Three-dimensional network in piper­azine-1,4-diium–picrate–piperazine (1/2/1)

Wang, Z.-L.; Jia, L.-H.

doi:10.1107/S1600536808005710

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Pages o665-o666

doi:10.1107/S1600536808005710

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Three-dimensional network in piperazine-1,4-diium–picrate–piperazine (1/2/1)

Zhong-Long Wang ^a ^* and Li-Hui Jia ^b

^aScience College, Three-Gorges University, Yichang 443002, People's Republic of China, and ^bSchool of Chemical Engineering and Pharmacy, Wuhan Institute of Chemical Technology, Wuhan 430074, People's Republic of China
^*Correspondence e-mail: zhonglong_wang@126.com

(Received 19 February 2008; accepted 29 February 2008; online 5 March 2008)

In the title compound, C₄H₁₂N₂²⁺·2C₆H₂N₃O₇⁻·C₄H₁₀N₂, the piperazine-1,4-diium cations and piperazine molecules lie on crystallographic inversion centres. In the crystal structure, intermolecular 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 intermolecular C—H⋯O hydrogen bonds and π–π stacking interactions [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

C₄H₁₂N₂²⁺·2C₆H₂N₃O₇⁻·C₄H₁₀N₂
M_r = 630.50
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.068
wR(F²) = 0.169
S = 1.13
2258 reflections
208 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.27 e Å⁻³

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⋯O5^iv	0.97	2.60	3.272 (5)	127
C10—H10A⋯O4^v	0.97	2.52	3.310 (5)	138
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z; (iii) -x, -y+2, -z+1; (iv) -x+1, -y+3, -z+2; (v) -x+1, -y+2, -z+2.

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.

Supporting information

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

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

checkCIF report

Comment top

Studies of picric acid (abbr. PA, pKa = 0.38) have been carried out for many years due to its formation of salts which involve electrostatic forces, multiple hydrogen bond modes (e.g. Hundal et al., 1997; Szumna et al., 2000) and π–π stacking interactions (Colquhoun et al., 1986) which can improve the quality of the crystalline materials. Recently, picrate anion containing molecular adducts have also been reported frequently in order to probe the competition between various intermolecular forces in crystal engineering (Anitha et al., 2006a, 2006b; Vembu et al., 2003; Ma et al., 2005; Akutagawa et al., 2003, Kavitha et al., 2005; Arnaud et al., 2007). As part of our study on molecular adducts involved with PA and piperazine (abbr. PP), we report here the molecular and supra-molecular structure of the title compound (I).

In (I), the asymmetric unit (atoms labelled without lower case suffixes in Fig.1) consists of one picrate anion, half a PA di-cation and half a neutral PA molecule. In the picrate anion, the nitro group at the 4-position is almost coplanar with the phenyl ring with a dihedral angle of only 4.1 (2)°, however, the nitro groups at the 2- and 6-positions are both significantly twisted out of the plane of the benzene ring, with dihedral angles of 45.2 (2)° and 21.7 (2)°, respectively. The rotations of the nitro groups at the 2- and 6- positions means that the picrate anion retains the approximate mirror symmetry which is also observed in the structure of a recently reported analog (Kavitha et al., 2006).

Analysis of the crystal packing of (I) shows that the component ions and molecules are linked into a simple three-dimensional network by a combination of N–H···O (or N), C–H···O hydrogen bonds and π–π stacking interactions which can be analyzed in terms of several substructures. First, by the co-operative hydrogen-bonding actions, i.e. bifurcated N4···O1(O7), bifurcated C8···O1(O2) and C7···O1 (-x, 2 - y, 1 - z) hydrogen bonds, the PA anions, PP di-cations and PP neutral molecules are linked into a one-dimensional tape structure parallel to the [110] direction generated by translation and inversion operations (Fig.2). Secondly, by a combinative actions of N5—H5A···O2 (x, 1 + y, z) and C2—H2···O6 (x, y - 1, z) hydrogen-bonds, the adjacent [110] 1-D tapes are joined together, forming a two-dimensional layer parallel to the (001) plane lying in domain of -0.299 < z < 1.299 (Fig.3). Finally, the neighbouring (001) layers are joined together by means of C9···O5 (-x + 1, -y + 3, -z + 2), C10···O4 (-x + 1, -y + 2, -z + 2) hydrogen bonds and π–π stacking interactions, which form the simple 3-D network. The geometry details of the π–π stacking interactions are as follows. The C1—C6 aryl rings of the anions at (x, y, z) and (1 - x, 2 - y, 2 - z) are strictly parallel, with an inter-planar spacing of 3.500 (2) Å; the ring-centroid separation is 3.764 (2) Å, corresponding to a ring offset of 1.387 (2) Å.

Related literature top

For related literature, see: Akutagawa et al. (2003); Allen et al. (1987); 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 top

All the reagents and solvents were used as obtained without further purification. 1:2 molar amount of anhydrous piperazine (0.2 mmol, 17.2 mg) and picric acid (0.4 mmol, 91.6 mg) were dissolved in 95% methanol (10 ml). The mixture was stirred for half an hour at ambient temperature and then filtered. The resulting yellow solution was kept in air for several days. Plate yellow crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution at the bottom of the vessel (yield: 45%, 56.7 mg, based on 2:1 organic salt; melting point: 512–514 K).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 (Spek, 2003).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Inter-ion hydrogen bonds are shown as dashed lines, atoms marked with 'a', 'b' and 'c' are at symmetry positions (-x, 2 - y, 1 - z), (1 - x, 3 - y, 1 - z) and (-1 + x, -1 + y, z), respectively. An additional piperazine molecule is shown to illustrate the hydrogen bonding.
	Fig. 2. Part of the crystal structure of (I), showing the formation of the one-dimensional tape running parallel to the [110] direction. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motifs have been omitted. [symmetry code: (iii) -x, -y + 2, -z + 1]
	Fig. 3. Part of the crystal structure of (I), showing the linkage of adjacent 2-D layers by C9—H9A···O5, C10—H10A···O4 hydrogen bonds and π-π stacking interactions, which form the three-dimensional network. The green outlined area shows the 2-D layer parallel to the (001) plane. For the sake of clarity, H atoms not involved in the motifs have been omitted.

piperazine-1,4-diium–picrate–piperazine (1/2/1) top

Crystal data top

C₄H₁₂N₂²⁺·2C₆H₂N₃O₇⁻·C₄H₁₀N₂	Z = 1
M_r = 630.50	F(000) = 328
Triclinic, P1	D_x = 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 = 2.7–26.2°
c = 11.3024 (8) Å	µ = 0.14 mm⁻¹
α = 98.140 (1)°	T = 299 K
β = 98.974 (1)°	Plate, yellow
γ = 109.250 (1)°	0.20 × 0.10 × 0.06 mm
V = 649.62 (8) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2258 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1917 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
0.3° wide ω exposures scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→9
T_min = 0.963, T_max = 0.992	k = −9→9
6131 measured reflections	l = −13→13

Refinement top

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0397P)² + 1.340P] where P = (F_o² + 2F_c²)/3
2258 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₄H₁₂N₂²⁺·2C₆H₂N₃O₇⁻·C₄H₁₀N₂	γ = 109.250 (1)°
M_r = 630.50	V = 649.62 (8) Å³
Triclinic, P1	Z = 1
a = 7.7150 (6) Å	Mo Kα radiation
b = 8.1658 (6) Å	µ = 0.14 mm⁻¹
c = 11.3024 (8) Å	T = 299 K
α = 98.140 (1)°	0.20 × 0.10 × 0.06 mm
β = 98.974 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2258 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1917 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.992	R_int = 0.028
6131 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.27 e Å⁻³
2258 reflections	Δρ_min = −0.27 e Å⁻³
208 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+3, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O6^iv	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···O5^v	0.97	2.60	3.272 (5)	127
C10—H10A···O4^vi	0.97	2.52	3.310 (5)	138

Symmetry codes: (i) −x, −y+2, −z+1; (iii) x, y+1, z; (iv) x, y−1, z; (v) −x+1, −y+3, −z+2; (vi) −x+1, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N₂²⁺·2C₆H₂N₃O₇⁻·C₄H₁₀N₂
M_r	630.50
Crystal system, space group	Triclinic, P1
Temperature (K)	299
a, b, c (Å)	7.7150 (6), 8.1658 (6), 11.3024 (8)
α, β, γ (°)	98.140 (1), 98.974 (1), 109.250 (1)
V (Å³)	649.62 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.20 × 0.10 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.963, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	6131, 2258, 1917
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.169, 1.13
No. of reflections	2258
No. of parameters	208
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.27

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

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···O5^iv	0.97	2.60	3.272 (5)	127
C10—H10A···O4^v	0.97	2.52	3.310 (5)	138

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x, −y+2, −z+1; (iv) −x+1, −y+3, −z+2; (v) −x+1, −y+2, −z+2.

Acknowledgements

This work received financial support from the Hubei Province Key Fundamental Project.

References

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