1-Phenyl-piperazine-1,4-diium tetra-chlorido-cobalt(II).

In the title mol-ecular salt, (C10H16N2)[CoCl4], the piperazine ring of the phenyl-piperazine dication adopts a chair conformation and the phenyl ring occupies an equatorial orientation. In the tetra-chlorido-cobaltate(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

(C10H16N2)[CoCl4]

M = 365.00

Monoclinic,

a = 7.7400 (9) Å

b = 20.278 (3) Å

c = 9.6257 (12) Å

β = 105.121 (8)°

V = 1458.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.89 mm−1

T = 173 K

0.46 × 0.32 × 0.28 mm

Data collection

Rigaku XtaLAB mini diffractometer

Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T min = 0.465, T max = 0.589

15030 measured reflections

3335 independent reflections

3034 reflections with F 2 > 2σ(F 2)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.054

S = 1.14

3335 reflections

166 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.36 e Å−3

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 ▶).

Crystal structure: contains datablock(s) General, I, 239R. DOI: 10.1107/S1600536814005790/hb7210sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814005790/hb7210Isup2.hkl

CCDC references: 991791, 991792

Additional supporting information: crystallographic information; 3D view; checkCIF report

(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

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)

Table 1

Selected bond lengths (Å)

Co1—Cl1	2.3182 (5)
Co1—Cl2	2.2431 (5)
Co1—Cl3	2.2738 (5)
Co1—Cl4	2.2811 (6)

Table 2

Hydrogen-bond geometry (Å, °)

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) ; (ii) .