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In the title compound, [Fe(C5H8NOS2)2(H2O)]CF3SO3, the Fe atom has five-coordinate square-pyramidal stereochemistry, with the Fe atom 0.472 (1) Å above the plane of four S atoms and a water mol­ecule O atom at the apex. The cation has m (Cs) symmetry, with the crystallographic mirror plane passing through the Fe, O and N atoms. One O atom of the anion forms a strong hydrogen bond with the coordinated water mol­ecule [O...O = 2.642 (5) Å]. This is the first report of a cationic [Fe(di­thio­carbamate)2L]n+ species.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803024462/cf6293sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803024462/cf6293Isup2.hkl
Contains datablock I

CCDC reference: 226688

Key indicators

  • Single-crystal X-ray study
  • T = 168 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in solvent or counterion
  • R factor = 0.042
  • wR factor = 0.094
  • Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT216_ALERT_3_B Disordered O3A (An/Solv) ADP max/min Ratio 7.60
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.99 PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .... S3 PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .... C7 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 43.00 Perc. PLAT432_ALERT_2_C Short Inter X...Y Contact O2 .. C1 = 2.92 Ang.
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 2000) and Xtal3.7 ADDREF and SORTRF (Hall et al., 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: Xtal3.7 CRYLSQ; molecular graphics: Xtal3.7; software used to prepare material for publication: Xtal3.7 BONDLA and CIFIO.

(I) top
Crystal data top
[Fe(C5H8NOS2)2(H2O)]CF3SO3F(000) = 1116
Mr = 547.44Dx = 1.68 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -p_2ac_2nCell parameters from 7138 reflections
a = 18.929 (6) Åθ = 2.1–26.1°
b = 10.197 (3) ŵ = 1.23 mm1
c = 11.214 (4) ÅT = 168 K
V = 2164.5 (12) Å3Needle, dark red
Z = 40.50 × 0.08 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2316 independent reflections
Radiation source: fixed tube1677 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
φ and ω scansθmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 2323
Tmin = 0.829, Tmax = 0.906k = 128
26787 measured reflectionsl = 1313
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters not refined
S = 0.99 w = 1/[σ2(Fo2) + (0.03Fo2)2]1/2
2157 reflections(Δ/σ)max = 0.018
169 parametersΔρmax = 0.94 e Å3
17 restraintsΔρmin = 0.61 e Å3
0 constraints
Special details top

Refinement. All reflections with Fsqrd > 0 were included in the refinement. The following restraints were used to model the trifluoromethanesulfonate anion. ATOMS CLASS IDEAL CALC DELTA SIGMA C7 F7a BOND 1.3200 1.3218 -.0018. 0030 C7 F7b BOND 1.3200 1.3259 -.0059. 0030 C7 F7c BOND 1.3200 1.3250 -.0050. 0030 S3 O3a BOND 1.4400 1.3996. 0404. 0030 S3 O3b BOND 1.4400 1.4415 -.0015. 0030 S3 O3c BOND 1.4400 1.4575 -.0175. 0030 F7a F7b BOND 2.1552 2.1546. 0006. 0030 F7a F7c BOND 2.1552 2.1547. 0005. 0030 F7c F7b BOND 2.1552 2.1460. 0092. 0030 O3a O3b BOND 2.4200 2.4425 -.0225. 0030 O3a O3c BOND 2.4200 2.4245 -.0045. 0030 O3c O3b BOND 2.4200 2.3987. 0213. 0030 S3 C7 F7a ANGLE 109.50 109.50. 00. 02 S3 C7 F7b ANGLE 109.50 109.50. 00. 02 C7 S3 O3a ANGLE 104.00 104.02 -.02. 02 C7 S3 O3b ANGLE 104.00 103.99. 01. 02 O3c S3 C7 F7a DIHED -60.00 - 60.09. 09. 10

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
F7a0.1315 (4)0.2921 (4)0.1701 (4)0.167 (10).50000
F7b0.0406 (3)0.3296 (6)0.0597 (6)0.188 (11).50000
F7c0.0700 (4)0.1314 (4)0.1009 (7)0.130 (8).50000
C70.0950 (3)0.250000.0772 (4)0.079 (7)
O3a0.1703 (2)0.3812 (2)0.0635 (3)0.117 (8).50000
O3b0.1061 (2)0.1924 (4)0.1426 (3)0.089 (5).50000
O3c0.2043 (3)0.1594 (4)0.0107 (6)0.072 (5).50000
S30.14978 (8)0.250000.05120 (14)0.0447 (9)
Fe0.07070 (3)0.250000.48871 (6)0.0219 (4)
S10.16273 (5)0.38901 (8)0.45124 (8)0.0262 (5)
S20.00247 (5)0.38877 (9)0.60008 (8)0.0268 (5)
N10.2750 (2)0.250000.3714 (4)0.026 (2)
N20.0819 (2)0.250000.7474 (3)0.025 (2)
O10.3858 (2)0.250000.2041 (3)0.042 (2)
O20.2175 (2)0.250000.8529 (4)0.042 (2)
O30.02481 (18)0.250000.3267 (3)0.039 (2)
C10.2108 (3)0.250000.4170 (4)0.023 (3)
C20.31528 (19)0.3698 (4)0.3486 (3)0.032 (2)
C30.3443 (2)0.3658 (4)0.2209 (4)0.038 (2)
C40.0341 (3)0.250000.6630 (4)0.022 (3)
C50.1116 (2)0.3709 (3)0.7993 (3)0.031 (2)
C60.1918 (2)0.3646 (4)0.7945 (4)0.040 (2)
H2a0.35350.37590.40340.041*
H2b0.28550.44450.35760.041*
H3a0.30600.36550.16600.049*
H3b0.37290.44090.20710.049*
H5a0.09540.44470.75540.040*
H5b0.09680.37870.88010.040*
H6a0.21080.44010.83240.049*
H6b0.20640.36320.71330.049*
H30.04970.25000.25550.057*
H3'0.02400.25000.32160.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F7a0.242 (11)0.190 (16)0.068 (4)0.019 (9)0.022 (5)0.067 (7)
F7b0.093 (7)0.169 (10)0.301 (16)0.080 (7)0.117 (9)0.058 (10)
F7c0.091 (7)0.144 (9)0.154 (8)0.011 (6)0.064 (6)0.075 (8)
C70.083 (7)0.086 (7)0.069 (6)0.000000.013 (5)0.00000
O3a0.117 (8)0.025 (4)0.209 (12)0.018 (5)0.075 (8)0.064 (5)
O3b0.161 (8)0.045 (4)0.060 (4)0.022 (4)0.052 (5)0.011 (3)
O3c0.068 (5)0.031 (4)0.117 (7)0.017 (3)0.016 (5)0.016 (4)
S30.0472 (10)0.0545 (10)0.0326 (8)0.000000.0069 (7)0.00000
Fe0.0198 (4)0.0237 (4)0.0224 (4)0.000000.0031 (3)0.00000
S10.0237 (5)0.0219 (5)0.0331 (5)0.0003 (4)0.0040 (4)0.0008 (4)
S20.0300 (5)0.0196 (4)0.0306 (5)0.0004 (4)0.0096 (4)0.0033 (4)
N10.028 (2)0.023 (2)0.027 (2)0.000000.007 (2)0.00000
N20.032 (2)0.018 (2)0.025 (2)0.000000.0086 (19)0.00000
O10.029 (2)0.048 (3)0.047 (2)0.000000.0160 (19)0.00000
O20.042 (2)0.030 (2)0.053 (3)0.000000.027 (2)0.00000
O30.025 (2)0.067 (3)0.027 (2)0.000000.0021 (16)0.00000
C10.024 (3)0.025 (3)0.019 (3)0.000000.000 (2)0.00000
C20.023 (2)0.031 (2)0.043 (2)0.0028 (16)0.0015 (17)0.0013 (18)
C30.028 (2)0.042 (2)0.045 (3)0.0027 (19)0.0046 (18)0.011 (2)
C40.023 (3)0.023 (3)0.019 (3)0.000000.003 (2)0.00000
C50.040 (2)0.019 (2)0.035 (2)0.0012 (17)0.0126 (18)0.0036 (16)
C60.043 (2)0.029 (2)0.047 (2)0.0074 (19)0.017 (2)0.001 (2)
Geometric parameters (Å, º) top
F7a—C71.322 (7)N2—C51.475 (4)
F7b—C71.326 (7)O1—C31.431 (4)
F7c—C71.325 (5)O2—C61.425 (5)
C7—S31.775 (5)O3—H3'0.925
O3a—S31.400 (3)O3—H30.927
O3b—S31.441 (4)C2—H2a0.950
O3c—S31.457 (5)C2—H2b0.952
Fe—O32.013 (4)C2—C31.534 (6)
Fe—S12.2849 (11)C3—H3b0.950
Fe—S22.2870 (11)C3—H3a0.952
S1—C11.727 (3)C5—H5a0.949
S2—C41.726 (3)C5—H5b0.952
N1—C11.318 (6)C5—C61.520 (6)
N1—C21.463 (4)C6—H6a0.950
N2—C41.309 (6)C6—H6b0.952
F7a—C7—F7c109.0 (5)N1—C1—S1124.86 (13)
F7a—C7—F7b108.9 (4)S1i—C1—S1110.3 (3)
F7a—C7—S3109.5 (4)H2a—C2—H2b109.2
F7c—C7—F7b108.1 (5)H2a—C2—N1109.7
F7c—C7—S3111.8 (4)H2a—C2—C3109.4
F7b—C7—S3109.5 (4)H2b—C2—N1109.9
O3a—S3—O3b118.6 (2)H2b—C2—C3109.4
O3a—S3—O3c116.1 (3)N1—C2—C3109.1 (3)
O3a—S3—C7104.02 (17)H3b—C3—H3a109.3
O3b—S3—O3c111.7 (3)H3b—C3—O1109.3
O3b—S3—C7104.0 (2)H3b—C3—C2109.6
O3c—S3—C799.3 (3)H3a—C3—O1109.3
O3—Fe—S199.38 (9)H3a—C3—C2109.3
O3—Fe—S2104.42 (9)O1—C3—C2110.0 (3)
S1i—Fe—S176.69 (4)N2—C4—S2124.93 (13)
S1—Fe—S2i156.19 (5)S2—C4—S2i110.1 (3)
S1—Fe—S298.46 (4)H5a—C5—H5b109.4
S2i—Fe—S276.45 (4)H5a—C5—N2109.6
C1—S1—Fe86.17 (14)H5a—C5—C6109.7
C4—S2—Fe86.70 (14)H5b—C5—N2109.5
C1—N1—C2123.3 (2)H5b—C5—C6109.4
C2—N1—C2i113.2 (3)N2—C5—C6109.3 (3)
C4—N2—C5123.3 (2)H6a—C6—H6b109.3
C5i—N2—C5113.4 (3)H6a—C6—O2109.3
C3—O1—C3i111.3 (3)H6a—C6—C5109.1
C6i—O2—C6110.1 (3)H6b—C6—O2109.1
H3'—O3—H3117.0H6b—C6—C5109.0
H3'—O3—Fe119.1O2—C6—C5111.0 (3)
H3—O3—Fe123.9
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O3b0.931.762.642 (5)158
O3—H3···O3bi0.931.762.642 (5)158
O3—H3···O1ii0.931.732.654 (5)174
Symmetry codes: (i) x, y+1/2, z; (ii) x1/2, y+1/2, z+1/2.
 

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