Bis(propane-1,3-diaminium) hexa-fluoridoferrate(III) fluoride trihydrate.

The asymmetric unit of the title iron hybrid fluoride, (C(3)H(12)N(2))(2)[FeF(6)]F·3H(2)O, contains two propane-1,3-diamin-ium [(H(2)dap)(2+)] cations, an octa-hedral [FeF(6)](3-) anion, an isolated F(-) anion and three water mol-ecules of solvation. Each [FeF(6)](3-) anion is surrounded by four separate hydrogen-bonded water mol-ecules in the equatorial sites and by five separate aminium cation donor groups. The axial F atoms are only involved in N-H⋯F hydrogen bonds, resulting in a three-dimensional structure.

Related literature

For general background to hybrid fluorides, their synthesis and their applications, see: Ben Ali et al. (2007 ▶, 2009 ▶); Adil et al. (2007 ▶); Latroche et al. (2006 ▶); Rother et al. (1998 ▶), Bentrup et al. (1998 ▶). For F⋯N inter­actions, see: Steiner (1998 ▶). For bond-valence sum (BVS) calculations, see: Brese & O’Keeffe (1991 ▶).

Experimental

Crystal data

(C3H12N2)2[FeF6]F·3H2O

M = 395.18

Triclinic,

a = 9.844 (1) Å

b = 9.847 (1) Å

c = 10.7740 (8) Å

α = 106.959 (7)°

β = 95.379 (6)°

γ = 118.914 (9)°

V = 839.35 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.98 mm−1

T = 295 K

0.32 × 0.07 × 0.07 mm

Data collection

SIEMENS AED2 diffractometer

2920 measured reflections

2920 independent reflections

2599 reflections with I > 2σ(I)

3 standard reflections every 120 min intensity decay: 4%

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.093

S = 1.14

2920 reflections

219 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.35 e Å−3

Data collection: STADI4 (Stoe & Cie, 1998 ▶); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018039/zs2036sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018039/zs2036Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C3H12N2)2[FeF6]F·3H2O	Z = 2
Mr = 395.18	F(000) = 414
Triclinic, P1	Dx = 1.564 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.844 (1) Å	Cell parameters from 24 reflections
b = 9.847 (1) Å	θ = 5–20°
c = 10.7740 (8) Å	µ = 0.98 mm−1
α = 106.959 (7)°	T = 295 K
β = 95.379 (6)°	Parallelepiped, colorless
γ = 118.914 (9)°	0.32 × 0.07 × 0.07 mm
V = 839.35 (17) Å3

SIEMENS AED2 diffractometer	Rint = 0.0000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.1°
graphite	h = −11→11
2θ/ω scans	k = −10→11
2920 measured reflections	l = −12→0
2920 independent reflections	3 standard reflections every 120 min
2599 reflections with I > 2σ(I)	intensity decay: 4%

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0485P)2 + 0.4679P] where P = (Fo2 + 2Fc2)/3
2920 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Fe	0.84562 (4)	0.12759 (4)	0.22030 (3)	0.02722 (13)
F1	0.7789 (3)	−0.0409 (2)	0.04636 (19)	0.0734 (6)
F2	0.9740 (2)	0.29714 (19)	0.15238 (16)	0.0467 (4)
F3	0.66528 (18)	0.1495 (2)	0.16599 (17)	0.0479 (4)
F4	0.7093 (2)	−0.0330 (2)	0.28815 (18)	0.0582 (5)
F5	0.91998 (19)	0.30634 (19)	0.39249 (15)	0.0460 (4)
F6	1.0227 (2)	0.1036 (2)	0.2722 (2)	0.0582 (5)
F7	0.79472 (17)	0.17081 (17)	0.74186 (14)	0.0363 (3)
C1	0.6954 (3)	0.3991 (3)	0.6071 (2)	0.0330 (5)
H1D	0.7029	0.4645	0.5530	0.0476 (17)*
H1E	0.6899	0.4560	0.6948	0.0476 (17)*
C2	0.5420 (3)	0.2254 (3)	0.5389 (3)	0.0327 (5)
H2D	0.5468	0.1674	0.4512	0.0476 (17)*
H2E	0.5322	0.1600	0.5935	0.0476 (17)*
C3	0.3974 (3)	0.2417 (3)	0.5219 (3)	0.0371 (6)
H3D	0.4063	0.3203	0.6061	0.0476 (17)*
H3E	0.3969	0.2869	0.4531	0.0476 (17)*
C4	0.6160 (3)	0.3197 (3)	0.9521 (3)	0.0371 (6)
H4D	0.5557	0.3222	1.0181	0.0476 (17)*
H4E	0.5624	0.3215	0.8729	0.0476 (17)*
C5	0.7874 (3)	0.4733 (3)	1.0111 (3)	0.0336 (5)
H5D	0.8430	0.4677	1.0868	0.0476 (17)*
H5E	0.8456	0.4743	0.9431	0.0476 (17)*
C6	0.7863 (3)	0.6330 (3)	1.0579 (3)	0.0368 (6)
H6D	0.7111	0.6271	0.9884	0.0476 (17)*
H6E	0.7498	0.6438	1.1388	0.0476 (17)*
N1	0.8414 (2)	0.3911 (2)	0.6246 (2)	0.0318 (4)
H1A	0.8289	0.3195	0.6639	0.0476 (17)*
H1B	0.9268	0.4928	0.6762	0.0476 (17)*
H1C	0.8567	0.3562	0.5442	0.0476 (17)*
N2	0.2431 (2)	0.0780 (3)	0.4826 (2)	0.0368 (5)
H2A	0.2398	0.0399	0.5484	0.0476 (17)*
H2B	0.2363	0.0043	0.4069	0.0476 (17)*
H2C	0.1607	0.0915	0.4689	0.0476 (17)*
N3	0.6179 (3)	0.1637 (3)	0.9144 (2)	0.0393 (5)
H3A	0.5179	0.0751	0.8720	0.0476 (17)*
H3B	0.6561	0.1562	0.9887	0.0476 (17)*
H3C	0.6809	0.1661	0.8599	0.0476 (17)*
N4	0.9502 (3)	0.7830 (2)	1.0873 (2)	0.0347 (5)
H4A	1.0194	0.7879	1.1504	0.0476 (17)*
H4B	0.9471	0.8756	1.1168	0.0476 (17)*
H4C	0.9820	0.7753	1.0123	0.0476 (17)*
O1W	1.0878 (3)	0.2596 (3)	0.5849 (3)	0.0568 (6)
O2W	0.6945 (3)	0.7508 (4)	0.7980 (3)	0.0660 (7)
O3W	0.6382 (3)	0.4155 (3)	0.2944 (3)	0.0590 (6)
H11	1.046 (6)	0.265 (6)	0.526 (5)	0.095 (18)*
H12	1.168 (5)	0.352 (5)	0.625 (4)	0.067 (12)*
H21	0.717 (5)	0.829 (5)	0.858 (4)	0.063 (12)*
H22	0.772 (5)	0.782 (5)	0.776 (4)	0.064 (12)*
H31	0.649 (5)	0.330 (4)	0.265 (4)	0.075 (12)*
H32	0.550 (5)	0.373 (5)	0.277 (4)	0.054 (11)*

	U11	U22	U33	U12	U13	U23
Fe	0.02654 (19)	0.02225 (19)	0.02768 (19)	0.00942 (14)	0.01073 (14)	0.00871 (14)
F1	0.0992 (16)	0.0461 (10)	0.0417 (10)	0.0295 (11)	0.0150 (10)	−0.0069 (8)
F2	0.0495 (9)	0.0373 (8)	0.0437 (9)	0.0118 (7)	0.0234 (7)	0.0211 (7)
F3	0.0338 (8)	0.0473 (9)	0.0622 (10)	0.0206 (7)	0.0079 (7)	0.0244 (8)
F4	0.0472 (10)	0.0500 (10)	0.0602 (10)	0.0053 (8)	0.0147 (8)	0.0373 (9)
F5	0.0473 (9)	0.0379 (8)	0.0333 (8)	0.0151 (7)	0.0146 (7)	0.0019 (6)
F6	0.0478 (10)	0.0597 (11)	0.0797 (13)	0.0361 (9)	0.0190 (9)	0.0295 (10)
F7	0.0372 (8)	0.0356 (7)	0.0377 (8)	0.0180 (6)	0.0152 (6)	0.0176 (6)
C1	0.0341 (13)	0.0253 (11)	0.0363 (13)	0.0133 (10)	0.0121 (10)	0.0119 (10)
C2	0.0322 (13)	0.0263 (12)	0.0356 (13)	0.0135 (10)	0.0113 (10)	0.0103 (10)
C3	0.0329 (13)	0.0285 (12)	0.0463 (15)	0.0130 (11)	0.0113 (11)	0.0161 (11)
C4	0.0283 (12)	0.0379 (14)	0.0374 (13)	0.0118 (11)	0.0116 (10)	0.0150 (11)
C5	0.0281 (12)	0.0323 (13)	0.0375 (13)	0.0134 (11)	0.0099 (10)	0.0146 (11)
C6	0.0327 (13)	0.0388 (14)	0.0419 (14)	0.0190 (11)	0.0154 (11)	0.0181 (11)
N1	0.0287 (10)	0.0243 (10)	0.0363 (11)	0.0094 (8)	0.0116 (8)	0.0123 (8)
N2	0.0306 (11)	0.0338 (11)	0.0416 (12)	0.0155 (9)	0.0113 (9)	0.0122 (9)
N3	0.0316 (11)	0.0329 (11)	0.0376 (11)	0.0054 (9)	0.0138 (9)	0.0137 (9)
N4	0.0370 (11)	0.0281 (10)	0.0380 (11)	0.0173 (9)	0.0120 (9)	0.0112 (9)
O1W	0.0420 (13)	0.0576 (15)	0.0708 (16)	0.0241 (12)	0.0092 (11)	0.0318 (13)
O2W	0.0440 (14)	0.0710 (17)	0.0466 (13)	0.0213 (12)	0.0098 (11)	−0.0055 (13)
O3W	0.0513 (15)	0.0470 (13)	0.0641 (15)	0.0233 (12)	0.0159 (12)	0.0085 (11)

Fe—F1	1.8968 (17)	C5—H5E	0.9700
Fe—F4	1.9083 (15)	C6—N4	1.487 (3)
Fe—F5	1.9157 (14)	C6—H6D	0.9700
Fe—F6	1.9234 (17)	C6—H6E	0.9700
Fe—F2	1.9405 (14)	N1—H1A	0.8900
Fe—F3	1.9468 (15)	N1—H1B	0.8900
C1—N1	1.475 (3)	N1—H1C	0.8900
C1—C2	1.519 (3)	N2—H2A	0.8900
C1—H1D	0.9700	N2—H2B	0.8900
C1—H1E	0.9700	N2—H2C	0.8900
C2—C3	1.508 (3)	N3—H3A	0.8900
C2—H2D	0.9700	N3—H3B	0.8900
C2—H2E	0.9700	N3—H3C	0.8900
C3—N2	1.483 (3)	N4—H4A	0.8900
C3—H3D	0.9700	N4—H4B	0.8900
C3—H3E	0.9700	N4—H4C	0.8900
C4—N3	1.480 (3)	O1W—H11	0.75 (5)
C4—C5	1.520 (3)	O1W—H12	0.81 (4)
C4—H4D	0.9700	O2W—H21	0.76 (4)
C4—H4E	0.9700	O2W—H22	0.76 (4)
C5—C6	1.511 (3)	O3W—H31	0.87 (4)
C5—H5D	0.9700	O3W—H32	0.73 (4)
F1—Fe—F4	92.30 (9)	C6—C5—C4	110.7 (2)
F1—Fe—F5	177.01 (8)	C6—C5—H5D	109.5
F4—Fe—F5	90.69 (8)	C4—C5—H5D	109.5
F1—Fe—F6	89.93 (10)	C6—C5—H5E	109.5
F4—Fe—F6	91.86 (8)	C4—C5—H5E	109.5
F5—Fe—F6	90.04 (8)	H5D—C5—H5E	108.1
F1—Fe—F2	89.21 (8)	N4—C6—C5	111.1 (2)
F4—Fe—F2	175.81 (8)	N4—C6—H6D	109.4
F5—Fe—F2	87.80 (7)	C5—C6—H6D	109.4
F6—Fe—F2	92.04 (8)	N4—C6—H6E	109.4
F1—Fe—F3	89.45 (9)	C5—C6—H6E	109.4
F4—Fe—F3	88.01 (8)	H6D—C6—H6E	108.0
F5—Fe—F3	90.59 (7)	C1—N1—H1A	109.5
F6—Fe—F3	179.36 (8)	C1—N1—H1B	109.5
F2—Fe—F3	88.10 (7)	H1A—N1—H1B	109.5
N1—C1—C2	112.05 (19)	C1—N1—H1C	109.5
N1—C1—H1D	109.2	H1A—N1—H1C	109.5
C2—C1—H1D	109.2	H1B—N1—H1C	109.5
N1—C1—H1E	109.2	C3—N2—H2A	109.5
C2—C1—H1E	109.2	C3—N2—H2B	109.5
H1D—C1—H1E	107.9	H2A—N2—H2B	109.5
C3—C2—C1	109.6 (2)	C3—N2—H2C	109.5
C3—C2—H2D	109.7	H2A—N2—H2C	109.5
C1—C2—H2D	109.7	H2B—N2—H2C	109.5
C3—C2—H2E	109.7	C4—N3—H3A	109.5
C1—C2—H2E	109.7	C4—N3—H3B	109.5
H2D—C2—H2E	108.2	H3A—N3—H3B	109.5
N2—C3—C2	112.1 (2)	C4—N3—H3C	109.5
N2—C3—H3D	109.2	H3A—N3—H3C	109.5
C2—C3—H3D	109.2	H3B—N3—H3C	109.5
N2—C3—H3E	109.2	C6—N4—H4A	109.5
C2—C3—H3E	109.2	C6—N4—H4B	109.5
H3D—C3—H3E	107.9	H4A—N4—H4B	109.5
N3—C4—C5	110.4 (2)	C6—N4—H4C	109.5
N3—C4—H4D	109.6	H4A—N4—H4C	109.5
C5—C4—H4D	109.6	H4B—N4—H4C	109.5
N3—C4—H4E	109.6	H11—O1W—H12	106 (5)
C5—C4—H4E	109.6	H21—O2W—H22	101 (4)
H4D—C4—H4E	108.1	H31—O3W—H32	100 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···F2i	0.89	2.03	2.826 (3)	148
N1—H1B···F5i	0.89	2.22	2.839 (3)	127
N2—H2A···F4ii	0.89	1.82	2.672 (3)	161
N2—H2B···F7ii	0.89	1.85	2.735 (3)	172
N2—H2C···O1Wiii	0.89	2.22	2.926 (3)	136
N2—H2C···F6iii	0.89	2.47	3.139 (3)	132
N3—H3A···F3ii	0.89	1.95	2.777 (3)	155
N3—H3A···F4ii	0.89	2.47	3.135 (3)	132
N3—H3B···F3iv	0.89	1.93	2.762 (3)	156
N4—H4A···F7v	0.89	1.86	2.728 (3)	164
N4—H4B···F6vi	0.89	2.09	2.886 (3)	149
N4—H4B···F1vi	0.89	2.33	3.029 (3)	135
O1W—H12···O3Wi	0.81 (4)	1.99 (4)	2.787 (4)	173 (4)
O2W—H21···F1vi	0.76 (4)	1.91 (4)	2.606 (3)	153 (4)
O2W—H22···F6i	0.76 (4)	1.99 (4)	2.747 (3)	171 (4)
O3W—H32···O2Wvii	0.73 (4)	2.04 (4)	2.766 (4)	173 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯F2i	0.89	2.03	2.826 (3)	148
N1—H1B⋯F5i	0.89	2.22	2.839 (3)	127
N2—H2A⋯F4ii	0.89	1.82	2.672 (3)	161
N2—H2B⋯F7ii	0.89	1.85	2.735 (3)	172
N2—H2C⋯O1Wiii	0.89	2.22	2.926 (3)	136
N2—H2C⋯F6iii	0.89	2.47	3.139 (3)	132
N3—H3A⋯F3ii	0.89	1.95	2.777 (3)	155
N3—H3A⋯F4ii	0.89	2.47	3.135 (3)	132
N3—H3B⋯F3iv	0.89	1.93	2.762 (3)	156
N4—H4A⋯F7v	0.89	1.86	2.728 (3)	164
N4—H4B⋯F6vi	0.89	2.09	2.886 (3)	149
N4—H4B⋯F1vi	0.89	2.33	3.029 (3)	135
O1W—H12⋯O3Wi	0.81 (4)	1.99 (4)	2.787 (4)	173 (4)
O2W—H21⋯F1vi	0.76 (4)	1.91 (4)	2.606 (3)	153 (4)
O2W—H22⋯F6i	0.76 (4)	1.99 (4)	2.747 (3)	171 (4)
O3W—H32⋯O2Wvii	0.73 (4)	2.04 (4)	2.766 (4)	173 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .