Ferrocenyl­phospho­nic acid

Yang, B.-Z.; Xu, C.; Duan, T.-K.; Chen, Q.; Zhang, Q.-F.

doi:10.1107/S1600536811027206

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1087

doi:10.1107/S1600536811027206

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Ferrocenylphosphonic acid

Bao-Zhang Yang,^a Chao Xu,^a Tai-Ke Duan,^a Qun Chen ^b and Qian-Feng Zhang ^a,^b ^*

^aInstitute of Molecular Engineering and Applied Chemsitry, Anhui University of Technology, Ma'anshan, Anhui 243002, People's Republic of China, and ^bDepartment of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, People's Republic of China
^*Correspondence e-mail: zhangqf@ahut.edu.cn

(Received 10 June 2011; accepted 7 July 2011; online 13 July 2011)

In the title compound, [Fe(C₅H₅)(C₅H₆O₃P)], the phosphate group is bonded to the ferrocene unit with a P—C bond length of 1.749 (3) Å. In the crystal, six ferrocenylphosphonic acid molecules are connected by 12 strong intermolecular O—H⋯O hydrogen bonds, leading to the formation of a highly distorted octahedral cage. The volume of the octahedral cage is about 270 Å³.

Related literature

For background to ferrocenylphosphonates and ferrocenyl derivatives, see: Alley & Henderson (2001 ); Henderson & Alley (2001 ); Oms et al. (2004a ,b , 2005 ).

Experimental

Crystal data

[Fe(C₅H₅)(C₅H₆O₃P)]
M_r = 266.01
Trigonal, $[R \overline 3]$
a = 19.7329 (9) Å
c = 14.7338 (4) Å
V = 4968.5 (5) Å³
Z = 18
Mo Kα radiation
μ = 1.49 mm⁻¹
T = 296 K
0.20 × 0.16 × 0.11 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.755, T_max = 0.853
26557 measured reflections
2500 independent reflections
1956 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.098
S = 1.03
2500 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.76	2.559 (3)	165
O3—H3⋯O1ⁱⁱ	0.82	1.79	2.557 (3)	154
Symmetry codes: (i) -x+y+1, -x+1, z; (ii) $[y+{\script{1\over 3}}, -x+y+{\script{2\over 3}}, -z-{\script{1\over 3}}]$ .

Data collection: SMART (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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027206/hy2442sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027206/hy2442Isup2.hkl

checkCIF report

Comment top

Ferrocene and ferrocenyl derivatives are well known for their redox activities and immobilization behaviors with metal ions (Alley & Henderson, 2001; Oms et al., 2004a). Ferrocenylphosphonates are ideal building block candidates for incorporation with transition metal ions due to the strong coordination behavior of P═O groups and the high stability of the formed P—O—M (M = metal ion) bonds (Henderson & Alley, 2001; Oms et al., 2005). However, only a few metal ferrocenylphosphonate compounds have been reported from related literature, probably due to the low yield of ferrocenylphosphonic acid in its synthesis (Oms et al., 2004b). In this paper, we reported the preparation of the crystalline ferrocenylphosphonic acid in a relatively high yield and its crystal structure.

The molecular structure of the title compound is depicted in Fig. 1. The Fe atom lies between two cyclopentadiene (Cp) planes, with an average Fe—Cp(centroid) of 1.649 (2) Å. The [PO(OH)₂] group is bonded to the ferrocene molecule via a P—C bond with a bond length of 1.749 (3) Å. The average bond length of P—O [1.543 (2) Å] is obviously longer than that of P═O [1.498 (2) Å]. The P atom is located in a slightly distorted tetrahedral environment, with the O—P—O and C—P—O bond angles in the ranges of 110.01 (13)–112.81 (13)° and 104.65 (13)—112.69 (13)°, respectively. The bond lengths and angles in the title compound are similar to those found in [FcCH₂P(O)(OH)₂] [Fc = (η⁵-C₅H₄)Fe(η⁵-C₅H₅)] (Oms et al., 2004b). It is interesting to note that six ferrocenylphosphonic acid molecules are connected by twelve strong intermolecular O—H···O hydrogen bonds (Table 1), leading to the formation of a highly distorted octahedral cage, as shown in Fig. 2. The volume of the cavity of the octahedral cage is about 270 Å³. The crystal packing is stabilized by these intermolecular hydrogen-bonding interactions.

Related literature top

For background to ferrocenylphosphonates and ferrocenyl derivatives, see: Alley & Henderson (2001); Henderson & Alley (2001); Oms et al. (2004a,b, 2005).

Experimental top

Ferrocenylphosphonic acid was prepared according to literature (Oms et al., 2004b). All synthesis was taken in oven-dried glassware under a nitrogen atmosphere using standard Schlenk techniques. Me₃SiBr (4.5 g, 30 mmol) was dropwise added to a solution of diethyl ferrocenylphosphonate (3.18 g, 10 mmol) in 20 ml CH₂Cl₂ at room temperature. After the mixture was stirred for 12 h, the solvent was removed under low pressure and the oil residues was dissolved in 20 ml MeCN and then treated with 5 ml H₂O to precipitate the title compound. The precipitate was collected and washed with CH₂Cl₂ and Et₂O (yield: 2.05 g, 80%). Single crystals suitable for X-ray analysis were obtained by recrystallization from methanol/Et₂O. Analysis, calculated, for C₁₀H₁₁FeO₃P: C 45.1, H 4.16%; found: C 45.0, H 4.04%.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Six ferrocenylphosphonic acid molecules are connected by intermolecular O—H···O hydrogen bonds (dashed lines), forming a distorted octahedral cage. [Symmetry codes: (i) 1/3+y, 2/3-x+y, -1/3-z; (ii) 1/3+x-y, -1/3+x, -1/3-z; (iii) 3/4-x, 2/3-y, -1/3-z; (iv) 1-y, x-y, z; (v) 1-x+y, 1-x, z.]

Ferrocenylphosphonic acid top

Crystal data top

[Fe(C₅H₅)(C₅H₆O₃P)]	D_x = 1.600 Mg m⁻³
M_r = 266.01	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 5069 reflections
Hall symbol: -R 3	θ = 2.8–22.9°
a = 19.7329 (9) Å	µ = 1.49 mm⁻¹
c = 14.7338 (4) Å	T = 296 K
V = 4968.5 (5) Å³	Block, red
Z = 18	0.20 × 0.16 × 0.11 mm
F(000) = 2448

Data collection top

Bruker APEX CCD diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	1956 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
T_min = 0.755, T_max = 0.853	k = −25→25
26557 measured reflections	l = −19→19

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.041P)² + 9.0107P] where P = (F_o² + 2F_c²)/3
2500 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Fe(C₅H₅)(C₅H₆O₃P)]	Z = 18
M_r = 266.01	Mo Kα radiation
Trigonal, R3	µ = 1.49 mm⁻¹
a = 19.7329 (9) Å	T = 296 K
c = 14.7338 (4) Å	0.20 × 0.16 × 0.11 mm
V = 4968.5 (5) Å³

Data collection top

Bruker APEX CCD diffractometer	2500 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1956 reflections with I > 2σ(I)
T_min = 0.755, T_max = 0.853	R_int = 0.044
26557 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.65 e Å⁻³
2500 reflections	Δρ_min = −0.51 e Å⁻³
136 parameters

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

	x	y	z	U_iso*/U_eq
Fe1	0.62280 (2)	0.51797 (2)	0.15180 (3)	0.05726 (16)
P1	0.69358 (4)	0.48371 (4)	−0.03885 (4)	0.04430 (18)
O1	0.61726 (12)	0.41531 (10)	−0.06806 (12)	0.0603 (5)
O2	0.74425 (14)	0.45939 (14)	0.01591 (14)	0.0750 (7)
H2	0.7540	0.4309	−0.0152	0.113*
O3	0.73972 (13)	0.53301 (11)	−0.12206 (14)	0.0659 (6)
H3	0.7485	0.5058	−0.1567	0.099*
C1	0.68160 (15)	0.54767 (14)	0.03269 (19)	0.0503 (6)
C2	0.73203 (19)	0.59400 (17)	0.1052 (2)	0.0733 (9)
H2A	0.7784	0.5961	0.1224	0.088*
C3	0.6995 (3)	0.6354 (2)	0.1457 (3)	0.1043 (17)
H3A	0.7200	0.6690	0.1952	0.125*
C4	0.6307 (3)	0.6176 (2)	0.0989 (3)	0.1058 (17)
H4	0.5984	0.6381	0.1118	0.127*
C5	0.6182 (2)	0.5633 (2)	0.0289 (3)	0.0745 (9)
H5	0.5766	0.5418	−0.0118	0.089*
C6	0.6355 (3)	0.4572 (3)	0.2550 (3)	0.0955 (12)
H6	0.6831	0.4657	0.2776	0.115*
C7	0.5957 (4)	0.4929 (3)	0.2849 (3)	0.121 (2)
H7	0.6112	0.5296	0.3314	0.145*
C8	0.5269 (3)	0.4645 (3)	0.2330 (4)	0.120 (2)
H8	0.4888	0.4788	0.2387	0.144*
C9	0.5268 (2)	0.4100 (2)	0.1706 (3)	0.0803 (10)
H9	0.4887	0.3818	0.1273	0.096*
C10	0.5939 (2)	0.40671 (18)	0.1861 (2)	0.0677 (8)
H10	0.6086	0.3752	0.1548	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0606 (3)	0.0423 (2)	0.0670 (3)	0.02441 (19)	0.0177 (2)	−0.00354 (18)
P1	0.0532 (4)	0.0378 (3)	0.0442 (4)	0.0245 (3)	−0.0017 (3)	−0.0026 (3)
O1	0.0731 (13)	0.0404 (10)	0.0487 (10)	0.0143 (9)	−0.0092 (9)	−0.0005 (8)
O2	0.1037 (17)	0.1009 (17)	0.0606 (12)	0.0813 (15)	−0.0152 (12)	−0.0171 (12)
O3	0.0780 (14)	0.0469 (11)	0.0628 (12)	0.0238 (10)	0.0178 (10)	0.0001 (9)
C1	0.0497 (14)	0.0372 (13)	0.0620 (16)	0.0202 (11)	0.0101 (12)	0.0008 (11)
C2	0.0607 (18)	0.0508 (17)	0.081 (2)	0.0074 (14)	0.0152 (16)	−0.0202 (15)
C3	0.118 (3)	0.0473 (19)	0.119 (3)	0.020 (2)	0.057 (3)	−0.019 (2)
C4	0.138 (4)	0.061 (2)	0.146 (4)	0.070 (3)	0.084 (3)	0.035 (2)
C5	0.079 (2)	0.068 (2)	0.096 (2)	0.0522 (18)	0.0258 (19)	0.0260 (18)
C6	0.107 (3)	0.098 (3)	0.065 (2)	0.039 (3)	−0.011 (2)	0.005 (2)
C7	0.180 (6)	0.080 (3)	0.076 (3)	0.045 (3)	0.052 (3)	−0.007 (2)
C8	0.120 (4)	0.098 (3)	0.173 (5)	0.076 (3)	0.103 (4)	0.068 (3)
C9	0.060 (2)	0.0574 (19)	0.103 (3)	0.0144 (16)	0.0086 (18)	0.0191 (19)
C10	0.092 (2)	0.0541 (17)	0.0598 (18)	0.0391 (17)	0.0121 (17)	0.0068 (14)

Geometric parameters (Å, º) top

Fe1—C1	2.022 (3)	C2—C3	1.400 (5)
Fe1—C7	2.028 (4)	C2—H2A	0.9300
Fe1—C6	2.028 (4)	C3—C4	1.401 (7)
Fe1—C8	2.032 (4)	C3—H3A	0.9300
Fe1—C2	2.033 (3)	C4—C5	1.417 (6)
Fe1—C10	2.037 (3)	C4—H4	0.9300
Fe1—C3	2.040 (4)	C5—H5	0.9300
Fe1—C9	2.041 (3)	C6—C7	1.366 (7)
Fe1—C5	2.042 (4)	C6—C10	1.371 (5)
Fe1—C4	2.046 (4)	C6—H6	0.9300
P1—O1	1.4975 (19)	C7—C8	1.407 (7)
P1—O2	1.537 (2)	C7—H7	0.9300
P1—O3	1.547 (2)	C8—C9	1.414 (6)
P1—C1	1.749 (3)	C8—H8	0.9300
O2—H2	0.8200	C9—C10	1.377 (5)
O3—H3	0.8200	C9—H9	0.9300
C1—C5	1.432 (4)	C10—H10	0.9300
C1—C2	1.435 (4)

C1—Fe1—C7	162.4 (2)	C2—C1—Fe1	69.69 (17)
C1—Fe1—C6	126.80 (16)	P1—C1—Fe1	125.37 (14)
C7—Fe1—C6	39.4 (2)	C3—C2—C1	108.4 (4)
C1—Fe1—C8	155.8 (2)	C3—C2—Fe1	70.2 (2)
C7—Fe1—C8	40.5 (2)	C1—C2—Fe1	68.87 (16)
C6—Fe1—C8	67.0 (2)	C3—C2—H2A	125.8
C1—Fe1—C2	41.44 (12)	C1—C2—H2A	125.8
C7—Fe1—C2	124.0 (2)	Fe1—C2—H2A	126.7
C6—Fe1—C2	106.88 (18)	C2—C3—C4	108.2 (4)
C8—Fe1—C2	161.9 (2)	C2—C3—Fe1	69.62 (18)
C1—Fe1—C10	109.79 (11)	C4—C3—Fe1	70.2 (2)
C7—Fe1—C10	66.42 (16)	C2—C3—H3A	125.9
C6—Fe1—C10	39.41 (15)	C4—C3—H3A	125.9
C8—Fe1—C10	66.91 (15)	Fe1—C3—H3A	125.9
C2—Fe1—C10	120.09 (15)	C3—C4—C5	109.3 (3)
C1—Fe1—C3	68.93 (13)	C3—C4—Fe1	69.7 (2)
C7—Fe1—C3	105.94 (19)	C5—C4—Fe1	69.55 (18)
C6—Fe1—C3	117.6 (2)	C3—C4—H4	125.4
C8—Fe1—C3	125.81 (19)	C5—C4—H4	125.4
C2—Fe1—C3	40.21 (14)	Fe1—C4—H4	126.9
C10—Fe1—C3	152.2 (2)	C4—C5—C1	107.0 (4)
C1—Fe1—C9	121.25 (14)	C4—C5—Fe1	69.9 (2)
C7—Fe1—C9	67.7 (2)	C1—C5—Fe1	68.65 (17)
C6—Fe1—C9	66.79 (17)	C4—C5—H5	126.5
C8—Fe1—C9	40.61 (19)	C1—C5—H5	126.5
C2—Fe1—C9	154.70 (15)	Fe1—C5—H5	126.5
C10—Fe1—C9	39.46 (15)	C7—C6—C10	108.9 (4)
C3—Fe1—C9	164.92 (17)	C7—C6—Fe1	70.3 (3)
C1—Fe1—C5	41.25 (12)	C10—C6—Fe1	70.6 (2)
C7—Fe1—C5	154.2 (2)	C7—C6—H6	125.6
C6—Fe1—C5	165.83 (17)	C10—C6—H6	125.6
C8—Fe1—C5	121.1 (2)	Fe1—C6—H6	125.1
C2—Fe1—C5	68.93 (15)	C6—C7—C8	107.9 (4)
C10—Fe1—C5	129.96 (14)	C6—C7—Fe1	70.3 (2)
C3—Fe1—C5	68.53 (19)	C8—C7—Fe1	69.9 (3)
C9—Fe1—C5	110.85 (16)	C6—C7—H7	126.0
C1—Fe1—C4	68.53 (12)	C8—C7—H7	126.0
C7—Fe1—C4	119.1 (2)	Fe1—C7—H7	125.3
C6—Fe1—C4	151.7 (2)	C7—C8—C9	106.9 (4)
C8—Fe1—C4	109.11 (17)	C7—C8—Fe1	69.6 (2)
C2—Fe1—C4	67.60 (18)	C9—C8—Fe1	70.0 (2)
C10—Fe1—C4	167.3 (2)	C7—C8—H8	126.5
C3—Fe1—C4	40.11 (19)	C9—C8—H8	126.5
C9—Fe1—C4	129.7 (2)	Fe1—C8—H8	125.5
C5—Fe1—C4	40.57 (17)	C10—C9—C8	107.0 (4)
O1—P1—O2	112.81 (13)	C10—C9—Fe1	70.09 (19)
O1—P1—O3	110.46 (11)	C8—C9—Fe1	69.4 (2)
O2—P1—O3	110.01 (13)	C10—C9—H9	126.5
O1—P1—C1	112.69 (13)	C8—C9—H9	126.5
O2—P1—C1	104.65 (13)	Fe1—C9—H9	125.6
O3—P1—C1	105.86 (12)	C6—C10—C9	109.2 (4)
P1—O2—H2	109.5	C6—C10—Fe1	70.0 (2)
P1—O3—H3	109.5	C9—C10—Fe1	70.44 (19)
C5—C1—C2	107.1 (3)	C6—C10—H10	125.4
C5—C1—P1	125.4 (2)	C9—C10—H10	125.4
C2—C1—P1	127.4 (2)	Fe1—C10—H10	125.8
C5—C1—Fe1	70.10 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.76	2.559 (3)	165
O3—H3···O1ⁱⁱ	0.82	1.79	2.557 (3)	154

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) y+1/3, −x+y+2/3, −z−1/3.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₅H₆O₃P)]
M_r	266.01
Crystal system, space group	Trigonal, R3
Temperature (K)	296
a, c (Å)	19.7329 (9), 14.7338 (4)
V (Å³)	4968.5 (5)
Z	18
Radiation type	Mo Kα
µ (mm⁻¹)	1.49
Crystal size (mm)	0.20 × 0.16 × 0.11

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.755, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	26557, 2500, 1956
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.098, 1.03
No. of reflections	2500
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.51

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.76	2.559 (3)	165
O3—H3···O1ⁱⁱ	0.82	1.79	2.557 (3)	154

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) y+1/3, −x+y+2/3, −z−1/3.

Acknowledgements

This work was supported by the Program for New Century Excellent Talents in Universities of China (NCET-08–0618).

References

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