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

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

doi:10.1107/S1600536810003727

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m256

doi:10.1107/S1600536810003727

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trans-Bis{1,2-bis[bis(2-methoxyethyl)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 27 January 2010; accepted 29 January 2010; online 6 February 2010)

The Fe atom in the title compound, [FeCl₂(C₁₄H₃₂O₄P₂)₂], has a distorted octahedral coordination with four P atoms in equatorial positions and two Cl atoms in apical positions.

Related literature

For the applications of similar complexes in dinitrogen binding, see: Gilbertson et al. (2007 ); Lyon (1993 ); MacKay & Fryzuk (2004 ). For related structures, see: Herbowski & Deutsch (1993 ); Miller et al. (2002 ).

Experimental

Crystal data

[FeCl₂(C₁₄H₃₂O₄P₂)₂]
M_r = 779.42
Monoclinic, P 2₁ /c
a = 12.3417 (7) Å
b = 12.1825 (7) Å
c = 25.3621 (15) Å
β = 100.124 (1)°
V = 3753.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 173 K
0.32 × 0.19 × 0.09 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ) T_min = 0.794, T_max = 0.935
41489 measured reflections
8193 independent reflections
7057 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.03
8193 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 1.70 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—P1	2.2581 (6)
Fe1—P2	2.2770 (5)
Fe1—P3	2.2792 (6)
Fe1—P4	2.2814 (5)
Fe1—Cl2	2.3491 (5)
Fe1—Cl1	2.3529 (5)

P1—Fe1—P3	175.71 (2)
P2—Fe1—P4	178.82 (2)
Cl2—Fe1—Cl1	179.11 (2)

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: 10.1107/S1600536810003727/sj2718sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003727/sj2718Isup2.hkl

checkCIF report

Comment top

Numerous iron-diphosphine complexes have shown the ability to coordinate dinitrogen (MacKay & Fryzuk, 2004). Because of this ability, these complexes have received interest as dinitrogen scrubbers for nitrogen-containing natural gas streams (Lyon, 1993). One requirement for a successful dinitrogen scrubber is high solubility in water, a solvent in which methane has limited solubility. Research in our group has explored the synthesis of iron-diphosphine complexes containing water-soluble phosphine ligands, specifically diphosphine ligands containing hydroxyl and methoxy functional groups (Gilbertson et al., 2007; Miller et al., 2002). One problem facing hydroxyl functionalized phosphine ligands is that the hydroxyl groups have been shown in some cases to coordinate to the metal center. The methoxy functionalized phosphines are not plagued by this problem and thus have been our recent focus. Here we report the synthesis and structural characterization of a water-soluble iron dichloride phosphine complex, trans-Fe(DMeOEtPE)₂Cl₂ (DMeOEtPE=1,2-bis(dimethoxyethylphosphino)ethane).

The Fe atom in trans-Fe(DMeOEtPE)₂Cl₂ has a distorted octahedral coordination with four P atoms in equatorial and two Cl atoms in apical positions (Fig. 1). The Fe(1)—P distances are in the range 2.2581 (6)-2.2814 (5) Å, and the Fe(1)—Cl(1,2) distances are 2.3529 (5) and 2.3491 (5) Å, respectively.

Related literature top

For the applications of similar complexes in dinitrogen binding, see: Gilbertson et al. (2007); Lyon (1993); MacKay & Fryzuk (2004). For related structures, see: Herbowski & Deutsch (1993); Miller et al. (2002).

Experimental top

1,2-bis(dimethoxyethylphosphino)ethane (DMeOEtPE) was synthesized as previously reported (Herbowski & Deutsch, 1993). trans-Fe(DMeOEtPE)₂Cl₂ was prepared by adding DMeOEtPE (0.826 g, 2.53 mmol) to a stirring solution of FeCl₂4H₂O (0.25 g, 1.26 mmol) in 30 ml of toluene under an argon atmosphere. The reaction was allowed to stir at room temperature for 24 hrs. The resulting green solution was carefully decanted into a clean flask, leaving a small amount of oily, red impurity in the original vessel. Approximately 20 ml of the toluene was removed under vacuum followed by addition of hexane (50 ml). Vacuum was applied to remove some of the hexane and chill the mixture. A green crystalline product was obtained by filtration followed by a hexane rinse and drying in vacuo. Yield 0.73 g, 74%. ³¹P{¹H} NMR (toluene-d⁸) at 233 K: 55 ppm.

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 the title compound with 50% probability displacement ellipsoids and the atom-numbering scheme. The H atoms are omitted for clarity.

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

Crystal data top

[FeCl₂(C₁₄H₃₂O₄P₂)₂]	F(000) = 1664
M_r = 779.42	D_x = 1.379 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5483 reflections
a = 12.3417 (7) Å	θ = 2.3–27.0°
b = 12.1825 (7) Å	µ = 0.76 mm⁻¹
c = 25.3621 (15) Å	T = 173 K
β = 100.124 (1)°	Block, light green
V = 3753.9 (4) Å³	0.32 × 0.19 × 0.09 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	8193 independent reflections
Radiation source: fine-focus sealed tube	7057 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 27.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −15→15
T_min = 0.794, T_max = 0.935	k = −15→15
41489 measured reflections	l = −32→32

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0481P)² + 2.6254P] where P = (F_o² + 2F_c²)/3
8193 reflections	(Δ/σ)_max = 0.001
388 parameters	Δρ_max = 1.70 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

[FeCl₂(C₁₄H₃₂O₄P₂)₂]	V = 3753.9 (4) Å³
M_r = 779.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.3417 (7) Å	µ = 0.76 mm⁻¹
b = 12.1825 (7) Å	T = 173 K
c = 25.3621 (15) Å	0.32 × 0.19 × 0.09 mm
β = 100.124 (1)°

Data collection top

Bruker APEX CCD area-detector diffractometer	8193 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	7057 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.935	R_int = 0.033
41489 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	Δρ_max = 1.70 e Å⁻³
8193 reflections	Δρ_min = −0.52 e Å⁻³
388 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	0.22245 (2)	0.97476 (2)	0.194352 (10)	0.01452 (8)
Cl1	0.08642 (4)	0.83773 (4)	0.187910 (19)	0.02216 (11)
Cl2	0.35615 (4)	1.11358 (4)	0.200262 (19)	0.02214 (11)
P1	0.30134 (4)	0.87521 (4)	0.136197 (19)	0.01708 (11)
P2	0.33088 (4)	0.87234 (4)	0.257867 (19)	0.01768 (11)
P3	0.13372 (4)	1.06472 (4)	0.253109 (19)	0.01742 (11)
P4	0.11197 (4)	1.07416 (4)	0.130031 (19)	0.01745 (11)
O1	0.19237 (15)	0.71639 (14)	−0.00460 (6)	0.0400 (4)
O2	0.54120 (13)	1.03024 (14)	0.07202 (7)	0.0341 (4)
O3	0.26896 (14)	0.60274 (13)	0.26502 (7)	0.0352 (4)
O4	0.57019 (19)	0.95126 (18)	0.38323 (9)	0.0639 (6)
O5	0.27939 (14)	1.12839 (14)	0.37116 (6)	0.0341 (4)
O6	−0.03861 (15)	0.96739 (14)	0.36821 (7)	0.0377 (4)
O7	−0.18270 (12)	0.98052 (14)	0.03537 (6)	0.0315 (4)
O8	0.15366 (13)	1.29630 (13)	0.01486 (6)	0.0295 (3)
C1	0.35201 (17)	0.74704 (16)	0.17059 (8)	0.0217 (4)
H1A	0.2895	0.6989	0.1748	0.026*
H1B	0.4001	0.7071	0.1497	0.026*
C2	0.41655 (16)	0.77930 (17)	0.22520 (8)	0.0213 (4)
H2A	0.4858	0.8165	0.2209	0.026*
H2B	0.4355	0.7130	0.2475	0.026*
C3	0.00598 (16)	1.12040 (17)	0.21359 (8)	0.0217 (4)
H3A	−0.0480	1.0606	0.2034	0.026*
H3B	−0.0269	1.1751	0.2350	0.026*
C4	0.03478 (17)	1.17450 (17)	0.16345 (8)	0.0222 (4)
H4A	0.0801	1.2408	0.1734	0.027*
H4B	−0.0333	1.1967	0.1390	0.027*
C5	0.21964 (16)	0.82790 (17)	0.07278 (8)	0.0214 (4)
H5A	0.1470	0.8038	0.0800	0.026*
H5B	0.2066	0.8916	0.0483	0.026*
C6	0.26683 (17)	0.73570 (17)	0.04360 (8)	0.0245 (4)
H6A	0.3398	0.7568	0.0358	0.029*
H6B	0.2756	0.6685	0.0659	0.029*
C7	0.2245 (3)	0.6320 (2)	−0.03610 (11)	0.0463 (7)
H7A	0.1692	0.6236	−0.0687	0.069*
H7B	0.2310	0.5632	−0.0158	0.069*
H7C	0.2957	0.6503	−0.0459	0.069*
C8	0.43141 (16)	0.92093 (18)	0.11705 (8)	0.0241 (4)
H8A	0.4839	0.9362	0.1505	0.029*
H8B	0.4615	0.8584	0.0993	0.029*
C9	0.43092 (18)	1.01955 (19)	0.08110 (9)	0.0274 (5)
H9A	0.3796	1.0081	0.0469	0.033*
H9B	0.4081	1.0862	0.0987	0.033*
C10	0.5572 (2)	1.1256 (2)	0.04272 (10)	0.0396 (6)
H10A	0.6340	1.1288	0.0375	0.059*
H10B	0.5405	1.1906	0.0625	0.059*
H10C	0.5084	1.1234	0.0078	0.059*
C11	0.26345 (18)	0.78176 (18)	0.30135 (9)	0.0267 (5)
H11A	0.2683	0.8187	0.3365	0.032*
H11B	0.1844	0.7774	0.2854	0.032*
C12	0.30510 (19)	0.66529 (18)	0.31191 (9)	0.0305 (5)
H12A	0.3865	0.6648	0.3207	0.037*
H12B	0.2758	0.6336	0.3425	0.037*
C13	0.3024 (3)	0.4922 (2)	0.27114 (13)	0.0592 (9)
H13A	0.2757	0.4521	0.2379	0.089*
H13B	0.2719	0.4590	0.3005	0.089*
H13C	0.3830	0.4885	0.2793	0.089*
C14	0.43117 (18)	0.94582 (18)	0.30686 (9)	0.0277 (5)
H14A	0.4756	0.9927	0.2869	0.033*
H14B	0.3900	0.9954	0.3272	0.033*
C15	0.5095 (2)	0.8796 (2)	0.34673 (10)	0.0425 (6)
H15A	0.4679	0.8278	0.3657	0.051*
H15B	0.5594	0.8367	0.3281	0.051*
C16	0.6081 (3)	0.9017 (3)	0.43294 (12)	0.0707 (10)
H16A	0.6508	0.9551	0.4570	0.106*
H16B	0.6549	0.8388	0.4280	0.106*
H16C	0.5452	0.8767	0.4485	0.106*
C17	0.18716 (18)	1.19478 (17)	0.28572 (8)	0.0245 (4)
H17A	0.1977	1.2466	0.2570	0.029*
H17B	0.1287	1.2259	0.3034	0.029*
C18	0.29249 (18)	1.19403 (18)	0.32654 (8)	0.0263 (4)
H18A	0.3533	1.1646	0.3100	0.032*
H18B	0.3117	1.2700	0.3386	0.032*
C19	0.3712 (2)	1.1381 (2)	0.41344 (9)	0.0408 (6)
H19A	0.3596	1.0917	0.4435	0.061*
H19B	0.3792	1.2147	0.4252	0.061*
H19C	0.4380	1.1145	0.4007	0.061*
C20	0.08209 (18)	0.98752 (17)	0.30572 (8)	0.0233 (4)
H20A	0.0556	0.9153	0.2908	0.028*
H20B	0.1447	0.9737	0.3352	0.028*
C21	−0.00960 (18)	1.04069 (18)	0.32942 (9)	0.0263 (5)
H21A	0.0156	1.1115	0.3464	0.032*
H21B	−0.0740	1.0548	0.3010	0.032*
C22	−0.1338 (2)	1.0037 (2)	0.38722 (10)	0.0391 (6)
H22A	−0.1518	0.9515	0.4138	0.059*
H22B	−0.1956	1.0084	0.3572	0.059*
H22C	−0.1199	1.0761	0.4038	0.059*
C23	0.00492 (16)	0.99868 (17)	0.08353 (8)	0.0228 (4)
H23A	0.0312	0.9902	0.0491	0.027*
H23B	−0.0010	0.9241	0.0983	0.027*
C24	−0.11012 (17)	1.04770 (19)	0.07170 (9)	0.0262 (4)
H24A	−0.1391	1.0552	0.1055	0.031*
H24B	−0.1066	1.1218	0.0561	0.031*
C25	−0.2284 (2)	0.8934 (2)	0.06156 (10)	0.0376 (6)
H25A	−0.2776	0.8497	0.0350	0.056*
H25B	−0.2702	0.9237	0.0877	0.056*
H25C	−0.1691	0.8466	0.0800	0.056*
C26	0.17307 (17)	1.16139 (17)	0.08401 (8)	0.0228 (4)
H26A	0.2262	1.2118	0.1055	0.027*
H26B	0.2150	1.1140	0.0631	0.027*
C27	0.09244 (18)	1.22924 (18)	0.04524 (9)	0.0262 (5)
H27A	0.0422	1.1805	0.0211	0.031*
H27B	0.0477	1.2758	0.0652	0.031*
C28	0.0831 (2)	1.3495 (2)	−0.02759 (10)	0.0394 (6)
H28A	0.1271	1.3948	−0.0478	0.059*
H28B	0.0310	1.3961	−0.0129	0.059*
H28C	0.0426	1.2943	−0.0514	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01472 (14)	0.01411 (14)	0.01440 (14)	−0.00007 (10)	0.00165 (10)	0.00078 (10)
Cl1	0.0221 (2)	0.0208 (2)	0.0230 (2)	−0.00560 (18)	0.00258 (18)	0.00148 (18)
Cl2	0.0229 (2)	0.0229 (2)	0.0202 (2)	−0.00762 (18)	0.00275 (18)	−0.00048 (18)
P1	0.0166 (2)	0.0176 (2)	0.0168 (2)	0.00109 (18)	0.00235 (18)	−0.00022 (18)
P2	0.0182 (2)	0.0183 (2)	0.0160 (2)	0.00186 (19)	0.00133 (19)	0.00167 (18)
P3	0.0191 (2)	0.0169 (2)	0.0163 (2)	0.00138 (19)	0.00322 (19)	0.00023 (18)
P4	0.0183 (2)	0.0175 (2)	0.0160 (2)	0.00196 (19)	0.00166 (18)	0.00139 (18)
O1	0.0503 (11)	0.0377 (10)	0.0264 (8)	0.0136 (8)	−0.0088 (8)	−0.0137 (7)
O2	0.0260 (8)	0.0392 (9)	0.0398 (9)	−0.0014 (7)	0.0135 (7)	0.0062 (7)
O3	0.0346 (9)	0.0241 (8)	0.0437 (10)	0.0014 (7)	−0.0018 (7)	0.0085 (7)
O4	0.0736 (15)	0.0545 (13)	0.0500 (13)	−0.0061 (11)	−0.0268 (11)	−0.0005 (10)
O5	0.0364 (9)	0.0427 (10)	0.0219 (8)	−0.0054 (7)	0.0012 (7)	0.0022 (7)
O6	0.0466 (10)	0.0339 (9)	0.0398 (10)	0.0134 (8)	0.0277 (8)	0.0145 (7)
O7	0.0244 (8)	0.0394 (9)	0.0278 (8)	−0.0064 (7)	−0.0036 (6)	0.0024 (7)
O8	0.0307 (8)	0.0320 (8)	0.0246 (8)	−0.0033 (7)	0.0017 (6)	0.0117 (6)
C1	0.0250 (10)	0.0188 (10)	0.0207 (10)	0.0052 (8)	0.0028 (8)	0.0005 (8)
C2	0.0187 (10)	0.0227 (10)	0.0220 (10)	0.0053 (8)	0.0025 (8)	0.0028 (8)
C3	0.0197 (10)	0.0243 (10)	0.0211 (10)	0.0065 (8)	0.0039 (8)	0.0004 (8)
C4	0.0236 (10)	0.0206 (10)	0.0214 (10)	0.0055 (8)	0.0014 (8)	0.0012 (8)
C5	0.0214 (10)	0.0231 (10)	0.0189 (10)	0.0025 (8)	0.0011 (8)	−0.0026 (8)
C6	0.0275 (11)	0.0246 (11)	0.0212 (10)	0.0006 (9)	0.0037 (8)	−0.0025 (8)
C7	0.0630 (18)	0.0407 (15)	0.0338 (14)	0.0007 (13)	0.0046 (13)	−0.0168 (11)
C8	0.0185 (10)	0.0291 (11)	0.0253 (11)	0.0011 (8)	0.0056 (8)	−0.0006 (9)
C9	0.0239 (11)	0.0335 (12)	0.0262 (11)	0.0010 (9)	0.0084 (9)	0.0023 (9)
C10	0.0457 (15)	0.0380 (14)	0.0393 (14)	−0.0083 (11)	0.0187 (12)	0.0014 (11)
C11	0.0253 (11)	0.0299 (12)	0.0258 (11)	0.0038 (9)	0.0074 (9)	0.0096 (9)
C12	0.0298 (12)	0.0294 (12)	0.0323 (12)	0.0027 (9)	0.0057 (9)	0.0131 (9)
C13	0.081 (2)	0.0315 (15)	0.062 (2)	0.0152 (15)	0.0033 (17)	0.0078 (14)
C14	0.0305 (12)	0.0256 (11)	0.0232 (11)	0.0013 (9)	−0.0056 (9)	−0.0031 (9)
C15	0.0469 (15)	0.0352 (14)	0.0361 (14)	0.0069 (11)	−0.0184 (11)	−0.0024 (11)
C16	0.084 (3)	0.079 (2)	0.0369 (16)	0.004 (2)	−0.0216 (16)	0.0008 (16)
C17	0.0288 (11)	0.0191 (10)	0.0256 (11)	0.0014 (8)	0.0049 (9)	−0.0036 (8)
C18	0.0327 (12)	0.0220 (10)	0.0239 (11)	−0.0015 (9)	0.0036 (9)	−0.0031 (8)
C19	0.0482 (15)	0.0464 (15)	0.0239 (12)	−0.0013 (12)	−0.0041 (11)	−0.0022 (11)
C20	0.0289 (11)	0.0212 (10)	0.0207 (10)	0.0035 (8)	0.0075 (8)	0.0027 (8)
C21	0.0296 (11)	0.0262 (11)	0.0251 (11)	0.0060 (9)	0.0102 (9)	0.0056 (9)
C22	0.0386 (14)	0.0470 (15)	0.0361 (13)	0.0066 (12)	0.0183 (11)	0.0061 (11)
C23	0.0222 (10)	0.0234 (10)	0.0206 (10)	0.0021 (8)	−0.0026 (8)	−0.0019 (8)
C24	0.0214 (10)	0.0299 (11)	0.0256 (11)	0.0013 (9)	−0.0008 (8)	0.0009 (9)
C25	0.0300 (13)	0.0387 (14)	0.0448 (15)	−0.0063 (10)	0.0083 (11)	−0.0005 (11)
C26	0.0230 (10)	0.0253 (10)	0.0201 (10)	0.0031 (8)	0.0033 (8)	0.0070 (8)
C27	0.0263 (11)	0.0274 (11)	0.0245 (11)	0.0011 (9)	0.0030 (8)	0.0080 (9)
C28	0.0464 (15)	0.0368 (14)	0.0329 (13)	0.0002 (11)	0.0009 (11)	0.0169 (11)

Geometric parameters (Å, º) top

Fe1—P1	2.2581 (6)	C8—H8B	0.9900
Fe1—P2	2.2770 (5)	C9—H9A	0.9900
Fe1—P3	2.2792 (6)	C9—H9B	0.9900
Fe1—P4	2.2814 (5)	C10—H10A	0.9800
Fe1—Cl2	2.3491 (5)	C10—H10B	0.9800
Fe1—Cl1	2.3529 (5)	C10—H10C	0.9800
P1—C5	1.835 (2)	C11—C12	1.517 (3)
P1—C8	1.843 (2)	C11—H11A	0.9900
P1—C1	1.843 (2)	C11—H11B	0.9900
P2—C14	1.827 (2)	C12—H12A	0.9900
P2—C2	1.843 (2)	C12—H12B	0.9900
P2—C11	1.857 (2)	C13—H13A	0.9800
P3—C20	1.836 (2)	C13—H13B	0.9800
P3—C3	1.842 (2)	C13—H13C	0.9800
P3—C17	1.854 (2)	C14—C15	1.505 (3)
P4—C26	1.836 (2)	C14—H14A	0.9900
P4—C4	1.845 (2)	C14—H14B	0.9900
P4—C23	1.853 (2)	C15—H15A	0.9900
O1—C7	1.401 (3)	C15—H15B	0.9900
O1—C6	1.414 (2)	C16—H16A	0.9800
O2—C10	1.411 (3)	C16—H16B	0.9800
O2—C9	1.426 (3)	C16—H16C	0.9800
O3—C13	1.409 (3)	C17—C18	1.513 (3)
O3—C12	1.417 (3)	C17—H17A	0.9900
O4—C15	1.391 (3)	C17—H17B	0.9900
O4—C16	1.402 (4)	C18—H18A	0.9900
O5—C18	1.418 (3)	C18—H18B	0.9900
O5—C19	1.421 (3)	C19—H19A	0.9800
O6—C22	1.417 (3)	C19—H19B	0.9800
O6—C21	1.420 (3)	C19—H19C	0.9800
O7—C25	1.421 (3)	C20—C21	1.517 (3)
O7—C24	1.425 (3)	C20—H20A	0.9900
O8—C28	1.417 (3)	C20—H20B	0.9900
O8—C27	1.427 (2)	C21—H21A	0.9900
C1—C2	1.523 (3)	C21—H21B	0.9900
C1—H1A	0.9900	C22—H22A	0.9800
C1—H1B	0.9900	C22—H22B	0.9800
C2—H2A	0.9900	C22—H22C	0.9800
C2—H2B	0.9900	C23—C24	1.521 (3)
C3—C4	1.529 (3)	C23—H23A	0.9900
C3—H3A	0.9900	C23—H23B	0.9900
C3—H3B	0.9900	C24—H24A	0.9900
C4—H4A	0.9900	C24—H24B	0.9900
C4—H4B	0.9900	C25—H25A	0.9800
C5—C6	1.517 (3)	C25—H25B	0.9800
C5—H5A	0.9900	C25—H25C	0.9800
C5—H5B	0.9900	C26—C27	1.515 (3)
C6—H6A	0.9900	C26—H26A	0.9900
C6—H6B	0.9900	C26—H26B	0.9900
C7—H7A	0.9800	C27—H27A	0.9900
C7—H7B	0.9800	C27—H27B	0.9900
C7—H7C	0.9800	C28—H28A	0.9800
C8—C9	1.508 (3)	C28—H28B	0.9800
C8—H8A	0.9900	C28—H28C	0.9800

P1—Fe1—P2	84.29 (2)	C12—C11—H11A	107.5
P1—Fe1—P3	175.71 (2)	P2—C11—H11A	107.5
P2—Fe1—P3	95.23 (2)	C12—C11—H11B	107.5
P1—Fe1—P4	95.17 (2)	P2—C11—H11B	107.5
P2—Fe1—P4	178.82 (2)	H11A—C11—H11B	107.0
P3—Fe1—P4	85.23 (2)	O3—C12—C11	107.94 (18)
P1—Fe1—Cl2	92.85 (2)	O3—C12—H12A	110.1
P2—Fe1—Cl2	91.75 (2)	C11—C12—H12A	110.1
P3—Fe1—Cl2	91.43 (2)	O3—C12—H12B	110.1
P4—Fe1—Cl2	89.33 (2)	C11—C12—H12B	110.1
P1—Fe1—Cl1	87.59 (2)	H12A—C12—H12B	108.4
P2—Fe1—Cl1	89.07 (2)	O3—C13—H13A	109.5
P3—Fe1—Cl1	88.14 (2)	O3—C13—H13B	109.5
P4—Fe1—Cl1	89.85 (2)	H13A—C13—H13B	109.5
Cl2—Fe1—Cl1	179.11 (2)	O3—C13—H13C	109.5
C5—P1—C8	103.52 (10)	H13A—C13—H13C	109.5
C5—P1—C1	103.72 (9)	H13B—C13—H13C	109.5
C8—P1—C1	98.16 (10)	C15—C14—P2	118.23 (16)
C5—P1—Fe1	120.51 (7)	C15—C14—H14A	107.8
C8—P1—Fe1	120.35 (7)	P2—C14—H14A	107.8
C1—P1—Fe1	107.17 (7)	C15—C14—H14B	107.8
C14—P2—C2	103.50 (10)	P2—C14—H14B	107.8
C14—P2—C11	102.01 (11)	H14A—C14—H14B	107.1
C2—P2—C11	104.70 (10)	O4—C15—C14	108.5 (2)
C14—P2—Fe1	117.16 (7)	O4—C15—H15A	110.0
C2—P2—Fe1	109.34 (6)	C14—C15—H15A	110.0
C11—P2—Fe1	118.47 (7)	O4—C15—H15B	110.0
C20—P3—C3	102.18 (10)	C14—C15—H15B	110.0
C20—P3—C17	104.79 (10)	H15A—C15—H15B	108.4
C3—P3—C17	97.55 (10)	O4—C16—H16A	109.5
C20—P3—Fe1	119.80 (7)	O4—C16—H16B	109.5
C3—P3—Fe1	106.55 (7)	H16A—C16—H16B	109.5
C17—P3—Fe1	121.90 (7)	O4—C16—H16C	109.5
C26—P4—C4	102.21 (9)	H16A—C16—H16C	109.5
C26—P4—C23	102.07 (10)	H16B—C16—H16C	109.5
C4—P4—C23	104.67 (9)	C18—C17—P3	119.71 (15)
C26—P4—Fe1	120.08 (7)	C18—C17—H17A	107.4
C4—P4—Fe1	108.37 (6)	P3—C17—H17A	107.4
C23—P4—Fe1	117.48 (7)	C18—C17—H17B	107.4
C7—O1—C6	114.15 (19)	P3—C17—H17B	107.4
C10—O2—C9	112.74 (18)	H17A—C17—H17B	106.9
C13—O3—C12	112.2 (2)	O5—C18—C17	110.17 (18)
C15—O4—C16	112.6 (2)	O5—C18—H18A	109.6
C18—O5—C19	111.58 (18)	C17—C18—H18A	109.6
C22—O6—C21	111.39 (17)	O5—C18—H18B	109.6
C25—O7—C24	112.52 (17)	C17—C18—H18B	109.6
C28—O8—C27	111.06 (17)	H18A—C18—H18B	108.1
C2—C1—P1	106.94 (14)	O5—C19—H19A	109.5
C2—C1—H1A	110.3	O5—C19—H19B	109.5
P1—C1—H1A	110.3	H19A—C19—H19B	109.5
C2—C1—H1B	110.3	O5—C19—H19C	109.5
P1—C1—H1B	110.3	H19A—C19—H19C	109.5
H1A—C1—H1B	108.6	H19B—C19—H19C	109.5
C1—C2—P2	108.53 (13)	C21—C20—P3	116.59 (14)
C1—C2—H2A	110.0	C21—C20—H20A	108.1
P2—C2—H2A	110.0	P3—C20—H20A	108.1
C1—C2—H2B	110.0	C21—C20—H20B	108.1
P2—C2—H2B	110.0	P3—C20—H20B	108.1
H2A—C2—H2B	108.4	H20A—C20—H20B	107.3
C4—C3—P3	108.03 (14)	O6—C21—C20	107.60 (17)
C4—C3—H3A	110.1	O6—C21—H21A	110.2
P3—C3—H3A	110.1	C20—C21—H21A	110.2
C4—C3—H3B	110.1	O6—C21—H21B	110.2
P3—C3—H3B	110.1	C20—C21—H21B	110.2
H3A—C3—H3B	108.4	H21A—C21—H21B	108.5
C3—C4—P4	108.11 (13)	O6—C22—H22A	109.5
C3—C4—H4A	110.1	O6—C22—H22B	109.5
P4—C4—H4A	110.1	H22A—C22—H22B	109.5
C3—C4—H4B	110.1	O6—C22—H22C	109.5
P4—C4—H4B	110.1	H22A—C22—H22C	109.5
H4A—C4—H4B	108.4	H22B—C22—H22C	109.5
C6—C5—P1	117.48 (14)	C24—C23—P4	117.85 (15)
C6—C5—H5A	107.9	C24—C23—H23A	107.8
P1—C5—H5A	107.9	P4—C23—H23A	107.8
C6—C5—H5B	107.9	C24—C23—H23B	107.8
P1—C5—H5B	107.9	P4—C23—H23B	107.8
H5A—C5—H5B	107.2	H23A—C23—H23B	107.2
O1—C6—C5	107.35 (16)	O7—C24—C23	111.16 (18)
O1—C6—H6A	110.2	O7—C24—H24A	109.4
C5—C6—H6A	110.2	C23—C24—H24A	109.4
O1—C6—H6B	110.2	O7—C24—H24B	109.4
C5—C6—H6B	110.2	C23—C24—H24B	109.4
H6A—C6—H6B	108.5	H24A—C24—H24B	108.0
O1—C7—H7A	109.5	O7—C25—H25A	109.5
O1—C7—H7B	109.5	O7—C25—H25B	109.5
H7A—C7—H7B	109.5	H25A—C25—H25B	109.5
O1—C7—H7C	109.5	O7—C25—H25C	109.5
H7A—C7—H7C	109.5	H25A—C25—H25C	109.5
H7B—C7—H7C	109.5	H25B—C25—H25C	109.5
C9—C8—P1	119.28 (15)	C27—C26—P4	115.60 (14)
C9—C8—H8A	107.5	C27—C26—H26A	108.4
P1—C8—H8A	107.5	P4—C26—H26A	108.4
C9—C8—H8B	107.5	C27—C26—H26B	108.4
P1—C8—H8B	107.5	P4—C26—H26B	108.4
H8A—C8—H8B	107.0	H26A—C26—H26B	107.4
O2—C9—C8	105.55 (17)	O8—C27—C26	108.24 (16)
O2—C9—H9A	110.6	O8—C27—H27A	110.1
C8—C9—H9A	110.6	C26—C27—H27A	110.1
O2—C9—H9B	110.6	O8—C27—H27B	110.1
C8—C9—H9B	110.6	C26—C27—H27B	110.1
H9A—C9—H9B	108.8	H27A—C27—H27B	108.4
O2—C10—H10A	109.5	O8—C28—H28A	109.5
O2—C10—H10B	109.5	O8—C28—H28B	109.5
H10A—C10—H10B	109.5	H28A—C28—H28B	109.5
O2—C10—H10C	109.5	O8—C28—H28C	109.5
H10A—C10—H10C	109.5	H28A—C28—H28C	109.5
H10B—C10—H10C	109.5	H28B—C28—H28C	109.5
C12—C11—P2	119.17 (15)

P2—Fe1—P1—C5	140.63 (8)	P1—C1—C2—P2	50.69 (16)
P4—Fe1—P1—C5	−38.31 (8)	C14—P2—C2—C1	−157.94 (14)
Cl2—Fe1—P1—C5	−127.90 (8)	C11—P2—C2—C1	95.55 (15)
Cl1—Fe1—P1—C5	51.32 (8)	Fe1—P2—C2—C1	−32.36 (15)
P2—Fe1—P1—C8	−88.10 (8)	C20—P3—C3—C4	−172.46 (14)
P4—Fe1—P1—C8	92.96 (8)	C17—P3—C3—C4	80.57 (15)
Cl2—Fe1—P1—C8	3.37 (8)	Fe1—P3—C3—C4	−45.98 (15)
Cl1—Fe1—P1—C8	−177.41 (8)	P3—C3—C4—P4	52.38 (16)
P2—Fe1—P1—C1	22.58 (7)	C26—P4—C4—C3	−164.32 (14)
P4—Fe1—P1—C1	−156.36 (7)	C23—P4—C4—C3	89.55 (15)
Cl2—Fe1—P1—C1	114.05 (7)	Fe1—P4—C4—C3	−36.56 (15)
Cl1—Fe1—P1—C1	−66.73 (7)	C8—P1—C5—C6	59.36 (18)
P1—Fe1—P2—C14	119.39 (9)	C1—P1—C5—C6	−42.70 (18)
P3—Fe1—P2—C14	−64.89 (9)	Fe1—P1—C5—C6	−162.48 (13)
Cl2—Fe1—P2—C14	26.70 (9)	C7—O1—C6—C5	−179.5 (2)
Cl1—Fe1—P2—C14	−152.94 (9)	P1—C5—C6—O1	−177.78 (14)
P1—Fe1—P2—C2	2.12 (7)	C5—P1—C8—C9	66.56 (18)
P3—Fe1—P2—C2	177.84 (7)	C1—P1—C8—C9	172.87 (17)
Cl2—Fe1—P2—C2	−90.57 (7)	Fe1—P1—C8—C9	−71.69 (18)
Cl1—Fe1—P2—C2	89.79 (7)	C10—O2—C9—C8	−174.59 (18)
P1—Fe1—P2—C11	−117.64 (9)	P1—C8—C9—O2	−177.44 (14)
P3—Fe1—P2—C11	58.08 (9)	C14—P2—C11—C12	−94.62 (19)
Cl2—Fe1—P2—C11	149.67 (9)	C2—P2—C11—C12	13.0 (2)
Cl1—Fe1—P2—C11	−29.97 (9)	Fe1—P2—C11—C12	135.13 (16)
P2—Fe1—P3—C20	−45.62 (8)	C13—O3—C12—C11	−179.2 (2)
P4—Fe1—P3—C20	133.28 (8)	P2—C11—C12—O3	−74.6 (2)
Cl2—Fe1—P3—C20	−137.51 (8)	C2—P2—C14—C15	−55.2 (2)
Cl1—Fe1—P3—C20	43.27 (8)	C11—P2—C14—C15	53.4 (2)
P2—Fe1—P3—C3	−160.70 (7)	Fe1—P2—C14—C15	−175.56 (17)
P4—Fe1—P3—C3	18.21 (7)	C16—O4—C15—C14	154.0 (3)
Cl2—Fe1—P3—C3	107.42 (7)	P2—C14—C15—O4	−174.0 (2)
Cl1—Fe1—P3—C3	−71.80 (7)	C20—P3—C17—C18	71.91 (18)
P2—Fe1—P3—C17	89.04 (8)	C3—P3—C17—C18	176.69 (17)
P4—Fe1—P3—C17	−92.06 (8)	Fe1—P3—C17—C18	−68.42 (18)
Cl2—Fe1—P3—C17	−2.85 (8)	C19—O5—C18—C17	−171.85 (19)
Cl1—Fe1—P3—C17	177.93 (8)	P3—C17—C18—O5	−62.4 (2)
P1—Fe1—P4—C26	−60.68 (8)	C3—P3—C20—C21	−40.69 (19)
P3—Fe1—P4—C26	123.61 (8)	C17—P3—C20—C21	60.61 (18)
Cl2—Fe1—P4—C26	32.12 (8)	Fe1—P3—C20—C21	−158.04 (14)
Cl1—Fe1—P4—C26	−148.24 (8)	C22—O6—C21—C20	−172.0 (2)
P1—Fe1—P4—C4	−177.42 (7)	P3—C20—C21—O6	178.90 (15)
P3—Fe1—P4—C4	6.87 (7)	C26—P4—C23—C24	−91.54 (18)
Cl2—Fe1—P4—C4	−84.62 (7)	C4—P4—C23—C24	14.69 (19)
Cl1—Fe1—P4—C4	95.02 (7)	Fe1—P4—C23—C24	134.91 (14)
P1—Fe1—P4—C23	64.33 (8)	C25—O7—C24—C23	84.0 (2)
P3—Fe1—P4—C23	−111.38 (8)	P4—C23—C24—O7	179.90 (14)
Cl2—Fe1—P4—C23	157.13 (8)	C4—P4—C26—C27	−56.39 (18)
Cl1—Fe1—P4—C23	−23.24 (8)	C23—P4—C26—C27	51.74 (18)
C5—P1—C1—C2	−177.30 (13)	Fe1—P4—C26—C27	−176.26 (13)
C8—P1—C1—C2	76.56 (15)	C28—O8—C27—C26	171.15 (19)
Fe1—P1—C1—C2	−48.80 (14)	P4—C26—C27—O8	176.70 (14)

Experimental details

Crystal data
Chemical formula	[FeCl₂(C₁₄H₃₂O₄P₂)₂]
M_r	779.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.3417 (7), 12.1825 (7), 25.3621 (15)
β (°)	100.124 (1)
V (Å³)	3753.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.32 × 0.19 × 0.09

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1995)
T_min, T_max	0.794, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	41489, 8193, 7057
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.03
No. of reflections	8193
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.70, −0.52

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

Selected geometric parameters (Å, º) top

Fe1—P1	2.2581 (6)	Fe1—P4	2.2814 (5)
Fe1—P2	2.2770 (5)	Fe1—Cl2	2.3491 (5)
Fe1—P3	2.2792 (6)	Fe1—Cl1	2.3529 (5)

P1—Fe1—P3	175.71 (2)	Cl2—Fe1—Cl1	179.11 (2)
P2—Fe1—P4	178.82 (2)

Acknowledgements

We thank the NSF for funding.

References

Bruker (2000). SMART and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gilbertson, J. D., Szymczak, N. K., Crossland, J. L., Miller, W. K., Lyon, D. K., Foxman, B. M., Davis, J. & Tyler, D. R. (2007). Inorg. Chem. 46, 1205–1214. Web of Science CSD CrossRef PubMed CAS Google Scholar
Herbowski, A. & Deutsch, E. A. (1993). J. Organomet. Chem. 460, 19–23. CrossRef CAS Web of Science Google Scholar
Lyon, D. K. (1993). Fe Phosphine Complexes for N₂ Removal from Natural Gas. US Patent No. 5 225 174. Google Scholar
MacKay, B. A. & Fryzuk, M. D. (2004). Chem. Rev. 104, 385–401. Web of Science CrossRef PubMed CAS 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. (1995). SADABS, University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar