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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 8| August 2012| Page o2388
https://doi.org/10.1107/S1600536812030103

2,2′-(Piperazine-1,4-di­yl)diethanaminium bis­­(2-hy­dr­oxy­benzoate)

Ignacy Cukrowski,a* Adedapo S. Adeyinkaa and David C. Lilesa

aDepartment of Chemistry, University of Pretoria, Private Bag X20, Hatfield 0028, South Africa
*Correspondence e-mail: ignacy.cukrowski@up.ac.za

(Received 26 April 2012; accepted 2 July 2012; online 7 July 2012)

The asymmetric unit of the title salt, C8H22N42+·2C7H5O3−, comprises half a 2,2′-(piperazine-1,4-di­yl)diethan­aminium dication plus a 2-hy­droxy­benzoate anion. In the crystal, the anions and cations are linked by N—H⋯O and O—H⋯O hydrogen bonds to form infinite two-dimensional networks parallel with the a unit-cell face. The conformation adopted by the cation in the crystal is very similar to that adopted by the same cation in the structures of the nitrate and tetra­hydrogen penta­borate salts.

Related literature

For the structures of the nitrate and tetra­hydrogen penta­borate salts of the 1,4-di(2-ammonio­eth­yl)piperazine cation, see: Junk & Smith (2005[Junk, P. C. & Smith, M. K. (2005). C. R. Chim. 8, 189-198.]); Jiang et al. (2009[Jiang, X., Liu, H.-X., Wu, S.-L. & Liang, Y.-X. (2009). Jiegou Huaxue (Chin. J. Struct. Chem.), 28, 723-729.]); Yang et al. (2011[Yang, Y., Sun, J.-B., Cui, M., Liu, R.-B., Wang, Y. & Meng, C.-G. (2011). J. Solid State Chem. 184, 1666-1670.]).

[Scheme 1]

Experimental

Crystal data

  • C8H22N42+·2C7H5O3−

  • Mr = 448.52

  • Monoclinic, P 21 /c

  • a = 11.5374 (4) Å

  • b = 6.4759 (2) Å

  • c = 15.5264 (6) Å

  • β = 104.207 (2)°

  • V = 1124.58 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 180 K

  • 0.37 × 0.10 × 0.05 mm
Data collection

  • Nonius KappaCCD diffractometer

  • Absorption correction: multi-scan (SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.852, Tmax = 0.995

  • 19655 measured reflections

  • 3261 independent reflections

  • 2013 reflections with I > 2σ(I)

  • Rint = 0.065
Refinement

  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.147

  • S = 1.08

  • 3261 reflections

  • 157 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.34 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯O14 0.929 (17) 1.992 (18) 2.8853 (17) 160.9 (14)
N1—H1B⋯O14i 0.900 (18) 1.923 (19) 2.7909 (17) 161.5 (14)
N1—H1C⋯O15ii 0.892 (18) 1.902 (19) 2.7843 (17) 169.9 (15)
O16—H16⋯O15 0.81 (2) 1.83 (2) 2.5641 (16) 149.4 (19)
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]), SCALEPACK and SORTAV (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]); program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]), POV-RAY (Cason, 2004[Cason, C. J. (2004). POV-RAY for Windows. Persistence of Vision Raytracer Pty Ltd, Victoria, Australia. URL: http://www.povray.org.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812030103/jj2133sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030103/jj2133Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812030103/jj2133Isup3.cml

checkCIF report


Comment top

The title compound [C8H22N42+ 2(C7H5O3-)] (1) was obtained as an unintended product during an attempt to prepare a 2-hydroxybenzoate salt of a singly protonated N,N'-di(2-aminoethyl)-2-aminoethane-1-ammonium ion (C6H19N4+ C7H5O3-). This occurred because the starting material, instead of being pure N,N'-di(2-aminoethyl)-ethane-1,2-diamine (C6H18N4), was a mixture of that compound and 1,4-di(2-aminoethyl)piperazine (C8H22N4). A similar situation appears to have occurred for a published structure which the authors (Yang, et al., 2011) claim to be a N,N'-di(2-ammonioethyl)-ethane-1,2-diamine (i.e. a doubly protonated ion derived from C6H18N4) salt of tetrahydrogenpentaborate (H4B5O10-) but with the central C2H4 moiety disordered over two sites. In fact the two "disordered" C2H4 sites together with the two adjacent N atoms form the central piperazine ring of a 1,4-di(2-ammonioethyl)piperazine ion (C8H22N42+) and the reported crystal structure is identical (within experimental error) with that of C8H22N42+ 2(H4B5O10-) (Jiang, et al., 2009).

The C8H22N42+ cation in 1 is symmetrical and lies across a crystallographic centre of inversion. Each ammonium group in the cations of 1 is the donor for three hydrogen bonds to the O atoms of the carboxylate groups of three different 2-hydroxybenzoate anions (Fig. 1). There is also an intra-molecular hydrogen bond between the hydroxy group and one of the carboxylate O atoms in the C7H5O3- anions. Thus both the O atoms of each carboxylate group are each acceptors for two hydrogen bonds. The hydrogen bonds link the cations and anions to form two-dimensional networks with the layers parallel with the A face of the unit cell (Fig. 2).

Fig. 3 illustrates that the conformation adopted by the C8H22N42+ cation in the crystal structure of 1 is very similar to the conformations adopted by the same cation in the crystal structures of the NO3- (Junk & Smith, 2005) and the H4B5O10- (Jiang, et al., 2009) salts despite the differences in the size and shape of the anions in the various structures.

Related literature top

For the structures of the nitrate and tetrahydrogen pentaborate salts of the 1,4-di(2-ammonioethyl)piperazine cation, see: Junk & Smith (2005); Jiang et al. (2009); Yang, et al. (2011).

Experimental top

2 ml of a 3.32 M aqueous solution of what was claimed by the supplier (QinHuangDao JinLei Chemical Co.Ltd) to be N,N'-di(2-aminoethyl)-ethane-1,2-diamine, but which turned out to be a mixture of that compound (C6H18N4, 6.64n mmol) and 1,4-di(2-aminoethyl)piperazine (C8H20N4, 5.57(1-n) mmol) was added to 0.96 g of 2-hydroxybenzoic acid (6.95 mmol), resulting in a clear colourless solution. 0.2 ml of ethanol was added to the solution and the mixture was heated for 3 h at 70 °C, the solution turned greenish yellow after one hour of heating. It was cooled to room temperature and then left covered for six days and then allowed to slowly evaporate by covering the container with perforated aluminium foil. Yellow crystals were obtained after four days of slow evaporation.

Refinement top

H1A, H1B and H1C were located by a difference map and their coordinates were refined. All of the remaining H atoms were placed in their calculated positions and then refined using the riding model with Atom—H lengths of 0.95 Å, (CH) or 0.99 Å (CH2). Isotropic displacement parameters for all hydrogen atoms were set to 1.20 times Ueq of the parent atom.

Structure description top

The title compound [C8H22N42+ 2(C7H5O3-)] (1) was obtained as an unintended product during an attempt to prepare a 2-hydroxybenzoate salt of a singly protonated N,N'-di(2-aminoethyl)-2-aminoethane-1-ammonium ion (C6H19N4+ C7H5O3-). This occurred because the starting material, instead of being pure N,N'-di(2-aminoethyl)-ethane-1,2-diamine (C6H18N4), was a mixture of that compound and 1,4-di(2-aminoethyl)piperazine (C8H22N4). A similar situation appears to have occurred for a published structure which the authors (Yang, et al., 2011) claim to be a N,N'-di(2-ammonioethyl)-ethane-1,2-diamine (i.e. a doubly protonated ion derived from C6H18N4) salt of tetrahydrogenpentaborate (H4B5O10-) but with the central C2H4 moiety disordered over two sites. In fact the two "disordered" C2H4 sites together with the two adjacent N atoms form the central piperazine ring of a 1,4-di(2-ammonioethyl)piperazine ion (C8H22N42+) and the reported crystal structure is identical (within experimental error) with that of C8H22N42+ 2(H4B5O10-) (Jiang, et al., 2009).

The C8H22N42+ cation in 1 is symmetrical and lies across a crystallographic centre of inversion. Each ammonium group in the cations of 1 is the donor for three hydrogen bonds to the O atoms of the carboxylate groups of three different 2-hydroxybenzoate anions (Fig. 1). There is also an intra-molecular hydrogen bond between the hydroxy group and one of the carboxylate O atoms in the C7H5O3- anions. Thus both the O atoms of each carboxylate group are each acceptors for two hydrogen bonds. The hydrogen bonds link the cations and anions to form two-dimensional networks with the layers parallel with the A face of the unit cell (Fig. 2).

Fig. 3 illustrates that the conformation adopted by the C8H22N42+ cation in the crystal structure of 1 is very similar to the conformations adopted by the same cation in the crystal structures of the NO3- (Junk & Smith, 2005) and the H4B5O10- (Jiang, et al., 2009) salts despite the differences in the size and shape of the anions in the various structures.

For the structures of the nitrate and tetrahydrogen pentaborate salts of the 1,4-di(2-ammonioethyl)piperazine cation, see: Junk & Smith (2005); Jiang et al. (2009); Yang, et al. (2011).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997), SCALEPACK and SORTAV (Blessing, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997), POV-RAY (Cason, 2004) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50° probability displacement ellipsoids. Broken lines indicate N—H···O and O—H···O hydrogen bonds. Symmetry codes: (ii) -x + 1, y - 1/2, -z + 3/2; (iii) -x + 1, y + 1/2, -z + 3/2.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed offset from along the b axis. Dashed lines indicate N—H···O and O—H···O hydrogen bonds. The intermolecular N—H···O hydrogen bonds form a two-dimensional network.
[Figure 3] Fig. 3. The structures of the 1,4-di(2-ammonioethyl)piperazine cations of the C7H5O3- (standard atom colours, 1), the NO3- (green, Junk & Smith, 2005) and the H4B5O10- (red, Jiang, et al., 2009) salts, superimposed on each other to show the similar conformations adopted by the cations in all three structures.
2,2'-(Piperazine-1,4-diyl)diethanaminium bis(2-hydroxybenzoate) top
Crystal data top
C8H22N42+·2C7H5O3−F(000) = 480
Mr = 448.52Dx = 1.325 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 26933 reflections
a = 11.5374 (4) Åθ = 1.0–30.0°
b = 6.4759 (2) ŵ = 0.10 mm−1
c = 15.5264 (6) ÅT = 180 K
β = 104.207 (2)°Block, yellow
V = 1124.58 (7) Å30.37 × 0.10 × 0.05 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		3261 independent reflections
Radiation source: fine-focus sealed tube2013 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
Thin slice ω and φ scansθmax = 30.0°, θmin = 3.6°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)		h = −16→16
Tmin = 0.852, Tmax = 0.995k = −8→9
19655 measured reflectionsl = −21→21
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: difference Fourier map
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0714P)2 + 0.0149P]
where P = (Fo2 + 2Fc2)/3
3261 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C8H22N42+·2C7H5O3−V = 1124.58 (7) Å3
Mr = 448.52Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.5374 (4) ŵ = 0.10 mm−1
b = 6.4759 (2) ÅT = 180 K
c = 15.5264 (6) Å0.37 × 0.10 × 0.05 mm
β = 104.207 (2)°
Data collection top
Nonius KappaCCD
diffractometer		3261 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)		2013 reflections with I > 2σ(I)
Tmin = 0.852, Tmax = 0.995Rint = 0.065
19655 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.34 e Å−3
3261 reflectionsΔρmin = −0.28 e Å−3
157 parameters
Special details top

Experimental. The –OH and –NH3 hydrogen atoms were located and their positions were refined satisfactorily.

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
xyzUiso*/Ueq
N10.39360 (12)0.1995 (2)0.71495 (9)0.0296 (3)
H1A0.4724 (16)0.215 (2)0.7117 (11)0.036*
H1B0.3890 (14)0.076 (3)0.7403 (10)0.036*
H1C0.3822 (14)0.299 (3)0.7516 (11)0.036*
C20.30579 (14)0.2076 (2)0.62703 (10)0.0355 (4)
H2A0.22420.18660.63520.043*
H2B0.32280.09450.58900.043*
C30.31138 (13)0.4123 (2)0.58149 (11)0.0328 (4)
H3A0.24670.41860.52620.039*
H3B0.29850.52570.62090.039*
N40.42749 (11)0.44057 (19)0.55982 (8)0.0321 (3)
C50.43393 (14)0.3166 (2)0.48157 (11)0.0350 (4)
H5A0.36910.35930.43020.042*
H5B0.42190.16910.49370.042*
C60.44661 (14)0.6567 (2)0.54111 (10)0.0332 (4)
H6A0.44460.74190.59370.040*
H6B0.38170.70440.49070.040*
C70.80219 (12)0.2749 (2)0.66915 (9)0.0261 (3)
C80.84808 (13)0.4670 (2)0.70044 (10)0.0307 (3)
H80.81290.53940.74080.037*
C90.94297 (13)0.5555 (2)0.67466 (11)0.0356 (4)
H90.97310.68630.69730.043*
C100.99343 (14)0.4510 (3)0.61536 (11)0.0390 (4)
H101.05840.51110.59680.047*
C110.95065 (15)0.2608 (3)0.58287 (11)0.0381 (4)
H110.98610.19080.54200.046*
C120.85550 (13)0.1702 (2)0.60957 (10)0.0306 (3)
C130.69936 (13)0.1830 (2)0.69894 (9)0.0273 (3)
O140.64524 (9)0.28943 (15)0.74448 (7)0.0321 (3)
O150.67079 (11)−0.00229 (16)0.67621 (7)0.0393 (3)
O160.81677 (11)−0.01682 (18)0.57563 (8)0.0418 (3)
H160.7652 (17)−0.055 (3)0.5996 (14)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0299 (7)0.0264 (7)0.0360 (7)−0.0006 (6)0.0145 (6)0.0013 (6)
C20.0369 (8)0.0391 (9)0.0326 (8)−0.0098 (7)0.0124 (7)−0.0004 (7)
C30.0312 (8)0.0365 (9)0.0327 (8)0.0006 (7)0.0115 (6)0.0030 (7)
N40.0301 (7)0.0310 (7)0.0359 (7)−0.0020 (5)0.0091 (5)0.0064 (6)
C50.0381 (8)0.0336 (8)0.0345 (9)−0.0029 (7)0.0111 (7)0.0020 (7)
C60.0362 (8)0.0299 (8)0.0339 (8)0.0013 (7)0.0094 (7)0.0017 (7)
C70.0249 (7)0.0260 (7)0.0270 (7)0.0011 (6)0.0057 (6)0.0028 (6)
C80.0265 (7)0.0302 (8)0.0359 (8)0.0007 (6)0.0084 (6)−0.0030 (7)
C90.0298 (8)0.0322 (8)0.0435 (9)−0.0052 (7)0.0068 (7)0.0011 (7)
C100.0289 (8)0.0464 (10)0.0434 (9)−0.0028 (7)0.0123 (7)0.0066 (8)
C110.0355 (8)0.0446 (10)0.0387 (9)0.0066 (7)0.0180 (7)0.0010 (7)
C120.0332 (8)0.0278 (7)0.0309 (8)0.0021 (6)0.0076 (6)0.0013 (6)
C130.0294 (7)0.0254 (7)0.0266 (7)−0.0011 (6)0.0061 (6)0.0025 (6)
O140.0321 (6)0.0299 (6)0.0379 (6)0.0002 (4)0.0154 (5)−0.0010 (5)
O150.0528 (7)0.0291 (6)0.0409 (6)−0.0125 (5)0.0210 (5)−0.0062 (5)
O160.0532 (8)0.0314 (6)0.0466 (7)−0.0046 (5)0.0234 (6)−0.0111 (5)
Geometric parameters (Å, º) top
N1—C21.488 (2)C6—H6B0.9900
N1—H1A0.929 (17)C7—C81.392 (2)
N1—H1B0.900 (18)C7—C121.404 (2)
N1—H1C0.892 (18)C7—C131.498 (2)
C2—C31.511 (2)C8—C91.379 (2)
C2—H2A0.9900C8—H80.9500
C2—H2B0.9900C9—C101.381 (2)
C3—N41.4706 (19)C9—H90.9500
C3—H3A0.9900C10—C111.376 (2)
C3—H3B0.9900C10—H100.9500
N4—C61.4572 (19)C11—C121.394 (2)
N4—C51.473 (2)C11—H110.9500
C5—C6i1.514 (2)C12—O161.3524 (18)
C5—H5A0.9900C13—O141.2575 (17)
C5—H5B0.9900C13—O151.2714 (17)
C6—C5i1.514 (2)O16—H160.81 (2)
C6—H6A0.9900
C2—N1—H1A113.7 (10)N4—C6—H6A109.6
C2—N1—H1B109.4 (10)C5i—C6—H6A109.6
H1A—N1—H1B106.6 (14)N4—C6—H6B109.6
C2—N1—H1C112.7 (10)C5i—C6—H6B109.6
H1A—N1—H1C104.7 (15)H6A—C6—H6B108.1
H1B—N1—H1C109.4 (15)C8—C7—C12118.06 (14)
N1—C2—C3111.24 (13)C8—C7—C13120.61 (13)
N1—C2—H2A109.4C12—C7—C13121.33 (13)
C3—C2—H2A109.4C9—C8—C7122.09 (14)
N1—C2—H2B109.4C9—C8—H8119.0
C3—C2—H2B109.4C7—C8—H8119.0
H2A—C2—H2B108.0C8—C9—C10118.95 (15)
N4—C3—C2111.24 (12)C8—C9—H9120.5
N4—C3—H3A109.4C10—C9—H9120.5
C2—C3—H3A109.4C11—C10—C9120.74 (15)
N4—C3—H3B109.4C11—C10—H10119.6
C2—C3—H3B109.4C9—C10—H10119.6
H3A—C3—H3B108.0C10—C11—C12120.36 (15)
C6—N4—C3110.87 (12)C10—C11—H11119.8
C6—N4—C5108.55 (12)C12—C11—H11119.8
C3—N4—C5110.73 (11)O16—C12—C11118.04 (14)
N4—C5—C6i111.26 (12)O16—C12—C7122.17 (13)
N4—C5—H5A109.4C11—C12—C7119.79 (14)
C6i—C5—H5A109.4O14—C13—O15122.86 (13)
N4—C5—H5B109.4O14—C13—C7119.76 (13)
C6i—C5—H5B109.4O15—C13—C7117.39 (13)
H5A—C5—H5B108.0C12—O16—H16107.4 (14)
N4—C6—C5i110.31 (13)
N1—C2—C3—N464.77 (17)C9—C10—C11—C12−0.1 (2)
C2—C3—N4—C6−162.96 (13)C10—C11—C12—O16179.96 (14)
C2—C3—N4—C576.48 (16)C10—C11—C12—C70.7 (2)
C6—N4—C5—C6i58.44 (17)C8—C7—C12—O16−179.88 (13)
C3—N4—C5—C6i−179.64 (12)C13—C7—C12—O160.5 (2)
C3—N4—C6—C5i−179.69 (12)C8—C7—C12—C11−0.7 (2)
C5—N4—C6—C5i−57.85 (17)C13—C7—C12—C11179.64 (13)
C12—C7—C8—C90.1 (2)C8—C7—C13—O148.1 (2)
C13—C7—C8—C9179.72 (13)C12—C7—C13—O14−172.27 (13)
C7—C8—C9—C100.5 (2)C8—C7—C13—O15−172.00 (13)
C8—C9—C10—C11−0.5 (2)C12—C7—C13—O157.6 (2)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O140.929 (17)1.992 (18)2.8853 (17)160.9 (14)
N1—H1B···O14ii0.900 (18)1.923 (19)2.7909 (17)161.5 (14)
N1—H1C···O15iii0.892 (18)1.902 (19)2.7843 (17)169.9 (15)
O16—H16···O150.81 (2)1.83 (2)2.5641 (16)149.4 (19)
Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formulaC8H22N42+·2C7H5O3−
Mr448.52
Crystal system, space groupMonoclinic, P21/c
Temperature (K)180
a, b, c (Å)11.5374 (4), 6.4759 (2), 15.5264 (6)
β (°) 104.207 (2)
V (Å3)1124.58 (7)
Z2
Radiation typeMo Kα
µ (mm−1)0.10
Crystal size (mm)0.37 × 0.10 × 0.05
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.852, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections		19655, 3261, 2013
Rint0.065
(sin θ/λ)max (Å−1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.147, 1.08
No. of reflections3261
No. of parameters157
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.34, −0.28

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997), SCALEPACK and SORTAV (Blessing, 1995), SIR92 (Altomare et al., 1994), ORTEP-3 for Windows (Farrugia, 1997), POV-RAY (Cason, 2004) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O140.929 (17)1.992 (18)2.8853 (17)160.9 (14)
N1—H1B···O14i0.900 (18)1.923 (19)2.7909 (17)161.5 (14)
N1—H1C···O15ii0.892 (18)1.902 (19)2.7843 (17)169.9 (15)
O16—H16···O150.81 (2)1.83 (2)2.5641 (16)149.4 (19)
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2.
 

Acknowledgements

The authors thank Dr John E. Davies of the University of Cambridge (England) for the data collection.

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals Google Scholar
 First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationCason, C. J. (2004). POV-RAY for Windows. Persistence of Vision Raytracer Pty Ltd, Victoria, Australia. URL: http://www.povray.org.  Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationJiang, X., Liu, H.-X., Wu, S.-L. & Liang, Y.-X. (2009). Jiegou Huaxue (Chin. J. Struct. Chem.), 28, 723–729.  CAS Google Scholar
 First citationJunk, P. C. & Smith, M. K. (2005). C. R. Chim. 8, 189–198.  Web of Science CSD CrossRef CAS Google Scholar
 First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationNonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationYang, Y., Sun, J.-B., Cui, M., Liu, R.-B., Wang, Y. & Meng, C.-G. (2011). J. Solid State Chem. 184, 1666–1670.  Web of Science CSD CrossRef CAS Google Scholar

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ISSN: 2056-9890
Volume 68| Part 8| August 2012| Page o2388
https://doi.org/10.1107/S1600536812030103
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