1,4-Bis(carb­oxy­meth­yl)piperazine-1,4-diium bis­(dihydrogen phosphate) dihydrate

Cheng, L.; Zhang, L.-M.; Wang, J.-Q.

doi:10.1107/S1600536810036342

organic compounds

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Volume 66| Part 10| October 2010| Page o2566

doi:10.1107/S1600536810036342

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1,4-Bis(carboxymethyl)piperazine-1,4-diium bis(dihydrogen phosphate) dihydrate

Lin Cheng,^a ^* Li-Min Zhang ^a and Jian-Quan Wang ^a

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 2 September 2010; accepted 10 September 2010; online 15 September 2010)

In the title salt, C₈H₁₆N₂O₄²⁺·2H₂PO₄⁻·2H₂O, the piperazine ring is located around an inversion center and adopts a chair conformation. The dihydrogen phosphate anions and free water molecules are linked via O—H⋯O hydrogen bonds into two-dimensional hydrogen-bonding layers, which are further connected through O—H⋯O and N—H⋯O hydrogen bonds involving the protonated piperazine into a three-dimensional supramolecular network.

Related literature

For related structures, see: Yang et al. (2008 ). For potential applications of optical, electrical, magnetic and microporous materials, see: Evans & Lin (2002 ); Zhang & Chen (2006 ).

Experimental

Crystal data

C₈H₁₆N₂O₄²⁺·2H₂PO₄⁻·2H₂O
M_r = 434.23
Monoclinic, P 2₁ /c
a = 8.716 (3) Å
b = 8.992 (3) Å
c = 12.991 (4) Å
β = 123.310 (17)°
V = 850.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 120 K
0.54 × 0.44 × 0.41 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.840, T_max = 0.875
3998 measured reflections
1668 independent reflections
1552 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.09
1668 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.84	1.69	2.5324 (18)	177
N1—H1⋯O5ⁱ	0.93	1.74	2.658 (2)	170
O4—H4⋯O1W	0.84	1.74	2.5729 (19)	172
O6—H6⋯O5ⁱⁱ	0.84	1.74	2.5700 (17)	169
O1W—H1WA⋯O6ⁱⁱⁱ	0.85	2.08	2.868 (2)	155
O1W—H1WB⋯O3^iv	0.85	2.02	2.8633 (19)	169
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+2, -y+1, -z+2; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036342/dn2598sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036342/dn2598Isup2.hkl

checkCIF report

Comment top

Recent years have witnessed an explosion of great interest in hybrid organic-inorganic framework solids not only for their intriguing architectures and topologies, but also for their potential applications in optical, electrical, magnetic, and microporous materials (Evans et al. 2002; Zhang et al. 2006). We have synthesized two series of hybrid organic-inorganic frameworks with 1,4-piperazinediacetic acid and lanthanide sulfates (Yang et al. 2008). Our aim is to obtain similar hybrid solids by using phosphates instead of sulfates. However, we fail to synthesize the aimed compounds and obtain a three-dimensional supramolecular network, C₈H₂₄N₂O₁₄P₂ (1.2H₂PO₄.2H₂O).

The title compound, is a dihydrogen phosphate, in which 1 is a protonated piperazine derivative and the piperazine ring located around inversion center adopts chair conformation (Fig. 1). The asymmetric unit of the title compound, contains half a protonated 1,4-piperazinediacetic acid, a dihydrogen phosphate and a free water molecule. In the carboxylates of protonated 1,4-piperazinediacetic acid, the distance of the C=O bonds is 1.209 (2) Å, which is shorter than those of C—O bond (1.311 (2) Å) and considered to have full double-bond character.

In the compound, the dihydrogen phosphates and free water molecules are linked to each other, via O—H···O hydrogen bonds into a two-dimensional hydrogen bonding layers (Table 1, Fig. 2), which are further connected through O—H···O and N—H···O hydrogen bonds involving the protonated 1,4-piperazinediacetic acid into a three-dimensional supramolecular network.

Related literature top

For related structures, see: Yang et al. (2008). For potential applications in optical, electrical, magnetic, and microporous materials, see: Evans & Lin (2002); Zhang & Chen (2006).

Experimental top

A mixture of H₂pda.2H₂O (0.024 g, 0.1 mmol), Nd₂O₃ (0.034 g, 0.1 mmol), H₃PO₄ (0.1 ml), and water (6 ml) were heated ina 15 ml Teflon-lined vessel at 160 ° for 3 days, followed by slow cooling (5 ° h^-1) to room temperature. After filtration, colorless block crystals were collected and dried in air (0.025 g, yield ca 57% based on H₂pda).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular view of compound (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Partial packing view of compound ( I ), showing the two-dimensional network formed by the hydrogen bonds showed as dashed lines, involving the dihydrogen phosphate and the water molecules. [Symmetry codes:(iv) -x+2, -y+1,-z+2; (v) -x+2, y+1/2, -z+3/2]

1,4-Bis(carboxymethyl)piperazine-1,4-diium bis(dihydrogen phosphate) dihydrate top

Crystal data top

C₈H₁₆N₂O₄²⁺·2H₂PO₄⁻·2H₂O	F(000) = 456
M_r = 434.23	D_x = 1.695 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 782 reflections
a = 8.716 (3) Å	θ = 2.4–28.0°
b = 8.992 (3) Å	µ = 0.33 mm⁻¹
c = 12.991 (4) Å	T = 120 K
β = 123.310 (17)°	Block, colourless
V = 850.9 (5) Å³	0.54 × 0.44 × 0.41 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1668 independent reflections
Radiation source: fine-focus sealed tube	1552 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scan	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→8
T_min = 0.840, T_max = 0.875	k = −11→10
3998 measured reflections	l = −10→16

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0583P)² + 0.4175P] where P = (F_o² + 2F_c²)/3
1668 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₈H₁₆N₂O₄²⁺·2H₂PO₄⁻·2H₂O	V = 850.9 (5) Å³
M_r = 434.23	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.716 (3) Å	µ = 0.33 mm⁻¹
b = 8.992 (3) Å	T = 120 K
c = 12.991 (4) Å	0.54 × 0.44 × 0.41 mm
β = 123.310 (17)°

Data collection top

Bruker SMART APEX CCD diffractometer	1668 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1552 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.875	R_int = 0.022
3998 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.09	Δρ_max = 0.49 e Å⁻³
1668 reflections	Δρ_min = −0.54 e Å⁻³
121 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.69897 (17)	0.37509 (13)	0.33962 (11)	0.0187 (3)
O2	0.64019 (19)	0.56082 (13)	0.42897 (12)	0.0213 (3)
H2	0.6898	0.5039	0.4903	0.032*
N1	0.57511 (19)	0.53648 (15)	0.12844 (13)	0.0131 (3)
H1	0.6924	0.4981	0.1622	0.016*
C1	0.6431 (2)	0.49837 (19)	0.33891 (15)	0.0156 (4)
C2	0.5654 (2)	0.60289 (19)	0.22984 (15)	0.0158 (3)
H2A	0.4360	0.6257	0.1991	0.019*
H2B	0.6353	0.6973	0.2566	0.019*
C3	0.5428 (2)	0.65335 (18)	0.03654 (15)	0.0159 (3)
H3A	0.6332	0.7346	0.0785	0.019*
H3B	0.4184	0.6958	−0.0006	0.019*
C4	0.4392 (2)	0.41261 (19)	0.06352 (16)	0.0163 (4)
H4A	0.3131	0.4513	0.0268	0.020*
H4B	0.4608	0.3343	0.1237	0.020*
P1	0.92100 (6)	0.43880 (4)	0.74544 (4)	0.01286 (17)
O3	0.79926 (16)	0.38920 (13)	0.61380 (11)	0.0174 (3)
O4	0.80098 (16)	0.51844 (14)	0.78556 (12)	0.0200 (3)
H4	0.8650	0.5820	0.8400	0.030*
O5	1.07757 (15)	0.54245 (12)	0.77465 (11)	0.0160 (3)
O6	1.00826 (16)	0.29822 (13)	0.83100 (11)	0.0172 (3)
H6	0.9690	0.2207	0.7879	0.026*
O1W	0.9695 (2)	0.73039 (16)	0.94132 (13)	0.0289 (3)
H1WA	1.0120	0.7221	1.0176	0.043*
H1WB	1.0505	0.7740	0.9349	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0218 (6)	0.0160 (6)	0.0182 (6)	0.0027 (5)	0.0109 (5)	0.0009 (5)
O2	0.0306 (8)	0.0185 (6)	0.0159 (6)	0.0063 (5)	0.0134 (6)	0.0025 (5)
N1	0.0134 (7)	0.0124 (6)	0.0139 (7)	−0.0002 (5)	0.0078 (6)	0.0002 (5)
C1	0.0140 (8)	0.0159 (8)	0.0163 (8)	−0.0012 (6)	0.0080 (7)	−0.0011 (6)
C2	0.0187 (8)	0.0139 (8)	0.0160 (8)	0.0018 (6)	0.0103 (7)	−0.0006 (6)
C3	0.0197 (8)	0.0118 (7)	0.0162 (8)	−0.0006 (6)	0.0098 (7)	0.0013 (6)
C4	0.0170 (8)	0.0159 (8)	0.0150 (8)	−0.0041 (6)	0.0082 (7)	−0.0003 (6)
P1	0.0137 (3)	0.0112 (3)	0.0146 (3)	−0.00065 (14)	0.0084 (2)	−0.00046 (14)
O3	0.0194 (6)	0.0157 (6)	0.0149 (6)	−0.0001 (5)	0.0081 (5)	−0.0004 (5)
O4	0.0180 (6)	0.0201 (6)	0.0253 (7)	−0.0030 (5)	0.0142 (6)	−0.0076 (5)
O5	0.0141 (6)	0.0120 (6)	0.0230 (7)	0.0003 (4)	0.0109 (5)	0.0017 (5)
O6	0.0226 (6)	0.0115 (6)	0.0154 (6)	−0.0025 (5)	0.0092 (5)	−0.0014 (4)
O1W	0.0355 (8)	0.0347 (8)	0.0219 (7)	−0.0153 (6)	0.0192 (6)	−0.0104 (6)

Geometric parameters (Å, º) top

O1—C1	1.209 (2)	C3—H3B	0.9900
O2—C1	1.311 (2)	C4—C3ⁱ	1.513 (2)
O2—H2	0.8400	C4—H4A	0.9900
N1—C2	1.490 (2)	C4—H4B	0.9900
N1—C3	1.497 (2)	P1—O3	1.5022 (13)
N1—C4	1.503 (2)	P1—O5	1.5186 (12)
N1—H1	0.9300	P1—O4	1.5740 (12)
C1—C2	1.515 (2)	P1—O6	1.5759 (13)
C2—H2A	0.9900	O4—H4	0.8400
C2—H2B	0.9900	O6—H6	0.8400
C3—C4ⁱ	1.513 (2)	O1W—H1WA	0.8499
C3—H3A	0.9900	O1W—H1WB	0.8505

C1—O2—H2	109.5	N1—C3—H3B	109.6
C2—N1—C3	110.29 (12)	C4ⁱ—C3—H3B	109.6
C2—N1—C4	112.53 (13)	H3A—C3—H3B	108.1
C3—N1—C4	109.14 (13)	N1—C4—C3ⁱ	110.54 (13)
C2—N1—H1	108.3	N1—C4—H4A	109.5
C3—N1—H1	108.3	C3ⁱ—C4—H4A	109.5
C4—N1—H1	108.3	N1—C4—H4B	109.5
O1—C1—O2	126.25 (16)	C3ⁱ—C4—H4B	109.5
O1—C1—C2	123.19 (15)	H4A—C4—H4B	108.1
O2—C1—C2	110.56 (14)	O3—P1—O5	116.28 (7)
N1—C2—C1	111.40 (13)	O3—P1—O4	109.25 (7)
N1—C2—H2A	109.3	O5—P1—O4	107.91 (7)
C1—C2—H2A	109.3	O3—P1—O6	109.29 (7)
N1—C2—H2B	109.3	O5—P1—O6	107.26 (7)
C1—C2—H2B	109.3	O4—P1—O6	106.41 (7)
H2A—C2—H2B	108.0	P1—O4—H4	109.5
N1—C3—C4ⁱ	110.32 (14)	P1—O6—H6	109.5
N1—C3—H3A	109.6	H1WA—O1W—H1WB	107.5
C4ⁱ—C3—H3A	109.6

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.69	2.5324 (18)	177
N1—H1···O5ⁱⁱ	0.93	1.74	2.658 (2)	170
O4—H4···O1W	0.84	1.74	2.5729 (19)	172
O6—H6···O5ⁱⁱⁱ	0.84	1.74	2.5700 (17)	169
O1W—H1WA···O6^iv	0.85	2.08	2.868 (2)	155
O1W—H1WB···O3^v	0.85	2.02	2.8633 (19)	169

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

Experimental details

Crystal data
Chemical formula	C₈H₁₆N₂O₄²⁺·2H₂PO₄⁻·2H₂O
M_r	434.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	8.716 (3), 8.992 (3), 12.991 (4)
β (°)	123.310 (17)
V (Å³)	850.9 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.54 × 0.44 × 0.41

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.840, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	3998, 1668, 1552
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.09
No. of reflections	1668
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.54

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.69	2.5324 (18)	177.2
N1—H1···O5ⁱ	0.93	1.74	2.658 (2)	170.2
O4—H4···O1W	0.84	1.74	2.5729 (19)	171.6
O6—H6···O5ⁱⁱ	0.84	1.74	2.5700 (17)	168.5
O1W—H1WA···O6ⁱⁱⁱ	0.85	2.08	2.868 (2)	154.6
O1W—H1WB···O3^iv	0.85	2.02	2.8633 (19)	168.6

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

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Evans, O. R. & Lin, W. B. (2002). Acc. Chem. Res. 35, 511–522. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, J., Lu, N., Zhang, G., Cheng, L. & Gou, S. H. (2008). Polyhedron, 27, 2119–2126. Web of Science CSD CrossRef CAS Google Scholar
Zhang, J. P. & Chen, X. M. (2006). Chem. Commun. pp. 1689–1699. Web of Science CSD CrossRef Google Scholar

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Volume 66| Part 10| October 2010| Page o2566

doi:10.1107/S1600536810036342

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

1,4-Bis(carb­­oxy­meth­yl)piperazine-1,4-diium bis­­(di­hydrogen phosphate) dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,4-Bis(carboxymethyl)piperazine-1,4-diium bis(dihydrogen phosphate) dihydrate