Tri­chlorido­(1-ethyl­piperazin-1-ium)cobalt(II)

Dhieb, A.C.; Janzen, D.E.; Rzaigui, M.; Smirani Sta, W.

doi:10.1107/S1600536814006989

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page m166

doi:10.1107/S1600536814006989

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Trichlorido(1-ethylpiperazin-1-ium)cobalt(II)

Abdelhamid Chiheb Dhieb,^a Daron E. Janzen,^b Mohamed Rzaigui ^a and Wajda Smirani Sta ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bDepartment of Chemistry and Biochemistry, St Catherine University, 2004 Randolph Avenue, #4282, St Paul, MN 55105, USA
^*Correspondence e-mail: wajda_sta@yahoo.fr

(Received 24 March 2014; accepted 28 March 2014; online 5 April 2014)

In the title complex, [Co(C₆H₁₅N₂)Cl₃], the Co²⁺ ion is coordinated in a distorted tetrahedral fashion by three chloride ions and one N atom of the piperazine ring; the ring adopts a chair conformation with the N—Co and N—C_Et bonds in equatorial orientations. In the crystal, molecules are connected by N—H⋯Cl hydrogen bonds, generating (10-1) sheets.

CCDC reference: 994292

Related literature

For related structures, see: Ciccarese et al. (1998 ); Clemente et al. (1999 ); Marzotto et al. (2000 ).

Experimental

Crystal data

[Co(C₆H₁₅N₂)Cl₃]
M_r = 280.49
Monoclinic, P 2₁ /n
a = 7.421 (3) Å
b = 18.160 (7) Å
c = 8.691 (4) Å
β = 90.524 (7)°
V = 1171.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.10 mm⁻¹
T = 173 K
0.32 × 0.13 × 0.13 mm

Data collection

Rigaku XtaLAB mini diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ) T_min = 0.529, T_max = 0.761
11015 measured reflections
2399 independent reflections
2099 reflections with F² > 2σ(F²)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.050
S = 1.08
2399 reflections
118 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—Cl1	2.2720 (8)
Co1—Cl2	2.2419 (10)
Co1—Cl3	2.2691 (8)
Co1—N1	2.0686 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1ⁱ	0.854 (19)	2.347 (18)	3.1794 (16)	165.4 (15)
N1—H1⋯Cl3ⁱⁱ	0.83 (2)	2.49 (2)	3.3192 (17)	176.0 (17)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z.

Data collection: CrystalClear-SM Expert (Rigaku, 2011 ); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ).

Supporting information

CCDC reference: 994292

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536814006989/hb7215sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814006989/hb7215Isup2.hkl

checkCIF report

Comment top

Piperazine (H₂ppz) and its derivatives, are cyclic diamines possessing a non-planar six-membered ring analogous to cyclohexane with two basic nitrogen atoms in the 1,4 positions. As these nitrogen atoms are basic, piperazine (H₂ppz) and its derivatives may coordinate metal ions as monodentate, bidentate or bidentate–chelate ligands. Several 1-methylpiperazine and 1,4-di- methylpiperazine platinum(II) complexes have been synthesized and characterized through X-ray diffraction (Ciccarese et al., 1998). The cobalt complexes [CoCl₃(HMe2ppz)] and [CoCl₃(H₂Meppz)] have shown interesting cytotoxic activity on human colon and carcinoma cells (Marzotto et al., 2000). In order to explore possible biological applications and to gather further chemical and structural information on metal complexes capable of interacting selectively with nitrogen donors of DNA nucleobases, we have extended to cobalt(II) the study on the behaviour and coordinating properties of piperazine derivatives. This study includes the synthesis and structural characterization of the new complex, (C₆H₁₅N₂)CoCl₃ (I).

Complex I is present as a neutral zwitterionic (amphiionic) species. The negative charge of the –CoCl₃ group is balanced by the positive charge at the ethylated N2 nitrogen atom of the 1-ethylpiperazin-1-ium ring. Zwitterionic complexes having the formula MX₃LH (where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); X = Cl, Br, I; LH = monoprotonated diamine), although rare, are already known. The six-membered piperazine ring in complex I possesses the characteristic chair conformation. The average of the Co(II)–Cl bond lengths, 2.261 Å, falls in the expected range. It is noteworthy that this Co(II)–Cl distance increases on increasing the number of chloride ions bonded to cobalt(II) atom, but also increases when the chloride ions are involved in strong hydrogen bonding. In the structure of I, the Co–Cl1, 2.2720 (8) Å, and Co–Cl3, 2.2691 (8) Å, distances are significantly longer than the Co–Cl2 distance, 2.2419 (10) Å , as the former are involved in strong hydrogen bonding while the latter is not. The Co(II)–N1 distance, 2.0686 (15) Å, is typical (Clemente et al., 1999).

The structure consists of a neutral Co(II) complex with a 4-Etppz ligand bonded through the secondary nitrogen atom and three chloride ligands. The tertiary nitrogen atom is protonated balancing the overall charge (Fig. 1). Each complex undergoes two hydrogen bonding interactions as donors (N1—H1 and N2—H2) and two interactions as accpetors (Cl1 and Cl3). Hydrogen bonding occurs in two-dimensional sheets (Fig. 2). Dimer donor-acceptor hydrogen-bonding interactions (related by inversion) dominate the hydrogen bonding motif (R²₂(8)) with additional single donor-acceptor hydrogen bonding interaction joining the dimer interactions. The same hydrogen-bonding pattern is found in the structure of the related [CoCl₃(H₂Meppz)] complex (Clemente et al., 1999).

Related literature top

For related structures, see: Ciccarese et al. (1998); Clemente et al. (1999); Marzotto et al. (2000).

Experimental top

The complex was synthesized by adding dropwise under stirring a blue-violet solution, previously prepared at 40°C, of anhydrous CoCl₂ in 10 ml EtOH, to a 1-ethylpiperazine (HEtppz) solution dissolved in 5 ml EtOH in a molar ratio 1:1. After mixing, an aqueous hydrochloric acid solution was added to the blue powder compound and was stirred for 2 h. After filtration, the filtrate was allowed to stand at room temperature. Blue crystals were obtained by slow evaporation.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. ORTEP-3 view of (C₆H₁₅N₂)CoCl₃ with displacement ellipsoids for non-H atoms drawn at the 30% probability level.
	Fig. 2. Perspective view of the crystal packing of the title complex. Hydrogen bonds are shown as dashed lines.

Trichlorido(1-ethylpiperazin-1-ium)cobalt(II) top

Crystal data top

[Co(C₆H₁₅N₂)Cl₃]	F(000) = 572.00
M_r = 280.49	D_x = 1.591 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 7042 reflections
a = 7.421 (3) Å	θ = 3.3–26.5°
b = 18.160 (7) Å	µ = 2.10 mm⁻¹
c = 8.691 (4) Å	T = 173 K
β = 90.524 (7)°	Prism, blue
V = 1171.1 (8) Å³	0.32 × 0.13 × 0.13 mm
Z = 4

Data collection top

Rigaku XtaLAB mini diffractometer	2099 reflections with F² > 2σ(F²)
Detector resolution: 6.849 pixels mm^-1	R_int = 0.025
ω scans	θ_max = 26.4°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −9→9
T_min = 0.529, T_max = 0.761	k = −22→22
11015 measured reflections	l = −10→10
2399 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0195P)² + 0.4P] where P = (F_o² + 2F_c²)/3
2399 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Co(C₆H₁₅N₂)Cl₃]	V = 1171.1 (8) Å³
M_r = 280.49	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.421 (3) Å	µ = 2.10 mm⁻¹
b = 18.160 (7) Å	T = 173 K
c = 8.691 (4) Å	0.32 × 0.13 × 0.13 mm
β = 90.524 (7)°

Data collection top

Rigaku XtaLAB mini diffractometer	2399 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	2099 reflections with F² > 2σ(F²)
T_min = 0.529, T_max = 0.761	R_int = 0.025
11015 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.27 e Å⁻³
2399 reflections	Δρ_min = −0.27 e Å⁻³
118 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Co1	0.50887 (3)	0.124866 (12)	−0.13052 (2)	0.02446 (7)
Cl1	0.62618 (6)	0.22726 (2)	−0.24155 (5)	0.03456 (11)
Cl2	0.21414 (6)	0.13426 (3)	−0.07964 (6)	0.04714 (13)
Cl3	0.58634 (6)	0.02448 (2)	−0.27061 (5)	0.03491 (11)
N1	0.62169 (18)	0.11055 (8)	0.08596 (15)	0.0237 (3)
N2	0.87397 (18)	0.13728 (7)	0.34217 (15)	0.0235 (3)
C1	0.6034 (3)	0.17490 (9)	0.19013 (19)	0.0301 (4)
C2	0.6795 (3)	0.15991 (10)	0.34991 (19)	0.0306 (4)
C3	0.8943 (3)	0.07188 (9)	0.23786 (19)	0.0306 (4)
C4	0.8130 (3)	0.08778 (10)	0.07959 (19)	0.0318 (4)
C5	0.9516 (3)	0.12430 (10)	0.50161 (19)	0.0324 (4)
C6	1.1522 (3)	0.10910 (10)	0.5011 (3)	0.0393 (5)
H1A	0.4743	0.1880	0.1985	0.0361*
H1B	0.6670	0.2176	0.1450	0.0361*
H2A	0.6688	0.2048	0.4137	0.0367*
H2B	0.6089	0.1203	0.3993	0.0367*
H2	0.932 (3)	0.1733 (10)	0.3034 (19)	0.022 (5)*
H3A	0.8333	0.0288	0.2837	0.0367*
H3B	1.0237	0.0598	0.2272	0.0367*
H4A	0.8835	0.1273	0.0298	0.0381*
H4B	0.8227	0.0430	0.0151	0.0381*
H5A	0.9283	0.1682	0.5660	0.0389*
H5B	0.8890	0.0820	0.5490	0.0389*
H6A	1.2141	0.1487	0.4461	0.0472*
H6B	1.1749	0.0620	0.4497	0.0472*
H6C	1.1974	0.1068	0.6073	0.0472*
H1	0.566 (3)	0.0763 (11)	0.128 (3)	0.032 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02308 (12)	0.02612 (12)	0.02421 (12)	−0.00175 (8)	0.00169 (8)	−0.00177 (9)
Cl1	0.0399 (3)	0.0238 (2)	0.0403 (3)	0.00338 (17)	0.01486 (18)	0.00187 (17)
Cl2	0.0227 (3)	0.0724 (4)	0.0464 (3)	−0.0018 (2)	0.00471 (18)	−0.0063 (3)
Cl3	0.0445 (3)	0.0260 (3)	0.0344 (3)	−0.00757 (17)	0.01151 (18)	−0.00670 (17)
N1	0.0221 (7)	0.0234 (8)	0.0257 (7)	−0.0032 (6)	0.0028 (6)	−0.0002 (6)
N2	0.0259 (7)	0.0209 (7)	0.0238 (7)	−0.0035 (6)	0.0013 (6)	0.0001 (6)
C1	0.0299 (9)	0.0289 (9)	0.0314 (9)	0.0056 (7)	−0.0011 (7)	−0.0051 (7)
C2	0.0278 (9)	0.0347 (10)	0.0294 (9)	0.0044 (7)	0.0039 (7)	−0.0085 (8)
C3	0.0312 (9)	0.0294 (9)	0.0312 (9)	0.0065 (7)	−0.0023 (7)	−0.0069 (7)
C4	0.0263 (9)	0.0406 (11)	0.0285 (9)	0.0069 (8)	0.0012 (7)	−0.0075 (8)
C5	0.0405 (10)	0.0347 (10)	0.0220 (9)	−0.0017 (8)	−0.0027 (7)	−0.0003 (7)
C6	0.0424 (11)	0.0400 (11)	0.0354 (10)	0.0069 (8)	−0.0107 (8)	0.0022 (8)

Geometric parameters (Å, º) top

Co1—Cl1	2.2720 (8)	C1—H1A	0.990
Co1—Cl2	2.2419 (10)	C1—H1B	0.990
Co1—Cl3	2.2691 (8)	C2—H2A	0.990
Co1—N1	2.0686 (15)	C2—H2B	0.990
N1—C1	1.485 (3)	C3—H3A	0.990
N1—C4	1.480 (3)	C3—H3B	0.990
N2—C2	1.502 (3)	C4—H4A	0.990
N2—C3	1.503 (3)	C4—H4B	0.990
N2—C5	1.514 (3)	C5—H5A	0.990
C1—C2	1.519 (3)	C5—H5B	0.990
C3—C4	1.525 (3)	C6—H6A	0.980
C5—C6	1.514 (3)	C6—H6B	0.980
N1—H1	0.83 (2)	C6—H6C	0.980
N2—H2	0.853 (18)

Cl1—Co1—Cl2	113.57 (3)	H1A—C1—H1B	107.846
Cl1—Co1—Cl3	109.25 (4)	N2—C2—H2A	109.442
Cl1—Co1—N1	109.61 (5)	N2—C2—H2B	109.452
Cl2—Co1—Cl3	114.80 (2)	C1—C2—H2A	109.445
Cl2—Co1—N1	102.57 (5)	C1—C2—H2B	109.448
Cl3—Co1—N1	106.53 (5)	H2A—C2—H2B	108.051
Co1—N1—C1	114.64 (11)	N2—C3—H3A	109.507
Co1—N1—C4	112.42 (10)	N2—C3—H3B	109.508
C1—N1—C4	109.62 (13)	C4—C3—H3A	109.504
C2—N2—C3	110.19 (13)	C4—C3—H3B	109.503
C2—N2—C5	111.05 (13)	H3A—C3—H3B	108.076
C3—N2—C5	112.93 (13)	N1—C4—H4A	108.972
N1—C1—C2	112.39 (14)	N1—C4—H4B	108.974
N2—C2—C1	110.95 (14)	C3—C4—H4A	108.977
N2—C3—C4	110.70 (14)	C3—C4—H4B	108.982
N1—C4—C3	113.02 (14)	H4A—C4—H4B	107.779
N2—C5—C6	113.06 (14)	N2—C5—H5A	108.969
Co1—N1—H1	107.3 (13)	N2—C5—H5B	108.974
C1—N1—H1	105.7 (14)	C6—C5—H5A	108.963
C4—N1—H1	106.6 (14)	C6—C5—H5B	108.971
C2—N2—H2	107.2 (12)	H5A—C5—H5B	107.768
C3—N2—H2	108.2 (12)	C5—C6—H6A	109.474
C5—N2—H2	107.0 (11)	C5—C6—H6B	109.466
N1—C1—H1A	109.127	C5—C6—H6C	109.477
N1—C1—H1B	109.120	H6A—C6—H6B	109.472
C2—C1—H1A	109.128	H6A—C6—H6C	109.470
C2—C1—H1B	109.129	H6B—C6—H6C	109.468

Cl1—Co1—N1—C1	55.30 (9)	C4—N1—C1—C2	−55.55 (16)
Cl1—Co1—N1—C4	−70.78 (9)	C2—N2—C3—C4	54.82 (16)
Cl2—Co1—N1—C1	−65.66 (8)	C3—N2—C2—C1	−55.64 (16)
Cl2—Co1—N1—C4	168.27 (7)	C2—N2—C5—C6	−174.02 (12)
Cl3—Co1—N1—C1	173.39 (7)	C5—N2—C2—C1	178.47 (12)
Cl3—Co1—N1—C4	47.31 (9)	C3—N2—C5—C6	61.63 (17)
Co1—N1—C1—C2	176.93 (8)	C5—N2—C3—C4	179.64 (12)
Co1—N1—C4—C3	−176.03 (9)	N1—C1—C2—N2	56.87 (17)
C1—N1—C4—C3	55.22 (17)	N2—C3—C4—N1	−55.84 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.854 (19)	2.347 (18)	3.1794 (16)	165.4 (15)
N1—H1···Cl3ⁱⁱ	0.83 (2)	2.49 (2)	3.3192 (17)	176.0 (17)

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

Selected bond lengths (Å) top

Co1—Cl1	2.2720 (8)	Co1—Cl3	2.2691 (8)
Co1—Cl2	2.2419 (10)	Co1—N1	2.0686 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.854 (19)	2.347 (18)	3.1794 (16)	165.4 (15)
N1—H1···Cl3ⁱⁱ	0.83 (2)	2.49 (2)	3.3192 (17)	176.0 (17)

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

Acknowledgements

We acknowledge the NSF–MRI grant No. 1125975 "MRI Consortium Acquisition of a Single Crystal X-ray Diffractometer for a Regional PUI Molecular Structure Facility".

References

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