Piperazine-1,4-diium bis-(perchlorate) dihydrate.

The asymmetric unit of the title compound, C(4)H(12)N(2) (2+)·2ClO(4) (-)·2H(2)O, contains half of a piperazinediium cation, one perchlorate anion and one water mol-ecule. The diprotonated piperazine ring, which is completed by crystallographic inversion symmetry, adopts a chair conformation. In the crystal structure, the cations and anions are linked by inter-molecular N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For background to simple mol­ecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Katrusiak & Szafrański (1999 ▶, 2006 ▶).

Experimental

Crystal data

C4H12N2 2+·2ClO4 −·2H2O

M = 323.09

Monoclinic,

a = 7.2588 (15) Å

b = 6.5089 (13) Å

c = 14.543 (4) Å

β = 113.56 (3)°

V = 629.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.56 mm−1

T = 293 K

0.28 × 0.26 × 0.20 mm

Data collection

Rigaku Mercury 2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.856, T max = 0.896

6362 measured reflections

1458 independent reflections

1130 reflections with I > 2σ(I)

R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.109

S = 1.07

1458 reflections

83 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030345/pv2304sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030345/pv2304Isup2.hkl

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

C4H12N22+·2ClO4−·2H2O	F(000) = 336
Mr = 323.09	Dx = 1.704 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1130 reflections
a = 7.2588 (15) Å	θ = 3.1–27.5°
b = 6.5089 (13) Å	µ = 0.56 mm−1
c = 14.543 (4) Å	T = 293 K
β = 113.56 (3)°	Block, colorless
V = 629.8 (3) Å3	0.28 × 0.26 × 0.20 mm
Z = 2

Rigaku Mercury 2 diffractometer	1458 independent reflections
Radiation source: fine-focus sealed tube	1130 reflections with I > 2σ(I)
graphite	Rint = 0.060
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −8→8
Tmin = 0.856, Tmax = 0.896	l = −18→18
6362 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.109	w = 1/[σ2(Fo2) + (0.0357P)2 + 0.361P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
1458 reflections	Δρmax = 0.28 e Å−3
83 parameters	Δρmin = −0.25 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (4)

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
C1	0.3021 (4)	1.0866 (4)	0.94987 (19)	0.0411 (6)
H1C	0.2516	1.0117	0.8870	0.049*
H1D	0.1989	1.1821	0.9491	0.049*
C2	0.3493 (4)	0.9393 (4)	1.03562 (19)	0.0426 (6)
H2B	0.3904	1.0149	1.0981	0.051*
H2A	0.2303	0.8603	1.0272	0.051*
Cl1	0.78737 (8)	0.59992 (10)	0.84112 (4)	0.0390 (2)
N1	0.5133 (3)	0.7985 (3)	1.03919 (15)	0.0401 (5)
H1B	0.4715	0.7234	0.9825	0.048*
H1A	0.5420	0.7115	1.0912	0.048*
O1	0.9198 (3)	0.7709 (4)	0.87194 (18)	0.0765 (7)
O2	0.7472 (3)	0.5298 (3)	0.92385 (14)	0.0561 (6)
O3	0.6016 (3)	0.6622 (3)	0.76257 (13)	0.0562 (6)
O4	0.8781 (4)	0.4421 (4)	0.80648 (18)	0.0853 (8)
O5	1.3089 (2)	0.5745 (3)	0.85594 (12)	0.0421 (5)
H5WB	1.3600	0.6040	0.8207	0.063*
H5WA	1.1857	0.5653	0.8324	0.063*

	U11	U22	U33	U12	U13	U23
C1	0.0416 (14)	0.0393 (14)	0.0403 (14)	0.0025 (11)	0.0140 (11)	0.0007 (11)
C2	0.0444 (14)	0.0446 (15)	0.0407 (14)	−0.0009 (12)	0.0189 (12)	0.0031 (11)
Cl1	0.0336 (3)	0.0498 (4)	0.0351 (3)	−0.0020 (3)	0.0152 (2)	−0.0022 (3)
N1	0.0538 (13)	0.0292 (10)	0.0348 (11)	−0.0025 (9)	0.0149 (9)	0.0020 (9)
O1	0.0532 (13)	0.0832 (17)	0.0868 (16)	−0.0303 (12)	0.0214 (12)	0.0037 (13)
O2	0.0542 (11)	0.0726 (14)	0.0442 (11)	−0.0003 (10)	0.0226 (9)	0.0140 (10)
O3	0.0415 (10)	0.0814 (15)	0.0391 (10)	0.0024 (10)	0.0091 (9)	0.0105 (10)
O4	0.0803 (16)	0.102 (2)	0.0775 (17)	0.0328 (15)	0.0362 (14)	−0.0225 (14)
O5	0.0373 (9)	0.0469 (11)	0.0433 (10)	0.0015 (8)	0.0174 (8)	0.0026 (8)

C1—N1i	1.487 (3)	Cl1—O1	1.421 (2)
C1—C2	1.500 (3)	Cl1—O2	1.4218 (19)
C1—H1C	0.97	Cl1—O3	1.4339 (19)
C1—H1D	0.97	N1—C1i	1.487 (3)
C2—N1	1.487 (3)	N1—H1B	0.90
C2—H2B	0.97	N1—H1A	0.90
C2—H2A	0.97	O5—H5WB	0.77
Cl1—O4	1.417 (2)	O5—H5WA	0.82
N1i—C1—C2	109.6 (2)	O4—Cl1—O2	110.46 (15)
N1i—C1—H1C	109.7	O1—Cl1—O2	109.05 (14)
C2—C1—H1C	109.7	O4—Cl1—O3	110.15 (14)
N1i—C1—H1D	109.7	O1—Cl1—O3	109.38 (14)
C2—C1—H1D	109.7	O2—Cl1—O3	108.62 (12)
H1C—C1—H1D	108.2	C2—N1—C1i	111.62 (19)
N1—C2—C1	109.7 (2)	C2—N1—H1B	109.3
N1—C2—H2B	109.7	C1i—N1—H1B	109.3
C1—C2—H2B	109.7	C2—N1—H1A	109.3
N1—C2—H2A	109.7	C1i—N1—H1A	109.3
C1—C2—H2A	109.7	H1B—N1—H1A	108.0
H2B—C2—H2A	108.2	H5WB—O5—H5WA	118.5
O4—Cl1—O1	109.16 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O5ii	0.90	2.00	2.875 (3)	165
N1—H1A···O5iii	0.90	2.14	2.883 (3)	140
N1—H1A···O3iv	0.90	2.49	3.060 (3)	122
N1—H1A···O2v	0.90	2.56	3.040 (3)	114
O5—H5WB···O3vi	0.77	2.26	2.999 (3)	161
O5—H5WA···O1	0.82	2.59	3.192 (3)	131
O5—H5WA···O4	0.82	2.26	3.040 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O5i	0.90	2.00	2.875 (3)	165
N1—H1A⋯O5ii	0.90	2.14	2.883 (3)	140
N1—H1A⋯O3iii	0.90	2.49	3.060 (3)	122
N1—H1A⋯O2iv	0.90	2.56	3.040 (3)	114
O5—H5WB⋯O3v	0.77	2.26	2.999 (3)	161
O5—H5WA⋯O1	0.82	2.59	3.192 (3)	131
O5—H5WA⋯O4	0.82	2.26	3.040 (3)	159

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