trans-Bis(acetonitrile-κN)bis­{1,2-bis­[bis­(3-hydroxy­prop­yl)phosphino]ethane-κ2P,P′}iron(II) dichloride

Gohdes, J.W.; Zakharov, L.N.; Tyler, D.R.

doi:10.1107/S1600536809021758

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m776

doi:10.1107/S1600536809021758

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trans-Bis(acetonitrile-κN)bis{1,2-bis[bis(3-hydroxypropyl)phosphino]ethane-κ²P,P′}iron(II) dichloride

J. W. Gohdes,^a Lev N. Zakharov ^b and David R. Tyler ^b ^*

^aDepartment of Chemistry, Pacific University, 2043 College Way, Forest Grove, OR, USA, and ^bDepartment of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403-1253, USA
^*Correspondence e-mail: dtyler@uoregon.edu

(Received 30 May 2009; accepted 8 June 2009; online 17 June 2009)

In the title compound, [Fe(CH₃CN)₂(C₁₄H₃₂O₄P₂)₂]Cl₂, the Fe^II atom lies on a crystallographic inversion center and has a distorted trans-FeN₂P₄ octahedral coordination environment arising from two P,P′-bidentate 1,2-bis[bis(3-hydroxypropyl)phosphino]ethane ligands in the equatorial plane and two acetonitrile molecules in the axial positions. One of the pendant –(CH₂)₃OH groups of the ligand is disordered over two sets of sites in a 0.597 (5):0.403 (5) ratio. In the crystal, O—H⋯Cl and O—H⋯O hydrogen bonding helps to establish the packing.

Related literature

For related compounds containing bidentate phosphine ligands, see: Gilbertson et al. (2007 ); Miller et al. (2002 ); Martins et al. (1998 ); Barron et al. (1987 ); George et al. (1997 ); Edwards et al. (2006 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Fe(C₂H₃N)₂(C₁₄H₃₂O₄P₂)₂]Cl₂
M_r = 861.53
Orthorhombic, P b c a
a = 18.3024 (12) Å
b = 11.5220 (8) Å
c = 19.8413 (13) Å
V = 4184.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 173 K
0.22 × 0.18 × 0.17 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.863, T_max = 0.892
24288 measured reflections
4571 independent reflections
4122 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.04
4571 reflections
269 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.88 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—N1	1.9077 (14)
Fe1—P1	2.2884 (4)
Fe1—P2	2.3049 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯Cl1	0.928 (17)	2.126 (18)	3.0493 (16)	173 (3)
O2—H2O⋯Cl1ⁱ	0.976 (18)	2.23 (2)	3.1777 (19)	164 (3)
O3—H3O⋯O1ⁱ	0.924 (17)	1.841 (18)	2.741 (2)	164 (2)
O4—H4O⋯Cl1ⁱⁱ	0.98 (2)	1.95 (2)	2.931 (6)	177 (3)
O4A—H4OA⋯Cl1ⁱⁱ	0.98 (2)	2.84 (11)	3.490 (10)	125 (9)
Symmetry codes: (i) x, y-1, z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536809021758/hb2994sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021758/hb2994Isup2.hkl

checkCIF report

Comment top

The bidentate phosphine 1,2-bis[di(3-hydroxypropyl)phosphino]ethane (DHPrPE) was developed as a water soluble ligand for use in making iron complexes capable of binding dinitrogen and hydrogen (Miller et al., 2002). It was found that the hydroxypropyl groups were non-innocent in reactions with iron(II), and a stable complex was isolated in which the chelating phosphine ligands are tridentate and coordinate through one of the hydroxypropyl groups in addition to both phosphines. This results in a coordinatively saturated complex where the alcohols ligands are cis to one another. The current work shows that addition of acetonitrile to this species results in the rearrangement to the trans geometry.

The stucture of the cation [Fe(DHPrPE)₂(CH₃CN)₂]²⁺ in the title compound, (I), is shown in Fig. 1. The four phosphine donors from the DHPrPE ligands form a square planar arrangement around the iron atom and the two coordinated acetonitrile ligands occupy the trans axial sites to form a distorted octahedral geometry around the iron. Such trans bis acetonitrile complexes of iron(II) with bidentate phosphines are not uncommon. The first reported structure was of the DMPE analog (Barron et al. 1987). An examination of similar compounds (George et al. 1997, Martins et al. 1998, Gilbertson et al. 2007 and Edwards et al. 2006) shows there are minor variations within the primary coordination sphere of all of these complexes. The Fe—N bond distances vary from 1.895 to 1.917 Å; the Fe—P bond distances vary from 2.255 to 2.3032 Å and the P—Fe—P bite angles are between 84.0° and 85.5°. The Fe—P distances in the title compound, 2.2883 (5) and 2.3044 (5) Å, are at the high end of the expected range while the bite angle of 84.2° is at the low end of the range, indicating significant steric crowding around the iron center.

Related literature top

For related compounds containing bidentate phosphine ligands, see: Gilbertson et al. (2007); Miller et al. (2002); Martins et al. (1998); Barron et al. (1987); George et al. (1997); Edwards et al. (2006). For reference structural data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by dissolving 60 mg of iron(II)chloride tetrahydrate (0.30 mmole) and 200 mg of 1,2-bis[di(3-hydroxypropyl)phosphino]ethane (0.61 mmole) in 3.0 ml of methanol to give a dark purple solution. After addition of 2.0 ml of acetonitrile, the solution slowly turned orange indicating formation of the title complex. Addition of diethylether and filtration yielded 215 mg (90%) of the title compound as an orange, crystalline powder and gave a single resonance in the ³¹P{¹H} NMR spectrum at 61.4 p.p.m.. Yellow blocks of (I) were grown by vapor diffusion of diethylether into a 3:1 methanol/acetonitrile solution of the complex.

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 stucture of the [Fe(DHPrPE)₂(CH₃CN)₂]²⁺ cation in (I) with 50% probability displacement elipsoids. Only the H atoms in the –OH and –CH₃ groups and only one position of the disordered hydroxypropyl group are shown for clarity. Symmetry code (i): –x, –y, –z.

trans-Bis(acetonitrile-κN)bis{1,2-bis[bis(3- hydroxypropyl)phosphino]ethane-κ²P,P'}iron(II) dichloride top

Crystal data top

[Fe(C₂H₃N)₂(C₁₄H₃₂O₄P₂)₂]Cl₂	F(000) = 1840
M_r = 861.53	D_x = 1.368 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5018 reflections
a = 18.3024 (12) Å	θ = 2.3–27.0°
b = 11.5220 (8) Å	µ = 0.69 mm⁻¹
c = 19.8413 (13) Å	T = 173 K
V = 4184.1 (5) Å³	Block, yellow
Z = 4	0.22 × 0.18 × 0.17 mm

Data collection top

Bruker APEX CCD diffractometer	4571 independent reflections
Radiation source: fine-focus sealed tube	4122 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −22→23
T_min = 0.863, T_max = 0.892	k = −14→13
24288 measured reflections	l = −25→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0451P)² + 3.5311P] where P = (F_o² + 2F_c²)/3
4571 reflections	(Δ/σ)_max = 0.001
269 parameters	Δρ_max = 0.88 e Å⁻³
7 restraints	Δρ_min = −1.01 e Å⁻³

Crystal data top

[Fe(C₂H₃N)₂(C₁₄H₃₂O₄P₂)₂]Cl₂	V = 4184.1 (5) Å³
M_r = 861.53	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 18.3024 (12) Å	µ = 0.69 mm⁻¹
b = 11.5220 (8) Å	T = 173 K
c = 19.8413 (13) Å	0.22 × 0.18 × 0.17 mm

Data collection top

Bruker APEX CCD diffractometer	4571 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4122 reflections with I > 2σ(I)
T_min = 0.863, T_max = 0.892	R_int = 0.024
24288 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	7 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.88 e Å⁻³
4571 reflections	Δρ_min = −1.01 e Å⁻³
269 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.0000	0.0000	0.0000	0.01629 (10)
Cl1	0.09382 (5)	0.65273 (5)	0.16061 (4)	0.0673 (2)
P1	0.08435 (2)	0.04855 (4)	0.08033 (2)	0.01886 (11)
P2	0.08545 (2)	−0.13647 (4)	−0.03165 (2)	0.01984 (11)
O1	0.17032 (9)	0.42889 (12)	0.11886 (8)	0.0372 (3)
O2	0.01646 (10)	−0.18587 (14)	0.26912 (9)	0.0484 (4)
O3	0.15466 (8)	−0.58403 (12)	−0.01831 (8)	0.0334 (3)
N1	0.04458 (8)	0.11038 (12)	−0.05870 (7)	0.0203 (3)
C1	0.07048 (10)	0.17507 (16)	−0.09498 (9)	0.0252 (4)
C2	0.10388 (16)	0.2552 (2)	−0.14267 (12)	0.0427 (6)
C3	0.17298 (10)	0.00506 (16)	0.04511 (10)	0.0253 (4)
H3A	0.1855	0.0542	0.0059	0.030*
H3B	0.2119	0.0134	0.0794	0.030*
C4	0.16574 (9)	−0.12177 (16)	0.02359 (9)	0.0245 (4)
H4A	0.1599	−0.1718	0.0638	0.029*
H4B	0.2103	−0.1465	−0.0008	0.029*
C5	0.09772 (10)	0.19994 (15)	0.10533 (9)	0.0229 (4)
H5A	0.0970	0.2487	0.0643	0.028*
H5B	0.0559	0.2239	0.1337	0.028*
C6	0.16840 (11)	0.22501 (16)	0.14399 (11)	0.0344 (5)
H6A	0.1734	0.1686	0.1813	0.041*
H6B	0.2106	0.2145	0.1134	0.041*
C7	0.16982 (12)	0.34726 (17)	0.17253 (11)	0.0351 (5)
H7A	0.1263	0.3600	0.2012	0.042*
H7B	0.2139	0.3577	0.2008	0.042*
C8	0.08669 (10)	−0.03375 (16)	0.15970 (9)	0.0249 (4)
H8A	0.0756	−0.1158	0.1490	0.030*
H8B	0.1374	−0.0313	0.1771	0.030*
C9	0.03621 (13)	0.00366 (17)	0.21634 (10)	0.0342 (5)
H9A	−0.0150	0.0000	0.2004	0.041*
H9B	0.0470	0.0852	0.2285	0.041*
C10	0.04449 (13)	−0.07267 (18)	0.27889 (10)	0.0369 (5)
H10A	0.0969	−0.0780	0.2909	0.044*
H10B	0.0186	−0.0358	0.3171	0.044*
C11	0.06233 (10)	−0.29074 (15)	−0.02366 (10)	0.0269 (4)
H11A	0.0364	−0.3019	0.0196	0.032*
H11B	0.0277	−0.3109	−0.0602	0.032*
C12	0.12616 (10)	−0.37655 (16)	−0.02629 (11)	0.0282 (4)
H12A	0.1533	−0.3665	−0.0690	0.034*
H12B	0.1601	−0.3611	0.0115	0.034*
C13	0.09764 (11)	−0.49987 (16)	−0.02144 (11)	0.0293 (4)
H13A	0.0667	−0.5070	0.0193	0.035*
H13B	0.0665	−0.5162	−0.0611	0.035*
C14	0.12156 (11)	−0.12509 (18)	−0.11788 (9)	0.0310 (4)	0.50
H14A	0.0997	−0.1892	−0.1443	0.037*	0.50
H14B	0.1025	−0.0519	−0.1372	0.037*	0.50
C15	0.2010 (2)	−0.1272 (5)	−0.1306 (2)	0.0463 (10)	0.597 (5)
H15A	0.2242	−0.0626	−0.1057	0.056*	0.597 (5)
H15B	0.2214	−0.2007	−0.1129	0.056*	0.597 (5)
C16	0.2200 (4)	−0.1169 (9)	−0.2031 (4)	0.067 (3)	0.597 (5)
H16A	0.1934	−0.0508	−0.2234	0.081*	0.597 (5)
H16B	0.2731	−0.1026	−0.2081	0.081*	0.597 (5)
O4	0.2003 (3)	−0.2228 (4)	−0.2368 (2)	0.0724 (14)	0.597 (5)
H4O	0.165 (3)	−0.196 (3)	−0.271 (2)	0.109*	0.597 (5)
C14A	0.12156 (11)	−0.12509 (18)	−0.11788 (9)	0.0310 (4)	0.50
H14C	0.1303	−0.2044	−0.1353	0.037*	0.50
H14D	0.0838	−0.0887	−0.1467	0.037*	0.50
C15A	0.1934 (3)	−0.0543 (8)	−0.1247 (3)	0.0463 (10)	0.403 (5)
H15C	0.2321	−0.0913	−0.0972	0.056*	0.403 (5)
H15D	0.1856	0.0252	−0.1072	0.056*	0.403 (5)
C16A	0.2184 (6)	−0.0479 (10)	−0.1982 (6)	0.067 (3)	0.403 (5)
H16C	0.1794	−0.0135	−0.2264	0.081*	0.403 (5)
H16D	0.2624	0.0019	−0.2019	0.081*	0.403 (5)
O4A	0.2344 (6)	−0.1593 (11)	−0.2206 (4)	0.090 (4)	0.403 (5)
H4OA	0.229 (7)	−0.155 (4)	−0.2695 (12)	0.135*	0.403 (5)
H1O	0.1497 (16)	0.4974 (19)	0.1345 (15)	0.065 (9)*
H2O	0.0490 (18)	−0.230 (3)	0.2395 (16)	0.103 (13)*
H3O	0.1677 (14)	−0.588 (2)	0.0266 (9)	0.047 (7)*
H2A	0.130 (2)	0.217 (4)	−0.171 (2)	0.098 (13)*
H2B	0.066 (2)	0.298 (3)	−0.1631 (18)	0.086 (12)*
H2C	0.1313 (18)	0.309 (3)	−0.1215 (16)	0.068 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01608 (17)	0.01771 (17)	0.01507 (17)	0.00023 (12)	0.00013 (12)	0.00109 (12)
Cl1	0.1218 (7)	0.0311 (3)	0.0492 (4)	0.0262 (3)	0.0298 (4)	0.0079 (3)
P1	0.0194 (2)	0.0194 (2)	0.0178 (2)	0.00012 (15)	−0.00260 (16)	0.00053 (16)
P2	0.0183 (2)	0.0216 (2)	0.0196 (2)	0.00237 (16)	−0.00001 (16)	−0.00075 (17)
O1	0.0469 (9)	0.0247 (7)	0.0400 (8)	0.0011 (6)	0.0088 (7)	0.0019 (6)
O2	0.0623 (11)	0.0361 (8)	0.0467 (10)	0.0004 (8)	0.0149 (8)	0.0059 (7)
O3	0.0328 (7)	0.0279 (7)	0.0393 (8)	0.0114 (6)	−0.0014 (6)	−0.0036 (6)
N1	0.0204 (7)	0.0217 (7)	0.0188 (7)	0.0009 (6)	−0.0002 (6)	−0.0011 (6)
C1	0.0281 (9)	0.0263 (9)	0.0212 (8)	−0.0027 (7)	0.0001 (7)	−0.0006 (7)
C2	0.0589 (15)	0.0407 (13)	0.0285 (11)	−0.0206 (12)	0.0064 (11)	0.0062 (10)
C3	0.0185 (8)	0.0289 (9)	0.0284 (9)	−0.0001 (7)	−0.0023 (7)	−0.0027 (7)
C4	0.0197 (8)	0.0294 (9)	0.0242 (9)	0.0051 (7)	−0.0026 (7)	−0.0024 (7)
C5	0.0248 (8)	0.0202 (8)	0.0237 (9)	−0.0014 (7)	−0.0060 (7)	0.0000 (7)
C6	0.0351 (10)	0.0230 (9)	0.0450 (12)	−0.0017 (8)	−0.0191 (9)	0.0013 (9)
C7	0.0402 (11)	0.0278 (10)	0.0374 (11)	−0.0054 (8)	−0.0154 (9)	0.0006 (8)
C8	0.0321 (9)	0.0226 (8)	0.0201 (8)	0.0008 (7)	−0.0056 (7)	0.0034 (7)
C9	0.0529 (13)	0.0278 (10)	0.0219 (9)	0.0086 (9)	0.0019 (9)	0.0006 (8)
C10	0.0547 (13)	0.0342 (11)	0.0218 (9)	0.0022 (9)	−0.0004 (9)	0.0030 (8)
C11	0.0226 (8)	0.0215 (8)	0.0365 (10)	0.0027 (7)	−0.0015 (7)	−0.0006 (8)
C12	0.0226 (9)	0.0253 (9)	0.0367 (10)	0.0047 (7)	0.0002 (8)	−0.0026 (8)
C13	0.0260 (9)	0.0242 (9)	0.0378 (11)	0.0064 (7)	−0.0033 (8)	−0.0034 (8)
C14	0.0340 (10)	0.0380 (11)	0.0212 (9)	0.0044 (8)	0.0048 (8)	−0.0031 (8)
C15	0.0307 (15)	0.077 (3)	0.0314 (15)	0.009 (2)	0.0063 (12)	0.012 (2)
C16	0.045 (2)	0.107 (7)	0.050 (3)	0.016 (5)	0.0194 (18)	0.032 (6)
O4	0.090 (4)	0.082 (3)	0.045 (2)	0.043 (3)	0.024 (2)	0.000 (2)
C14A	0.0340 (10)	0.0380 (11)	0.0212 (9)	0.0044 (8)	0.0048 (8)	−0.0031 (8)
C15A	0.0307 (15)	0.077 (3)	0.0314 (15)	0.009 (2)	0.0063 (12)	0.012 (2)
C16A	0.045 (2)	0.107 (7)	0.050 (3)	0.016 (5)	0.0194 (18)	0.032 (6)
O4A	0.083 (7)	0.143 (10)	0.043 (4)	0.043 (5)	0.005 (4)	−0.008 (5)

Geometric parameters (Å, º) top

Fe1—N1ⁱ	1.9077 (14)	C8—C9	1.517 (3)
Fe1—N1	1.9077 (14)	C8—H8A	0.9900
Fe1—P1	2.2884 (4)	C8—H8B	0.9900
Fe1—P1ⁱ	2.2884 (4)	C9—C10	1.529 (3)
Fe1—P2ⁱ	2.3049 (4)	C9—H9A	0.9900
Fe1—P2	2.3049 (4)	C9—H9B	0.9900
P1—C5	1.8300 (18)	C10—H10A	0.9900
P1—C3	1.8358 (18)	C10—H10B	0.9900
P1—C8	1.8387 (18)	C11—C12	1.531 (2)
P2—C11	1.8341 (19)	C11—H11A	0.9900
P2—C14	1.8388 (19)	C11—H11B	0.9900
P2—C4	1.8409 (18)	C12—C13	1.517 (3)
O1—C7	1.421 (2)	C12—H12A	0.9900
O1—H1O	0.928 (17)	C12—H12B	0.9900
O2—C10	1.415 (3)	C13—H13A	0.9900
O2—H2O	0.976 (18)	C13—H13B	0.9900
O3—C13	1.426 (2)	C14—C15	1.477 (4)
O3—H3O	0.924 (17)	C14—H14A	0.9900
N1—C1	1.140 (2)	C14—H14B	0.9900
C1—C2	1.457 (3)	C15—C16	1.483 (8)
C2—H2A	0.87 (4)	C15—H15A	0.9900
C2—H2B	0.94 (4)	C15—H15B	0.9900
C2—H2C	0.90 (3)	C16—O4	1.438 (10)
C3—C4	1.528 (3)	C16—H16A	0.9900
C3—H3A	0.9900	C16—H16B	0.9900
C3—H3B	0.9900	C16—H4OA	1.40 (2)
C4—H4A	0.9900	O4—H4O	0.98 (2)
C4—H4B	0.9900	O4—H4OA	1.15 (9)
C5—C6	1.531 (2)	C15A—C16A	1.531 (13)
C5—H5A	0.9900	C15A—H15C	0.9900
C5—H5B	0.9900	C15A—H15D	0.9900
C6—C7	1.518 (3)	C16A—O4A	1.390 (15)
C6—H6A	0.9900	C16A—H16C	0.9900
C6—H6B	0.9900	C16A—H16D	0.9900
C7—H7A	0.9900	O4A—H4O	1.67 (3)
C7—H7B	0.9900	O4A—H4OA	0.98 (2)

N1ⁱ—Fe1—N1	180.0	C9—C8—H8B	107.7
N1ⁱ—Fe1—P1	91.51 (4)	P1—C8—H8B	107.7
N1—Fe1—P1	88.49 (4)	H8A—C8—H8B	107.1
N1ⁱ—Fe1—P1ⁱ	88.49 (4)	C8—C9—C10	112.18 (17)
N1—Fe1—P1ⁱ	91.51 (4)	C8—C9—H9A	109.2
P1—Fe1—P1ⁱ	180.00 (3)	C10—C9—H9A	109.2
N1ⁱ—Fe1—P2ⁱ	89.90 (4)	C8—C9—H9B	109.2
N1—Fe1—P2ⁱ	90.10 (4)	C10—C9—H9B	109.2
P1—Fe1—P2ⁱ	95.813 (16)	H9A—C9—H9B	107.9
P1ⁱ—Fe1—P2ⁱ	84.187 (16)	O2—C10—C9	112.52 (17)
N1ⁱ—Fe1—P2	90.10 (4)	O2—C10—H10A	109.1
N1—Fe1—P2	89.90 (4)	C9—C10—H10A	109.1
P1—Fe1—P2	84.187 (16)	O2—C10—H10B	109.1
P1ⁱ—Fe1—P2	95.813 (16)	C9—C10—H10B	109.1
P2ⁱ—Fe1—P2	180.00 (3)	H10A—C10—H10B	107.8
C5—P1—C3	104.19 (8)	C12—C11—P2	116.53 (13)
C5—P1—C8	104.85 (8)	C12—C11—H11A	108.2
C3—P1—C8	99.48 (9)	P2—C11—H11A	108.2
C5—P1—Fe1	120.80 (6)	C12—C11—H11B	108.2
C3—P1—Fe1	105.32 (6)	P2—C11—H11B	108.2
C8—P1—Fe1	119.09 (6)	H11A—C11—H11B	107.3
C11—P2—C14	103.44 (9)	C13—C12—C11	109.88 (15)
C11—P2—C4	102.82 (9)	C13—C12—H12A	109.7
C14—P2—C4	105.10 (9)	C11—C12—H12A	109.7
C11—P2—Fe1	118.75 (6)	C13—C12—H12B	109.7
C14—P2—Fe1	116.66 (7)	C11—C12—H12B	109.7
C4—P2—Fe1	108.46 (6)	H12A—C12—H12B	108.2
C7—O1—H1O	108.1 (19)	O3—C13—C12	112.82 (16)
C10—O2—H2O	110 (2)	O3—C13—H13A	109.0
C13—O3—H3O	105.3 (17)	C12—C13—H13A	109.0
C1—N1—Fe1	178.43 (15)	O3—C13—H13B	109.0
N1—C1—C2	178.4 (2)	C12—C13—H13B	109.0
C1—C2—H2A	110 (3)	H13A—C13—H13B	107.8
C1—C2—H2B	108 (2)	C15—C14—P2	120.8 (2)
H2A—C2—H2B	113 (3)	C15—C14—H14A	107.1
C1—C2—H2C	112 (2)	P2—C14—H14A	107.1
H2A—C2—H2C	111 (3)	C15—C14—H14B	107.1
H2B—C2—H2C	104 (3)	P2—C14—H14B	107.1
C4—C3—P1	106.90 (12)	H14A—C14—H14B	106.8
C4—C3—H3A	110.3	C16—C15—C14	113.3 (4)
P1—C3—H3A	110.3	C16—C15—H15A	108.9
C4—C3—H3B	110.3	C14—C15—H15A	108.9
P1—C3—H3B	110.3	C16—C15—H15B	108.9
H3A—C3—H3B	108.6	C14—C15—H15B	108.9
C3—C4—P2	108.88 (12)	H15A—C15—H15B	107.7
C3—C4—H4A	109.9	O4—C16—C15	108.9 (6)
P2—C4—H4A	109.9	O4—C16—H16A	109.9
C3—C4—H4B	109.9	C15—C16—H16A	109.9
P2—C4—H4B	109.9	O4—C16—H16B	109.9
H4A—C4—H4B	108.3	C15—C16—H16B	109.9
C6—C5—P1	115.37 (12)	H16A—C16—H16B	108.3
C6—C5—H5A	108.4	O4—C16—H4OA	48 (4)
P1—C5—H5A	108.4	C15—C16—H4OA	157 (3)
C6—C5—H5B	108.4	H16A—C16—H4OA	85.2
P1—C5—H5B	108.4	H16B—C16—H4OA	80.6
H5A—C5—H5B	107.5	C16—O4—H4O	102.7 (19)
C7—C6—C5	112.10 (16)	C16—O4—H4OA	64.3 (16)
C7—C6—H6A	109.2	H4O—O4—H4OA	73 (5)
C5—C6—H6A	109.2	C16A—C15A—H15C	109.4
C7—C6—H6B	109.2	C16A—C15A—H15D	109.4
C5—C6—H6B	109.2	H15C—C15A—H15D	108.0
H6A—C6—H6B	107.9	O4A—C16A—C15A	108.8 (8)
O1—C7—C6	109.56 (17)	O4A—C16A—H16C	109.9
O1—C7—H7A	109.8	C15A—C16A—H16C	109.9
C6—C7—H7A	109.8	O4A—C16A—H16D	109.9
O1—C7—H7B	109.8	C15A—C16A—H16D	109.9
C6—C7—H7B	109.8	H16C—C16A—H16D	108.3
H7A—C7—H7B	108.2	C16A—O4A—H4O	105.5 (16)
C9—C8—P1	118.28 (13)	C16A—O4A—H4OA	104 (2)
C9—C8—H8A	107.7	H4O—O4A—H4OA	49 (8)
P1—C8—H8A	107.7

N1ⁱ—Fe1—P1—C5	−126.74 (8)	Fe1—P1—C3—C4	−52.35 (13)
N1—Fe1—P1—C5	53.26 (8)	P1—C3—C4—P2	52.78 (15)
P2ⁱ—Fe1—P1—C5	−36.69 (7)	C11—P2—C4—C3	−157.24 (13)
P2—Fe1—P1—C5	143.31 (7)	C14—P2—C4—C3	94.80 (14)
N1ⁱ—Fe1—P1—C3	115.91 (8)	Fe1—P2—C4—C3	−30.65 (14)
N1—Fe1—P1—C3	−64.09 (8)	C3—P1—C5—C6	−45.93 (17)
P2ⁱ—Fe1—P1—C3	−154.03 (6)	C8—P1—C5—C6	58.13 (16)
P2—Fe1—P1—C3	25.97 (6)	Fe1—P1—C5—C6	−163.84 (12)
N1ⁱ—Fe1—P1—C8	5.56 (8)	P1—C5—C6—C7	−170.84 (15)
N1—Fe1—P1—C8	−174.44 (8)	C5—C6—C7—O1	−64.9 (2)
P2ⁱ—Fe1—P1—C8	95.61 (7)	C5—P1—C8—C9	53.06 (17)
P2—Fe1—P1—C8	−84.39 (7)	C3—P1—C8—C9	160.61 (15)
N1ⁱ—Fe1—P2—C11	24.40 (9)	Fe1—P1—C8—C9	−85.84 (16)
N1—Fe1—P2—C11	−155.60 (9)	P1—C8—C9—C10	−179.89 (14)
P1—Fe1—P2—C11	115.91 (8)	C8—C9—C10—O2	−70.4 (2)
P1ⁱ—Fe1—P2—C11	−64.09 (8)	C14—P2—C11—C12	65.29 (17)
N1ⁱ—Fe1—P2—C14	149.30 (9)	C4—P2—C11—C12	−43.92 (17)
N1—Fe1—P2—C14	−30.70 (9)	Fe1—P2—C11—C12	−163.61 (12)
P1—Fe1—P2—C14	−119.19 (8)	P2—C11—C12—C13	−178.05 (14)
P1ⁱ—Fe1—P2—C14	60.81 (8)	C11—C12—C13—O3	−175.41 (17)
N1ⁱ—Fe1—P2—C4	−92.34 (8)	C11—P2—C14—C15	−97.4 (3)
N1—Fe1—P2—C4	87.66 (8)	C4—P2—C14—C15	10.1 (3)
P1—Fe1—P2—C4	−0.84 (7)	Fe1—P2—C14—C15	130.3 (3)
P1ⁱ—Fe1—P2—C4	179.16 (7)	P2—C14—C15—C16	−179.9 (5)
C5—P1—C3—C4	179.56 (12)	C14—C15—C16—O4	−71.1 (7)
C8—P1—C3—C4	71.49 (14)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Cl1	0.93 (2)	2.13 (2)	3.0493 (16)	173 (3)
O2—H2O···Cl1ⁱⁱ	0.98 (2)	2.23 (2)	3.1777 (19)	164 (3)
O3—H3O···O1ⁱⁱ	0.92 (2)	1.84 (2)	2.741 (2)	164 (2)
O4—H4O···Cl1ⁱⁱⁱ	0.98 (2)	1.95 (2)	2.931 (6)	177 (3)
O4A—H4OA···Cl1ⁱⁱⁱ	0.98 (2)	2.84 (11)	3.490 (10)	125 (9)

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

Experimental details

Crystal data
Chemical formula	[Fe(C₂H₃N)₂(C₁₄H₃₂O₄P₂)₂]Cl₂
M_r	861.53
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	18.3024 (12), 11.5220 (8), 19.8413 (13)
V (Å³)	4184.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.22 × 0.18 × 0.17

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.863, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	24288, 4571, 4122
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.04
No. of reflections	4571
No. of parameters	269
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.88, −1.01

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

Selected bond lengths (Å) top

Fe1—N1	1.9077 (14)	Fe1—P2	2.3049 (4)
Fe1—P1	2.2884 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Cl1	0.928 (17)	2.126 (18)	3.0493 (16)	173 (3)
O2—H2O···Cl1ⁱ	0.976 (18)	2.23 (2)	3.1777 (19)	164 (3)
O3—H3O···O1ⁱ	0.924 (17)	1.841 (18)	2.741 (2)	164 (2)
O4—H4O···Cl1ⁱⁱ	0.98 (2)	1.95 (2)	2.931 (6)	177 (3)
O4A—H4OA···Cl1ⁱⁱ	0.98 (2)	2.84 (11)	3.490 (10)	125 (9)

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

Acknowledgements

We thank the NSF (CHE-0809393) for funding.

References

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