organic compounds
Piperazine-1,4-diium bis(4-nitrobenzoate) dihydrate
aDepartment of Physics, Presidency College, Chennai 600 005, Tamil Nadu, India, and bDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203, Tamil Nadu, India
*Correspondence e-mail: ppkpresidency@gmail.com, phdguna@gmail.com
The 4H12N22+·2C7H4NO4− ·2H2O, is composed of half a protonated piperazine dication, located about an inversion center, a benzoate anion and a water molecule of crystallization. In the crystal, the various units are linked by N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, forming a supramolecular three-dimensional framework.
of the title molecular salt, CKeywords: crystal structure; piperazine; nitro benzoic acid; piperazine-1,4-diium; molecular salt; hydrogen bonding.
CCDC reference: 1573567
Structure description
Piperazine derivatives are found in a number of biologically active compounds, including several marketed drugs, and the piperazine ring is considered to be a privileged structure in drug discovery (Suzuki et al., 1997). Piperazines are frequently used as building blocks for pharmaceuticals (Kaloustian et al., 1976), and exhibit a substantial degree of selective RNA binding (Dega-Szafran et al., 2002).
The ). The piperazine dication is located about an inversion center and the ring has a chair conformation. The geometric parameters agree well with those reported for a similar compound, piperazine-1,4-diium bis(4-aminobenzenesulfonate) (Kumar et al., 2015).
of the title molecular salt comprises half a protonated piperazine dication, a benzoate anion and a water molecule of crystallization (Fig. 1In the crystal, the various units are linked by N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, forming a supramolecular three-dimensional framework (Table 1 and Fig. 2).
Synthesis and crystallization
4.3 g (0.057 mol) of piperazine and 8.4 g (0.029 mol) of 4-nitrobenzoic acid were dissolved in 50 ml of double-distilled water and stirred at room temperature for 5 h to obtain an homogeneous solution. The solution was filtered and allowed to evaporate in a dust-free atmosphere. After a few days, yellow block-like crystals were obtained (yield 94%, m.p. 370 K).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1573567
https://doi.org/10.1107/S2414314617012913/su4164sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012913/su4164Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617012913/su4164Isup3.cml
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).0.5C4H12N22+·C7H4NO4−·H2O | Z = 2 |
Mr = 228.21 | F(000) = 240 |
Triclinic, P1 | Dx = 1.475 Mg m−3 |
a = 6.5793 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.8094 (5) Å | Cell parameters from 2927 reflections |
c = 12.3767 (9) Å | θ = 6.2–30.1° |
α = 92.085 (4)° | µ = 0.12 mm−1 |
β = 99.427 (3)° | T = 296 K |
γ = 109.301 (4)° | Block, yellow |
V = 513.81 (7) Å3 | 0.20 × 0.20 × 0.15 mm |
Bruker Kappa APEXII CCD diffractometer | 2019 independent reflections |
Radiation source: fine-focus sealed tube | 1369 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 0 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω and φ scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | k = −8→8 |
Tmin = 0.976, Tmax = 0.982 | l = −15→15 |
10658 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)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.1764P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
2019 reflections | Δρmax = 0.16 e Å−3 |
162 parameters | Δρmin = −0.17 e Å−3 |
6 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.069 (7) |
Refinement. The NH2 and water H atoms were located in difference-Fourier maps and refined with distance restraints: N—H = O—H = 0.90 (2) Å and H···H = 1.48 (2) Å. The C-bound H atoms were fixed geometrically and allowed to ride on their parent atoms: C—H = 0.93 - 0.97 Å with Uiso(H) = 1.2Ueq(C). |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3881 (3) | 0.7745 (2) | 0.62147 (14) | 0.0307 (4) | |
C2 | 0.1832 (3) | 0.7949 (3) | 0.60281 (15) | 0.0380 (5) | |
H2 | 0.1225 | 0.8221 | 0.6620 | 0.046* | |
C3 | 0.0685 (3) | 0.7751 (3) | 0.49680 (15) | 0.0397 (5) | |
H3 | −0.0688 | 0.7898 | 0.4840 | 0.048* | |
C4 | 0.1595 (3) | 0.7335 (3) | 0.41069 (14) | 0.0344 (4) | |
C5 | 0.3615 (3) | 0.7113 (3) | 0.42579 (15) | 0.0413 (5) | |
H5 | 0.4204 | 0.6824 | 0.3663 | 0.050* | |
C6 | 0.4745 (3) | 0.7332 (3) | 0.53230 (15) | 0.0392 (5) | |
H6 | 0.6125 | 0.7199 | 0.5444 | 0.047* | |
C7 | 0.5200 (3) | 0.7940 (3) | 0.73631 (15) | 0.0380 (5) | |
C8 | 0.5409 (3) | 0.3454 (3) | 0.93267 (14) | 0.0353 (4) | |
H8A | 0.4891 | 0.3739 | 0.8590 | 0.042* | |
H8B | 0.5943 | 0.2294 | 0.9265 | 0.042* | |
C9 | 0.7243 (3) | 0.5354 (3) | 0.99088 (15) | 0.0354 (4) | |
H9A | 0.7843 | 0.5032 | 1.0622 | 0.042* | |
H9B | 0.8405 | 0.5752 | 0.9483 | 0.042* | |
N1 | 0.0338 (3) | 0.7086 (3) | 0.29788 (13) | 0.0487 (5) | |
N2 | 0.6427 (2) | 0.7116 (2) | 1.00540 (12) | 0.0334 (4) | |
O1 | 0.1169 (3) | 0.6756 (3) | 0.22173 (13) | 0.0826 (6) | |
O2 | −0.1475 (3) | 0.7239 (3) | 0.28617 (13) | 0.0698 (5) | |
O3 | 0.4310 (2) | 0.8115 (2) | 0.81642 (10) | 0.0483 (4) | |
O4 | 0.7073 (2) | 0.7872 (3) | 0.74364 (12) | 0.0700 (5) | |
O5 | 1.0952 (2) | 0.9029 (2) | 0.88996 (11) | 0.0438 (4) | |
H2A | 0.588 (3) | 0.752 (3) | 0.9379 (12) | 0.052 (6)* | |
H2B | 0.753 (3) | 0.828 (3) | 1.0429 (14) | 0.055 (6)* | |
H5B | 1.187 (3) | 0.863 (4) | 0.8539 (17) | 0.071 (8)* | |
H5A | 0.971 (3) | 0.884 (4) | 0.8424 (17) | 0.082 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0281 (9) | 0.0282 (9) | 0.0337 (10) | 0.0086 (7) | 0.0028 (7) | 0.0026 (7) |
C2 | 0.0356 (10) | 0.0517 (12) | 0.0316 (10) | 0.0195 (9) | 0.0099 (8) | 0.0041 (8) |
C3 | 0.0273 (10) | 0.0534 (12) | 0.0394 (11) | 0.0165 (9) | 0.0026 (8) | 0.0067 (9) |
C4 | 0.0359 (10) | 0.0337 (10) | 0.0284 (10) | 0.0080 (8) | −0.0003 (8) | 0.0027 (7) |
C5 | 0.0449 (12) | 0.0483 (11) | 0.0352 (11) | 0.0200 (9) | 0.0121 (9) | 0.0002 (8) |
C6 | 0.0304 (10) | 0.0464 (11) | 0.0448 (12) | 0.0188 (9) | 0.0063 (8) | 0.0031 (9) |
C7 | 0.0368 (11) | 0.0379 (10) | 0.0374 (11) | 0.0154 (9) | −0.0028 (8) | −0.0002 (8) |
C8 | 0.0370 (10) | 0.0389 (10) | 0.0308 (10) | 0.0148 (8) | 0.0053 (8) | −0.0005 (8) |
C9 | 0.0282 (9) | 0.0434 (10) | 0.0352 (10) | 0.0138 (8) | 0.0042 (7) | 0.0044 (8) |
N1 | 0.0537 (11) | 0.0490 (10) | 0.0354 (10) | 0.0133 (9) | −0.0041 (8) | 0.0025 (8) |
N2 | 0.0303 (8) | 0.0332 (8) | 0.0308 (9) | 0.0059 (7) | 0.0001 (7) | 0.0011 (7) |
O1 | 0.0929 (14) | 0.1240 (16) | 0.0322 (9) | 0.0438 (12) | 0.0045 (9) | −0.0088 (9) |
O2 | 0.0550 (10) | 0.0952 (13) | 0.0524 (10) | 0.0289 (9) | −0.0153 (8) | 0.0047 (9) |
O3 | 0.0507 (9) | 0.0685 (10) | 0.0309 (7) | 0.0293 (7) | 0.0029 (6) | 0.0072 (6) |
O4 | 0.0425 (9) | 0.1151 (14) | 0.0537 (10) | 0.0404 (9) | −0.0115 (7) | −0.0104 (9) |
O5 | 0.0361 (8) | 0.0481 (8) | 0.0389 (8) | 0.0074 (7) | 0.0006 (6) | −0.0047 (6) |
C1—C6 | 1.382 (2) | C8—N2i | 1.487 (2) |
C1—C2 | 1.384 (2) | C8—C9 | 1.505 (3) |
C1—C7 | 1.516 (2) | C8—H8A | 0.9700 |
C2—C3 | 1.380 (3) | C8—H8B | 0.9700 |
C2—H2 | 0.9300 | C9—N2 | 1.484 (2) |
C3—C4 | 1.369 (2) | C9—H9A | 0.9700 |
C3—H3 | 0.9300 | C9—H9B | 0.9700 |
C4—C5 | 1.370 (3) | N1—O1 | 1.213 (2) |
C4—N1 | 1.474 (2) | N1—O2 | 1.217 (2) |
C5—C6 | 1.380 (3) | N2—C8i | 1.487 (2) |
C5—H5 | 0.9300 | N2—H2A | 0.940 (14) |
C6—H6 | 0.9300 | N2—H2B | 0.922 (15) |
C7—O4 | 1.237 (2) | O5—H5B | 0.908 (15) |
C7—O3 | 1.252 (2) | O5—H5A | 0.892 (16) |
C6—C1—C2 | 118.80 (16) | N2i—C8—H8A | 109.6 |
C6—C1—C7 | 118.92 (15) | C9—C8—H8A | 109.6 |
C2—C1—C7 | 122.28 (16) | N2i—C8—H8B | 109.6 |
C3—C2—C1 | 120.31 (17) | C9—C8—H8B | 109.6 |
C3—C2—H2 | 119.8 | H8A—C8—H8B | 108.1 |
C1—C2—H2 | 119.8 | N2—C9—C8 | 110.25 (14) |
C4—C3—C2 | 119.09 (17) | N2—C9—H9A | 109.6 |
C4—C3—H3 | 120.5 | C8—C9—H9A | 109.6 |
C2—C3—H3 | 120.5 | N2—C9—H9B | 109.6 |
C3—C4—C5 | 122.35 (16) | C8—C9—H9B | 109.6 |
C3—C4—N1 | 118.67 (16) | H9A—C9—H9B | 108.1 |
C5—C4—N1 | 118.97 (17) | O1—N1—O2 | 123.50 (18) |
C4—C5—C6 | 117.74 (17) | O1—N1—C4 | 118.42 (18) |
C4—C5—H5 | 121.1 | O2—N1—C4 | 118.08 (18) |
C6—C5—H5 | 121.1 | C9—N2—C8i | 111.36 (14) |
C5—C6—C1 | 121.70 (17) | C9—N2—H2A | 112.4 (11) |
C5—C6—H6 | 119.1 | C8i—N2—H2A | 106.2 (12) |
C1—C6—H6 | 119.1 | C9—N2—H2B | 111.1 (13) |
O4—C7—O3 | 124.85 (17) | C8i—N2—H2B | 108.3 (12) |
O4—C7—C1 | 117.09 (17) | H2A—N2—H2B | 107.3 (15) |
O3—C7—C1 | 118.05 (16) | H5B—O5—H5A | 108.0 (17) |
N2i—C8—C9 | 110.14 (14) | ||
C6—C1—C2—C3 | −0.3 (3) | C6—C1—C7—O4 | 5.3 (3) |
C7—C1—C2—C3 | −179.75 (17) | C2—C1—C7—O4 | −175.23 (18) |
C1—C2—C3—C4 | 0.5 (3) | C6—C1—C7—O3 | −173.33 (17) |
C2—C3—C4—C5 | −0.2 (3) | C2—C1—C7—O3 | 6.2 (3) |
C2—C3—C4—N1 | 178.82 (17) | N2i—C8—C9—N2 | −56.7 (2) |
C3—C4—C5—C6 | −0.3 (3) | C3—C4—N1—O1 | 178.66 (19) |
N1—C4—C5—C6 | −179.32 (17) | C5—C4—N1—O1 | −2.3 (3) |
C4—C5—C6—C1 | 0.5 (3) | C3—C4—N1—O2 | −0.8 (3) |
C2—C1—C6—C5 | −0.3 (3) | C5—C4—N1—O2 | 178.29 (18) |
C7—C1—C6—C5 | 179.25 (17) | C8—C9—N2—C8i | 57.4 (2) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.94 (2) | 1.82 (2) | 2.747 (2) | 169 (2) |
N2—H2B···O5ii | 0.92 (2) | 1.85 (2) | 2.751 (2) | 162 (2) |
O5—H5A···O4 | 0.89 (2) | 1.85 (2) | 2.733 (2) | 168 (2) |
O5—H5B···O3iii | 0.91 (2) | 1.88 (2) | 2.761 (2) | 164 (2) |
C8—H8A···O2iv | 0.97 | 2.51 | 3.326 (3) | 141 |
C9—H9B···O5 | 0.97 | 2.52 | 3.312 (2) | 139 |
Symmetry codes: (ii) −x+2, −y+2, −z+2; (iii) x+1, y, z; (iv) −x, −y+1, −z+1. |
Acknowledgements
The authors acknowledge the SAIF, IIT Madras, Chennai, for the data collection.
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