Aqua­bis(4-morpholinyldi­thio­carbamato)­iron(III) tri­fluoro­methane­sulfonate

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 (C_s) 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.

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

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Computing details

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)

Crystal data

[Fe(C5H8NOS2)2(H2O)]CF3SO3	F(000) = 1116
Mr = 547.44	Dx = 1.68 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p_2ac_2n	Cell parameters from 7138 reflections
a = 18.929 (6) Å	θ = 2.1–26.1°
b = 10.197 (3) Å	µ = 1.23 mm^−1
c = 11.214 (4) Å	T = 168 K
V = 2164.5 (12) Å^3	Needle, dark red
Z = 4	0.50 × 0.08 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2316 independent reflections
Radiation source: fixed tube	1677 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
φ and ω scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −23→23
Tmin = 0.829, Tmax = 0.906	k = −12→8
26787 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters not refined
S = 0.99	w = 1/[σ^2(Fo^2) + (0.03Fo^2)^2]^1/2
2157 reflections	(Δ/σ)max = 0.018
169 parameters	Δρmax = 0.94 e Å^−3
17 restraints	Δρmin = −0.61 e Å^−3
0 constraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
F7a	0.1315 (4)	0.2921 (4)	−0.1701 (4)	0.167 (10)	.50000
F7b	0.0406 (3)	0.3296 (6)	−0.0597 (6)	0.188 (11)	.50000
F7c	0.0700 (4)	0.1314 (4)	−0.1009 (7)	0.130 (8)	.50000
C7	0.0950 (3)	0.25000	−0.0772 (4)	0.079 (7)
O3a	0.1703 (2)	0.3812 (2)	0.0635 (3)	0.117 (8)	.50000
O3b	0.1061 (2)	0.1924 (4)	0.1426 (3)	0.089 (5)	.50000
O3c	0.2043 (3)	0.1594 (4)	0.0107 (6)	0.072 (5)	.50000
S3	0.14978 (8)	0.25000	0.05120 (14)	0.0447 (9)
Fe	0.07070 (3)	0.25000	0.48871 (6)	0.0219 (4)
S1	0.16273 (5)	0.38901 (8)	0.45124 (8)	0.0262 (5)
S2	0.00247 (5)	0.38877 (9)	0.60008 (8)	0.0268 (5)
N1	0.2750 (2)	0.25000	0.3714 (4)	0.026 (2)
N2	−0.0819 (2)	0.25000	0.7474 (3)	0.025 (2)
O1	0.3858 (2)	0.25000	0.2041 (3)	0.042 (2)
O2	−0.2175 (2)	0.25000	0.8529 (4)	0.042 (2)
O3	0.02481 (18)	0.25000	0.3267 (3)	0.039 (2)
C1	0.2108 (3)	0.25000	0.4170 (4)	0.023 (3)
C2	0.31528 (19)	0.3698 (4)	0.3486 (3)	0.032 (2)
C3	0.3443 (2)	0.3658 (4)	0.2209 (4)	0.038 (2)
C4	−0.0341 (3)	0.25000	0.6630 (4)	0.022 (3)
C5	−0.1116 (2)	0.3709 (3)	0.7993 (3)	0.031 (2)
C6	−0.1918 (2)	0.3646 (4)	0.7945 (4)	0.040 (2)
H2a	0.3535	0.3759	0.4034	0.041*
H2b	0.2855	0.4445	0.3576	0.041*
H3a	0.3060	0.3655	0.1660	0.049*
H3b	0.3729	0.4409	0.2071	0.049*
H5a	−0.0954	0.4447	0.7554	0.040*
H5b	−0.0968	0.3787	0.8801	0.040*
H6a	−0.2108	0.4401	0.8324	0.049*
H6b	−0.2064	0.3632	0.7133	0.049*
H3	0.0497	0.2500	0.2555	0.057*
H3'	−0.0240	0.2500	0.3216	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F7a	0.242 (11)	0.190 (16)	0.068 (4)	0.019 (9)	−0.022 (5)	0.067 (7)
F7b	0.093 (7)	0.169 (10)	0.301 (16)	0.080 (7)	−0.117 (9)	−0.058 (10)
F7c	0.091 (7)	0.144 (9)	0.154 (8)	−0.011 (6)	−0.064 (6)	−0.075 (8)
C7	0.083 (7)	0.086 (7)	0.069 (6)	0.00000	−0.013 (5)	0.00000
O3a	0.117 (8)	0.025 (4)	0.209 (12)	0.018 (5)	−0.075 (8)	−0.064 (5)
O3b	0.161 (8)	0.045 (4)	0.060 (4)	0.022 (4)	0.052 (5)	0.011 (3)
O3c	0.068 (5)	0.031 (4)	0.117 (7)	0.017 (3)	−0.016 (5)	−0.016 (4)
S3	0.0472 (10)	0.0545 (10)	0.0326 (8)	0.00000	−0.0069 (7)	0.00000
Fe	0.0198 (4)	0.0237 (4)	0.0224 (4)	0.00000	0.0031 (3)	0.00000
S1	0.0237 (5)	0.0219 (5)	0.0331 (5)	0.0003 (4)	0.0040 (4)	0.0008 (4)
S2	0.0300 (5)	0.0196 (4)	0.0306 (5)	0.0004 (4)	0.0096 (4)	0.0033 (4)
N1	0.028 (2)	0.023 (2)	0.027 (2)	0.00000	0.007 (2)	0.00000
N2	0.032 (2)	0.018 (2)	0.025 (2)	0.00000	0.0086 (19)	0.00000
O1	0.029 (2)	0.048 (3)	0.047 (2)	0.00000	0.0160 (19)	0.00000
O2	0.042 (2)	0.030 (2)	0.053 (3)	0.00000	0.027 (2)	0.00000
O3	0.025 (2)	0.067 (3)	0.027 (2)	0.00000	−0.0021 (16)	0.00000
C1	0.024 (3)	0.025 (3)	0.019 (3)	0.00000	0.000 (2)	0.00000
C2	0.023 (2)	0.031 (2)	0.043 (2)	−0.0028 (16)	0.0015 (17)	0.0013 (18)
C3	0.028 (2)	0.042 (2)	0.045 (3)	−0.0027 (19)	0.0046 (18)	0.011 (2)
C4	0.023 (3)	0.023 (3)	0.019 (3)	0.00000	0.003 (2)	0.00000
C5	0.040 (2)	0.019 (2)	0.035 (2)	0.0012 (17)	0.0126 (18)	−0.0036 (16)
C6	0.043 (2)	0.029 (2)	0.047 (2)	0.0074 (19)	0.017 (2)	0.001 (2)

Geometric parameters (Å, º)

F7a—C7	1.322 (7)	N2—C5	1.475 (4)
F7b—C7	1.326 (7)	O1—C3	1.431 (4)
F7c—C7	1.325 (5)	O2—C6	1.425 (5)
C7—S3	1.775 (5)	O3—H3'	0.925
O3a—S3	1.400 (3)	O3—H3	0.927
O3b—S3	1.441 (4)	C2—H2a	0.950
O3c—S3	1.457 (5)	C2—H2b	0.952
Fe—O3	2.013 (4)	C2—C3	1.534 (6)
Fe—S1	2.2849 (11)	C3—H3b	0.950
Fe—S2	2.2870 (11)	C3—H3a	0.952
S1—C1	1.727 (3)	C5—H5a	0.949
S2—C4	1.726 (3)	C5—H5b	0.952
N1—C1	1.318 (6)	C5—C6	1.520 (6)
N1—C2	1.463 (4)	C6—H6a	0.950
N2—C4	1.309 (6)	C6—H6b	0.952
F7a—C7—F7c	109.0 (5)	N1—C1—S1	124.86 (13)
F7a—C7—F7b	108.9 (4)	S1^i—C1—S1	110.3 (3)
F7a—C7—S3	109.5 (4)	H2a—C2—H2b	109.2
F7c—C7—F7b	108.1 (5)	H2a—C2—N1	109.7
F7c—C7—S3	111.8 (4)	H2a—C2—C3	109.4
F7b—C7—S3	109.5 (4)	H2b—C2—N1	109.9
O3a—S3—O3b	118.6 (2)	H2b—C2—C3	109.4
O3a—S3—O3c	116.1 (3)	N1—C2—C3	109.1 (3)
O3a—S3—C7	104.02 (17)	H3b—C3—H3a	109.3
O3b—S3—O3c	111.7 (3)	H3b—C3—O1	109.3
O3b—S3—C7	104.0 (2)	H3b—C3—C2	109.6
O3c—S3—C7	99.3 (3)	H3a—C3—O1	109.3
O3—Fe—S1	99.38 (9)	H3a—C3—C2	109.3
O3—Fe—S2	104.42 (9)	O1—C3—C2	110.0 (3)
S1^i—Fe—S1	76.69 (4)	N2—C4—S2	124.93 (13)
S1—Fe—S2^i	156.19 (5)	S2—C4—S2^i	110.1 (3)
S1—Fe—S2	98.46 (4)	H5a—C5—H5b	109.4
S2^i—Fe—S2	76.45 (4)	H5a—C5—N2	109.6
C1—S1—Fe	86.17 (14)	H5a—C5—C6	109.7
C4—S2—Fe	86.70 (14)	H5b—C5—N2	109.5
C1—N1—C2	123.3 (2)	H5b—C5—C6	109.4
C2—N1—C2^i	113.2 (3)	N2—C5—C6	109.3 (3)
C4—N2—C5	123.3 (2)	H6a—C6—H6b	109.3
C5^i—N2—C5	113.4 (3)	H6a—C6—O2	109.3
C3—O1—C3^i	111.3 (3)	H6a—C6—C5	109.1
C6^i—O2—C6	110.1 (3)	H6b—C6—O2	109.1
H3'—O3—H3	117.0	H6b—C6—C5	109.0
H3'—O3—Fe	119.1	O2—C6—C5	111.0 (3)
H3—O3—Fe	123.9

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O3b	0.93	1.76	2.642 (5)	158
O3—H3···O3b^i	0.93	1.76	2.642 (5)	158
O3—H3′···O1^ii	0.93	1.73	2.654 (5)	174

Symmetry codes: (i) x, −y+1/2, z; (ii) x−1/2, −y+1/2, −z+1/2.