Crystal structure of tris-(1,10-phenanthroline-κ(2) N,N')iron(II) bis-[bis-(tri-fluoro-methyl-sulfon-yl)imide] monohydrate.

The crystal structure of the title complex, [Fe(C12H8N2)3][(CF3SO2)2N]2·H2O, is constructed by one octa-hedral [Fe(phen)3](2+) (phen = 1,10-phenanthroline) cation (point group symmetry 2), two Tf2N(-) [bis-(tri-fluoromethyl-sulfon-yl)imide] anions, and one water mol-ecule of crystallization (point group 2). The Fe-N bond lengths are indicative of a d (6) low-spin state for the Fe(II) ion in the complex. The dihedral angle between the phen ligands in the cation is 87.64 (6)°. The Tf2N(-) counter-anion is non-coordinating, with the -CF3 groups arranged in a trans fashion with respect to each other, leading to an anti,anti conformation of the -CF3 groups and -SO2N- moieties relative to the S-C bonds. The water mol-ecule of crystallization connects two O atoms of the Tf2N(-) anions through weak hydrogen bonds. C-H⋯O hydrogen-bonding inter-actions are also observed, consolidating the packing of the mol-ecules into a three-dimensional network structure.

Related literature

For the synthesis of the anhydrous title complex, see: Teramoto et al. (2014 ▸). For typical Fe—N bond lengths of low-spin d 6 FeII ions, see: Deng et al. (2001 ▸); Setifi et al. (2013 ▸). Crystal structures of complexes with the [Fe(phen)3]2+ cation were reported by Koh (1994 ▸), Potočňák et al. (2014 ▸) and Zhong (2012 ▸). In the crystal structure of the ionic liquid choline bis­(tri­fluoro­methyl­sulfon­yl)imide (Nockemann et al., 2009 ▸), the free Tf2N− anion has a similar conformation to that in the title compound.

Experimental

Crystal data

[Fe(C12H8N2)3](C2F6NO4S2)2·H2O

M = 1174.78

Monoclinic,

a = 20.7745 (15) Å

b = 16.0107 (12) Å

c = 13.3084 (10) Å

β = 91.657 (1)°

V = 4424.7 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.65 mm−1

T = 100 K

0.42 × 0.11 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T min = 0.773, T max = 0.938

13659 measured reflections

4910 independent reflections

3247 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.122

S = 1.02

4910 reflections

338 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.90 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989014026966/wm5100sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026966/wm5100Isup2.hkl

Click here for additional data file.

3 2+ 2 − 2 x y z . DOI: 10.1107/S2056989014026966/wm5100fig1.tif

View of the [Fe(phen)3]2+, Tf2N− and H2O mol­ecular units. Displacement ellipsoids are represented at the 30% probability level. Hydrogen atoms were omitted for clarity. [Symmetry code: i) −x + 1,y,-z + .]

Click here for additional data file.

2 2 − x y z x y z . DOI: 10.1107/S2056989014026966/wm5100fig2.tif

Hydrogen bonds between the H2O mol­ecule and Tf2N− anions. [Symmetry codes: ii) x − ,y − 1/2,z, iii) −x + , y − , −z + .]

CCDC reference: 1038289

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Fe(C12H8N2)3](C2F6NO4S2)2·H2O	F(000) = 2368
Mr = 1174.78	Dx = 1.764 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1623 reflections
a = 20.7745 (15) Å	θ = 2.2–23.5°
b = 16.0107 (12) Å	µ = 0.65 mm−1
c = 13.3084 (10) Å	T = 100 K
β = 91.657 (1)°	Block, red
V = 4424.7 (6) Å3	0.42 × 0.11 × 0.10 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	4910 independent reflections
Radiation source: fine-focus sealed tube	3247 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Detector resolution: 8.333 pixels mm-1	θmax = 27.2°, θmin = 1.6°
phi and ω scans	h = −26→24
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −17→20
Tmin = 0.773, Tmax = 0.938	l = −17→16
13659 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.4369P] where P = (Fo2 + 2Fc2)/3
4910 reflections	(Δ/σ)max = 0.001
338 parameters	Δρmax = 0.71 e Å−3
2 restraints	Δρmin = −0.90 e Å−3

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.

	x	y	z	Uiso*/Ueq
Fe1	0.5000	0.81145 (4)	0.2500	0.01247 (17)
S1	0.70284 (4)	0.87060 (6)	0.73999 (6)	0.0194 (2)
S2	0.81435 (4)	0.96272 (6)	0.78549 (6)	0.0190 (2)
N1	0.41901 (12)	0.80991 (17)	0.32441 (19)	0.0128 (6)
N2	0.52464 (12)	0.72317 (17)	0.34722 (19)	0.0136 (6)
N3	0.53087 (12)	0.90330 (18)	0.33681 (19)	0.0141 (6)
N4	0.77157 (14)	0.88188 (19)	0.7924 (2)	0.0231 (7)
O1	0.66576 (12)	0.81717 (18)	0.80049 (19)	0.0320 (7)
O2	0.67338 (11)	0.94387 (16)	0.69810 (18)	0.0243 (6)
O3	0.80627 (11)	1.01191 (16)	0.69622 (17)	0.0235 (6)
O4	0.87849 (11)	0.94170 (17)	0.81960 (19)	0.0264 (6)
O5	0.5000	0.5160 (4)	0.7500	0.102 (2)
H5W	0.4670 (6)	0.4824 (12)	0.742 (7)	0.153*
F1	0.75397 (11)	0.73840 (14)	0.65849 (17)	0.0369 (6)
F2	0.75628 (11)	0.84768 (16)	0.56672 (17)	0.0409 (6)
F3	0.66724 (10)	0.78257 (14)	0.58392 (17)	0.0343 (6)
F4	0.78834 (11)	0.98981 (14)	0.97358 (15)	0.0318 (6)
F5	0.82027 (10)	1.09733 (13)	0.89196 (16)	0.0281 (5)
F6	0.72349 (9)	1.05100 (14)	0.86804 (15)	0.0283 (5)
C1	0.36704 (15)	0.8593 (2)	0.3148 (2)	0.0150 (7)
H1	0.3646	0.8974	0.2601	0.018*
C2	0.31626 (16)	0.8573 (2)	0.3816 (2)	0.0175 (8)
H2	0.2807	0.8941	0.3725	0.021*
C3	0.31802 (15)	0.8018 (2)	0.4603 (3)	0.0177 (8)
H3	0.2841	0.8008	0.5067	0.021*
C4	0.37042 (16)	0.7465 (2)	0.4717 (2)	0.0160 (7)
C5	0.42054 (15)	0.7547 (2)	0.4026 (2)	0.0143 (7)
C6	0.37791 (16)	0.6843 (2)	0.5492 (3)	0.0190 (8)
H6	0.3445	0.6769	0.5956	0.023*
C7	0.43081 (16)	0.6365 (2)	0.5575 (2)	0.0197 (8)
H7	0.4339	0.5955	0.6090	0.024*
C8	0.47740 (15)	0.7066 (2)	0.4134 (2)	0.0153 (7)
C9	0.48305 (16)	0.6464 (2)	0.4898 (2)	0.0164 (7)
C10	0.54083 (16)	0.5999 (2)	0.4945 (3)	0.0206 (8)
H10	0.5475	0.5585	0.5449	0.025*
C11	0.58709 (17)	0.6152 (2)	0.4258 (2)	0.0193 (8)
H11	0.6255	0.5830	0.4268	0.023*
C12	0.57795 (16)	0.6777 (2)	0.3545 (2)	0.0173 (8)
H12	0.6114	0.6884	0.3090	0.021*
C13	0.56412 (15)	0.9013 (2)	0.4249 (2)	0.0177 (8)
H13	0.5741	0.8486	0.4542	0.021*
C14	0.58467 (16)	0.9738 (2)	0.4751 (3)	0.0199 (8)
H14	0.6086	0.9698	0.5368	0.024*
C15	0.57025 (16)	1.0499 (2)	0.4352 (3)	0.0209 (8)
H15	0.5840	1.0993	0.4692	0.025*
C16	0.53488 (16)	1.0558 (2)	0.3435 (3)	0.0178 (8)
C17	0.51693 (15)	0.9803 (2)	0.2973 (2)	0.0153 (7)
C18	0.51659 (16)	1.1325 (2)	0.2942 (3)	0.0214 (8)
H18	0.5282	1.1843	0.3246	0.026*
C19	0.72140 (18)	0.8058 (2)	0.6315 (3)	0.0236 (8)
C20	0.78431 (17)	1.0287 (2)	0.8856 (3)	0.0213 (8)

	U11	U22	U33	U12	U13	U23
Fe1	0.0125 (3)	0.0142 (4)	0.0107 (3)	0.000	0.0000 (3)	0.000
S1	0.0223 (5)	0.0212 (5)	0.0148 (4)	0.0016 (4)	−0.0001 (4)	0.0002 (4)
S2	0.0201 (5)	0.0208 (5)	0.0161 (4)	0.0048 (4)	−0.0013 (4)	−0.0022 (4)
N1	0.0138 (14)	0.0118 (15)	0.0125 (14)	−0.0030 (12)	−0.0016 (11)	−0.0011 (11)
N2	0.0119 (14)	0.0160 (16)	0.0128 (14)	0.0010 (12)	−0.0006 (11)	−0.0017 (12)
N3	0.0112 (13)	0.0188 (16)	0.0124 (14)	0.0001 (12)	0.0017 (11)	−0.0010 (12)
N4	0.0255 (16)	0.0209 (18)	0.0223 (16)	0.0033 (14)	−0.0104 (14)	−0.0022 (13)
O1	0.0329 (15)	0.0405 (19)	0.0229 (14)	−0.0055 (13)	0.0053 (12)	0.0070 (13)
O2	0.0242 (13)	0.0233 (16)	0.0249 (14)	0.0049 (11)	−0.0071 (11)	−0.0013 (11)
O3	0.0247 (13)	0.0297 (16)	0.0162 (13)	0.0038 (11)	0.0001 (11)	0.0037 (11)
O4	0.0198 (13)	0.0316 (17)	0.0276 (14)	0.0076 (12)	−0.0043 (11)	−0.0029 (12)
O5	0.088 (5)	0.098 (6)	0.120 (6)	0.000	−0.005 (5)	0.000
F1	0.0399 (14)	0.0241 (14)	0.0461 (15)	0.0071 (11)	−0.0105 (12)	−0.0124 (11)
F2	0.0504 (15)	0.0476 (17)	0.0257 (12)	−0.0160 (12)	0.0163 (12)	−0.0074 (11)
F3	0.0352 (13)	0.0325 (14)	0.0343 (13)	−0.0027 (11)	−0.0124 (11)	−0.0101 (11)
F4	0.0465 (14)	0.0333 (14)	0.0153 (11)	0.0019 (11)	−0.0021 (10)	0.0005 (10)
F5	0.0301 (12)	0.0205 (13)	0.0334 (13)	−0.0013 (10)	−0.0050 (10)	−0.0065 (10)
F6	0.0210 (11)	0.0354 (14)	0.0283 (12)	0.0071 (10)	−0.0019 (9)	−0.0127 (10)
C1	0.0140 (16)	0.0155 (19)	0.0152 (17)	0.0005 (14)	−0.0026 (14)	−0.0021 (14)
C2	0.0137 (17)	0.018 (2)	0.0201 (18)	0.0011 (14)	−0.0022 (14)	−0.0013 (15)
C3	0.0131 (16)	0.020 (2)	0.0195 (18)	−0.0058 (14)	0.0033 (14)	−0.0044 (15)
C4	0.0156 (17)	0.017 (2)	0.0156 (17)	−0.0053 (14)	−0.0012 (14)	−0.0030 (14)
C5	0.0174 (17)	0.0144 (19)	0.0111 (16)	−0.0036 (14)	−0.0003 (14)	−0.0037 (13)
C6	0.0212 (18)	0.0158 (19)	0.0201 (18)	−0.0044 (15)	0.0036 (15)	−0.0002 (15)
C7	0.0262 (19)	0.020 (2)	0.0136 (17)	−0.0033 (16)	0.0047 (15)	0.0024 (15)
C8	0.0170 (17)	0.0142 (19)	0.0145 (17)	−0.0051 (14)	−0.0006 (14)	−0.0030 (14)
C9	0.0202 (18)	0.016 (2)	0.0125 (17)	−0.0021 (15)	−0.0025 (14)	−0.0031 (14)
C10	0.0284 (19)	0.019 (2)	0.0143 (17)	0.0016 (16)	−0.0038 (15)	0.0010 (15)
C11	0.0193 (17)	0.021 (2)	0.0172 (18)	0.0057 (15)	−0.0021 (14)	0.0007 (15)
C12	0.0168 (17)	0.019 (2)	0.0157 (17)	0.0019 (15)	0.0002 (14)	−0.0026 (14)
C13	0.0139 (17)	0.025 (2)	0.0135 (17)	0.0044 (15)	−0.0012 (14)	0.0009 (15)
C14	0.0147 (17)	0.029 (2)	0.0163 (18)	0.0011 (16)	−0.0010 (14)	−0.0068 (15)
C15	0.0174 (18)	0.022 (2)	0.0231 (19)	−0.0041 (15)	0.0027 (15)	−0.0117 (16)
C16	0.0153 (17)	0.019 (2)	0.0195 (18)	−0.0003 (15)	0.0032 (14)	−0.0038 (15)
C17	0.0127 (17)	0.019 (2)	0.0148 (17)	0.0025 (14)	0.0038 (14)	−0.0014 (14)
C18	0.0191 (19)	0.015 (2)	0.030 (2)	0.0010 (14)	0.0018 (15)	−0.0055 (16)
C19	0.028 (2)	0.019 (2)	0.023 (2)	−0.0039 (17)	−0.0014 (16)	−0.0033 (16)
C20	0.0235 (19)	0.025 (2)	0.0156 (18)	0.0052 (16)	−0.0017 (15)	−0.0019 (15)

Fe1—N1	1.977 (3)	C2—C3	1.372 (5)
Fe1—N1i	1.977 (3)	C2—H2	0.9500
Fe1—N2	1.974 (3)	C3—C4	1.408 (5)
Fe1—N2i	1.974 (3)	C3—H3	0.9500
Fe1—N3	1.966 (3)	C4—C5	1.415 (4)
Fe1—N3i	1.966 (3)	C4—C6	1.439 (5)
S1—O1	1.417 (3)	C5—C8	1.414 (5)
S1—O2	1.429 (3)	C6—C7	1.341 (5)
S1—N4	1.581 (3)	C6—H6	0.9500
S1—C19	1.827 (4)	C7—C9	1.439 (5)
S2—O3	1.431 (2)	C7—H7	0.9500
S2—O4	1.435 (2)	C8—C9	1.403 (5)
S2—N4	1.574 (3)	C9—C10	1.413 (5)
S2—C20	1.824 (4)	C10—C11	1.368 (5)
N1—C1	1.341 (4)	C10—H10	0.9500
N1—C5	1.366 (4)	C11—C12	1.388 (5)
N2—C8	1.364 (4)	C11—H11	0.9500
N2—C12	1.326 (4)	C12—H12	0.9500
N3—C13	1.343 (4)	C13—C14	1.400 (5)
N3—C17	1.368 (4)	C13—H13	0.9500
O5—H5W	0.875 (10)	C14—C15	1.360 (5)
F1—C19	1.318 (4)	C14—H14	0.9500
F2—C19	1.324 (4)	C15—C16	1.410 (5)
F3—C19	1.329 (4)	C15—H15	0.9500
F4—C20	1.327 (4)	C16—C17	1.401 (5)
F5—C20	1.330 (4)	C16—C18	1.439 (5)
F6—C20	1.327 (4)	C17—C17i	1.425 (6)
C1—C2	1.400 (4)	C18—C18i	1.345 (7)
C1—H1	0.9500	C18—H18	0.9500
N3—Fe1—N3i	83.17 (16)	C7—C6—C4	121.7 (3)
N3—Fe1—N2i	174.17 (11)	C7—C6—H6	119.1
N3i—Fe1—N2i	94.38 (11)	C4—C6—H6	119.1
N3—Fe1—N2	94.38 (11)	C6—C7—C9	121.1 (3)
N3i—Fe1—N2	174.17 (11)	C6—C7—H7	119.5
N2i—Fe1—N2	88.54 (16)	C9—C7—H7	119.5
N3—Fe1—N1i	92.05 (11)	N2—C8—C9	123.7 (3)
N3i—Fe1—N1i	89.01 (11)	N2—C8—C5	116.3 (3)
N2i—Fe1—N1i	82.60 (11)	C9—C8—C5	120.0 (3)
N2—Fe1—N1i	96.38 (11)	C8—C9—C10	116.6 (3)
N3—Fe1—N1	89.01 (11)	C8—C9—C7	118.7 (3)
N3i—Fe1—N1	92.05 (11)	C10—C9—C7	124.7 (3)
N2i—Fe1—N1	96.38 (11)	C11—C10—C9	119.2 (3)
N2—Fe1—N1	82.60 (11)	C11—C10—H10	120.4
N1i—Fe1—N1	178.58 (17)	C9—C10—H10	120.4
O1—S1—O2	118.91 (16)	C10—C11—C12	120.1 (3)
O1—S1—N4	108.49 (16)	C10—C11—H11	120.0
O2—S1—N4	116.70 (16)	C12—C11—H11	120.0
O1—S1—C19	103.70 (17)	N2—C12—C11	122.9 (3)
O2—S1—C19	104.80 (16)	N2—C12—H12	118.6
N4—S1—C19	101.81 (17)	C11—C12—H12	118.6
O3—S2—O4	118.49 (16)	N3—C13—C14	122.6 (3)
O3—S2—N4	116.61 (16)	N3—C13—H13	118.7
O4—S2—N4	108.02 (16)	C14—C13—H13	118.7
O3—S2—C20	104.65 (16)	C15—C14—C13	119.8 (3)
O4—S2—C20	103.83 (15)	C15—C14—H14	120.1
N4—S2—C20	103.19 (17)	C13—C14—H14	120.1
C1—N1—C5	117.1 (3)	C14—C15—C16	120.1 (3)
C1—N1—Fe1	129.7 (2)	C14—C15—H15	120.0
C5—N1—Fe1	112.9 (2)	C16—C15—H15	120.0
C12—N2—C8	117.4 (3)	C17—C16—C15	116.6 (3)
C12—N2—Fe1	129.9 (2)	C17—C16—C18	118.2 (3)
C8—N2—Fe1	112.6 (2)	C15—C16—C18	125.2 (3)
C13—N3—C17	117.1 (3)	N3—C17—C16	123.9 (3)
C13—N3—Fe1	130.2 (2)	N3—C17—C17i	115.67 (18)
C17—N3—Fe1	112.7 (2)	C16—C17—C17i	120.4 (2)
S1—N4—S2	124.92 (19)	C18i—C18—C16	121.4 (2)
N1—C1—C2	123.0 (3)	C18i—C18—H18	119.3
N1—C1—H1	118.5	C16—C18—H18	119.3
C2—C1—H1	118.5	F1—C19—F2	107.8 (3)
C3—C2—C1	119.7 (3)	F1—C19—F3	108.7 (3)
C3—C2—H2	120.1	F2—C19—F3	107.6 (3)
C1—C2—H2	120.1	F1—C19—S1	111.6 (3)
C2—C3—C4	119.5 (3)	F2—C19—S1	111.1 (3)
C2—C3—H3	120.2	F3—C19—S1	109.9 (3)
C4—C3—H3	120.2	F4—C20—F5	108.1 (3)
C3—C4—C5	116.9 (3)	F4—C20—F6	108.5 (3)
C3—C4—C6	125.4 (3)	F5—C20—F6	108.6 (3)
C5—C4—C6	117.6 (3)	F4—C20—S2	111.0 (3)
N1—C5—C8	115.5 (3)	F5—C20—S2	108.8 (2)
N1—C5—C4	123.6 (3)	F6—C20—S2	111.8 (2)
C8—C5—C4	120.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5W···O4ii	0.88 (1)	2.23 (6)	2.963 (4)	141 (7)
C2—H2···O3iii	0.95	2.50	3.433 (4)	166
C14—H14···O2	0.95	2.53	3.481 (5)	174

Table 1

Selected bond lengths ()

Fe1N1	1.977(3)
Fe1N2	1.974(3)
Fe1N3	1.966(3)

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O5H5WO4i	0.88(1)	2.23(6)	2.963(4)	141(7)
C2H2O3ii	0.95	2.50	3.433(4)	166
C14H14O2	0.95	2.53	3.481(5)	174

Symmetry codes: (i) ; (ii) .