Bis{1,2-bis­[bis­(3-hydroxy­prop­yl)phosphino]ethane}dichloridoiron(II)

Crossland, J.L.; Zakharov, L.N.; Tyler, D.R.

doi:10.1107/S160053681001768X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page m678

https://doi.org/10.1107/S160053681001768X

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Bis{1,2-bis[bis(3-hydroxypropyl)phosphino]ethane}dichloridoiron(II)

Justin L. Crossland,^a Lev N. Zakharov ^a and David R. Tyler ^a ^*

^aDepartment of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403-1253, USA
^*Correspondence e-mail: dtyler@uoregon.edu

(Received 5 May 2010; accepted 13 May 2010; online 22 May 2010)

In the title compound, [FeCl₂(C₁₄H₃₂O₄P₂)₂], the Fe^II atom (site symmetry $[\overline{1}]$ ) adopts a distorted trans-FeCl₂P₄ octahedral geometry with two P,P′-bidentate ligands in the equatorial positions and two chloride ions in the axial positions. In the crystal, molecules are linked by O—H⋯O and O—H⋯Cl hydrogen bonds, generating a three-dimensional network.

Related literature

For background to the applications of iron–diphosphine complexes, see: Lyon (1993 ); Miller et al. (2002 ). For further synthetic details, see: Baxley et al. (1996 ).

Experimental

Crystal data

[FeCl₂(C₁₄H₃₂O₄P₂)₂]
M_r = 779.42
Triclinic, $[P \overline 1]$
a = 8.7120 (4) Å
b = 10.4252 (5) Å
c = 10.7441 (5) Å
α = 96.086 (1)°
β = 104.215 (1)°
γ = 105.860 (1)°
V = 894.12 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 173 K
0.29 × 0.26 × 0.18 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.802, T_max = 0.870
10053 measured reflections
3863 independent reflections
3693 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.068
S = 1.06
3863 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—P1	2.2790 (3)
Fe1—P2	2.3008 (3)
Fe1—Cl1	2.3507 (3)

P1—Fe1—P2	85.008 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O3ⁱ	0.79 (3)	1.98 (3)	2.7660 (18)	174 (3)
O2—H2O⋯O1ⁱⁱ	0.73 (2)	2.12 (2)	2.8548 (17)	174 (2)
O3—H3O⋯O4ⁱⁱⁱ	0.81 (3)	1.93 (3)	2.7370 (19)	171 (3)
O4—H4O⋯Cl1^iv	0.84 (3)	2.28 (3)	3.1150 (13)	171 (3)
Symmetry codes: (i) x+1, y, z+1; (ii) -x+2, -y+2, -z+1; (iii) -x, -y+1, -z-1; (iv) x, y, z-1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681001768X/hb5437sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001768X/hb5437Isup2.hkl

checkCIF report

Comment top

Iron-diphosphine complexes containing water-soluble phosphine ligands have shown promise as dinitrogen scrubbers for nitrogen-containing natural gas streams (Lyon, 1993). Sulfonated phosphines have been used to impart water-solubility, however the sulfonate groups are often non-innocent and can prevent iron complexes from binding N₂. We have focused on hydroxyl functionalized phosphine ligands, such as DHPrPE (DHPrPE = 1,2-bis(dihydroxypropylphosphino)ethane) to synthesize water-soluble iron complexes capable of binding dinitrogen (Miller et al., 2002). However, using this particular ligand we were previously unable to isolate the trans dichloride complex, which is the required isomer to achieve dinitrogen binding. Here we report the synthesis and structural characterization of trans-Fe(DHPrPE)₂Cl₂ (DHPrPE = 1,2-bis(dihydroxypropylphosphino)ethane).

The structure of Fe[(CH₂CH₂)P₂(CH₂CH₂CH₂OH)₂]₂Cl₂ is centrosymmetyrical. The Fe atom has a distorted octahedral coordination with four P atoms in equatorial positions and two Cl atoms in apical positions (Fig. 1). The Fe(1)—Cl distance is 2.3507 (3) Å, the Fe(1)—P(1,2) distances are 2.2790 (3) and 2.3008 (3) Å, respectively. All -OH groups are involved in intra- and inter-molecular O—H···Cl and O—H···O H-bonds (Table 1).

Related literature top

For background to the applications of iron–diphosphine complexes, see: Lyon (1993); Miller et al. (2002). For further synthetic details, see: Baxley et al. (1996).

Experimental top

1,2-bis(dihydroxypropylphosphino)ethane (DHPrPE) was synthesized as previously reported (Baxley et al., 1996). trans-Fe(DHPrPE)₂Cl₂ was prepared by adding DHPrPE (0.33 g, 1.01 mmol) to a stirring solution of FeCl₂(H₂O)₄ (0.10 g, 0.505 mmol) in 20 ml of methanol, giving a deep purple solution. The ³¹P{¹H} NMR spectrum of the purple solution at 233 K showed three resonances (79, 71, and 53 ppm), likely due to a mixture of trans and cis isomers. The purple solution was layered with diethyl ether and allowed to stand at room temperature for one week. After this time a few lime green blocks of (I) were isolated from the purple mother liquor. The ³¹P{¹H} NMR spectrum of the green crystals at 233 K showed a single resonance at 53 ppm.

Structure description top

For background to the applications of iron–diphosphine complexes, see: Lyon (1993); Miller et al. (2002). For further synthetic details, see: Baxley et al. (1996).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I) with 50% probability displacement ellipsoids (H atoms are omitted for clarity). Symmetry code: (i): -x+1, -y+1, -z.

Bis{1,2-bis[bis(3-hydroxypropyl)phosphino]ethane}dichloridoiron(II) top

Crystal data top

[FeCl₂(C₁₄H₃₂O₄P₂)₂]	Z = 1
M_r = 779.42	F(000) = 416
Triclinic, P1	D_x = 1.448 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7120 (4) Å	Cell parameters from 7234 reflections
b = 10.4252 (5) Å	θ = 2.5–28.3°
c = 10.7441 (5) Å	µ = 0.80 mm⁻¹
α = 96.086 (1)°	T = 173 K
β = 104.215 (1)°	Block, lime green
γ = 105.860 (1)°	0.29 × 0.26 × 0.18 mm
V = 894.12 (7) Å³

Data collection top

Bruker APEX CCD diffractometer	3863 independent reflections
Radiation source: fine-focus sealed tube	3693 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
phi and ω scans	θ_max = 27.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.802, T_max = 0.870	k = −13→13
10053 measured reflections	l = −13→13

Refinement top

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0355P)² + 0.5361P] where P = (F_o² + 2F_c²)/3
3863 reflections	(Δ/σ)_max = 0.001
212 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[FeCl₂(C₁₄H₃₂O₄P₂)₂]	γ = 105.860 (1)°
M_r = 779.42	V = 894.12 (7) Å³
Triclinic, P1	Z = 1
a = 8.7120 (4) Å	Mo Kα radiation
b = 10.4252 (5) Å	µ = 0.80 mm⁻¹
c = 10.7441 (5) Å	T = 173 K
α = 96.086 (1)°	0.29 × 0.26 × 0.18 mm
β = 104.215 (1)°

Data collection top

Bruker APEX CCD diffractometer	3863 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3693 reflections with I > 2σ(I)
T_min = 0.802, T_max = 0.870	R_int = 0.015
10053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.47 e Å⁻³
3863 reflections	Δρ_min = −0.47 e Å⁻³
212 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.5000	0.5000	0.0000	0.01036 (8)
Cl1	0.31246 (4)	0.50199 (3)	0.12398 (3)	0.01664 (9)
P1	0.69987 (4)	0.68781 (3)	0.13091 (3)	0.01216 (9)
P2	0.40130 (4)	0.65190 (3)	−0.11033 (3)	0.01239 (9)
O1	0.68912 (15)	0.87217 (12)	0.56263 (11)	0.0248 (2)
O2	1.34336 (14)	0.95555 (12)	0.22692 (12)	0.0234 (2)
O3	−0.07362 (16)	0.74720 (14)	−0.34828 (12)	0.0309 (3)
O4	0.19987 (17)	0.52861 (13)	−0.62339 (12)	0.0335 (3)
C1	0.70197 (17)	0.82669 (14)	0.03860 (14)	0.0154 (3)
H1A	0.7685	0.9149	0.0967	0.019*
H1B	0.7522	0.8142	−0.0332	0.019*
C2	0.52256 (18)	0.82418 (14)	−0.01648 (14)	0.0158 (3)
H2A	0.5174	0.8919	−0.0741	0.019*
H2B	0.4763	0.8465	0.0554	0.019*
C3	0.65904 (18)	0.75708 (14)	0.28043 (14)	0.0168 (3)
H3A	0.5491	0.7722	0.2545	0.020*
H3B	0.6497	0.6867	0.3356	0.020*
C4	0.78515 (19)	0.88863 (15)	0.36498 (15)	0.0206 (3)
H4A	0.8880	0.8695	0.4096	0.025*
H4B	0.8144	0.9541	0.3078	0.025*
C5	0.7216 (2)	0.95323 (15)	0.46720 (15)	0.0213 (3)
H5A	0.8050	1.0417	0.5123	0.026*
H5B	0.6177	0.9709	0.4225	0.026*
C6	0.92139 (17)	0.69512 (14)	0.18114 (14)	0.0166 (3)
H6A	0.9467	0.6712	0.2690	0.020*
H6B	0.9368	0.6247	0.1202	0.020*
C7	1.04890 (17)	0.83151 (14)	0.18558 (14)	0.0168 (3)
H7A	1.0265	0.8555	0.0976	0.020*
H7B	1.0349	0.9028	0.2464	0.020*
C8	1.22756 (18)	0.82938 (15)	0.22905 (15)	0.0192 (3)
H8A	1.2522	0.8099	0.3188	0.023*
H8B	1.2409	0.7557	0.1706	0.023*
C9	0.18524 (17)	0.65570 (14)	−0.13785 (14)	0.0160 (3)
H9A	0.1138	0.5890	−0.2176	0.019*
H9B	0.1454	0.6270	−0.0634	0.019*
C10	0.16433 (19)	0.79529 (15)	−0.15321 (16)	0.0204 (3)
H10A	0.2110	0.8562	−0.0667	0.024*
H10B	0.2292	0.8347	−0.2114	0.024*
C11	−0.01607 (19)	0.78978 (15)	−0.20895 (16)	0.0215 (3)
H11A	−0.0872	0.7260	−0.1688	0.026*
H11B	−0.0269	0.8808	−0.1860	0.026*
C12	0.43480 (19)	0.67282 (16)	−0.27098 (14)	0.0197 (3)
H12A	0.4471	0.7684	−0.2800	0.024*
H12B	0.5416	0.6569	−0.2715	0.024*
C13	0.3005 (3)	0.58188 (19)	−0.39026 (16)	0.0370 (5)
H13A	0.2926	0.4861	−0.3855	0.044*
H13B	0.1920	0.5936	−0.3886	0.044*
C14	0.3314 (3)	0.6099 (2)	−0.51359 (17)	0.0419 (5)
H14A	0.3452	0.7069	−0.5168	0.050*
H14B	0.4365	0.5930	−0.5180	0.050*
H1O	0.758 (3)	0.837 (2)	0.583 (2)	0.045 (7)*
H2O	1.337 (3)	1.004 (2)	0.279 (2)	0.031 (6)*
H3O	−0.109 (3)	0.665 (3)	−0.364 (3)	0.053 (8)*
H4O	0.238 (3)	0.531 (3)	−0.688 (3)	0.059 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01193 (14)	0.00882 (13)	0.00954 (13)	0.00263 (10)	0.00279 (10)	0.00068 (10)
Cl1	0.01817 (17)	0.01714 (17)	0.01571 (17)	0.00498 (13)	0.00786 (13)	0.00194 (12)
P1	0.01309 (17)	0.00982 (16)	0.01179 (17)	0.00240 (13)	0.00236 (13)	0.00038 (12)
P2	0.01403 (17)	0.01074 (17)	0.01157 (17)	0.00349 (13)	0.00256 (13)	0.00212 (13)
O1	0.0274 (6)	0.0288 (6)	0.0194 (6)	0.0108 (5)	0.0071 (5)	0.0024 (5)
O2	0.0183 (5)	0.0214 (6)	0.0274 (6)	0.0007 (4)	0.0093 (5)	−0.0008 (5)
O3	0.0328 (7)	0.0297 (7)	0.0267 (6)	0.0113 (5)	−0.0006 (5)	0.0082 (5)
O4	0.0410 (7)	0.0356 (7)	0.0143 (6)	−0.0014 (6)	0.0085 (5)	−0.0019 (5)
C1	0.0158 (7)	0.0116 (6)	0.0159 (7)	0.0016 (5)	0.0022 (5)	0.0025 (5)
C2	0.0178 (7)	0.0111 (6)	0.0163 (7)	0.0037 (5)	0.0022 (5)	0.0018 (5)
C3	0.0192 (7)	0.0155 (7)	0.0136 (6)	0.0034 (5)	0.0048 (5)	−0.0009 (5)
C4	0.0207 (7)	0.0189 (7)	0.0173 (7)	0.0020 (6)	0.0045 (6)	−0.0038 (6)
C5	0.0256 (8)	0.0191 (7)	0.0166 (7)	0.0064 (6)	0.0042 (6)	−0.0024 (6)
C6	0.0146 (7)	0.0135 (7)	0.0197 (7)	0.0040 (5)	0.0023 (5)	0.0017 (5)
C7	0.0149 (7)	0.0148 (7)	0.0192 (7)	0.0037 (5)	0.0037 (5)	0.0023 (5)
C8	0.0152 (7)	0.0175 (7)	0.0223 (7)	0.0038 (5)	0.0039 (6)	0.0002 (6)
C9	0.0155 (7)	0.0134 (6)	0.0183 (7)	0.0050 (5)	0.0029 (5)	0.0033 (5)
C10	0.0186 (7)	0.0146 (7)	0.0275 (8)	0.0063 (6)	0.0040 (6)	0.0057 (6)
C11	0.0205 (7)	0.0176 (7)	0.0275 (8)	0.0087 (6)	0.0053 (6)	0.0053 (6)
C12	0.0220 (7)	0.0227 (7)	0.0154 (7)	0.0067 (6)	0.0057 (6)	0.0075 (6)
C13	0.0521 (12)	0.0281 (9)	0.0166 (8)	−0.0088 (8)	0.0096 (8)	0.0009 (7)
C14	0.0450 (11)	0.0479 (12)	0.0166 (8)	−0.0061 (9)	0.0030 (8)	0.0052 (8)

Geometric parameters (Å, º) top

Fe1—P1ⁱ	2.2790 (3)	C4—H4A	0.9900
Fe1—P1	2.2790 (3)	C4—H4B	0.9900
Fe1—P2	2.3008 (3)	C5—H5A	0.9900
Fe1—P2ⁱ	2.3008 (3)	C5—H5B	0.9900
Fe1—Cl1ⁱ	2.3507 (3)	C6—C7	1.5344 (19)
Fe1—Cl1	2.3507 (3)	C6—H6A	0.9900
P1—C1	1.8383 (14)	C6—H6B	0.9900
P1—C3	1.8449 (14)	C7—C8	1.518 (2)
P1—C6	1.8496 (14)	C7—H7A	0.9900
P2—C9	1.8445 (14)	C7—H7B	0.9900
P2—C12	1.8452 (15)	C8—H8A	0.9900
P2—C2	1.8478 (14)	C8—H8B	0.9900
O1—C5	1.4287 (19)	C9—C10	1.5360 (19)
O1—H1O	0.79 (3)	C9—H9A	0.9900
O2—C8	1.4285 (18)	C9—H9B	0.9900
O2—H2O	0.73 (2)	C10—C11	1.521 (2)
O3—C11	1.435 (2)	C10—H10A	0.9900
O3—H3O	0.81 (3)	C10—H10B	0.9900
O4—C14	1.420 (2)	C11—H11A	0.9900
O4—H4O	0.84 (3)	C11—H11B	0.9900
C1—C2	1.5212 (19)	C12—C13	1.520 (2)
C1—H1A	0.9900	C12—H12A	0.9900
C1—H1B	0.9900	C12—H12B	0.9900
C2—H2A	0.9900	C13—C14	1.459 (2)
C2—H2B	0.9900	C13—H13A	0.9900
C3—C4	1.528 (2)	C13—H13B	0.9900
C3—H3A	0.9900	C14—H14A	0.9900
C3—H3B	0.9900	C14—H14B	0.9900
C4—C5	1.521 (2)

P1ⁱ—Fe1—P1	180.0	O1—C5—H5B	108.8
P1ⁱ—Fe1—P2	94.992 (12)	C4—C5—H5B	108.8
P1—Fe1—P2	85.008 (12)	H5A—C5—H5B	107.7
P1ⁱ—Fe1—P2ⁱ	85.008 (12)	C7—C6—P1	116.21 (10)
P1—Fe1—P2ⁱ	94.992 (12)	C7—C6—H6A	108.2
P2—Fe1—P2ⁱ	180.0	P1—C6—H6A	108.2
P1ⁱ—Fe1—Cl1ⁱ	93.761 (12)	C7—C6—H6B	108.2
P1—Fe1—Cl1ⁱ	86.239 (12)	P1—C6—H6B	108.2
P2—Fe1—Cl1ⁱ	91.646 (12)	H6A—C6—H6B	107.4
P2ⁱ—Fe1—Cl1ⁱ	88.354 (12)	C8—C7—C6	112.88 (12)
P1ⁱ—Fe1—Cl1	86.239 (12)	C8—C7—H7A	109.0
P1—Fe1—Cl1	93.761 (12)	C6—C7—H7A	109.0
P2—Fe1—Cl1	88.354 (12)	C8—C7—H7B	109.0
P2ⁱ—Fe1—Cl1	91.646 (12)	C6—C7—H7B	109.0
Cl1ⁱ—Fe1—Cl1	180.0	H7A—C7—H7B	107.8
C1—P1—C3	101.59 (7)	O2—C8—C7	111.79 (12)
C1—P1—C6	102.93 (7)	O2—C8—H8A	109.3
C3—P1—C6	105.40 (7)	C7—C8—H8A	109.3
C1—P1—Fe1	106.37 (5)	O2—C8—H8B	109.3
C3—P1—Fe1	116.80 (5)	C7—C8—H8B	109.3
C6—P1—Fe1	121.13 (5)	H8A—C8—H8B	107.9
C9—P2—C12	101.59 (7)	C10—C9—P2	114.10 (10)
C9—P2—C2	101.99 (6)	C10—C9—H9A	108.7
C12—P2—C2	99.55 (7)	P2—C9—H9A	108.7
C9—P2—Fe1	122.82 (5)	C10—C9—H9B	108.7
C12—P2—Fe1	119.70 (5)	P2—C9—H9B	108.7
C2—P2—Fe1	107.56 (5)	H9A—C9—H9B	107.6
C5—O1—H1O	110.5 (18)	C11—C10—C9	113.31 (12)
C8—O2—H2O	104.6 (17)	C11—C10—H10A	108.9
C11—O3—H3O	107.7 (19)	C9—C10—H10A	108.9
C14—O4—H4O	106.7 (19)	C11—C10—H10B	108.9
C2—C1—P1	107.68 (9)	C9—C10—H10B	108.9
C2—C1—H1A	110.2	H10A—C10—H10B	107.7
P1—C1—H1A	110.2	O3—C11—C10	112.15 (13)
C2—C1—H1B	110.2	O3—C11—H11A	109.2
P1—C1—H1B	110.2	C10—C11—H11A	109.2
H1A—C1—H1B	108.5	O3—C11—H11B	109.2
C1—C2—P2	107.90 (9)	C10—C11—H11B	109.2
C1—C2—H2A	110.1	H11A—C11—H11B	107.9
P2—C2—H2A	110.1	C13—C12—P2	116.73 (11)
C1—C2—H2B	110.1	C13—C12—H12A	108.1
P2—C2—H2B	110.1	P2—C12—H12A	108.1
H2A—C2—H2B	108.4	C13—C12—H12B	108.1
C4—C3—P1	117.88 (10)	P2—C12—H12B	108.1
C4—C3—H3A	107.8	H12A—C12—H12B	107.3
P1—C3—H3A	107.8	C14—C13—C12	113.40 (15)
C4—C3—H3B	107.8	C14—C13—H13A	108.9
P1—C3—H3B	107.8	C12—C13—H13A	108.9
H3A—C3—H3B	107.2	C14—C13—H13B	108.9
C5—C4—C3	113.34 (13)	C12—C13—H13B	108.9
C5—C4—H4A	108.9	H13A—C13—H13B	107.7
C3—C4—H4A	108.9	O4—C14—C13	112.24 (16)
C5—C4—H4B	108.9	O4—C14—H14A	109.2
C3—C4—H4B	108.9	C13—C14—H14A	109.2
H4A—C4—H4B	107.7	O4—C14—H14B	109.2
O1—C5—C4	113.85 (13)	C13—C14—H14B	109.2
O1—C5—H5A	108.8	H14A—C14—H14B	107.9
C4—C5—H5A	108.8

P2—Fe1—P1—C1	−18.86 (5)	C6—P1—C1—C2	176.02 (9)
P2ⁱ—Fe1—P1—C1	161.14 (5)	Fe1—P1—C1—C2	47.68 (10)
Cl1ⁱ—Fe1—P1—C1	73.13 (5)	P1—C1—C2—P2	−54.31 (11)
Cl1—Fe1—P1—C1	−106.87 (5)	C9—P2—C2—C1	168.04 (10)
P2—Fe1—P1—C3	93.66 (5)	C12—P2—C2—C1	−87.83 (10)
P2ⁱ—Fe1—P1—C3	−86.34 (5)	Fe1—P2—C2—C1	37.63 (10)
Cl1ⁱ—Fe1—P1—C3	−174.36 (5)	C1—P1—C3—C4	−60.57 (12)
Cl1—Fe1—P1—C3	5.64 (5)	C6—P1—C3—C4	46.50 (13)
P1ⁱ—Fe1—P1—C6	117 (100)	Fe1—P1—C3—C4	−175.77 (9)
P2—Fe1—P1—C6	−135.60 (6)	P1—C3—C4—C5	166.97 (11)
P2ⁱ—Fe1—P1—C6	44.40 (6)	C3—C4—C5—O1	63.80 (17)
Cl1ⁱ—Fe1—P1—C6	−43.61 (6)	C1—P1—C6—C7	22.64 (12)
Cl1—Fe1—P1—C6	136.39 (6)	C3—P1—C6—C7	−83.45 (12)
P1ⁱ—Fe1—P2—C9	55.49 (6)	Fe1—P1—C6—C7	141.10 (9)
P1—Fe1—P2—C9	−124.51 (6)	P1—C6—C7—C8	179.38 (10)
Cl1ⁱ—Fe1—P2—C9	149.41 (6)	C6—C7—C8—O2	177.46 (12)
Cl1—Fe1—P2—C9	−30.59 (6)	C12—P2—C9—C10	−69.66 (12)
P1ⁱ—Fe1—P2—C12	−74.53 (6)	C2—P2—C9—C10	32.86 (12)
P1—Fe1—P2—C12	105.47 (6)	Fe1—P2—C9—C10	153.12 (9)
Cl1ⁱ—Fe1—P2—C12	19.39 (6)	P2—C9—C10—C11	165.53 (11)
Cl1—Fe1—P2—C12	−160.61 (6)	C9—C10—C11—O3	−80.07 (16)
P1ⁱ—Fe1—P2—C2	173.09 (5)	C9—P2—C12—C13	−48.66 (15)
P1—Fe1—P2—C2	−6.91 (5)	C2—P2—C12—C13	−153.12 (14)
Cl1ⁱ—Fe1—P2—C2	−92.99 (5)	Fe1—P2—C12—C13	90.26 (14)
Cl1—Fe1—P2—C2	87.01 (5)	P2—C12—C13—C14	176.65 (16)
C3—P1—C1—C2	−74.99 (10)	C12—C13—C14—O4	−176.86 (17)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O3ⁱⁱ	0.79 (3)	1.98 (3)	2.7660 (18)	174 (3)
O2—H2O···O1ⁱⁱⁱ	0.73 (2)	2.12 (2)	2.8548 (17)	174 (2)
O3—H3O···O4^iv	0.81 (3)	1.93 (3)	2.7370 (19)	171 (3)
O4—H4O···Cl1^v	0.84 (3)	2.28 (3)	3.1150 (13)	171 (3)

Symmetry codes: (ii) x+1, y, z+1; (iii) −x+2, −y+2, −z+1; (iv) −x, −y+1, −z−1; (v) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[FeCl₂(C₁₄H₃₂O₄P₂)₂]
M_r	779.42
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.7120 (4), 10.4252 (5), 10.7441 (5)
α, β, γ (°)	96.086 (1), 104.215 (1), 105.860 (1)
V (Å³)	894.12 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.80
Crystal size (mm)	0.29 × 0.26 × 0.18

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.802, 0.870
No. of measured, independent and observed [I > 2σ(I)] reflections	10053, 3863, 3693
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.068, 1.06
No. of reflections	3863
No. of parameters	212
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.47

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Fe1—P1	2.2790 (3)	Fe1—Cl1	2.3507 (3)
Fe1—P2	2.3008 (3)

P1—Fe1—P2	85.008 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O3ⁱ	0.79 (3)	1.98 (3)	2.7660 (18)	174 (3)
O2—H2O···O1ⁱⁱ	0.73 (2)	2.12 (2)	2.8548 (17)	174 (2)
O3—H3O···O4ⁱⁱⁱ	0.81 (3)	1.93 (3)	2.7370 (19)	171 (3)
O4—H4O···Cl1^iv	0.84 (3)	2.28 (3)	3.1150 (13)	171 (3)

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

Acknowledgements

We thank the NSF for funding.

References

Baxley, G. T., Miller, W. K., Lyon, D. K., Miller, B. E., Nieckarz, G. F., Weakley, T. J. R. & Tyler, D. R. (1996). Inorg. Chem. 35, 6688–6693. CSD CrossRef PubMed CAS Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lyon, D. K. (1993). US Patent No. 5 225 174. Google Scholar
Miller, W. K., Gilbertson, J. D., Leiva-Paredes, C., Bernatis, P. R., Weakley, T. J. R., Lyon, D. K. & Tyler, D. R. (2002). Inorg. Chem. 41, 5453–5465. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar