Single crystals of a new mixed-valence compound, [Fe
7(C
4H
9NO
2)
6Cl
6]·2CH
3CN·H
2O, were synthesized by solvothermal methods. The crystal structure consists of discrete heptanuclear complexes which are linked by weak intermolecular C—H
Cl hydrogen bonds to form a two-dimensional network. In each complex, a central Fe atom is connected to six surrounding Fe centres by alkoxo-type O atoms from the organic ligand. Bond-valence sum calculations indicate that the central Fe ion is Fe
II, as are two of the outer Fe centers, while the remaining four Fe centers are Fe
III. Although the outer Fe atoms are crystallographically equivalent, it is uncertain whether this arises from positional disorder or charge delocalization. The molecular structure has
S6 point symmetry.
Supporting information
CCDC reference: 270508
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (C-C) = 0.017 Å
- H-atom completeness 97%
- Disorder in solvent or counterion
- R factor = 0.065
- wR factor = 0.169
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
No syntax errors found
Alert level B
RINTA01_ALERT_3_B The value of Rint is greater than 0.15
Rint given 0.180
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 ......... 0.18
PLAT341_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ... 17
PLAT395_ALERT_2_B Deviating X-O-Y Angle from 120 Deg for <O1WB 180.00 Deg.
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.402 0.624
Tmin' and Tmax expected: 0.481 0.624
RR' = 0.835
Please check that your absorption correction is appropriate.
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
identifier.
block
CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.81
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C5
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.43
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 14.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
PLAT731_ALERT_1_C Bond Calc 0.89(7), Rep 0.89(2) ...... 3.50 su-Rat
N1 -H1 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.89(5), Rep 0.89(2) ...... 2.50 su-Rat
N1 -H2 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.89(7), Rep 0.89(2) ...... 3.50 su-Rat
N1 -H1 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.89(5), Rep 0.89(2) ...... 2.50 su-Rat
N1 -H2 1.555 1.555
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.14 Ratio
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:C28 H62 Cl6 Fe7 N8 O13
Atom count from the _atom_site data: C28 H59.94 Cl6 Fe7 N8 O13
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 3
From the CIF: _chemical_formula_sum C28 H62 Cl6 Fe7 N8 O13
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 84.00 84.00 0.00
H 186.00 179.82 6.18
Cl 18.00 18.00 0.00
Fe 21.00 21.00 0.00
N 24.00 24.00 0.00
O 39.00 39.00 0.00
0 ALERT level A = In general: serious problem
4 ALERT level B = Potentially serious problem
16 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
5 ALERT type 3 Indicator that the structure quality may be low
4 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: EXPOSE in IPDS II (Stoe, 2000); cell refinement: CELL in IPDS II; data reduction: INTEGRATE in IPDS II (Stoe, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Hexakis(µ
4-2-amino-2-methylpropane-1,3-diolato)hexachloroheptairon(II,III)
acetonitrile disolvate monohydrate
top
Crystal data top
[Fe7(C4H9NO2)6Cl6]·2CH3CN·H2O | Dx = 1.761 Mg m−3 |
Mr = 1322.51 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, R3 | Cell parameters from 3857 reflections |
Hall symbol: -R 3 | θ = 2.2–25.8° |
a = 12.4150 (7) Å | µ = 2.36 mm−1 |
c = 28.030 (3) Å | T = 153 K |
V = 3741.5 (5) Å3 | Brown, block |
Z = 3 | 0.30 × 0.30 × 0.20 mm |
F(000) = 2022 | |
Data collection top
Stoe IPDS diffractometer | 1622 independent reflections |
Radiation source: fine-focus sealed tube | 916 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.180 |
Detector resolution: 0.81 pixels mm-1 | θmax = 25.9°, θmin = 2.0° |
φ oscillation scans | h = −15→15 |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | k = −15→15 |
Tmin = 0.402, Tmax = 0.624 | l = −34→34 |
9917 measured reflections | |
Refinement top
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0981P)2] where P = (Fo2 + 2Fc2)/3 |
1622 reflections | (Δ/σ)max < 0.001 |
105 parameters | Δρmax = 1.52 e Å−3 |
2 restraints | Δρmin = −1.12 e Å−3 |
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 >
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 | 0.1667 | 0.0145 (6) | |
Fe2 | 0.06706 (10) | 0.64746 (11) | 0.15927 (3) | 0.0269 (4) | |
Cl1 | −0.0502 (2) | 0.6934 (3) | 0.10790 (7) | 0.0521 (7) | |
N1 | 0.2415 (7) | 0.9585 (7) | 0.1115 (3) | 0.0409 (18) | |
H1 | 0.161 (3) | 0.924 (8) | 0.105 (3) | 0.049* | |
H2 | 0.264 (8) | 1.035 (4) | 0.102 (3) | 0.049* | |
N2 | 0.0000 | 1.0000 | 0.2987 (6) | 0.067 (4) | |
O1 | 0.2420 (5) | 0.7474 (5) | 0.12845 (16) | 0.0298 (12) | |
O2 | 0.4639 (5) | 0.9850 (5) | 0.13216 (16) | 0.0352 (13) | |
C1 | 0.3060 (8) | 0.9262 (8) | 0.0735 (2) | 0.035 (2) | |
C2 | 0.2578 (8) | 0.7853 (8) | 0.0788 (2) | 0.0345 (19) | |
H2A | 0.1771 | 0.7380 | 0.0621 | 0.041* | |
H2B | 0.3174 | 0.7651 | 0.0635 | 0.041* | |
C3 | 0.4419 (8) | 1.0029 (8) | 0.0839 (3) | 0.043 (2) | |
H3A | 0.4891 | 0.9781 | 0.0625 | 0.052* | |
H3B | 0.4704 | 1.0919 | 0.0782 | 0.052* | |
C4 | 0.2787 (9) | 0.9527 (9) | 0.0231 (3) | 0.054 (3) | |
H4C | 0.3174 | 1.0428 | 0.0184 | 0.081* | |
H4A | 0.1885 | 0.9138 | 0.0186 | 0.081* | |
H4B | 0.3126 | 0.9186 | −0.0002 | 0.081* | |
C5 | 0.0000 | 1.0000 | 0.2598 (7) | 0.050 (4) | |
C6 | 0.0000 | 1.0000 | 0.2062 (6) | 0.076 (6) | |
H6A | −0.0805 | 0.9859 | 0.1946 | 0.114* | 0.33 |
H6B | 0.0141 | 0.9337 | 0.1946 | 0.114* | 0.33 |
H6C | 0.0663 | 1.0805 | 0.1946 | 0.114* | 0.33 |
O1WA | 0.0000 | 1.0000 | 0.0492 (12) | 0.026 (8)* | 0.25 |
O1WB | 0.0000 | 1.0000 | 0.0203 (12) | 0.028 (8)* | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0169 (8) | 0.0169 (8) | 0.0099 (10) | 0.0084 (4) | 0.000 | 0.000 |
Fe2 | 0.0290 (7) | 0.0448 (8) | 0.0131 (5) | 0.0231 (6) | 0.0000 (4) | 0.0002 (4) |
Cl1 | 0.0451 (14) | 0.102 (2) | 0.0293 (10) | 0.0515 (15) | −0.0016 (9) | 0.0024 (11) |
N1 | 0.048 (5) | 0.032 (4) | 0.043 (4) | 0.021 (4) | 0.000 (4) | 0.007 (3) |
N2 | 0.066 (7) | 0.066 (7) | 0.068 (11) | 0.033 (4) | 0.000 | 0.000 |
O1 | 0.039 (3) | 0.037 (3) | 0.018 (2) | 0.022 (3) | 0.006 (2) | 0.006 (2) |
O2 | 0.036 (3) | 0.037 (3) | 0.027 (3) | 0.015 (3) | 0.002 (2) | 0.008 (2) |
C1 | 0.066 (6) | 0.038 (5) | 0.012 (3) | 0.035 (5) | −0.004 (4) | 0.004 (3) |
C2 | 0.044 (5) | 0.046 (5) | 0.016 (3) | 0.025 (5) | 0.002 (3) | 0.005 (3) |
C3 | 0.052 (6) | 0.041 (6) | 0.028 (4) | 0.017 (5) | 0.006 (4) | 0.017 (4) |
C4 | 0.084 (8) | 0.057 (6) | 0.026 (4) | 0.038 (6) | −0.013 (4) | 0.012 (4) |
C5 | 0.044 (7) | 0.044 (7) | 0.060 (11) | 0.022 (3) | 0.000 | 0.000 |
C6 | 0.086 (10) | 0.086 (10) | 0.056 (11) | 0.043 (5) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Fe1—O1i | 2.138 (5) | O2—C3 | 1.419 (9) |
Fe1—O1 | 2.138 (5) | O2—Fe2v | 1.994 (5) |
Fe1—O1ii | 2.138 (5) | O2—Fe2iii | 2.005 (5) |
Fe1—O1iii | 2.138 (5) | C1—C3 | 1.495 (12) |
Fe1—O1iv | 2.138 (5) | C1—C4 | 1.528 (9) |
Fe1—O1v | 2.138 (5) | C1—C2 | 1.548 (11) |
Fe2—O1iv | 2.203 (5) | C2—H2A | 0.9900 |
Fe2—O1 | 2.076 (5) | C2—H2B | 0.9900 |
Fe2—O2iv | 1.994 (5) | C3—H3A | 0.9900 |
Fe2—O2ii | 2.005 (5) | C3—H3B | 0.9900 |
Fe2—N1iv | 2.168 (7) | C4—H4C | 0.9800 |
N1—Fe2v | 2.168 (7) | C4—H4A | 0.9800 |
Fe2—Cl1 | 2.313 (2) | C4—H4B | 0.9800 |
N1—C1 | 1.501 (11) | C5—C6 | 1.50 (2) |
N1—H1 | 0.89 (2) | C6—H6A | 0.9800 |
N1—H2 | 0.89 (2) | C6—H6B | 0.9800 |
N2—C5 | 1.09 (2) | C6—H6C | 0.9800 |
O1—C2 | 1.451 (8) | O1WB—O1WBvi | 1.14 (7) |
O1—Fe2v | 2.203 (5) | | |
| | | |
O1i—Fe1—O1 | 180 | Fe2—O1—Fe1 | 98.8 (2) |
O1i—Fe1—O1ii | 82.91 (16) | C2—O1—Fe2v | 109.1 (4) |
O1—Fe1—O1ii | 97.09 (16) | Fe2—O1—Fe2v | 97.57 (19) |
O1i—Fe1—O1iii | 82.91 (16) | Fe1—O1—Fe2v | 94.96 (19) |
O1—Fe1—O1iii | 97.09 (16) | C3—O2—Fe2v | 114.9 (5) |
O1ii—Fe1—O1iii | 97.09 (16) | C3—O2—Fe2iii | 129.6 (5) |
O1i—Fe1—O1iv | 97.09 (16) | Fe2v—O2—Fe2iii | 107.3 (2) |
O1—Fe1—O1iv | 82.91 (16) | C3—C1—N1 | 105.9 (6) |
O1ii—Fe1—O1iv | 82.91 (16) | C3—C1—C4 | 110.1 (7) |
O1iii—Fe1—O1iv | 180 | N1—C1—C4 | 113.2 (7) |
O1i—Fe1—O1v | 97.09 (16) | C3—C1—C2 | 112.1 (7) |
O1—Fe1—O1v | 82.91 (16) | N1—C1—C2 | 106.1 (6) |
O1ii—Fe1—O1v | 180 | C4—C1—C2 | 109.3 (6) |
O1iii—Fe1—O1v | 82.91 (16) | O1—C2—C1 | 111.8 (6) |
O1iv—Fe1—O1v | 97.09 (16) | O1—C2—H2A | 109.3 |
O2iv—Fe2—O2ii | 161.6 (2) | C1—C2—H2A | 109.3 |
O2iv—Fe2—O1 | 79.1 (2) | O1—C2—H2B | 109.3 |
O2ii—Fe2—O1 | 99.2 (2) | C1—C2—H2B | 109.3 |
O2iv—Fe2—O1iv | 85.7 (2) | H2A—C2—H2B | 107.9 |
O2ii—Fe2—O1iv | 75.8 (2) | O2—C3—C1 | 109.3 (6) |
O1—Fe2—O1iv | 82.8 (3) | O2—C3—H3A | 109.8 |
O2iv—Fe2—N1iv | 79.9 (2) | C1—C3—H3A | 109.8 |
O2ii—Fe2—N1iv | 94.2 (3) | O2—C3—H3B | 109.8 |
O1—Fe2—N1iv | 150.5 (2) | C1—C3—H3B | 109.8 |
N1iv—Fe2—O1iv | 75.2 (2) | H3A—C3—H3B | 108.3 |
O1—Fe2—Cl1 | 101.15 (15) | C1—C4—H4C | 109.5 |
N1iv—Fe2—Cl1 | 103.4 (2) | C1—C4—H4A | 109.5 |
O1iv—Fe2—Cl1 | 171.65 (16) | H4C—C4—H4A | 109.5 |
O2iv—Fe2—Cl1 | 102.20 (17) | C1—C4—H4B | 109.5 |
O2ii—Fe2—Cl1 | 96.16 (16) | H4C—C4—H4B | 109.5 |
C1—N1—Fe2v | 99.2 (5) | H4A—C4—H4B | 109.5 |
C1—N1—H1 | 111 (6) | N2—C5—C6 | 180.000 (6) |
Fe2v—N1—H1 | 123 (6) | C5—C6—H6A | 109.5 |
C1—N1—H2 | 99 (6) | C5—C6—H6B | 109.5 |
Fe2v—N1—H2 | 125 (6) | H6A—C6—H6B | 109.5 |
H1—N1—H2 | 97 (8) | C5—C6—H6C | 109.5 |
C2—O1—Fe2 | 121.6 (5) | H6A—C6—H6C | 109.5 |
C2—O1—Fe1 | 128.0 (4) | H6B—C6—H6C | 109.5 |
| | | |
O2iv—Fe2—O1—C2 | −121.6 (5) | O1iv—Fe1—O1—Fe2 | −5.76 (18) |
O2ii—Fe2—O1—C2 | 77.0 (5) | O1v—Fe1—O1—Fe2 | −103.9 (3) |
N1iv—Fe2—O1—C2 | −166.9 (6) | O1ii—Fe1—O1—Fe2v | 174.62 (19) |
O1iv—Fe2—O1—C2 | 151.4 (5) | O1iii—Fe1—O1—Fe2v | −87.3 (3) |
Cl1—Fe2—O1—C2 | −21.2 (5) | O1iv—Fe1—O1—Fe2v | 92.7 (3) |
O2iv—Fe2—O1—Fe1 | 92.6 (2) | O1v—Fe1—O1—Fe2v | −5.38 (19) |
O2ii—Fe2—O1—Fe1 | −68.7 (2) | Fe2v—N1—C1—C3 | −56.8 (6) |
N1iv—Fe2—O1—Fe1 | 47.3 (6) | Fe2v—N1—C1—C4 | −177.6 (6) |
O1iv—Fe2—O1—Fe1 | 5.59 (19) | Fe2v—N1—C1—C2 | 62.6 (6) |
Cl1—Fe2—O1—Fe1 | −166.94 (15) | Fe2—O1—C2—C1 | 106.0 (7) |
O2iv—Fe2—O1—Fe2v | −3.6 (2) | Fe1—O1—C2—C1 | −118.9 (6) |
O2ii—Fe2—O1—Fe2v | −164.98 (19) | Fe2v—O1—C2—C1 | −6.1 (8) |
N1iv—Fe2—O1—Fe2v | −48.9 (6) | C3—C1—C2—O1 | 77.0 (8) |
O1iv—Fe2—O1—Fe2v | −90.7 (2) | N1—C1—C2—O1 | −38.3 (8) |
Cl1—Fe2—O1—Fe2v | 96.80 (16) | C4—C1—C2—O1 | −160.6 (7) |
O1ii—Fe1—O1—C2 | −66.4 (5) | Fe2v—O2—C3—C1 | −18.3 (8) |
O1iii—Fe1—O1—C2 | 31.7 (6) | Fe2iii—O2—C3—C1 | 125.7 (6) |
O1iv—Fe1—O1—C2 | −148.3 (6) | N1—C1—C3—O2 | 52.3 (8) |
O1v—Fe1—O1—C2 | 113.6 (5) | C4—C1—C3—O2 | 175.1 (7) |
O1ii—Fe1—O1—Fe2 | 76.1 (3) | C2—C1—C3—O2 | −63.0 (8) |
O1iii—Fe1—O1—Fe2 | 174.24 (18) | | |
Symmetry codes: (i) −x+2/3, −y+4/3, −z+1/3; (ii) −y+1, x−y+1, z; (iii) −x+y, −x+1, z; (iv) x−y+2/3, x+1/3, −z+1/3; (v) y−1/3, −x+y+1/3, −z+1/3; (vi) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.89 (2) | 2.75 (6) | 3.470 (8) | 139 (8) |
N1—H2···Cl1vii | 0.89 (2) | 2.52 (4) | 3.370 (8) | 158 (8) |
Symmetry code: (vii) −y+1, x−y+2, z. |