Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034666/cf2123sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034666/cf2123Isup2.hkl |
CCDC reference: 657848
Crystals suitable for single-crystal X-ray analysis were obtained at room temperature by slow evaporation of an aqueous solution of 4-nitrophenylpiperazine and hydrochloric acid (1:1).
H atoms were included using a riding model with C—H = 0.97 or 0.93 Å, O—H = 0.85 or 0.87 Å, N—H = 0.90 Å, and Uiso = 1.2Ueq of the parent atom.
4-Nitrophenylpiperazinium chloride monohydrate (I) has been used as an intermediate in the synthesis of anticancer durgs, transcriptase inhibitors and antifungal reagents (Saczewski et al., 2006; Chen et al., 2000; Hepperle et al., 1999). It is also an important reagent for potassium channel openers, which show considerable biomolecular current-voltage rectification characteristics (Wu et al., 2005; Lan et al., 2005, 2006).
The basic structural unit of (I) consists of a 4-nitrophenylpiperazinium cation, a chloride ion and a water molecule. The molecular structure and atom-labeling scheme are shown in Fig. 1. The bonds N3—O1, N3—O2 [1.224 (2), 1.218 (2) Å, respectively] have partial double-bond character. The shorter intramolecular distance of H2b···H6a and H4a···H10a [1.97 and 1.98 Å] demonstrates the existence of H···H contacts.
The chloride anion forms one N—H···Cl and two O—H···Cl hydrogen bonds, namely one to piperazinium atom N1H1c, and two to the H atom of the water molecule (O3H3D, O3H3c) (Table 1). The H···Cl1 interaction lengths of the hydrogen bonds range from 2.21 to 2.317 (18) Å (Sopo & Sillanpää, 2007).
The H atoms of the piperazinium cation form hydrogen bonds to the chloride ion and to water atom O3 in an adjacent unit, forming a three-dimensional hydrogen-bond network (Fig. 2). Thus, the piperazinium cation plays an important role by acting as a bridge between the water O atom and the chloride ion.
The NO2 groups also help to stabilize the crystal structure. The hydrogen bonds C3—H3b···O1iv [symmetry code: (iv) -x + 1, -y + 2, -z + 1] are responsible for two-membered aggregates (Fig. 3), and C1—H1b···O2v [symmetry code: (v) x, y - 1, z - 1] for zigzag molecular chains (Fig. 4) (Zou et al., 2005).
π···π Stacking interactions between pairs of antiparallel benzene rings are observed [mean separation of 3.66 Å] (Fig. 5) (How et al., 2007).
For related literature, see: Chen et al. (2000); Hepperle et al. (1999); How et al. (2007); Lan et al. (2005, 2006); Saczewski et al. (2006); Sopo & Sillanpää (2007); Wu et al. (2005); Zou et al. (2005).
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.
C10H14N3O2+·Cl−·H2O | Z = 2 |
Mr = 261.71 | F(000) = 276 |
Triclinic, P1 | Dx = 1.401 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.404 (2) Å | Cell parameters from 899 reflections |
b = 9.212 (3) Å | θ = 3.5–27.1° |
c = 9.757 (3) Å | µ = 0.31 mm−1 |
α = 110.111 (4)° | T = 293 K |
β = 90.209 (4)° | Prism, brown |
γ = 96.484 (4)° | 0.15 × 0.10 × 0.10 mm |
V = 620.3 (3) Å3 |
Bruker APEX CCD area-detector diffractometer | 2390 independent reflections |
Radiation source: fine-focus sealed tube | 2078 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997b) | h = −8→9 |
Tmin = 0.955, Tmax = 0.970 | k = −9→11 |
2866 measured reflections | l = −10→12 |
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)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0696P)2 + 0.1053P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2390 reflections | Δρmax = 0.27 e Å−3 |
163 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.085 (9) |
C10H14N3O2+·Cl−·H2O | γ = 96.484 (4)° |
Mr = 261.71 | V = 620.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.404 (2) Å | Mo Kα radiation |
b = 9.212 (3) Å | µ = 0.31 mm−1 |
c = 9.757 (3) Å | T = 293 K |
α = 110.111 (4)° | 0.15 × 0.10 × 0.10 mm |
β = 90.209 (4)° |
Bruker APEX CCD area-detector diffractometer | 2390 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997b) | 2078 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.970 | Rint = 0.020 |
2866 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.27 e Å−3 |
2390 reflections | Δρmin = −0.30 e Å−3 |
163 parameters |
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 | ||
Cl1 | 0.21896 (6) | 0.24305 (5) | 0.06332 (5) | 0.0512 (2) | |
N1 | 0.6240 (2) | 0.36182 (16) | 0.15956 (17) | 0.0453 (4) | |
H1C | 0.5109 | 0.3277 | 0.1189 | 0.054* | |
H1D | 0.6921 | 0.2830 | 0.1256 | 0.054* | |
N2 | 0.8687 (2) | 0.61144 (16) | 0.35096 (15) | 0.0406 (4) | |
N3 | 0.6741 (2) | 1.20158 (19) | 0.66763 (19) | 0.0527 (4) | |
O1 | 0.6553 (2) | 1.29264 (17) | 0.60370 (19) | 0.0710 (5) | |
O2 | 0.6467 (3) | 1.2324 (2) | 0.79697 (18) | 0.0825 (6) | |
O3 | 0.1758 (2) | 0.88143 (18) | 0.8816 (2) | 0.0721 (5) | |
C1 | 0.7023 (3) | 0.4943 (2) | 0.11475 (19) | 0.0460 (4) | |
H1A | 0.6205 | 0.5738 | 0.1384 | 0.055* | |
H1B | 0.7165 | 0.4581 | 0.0100 | 0.055* | |
C2 | 0.8841 (3) | 0.5617 (2) | 0.19315 (19) | 0.0450 (4) | |
H2A | 0.9681 | 0.4841 | 0.1632 | 0.054* | |
H2B | 0.9327 | 0.6501 | 0.1665 | 0.054* | |
C3 | 0.6164 (3) | 0.4062 (2) | 0.3206 (2) | 0.0456 (4) | |
H3A | 0.5761 | 0.3147 | 0.3454 | 0.055* | |
H3B | 0.5295 | 0.4805 | 0.3564 | 0.055* | |
C4 | 0.8020 (3) | 0.4773 (2) | 0.3922 (2) | 0.0458 (4) | |
H4A | 0.7947 | 0.5100 | 0.4975 | 0.055* | |
H4B | 0.8864 | 0.4001 | 0.3625 | 0.055* | |
C5 | 0.8183 (2) | 0.75675 (18) | 0.42769 (17) | 0.0354 (4) | |
C6 | 0.8009 (2) | 0.86723 (19) | 0.36100 (18) | 0.0403 (4) | |
H6A | 0.8202 | 0.8418 | 0.2618 | 0.048* | |
C7 | 0.7560 (2) | 1.0121 (2) | 0.4393 (2) | 0.0416 (4) | |
H7A | 0.7459 | 1.0846 | 0.3937 | 0.050* | |
C8 | 0.7259 (2) | 1.04990 (19) | 0.58589 (19) | 0.0402 (4) | |
C9 | 0.7443 (2) | 0.9451 (2) | 0.65606 (19) | 0.0436 (4) | |
H9A | 0.7259 | 0.9725 | 0.7556 | 0.052* | |
C10 | 0.7898 (2) | 0.8006 (2) | 0.57808 (19) | 0.0412 (4) | |
H10A | 0.8022 | 0.7301 | 0.6255 | 0.049* | |
H3C | 0.070 (4) | 0.851 (4) | 0.908 (4) | 0.161 (17)* | |
H3D | 0.192 (4) | 0.978 (2) | 0.932 (4) | 0.119 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0505 (3) | 0.0478 (3) | 0.0549 (3) | −0.0029 (2) | −0.0015 (2) | 0.0202 (2) |
N1 | 0.0411 (8) | 0.0349 (7) | 0.0528 (9) | 0.0034 (6) | −0.0028 (7) | 0.0068 (6) |
N2 | 0.0429 (8) | 0.0333 (7) | 0.0426 (8) | 0.0026 (6) | 0.0010 (6) | 0.0099 (6) |
N3 | 0.0486 (9) | 0.0427 (9) | 0.0552 (10) | 0.0057 (7) | −0.0011 (7) | 0.0021 (7) |
O1 | 0.0838 (12) | 0.0447 (8) | 0.0861 (11) | 0.0203 (8) | 0.0102 (9) | 0.0208 (8) |
O2 | 0.1138 (15) | 0.0672 (10) | 0.0509 (9) | 0.0295 (10) | 0.0062 (9) | −0.0054 (8) |
O3 | 0.0616 (10) | 0.0425 (8) | 0.1024 (13) | 0.0119 (7) | 0.0190 (9) | 0.0109 (8) |
C1 | 0.0560 (11) | 0.0383 (9) | 0.0385 (9) | 0.0058 (8) | 0.0029 (8) | 0.0068 (7) |
C2 | 0.0470 (10) | 0.0372 (9) | 0.0463 (10) | 0.0077 (7) | 0.0134 (8) | 0.0078 (7) |
C3 | 0.0466 (10) | 0.0373 (9) | 0.0548 (11) | 0.0042 (7) | 0.0057 (8) | 0.0186 (8) |
C4 | 0.0515 (11) | 0.0353 (8) | 0.0520 (10) | 0.0068 (7) | −0.0044 (8) | 0.0165 (8) |
C5 | 0.0315 (8) | 0.0347 (8) | 0.0372 (8) | −0.0006 (6) | −0.0005 (6) | 0.0104 (7) |
C6 | 0.0455 (10) | 0.0403 (9) | 0.0340 (8) | 0.0025 (7) | 0.0034 (7) | 0.0125 (7) |
C7 | 0.0435 (9) | 0.0368 (8) | 0.0459 (10) | 0.0021 (7) | 0.0009 (7) | 0.0170 (7) |
C8 | 0.0369 (9) | 0.0352 (8) | 0.0426 (9) | 0.0024 (7) | −0.0002 (7) | 0.0068 (7) |
C9 | 0.0462 (10) | 0.0460 (9) | 0.0341 (8) | 0.0008 (7) | 0.0021 (7) | 0.0097 (7) |
C10 | 0.0449 (10) | 0.0410 (9) | 0.0386 (9) | 0.0017 (7) | 0.0001 (7) | 0.0159 (7) |
N1—C3 | 1.484 (2) | C2—H2B | 0.970 |
N1—C1 | 1.491 (2) | C3—C4 | 1.510 (3) |
N1—H1C | 0.900 | C3—H3A | 0.970 |
N1—H1D | 0.900 | C3—H3B | 0.970 |
N2—C5 | 1.385 (2) | C4—H4A | 0.970 |
N2—C2 | 1.457 (2) | C4—H4B | 0.970 |
N2—C4 | 1.462 (2) | C5—C6 | 1.400 (2) |
N3—O2 | 1.218 (2) | C5—C10 | 1.405 (2) |
N3—O1 | 1.224 (2) | C6—C7 | 1.370 (2) |
N3—C8 | 1.446 (2) | C6—H6A | 0.930 |
O3—H3C | 0.871 (18) | C7—C8 | 1.376 (2) |
O3—H3D | 0.853 (18) | C7—H7A | 0.930 |
C1—C2 | 1.503 (3) | C8—C9 | 1.379 (3) |
C1—H1A | 0.970 | C9—C10 | 1.368 (2) |
C1—H1B | 0.970 | C9—H9A | 0.930 |
C2—H2A | 0.970 | C10—H10A | 0.930 |
C3—N1—C1 | 112.33 (13) | N1—C3—H3B | 109.6 |
C3—N1—H1C | 109.1 | C4—C3—H3B | 109.6 |
C1—N1—H1C | 109.1 | H3A—C3—H3B | 108.2 |
C3—N1—H1D | 109.1 | N2—C4—C3 | 110.52 (14) |
C1—N1—H1D | 109.1 | N2—C4—H4A | 109.5 |
H1C—N1—H1D | 107.9 | C3—C4—H4A | 109.5 |
C5—N2—C2 | 120.40 (14) | N2—C4—H4B | 109.5 |
C5—N2—C4 | 119.96 (14) | C3—C4—H4B | 109.5 |
C2—N2—C4 | 109.57 (13) | H4A—C4—H4B | 108.1 |
O2—N3—O1 | 122.48 (17) | N2—C5—C6 | 121.83 (15) |
O2—N3—C8 | 118.60 (17) | N2—C5—C10 | 120.60 (14) |
O1—N3—C8 | 118.90 (17) | C6—C5—C10 | 117.52 (15) |
H3C—O3—H3D | 103 (2) | C7—C6—C5 | 121.15 (15) |
N1—C1—C2 | 109.55 (15) | C7—C6—H6A | 119.4 |
N1—C1—H1A | 109.8 | C5—C6—H6A | 119.4 |
C2—C1—H1A | 109.8 | C6—C7—C8 | 119.67 (16) |
N1—C1—H1B | 109.8 | C6—C7—H7A | 120.2 |
C2—C1—H1B | 109.8 | C8—C7—H7A | 120.2 |
H1A—C1—H1B | 108.2 | C7—C8—C9 | 120.92 (16) |
N2—C2—C1 | 111.17 (15) | C7—C8—N3 | 119.60 (16) |
N2—C2—H2A | 109.4 | C9—C8—N3 | 119.48 (16) |
C1—C2—H2A | 109.4 | C10—C9—C8 | 119.44 (16) |
N2—C2—H2B | 109.4 | C10—C9—H9A | 120.3 |
C1—C2—H2B | 109.4 | C8—C9—H9A | 120.3 |
H2A—C2—H2B | 108.0 | C9—C10—C5 | 121.27 (15) |
N1—C3—C4 | 110.06 (15) | C9—C10—H10A | 119.4 |
N1—C3—H3A | 109.6 | C5—C10—H10A | 119.4 |
C4—C3—H3A | 109.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3D···Cl1i | 0.85 (2) | 2.32 (2) | 3.1681 (18) | 176 (3) |
O3—H3C···Cl1ii | 0.87 (2) | 2.27 (2) | 3.135 (2) | 170 (4) |
N1—H1D···O3iii | 0.90 | 1.88 | 2.741 (2) | 161 |
N1—H1C···Cl1 | 0.90 | 2.21 | 3.0994 (17) | 168 |
Symmetry codes: (i) x, y+1, z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H14N3O2+·Cl−·H2O |
Mr | 261.71 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.404 (2), 9.212 (3), 9.757 (3) |
α, β, γ (°) | 110.111 (4), 90.209 (4), 96.484 (4) |
V (Å3) | 620.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997b) |
Tmin, Tmax | 0.955, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2866, 2390, 2078 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.120, 1.04 |
No. of reflections | 2390 |
No. of parameters | 163 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.30 |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b) and ORTEP-3 (Farrugia, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3D···Cl1i | 0.853 (18) | 2.317 (18) | 3.1681 (18) | 176 (3) |
O3—H3C···Cl1ii | 0.871 (18) | 2.273 (19) | 3.135 (2) | 170 (4) |
N1—H1D···O3iii | 0.90 | 1.88 | 2.741 (2) | 160.8 |
N1—H1C···Cl1 | 0.90 | 2.21 | 3.0994 (17) | 168.4 |
Symmetry codes: (i) x, y+1, z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
4-Nitrophenylpiperazinium chloride monohydrate (I) has been used as an intermediate in the synthesis of anticancer durgs, transcriptase inhibitors and antifungal reagents (Saczewski et al., 2006; Chen et al., 2000; Hepperle et al., 1999). It is also an important reagent for potassium channel openers, which show considerable biomolecular current-voltage rectification characteristics (Wu et al., 2005; Lan et al., 2005, 2006).
The basic structural unit of (I) consists of a 4-nitrophenylpiperazinium cation, a chloride ion and a water molecule. The molecular structure and atom-labeling scheme are shown in Fig. 1. The bonds N3—O1, N3—O2 [1.224 (2), 1.218 (2) Å, respectively] have partial double-bond character. The shorter intramolecular distance of H2b···H6a and H4a···H10a [1.97 and 1.98 Å] demonstrates the existence of H···H contacts.
The chloride anion forms one N—H···Cl and two O—H···Cl hydrogen bonds, namely one to piperazinium atom N1H1c, and two to the H atom of the water molecule (O3H3D, O3H3c) (Table 1). The H···Cl1 interaction lengths of the hydrogen bonds range from 2.21 to 2.317 (18) Å (Sopo & Sillanpää, 2007).
The H atoms of the piperazinium cation form hydrogen bonds to the chloride ion and to water atom O3 in an adjacent unit, forming a three-dimensional hydrogen-bond network (Fig. 2). Thus, the piperazinium cation plays an important role by acting as a bridge between the water O atom and the chloride ion.
The NO2 groups also help to stabilize the crystal structure. The hydrogen bonds C3—H3b···O1iv [symmetry code: (iv) -x + 1, -y + 2, -z + 1] are responsible for two-membered aggregates (Fig. 3), and C1—H1b···O2v [symmetry code: (v) x, y - 1, z - 1] for zigzag molecular chains (Fig. 4) (Zou et al., 2005).
π···π Stacking interactions between pairs of antiparallel benzene rings are observed [mean separation of 3.66 Å] (Fig. 5) (How et al., 2007).