metal-organic compounds
1-Phenylpiperazine-1,4-diium tetrachloridocobalt(II)
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
In the title molecular salt, (C10H16N2)[CoCl4], the piperazine ring of the phenylpiperazine dication adopts a chair conformation and the phenyl ring occupies an equatorial orientation. In the tetrachloridocobaltate(II) dianion, the Co—Cl bond lengths for the chloride ions not accepting hydrogen bonds are significantly shorter than those for the chloride ions accepting such bonds. In the crystal, the components are linked by N—H⋯Cl hydrogen bonds, generating [001] chains.
Related literature
For background to organic-inorganic hybrid materials, see: Bringley & Rajeswaran (2006); Brammer et al. (2002). For phenylpiperazinium cations, see: Ben Garbia et al. (2005). For related structures, see: Mghandef & Boughzala (2014); Wang et al. (2012).
Experimental
Crystal data
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Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell 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
10.1107/S1600536814005790/hb7210sup1.cif
contains datablocks General, I, 239R. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005790/hb7210Isup2.hkl
A mixture of CoCl2·H2O and phenylpiperazine was dissolved in an aqueous solution of hydrochloric acid (molar ratio 1:1:1). The obtained solution was stirred for 2 h and then kept at room temperature. Blue prisms of the title compound were obtained two weeks later.
Many hydrogen atoms were treated in calculated positions and refined in the model as riding with distances of C—H = 0.95 and 0.99 Å for the phenyl and methylene groups, respectively, and with Uiso(H) = k×Ueq(C), k = 1.2. Hydrogen atoms H1A, H1B, and H2 were located in the
and their positions were refined with Uiso(H) = k×Ueq(C), k =1.2.Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell
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).Fig. 1. ORTEP-3 view of the title compound with displacement ellipsoids drawn at the 30% probability level. | |
Fig. 2. View of the atomic arrangement of the title compound along the a axis. Hydrogen bonds are shown as dashed lines. | |
Fig. 3. Graph-set description of ring types hydrogen bonding. Hydrogen bonds are shown as dashed lines. |
(C10H16N2)[CoCl4] | F(000) = 740.00 |
Mr = 365.00 | Dx = 1.662 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 14000 reflections |
a = 7.7400 (9) Å | θ = 3.0–27.6° |
b = 20.278 (3) Å | µ = 1.89 mm−1 |
c = 9.6257 (12) Å | T = 173 K |
β = 105.121 (8)° | Prism, blue |
V = 1458.5 (3) Å3 | 0.46 × 0.32 × 0.28 mm |
Z = 4 |
Rigaku XtaLAB mini diffractometer | 3034 reflections with F2 > 2σ(F2) |
Detector resolution: 6.849 pixels mm-1 | Rint = 0.023 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | h = −10→10 |
Tmin = 0.465, Tmax = 0.589 | k = −26→26 |
15030 measured reflections | l = −12→12 |
3335 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0197P)2 + 0.6924P] where P = (Fo2 + 2Fc2)/3 |
3335 reflections | (Δ/σ)max = 0.001 |
166 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Primary atom site location: structure-invariant direct methods |
(C10H16N2)[CoCl4] | V = 1458.5 (3) Å3 |
Mr = 365.00 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7400 (9) Å | µ = 1.89 mm−1 |
b = 20.278 (3) Å | T = 173 K |
c = 9.6257 (12) Å | 0.46 × 0.32 × 0.28 mm |
β = 105.121 (8)° |
Rigaku XtaLAB mini diffractometer | 3335 independent reflections |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | 3034 reflections with F2 > 2σ(F2) |
Tmin = 0.465, Tmax = 0.589 | Rint = 0.023 |
15030 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.26 e Å−3 |
3335 reflections | Δρmin = −0.36 e Å−3 |
166 parameters |
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). |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.14256 (3) | 0.110059 (11) | 0.71031 (2) | 0.01829 (7) | |
Cl1 | 0.17830 (5) | 0.025120 (19) | 0.87659 (4) | 0.02225 (9) | |
Cl2 | 0.12699 (6) | 0.20091 (2) | 0.83944 (4) | 0.02466 (10) | |
Cl3 | −0.10305 (5) | 0.08669 (2) | 0.52831 (4) | 0.02264 (9) | |
Cl4 | 0.38614 (5) | 0.10918 (2) | 0.61855 (4) | 0.02585 (10) | |
N1 | 0.16483 (19) | 0.05757 (7) | 0.32178 (15) | 0.0196 (3) | |
N2 | 0.36753 (17) | 0.11889 (6) | 0.14374 (14) | 0.0156 (3) | |
C1 | 0.0927 (3) | 0.11496 (8) | 0.22774 (18) | 0.0212 (4) | |
C2 | 0.2443 (2) | 0.15844 (8) | 0.20870 (18) | 0.0195 (4) | |
C3 | 0.4446 (2) | 0.06256 (8) | 0.24379 (18) | 0.0207 (4) | |
C4 | 0.2953 (3) | 0.01865 (8) | 0.26558 (18) | 0.0213 (4) | |
C5 | 0.5097 (2) | 0.15791 (8) | 0.10288 (16) | 0.0171 (3) | |
C6 | 0.5541 (3) | 0.22071 (9) | 0.15569 (19) | 0.0255 (4) | |
C7 | 0.6844 (3) | 0.25474 (9) | 0.1091 (2) | 0.0291 (4) | |
C8 | 0.7669 (3) | 0.22656 (9) | 0.01261 (19) | 0.0261 (4) | |
C9 | 0.7195 (3) | 0.16350 (9) | −0.03960 (18) | 0.0234 (4) | |
C10 | 0.5899 (3) | 0.12865 (8) | 0.00517 (18) | 0.0204 (4) | |
H1C | 0.0121 | 0.1409 | 0.2714 | 0.0255* | |
H1D | 0.0222 | 0.0990 | 0.1326 | 0.0255* | |
H1A | 0.221 (3) | 0.0719 (12) | 0.411 (3) | 0.040 (7)* | |
H1B | 0.076 (3) | 0.0334 (11) | 0.326 (3) | 0.027 (6)* | |
H2A | 0.1951 | 0.1961 | 0.1451 | 0.0234* | |
H2B | 0.3115 | 0.1762 | 0.3032 | 0.0234* | |
H2 | 0.305 (3) | 0.1003 (10) | 0.063 (3) | 0.025 (5)* | |
H3A | 0.5136 | 0.0803 | 0.3377 | 0.0248* | |
H3B | 0.5271 | 0.0364 | 0.2024 | 0.0248* | |
H4A | 0.2329 | −0.0020 | 0.1729 | 0.0256* | |
H4B | 0.3465 | −0.0169 | 0.3344 | 0.0256* | |
H6 | 0.4972 | 0.2401 | 0.2220 | 0.0306* | |
H7 | 0.7172 | 0.2980 | 0.1441 | 0.0349* | |
H8 | 0.8561 | 0.2503 | −0.0181 | 0.0313* | |
H9 | 0.7761 | 0.1442 | −0.1062 | 0.0281* | |
H10 | 0.5565 | 0.0855 | −0.0303 | 0.0245* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01922 (12) | 0.02023 (12) | 0.01622 (11) | 0.00007 (8) | 0.00605 (9) | 0.00011 (8) |
Cl1 | 0.0271 (2) | 0.01947 (19) | 0.01833 (18) | −0.00352 (15) | 0.00258 (15) | 0.00167 (15) |
Cl2 | 0.0297 (3) | 0.0210 (2) | 0.0247 (2) | 0.00116 (16) | 0.00976 (17) | −0.00198 (16) |
Cl3 | 0.01909 (19) | 0.0276 (2) | 0.02077 (19) | −0.00029 (15) | 0.00430 (15) | 0.00099 (16) |
Cl4 | 0.0190 (2) | 0.0383 (3) | 0.0214 (2) | −0.00280 (16) | 0.00730 (16) | −0.00424 (17) |
N1 | 0.0193 (7) | 0.0222 (8) | 0.0189 (7) | −0.0024 (6) | 0.0078 (6) | 0.0004 (6) |
N2 | 0.0167 (7) | 0.0167 (7) | 0.0139 (7) | −0.0018 (5) | 0.0048 (5) | −0.0016 (5) |
C1 | 0.0188 (8) | 0.0235 (9) | 0.0228 (9) | 0.0029 (7) | 0.0079 (7) | 0.0035 (7) |
C2 | 0.0208 (8) | 0.0184 (8) | 0.0217 (8) | 0.0023 (6) | 0.0095 (7) | −0.0008 (7) |
C3 | 0.0192 (8) | 0.0211 (9) | 0.0232 (8) | 0.0038 (7) | 0.0080 (7) | 0.0050 (7) |
C4 | 0.0243 (9) | 0.0180 (8) | 0.0243 (8) | 0.0009 (7) | 0.0111 (7) | 0.0019 (7) |
C5 | 0.0160 (8) | 0.0194 (8) | 0.0155 (8) | −0.0018 (6) | 0.0033 (6) | 0.0018 (6) |
C6 | 0.0285 (9) | 0.0239 (9) | 0.0267 (9) | −0.0053 (7) | 0.0118 (8) | −0.0064 (8) |
C7 | 0.0293 (10) | 0.0231 (9) | 0.0360 (10) | −0.0087 (7) | 0.0106 (8) | −0.0050 (8) |
C8 | 0.0204 (9) | 0.0296 (10) | 0.0285 (9) | −0.0056 (7) | 0.0066 (7) | 0.0064 (8) |
C9 | 0.0208 (8) | 0.0307 (10) | 0.0204 (8) | 0.0016 (7) | 0.0082 (7) | 0.0019 (7) |
C10 | 0.0209 (8) | 0.0208 (8) | 0.0201 (8) | −0.0007 (7) | 0.0062 (7) | −0.0011 (7) |
Co1—Cl1 | 2.3182 (5) | N1—H1A | 0.90 (3) |
Co1—Cl2 | 2.2431 (5) | N1—H1B | 0.86 (3) |
Co1—Cl3 | 2.2738 (5) | N2—H2 | 0.89 (2) |
Co1—Cl4 | 2.2811 (6) | C1—H1C | 0.990 |
N1—C1 | 1.491 (2) | C1—H1D | 0.990 |
N1—C4 | 1.490 (3) | C2—H2A | 0.990 |
N2—C2 | 1.502 (3) | C2—H2B | 0.990 |
N2—C3 | 1.513 (2) | C3—H3A | 0.990 |
N2—C5 | 1.489 (3) | C3—H3B | 0.990 |
C1—C2 | 1.517 (3) | C4—H4A | 0.990 |
C3—C4 | 1.516 (3) | C4—H4B | 0.990 |
C5—C6 | 1.381 (3) | C6—H6 | 0.950 |
C5—C10 | 1.388 (3) | C7—H7 | 0.950 |
C6—C7 | 1.389 (3) | C8—H8 | 0.950 |
C7—C8 | 1.381 (3) | C9—H9 | 0.950 |
C8—C9 | 1.388 (3) | C10—H10 | 0.950 |
C9—C10 | 1.385 (3) | ||
Cl1—Co1—Cl2 | 103.983 (19) | N1—C1—H1C | 109.580 |
Cl1—Co1—Cl3 | 107.597 (18) | N1—C1—H1D | 109.572 |
Cl1—Co1—Cl4 | 107.440 (18) | C2—C1—H1C | 109.578 |
Cl2—Co1—Cl3 | 116.304 (19) | C2—C1—H1D | 109.582 |
Cl2—Co1—Cl4 | 112.971 (19) | H1C—C1—H1D | 108.117 |
Cl3—Co1—Cl4 | 108.021 (19) | N2—C2—H2A | 109.754 |
C1—N1—C4 | 112.03 (14) | N2—C2—H2B | 109.749 |
C2—N2—C3 | 109.03 (13) | C1—C2—H2A | 109.748 |
C2—N2—C5 | 114.81 (12) | C1—C2—H2B | 109.747 |
C3—N2—C5 | 111.93 (12) | H2A—C2—H2B | 108.227 |
N1—C1—C2 | 110.37 (13) | N2—C3—H3A | 109.634 |
N2—C2—C1 | 109.60 (13) | N2—C3—H3B | 109.651 |
N2—C3—C4 | 110.07 (12) | C4—C3—H3A | 109.646 |
N1—C4—C3 | 110.63 (14) | C4—C3—H3B | 109.646 |
N2—C5—C6 | 121.53 (16) | H3A—C3—H3B | 108.161 |
N2—C5—C10 | 116.34 (14) | N1—C4—H4A | 109.525 |
C6—C5—C10 | 122.09 (17) | N1—C4—H4B | 109.519 |
C5—C6—C7 | 118.12 (18) | C3—C4—H4A | 109.521 |
C6—C7—C8 | 120.89 (17) | C3—C4—H4B | 109.518 |
C7—C8—C9 | 120.01 (18) | H4A—C4—H4B | 108.083 |
C8—C9—C10 | 120.14 (18) | C5—C6—H6 | 120.943 |
C5—C10—C9 | 118.76 (16) | C7—C6—H6 | 120.939 |
C1—N1—H1A | 109.7 (15) | C6—C7—H7 | 119.555 |
C1—N1—H1B | 107.3 (13) | C8—C7—H7 | 119.550 |
C4—N1—H1A | 108.0 (16) | C7—C8—H8 | 119.998 |
C4—N1—H1B | 110.1 (15) | C9—C8—H8 | 119.996 |
H1A—N1—H1B | 110 (3) | C8—C9—H9 | 119.930 |
C2—N2—H2 | 109.3 (15) | C10—C9—H9 | 119.935 |
C3—N2—H2 | 105.8 (13) | C5—C10—H10 | 120.626 |
C5—N2—H2 | 105.5 (15) | C9—C10—H10 | 120.617 |
C1—N1—C4—C3 | 55.10 (15) | N1—C1—C2—N2 | 58.69 (16) |
C4—N1—C1—C2 | −56.04 (16) | N2—C3—C4—N1 | −56.76 (16) |
C2—N2—C3—C4 | 59.86 (14) | N2—C5—C6—C7 | −178.07 (11) |
C3—N2—C2—C1 | −60.67 (13) | N2—C5—C10—C9 | 178.25 (11) |
C2—N2—C5—C6 | 16.73 (17) | C6—C5—C10—C9 | 0.5 (3) |
C2—N2—C5—C10 | −161.00 (11) | C10—C5—C6—C7 | −0.5 (3) |
C5—N2—C2—C1 | 172.84 (10) | C5—C6—C7—C8 | 0.1 (3) |
C3—N2—C5—C6 | −108.25 (14) | C6—C7—C8—C9 | 0.2 (3) |
C3—N2—C5—C10 | 74.02 (15) | C7—C8—C9—C10 | −0.2 (3) |
C5—N2—C3—C4 | −172.01 (11) | C8—C9—C10—C5 | −0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl4 | 0.90 (3) | 2.21 (3) | 3.1043 (14) | 173 (3) |
N1—H1B···Cl1i | 0.85 (2) | 2.66 (3) | 3.2963 (14) | 132.2 (18) |
N2—H2···Cl1ii | 0.89 (3) | 2.36 (2) | 3.2262 (13) | 164.6 (17) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl4 | 0.90 (3) | 2.21 (3) | 3.1043 (14) | 173 (3) |
N1—H1B···Cl1i | 0.85 (2) | 2.66 (3) | 3.2963 (14) | 132.2 (18) |
N2—H2···Cl1ii | 0.89 (3) | 2.36 (2) | 3.2262 (13) | 164.6 (17) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y, z−1. |
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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Organic-inorganic hybrid materials have received extensive attention in recent years owing to their great fundamental and practical interest such as second-order nonlinear optical (NLO) responses, magnetism, luminescence, photography and drug delivery (Bringley & Rajeswaran, 2006). However, the energetics of NH····Cl—M (M = metal) hydrogen bonds and their possible roles in supramolecular chemistry have only been recently described in detail (Brammer et al., 2002). It is therefore vital to design and synthesize new organic inorganic hybrid compound to explore their various properties.
The title inorganic-organic hybrid compound contains two basic components, the one [CoCl4]2– anion and one (C10H16N2)2+ organic dication (Fig.1). The structure can be described by tetrachloridocobalt(II) units which form a hydrogen-bonded one-dimensional network with the phenylpiperazinium (N–H···Cl: 3.1043 (14) Å, 3.2963 (14) Å, 3.2262 (13) Å of infinite ribbons located at y = 0 and y = 1/2 that translate along the c direction (Fig. 2). The vander Waals contacts between these ribbons give rise to a three-dimensional network in the structure and add stability to this structure. In the [CoCl4] tetrahedra, the Co—Cl bond lengths and Cl–Co–Cl angles, ranging from 2.2431 (5) to 2.3182 (5) Å and from 103.983 (1) to 116.304 (19)° respectively, are in agreement with those found in 1-(4-hydroxyphenyl)piperazine-1,4-diium tetrachloridocobalt(II) monohydrate (Mghandef & Boughzala, 2014). The nearest Co···Co intra-chain distance is 6.044 Å, while that between adjacent chains is 7.441 Å. The organic cation, (C10H16N2)2+, contains a piperazindium ring in a chair conformation and a planar aromatic ring (atoms C5—C10 r.m.s. deviation = 0.003 Å). In this dication, the bond lengths of C5—C6, C5—C10, C6—C7, C7—C8, C8—C9 and C9—C10 are between single bonds and double bonds and are similar to those of benzene (Ben Garbia et al., 2005). Furthermore, the distances N1—C4, N1—C1, N2—C5, N2—C2, N2—C3, C1—C2 and C3—C4 indicate single bonds.
In this compound, H1A and H2A attached to the N1 nitrogen atom and H2 attached to N2 nitrogen atom play an important role in forming the molecular association through hydrogen bonding. Here two chlorine atoms, Cl1 and Cl4, act as acceptors of N–H···Cl H-bonds. The chlorine atoms Cl2 and Cl3 do not participate in the hydrogen bonding network. The deviation from the perfect tetrahedral arrangement around Co(II) in the title compound can be explained by involvment of the chlorine ions in hydrogen bonding. Three different [CoCl4]2– anions are act as hydrogen-bonding acceptors to each phenylpiperazinium dication forming two different hydrogen-bonding ring motifs, R24(14) and R44(12) (Fig.3). As Cl2 and Cl3 do not act as hydrogen-bond acceptors, the bond angles Cl2–Co–Cl3 and Cl2–Co–Cl4 (116.304 (19)° and 112.971 (19)°, respectively) display comparatively large deviations from the expected tetrahedral arrangement around Co(II). Similar features have been also observed in the structure of dimorpholinium tetrachloridocobaltate(II) (Wang et al., 2012), where three chlorine atoms are engaged in the hydrogen-bonding network and distortions from tetrahedral predictions are present in the Cl–Co–Cl angles. The structure of dimorpholinium tetrachloridocobaltate(II) also displays a R44(12) hydrogen bonding motif, but does not possess a second unique R24(14) motif that the title compound does exhibit.