catena-Poly[(S)-2-methyl­piperazine-1,4-diium [[trichloridobismuthate(III)]-di-μ-chlorido]]

Ru, Z.-L.

doi:10.1107/S1600536810031417

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page m1079

https://doi.org/10.1107/S1600536810031417

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catena-Poly[(S)-2-methylpiperazine-1,4-diium [[trichloridobismuthate(III)]-di-μ-chlorido]]

Zong-Ling Ru ^a ^*

^aDepartment of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayrzl@yahoo.com.cn

(Received 2 August 2010; accepted 5 August 2010; online 11 August 2010)

In the crystal structure of the title compound, {(C₅H₁₄N₂)[BiCl₅]}_n, the Bi^III cation is coordinated by six Cl⁻ anions in a distorted octahedral geometry. Two Cl⁻ anions bridge neighboring Bi^III cations, forming a zigzag polymeric chain along the a axis. The discrete methylpiperazinediium cation adopts a normal chair conformation and is linked to the polymeric chains by N—H⋯Cl hydrogen bonding.

Related literature

For transition-metal complexes of 2-methylpiperazine, see: Ye et al. (2009 ).

Experimental

Crystal data

(C₅H₁₄N₂)[BiCl₅]
M_r = 488.41
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.719 (1) Å
b = 10.8997 (16) Å
c = 16.302 (3) Å
V = 1371.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 13.79 mm⁻¹
T = 293 K
0.28 × 0.26 × 0.24 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.8, T_max = 0.9
14082 measured reflections
3150 independent reflections
3009 reflections with I > 2σ(I)
R_int = 0.089

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.066
S = 1.03
3150 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 1.57 e Å⁻³
Δρ_min = −1.63 e Å⁻³
Absolute structure: Flack (1983 ), 1327 Friedel pairs
Flack parameter: −0.021 (9)

Table 1
Selected bond lengths (Å)

Bi1—Cl1	2.8245 (18)
Bi1—Cl2	2.597 (2)
Bi1—Cl3	2.561 (2)
Bi1—Cl4	2.6135 (18)
Bi1—Cl5	2.875 (2)
Bi1—Cl5ⁱ	2.820 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H6A⋯Cl1ⁱⁱ	0.97	2.30	3.262 (7)	171
N1—H6B⋯Cl2	0.97	2.48	3.255 (7)	137
N1—H6B⋯Cl3	0.97	2.61	3.244 (6)	124
N2—H7A⋯Cl4ⁱⁱⁱ	0.97	2.33	3.242 (7)	156
N2—H7B⋯Cl1^iv	0.97	2.25	3.184 (6)	161
Symmetry codes: (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (iv) x, y-1, z.

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: https://doi.org/10.1107/S1600536810031417/xu5013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031417/xu5013Isup2.hkl

checkCIF report

Comment top

The chiral 2-methylpiperazine has shown tremendous scope in the synthesis of transition metal complexes (Ye et al., 2009). The construction of new members of this family of ligands is an important direction in the development of coordination chemistry. we report here the crystal structure of the title compound.

In the crystal of the title compound, C₅H₁₄N₂.BiCl₅ (Fig.1), the Bi³⁺ cations are coordinated by six Cl^-anions with distances ranging from 2.561 (2) to 2.875 (2) Å (Table 1). The values of bond angles Cl–Bi–Cl are near to 90 or 180°, which make the [BiCl₆]^3- octahedral geometry. The protonated piperazine ring adopts a chair conformation. The Bi³⁺ cations conneted through bridging chlorine atom to form a one-dimensional chain structure. The crystal structure is stabilized by intermolecular N—H···Cl hydrogen bonds (Table 2).

Related literature top

For transition-metal complexes of 2-methylpiperazine, see: Ye et al. (2009).

Experimental top

A mixture of (S)-2-methylpiperazine (2 mmol, 0.2 g), BiCl₃ (2 mmol, 0.62 g) and 20% aqueous HCl (20 ml) in 10 ml water was heated at 353 K for 0.5 h. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed after 8 d.

Structure description top

For transition-metal complexes of 2-methylpiperazine, see: Ye et al. (2009).

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

catena-Poly[(S)-2-methylpiperazine-1,4-diium [[trichloridobismuthate(III)]-di-µ-chlorido]] top

Crystal data top

(C₅H₁₄N₂)[BiCl₅]	F(000) = 904
M_r = 488.41	D_x = 2.365 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3009 reflections
a = 7.719 (1) Å	θ = 2.5–27.5°
b = 10.8997 (16) Å	µ = 13.79 mm⁻¹
c = 16.302 (3) Å	T = 293 K
V = 1371.6 (3) Å³	Block, colorless
Z = 4	0.28 × 0.26 × 0.24 mm

Data collection top

Rigaku SCXmini diffractometer	3150 independent reflections
Radiation source: fine-focus sealed tube	3009 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.089
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −9→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.8, T_max = 0.9	l = −21→21
14082 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)] = 0.031	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.066	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 1.57 e Å⁻³
3150 reflections	Δρ_min = −1.63 e Å⁻³
120 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0300 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1327 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.021 (9)

Crystal data top

(C₅H₁₄N₂)[BiCl₅]	V = 1371.6 (3) Å³
M_r = 488.41	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.719 (1) Å	µ = 13.79 mm⁻¹
b = 10.8997 (16) Å	T = 293 K
c = 16.302 (3) Å	0.28 × 0.26 × 0.24 mm

Data collection top

Rigaku SCXmini diffractometer	3150 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	3009 reflections with I > 2σ(I)
T_min = 0.8, T_max = 0.9	R_int = 0.089
14082 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 1.57 e Å⁻³
S = 1.03	Δρ_min = −1.63 e Å⁻³
3150 reflections	Absolute structure: Flack (1983), 1327 Friedel pairs
120 parameters	Absolute structure parameter: −0.021 (9)
0 restraints

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
Bi1	0.33206 (3)	0.57633 (2)	0.946205 (14)	0.02412 (11)
C1	0.1786 (10)	0.1571 (6)	0.7856 (4)	0.0296 (15)
H1	0.0737	0.1733	0.8177	0.036*
C2	0.1931 (12)	0.0212 (7)	0.7715 (5)	0.0391 (19)
H2A	0.0899	−0.0077	0.7436	0.047*
H2B	0.2917	0.0049	0.7362	0.047*
C3	0.3672 (10)	−0.0026 (8)	0.8968 (6)	0.049 (2)
H3A	0.4720	−0.0201	0.8661	0.058*
H3B	0.3740	−0.0456	0.9487	0.058*
C4	0.3548 (12)	0.1343 (8)	0.9124 (4)	0.041 (2)
H4A	0.2566	0.1512	0.9477	0.050*
H4B	0.4589	0.1625	0.9399	0.050*
C5	0.1685 (13)	0.2283 (9)	0.7064 (5)	0.059 (2)
H5A	0.1539	0.3139	0.7183	0.089*
H5B	0.0717	0.1997	0.6748	0.089*
H5C	0.2734	0.2166	0.6758	0.089*
Cl1	0.3347 (3)	0.68787 (17)	0.78982 (11)	0.0414 (4)
Cl2	0.0920 (2)	0.4253 (2)	0.89851 (12)	0.0378 (4)
Cl3	0.5685 (2)	0.4239 (2)	0.90419 (13)	0.0389 (4)
Cl4	0.3272 (3)	0.47345 (19)	1.09100 (11)	0.0412 (4)
Cl5	0.0888 (3)	0.7630 (2)	0.99374 (14)	0.0414 (5)
N1	0.3338 (8)	0.2005 (5)	0.8340 (4)	0.0331 (13)
H6A	0.4376	0.1895	0.8012	0.040*
H6B	0.3211	0.2875	0.8449	0.040*
N2	0.2143 (8)	−0.0475 (5)	0.8499 (4)	0.0387 (16)
H7A	0.1108	−0.0363	0.8828	0.046*
H7B	0.2270	−0.1345	0.8388	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.02674 (15)	0.02120 (14)	0.02443 (15)	−0.00003 (11)	−0.00047 (11)	−0.00161 (10)
C1	0.033 (3)	0.030 (4)	0.026 (3)	0.001 (3)	0.002 (3)	0.005 (3)
C2	0.054 (5)	0.032 (4)	0.031 (4)	−0.013 (4)	−0.001 (4)	−0.007 (3)
C3	0.045 (5)	0.040 (5)	0.060 (5)	−0.004 (4)	−0.017 (4)	0.021 (4)
C4	0.051 (5)	0.045 (5)	0.028 (4)	−0.013 (4)	−0.011 (4)	0.011 (3)
C5	0.062 (5)	0.076 (7)	0.040 (5)	0.004 (7)	0.000 (5)	0.023 (5)
Cl1	0.0513 (10)	0.0414 (10)	0.0316 (9)	0.0075 (11)	0.0079 (10)	0.0036 (8)
Cl2	0.0344 (9)	0.0359 (10)	0.0432 (10)	−0.0050 (9)	−0.0056 (8)	−0.0058 (10)
Cl3	0.0326 (8)	0.0350 (10)	0.0490 (11)	0.0048 (9)	0.0058 (8)	−0.0045 (11)
Cl4	0.0382 (9)	0.0521 (11)	0.0333 (9)	−0.0029 (11)	−0.0032 (9)	0.0123 (8)
Cl5	0.0440 (9)	0.0356 (11)	0.0446 (11)	0.0132 (8)	0.0096 (8)	0.0003 (9)
N1	0.043 (3)	0.026 (3)	0.031 (3)	−0.005 (3)	0.000 (3)	0.002 (2)
N2	0.039 (3)	0.024 (3)	0.053 (4)	−0.002 (3)	−0.003 (3)	0.001 (3)

Geometric parameters (Å, º) top

Bi1—Cl1	2.8245 (18)	C3—C4	1.517 (12)
Bi1—Cl2	2.597 (2)	C3—H3A	0.9700
Bi1—Cl3	2.561 (2)	C3—H3B	0.9700
Bi1—Cl4	2.6135 (18)	C4—N1	1.476 (9)
Bi1—Cl5	2.875 (2)	C4—H4A	0.9700
Bi1—Cl5ⁱ	2.820 (2)	C4—H4B	0.9700
C1—C2	1.504 (10)	C5—H5A	0.9600
C1—C5	1.509 (10)	C5—H5B	0.9600
C1—N1	1.510 (10)	C5—H5C	0.9600
C1—H1	0.9800	N1—H6A	0.9700
C2—N2	1.490 (10)	N1—H6B	0.9700
C2—H2A	0.9700	N2—H7A	0.9700
C2—H2B	0.9700	N2—H7B	0.9700
C3—N2	1.489 (10)

Cl3—Bi1—Cl2	90.97 (6)	C4—C3—H3A	109.4
Cl3—Bi1—Cl4	88.48 (7)	N2—C3—H3B	109.4
Cl2—Bi1—Cl4	89.32 (7)	C4—C3—H3B	109.4
Cl3—Bi1—Cl5ⁱ	89.71 (8)	H3A—C3—H3B	108.0
Cl2—Bi1—Cl5ⁱ	177.10 (7)	N1—C4—C3	110.0 (6)
Cl4—Bi1—Cl5ⁱ	87.88 (7)	N1—C4—H4A	109.7
Cl3—Bi1—Cl1	91.88 (7)	C3—C4—H4A	109.7
Cl2—Bi1—Cl1	90.44 (7)	N1—C4—H4B	109.7
Cl4—Bi1—Cl1	179.57 (7)	C3—C4—H4B	109.7
Cl5ⁱ—Bi1—Cl1	92.35 (7)	H4A—C4—H4B	108.2
Cl3—Bi1—Cl5	175.20 (8)	C1—C5—H5A	109.5
Cl2—Bi1—Cl5	93.63 (8)	C1—C5—H5B	109.5
Cl4—Bi1—Cl5	92.91 (7)	H5A—C5—H5B	109.5
Cl5ⁱ—Bi1—Cl5	85.753 (13)	C1—C5—H5C	109.5
Cl1—Bi1—Cl5	86.75 (6)	H5A—C5—H5C	109.5
C2—C1—C5	112.3 (7)	H5B—C5—H5C	109.5
C2—C1—N1	109.2 (7)	Bi1ⁱⁱ—Cl5—Bi1	172.74 (9)
C5—C1—N1	109.0 (6)	C4—N1—C1	112.7 (6)
C2—C1—H1	108.7	C4—N1—H6A	109.0
C5—C1—H1	108.7	C1—N1—H6A	109.2
N1—C1—H1	108.7	C4—N1—H6B	109.3
N2—C2—C1	111.8 (6)	C1—N1—H6B	108.8
N2—C2—H2A	109.3	H6A—N1—H6B	107.8
C1—C2—H2A	109.3	C3—N2—C2	111.2 (6)
N2—C2—H2B	109.3	C3—N2—H7A	109.1
C1—C2—H2B	109.3	C2—N2—H7A	108.7
H2A—C2—H2B	107.9	C3—N2—H7B	109.7
N2—C3—C4	111.1 (7)	C2—N2—H7B	110.0
N2—C3—H3A	109.4	H7A—N2—H7B	108.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H6A···Cl1ⁱⁱⁱ	0.97	2.30	3.262 (7)	171
N1—H6B···Cl2	0.97	2.48	3.255 (7)	137
N1—H6B···Cl3	0.97	2.61	3.244 (6)	124
N2—H7A···Cl4^iv	0.97	2.33	3.242 (7)	156
N2—H7B···Cl1^v	0.97	2.25	3.184 (6)	161

Symmetry codes: (iii) −x+1, y−1/2, −z+3/2; (iv) x−1/2, −y+1/2, −z+2; (v) x, y−1, z.

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[BiCl₅]
M_r	488.41
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.719 (1), 10.8997 (16), 16.302 (3)
V (Å³)	1371.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	13.79
Crystal size (mm)	0.28 × 0.26 × 0.24

Data collection
Diffractometer	Rigaku SCXmini
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	14082, 3150, 3009
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.066, 1.03
No. of reflections	3150
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.57, −1.63
Absolute structure	Flack (1983), 1327 Friedel pairs
Absolute structure parameter	−0.021 (9)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Bi1—Cl1	2.8245 (18)	Bi1—Cl4	2.6135 (18)
Bi1—Cl2	2.597 (2)	Bi1—Cl5	2.875 (2)
Bi1—Cl3	2.561 (2)	Bi1—Cl5ⁱ	2.820 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H6A···Cl1ⁱⁱ	0.97	2.30	3.262 (7)	170.7
N1—H6B···Cl2	0.97	2.48	3.255 (7)	136.8
N1—H6B···Cl3	0.97	2.61	3.244 (6)	123.5
N2—H7A···Cl4ⁱⁱⁱ	0.97	2.33	3.242 (7)	155.7
N2—H7B···Cl1^iv	0.97	2.25	3.184 (6)	160.6

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

Acknowledgements

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

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, H.-Y., Fu, D.-W., Zhang, Y., Zhang, W., Xiong, R.-G. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 42–43. Web of Science CSD CrossRef PubMed CAS Google Scholar

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