Three-dimensional network in piper-azine-1,4-diium-picrate-piperazine (1/2/1).

In the title compound, C(4)H(12)N(2) (2+)·2C(6)H(2)N(3)O(7) (-)·C(4)H(10)N(2), the piperazine-1,4-diium cations and piperazine mol-ecules lie on crystallographic inversion centres. In the crystal structure, inter-molecular N-H⋯O and N-H⋯N hydrogen bonds link the components to form two-dimensional layers parallel to the (001) plane. These layers are, in turn, connected by weak inter-molecular C-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance between parallel aryl rings = 3.764 (2) Å, interplanar spacing = 3.500 (2) Å and ring offset = 1.387 (2) Å], forming a three-dimensional framework.

Related literature

For related literature, see: Akutagawa et al. (2003 ▶); Anitha et al. (2006a ▶,b ▶); Arnaud et al. (2007 ▶); Colquhoun et al. (1986 ▶); Hundal et al. (1997 ▶); Kavitha et al. (2005 ▶, 2006 ▶); Ma et al. (2005 ▶); Szumna et al. (2000 ▶); Vembu et al. (2003 ▶).

Experimental

Crystal data

C4H12N2 2+·2C6H2N3O7 −·C4H10N2

M = 630.50

Triclinic,

a = 7.7150 (6) Å

b = 8.1658 (6) Å

c = 11.3024 (8) Å

α = 98.140 (1)°

β = 98.974 (1)°

γ = 109.250 (1)°

V = 649.62 (8) Å3

Z = 1

Mo Kα radiation

μ = 0.14 mm−1

T = 299 (2) K

0.20 × 0.10 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.963, T max = 0.992

6131 measured reflections

2258 independent reflections

1917 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.169

S = 1.13

2258 reflections

208 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005710/lh2598sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005710/lh2598Isup2.hkl

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

C4H12N22+·2C6H2N3O7–·C4H10N2	Z = 1
Mr = 630.50	F000 = 328
Triclinic, P1	Dx = 1.612 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.7150 (6) Å	Cell parameters from 2518 reflections
b = 8.1658 (6) Å	θ = 2.7–26.2º
c = 11.3024 (8) Å	µ = 0.14 mm−1
α = 98.140 (1)º	T = 299 (2) K
β = 98.974 (1)º	Plate, yellow
γ = 109.250 (1)º	0.20 × 0.10 × 0.06 mm
V = 649.62 (8) Å3

Bruker SMART APEX CCD area-detector diffractometer	2258 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1917 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.028
T = 299(2) K	θmax = 25.0º
0.3° wide ω exposures scans	θmin = 2.7º
Absorption correction: multi-scan(SADABS; Sheldrick, 1997)	h = −9→9
Tmin = 0.963, Tmax = 0.992	k = −9→9
6131 measured reflections	l = −13→13

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)] = 0.068	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.169	w = 1/[σ2(Fo2) + (0.0397P)2 + 1.340P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
2258 reflections	Δρmax = 0.27 e Å−3
208 parameters	Δρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	0.1576 (5)	0.8052 (4)	0.9002 (3)	0.0332 (8)
C2	0.2353 (5)	0.7965 (5)	1.0152 (3)	0.0378 (9)
H2	0.2296	0.6883	1.0348	0.045*
C3	0.3230 (5)	0.9530 (5)	1.1019 (3)	0.0348 (8)
C4	0.3317 (5)	1.1141 (5)	1.0738 (3)	0.0380 (9)
H4	0.3912	1.2181	1.1329	0.046*
C5	0.2518 (5)	1.1200 (5)	0.9578 (3)	0.0371 (8)
C6	0.1526 (5)	0.9660 (5)	0.8609 (3)	0.0333 (8)
C7	0.1883 (5)	1.0168 (5)	0.4896 (3)	0.0392 (9)
H7A	0.3073	1.0068	0.5226	0.047*
H7B	0.1971	1.0570	0.4132	0.047*
C8	0.0332 (5)	0.8378 (5)	0.4654 (3)	0.0381 (9)
H8A	0.0549	0.7561	0.4034	0.046*
H8B	0.0337	0.7912	0.5397	0.046*
C9	0.3474 (5)	1.5596 (5)	0.4793 (4)	0.0405 (9)
H9A	0.4124	1.6869	0.4938	0.049*
H9B	0.2133	1.5352	0.4581	0.049*
C10	0.5940 (5)	1.5299 (5)	0.6247 (3)	0.0386 (9)
H10A	0.6210	1.4848	0.6976	0.046*
H10B	0.6639	1.6566	0.6425	0.046*
N1	0.0732 (4)	0.6390 (4)	0.8092 (3)	0.0405 (8)
N2	0.4143 (5)	0.9504 (4)	1.2226 (3)	0.0443 (8)
N3	0.2705 (6)	1.2965 (4)	0.9349 (3)	0.0528 (9)
N4	0.1521 (4)	1.1476 (4)	0.5768 (3)	0.0364 (7)
H4A	0.157 (6)	1.118 (5)	0.647 (4)	0.044*
H4B	0.228 (6)	1.255 (6)	0.584 (4)	0.044*
N5	0.3922 (5)	1.4953 (4)	0.5905 (3)	0.0383 (7)
H5A	0.359 (6)	1.548 (5)	0.649 (4)	0.046*
O1	0.0655 (4)	0.9638 (4)	0.7581 (2)	0.0471 (7)
O2	0.1103 (5)	0.6367 (4)	0.7077 (3)	0.0579 (8)
O3	−0.0265 (5)	0.5088 (4)	0.8379 (3)	0.0720 (10)
O4	0.4179 (6)	0.8106 (4)	1.2447 (3)	0.0925 (14)
O5	0.4870 (5)	1.0892 (4)	1.2985 (3)	0.0599 (9)
O6	0.3035 (6)	1.4152 (4)	1.0227 (3)	0.0831 (12)
O7	0.2583 (6)	1.3203 (4)	0.8304 (3)	0.0799 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0349 (19)	0.0294 (18)	0.0331 (19)	0.0089 (15)	0.0063 (15)	0.0074 (15)
C2	0.044 (2)	0.0331 (19)	0.036 (2)	0.0137 (17)	0.0052 (17)	0.0123 (16)
C3	0.041 (2)	0.039 (2)	0.0265 (18)	0.0153 (16)	0.0073 (15)	0.0104 (15)
C4	0.043 (2)	0.0330 (19)	0.037 (2)	0.0147 (16)	0.0079 (16)	0.0037 (15)
C5	0.048 (2)	0.034 (2)	0.0346 (19)	0.0204 (17)	0.0097 (17)	0.0113 (15)
C6	0.0357 (19)	0.038 (2)	0.0319 (19)	0.0159 (16)	0.0114 (16)	0.0127 (15)
C7	0.0343 (19)	0.041 (2)	0.043 (2)	0.0122 (16)	0.0077 (16)	0.0143 (17)
C8	0.045 (2)	0.0317 (19)	0.040 (2)	0.0151 (16)	0.0065 (17)	0.0120 (16)
C9	0.035 (2)	0.0284 (18)	0.055 (2)	0.0098 (15)	0.0019 (17)	0.0097 (17)
C10	0.047 (2)	0.0268 (18)	0.0346 (19)	0.0065 (16)	0.0011 (16)	0.0090 (15)
N1	0.0443 (19)	0.0374 (18)	0.0353 (18)	0.0124 (15)	0.0026 (14)	0.0059 (14)
N2	0.052 (2)	0.0418 (19)	0.0361 (18)	0.0139 (16)	0.0038 (15)	0.0122 (15)
N3	0.081 (3)	0.0366 (19)	0.045 (2)	0.0290 (18)	0.0066 (18)	0.0097 (16)
N4	0.0375 (17)	0.0305 (16)	0.0325 (17)	0.0015 (13)	0.0018 (13)	0.0119 (13)
N5	0.0465 (19)	0.0312 (16)	0.0364 (17)	0.0113 (14)	0.0139 (14)	0.0050 (13)
O1	0.0584 (17)	0.0417 (15)	0.0355 (15)	0.0130 (13)	−0.0024 (13)	0.0163 (12)
O2	0.083 (2)	0.0518 (18)	0.0359 (16)	0.0215 (16)	0.0153 (15)	0.0029 (13)
O3	0.082 (2)	0.0404 (17)	0.070 (2)	−0.0071 (16)	0.0138 (18)	0.0096 (16)
O4	0.140 (4)	0.0456 (19)	0.063 (2)	0.017 (2)	−0.035 (2)	0.0223 (17)
O5	0.082 (2)	0.0534 (19)	0.0335 (15)	0.0252 (17)	−0.0068 (15)	−0.0042 (14)
O6	0.150 (4)	0.0452 (19)	0.061 (2)	0.053 (2)	0.010 (2)	0.0046 (16)
O7	0.142 (4)	0.0444 (19)	0.049 (2)	0.030 (2)	0.005 (2)	0.0194 (15)

C1—C2	1.366 (5)	C9—N5	1.465 (5)
C1—C6	1.454 (5)	C9—C10ii	1.504 (5)
C1—N1	1.461 (5)	C9—H9A	0.9700
C2—C3	1.385 (5)	C9—H9B	0.9700
C2—H2	0.9300	C10—N5	1.465 (5)
C3—C4	1.380 (5)	C10—C9ii	1.504 (5)
C3—N2	1.441 (5)	C10—H10A	0.9700
C4—C5	1.373 (5)	C10—H10B	0.9700
C4—H4	0.9300	N1—O3	1.210 (4)
C5—C6	1.442 (5)	N1—O2	1.224 (4)
C5—N3	1.464 (5)	N2—O4	1.210 (4)
C6—O1	1.243 (4)	N2—O5	1.221 (4)
C7—N4	1.475 (5)	N3—O6	1.215 (4)
C7—C8	1.508 (5)	N3—O7	1.219 (4)
C7—H7A	0.9700	N4—C8i	1.484 (5)
C7—H7B	0.9700	N4—H4A	0.86 (4)
C8—N4i	1.484 (5)	N4—H4B	0.86 (4)
C8—H8A	0.9700	N5—H5A	0.86 (4)
C8—H8B	0.9700
C2—C1—C6	125.4 (3)	N5—C9—C10ii	110.2 (3)
C2—C1—N1	117.1 (3)	N5—C9—H9A	109.6
C6—C1—N1	117.5 (3)	C10ii—C9—H9A	109.6
C1—C2—C3	118.3 (3)	N5—C9—H9B	109.6
C1—C2—H2	120.8	C10ii—C9—H9B	109.6
C3—C2—H2	120.8	H9A—C9—H9B	108.1
C4—C3—C2	121.2 (3)	N5—C10—C9ii	109.1 (3)
C4—C3—N2	118.7 (3)	N5—C10—H10A	109.9
C2—C3—N2	120.0 (3)	C9ii—C10—H10A	109.9
C5—C4—C3	119.5 (3)	N5—C10—H10B	109.9
C5—C4—H4	120.2	C9ii—C10—H10B	109.9
C3—C4—H4	120.2	H10A—C10—H10B	108.3
C4—C5—C6	124.3 (3)	O3—N1—O2	122.7 (3)
C4—C5—N3	116.0 (3)	O3—N1—C1	118.9 (3)
C6—C5—N3	119.7 (3)	O2—N1—C1	118.3 (3)
O1—C6—C5	126.4 (3)	O4—N2—O5	122.3 (3)
O1—C6—C1	122.4 (3)	O4—N2—C3	118.7 (3)
C5—C6—C1	111.1 (3)	O5—N2—C3	119.0 (3)
N4—C7—C8	110.9 (3)	O6—N3—O7	122.6 (4)
N4—C7—H7A	109.5	O6—N3—C5	117.9 (3)
C8—C7—H7A	109.5	O7—N3—C5	119.5 (3)
N4—C7—H7B	109.5	C7—N4—C8i	112.2 (3)
C8—C7—H7B	109.5	C7—N4—H4A	109 (3)
H7A—C7—H7B	108.0	C8i—N4—H4A	109 (3)
N4i—C8—C7	110.4 (3)	C7—N4—H4B	114 (3)
N4i—C8—H8A	109.6	C8i—N4—H4B	102 (3)
C7—C8—H8A	109.6	H4A—N4—H4B	110 (4)
N4i—C8—H8B	109.6	C10—N5—C9	110.9 (3)
C7—C8—H8B	109.6	C10—N5—H5A	109 (3)
H8A—C8—H8B	108.1	C9—N5—H5A	109 (3)
C6—C1—C2—C3	−2.3 (6)	N4—C7—C8—N4i	55.1 (4)
N1—C1—C2—C3	177.5 (3)	C2—C1—N1—O3	44.6 (5)
C1—C2—C3—C4	0.2 (6)	C6—C1—N1—O3	−135.6 (4)
C1—C2—C3—N2	−177.1 (3)	C2—C1—N1—O2	−133.7 (4)
C2—C3—C4—C5	0.2 (6)	C6—C1—N1—O2	46.1 (5)
N2—C3—C4—C5	177.5 (3)	C4—C3—N2—O4	−175.0 (4)
C3—C4—C5—C6	1.6 (6)	C2—C3—N2—O4	2.4 (6)
C3—C4—C5—N3	−178.8 (3)	C4—C3—N2—O5	4.3 (5)
C4—C5—C6—O1	173.8 (4)	C2—C3—N2—O5	−178.4 (4)
N3—C5—C6—O1	−5.7 (6)	C4—C5—N3—O6	−20.6 (6)
C4—C5—C6—C1	−3.2 (5)	C6—C5—N3—O6	159.0 (4)
N3—C5—C6—C1	177.2 (3)	C4—C5—N3—O7	157.2 (4)
C2—C1—C6—O1	−173.5 (4)	C6—C5—N3—O7	−23.2 (6)
N1—C1—C6—O1	6.7 (5)	C8—C7—N4—C8i	−56.1 (4)
C2—C1—C6—C5	3.7 (5)	C9ii—C10—N5—C9	−58.5 (4)
N1—C1—C6—C5	−176.1 (3)	C10ii—C9—N5—C10	59.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1	0.86 (4)	1.95 (4)	2.745 (4)	153 (4)
N4—H4A···O7	0.86 (4)	2.31 (4)	2.870 (5)	123 (3)
N4—H4B···N5	0.86 (4)	1.94 (4)	2.799 (4)	176 (4)
N5—H5A···O2iii	0.86 (4)	2.41 (4)	3.153 (5)	145 (4)
C2—H2···O6iv	0.93	2.47	3.335 (5)	155
C7—H7B···O1i	0.97	2.52	3.211 (5)	128
C8—H8B···O1	0.97	2.60	3.267 (5)	127
C8—H8B···O2	0.97	2.52	3.458 (5)	162
C9—H9A···O5v	0.97	2.60	3.272 (5)	127
C10—H10A···O4vi	0.97	2.52	3.310 (5)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1	0.86 (4)	1.95 (4)	2.745 (4)	153 (4)
N4—H4A⋯O7	0.86 (4)	2.31 (4)	2.870 (5)	123 (3)
N4—H4B⋯N5	0.86 (4)	1.94 (4)	2.799 (4)	176 (4)
N5—H5A⋯O2i	0.86 (4)	2.41 (4)	3.153 (5)	145 (4)
C2—H2⋯O6ii	0.93	2.47	3.335 (5)	155
C7—H7B⋯O1iii	0.97	2.52	3.211 (5)	128
C8—H8B⋯O1	0.97	2.60	3.267 (5)	127
C8—H8B⋯O2	0.97	2.52	3.458 (5)	162
C9—H9A⋯O5iv	0.97	2.60	3.272 (5)	127
C10—H10A⋯O4v	0.97	2.52	3.310 (5)	138

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