) | 0.5411 (5) | 0.027 (2) | |
C3 | 0.2273 (10) | 0.3254 (9) | 0.5734 (6) | 0.035 (3) | |
H3 | 0.1719 | 0.2499 | 0.5581 | 0.042* | |
C4 | 0.2888 (12) | 0.3367 (11) | 0.6284 (7) | 0.041 (3) | |
H4 | 0.2783 | 0.2694 | 0.6503 | 0.050* | |
C5 | 0.3638 (9) | 0.4468 (10) | 0.6493 (6) | 0.032 (3) | |
H5 | 0.4042 | 0.4567 | 0.6872 | 0.039* | |
C6 | 0.3821 (9) | 0.5442 (10) | 0.6165 (5) | 0.032 (2) | |
H6 | 0.4378 | 0.6197 | 0.6316 | 0.038* | |
N11 | 0.2157 (7) | 0.5332 (8) | 0.4630 (4) | 0.0276 (19) | |
C12 | 0.1896 (8) | 0.4246 (10) | 0.4825 (5) | 0.029 (2) | |
C13 | 0.1150 (10) | 0.3242 (9) | 0.4515 (6) | 0.037 (3) | |
H13 | 0.0960 | 0.2495 | 0.4676 | 0.045* | |
C14 | 0.0669 (10) | 0.3330 (10) | 0.3956 (6) | 0.041 (3) | |
H14 | 0.0165 | 0.2644 | 0.3725 | 0.050* | |
C15 | 0.0931 (9) | 0.4413 (10) | 0.3743 (6) | 0.037 (3) | |
H15 | 0.0645 | 0.4501 | 0.3355 | 0.044* | |
C16 | 0.1657 (9) | 0.5421 (10) | 0.4126 (7) | 0.040 (3) | |
H16 | 0.1775 | 0.6169 | 0.4008 | 0.048* | |
Br1 | 0.2892 (3) | 0.8867 (2) | 0.7500 | 0.0750 (9) | |
Br2 | 0.0000 | 0.0000 | 0.5000 | 0.0702 (14) | |
O1 | 0.0000 | 0.0000 | 0.3621 (5) | 0.028 (2) | |
O2 | 0.5290 (13) | 0.3246 (9) | 0.7500 | 0.041 (3) | |
O3 | 0.3333 | 0.6667 | 0.7500 | 0.072 (7) | |
O4 | 0.264 (4) | 0.138 (4) | 0.7500 | 0.062 (14)* | 0.39 (5) |
O4' | 0.369 (6) | 0.187 (6) | 0.7500 | 0.16 (2)* | 0.61 (5) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0175 (7) | 0.0175 (7) | 0.0359 (13) | 0.0088 (4) | 0.000 | 0.000 |
N1 | 0.020 (4) | 0.022 (4) | 0.050 (6) | 0.013 (4) | 0.003 (4) | −0.001 (4) |
C2 | 0.017 (4) | 0.013 (4) | 0.044 (6) | 0.003 (4) | 0.000 (4) | −0.004 (4) |
C3 | 0.037 (6) | 0.012 (5) | 0.058 (8) | 0.013 (5) | 0.008 (5) | 0.008 (4) |
C4 | 0.046 (7) | 0.032 (7) | 0.056 (8) | 0.027 (6) | 0.003 (6) | 0.004 (6) |
C5 | 0.022 (5) | 0.033 (6) | 0.047 (7) | 0.018 (5) | 0.000 (4) | 0.009 (5) |
C6 | 0.027 (5) | 0.032 (6) | 0.041 (6) | 0.019 (5) | −0.003 (4) | −0.010 (5) |
N11 | 0.026 (4) | 0.034 (5) | 0.033 (5) | 0.022 (4) | 0.001 (4) | 0.003 (4) |
C12 | 0.018 (5) | 0.024 (5) | 0.045 (6) | 0.012 (4) | 0.011 (4) | 0.011 (5) |
C13 | 0.024 (5) | 0.019 (5) | 0.052 (8) | −0.002 (4) | −0.006 (5) | −0.014 (5) |
C14 | 0.026 (6) | 0.026 (6) | 0.066 (9) | 0.009 (5) | −0.001 (5) | −0.013 (5) |
C15 | 0.023 (5) | 0.035 (6) | 0.058 (8) | 0.017 (5) | −0.011 (5) | −0.014 (5) |
C16 | 0.018 (5) | 0.022 (5) | 0.078 (9) | 0.007 (4) | −0.008 (5) | 0.001 (5) |
Br1 | 0.093 (2) | 0.0573 (14) | 0.0598 (13) | 0.0265 (13) | 0.000 | 0.000 |
Br2 | 0.0203 (8) | 0.0203 (8) | 0.170 (4) | 0.0102 (4) | 0.000 | 0.000 |
O1 | 0.033 (4) | 0.033 (4) | 0.018 (6) | 0.0164 (18) | 0.000 | 0.000 |
O2 | 0.105 (8) | 0.026 (5) | 0.009 (4) | 0.044 (5) | 0.000 | 0.000 |
O3 | 0.054 (9) | 0.054 (9) | 0.11 (2) | 0.027 (5) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Fe1—N1 | 1.973 (9) | C5—C6 | 1.376 (16) |
Fe1—N1i | 1.973 (9) | C5—H5 | 0.9500 |
Fe1—N1ii | 1.973 (9) | C6—H6 | 0.9500 |
Fe1—N11i | 1.989 (9) | N11—C16 | 1.308 (16) |
Fe1—N11 | 1.989 (10) | N11—C12 | 1.357 (14) |
Fe1—N11ii | 1.989 (9) | C12—C13 | 1.363 (15) |
N1—C6 | 1.344 (15) | C13—C14 | 1.40 (2) |
N1—C2 | 1.371 (13) | C13—H13 | 0.9500 |
C2—C3 | 1.405 (14) | C14—C15 | 1.366 (17) |
C2—C12 | 1.480 (15) | C14—H14 | 0.9500 |
C3—C4 | 1.40 (2) | C15—C16 | 1.445 (16) |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.357 (18) | C16—H16 | 0.9500 |
C4—H4 | 0.9500 | | |
| | | |
N1—Fe1—N1i | 92.7 (4) | C3—C4—H4 | 121.0 |
N1—Fe1—N1ii | 92.7 (4) | C4—C5—C6 | 121.0 (11) |
N1i—Fe1—N1ii | 92.7 (4) | C4—C5—H5 | 119.5 |
N1—Fe1—N11i | 171.9 (3) | C6—C5—H5 | 119.5 |
N1i—Fe1—N11i | 81.8 (3) | N1—C6—C5 | 122.8 (10) |
N1ii—Fe1—N11i | 93.5 (3) | N1—C6—H6 | 118.6 |
N1—Fe1—N11 | 81.8 (3) | C5—C6—H6 | 118.6 |
N1i—Fe1—N11 | 93.5 (3) | C16—N11—C12 | 118.6 (10) |
N1ii—Fe1—N11 | 171.9 (3) | C16—N11—Fe1 | 125.8 (7) |
N11i—Fe1—N11 | 92.6 (4) | C12—N11—Fe1 | 115.6 (7) |
N1—Fe1—N11ii | 93.5 (3) | N11—C12—C13 | 123.2 (11) |
N1i—Fe1—N11ii | 171.9 (3) | N11—C12—C2 | 112.9 (10) |
N1ii—Fe1—N11ii | 81.8 (3) | C13—C12—C2 | 124.0 (10) |
N11i—Fe1—N11ii | 92.6 (4) | C12—C13—C14 | 118.8 (11) |
N11—Fe1—N11ii | 92.6 (4) | C12—C13—H13 | 120.6 |
C6—N1—C2 | 117.7 (10) | C14—C13—H13 | 120.6 |
C6—N1—Fe1 | 128.1 (8) | C15—C14—C13 | 119.3 (10) |
C2—N1—Fe1 | 114.3 (7) | C15—C14—H14 | 120.3 |
N1—C2—C3 | 121.2 (10) | C13—C14—H14 | 120.3 |
N1—C2—C12 | 115.3 (10) | C14—C15—C16 | 117.9 (11) |
C3—C2—C12 | 123.5 (10) | C14—C15—H15 | 121.0 |
C4—C3—C2 | 119.3 (10) | C16—C15—H15 | 121.0 |
C4—C3—H3 | 120.4 | N11—C16—C15 | 121.8 (10) |
C2—C3—H3 | 120.4 | N11—C16—H16 | 119.1 |
C5—C4—C3 | 117.9 (11) | C15—C16—H16 | 119.1 |
C5—C4—H4 | 121.0 | | |
| | | |
N1i—Fe1—N1—C6 | −85.8 (7) | N11i—Fe1—N11—C16 | 5.5 (10) |
N1ii—Fe1—N1—C6 | 7.1 (9) | N11ii—Fe1—N11—C16 | −87.2 (8) |
N11—Fe1—N1—C6 | −178.9 (9) | N1—Fe1—N11—C12 | −2.7 (7) |
N11ii—Fe1—N1—C6 | 89.0 (9) | N1i—Fe1—N11—C12 | −95.0 (7) |
N1i—Fe1—N1—C2 | 93.5 (9) | N11i—Fe1—N11—C12 | −176.9 (7) |
N1ii—Fe1—N1—C2 | −173.6 (7) | N11ii—Fe1—N11—C12 | 90.4 (9) |
N11—Fe1—N1—C2 | 0.4 (7) | C16—N11—C12—C13 | 0.9 (15) |
N11ii—Fe1—N1—C2 | −91.6 (7) | Fe1—N11—C12—C13 | −176.9 (9) |
C6—N1—C2—C3 | 3.2 (14) | C16—N11—C12—C2 | −178.0 (9) |
Fe1—N1—C2—C3 | −176.2 (8) | Fe1—N11—C12—C2 | 4.3 (10) |
C6—N1—C2—C12 | −178.9 (8) | N1—C2—C12—N11 | −3.9 (11) |
Fe1—N1—C2—C12 | 1.7 (10) | C3—C2—C12—N11 | 174.0 (10) |
N1—C2—C3—C4 | −2.9 (17) | N1—C2—C12—C13 | 177.3 (10) |
C12—C2—C3—C4 | 179.3 (11) | C3—C2—C12—C13 | −4.8 (15) |
C2—C3—C4—C5 | 2.4 (19) | N11—C12—C13—C14 | 3.1 (17) |
C3—C4—C5—C6 | −2.3 (19) | C2—C12—C13—C14 | −178.2 (10) |
C2—N1—C6—C5 | −3.1 (15) | C12—C13—C14—C15 | −1.8 (18) |
Fe1—N1—C6—C5 | 176.2 (8) | C13—C14—C15—C16 | −2.9 (17) |
C4—C5—C6—N1 | 2.7 (17) | C12—N11—C16—C15 | −6.0 (16) |
N1—Fe1—N11—C16 | 179.7 (9) | Fe1—N11—C16—C15 | 171.6 (8) |
N1i—Fe1—N11—C16 | 87.4 (10) | C14—C15—C16—N11 | 7.1 (17) |
Symmetry codes: (i) −x+y, −x+1, z; (ii) −y+1, x−y+1, z. |
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