Literature DB >> 21587380

(R)-2-Methyl-piperazine-1,4-diium diaqua-tetra-chloridoferrate(II).

Abstract

In the title salt, (C(5)H(14)N(2))[FeCl(4)(H(2)O)(2)], the Fe(II) cation is coordinated by four Cl(-) anions and two water mol-ecules in a distorted octa-hedral geometry. The piperazine ring adopts a normal chair conformation. Inter-molecular N-H⋯Cl, N-H⋯(Cl,Cl) and O-H⋯Cl hydrogen bonding is present in the crystal structure.

Entities: Chemical Disease Species

Year: 2010 PMID： 21587380 PMCID： PMC2983358 DOI： 10.1107/S1600536810035506

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

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 = 335.86 Monoclinic, 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[F 2 > 2σ(F 2)] = 0.023 wR(F 2) = 0.050 S = 1.08 2558 reflections 129 parameters 1 restraint H-atom parameters constrained Δρmax = 0.19 e Å−3 Δρmin = −0.24 e Å−3 Absolute structure: Flack (1983 ▶), 1156 Friedel pairs Flack parameter: 0.010 (14) 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. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035506/xu5019sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035506/xu5019Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(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

Rigaku SCXmini diffractometer	2558 independent reflections
Radiation source: fine-focus sealed tube	2456 reflections with I > 2σ(I)
graphite	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 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	Flack parameter: 0.010 (14)

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.

	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*

	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)

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)

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

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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Piperazinediium tetra-chloridozincate(II).

Authors: Pamela A Sutherland; William T A Harrison
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2009-04-25

2 in total