(R)-2-Methyl­piperazine-1,4-diium diaqua­tetra­chloridoferrate(II)

Peng, C.-H.; Li, Y.-P.

doi:10.1107/S1600536810035506

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1224

doi:10.1107/S1600536810035506

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(R)-2-Methylpiperazine-1,4-diium diaquatetrachloridoferrate(II)

Cong-Hu Peng ^a ^* and Yun-Peng Li ^b

^aDepartment of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China, and ^bAnyang Administration of Work Safety, Henan Province 455000, People's Republic of China
^*Correspondence e-mail: ayitpch@yahoo.com.cn

(Received 17 August 2010; accepted 3 September 2010; online 8 September 2010)

In the title salt, (C₅H₁₄N₂)[FeCl₄(H₂O)₂], the Fe^II cation is coordinated by four Cl⁻ anions and two water molecules in a distorted octahedral geometry. The piperazine ring adopts a normal chair conformation. Intermolecular N—H⋯Cl, N—H⋯(Cl,Cl) and O—H⋯Cl hydrogen bonding is present in the crystal structure.

Related literature

For hydrogen bonding in metal–chlorido complexes, see: Brammer et al. (2001 ); Bremner & Harrison (2003 ); Kefi & Nasr (2005 ). For the crystal structure of a related compound, piperazindiium tetrachloridozincate(II), see: Sutherland & Harrison (2009 ).

Experimental

Crystal data

(C₅H₁₄N₂)[FeCl₄(H₂O)₂]
M_r = 335.86
Monoclinic, P 2₁
a = 8.6013 (17) Å
b = 6.4495 (13) Å
c = 12.024 (2) Å
β = 101.64 (3)°
V = 653.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.95 mm⁻¹
T = 291 K
0.28 × 0.24 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.8, T_max = 0.9
6105 measured reflections
2558 independent reflections
2456 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.050
S = 1.08
2558 reflections
129 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1156 Friedel pairs
Flack parameter: 0.010 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl2ⁱ	0.90	2.62	3.443 (2)	152
N1—H1C⋯Cl4ⁱ	0.90	2.81	3.379 (3)	122
N1—H1D⋯Cl4ⁱⁱ	0.90	2.28	3.169 (3)	167
N2—H2C⋯Cl1ⁱⁱⁱ	0.90	2.26	3.145 (3)	168
N2—H2D⋯Cl3	0.90	2.45	3.275 (2)	152
O1—H11⋯Cl3^iv	0.82	2.33	3.147 (2)	173
O1—H12⋯Cl3^v	0.89	2.24	3.127 (2)	176
O2—H21⋯Cl2ⁱⁱⁱ	0.93	2.19	3.119 (2)	174
O2—H22⋯Cl2^vi	0.86	2.31	3.1590 (18)	168
Symmetry codes: (i) x-1, y-1, z; (ii) x-1, y, z; (iii) x, y-1, z; (iv) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (v) x, y+1, z; (vi) $[-x+2, y-{\script{1\over 2}}, -z+2]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035506/xu5019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035506/xu5019Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to hydrogen bonding networks in molecular salts containing metal-chlorido complexes (Brammer et al., 2001; Bremner & Harrison, 2003; Kefi & Nasr, 2005). The crystal structure of piperazinediium tetrachloridozincate(II) has been reported (Sutherland & Harrison, 2009). The construction of new members of this family is an important direction in the development of coordination chemistry. We report here the crystal structure of the title compound.

The crystal structure of the title compound (Fig. 1) contains the protonated piperazindiium cations and trans-Fe(H₂O)₂Cl₄ octahedral anions. The piperazine ring adopts a chair conformation. An extensive network of N—H···Cl, N—H··· (Cl,Cl) and O—H···Cl hydrogen bonds results in a structure with a three-dimensional hydrogen-bond network (Fig. 2).

Related literature top

For hydrogen bonding in metal–chlorido complexes, see: Brammer et al. (2001); Bremner & Harrison (2003); Kefi & Nasr (2005). For the crystal structure of a related compound, piperazindiium tetrachloridozincate(II), see: Sutherland & Harrison (2009).

Experimental top

(R)-2-Methylpiperazine (2 mmol, 0.2 g), FeCl₃(2 mmol, 0.31 g), KI (1 mmol, 0.17), I₂ (0.5 mmol, 0.13 g) and 5% aqueous HCl (5 ml) were dissolved in 10 ml water, the solution was heated to 353 K (0.5 h), forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed after 6 d.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level
	Fig. 2. The packing viewed along the a axis. Hydrogen bonds are drawn as dashed lines

(R)-2-Methylpiperazine-1,4-diium diaquatetrachloridoferrate(II) top

Crystal data top

(C₅H₁₄N₂)[FeCl₄(H₂O)₂]	F(000) = 344
M_r = 335.86	D_x = 1.707 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2456 reflections
a = 8.6013 (17) Å	θ = 3.2–26.0°
b = 6.4495 (13) Å	µ = 1.95 mm⁻¹
c = 12.024 (2) Å	T = 291 K
β = 101.64 (3)°	Block, yellow
V = 653.3 (2) Å³	0.28 × 0.24 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	2558 independent reflections
Radiation source: fine-focus sealed tube	2456 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.8, T_max = 0.9	l = −14→14
6105 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0172P)² + 0.0801P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.050	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.19 e Å⁻³
2558 reflections	Δρ_min = −0.24 e Å⁻³
129 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.116 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1156 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.010 (14)

Crystal data top

(C₅H₁₄N₂)[FeCl₄(H₂O)₂]	V = 653.3 (2) Å³
M_r = 335.86	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.6013 (17) Å	µ = 1.95 mm⁻¹
b = 6.4495 (13) Å	T = 291 K
c = 12.024 (2) Å	0.28 × 0.24 × 0.20 mm
β = 101.64 (3)°

Data collection top

Rigaku SCXmini diffractometer	2558 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2456 reflections with I > 2σ(I)
T_min = 0.8, T_max = 0.9	R_int = 0.025
6105 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.050	Δρ_max = 0.19 e Å⁻³
S = 1.08	Δρ_min = −0.24 e Å⁻³
2558 reflections	Absolute structure: Flack (1983), 1156 Friedel pairs
129 parameters	Absolute structure parameter: 0.010 (14)
1 restraint

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	0.92584 (4)	0.85265 (6)	0.73702 (3)	0.02261 (10)
Cl1	0.63527 (7)	0.89798 (9)	0.69296 (5)	0.03230 (17)
Cl2	0.95176 (8)	1.16607 (10)	0.86527 (5)	0.03236 (16)
Cl3	0.88976 (8)	0.53109 (10)	0.60858 (5)	0.03094 (16)
Cl4	1.21704 (8)	0.81475 (10)	0.77621 (7)	0.0463 (2)
N1	0.2717 (2)	0.3313 (4)	0.75683 (15)	0.0271 (5)
H1C	0.1922	0.2493	0.7690	0.033*
H1D	0.2396	0.4639	0.7587	0.033*
N2	0.5845 (2)	0.3786 (4)	0.71209 (16)	0.0309 (5)
H2C	0.6147	0.2453	0.7103	0.037*
H2D	0.6648	0.4588	0.6994	0.037*
O1	0.9382 (2)	1.0515 (3)	0.59861 (15)	0.0433 (5)
H11	0.9818	1.0347	0.5446	0.065*
H12	0.9188	1.1870	0.6013	0.065*
O2	0.91049 (19)	0.6462 (3)	0.87073 (13)	0.0303 (4)
H21	0.9234	0.5037	0.8634	0.045*
H22	0.9545	0.6697	0.9406	0.045*
C1	0.4148 (3)	0.2974 (4)	0.84969 (18)	0.0242 (5)
H1A	0.4447	0.1506	0.8508	0.029*
C2	0.5510 (3)	0.4269 (4)	0.82553 (19)	0.0271 (6)
H2A	0.5248	0.5727	0.8289	0.032*
H2B	0.6452	0.4003	0.8833	0.032*
C3	0.4415 (3)	0.4152 (5)	0.6213 (2)	0.0339 (6)
H3A	0.4649	0.3796	0.5480	0.041*
H3B	0.4127	0.5607	0.6198	0.041*
C4	0.3052 (3)	0.2856 (4)	0.64264 (19)	0.0317 (6)
H4A	0.2115	0.3146	0.5849	0.038*
H4B	0.3308	0.1398	0.6379	0.038*
C5	0.3760 (3)	0.3539 (5)	0.9633 (2)	0.0399 (6)
H5A	0.3347	0.4926	0.9600	0.060*
H5B	0.4705	0.3458	1.0213	0.060*
H5C	0.2981	0.2593	0.9807	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02514 (17)	0.01809 (17)	0.02560 (17)	−0.00031 (12)	0.00748 (12)	0.00170 (13)
Cl1	0.0251 (3)	0.0260 (4)	0.0452 (4)	0.0010 (2)	0.0056 (2)	−0.0016 (3)
Cl2	0.0461 (4)	0.0235 (3)	0.0255 (3)	0.0002 (3)	0.0024 (3)	−0.0033 (3)
Cl3	0.0468 (4)	0.0231 (3)	0.0269 (3)	0.0018 (3)	0.0171 (3)	−0.0002 (3)
Cl4	0.0270 (4)	0.0260 (5)	0.0866 (6)	0.0004 (3)	0.0131 (3)	0.0033 (4)
N1	0.0224 (10)	0.0257 (12)	0.0326 (11)	−0.0024 (9)	0.0039 (8)	0.0032 (10)
N2	0.0295 (11)	0.0285 (13)	0.0388 (11)	−0.0037 (10)	0.0163 (8)	−0.0018 (11)
O1	0.0727 (14)	0.0263 (10)	0.0418 (11)	0.0091 (10)	0.0376 (10)	0.0080 (9)
O2	0.0425 (10)	0.0245 (10)	0.0224 (8)	−0.0018 (8)	0.0033 (7)	0.0017 (8)
C1	0.0243 (12)	0.0214 (14)	0.0249 (12)	−0.0003 (10)	0.0005 (9)	0.0041 (10)
C2	0.0235 (12)	0.0272 (15)	0.0300 (13)	−0.0037 (11)	0.0044 (10)	−0.0014 (11)
C3	0.0438 (15)	0.0347 (16)	0.0247 (12)	−0.0036 (12)	0.0106 (10)	0.0005 (11)
C4	0.0350 (14)	0.0298 (15)	0.0273 (13)	−0.0028 (11)	−0.0007 (10)	−0.0031 (11)
C5	0.0432 (15)	0.0486 (17)	0.0298 (13)	−0.0074 (14)	0.0122 (11)	0.0019 (13)

Geometric parameters (Å, º) top

Fe1—O2	2.1122 (17)	O2—H21	0.9315
Fe1—O1	2.1205 (18)	O2—H22	0.8622
Fe1—Cl1	2.4654 (9)	C1—C2	1.514 (3)
Fe1—Cl4	2.4655 (8)	C1—C5	1.515 (3)
Fe1—Cl2	2.5249 (9)	C1—H1A	0.9800
Fe1—Cl3	2.5669 (8)	C2—H2A	0.9700
N1—C4	1.488 (3)	C2—H2B	0.9700
N1—C1	1.502 (3)	C3—C4	1.503 (3)
N1—H1C	0.9000	C3—H3A	0.9700
N1—H1D	0.9000	C3—H3B	0.9700
N2—C2	1.483 (3)	C4—H4A	0.9700
N2—C3	1.490 (3)	C4—H4B	0.9700
N2—H2C	0.9000	C5—H5A	0.9600
N2—H2D	0.9000	C5—H5B	0.9600
O1—H11	0.8195	C5—H5C	0.9600
O1—H12	0.8919

O2—Fe1—O1	177.97 (9)	H21—O2—H22	103.2
O2—Fe1—Cl1	91.26 (5)	N1—C1—C2	109.07 (19)
O1—Fe1—Cl1	88.22 (6)	N1—C1—C5	109.81 (19)
O2—Fe1—Cl4	90.52 (5)	C2—C1—C5	111.1 (2)
O1—Fe1—Cl4	90.00 (6)	N1—C1—H1A	108.9
Cl1—Fe1—Cl4	178.22 (3)	C2—C1—H1A	108.9
O2—Fe1—Cl2	92.94 (5)	C5—C1—H1A	108.9
O1—Fe1—Cl2	89.03 (6)	N2—C2—C1	111.2 (2)
Cl1—Fe1—Cl2	89.83 (3)	N2—C2—H2A	109.4
Cl4—Fe1—Cl2	90.09 (3)	C1—C2—H2A	109.4
O2—Fe1—Cl3	85.99 (5)	N2—C2—H2B	109.4
O1—Fe1—Cl3	92.03 (6)	C1—C2—H2B	109.4
Cl1—Fe1—Cl3	88.41 (3)	H2A—C2—H2B	108.0
Cl4—Fe1—Cl3	91.70 (3)	N2—C3—C4	110.1 (2)
Cl2—Fe1—Cl3	177.92 (3)	N2—C3—H3A	109.6
C4—N1—C1	112.03 (19)	C4—C3—H3A	109.6
C4—N1—H1C	109.2	N2—C3—H3B	109.6
C1—N1—H1C	109.2	C4—C3—H3B	109.6
C4—N1—H1D	109.2	H3A—C3—H3B	108.2
C1—N1—H1D	109.2	N1—C4—C3	110.5 (2)
H1C—N1—H1D	107.9	N1—C4—H4A	109.5
C2—N2—C3	110.8 (2)	C3—C4—H4A	109.5
C2—N2—H2C	109.5	N1—C4—H4B	109.5
C3—N2—H2C	109.5	C3—C4—H4B	109.5
C2—N2—H2D	109.5	H4A—C4—H4B	108.1
C3—N2—H2D	109.5	C1—C5—H5A	109.5
H2C—N2—H2D	108.1	C1—C5—H5B	109.5
Fe1—O1—H11	130.2	H5A—C5—H5B	109.5
Fe1—O1—H12	121.6	C1—C5—H5C	109.5
H11—O1—H12	106.1	H5A—C5—H5C	109.5
Fe1—O2—H21	121.5	H5B—C5—H5C	109.5
Fe1—O2—H22	123.2

C4—N1—C1—C2	55.9 (3)	C5—C1—C2—N2	−177.4 (2)
C4—N1—C1—C5	177.8 (2)	C2—N2—C3—C4	−57.9 (3)
C3—N2—C2—C1	58.3 (3)	C1—N1—C4—C3	−56.9 (3)
N1—C1—C2—N2	−56.3 (3)	N2—C3—C4—N1	56.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl2ⁱ	0.90	2.62	3.443 (2)	152
N1—H1C···Cl4ⁱ	0.90	2.81	3.379 (3)	122
N1—H1D···Cl4ⁱⁱ	0.90	2.28	3.169 (3)	167
N2—H2C···Cl1ⁱⁱⁱ	0.90	2.26	3.145 (3)	168
N2—H2D···Cl3	0.90	2.45	3.275 (2)	152
O1—H11···Cl3^iv	0.82	2.33	3.147 (2)	173
O1—H12···Cl3^v	0.89	2.24	3.127 (2)	176
O2—H21···Cl2ⁱⁱⁱ	0.93	2.19	3.119 (2)	174
O2—H22···Cl2^vi	0.86	2.31	3.1590 (18)	168

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

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[FeCl₄(H₂O)₂]
M_r	335.86
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	291
a, b, c (Å)	8.6013 (17), 6.4495 (13), 12.024 (2)
β (°)	101.64 (3)
V (Å³)	653.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.8, 0.9
No. of measured, independent and observed [I > 2σ(I)] reflections	6105, 2558, 2456
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.050, 1.08
No. of reflections	2558
No. of parameters	129
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24
Absolute structure	Flack (1983), 1156 Friedel pairs
Absolute structure parameter	0.010 (14)

Computer programs: CrystalClear (Rigaku, 2005), 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
N1—H1C···Cl2ⁱ	0.90	2.62	3.443 (2)	152
N1—H1C···Cl4ⁱ	0.90	2.81	3.379 (3)	122
N1—H1D···Cl4ⁱⁱ	0.90	2.28	3.169 (3)	167
N2—H2C···Cl1ⁱⁱⁱ	0.90	2.26	3.145 (3)	168
N2—H2D···Cl3	0.90	2.45	3.275 (2)	152
O1—H11···Cl3^iv	0.82	2.33	3.147 (2)	173
O1—H12···Cl3^v	0.89	2.24	3.127 (2)	176
O2—H21···Cl2ⁱⁱⁱ	0.93	2.19	3.119 (2)	174
O2—H22···Cl2^vi	0.86	2.31	3.1590 (18)	168

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

Acknowledgements

This work was supported by a start-up grant from Anyang Institute of Technology, China.

References

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