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Single crystals of a new mixed-valence compound, [Fe7(C4H9NO2)6Cl6]·2CH3CN·H2O, 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 FeII, as are two of the outer Fe centers, while the remaining four Fe centers are FeIII. 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680500557X/om6230sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680500557X/om6230Isup2.hkl
Contains datablock I

CCDC reference: 270508

Key indicators

  • Single-crystal X-ray study
  • T = 153 K
  • Mean [sigma](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

Computing details top

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(µ4-2-amino-2-methylpropane-1,3-diolato)hexachloroheptairon(II,III) acetonitrile disolvate monohydrate top
Crystal data top
[Fe7(C4H9NO2)6Cl6]·2CH3CN·H2ODx = 1.761 Mg m3
Mr = 1322.51Mo Kα radiation, λ = 0.71073 Å
Hexagonal, R3Cell parameters from 3857 reflections
Hall symbol: -R 3θ = 2.2–25.8°
a = 12.4150 (7) ŵ = 2.36 mm1
c = 28.030 (3) ÅT = 153 K
V = 3741.5 (5) Å3Brown, block
Z = 30.30 × 0.30 × 0.20 mm
F(000) = 2022
Data collection top
Stoe IPDS
diffractometer
1622 independent reflections
Radiation source: fine-focus sealed tube916 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.180
Detector resolution: 0.81 pixels mm-1θmax = 25.9°, θmin = 2.0°
φ oscillation scansh = 1515
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2003)
k = 1515
Tmin = 0.402, Tmax = 0.624l = 3434
9917 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H-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 parametersΔρmax = 1.52 e Å3
2 restraintsΔρmin = 1.12 e Å3
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
xyzUiso*/UeqOcc. (<1)
Fe10.33330.66670.16670.0145 (6)
Fe20.06706 (10)0.64746 (11)0.15927 (3)0.0269 (4)
Cl10.0502 (2)0.6934 (3)0.10790 (7)0.0521 (7)
N10.2415 (7)0.9585 (7)0.1115 (3)0.0409 (18)
H10.161 (3)0.924 (8)0.105 (3)0.049*
H20.264 (8)1.035 (4)0.102 (3)0.049*
N20.00001.00000.2987 (6)0.067 (4)
O10.2420 (5)0.7474 (5)0.12845 (16)0.0298 (12)
O20.4639 (5)0.9850 (5)0.13216 (16)0.0352 (13)
C10.3060 (8)0.9262 (8)0.0735 (2)0.035 (2)
C20.2578 (8)0.7853 (8)0.0788 (2)0.0345 (19)
H2A0.17710.73800.06210.041*
H2B0.31740.76510.06350.041*
C30.4419 (8)1.0029 (8)0.0839 (3)0.043 (2)
H3A0.48910.97810.06250.052*
H3B0.47041.09190.07820.052*
C40.2787 (9)0.9527 (9)0.0231 (3)0.054 (3)
H4C0.31741.04280.01840.081*
H4A0.18850.91380.01860.081*
H4B0.31260.91860.00020.081*
C50.00001.00000.2598 (7)0.050 (4)
C60.00001.00000.2062 (6)0.076 (6)
H6A0.08050.98590.19460.114*0.33
H6B0.01410.93370.19460.114*0.33
H6C0.06631.08050.19460.114*0.33
O1WA0.00001.00000.0492 (12)0.026 (8)*0.25
O1WB0.00001.00000.0203 (12)0.028 (8)*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0169 (8)0.0169 (8)0.0099 (10)0.0084 (4)0.0000.000
Fe20.0290 (7)0.0448 (8)0.0131 (5)0.0231 (6)0.0000 (4)0.0002 (4)
Cl10.0451 (14)0.102 (2)0.0293 (10)0.0515 (15)0.0016 (9)0.0024 (11)
N10.048 (5)0.032 (4)0.043 (4)0.021 (4)0.000 (4)0.007 (3)
N20.066 (7)0.066 (7)0.068 (11)0.033 (4)0.0000.000
O10.039 (3)0.037 (3)0.018 (2)0.022 (3)0.006 (2)0.006 (2)
O20.036 (3)0.037 (3)0.027 (3)0.015 (3)0.002 (2)0.008 (2)
C10.066 (6)0.038 (5)0.012 (3)0.035 (5)0.004 (4)0.004 (3)
C20.044 (5)0.046 (5)0.016 (3)0.025 (5)0.002 (3)0.005 (3)
C30.052 (6)0.041 (6)0.028 (4)0.017 (5)0.006 (4)0.017 (4)
C40.084 (8)0.057 (6)0.026 (4)0.038 (6)0.013 (4)0.012 (4)
C50.044 (7)0.044 (7)0.060 (11)0.022 (3)0.0000.000
C60.086 (10)0.086 (10)0.056 (11)0.043 (5)0.0000.000
Geometric parameters (Å, º) top
Fe1—O1i2.138 (5)O2—C31.419 (9)
Fe1—O12.138 (5)O2—Fe2v1.994 (5)
Fe1—O1ii2.138 (5)O2—Fe2iii2.005 (5)
Fe1—O1iii2.138 (5)C1—C31.495 (12)
Fe1—O1iv2.138 (5)C1—C41.528 (9)
Fe1—O1v2.138 (5)C1—C21.548 (11)
Fe2—O1iv2.203 (5)C2—H2A0.9900
Fe2—O12.076 (5)C2—H2B0.9900
Fe2—O2iv1.994 (5)C3—H3A0.9900
Fe2—O2ii2.005 (5)C3—H3B0.9900
Fe2—N1iv2.168 (7)C4—H4C0.9800
N1—Fe2v2.168 (7)C4—H4A0.9800
Fe2—Cl12.313 (2)C4—H4B0.9800
N1—C11.501 (11)C5—C61.50 (2)
N1—H10.89 (2)C6—H6A0.9800
N1—H20.89 (2)C6—H6B0.9800
N2—C51.09 (2)C6—H6C0.9800
O1—C21.451 (8)O1WB—O1WBvi1.14 (7)
O1—Fe2v2.203 (5)
O1i—Fe1—O1180Fe2—O1—Fe198.8 (2)
O1i—Fe1—O1ii82.91 (16)C2—O1—Fe2v109.1 (4)
O1—Fe1—O1ii97.09 (16)Fe2—O1—Fe2v97.57 (19)
O1i—Fe1—O1iii82.91 (16)Fe1—O1—Fe2v94.96 (19)
O1—Fe1—O1iii97.09 (16)C3—O2—Fe2v114.9 (5)
O1ii—Fe1—O1iii97.09 (16)C3—O2—Fe2iii129.6 (5)
O1i—Fe1—O1iv97.09 (16)Fe2v—O2—Fe2iii107.3 (2)
O1—Fe1—O1iv82.91 (16)C3—C1—N1105.9 (6)
O1ii—Fe1—O1iv82.91 (16)C3—C1—C4110.1 (7)
O1iii—Fe1—O1iv180N1—C1—C4113.2 (7)
O1i—Fe1—O1v97.09 (16)C3—C1—C2112.1 (7)
O1—Fe1—O1v82.91 (16)N1—C1—C2106.1 (6)
O1ii—Fe1—O1v180C4—C1—C2109.3 (6)
O1iii—Fe1—O1v82.91 (16)O1—C2—C1111.8 (6)
O1iv—Fe1—O1v97.09 (16)O1—C2—H2A109.3
O2iv—Fe2—O2ii161.6 (2)C1—C2—H2A109.3
O2iv—Fe2—O179.1 (2)O1—C2—H2B109.3
O2ii—Fe2—O199.2 (2)C1—C2—H2B109.3
O2iv—Fe2—O1iv85.7 (2)H2A—C2—H2B107.9
O2ii—Fe2—O1iv75.8 (2)O2—C3—C1109.3 (6)
O1—Fe2—O1iv82.8 (3)O2—C3—H3A109.8
O2iv—Fe2—N1iv79.9 (2)C1—C3—H3A109.8
O2ii—Fe2—N1iv94.2 (3)O2—C3—H3B109.8
O1—Fe2—N1iv150.5 (2)C1—C3—H3B109.8
N1iv—Fe2—O1iv75.2 (2)H3A—C3—H3B108.3
O1—Fe2—Cl1101.15 (15)C1—C4—H4C109.5
N1iv—Fe2—Cl1103.4 (2)C1—C4—H4A109.5
O1iv—Fe2—Cl1171.65 (16)H4C—C4—H4A109.5
O2iv—Fe2—Cl1102.20 (17)C1—C4—H4B109.5
O2ii—Fe2—Cl196.16 (16)H4C—C4—H4B109.5
C1—N1—Fe2v99.2 (5)H4A—C4—H4B109.5
C1—N1—H1111 (6)N2—C5—C6180.000 (6)
Fe2v—N1—H1123 (6)C5—C6—H6A109.5
C1—N1—H299 (6)C5—C6—H6B109.5
Fe2v—N1—H2125 (6)H6A—C6—H6B109.5
H1—N1—H297 (8)C5—C6—H6C109.5
C2—O1—Fe2121.6 (5)H6A—C6—H6C109.5
C2—O1—Fe1128.0 (4)H6B—C6—H6C109.5
O2iv—Fe2—O1—C2121.6 (5)O1iv—Fe1—O1—Fe25.76 (18)
O2ii—Fe2—O1—C277.0 (5)O1v—Fe1—O1—Fe2103.9 (3)
N1iv—Fe2—O1—C2166.9 (6)O1ii—Fe1—O1—Fe2v174.62 (19)
O1iv—Fe2—O1—C2151.4 (5)O1iii—Fe1—O1—Fe2v87.3 (3)
Cl1—Fe2—O1—C221.2 (5)O1iv—Fe1—O1—Fe2v92.7 (3)
O2iv—Fe2—O1—Fe192.6 (2)O1v—Fe1—O1—Fe2v5.38 (19)
O2ii—Fe2—O1—Fe168.7 (2)Fe2v—N1—C1—C356.8 (6)
N1iv—Fe2—O1—Fe147.3 (6)Fe2v—N1—C1—C4177.6 (6)
O1iv—Fe2—O1—Fe15.59 (19)Fe2v—N1—C1—C262.6 (6)
Cl1—Fe2—O1—Fe1166.94 (15)Fe2—O1—C2—C1106.0 (7)
O2iv—Fe2—O1—Fe2v3.6 (2)Fe1—O1—C2—C1118.9 (6)
O2ii—Fe2—O1—Fe2v164.98 (19)Fe2v—O1—C2—C16.1 (8)
N1iv—Fe2—O1—Fe2v48.9 (6)C3—C1—C2—O177.0 (8)
O1iv—Fe2—O1—Fe2v90.7 (2)N1—C1—C2—O138.3 (8)
Cl1—Fe2—O1—Fe2v96.80 (16)C4—C1—C2—O1160.6 (7)
O1ii—Fe1—O1—C266.4 (5)Fe2v—O2—C3—C118.3 (8)
O1iii—Fe1—O1—C231.7 (6)Fe2iii—O2—C3—C1125.7 (6)
O1iv—Fe1—O1—C2148.3 (6)N1—C1—C3—O252.3 (8)
O1v—Fe1—O1—C2113.6 (5)C4—C1—C3—O2175.1 (7)
O1ii—Fe1—O1—Fe276.1 (3)C2—C1—C3—O263.0 (8)
O1iii—Fe1—O1—Fe2174.24 (18)
Symmetry codes: (i) x+2/3, y+4/3, z+1/3; (ii) y+1, xy+1, z; (iii) x+y, x+1, z; (iv) xy+2/3, x+1/3, z+1/3; (v) y1/3, x+y+1/3, z+1/3; (vi) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.89 (2)2.75 (6)3.470 (8)139 (8)
N1—H2···Cl1vii0.89 (2)2.52 (4)3.370 (8)158 (8)
Symmetry code: (vii) y+1, xy+2, z.
 

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