1-Phenyl-piperazine-1,4-diium bis-(hydrogen sulfate).

In the title compound, C(10)H(16)N(2) (2+)·2HSO(4) (-), the S atoms adopt slightly distorted tetra-hedral geometry and the diprotonated piperazine ring adopts a chair conformation. In the crystal, the 1-phenyl-piperazine-1,4-diium cations are anchored between chains formed by the sulfate entities via inter-molecular bifurcated N-H⋯(O,O) and weak C-H⋯O hydrogen bonds. These hydrogen bonds contribute to the cohesion and stability of the network of the crystal structure.

Related literature

For pharmacological properties of phenyl­piperazine, see: Cohen et al. (1982 ▶); Conrado et al. (2008 ▶); Neves et al. (2003 ▶). For related structures, see: Ben Gharbia et al. (2005 ▶). For a discussion on hydrogen bonding, see: Brown (1976 ▶); Blessing (1986 ▶). For structural discussion, see: Arbuckle et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C10H16N2 2+·2HSO4 −

M = 358.38

Monoclinic,

a = 17.535 (6) Å

b = 10.996 (2) Å

c = 7.631 (2) Å

β = 99.86 (2)°

V = 1449.7 (7) Å3

Z = 4

Ag Kα radiation

λ = 0.56083 Å

μ = 0.22 mm−1

T = 293 K

0.5 × 0.4 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

8212 measured reflections

7100 independent reflections

4535 reflections with I > 2σ(I)

R int = 0.022

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.127

S = 1.03

7100 reflections

201 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.46 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-32 for Windows (Farrugia, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037001/pv2328sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037001/pv2328Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H16N22+·2HSO4−	F(000) = 752
Mr = 358.38	Dx = 1.642 Mg m−3
Monoclinic, P21/c	Ag Kα radiation, λ = 0.56083 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 17.535 (6) Å	θ = 9–11°
b = 10.996 (2) Å	µ = 0.22 mm−1
c = 7.631 (2) Å	T = 293 K
β = 99.86 (2)°	Prism, colorless
V = 1449.7 (7) Å3	0.5 × 0.4 × 0.1 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	Rint = 0.022
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.4°
graphite	h = −3→29
non–profiled ω scans	k = −18→0
8212 measured reflections	l = −12→12
7100 independent reflections	2 standard reflections every 120 min
4535 reflections with I > 2σ(I)	intensity decay: 1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0603P)2 + 0.1738P] where P = (Fo2 + 2Fc2)/3
7100 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.958198 (19)	0.80824 (3)	0.59663 (4)	0.02129 (8)
S2	0.68841 (2)	0.18262 (3)	0.36929 (5)	0.02431 (8)
O7	0.66990 (8)	0.31003 (10)	0.32493 (15)	0.0332 (2)
O3	0.97861 (7)	0.68051 (10)	0.64169 (14)	0.0306 (2)
N2	0.73629 (7)	0.53363 (10)	0.45259 (15)	0.0215 (2)
H2	0.7163	0.4579	0.4607	0.026*
O2	0.97180 (7)	0.88315 (10)	0.75428 (14)	0.0295 (2)
N1	0.89625 (7)	0.46159 (12)	0.49684 (18)	0.0273 (2)
H1A	0.9333	0.4041	0.5136	0.033*
H1B	0.9194	0.5342	0.4913	0.033*
O1	1.01876 (7)	0.85308 (12)	0.48419 (14)	0.0355 (3)
H1	1.0036	0.8368	0.3791	0.053*
O4	0.88248 (7)	0.81856 (12)	0.49109 (16)	0.0366 (3)
O5	0.63020 (7)	0.13868 (12)	0.48817 (15)	0.0356 (3)
H5	0.6438	0.1639	0.5898	0.053*
O6	0.67139 (8)	0.10676 (11)	0.21389 (16)	0.0371 (3)
C3	0.79171 (8)	0.55729 (14)	0.62253 (19)	0.0258 (3)
H3A	0.7639	0.5567	0.7220	0.031*
H3B	0.8152	0.6368	0.6173	0.031*
C2	0.77975 (9)	0.53263 (14)	0.29912 (19)	0.0266 (3)
H2A	0.8023	0.6122	0.2876	0.032*
H2B	0.7442	0.5155	0.1900	0.032*
C5	0.67057 (8)	0.61993 (13)	0.42348 (19)	0.0244 (3)
C1	0.84293 (8)	0.43819 (14)	0.3260 (2)	0.0284 (3)
H1C	0.8203	0.3578	0.3284	0.034*
H1D	0.8716	0.4412	0.2281	0.034*
C4	0.85375 (9)	0.46091 (15)	0.6493 (2)	0.0293 (3)
H4A	0.8895	0.4765	0.7588	0.035*
H4B	0.8304	0.3817	0.6588	0.035*
O8	0.76519 (7)	0.17042 (14)	0.47005 (18)	0.0465 (3)
C10	0.68447 (10)	0.74340 (14)	0.4204 (3)	0.0346 (3)
H10	0.7348	0.7735	0.4384	0.042*
C6	0.59670 (9)	0.57280 (16)	0.3966 (2)	0.0347 (3)
H6	0.5887	0.4892	0.3987	0.042*
C9	0.62142 (12)	0.82154 (17)	0.3896 (3)	0.0468 (5)
H9	0.6293	0.9051	0.3871	0.056*
C8	0.54742 (13)	0.7761 (2)	0.3629 (3)	0.0532 (5)
H8	0.5055	0.8291	0.3422	0.064*
C7	0.53462 (10)	0.6521 (2)	0.3664 (3)	0.0489 (5)
H7	0.4843	0.6221	0.3485	0.059*

	U11	U22	U33	U12	U13	U23
S1	0.02138 (14)	0.02425 (15)	0.01794 (14)	−0.00207 (12)	0.00249 (10)	−0.00047 (11)
S2	0.02718 (16)	0.02462 (15)	0.02126 (15)	−0.00051 (13)	0.00451 (12)	0.00042 (12)
O7	0.0483 (7)	0.0228 (5)	0.0284 (5)	−0.0016 (5)	0.0067 (5)	−0.0006 (4)
O3	0.0446 (6)	0.0249 (5)	0.0219 (5)	0.0038 (5)	0.0047 (4)	0.0000 (4)
N2	0.0196 (5)	0.0189 (5)	0.0255 (5)	−0.0014 (4)	0.0029 (4)	0.0000 (4)
O2	0.0372 (6)	0.0288 (5)	0.0225 (5)	−0.0006 (4)	0.0055 (4)	−0.0059 (4)
N1	0.0198 (5)	0.0266 (6)	0.0352 (6)	−0.0001 (4)	0.0037 (5)	0.0005 (5)
O1	0.0341 (6)	0.0512 (7)	0.0225 (5)	−0.0180 (5)	0.0087 (4)	−0.0030 (5)
O4	0.0250 (5)	0.0474 (7)	0.0343 (6)	−0.0012 (5)	−0.0036 (4)	0.0024 (5)
O5	0.0398 (6)	0.0412 (7)	0.0275 (5)	−0.0149 (5)	0.0103 (5)	−0.0031 (5)
O6	0.0545 (8)	0.0298 (5)	0.0286 (5)	0.0002 (5)	0.0116 (5)	−0.0078 (4)
C3	0.0247 (6)	0.0278 (6)	0.0241 (6)	−0.0011 (5)	0.0015 (5)	−0.0018 (5)
C2	0.0252 (6)	0.0316 (7)	0.0234 (6)	0.0017 (5)	0.0052 (5)	0.0003 (5)
C5	0.0221 (6)	0.0232 (6)	0.0279 (6)	0.0029 (5)	0.0040 (5)	0.0030 (5)
C1	0.0243 (6)	0.0297 (7)	0.0320 (7)	−0.0002 (6)	0.0068 (5)	−0.0057 (6)
C4	0.0251 (6)	0.0347 (8)	0.0273 (7)	0.0015 (6)	0.0019 (5)	0.0049 (6)
O8	0.0297 (6)	0.0652 (9)	0.0419 (7)	0.0035 (6)	−0.0015 (5)	0.0122 (7)
C10	0.0301 (8)	0.0244 (7)	0.0494 (10)	0.0011 (6)	0.0071 (7)	0.0036 (6)
C6	0.0234 (7)	0.0330 (8)	0.0467 (9)	−0.0006 (6)	0.0029 (6)	0.0045 (7)
C9	0.0468 (11)	0.0280 (8)	0.0661 (13)	0.0109 (8)	0.0110 (10)	0.0070 (8)
C8	0.0408 (10)	0.0490 (11)	0.0707 (15)	0.0220 (9)	0.0123 (10)	0.0172 (11)
C7	0.0211 (7)	0.0548 (12)	0.0698 (14)	0.0061 (8)	0.0050 (8)	0.0140 (11)

S1—O4	1.4347 (13)	C3—H3B	0.9700
S1—O2	1.4438 (11)	C2—C1	1.507 (2)
S1—O3	1.4754 (11)	C2—H2A	0.9700
S1—O1	1.5553 (12)	C2—H2B	0.9700
S2—O8	1.4378 (14)	C5—C6	1.377 (2)
S2—O6	1.4387 (12)	C5—C10	1.380 (2)
S2—O7	1.4647 (12)	C1—H1C	0.9700
S2—O5	1.5542 (12)	C1—H1D	0.9700
N2—C5	1.4799 (18)	C4—H4A	0.9700
N2—C2	1.5027 (19)	C4—H4B	0.9700
N2—C3	1.5041 (18)	C10—C9	1.388 (2)
N2—H2	0.9100	C10—H10	0.9300
N1—C4	1.485 (2)	C6—C7	1.383 (2)
N1—C1	1.491 (2)	C6—H6	0.9300
N1—H1A	0.9000	C9—C8	1.373 (3)
N1—H1B	0.9000	C9—H9	0.9300
O1—H1	0.8200	C8—C7	1.383 (3)
O5—H5	0.8200	C8—H8	0.9300
C3—C4	1.507 (2)	C7—H7	0.9300
C3—H3A	0.9700
O4—S1—O2	115.31 (8)	C1—C2—H2A	109.4
O4—S1—O3	111.75 (7)	N2—C2—H2B	109.4
O2—S1—O3	110.49 (7)	C1—C2—H2B	109.4
O4—S1—O1	108.60 (8)	H2A—C2—H2B	108.0
O2—S1—O1	104.35 (7)	C6—C5—C10	122.13 (15)
O3—S1—O1	105.60 (7)	C6—C5—N2	117.99 (13)
O8—S2—O6	115.46 (9)	C10—C5—N2	119.87 (13)
O8—S2—O7	111.29 (8)	N1—C1—C2	109.67 (12)
O6—S2—O7	110.95 (7)	N1—C1—H1C	109.7
O8—S2—O5	107.90 (8)	C2—C1—H1C	109.7
O6—S2—O5	103.68 (7)	N1—C1—H1D	109.7
O7—S2—O5	106.89 (8)	C2—C1—H1D	109.7
C5—N2—C2	111.93 (11)	H1C—C1—H1D	108.2
C5—N2—C3	112.96 (11)	N1—C4—C3	109.71 (12)
C2—N2—C3	109.52 (11)	N1—C4—H4A	109.7
C5—N2—H2	107.4	C3—C4—H4A	109.7
C2—N2—H2	107.4	N1—C4—H4B	109.7
C3—N2—H2	107.4	C3—C4—H4B	109.7
C4—N1—C1	111.13 (12)	H4A—C4—H4B	108.2
C4—N1—H1A	109.4	C5—C10—C9	118.29 (17)
C1—N1—H1A	109.4	C5—C10—H10	120.9
C4—N1—H1B	109.4	C9—C10—H10	120.9
C1—N1—H1B	109.4	C5—C6—C7	118.74 (17)
H1A—N1—H1B	108.0	C5—C6—H6	120.6
S1—O1—H1	109.5	C7—C6—H6	120.6
S2—O5—H5	109.5	C8—C9—C10	120.33 (18)
N2—C3—C4	109.89 (12)	C8—C9—H9	119.8
N2—C3—H3A	109.7	C10—C9—H9	119.8
C4—C3—H3A	109.7	C9—C8—C7	120.56 (18)
N2—C3—H3B	109.7	C9—C8—H8	119.7
C4—C3—H3B	109.7	C7—C8—H8	119.7
H3A—C3—H3B	108.2	C8—C7—C6	119.95 (18)
N2—C2—C1	110.98 (12)	C8—C7—H7	120.0
N2—C2—H2A	109.4	C6—C7—H7	120.0

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3i	0.82	1.80	2.6140 (17)	172
O5—H5···O7ii	0.82	1.80	2.6066 (18)	169
N1—H1A···O2iii	0.90	2.23	2.8636 (19)	128
N1—H1A···O3iv	0.90	2.30	3.0279 (19)	138
N1—H1B···O3	0.90	2.14	2.9251 (18)	145
N1—H1B···O2i	0.90	2.35	2.9892 (18)	128
N2—H2···O7	0.91	2.02	2.8216 (16)	146
N2—H2···O6ii	0.91	2.32	2.9037 (17)	122
C1—H1C···O8	0.97	2.59	3.500 (2)	156
C1—H1D···O2i	0.97	2.60	3.113 (2)	114
C3—H3A···O6ii	0.97	2.42	2.949 (2)	114
C3—H3B···O4	0.97	2.59	3.513 (2)	159
C6—H6···O7	0.93	2.55	3.246 (2)	132
C10—H10···O4	0.93	2.60	3.520 (2)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3i	0.82	1.80	2.6140 (17)	172
O5—H5⋯O7ii	0.82	1.80	2.6066 (18)	169
N1—H1A⋯O2iii	0.90	2.23	2.8636 (19)	128
N1—H1A⋯O3iv	0.90	2.30	3.0279 (19)	138
N1—H1B⋯O3	0.90	2.14	2.9251 (18)	145
N1—H1B⋯O2i	0.90	2.35	2.9892 (18)	128
N2—H2⋯O7	0.91	2.02	2.8216 (16)	146
N2—H2⋯O6ii	0.91	2.32	2.9037 (17)	122

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .