metal-organic compounds
N-Methylpiperazinediium pentachloridoantimonate(III) monohydrate
aCollege of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, People's Republic of China, and bCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
*Correspondence e-mail: apharm@sina.com
The 5H14N2)[SbCl5]·H2O, consists of an N-methylpiperazinediium cation, a pentachloridoantimonate anion with the SbIII ion in a slightly distorted square-pyramidal coordination environment, and one solvent water molecule. The is stabilized by intermolecular N—H⋯Cl, O—H⋯Cl and N—H⋯O hydrogen bonds.
of the title compound, (CRelated literature
For related literature, see: Baker & Williams (1978); Bujak & Zaleski (1999); Clemente & Marzotto (2003); Feng et al. (2007); Knodler et al. (1988); Linden et al. (1999); Marsh (1995).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536807064161/lh2556sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064161/lh2556Isup2.hkl
SbCl3, N-methylpiperazine and 30% aqueous HCl in a molar ratio of 1:1:1 were mixed and dissolved in sufficient ethanol by heating to 373 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were fromed, collected and washed with dilute aqueous HCl.
H atoms were included in calculated positions with O—H = 0.82, N—H = 0.90 - 0.91 and C—H = 0.96–0.97 Å and included in the riding-model approximation with Uiso(H) = 1.2Ueq(C,N,O) or 1.5Ueq(C) for methyl H atoms.
Halogenoantimonates constitute a group of salts in which a number of compounds have been reported (e.g. Feng et al., 2007; Bujak & Zaleski, 1999; Knodler et al., 1988; Baker & Williams, 1978 and see: Clemente & Marzotto (2003); Marsh et al. (1995) for corrected space groups of some of these types of compounds). In our laboratory, a compound containing pentachloridoantimonate has been synthesized, its
is reported herein.As shown in Fig. 1, an
consisting of N-methylpiperazinium and (SbCl5)2+, and one water molecule comprise the formula unit. In the selected The SbCl5 anion is linked to N-methylpiperazinium and the water molecule by N—H···Cl and O—H···Cl hydrogen bonds.The Sb atom is coordinated by five Cl atoms, with Sb—Cl distances ranging from 2.4110 (10) to 2.9112 (11) Å. The Sb—Cl distances are slightly different to the values of 2.499 (4)–2.768 (4)Å reported by Bujak & Zaleski (1999). In the title compound the difference between the longest bond (Sb1—Cl5) and shortest bond (Sb1—Cl2) is ca 0.50 Å. The slight deformation of the square-pyramidal coordination environment may be attributed to the presence of relatively strong N—H···Cl hydrogen bonds. The atoms Cl1/Cl3/Cl4/Cl5 form the basal plane, while atom Cl2 is the apical atom. The structure of the anion is similar to that of the (TiCl5)2- anion (Linden et al., 1999).
The six-membered piperazine ring is in chair conformation. The
is stabilized by N—H···Cl, O—H···Cl and N—H···O hydrogen bonds, and by weak C—H···Cl and C—H···O hydrogen bonds (Fig. 2).For related literature, see: Baker & Williams (1978); Bujak & Zaleski (1999); Clemente & Marzotto (2003); Feng et al. (2007); Knodler et al. (1988); Linden et al. (1999); Marsh (1995).
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.(C5H14N2)[SbCl5]·H2O | F(000) = 816 |
Mr = 419.20 | Dx = 1.912 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3256 reflections |
a = 9.600 (4) Å | θ = 2.1–25.0° |
b = 7.934 (3) Å | µ = 2.79 mm−1 |
c = 19.966 (6) Å | T = 273 K |
β = 106.765 (16)° | Block, brown |
V = 1456.1 (9) Å3 | 0.33 × 0.18 × 0.14 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 2577 independent reflections |
Radiation source: fine-focus sealed tube | 2400 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→11 |
Tmin = 0.460, Tmax = 0.696 | k = −9→9 |
7167 measured reflections | l = −16→23 |
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0213P)2 + 0.8984P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
2577 reflections | Δρmax = 0.35 e Å−3 |
129 parameters | Δρmin = −0.48 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0050 (3) |
(C5H14N2)[SbCl5]·H2O | V = 1456.1 (9) Å3 |
Mr = 419.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.600 (4) Å | µ = 2.79 mm−1 |
b = 7.934 (3) Å | T = 273 K |
c = 19.966 (6) Å | 0.33 × 0.18 × 0.14 mm |
β = 106.765 (16)° |
Bruker SMART CCD diffractometer | 2577 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2400 reflections with I > 2σ(I) |
Tmin = 0.460, Tmax = 0.696 | Rint = 0.021 |
7167 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.35 e Å−3 |
2577 reflections | Δρmin = −0.48 e Å−3 |
129 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 | ||
O1 | 0.6846 (3) | 1.0018 (3) | 0.96651 (12) | 0.0597 (6) | |
H1F | 0.6811 | 1.0770 | 0.9378 | 0.072* | |
H1G | 0.7246 | 0.9149 | 0.9607 | 0.072* | |
N1 | 0.8129 (3) | 0.3813 (3) | 0.60274 (12) | 0.0430 (6) | |
H1A | 0.8580 | 0.2814 | 0.6042 | 0.052* | |
H1B | 0.7664 | 0.4045 | 0.5577 | 0.052* | |
N2 | 0.7418 (2) | 0.6714 (3) | 0.67442 (12) | 0.0386 (5) | |
H2 | 0.7903 | 0.6427 | 0.7192 | 0.046* | |
C1 | 0.6710 (4) | 0.8384 (4) | 0.67596 (18) | 0.0546 (8) | |
H1C | 0.7433 | 0.9196 | 0.6988 | 0.082* | |
H1D | 0.5999 | 0.8284 | 0.7011 | 0.082* | |
H1E | 0.6242 | 0.8747 | 0.6290 | 0.082* | |
C2 | 0.9227 (3) | 0.5143 (4) | 0.63140 (17) | 0.0432 (7) | |
H2A | 0.9879 | 0.5239 | 0.6024 | 0.052* | |
H2B | 0.9800 | 0.4835 | 0.6783 | 0.052* | |
C3 | 0.8497 (3) | 0.6806 (4) | 0.63348 (16) | 0.0434 (7) | |
H3A | 0.9230 | 0.7645 | 0.6544 | 0.052* | |
H3B | 0.8006 | 0.7163 | 0.5861 | 0.052* | |
C4 | 0.6329 (3) | 0.5373 (4) | 0.64511 (18) | 0.0490 (8) | |
H4A | 0.5765 | 0.5684 | 0.5981 | 0.059* | |
H4B | 0.5665 | 0.5278 | 0.6735 | 0.059* | |
C5 | 0.7048 (3) | 0.3696 (4) | 0.64308 (18) | 0.0524 (8) | |
H5A | 0.7533 | 0.3331 | 0.6904 | 0.063* | |
H5B | 0.6315 | 0.2864 | 0.6216 | 0.063* | |
Sb1 | 0.82184 (2) | 0.48123 (2) | 0.906548 (10) | 0.03847 (9) | |
Cl1 | 0.71738 (9) | 0.22687 (12) | 0.83017 (4) | 0.0586 (2) | |
Cl2 | 0.63328 (9) | 0.65958 (12) | 0.83543 (5) | 0.0628 (2) | |
Cl3 | 0.67147 (9) | 0.43460 (13) | 0.98606 (5) | 0.0607 (2) | |
Cl4 | 0.95679 (9) | 0.75059 (10) | 0.98509 (4) | 0.0497 (2) | |
Cl5 | 0.98660 (8) | 0.58815 (10) | 0.81238 (4) | 0.04343 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0592 (15) | 0.0667 (16) | 0.0495 (14) | 0.0137 (11) | 0.0096 (12) | 0.0028 (11) |
N1 | 0.0458 (14) | 0.0450 (14) | 0.0374 (13) | 0.0000 (11) | 0.0106 (11) | −0.0041 (11) |
N2 | 0.0367 (13) | 0.0475 (14) | 0.0324 (13) | 0.0034 (11) | 0.0114 (10) | 0.0027 (11) |
C1 | 0.053 (2) | 0.0537 (19) | 0.061 (2) | 0.0157 (16) | 0.0214 (17) | 0.0051 (17) |
C2 | 0.0366 (16) | 0.0524 (18) | 0.0428 (18) | −0.0024 (13) | 0.0150 (14) | −0.0043 (14) |
C3 | 0.0448 (17) | 0.0477 (17) | 0.0432 (17) | −0.0071 (14) | 0.0213 (14) | −0.0033 (14) |
C4 | 0.0324 (15) | 0.063 (2) | 0.052 (2) | −0.0043 (14) | 0.0140 (14) | −0.0037 (16) |
C5 | 0.0505 (19) | 0.0527 (19) | 0.059 (2) | −0.0117 (15) | 0.0233 (16) | −0.0005 (17) |
Sb1 | 0.03744 (13) | 0.04726 (14) | 0.03172 (13) | 0.00487 (8) | 0.01155 (9) | 0.00274 (8) |
Cl1 | 0.0575 (5) | 0.0664 (5) | 0.0521 (5) | −0.0089 (4) | 0.0163 (4) | −0.0123 (4) |
Cl2 | 0.0541 (5) | 0.0779 (6) | 0.0553 (5) | 0.0234 (4) | 0.0140 (4) | 0.0178 (4) |
Cl3 | 0.0572 (5) | 0.0802 (6) | 0.0548 (5) | 0.0108 (4) | 0.0323 (4) | 0.0108 (5) |
Cl4 | 0.0565 (5) | 0.0523 (4) | 0.0457 (4) | 0.0030 (4) | 0.0232 (4) | −0.0021 (4) |
Cl5 | 0.0432 (4) | 0.0520 (4) | 0.0346 (4) | 0.0007 (3) | 0.0104 (3) | −0.0005 (3) |
O1—H1F | 0.8219 | C2—H2A | 0.9700 |
O1—H1G | 0.8128 | C2—H2B | 0.9700 |
N1—C2 | 1.485 (4) | C3—H3A | 0.9700 |
N1—C5 | 1.488 (4) | C3—H3B | 0.9700 |
N1—H1A | 0.9000 | C4—C5 | 1.505 (4) |
N1—H1B | 0.9000 | C4—H4A | 0.9700 |
N2—C4 | 1.488 (4) | C4—H4B | 0.9700 |
N2—C1 | 1.493 (4) | C5—H5A | 0.9700 |
N2—C3 | 1.496 (3) | C5—H5B | 0.9700 |
N2—H2 | 0.9100 | Sb1—Cl2 | 2.4110 (10) |
C1—H1C | 0.9600 | Sb1—Cl3 | 2.4623 (10) |
C1—H1D | 0.9600 | Sb1—Cl1 | 2.5538 (11) |
C1—H1E | 0.9600 | Sb1—Cl4 | 2.7446 (11) |
C2—C3 | 1.500 (4) | Sb1—Cl5 | 2.9112 (11) |
H1F—O1—H1G | 116.3 | C2—C3—H3A | 109.2 |
C2—N1—C5 | 111.3 (2) | N2—C3—H3B | 109.2 |
C2—N1—H1A | 109.4 | C2—C3—H3B | 109.2 |
C5—N1—H1A | 109.4 | H3A—C3—H3B | 107.9 |
C2—N1—H1B | 109.4 | N2—C4—C5 | 111.5 (2) |
C5—N1—H1B | 109.4 | N2—C4—H4A | 109.3 |
H1A—N1—H1B | 108.0 | C5—C4—H4A | 109.3 |
C4—N2—C1 | 111.7 (2) | N2—C4—H4B | 109.3 |
C4—N2—C3 | 109.8 (2) | C5—C4—H4B | 109.3 |
C1—N2—C3 | 111.1 (2) | H4A—C4—H4B | 108.0 |
C4—N2—H2 | 108.0 | N1—C5—C4 | 110.9 (3) |
C1—N2—H2 | 108.0 | N1—C5—H5A | 109.5 |
C3—N2—H2 | 108.0 | C4—C5—H5A | 109.5 |
N2—C1—H1C | 109.5 | N1—C5—H5B | 109.5 |
N2—C1—H1D | 109.5 | C4—C5—H5B | 109.5 |
H1C—C1—H1D | 109.5 | H5A—C5—H5B | 108.0 |
N2—C1—H1E | 109.5 | Cl2—Sb1—Cl3 | 89.29 (4) |
H1C—C1—H1E | 109.5 | Cl2—Sb1—Cl1 | 90.76 (4) |
H1D—C1—H1E | 109.5 | Cl3—Sb1—Cl1 | 93.67 (4) |
N1—C2—C3 | 110.5 (2) | Cl2—Sb1—Cl4 | 91.71 (4) |
N1—C2—H2A | 109.5 | Cl3—Sb1—Cl4 | 90.95 (4) |
C3—C2—H2A | 109.5 | Cl1—Sb1—Cl4 | 174.79 (3) |
N1—C2—H2B | 109.5 | Cl5—Sb1—Cl1 | 92.15 (4) |
C3—C2—H2B | 109.5 | Cl5—Sb1—Cl2 | 84.50 (4) |
H2A—C2—H2B | 108.1 | Cl5—Sb1—Cl3 | 171.54 (4) |
N2—C3—C2 | 112.0 (2) | Cl5—Sb1—Cl4 | 83.52 (4) |
N2—C3—H3A | 109.2 | ||
C5—N1—C2—C3 | −55.7 (3) | C1—N2—C4—C5 | 179.5 (3) |
C4—N2—C3—C2 | −56.1 (3) | C3—N2—C4—C5 | 55.8 (3) |
C1—N2—C3—C2 | 179.8 (3) | C2—N1—C5—C4 | 55.9 (3) |
N1—C2—C3—N2 | 56.2 (3) | N2—C4—C5—N1 | −56.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1F···Cl1i | 0.82 | 2.57 | 3.346 (4) | 159 |
O1—H1G···Cl4 | 0.82 | 2.51 | 3.223 (5) | 147 |
N1—H1A···Cl5ii | 0.90 | 2.43 | 3.179 (4) | 141 |
N1—H1B···O1iii | 0.90 | 1.91 | 2.801 (5) | 168 |
N2—H2···Cl5 | 0.91 | 2.28 | 3.133 (5) | 157 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C5H14N2)[SbCl5]·H2O |
Mr | 419.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 9.600 (4), 7.934 (3), 19.966 (6) |
β (°) | 106.765 (16) |
V (Å3) | 1456.1 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.79 |
Crystal size (mm) | 0.33 × 0.18 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.460, 0.696 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7167, 2577, 2400 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.054, 1.07 |
No. of reflections | 2577 |
No. of parameters | 129 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.48 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL.
Sb1—Cl2 | 2.4110 (10) | Sb1—Cl4 | 2.7446 (11) |
Sb1—Cl3 | 2.4623 (10) | Sb1—Cl5 | 2.9112 (11) |
Sb1—Cl1 | 2.5538 (11) | ||
Cl2—Sb1—Cl3 | 89.29 (4) | Cl2—Sb1—Cl4 | 91.71 (4) |
Cl2—Sb1—Cl1 | 90.76 (4) | Cl3—Sb1—Cl4 | 90.95 (4) |
Cl3—Sb1—Cl1 | 93.67 (4) | Cl1—Sb1—Cl4 | 174.79 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1F···Cl1i | 0.82 | 2.57 | 3.346 (4) | 159 |
O1—H1G···Cl4 | 0.82 | 2.51 | 3.223 (5) | 147 |
N1—H1A···Cl5ii | 0.90 | 2.43 | 3.179 (4) | 141 |
N1—H1B···O1iii | 0.90 | 1.91 | 2.801 (5) | 168 |
N2—H2···Cl5 | 0.91 | 2.28 | 3.133 (5) | 157 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+3/2, z−1/2. |
References
Baker, W. A. & Williams, D. E. (1978). Acta Cryst. B34, 1111–1116. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2000). SMART (Version 5.618), SADABS (Version 2.05), SAINT (Version 6.02a) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Halogenoantimonates constitute a group of salts in which a number of compounds have been reported (e.g. Feng et al., 2007; Bujak & Zaleski, 1999; Knodler et al., 1988; Baker & Williams, 1978 and see: Clemente & Marzotto (2003); Marsh et al. (1995) for corrected space groups of some of these types of compounds). In our laboratory, a compound containing pentachloridoantimonate has been synthesized, its crystal structure is reported herein.
As shown in Fig. 1, an ion pair consisting of N-methylpiperazinium and (SbCl5)2+, and one water molecule comprise the formula unit. In the selected asymmetric unit The SbCl5 anion is linked to N-methylpiperazinium and the water molecule by N—H···Cl and O—H···Cl hydrogen bonds.
The Sb atom is coordinated by five Cl atoms, with Sb—Cl distances ranging from 2.4110 (10) to 2.9112 (11) Å. The Sb—Cl distances are slightly different to the values of 2.499 (4)–2.768 (4)Å reported by Bujak & Zaleski (1999). In the title compound the difference between the longest bond (Sb1—Cl5) and shortest bond (Sb1—Cl2) is ca 0.50 Å. The slight deformation of the square-pyramidal coordination environment may be attributed to the presence of relatively strong N—H···Cl hydrogen bonds. The atoms Cl1/Cl3/Cl4/Cl5 form the basal plane, while atom Cl2 is the apical atom. The structure of the anion is similar to that of the (TiCl5)2- anion (Linden et al., 1999).
The six-membered piperazine ring is in chair conformation. The crystal structure is stabilized by N—H···Cl, O—H···Cl and N—H···O hydrogen bonds, and by weak C—H···Cl and C—H···O hydrogen bonds (Fig. 2).