metal-organic compounds
Diisonicotinium pentachloridoantimonate(III) monohydrate
aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: clz1977@sina.com
In the title compound, (C6H6NO2)2[SbCl5]·H2O, the SbIII atom exhibits a distorted square-pyramidal coordination geometry. The is stabilized by intermolecular N—H⋯Cl, N—H⋯O, O—H⋯Cl and O—H⋯O hydrogen bonds, forming an extended three-dimensional network.
Related literature
For related structures, see: Bujak & Zaleski (1999); Feng et al. (2007); Shen-Tu et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536809019072/rz2323sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809019072/rz2323Isup2.hkl
SbCl3, isonicotinic acid and 20% aqueous HCl in a molar ratio of 1:1:3 were mixed and dissolved in water by heating to 373 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed, collected and washed with dilute aqueous HCl.
All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å, O—H = 0.85 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O). The deepest residual electron density hole is located 1.47 Å from atom H5A.
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. A view of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. | |
Fig. 2. The crystal packing of the title compound viewed approximately along the b axis. Hydrogen bonds are drawn as dashed lines. |
(C6H6NO2)2[SbCl5]·H2O | F(000) = 1104 |
Mr = 565.25 | Dx = 1.842 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4071 reflections |
a = 10.334 (2) Å | θ = 3.1–27.5° |
b = 8.7319 (17) Å | µ = 2.03 mm−1 |
c = 23.615 (7) Å | T = 291 K |
β = 106.98 (3)° | Block, colourless |
V = 2038.0 (9) Å3 | 0.25 × 0.20 × 0.20 mm |
Z = 4 |
Rigaku SCXmini diffractometer | 4675 independent reflections |
Radiation source: fine-focus sealed tube | 4071 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −13→12 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −11→11 |
Tmin = 0.61, Tmax = 0.67 | l = −30→30 |
19258 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)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0112P)2 + 1.8681P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max < 0.001 |
4675 reflections | Δρmax = 0.76 e Å−3 |
227 parameters | Δρmin = −1.76 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0094 (3) |
(C6H6NO2)2[SbCl5]·H2O | V = 2038.0 (9) Å3 |
Mr = 565.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.334 (2) Å | µ = 2.03 mm−1 |
b = 8.7319 (17) Å | T = 291 K |
c = 23.615 (7) Å | 0.25 × 0.20 × 0.20 mm |
β = 106.98 (3)° |
Rigaku SCXmini diffractometer | 4675 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 4071 reflections with I > 2σ(I) |
Tmin = 0.61, Tmax = 0.67 | Rint = 0.061 |
19258 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.76 e Å−3 |
4675 reflections | Δρmin = −1.76 e Å−3 |
227 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 | 0.7498 (3) | 0.9688 (4) | 0.04677 (14) | 0.0569 (9) | |
H1C | 0.8214 | 1.0222 | 0.0583 | 0.085* | |
O2 | 0.8222 (3) | 0.8846 (4) | 0.14010 (14) | 0.0583 (10) | |
N1 | 0.4007 (4) | 0.6022 (5) | 0.0507 (2) | 0.0561 (11) | |
H1B | 0.3308 | 0.5436 | 0.0427 | 0.067* | |
C1 | 0.4199 (5) | 0.6891 (5) | 0.0081 (2) | 0.0527 (13) | |
H1A | 0.3586 | 0.6866 | −0.0296 | 0.063* | |
C6 | 0.7409 (5) | 0.8855 (5) | 0.0914 (2) | 0.0419 (11) | |
C2 | 0.5301 (5) | 0.7820 (5) | 0.01973 (19) | 0.0425 (11) | |
H2B | 0.5451 | 0.8430 | −0.0100 | 0.051* | |
C5 | 0.4841 (6) | 0.6009 (6) | 0.1054 (2) | 0.0586 (14) | |
H5A | 0.4668 | 0.5372 | 0.1338 | 0.070* | |
C4 | 0.5956 (5) | 0.6935 (6) | 0.1197 (2) | 0.0489 (12) | |
H4A | 0.6541 | 0.6947 | 0.1580 | 0.059* | |
C3 | 0.6198 (4) | 0.7850 (5) | 0.07631 (18) | 0.0376 (10) | |
Cl5 | 0.21814 (12) | 0.35116 (14) | 0.08488 (5) | 0.0501 (3) | |
O1W | 0.9650 (5) | 0.1234 (6) | 0.0754 (3) | 0.195 (4) | |
H1WA | 1.0285 | 0.0715 | 0.0984 | 0.292* | |
H1WB | 0.9982 | 0.2007 | 0.0627 | 0.292* | |
Sb1 | 0.38449 (3) | 0.14611 (3) | 0.173118 (11) | 0.03103 (11) | |
Cl1 | 0.51635 (14) | −0.04608 (16) | 0.24298 (6) | 0.0646 (4) | |
Cl3 | 0.18317 (14) | 0.09286 (16) | 0.21279 (7) | 0.0642 (4) | |
Cl2 | 0.60393 (12) | 0.19468 (15) | 0.13735 (5) | 0.0521 (3) | |
Cl4 | 0.30831 (13) | −0.04201 (14) | 0.09880 (6) | 0.0554 (3) | |
O3 | −0.0419 (4) | 0.6811 (4) | 0.04218 (15) | 0.0734 (12) | |
H3A | −0.0944 | 0.6770 | 0.0070 | 0.110* | |
O4 | −0.1684 (4) | 0.4904 (5) | 0.05540 (16) | 0.0797 (13) | |
N2 | 0.1577 (4) | 0.5697 (5) | 0.25122 (17) | 0.0513 (11) | |
H2A | 0.2057 | 0.5670 | 0.2877 | 0.062* | |
C12 | −0.0780 (5) | 0.5765 (6) | 0.0741 (2) | 0.0474 (12) | |
C9 | 0.0065 (4) | 0.5778 (5) | 0.13730 (19) | 0.0388 (10) | |
C8 | −0.0139 (5) | 0.4684 (6) | 0.1746 (2) | 0.0497 (12) | |
H8A | −0.0816 | 0.3958 | 0.1610 | 0.060* | |
C11 | 0.1813 (5) | 0.6798 (6) | 0.2169 (2) | 0.0565 (14) | |
H11A | 0.2490 | 0.7516 | 0.2321 | 0.068* | |
C10 | 0.1047 (5) | 0.6868 (5) | 0.1585 (2) | 0.0528 (13) | |
H10A | 0.1190 | 0.7639 | 0.1339 | 0.063* | |
C7 | 0.0648 (5) | 0.4649 (6) | 0.2321 (2) | 0.0533 (13) | |
H7A | 0.0525 | 0.3886 | 0.2576 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.051 (2) | 0.072 (3) | 0.046 (2) | −0.0181 (18) | 0.0115 (17) | 0.0049 (18) |
O2 | 0.052 (2) | 0.071 (3) | 0.0415 (19) | 0.0017 (18) | −0.0026 (17) | −0.0019 (17) |
N1 | 0.060 (3) | 0.047 (3) | 0.062 (3) | −0.012 (2) | 0.019 (2) | −0.002 (2) |
C1 | 0.058 (3) | 0.051 (3) | 0.044 (3) | −0.010 (3) | 0.007 (3) | −0.004 (2) |
C6 | 0.039 (3) | 0.050 (3) | 0.036 (2) | 0.003 (2) | 0.009 (2) | −0.006 (2) |
C2 | 0.048 (3) | 0.047 (3) | 0.031 (2) | −0.007 (2) | 0.009 (2) | 0.000 (2) |
C5 | 0.077 (4) | 0.050 (3) | 0.058 (3) | 0.001 (3) | 0.033 (3) | 0.014 (3) |
C4 | 0.055 (3) | 0.058 (3) | 0.036 (3) | 0.006 (3) | 0.016 (2) | 0.007 (2) |
C3 | 0.040 (3) | 0.044 (3) | 0.032 (2) | 0.004 (2) | 0.015 (2) | −0.002 (2) |
Cl5 | 0.0542 (7) | 0.0498 (7) | 0.0434 (6) | 0.0001 (6) | 0.0096 (6) | 0.0118 (6) |
O1W | 0.074 (4) | 0.146 (5) | 0.316 (9) | −0.059 (4) | −0.017 (5) | 0.112 (6) |
Sb1 | 0.03618 (18) | 0.02999 (17) | 0.02550 (15) | 0.00013 (12) | 0.00678 (12) | 0.00076 (12) |
Cl1 | 0.0674 (9) | 0.0654 (9) | 0.0561 (8) | 0.0156 (7) | 0.0105 (7) | 0.0324 (7) |
Cl3 | 0.0663 (9) | 0.0638 (9) | 0.0750 (10) | −0.0064 (7) | 0.0401 (8) | −0.0022 (7) |
Cl2 | 0.0472 (7) | 0.0707 (9) | 0.0378 (6) | 0.0062 (6) | 0.0115 (6) | 0.0107 (6) |
Cl4 | 0.0676 (9) | 0.0479 (7) | 0.0506 (7) | −0.0077 (6) | 0.0169 (7) | −0.0207 (6) |
O3 | 0.094 (3) | 0.070 (3) | 0.041 (2) | −0.026 (2) | −0.005 (2) | 0.0129 (18) |
O4 | 0.079 (3) | 0.102 (3) | 0.043 (2) | −0.046 (3) | −0.006 (2) | 0.007 (2) |
N2 | 0.053 (3) | 0.058 (3) | 0.034 (2) | 0.012 (2) | −0.0022 (19) | −0.002 (2) |
C12 | 0.051 (3) | 0.049 (3) | 0.037 (3) | −0.002 (2) | 0.006 (2) | −0.002 (2) |
C9 | 0.039 (3) | 0.039 (3) | 0.035 (2) | 0.004 (2) | 0.005 (2) | −0.005 (2) |
C8 | 0.053 (3) | 0.053 (3) | 0.039 (3) | −0.008 (2) | 0.008 (2) | −0.003 (2) |
C11 | 0.049 (3) | 0.049 (3) | 0.057 (3) | −0.004 (2) | −0.006 (3) | −0.006 (3) |
C10 | 0.055 (3) | 0.046 (3) | 0.050 (3) | −0.005 (2) | 0.002 (3) | 0.007 (2) |
C7 | 0.060 (3) | 0.057 (3) | 0.039 (3) | −0.001 (3) | 0.008 (3) | 0.007 (2) |
O1—C6 | 1.306 (5) | Sb1—Cl1 | 2.4661 (13) |
O1—H1C | 0.8500 | Sb1—Cl3 | 2.5613 (15) |
O2—C6 | 1.210 (5) | Sb1—Cl2 | 2.6748 (14) |
N1—C1 | 1.322 (6) | O3—C12 | 1.306 (6) |
N1—C5 | 1.325 (6) | O3—H3A | 0.8500 |
N1—H1B | 0.8600 | O4—C12 | 1.180 (5) |
C1—C2 | 1.359 (6) | N2—C7 | 1.307 (6) |
C1—H1A | 0.9300 | N2—C11 | 1.326 (6) |
C6—C3 | 1.484 (6) | N2—H2A | 0.8600 |
C2—C3 | 1.386 (6) | C12—C9 | 1.493 (6) |
C2—H2B | 0.9300 | C9—C8 | 1.357 (6) |
C5—C4 | 1.366 (7) | C9—C10 | 1.375 (6) |
C5—H5A | 0.9300 | C8—C7 | 1.365 (6) |
C4—C3 | 1.379 (6) | C8—H8A | 0.9300 |
C4—H4A | 0.9300 | C11—C10 | 1.375 (6) |
O1W—H1WA | 0.8500 | C11—H11A | 0.9300 |
O1W—H1WB | 0.8499 | C10—H10A | 0.9300 |
Sb1—Cl5 | 2.9002 (14) | C7—H7A | 0.9300 |
Sb1—Cl4 | 2.3646 (12) | ||
C6—O1—H1C | 107.9 | Cl4—Sb1—Cl3 | 90.89 (5) |
C1—N1—C5 | 123.2 (5) | Cl1—Sb1—Cl3 | 88.91 (5) |
C1—N1—H1B | 118.4 | Cl4—Sb1—Cl2 | 90.28 (5) |
C5—N1—H1B | 118.4 | Cl1—Sb1—Cl2 | 88.01 (5) |
N1—C1—C2 | 119.4 (5) | Cl3—Sb1—Cl2 | 176.73 (4) |
N1—C1—H1A | 120.3 | C12—O3—H3A | 109.1 |
C2—C1—H1A | 120.3 | C7—N2—C11 | 123.0 (4) |
O2—C6—O1 | 125.3 (5) | C7—N2—H2A | 118.5 |
O2—C6—C3 | 121.8 (4) | C11—N2—H2A | 118.5 |
O1—C6—C3 | 112.8 (4) | O4—C12—O3 | 123.9 (5) |
C1—C2—C3 | 119.4 (5) | O4—C12—C9 | 123.2 (5) |
C1—C2—H2B | 120.3 | O3—C12—C9 | 112.9 (4) |
C3—C2—H2B | 120.3 | C8—C9—C10 | 119.2 (4) |
N1—C5—C4 | 119.9 (5) | C8—C9—C12 | 119.2 (4) |
N1—C5—H5A | 120.1 | C10—C9—C12 | 121.6 (4) |
C4—C5—H5A | 120.1 | C9—C8—C7 | 120.1 (5) |
C5—C4—C3 | 118.7 (5) | C9—C8—H8A | 119.9 |
C5—C4—H4A | 120.6 | C7—C8—H8A | 119.9 |
C3—C4—H4A | 120.6 | N2—C11—C10 | 119.3 (5) |
C4—C3—C2 | 119.3 (4) | N2—C11—H11A | 120.3 |
C4—C3—C6 | 119.2 (4) | C10—C11—H11A | 120.3 |
C2—C3—C6 | 121.5 (4) | C9—C10—C11 | 118.8 (5) |
H1WA—O1W—H1WB | 109.5 | C9—C10—H10A | 120.6 |
Cl5—Sb1—Cl1 | 175.24 (4) | C11—C10—H10A | 120.6 |
Cl5—Sb1—Cl3 | 90.03 (4) | N2—C7—C8 | 119.4 (5) |
Cl5—Sb1—Cl2 | 93.12 (4) | N2—C7—H7A | 120.3 |
Cl5—Sb1—Cl4 | 84.06 (4) | C8—C7—H7A | 120.3 |
Cl4—Sb1—Cl1 | 91.32 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···O1Wi | 0.85 | 1.67 | 2.520 (5) | 175 |
N1—H1B···O4ii | 0.86 | 2.45 | 3.031 (6) | 126 |
O1W—H1WA···Cl3iii | 0.85 | 2.71 | 3.378 (7) | 136 |
O1W—H1WB···Cl5iii | 0.85 | 2.54 | 3.241 (4) | 140 |
O3—H3A···Cl5ii | 0.85 | 2.19 | 3.034 (4) | 175 |
N2—H2A···O2iv | 0.86 | 2.41 | 2.988 (5) | 125 |
N2—H2A···Cl2v | 0.86 | 2.49 | 3.224 (4) | 144 |
N1—H1B···Cl5 | 0.86 | 2.42 | 3.147 (4) | 143 |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C6H6NO2)2[SbCl5]·H2O |
Mr | 565.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 10.334 (2), 8.7319 (17), 23.615 (7) |
β (°) | 106.98 (3) |
V (Å3) | 2038.0 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.03 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.61, 0.67 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19258, 4675, 4071 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.085, 1.19 |
No. of reflections | 4675 |
No. of parameters | 227 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −1.76 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···O1Wi | 0.85 | 1.67 | 2.520 (5) | 175.0 |
N1—H1B···O4ii | 0.86 | 2.45 | 3.031 (6) | 125.5 |
O1W—H1WA···Cl3iii | 0.85 | 2.71 | 3.378 (7) | 136.0 |
O1W—H1WB···Cl5iii | 0.85 | 2.54 | 3.241 (4) | 140.0 |
O3—H3A···Cl5ii | 0.85 | 2.19 | 3.034 (4) | 174.8 |
N2—H2A···O2iv | 0.86 | 2.41 | 2.988 (5) | 125.0 |
N2—H2A···Cl2v | 0.86 | 2.49 | 3.224 (4) | 143.5 |
N1—H1B···Cl5 | 0.86 | 2.42 | 3.147 (4) | 142.8 |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2. |
References
Bujak, M. & Zaleski, J. (1999). Acta Cryst. C55, 1775–1778. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Feng, W.-J., Wang, H.-B., Ma, X.-J., Li, H.-Y. & Jin, Z.-M. (2007). Acta Cryst. E63, m1786–m1787. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen-Tu, C., Li, H. Y., Ma, X. J., Huang, W. & Jin, Z. M. (2008). Acta Cryst. E64, m146. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Recently, the crystal structure of some halogenoantimonate salts has been reported (Feng et al.,2007; Bujak & Zaleski, 1999; Shen-Tu et al. 2008). As a contribution to this field, the synthesis and crystal structure of the title compound is reported herein.
The asymmetric unit of the title compound (Fig. 1) contains two protonated isonicotinic acid cations, a pentachloridoantimonate anion and a water molecule. The antimony(III) ion is in a distorted square-pyramidal coordination geometry, with the Sb—Cl distances ranging from 2.3642 (12) to 2.9002 (14) Å. This range of values is in agreement with that observed in N-methylpiperazinediium pentachloridoantimonate(III) monohydrate (2.4110 (10)–2.9112 (11) Å; Shen-Tu et al., 2008) and slightly larger than that reported for bis(ethyldimethylammonium) pentachloroantimonate(III) (2.499 (4)–2.768 (4) Å; Bujak & Zaleski, 1999). The crystal structure is stabilized by intermolecular N—H···Cl, N—H···O, O—H···Cl and O—H···O hydrogen bonds (Table 1), forming an extended three-dimensional network (Fig. 2).