Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110001940/gd3320sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110001940/gd33202CADHPsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110001940/gd33204CADHPsup3.hkl |
CCDC references: 774078; 774079
Ethanol solutions containing equimolar quantities of 2-chloroaniline and orthophosphoric acid were mixed to produce a white precipitate, which was filtered off, dried for a few hours, dissolved in ethanol and allowed to recrystallize to afford colourless single crystals of 2CADHP after a period of about two weeks.
Colourless crystals of 4CADHP were obtained from a solution of 4-chloroaniline and orthophosphoric acid mixed at a 1:1 stoichiometric ratio in a mixed solvent of ethanol and water in equal proportions (50:50 v/v) upon gentle heating. The solution thus prepared was allowed to crystallize.
The positions of the H atoms bound to N and O atoms were identified from difference electron-density maps, but were subsequently geometrically optimized (O—H = 0.82 Å and N—H = 0.89 Å) and allowed to ride at the best staggered positions, with Uiso(H) = 1.5Ueq(O,N), except for O2 of 2CADHP whose O—H vector was allowed to rotate around the P—O bond. H atoms bound to C atoms were treated as riding atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C6H7ClN+·H2PO4− | F(000) = 464 |
Mr = 225.56 | Dx = 1.681 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2577 reflections |
a = 11.3143 (6) Å | θ = 2.6–37.6° |
b = 4.7466 (2) Å | µ = 0.59 mm−1 |
c = 17.5024 (9) Å | T = 292 K |
β = 108.540 (3)° | Prism, colourless |
V = 891.17 (8) Å3 | 0.25 × 0.20 × 0.15 mm |
Z = 4 |
Bruker Kappa APEX2 CCD area-detector diffractometer | 2044 independent reflections |
Radiation source: fine-focus sealed tube | 1902 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω and ϕ scan | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker 1999) | h = −14→14 |
Tmin = 0.867, Tmax = 0.917 | k = −6→5 |
9738 measured reflections | l = −22→22 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.5784P] where P = (Fo2 + 2Fc2)/3 |
2044 reflections | (Δ/σ)max < 0.001 |
122 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
C6H7ClN+·H2PO4− | V = 891.17 (8) Å3 |
Mr = 225.56 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.3143 (6) Å | µ = 0.59 mm−1 |
b = 4.7466 (2) Å | T = 292 K |
c = 17.5024 (9) Å | 0.25 × 0.20 × 0.15 mm |
β = 108.540 (3)° |
Bruker Kappa APEX2 CCD area-detector diffractometer | 2044 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 1999) | 1902 reflections with I > 2σ(I) |
Tmin = 0.867, Tmax = 0.917 | Rint = 0.018 |
9738 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.39 e Å−3 |
2044 reflections | Δρmin = −0.47 e Å−3 |
122 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 | 0.33498 (4) | 0.64044 (10) | 0.07416 (3) | 0.04460 (14) | |
N1 | 0.37364 (12) | 1.0574 (3) | 0.20551 (8) | 0.0286 (3) | |
H1A | 0.3708 | 0.9044 | 0.2343 | 0.045 (6)* | |
H1B | 0.3022 | 1.0743 | 0.1654 | 0.043 (6)* | |
H1C | 0.3852 | 1.2088 | 0.2370 | 0.043 (6)* | |
C1 | 0.47615 (13) | 1.0322 (3) | 0.17262 (9) | 0.0251 (3) | |
C2 | 0.46861 (14) | 0.8402 (3) | 0.11197 (9) | 0.0296 (3) | |
C3 | 0.56680 (17) | 0.8111 (4) | 0.08157 (11) | 0.0398 (4) | |
H3 | 0.5621 | 0.6805 | 0.0411 | 0.048* | |
C4 | 0.67135 (16) | 0.9755 (4) | 0.11129 (11) | 0.0403 (4) | |
H4 | 0.7373 | 0.9564 | 0.0907 | 0.048* | |
C5 | 0.67890 (15) | 1.1683 (4) | 0.17127 (12) | 0.0394 (4) | |
H5 | 0.7495 | 1.2806 | 0.1907 | 0.047* | |
C6 | 0.58152 (15) | 1.1959 (4) | 0.20286 (10) | 0.0339 (3) | |
H6 | 0.5872 | 1.3239 | 0.2441 | 0.041* | |
P1 | 0.46720 (3) | 0.59433 (8) | 0.37887 (2) | 0.02464 (12) | |
O1 | 0.37359 (10) | 0.6990 (3) | 0.42244 (7) | 0.0325 (3) | |
H1D | 0.4056 | 0.6818 | 0.4713 | 0.049* | |
O2 | 0.56282 (12) | 0.8335 (3) | 0.38337 (10) | 0.0447 (3) | |
H2D | 0.5365 | 0.9815 | 0.3959 | 0.067* | |
O3 | 0.53878 (11) | 0.3420 (2) | 0.42139 (7) | 0.0324 (3) | |
O4 | 0.39025 (11) | 0.5470 (3) | 0.29244 (7) | 0.0352 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0364 (2) | 0.0442 (3) | 0.0524 (3) | −0.01116 (18) | 0.01287 (19) | −0.0176 (2) |
N1 | 0.0243 (6) | 0.0287 (7) | 0.0343 (6) | −0.0005 (5) | 0.0115 (5) | −0.0029 (5) |
C1 | 0.0229 (6) | 0.0247 (7) | 0.0279 (7) | 0.0020 (5) | 0.0084 (5) | 0.0026 (6) |
C2 | 0.0267 (7) | 0.0288 (8) | 0.0328 (7) | −0.0014 (6) | 0.0090 (6) | −0.0013 (6) |
C3 | 0.0393 (9) | 0.0438 (10) | 0.0411 (9) | 0.0008 (8) | 0.0197 (7) | −0.0082 (8) |
C4 | 0.0309 (8) | 0.0491 (11) | 0.0466 (9) | 0.0039 (8) | 0.0206 (7) | 0.0045 (8) |
C5 | 0.0257 (7) | 0.0405 (10) | 0.0518 (10) | −0.0050 (7) | 0.0118 (7) | 0.0021 (8) |
C6 | 0.0287 (7) | 0.0324 (8) | 0.0400 (8) | −0.0030 (6) | 0.0101 (6) | −0.0054 (7) |
P1 | 0.02322 (19) | 0.0191 (2) | 0.0331 (2) | 0.00011 (13) | 0.01108 (15) | −0.00416 (14) |
O1 | 0.0262 (5) | 0.0394 (7) | 0.0341 (6) | 0.0079 (5) | 0.0126 (4) | −0.0008 (5) |
O2 | 0.0368 (6) | 0.0235 (6) | 0.0835 (10) | −0.0073 (5) | 0.0329 (7) | −0.0143 (6) |
O3 | 0.0353 (6) | 0.0230 (5) | 0.0389 (6) | 0.0059 (4) | 0.0117 (5) | −0.0023 (5) |
O4 | 0.0398 (6) | 0.0322 (6) | 0.0325 (6) | 0.0011 (5) | 0.0101 (5) | −0.0043 (5) |
Cl1—C2 | 1.7281 (16) | C4—H4 | 0.9300 |
N1—C1 | 1.4545 (18) | C5—C6 | 1.387 (2) |
N1—H1A | 0.8900 | C5—H5 | 0.9300 |
N1—H1B | 0.8900 | C6—H6 | 0.9300 |
N1—H1C | 0.8900 | P1—O4 | 1.5031 (12) |
C1—C6 | 1.380 (2) | P1—O3 | 1.5036 (12) |
C1—C2 | 1.381 (2) | P1—O2 | 1.5529 (12) |
C2—C3 | 1.383 (2) | P1—O1 | 1.5696 (11) |
C3—C4 | 1.374 (3) | O1—H1D | 0.8200 |
C3—H3 | 0.9300 | O2—H2D | 0.8200 |
C4—C5 | 1.375 (3) | ||
C1—N1—H1A | 109.5 | C3—C4—H4 | 119.9 |
C1—N1—H1B | 109.5 | C5—C4—H4 | 119.9 |
H1A—N1—H1B | 109.5 | C4—C5—C6 | 120.20 (16) |
C1—N1—H1C | 109.5 | C4—C5—H5 | 119.9 |
H1A—N1—H1C | 109.5 | C6—C5—H5 | 119.9 |
H1B—N1—H1C | 109.5 | C1—C6—C5 | 119.52 (16) |
C6—C1—C2 | 120.08 (14) | C1—C6—H6 | 120.2 |
C6—C1—N1 | 120.15 (14) | C5—C6—H6 | 120.2 |
C2—C1—N1 | 119.76 (13) | O4—P1—O3 | 115.32 (7) |
C1—C2—C3 | 120.05 (15) | O4—P1—O2 | 109.36 (8) |
C1—C2—Cl1 | 119.28 (12) | O3—P1—O2 | 107.48 (7) |
C3—C2—Cl1 | 120.67 (13) | O4—P1—O1 | 105.78 (7) |
C4—C3—C2 | 119.86 (16) | O3—P1—O1 | 110.63 (7) |
C4—C3—H3 | 120.1 | O2—P1—O1 | 108.10 (7) |
C2—C3—H3 | 120.1 | P1—O1—H1D | 109.5 |
C3—C4—C5 | 120.28 (16) | P1—O2—H2D | 109.5 |
C6—C1—C2—C3 | 0.2 (2) | C2—C3—C4—C5 | 0.2 (3) |
N1—C1—C2—C3 | −178.68 (15) | C3—C4—C5—C6 | 0.7 (3) |
C6—C1—C2—Cl1 | −179.20 (13) | C2—C1—C6—C5 | 0.7 (3) |
N1—C1—C2—Cl1 | 1.9 (2) | N1—C1—C6—C5 | 179.57 (15) |
C1—C2—C3—C4 | −0.6 (3) | C4—C5—C6—C1 | −1.2 (3) |
Cl1—C2—C3—C4 | 178.74 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4 | 0.89 | 1.95 | 2.8348 (19) | 170 |
N1—H1B···O1i | 0.89 | 2.17 | 3.0509 (18) | 169 |
N1—H1C···O4ii | 0.89 | 1.87 | 2.7515 (18) | 172 |
O1—H1D···O3iii | 0.82 | 1.78 | 2.6017 (17) | 174 |
O2—H2D···O3ii | 0.82 | 1.77 | 2.5411 (17) | 157 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1. |
C6H7ClN+·H2PO4− | F(000) = 928 |
Mr = 225.56 | Dx = 1.554 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5587 reflections |
a = 9.7371 (19) Å | θ = 2.7–32.2° |
b = 7.8756 (16) Å | µ = 0.55 mm−1 |
c = 25.141 (5) Å | T = 292 K |
V = 1927.9 (7) Å3 | Block, colourless |
Z = 8 | 0.25 × 0.20 × 0.20 mm |
Bruker Kappa APEX2 CCD area-detector diffractometer | 1687 independent reflections |
Radiation source: fine-focus sealed tube | 1483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and ϕ scan | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker 1999) | h = −11→6 |
Tmin = 0.876, Tmax = 0.899 | k = −8→9 |
8591 measured reflections | l = −29→29 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0676P)2 + 1.7857P] where P = (Fo2 + 2Fc2)/3 |
1687 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C6H7ClN+·H2PO4− | V = 1927.9 (7) Å3 |
Mr = 225.56 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.7371 (19) Å | µ = 0.55 mm−1 |
b = 7.8756 (16) Å | T = 292 K |
c = 25.141 (5) Å | 0.25 × 0.20 × 0.20 mm |
Bruker Kappa APEX2 CCD area-detector diffractometer | 1687 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 1999) | 1483 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.899 | Rint = 0.037 |
8591 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.50 e Å−3 |
1687 reflections | Δρmin = −0.31 e Å−3 |
123 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 | ||
P1 | 0.61909 (6) | 0.19672 (8) | 0.46396 (2) | 0.0289 (2) | |
Cl1 | 0.61167 (12) | 0.36351 (16) | 0.80580 (3) | 0.0813 (4) | |
O1 | 0.7408 (3) | 0.1346 (3) | 0.43001 (9) | 0.0736 (8) | |
H1D | 0.7639 | 0.0395 | 0.4398 | 0.093 (15)* | |
O2 | 0.4834 (3) | 0.1235 (3) | 0.44054 (9) | 0.0703 (8) | |
H2D | 0.4699 | 0.0284 | 0.4527 | 0.102 (16)* | |
O3 | 0.63585 (16) | 0.1436 (2) | 0.52159 (7) | 0.0308 (4) | |
O4 | 0.60899 (17) | 0.3847 (2) | 0.45644 (8) | 0.0387 (5) | |
N1 | 0.6296 (2) | 0.4693 (3) | 0.57205 (8) | 0.0312 (5) | |
H1A | 0.5527 | 0.5201 | 0.5614 | 0.041 (7)* | |
H1B | 0.6371 | 0.3689 | 0.5561 | 0.069 (11)* | |
H1C | 0.7014 | 0.5337 | 0.5635 | 0.046 (8)* | |
C1 | 0.6256 (2) | 0.4451 (3) | 0.62989 (9) | 0.0293 (5) | |
C2 | 0.5171 (3) | 0.3573 (4) | 0.65153 (10) | 0.0398 (6) | |
H2 | 0.4475 | 0.3155 | 0.6298 | 0.048* | |
C3 | 0.5125 (3) | 0.3318 (4) | 0.70585 (11) | 0.0475 (7) | |
H3 | 0.4404 | 0.2714 | 0.7210 | 0.057* | |
C4 | 0.6158 (3) | 0.3967 (4) | 0.73744 (11) | 0.0468 (8) | |
C5 | 0.7237 (3) | 0.4844 (4) | 0.71567 (11) | 0.0516 (8) | |
H5 | 0.7930 | 0.5271 | 0.7374 | 0.062* | |
C6 | 0.7288 (3) | 0.5091 (4) | 0.66095 (10) | 0.0430 (7) | |
H6 | 0.8014 | 0.5684 | 0.6456 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0317 (4) | 0.0256 (4) | 0.0295 (4) | −0.0008 (2) | −0.0001 (2) | 0.0046 (2) |
Cl1 | 0.1035 (8) | 0.1110 (9) | 0.0294 (4) | 0.0185 (6) | 0.0018 (4) | 0.0117 (4) |
O1 | 0.0992 (19) | 0.0690 (16) | 0.0525 (12) | 0.0503 (15) | 0.0374 (13) | 0.0272 (12) |
O2 | 0.0885 (17) | 0.0660 (16) | 0.0564 (13) | −0.0453 (13) | −0.0389 (13) | 0.0316 (12) |
O3 | 0.0313 (9) | 0.0311 (9) | 0.0301 (9) | −0.0035 (7) | −0.0023 (7) | 0.0037 (7) |
O4 | 0.0350 (10) | 0.0291 (10) | 0.0519 (11) | 0.0000 (7) | −0.0002 (8) | 0.0095 (8) |
N1 | 0.0320 (11) | 0.0298 (11) | 0.0318 (11) | 0.0023 (8) | −0.0008 (8) | 0.0026 (9) |
C1 | 0.0309 (12) | 0.0277 (13) | 0.0294 (12) | 0.0051 (9) | 0.0000 (9) | 0.0026 (10) |
C2 | 0.0332 (13) | 0.0479 (16) | 0.0384 (14) | −0.0019 (12) | −0.0016 (11) | 0.0044 (12) |
C3 | 0.0422 (15) | 0.0597 (19) | 0.0406 (15) | 0.0015 (13) | 0.0097 (12) | 0.0097 (13) |
C4 | 0.0578 (18) | 0.0544 (19) | 0.0283 (13) | 0.0134 (14) | 0.0001 (12) | 0.0040 (12) |
C5 | 0.0597 (18) | 0.0521 (18) | 0.0431 (15) | −0.0044 (15) | −0.0180 (14) | −0.0026 (14) |
C6 | 0.0430 (15) | 0.0456 (16) | 0.0404 (14) | −0.0092 (13) | −0.0055 (11) | 0.0056 (12) |
P1—O4 | 1.4957 (19) | C1—C6 | 1.369 (4) |
P1—O3 | 1.5168 (17) | C1—C2 | 1.375 (3) |
P1—O1 | 1.541 (2) | C2—C3 | 1.381 (4) |
P1—O2 | 1.557 (2) | C2—H2 | 0.9300 |
Cl1—C4 | 1.739 (3) | C3—C4 | 1.379 (4) |
O1—H1D | 0.8200 | C3—H3 | 0.9300 |
O2—H2D | 0.8200 | C4—C5 | 1.372 (4) |
N1—C1 | 1.467 (3) | C5—C6 | 1.390 (4) |
N1—H1A | 0.8900 | C5—H5 | 0.9300 |
N1—H1B | 0.8900 | C6—H6 | 0.9300 |
N1—H1C | 0.8900 | ||
O4—P1—O3 | 113.62 (11) | C2—C1—N1 | 118.5 (2) |
O4—P1—O1 | 107.15 (12) | C1—C2—C3 | 119.3 (3) |
O3—P1—O1 | 111.03 (11) | C1—C2—H2 | 120.4 |
O4—P1—O2 | 105.25 (12) | C3—C2—H2 | 120.4 |
O3—P1—O2 | 110.52 (11) | C4—C3—C2 | 119.5 (3) |
O1—P1—O2 | 109.00 (17) | C4—C3—H3 | 120.2 |
P1—O1—H1D | 109.5 | C2—C3—H3 | 120.2 |
P1—O2—H2D | 109.5 | C5—C4—C3 | 121.0 (3) |
C1—N1—H1A | 109.5 | C5—C4—Cl1 | 119.2 (2) |
C1—N1—H1B | 109.5 | C3—C4—Cl1 | 119.8 (2) |
H1A—N1—H1B | 109.5 | C4—C5—C6 | 119.5 (3) |
C1—N1—H1C | 109.5 | C4—C5—H5 | 120.2 |
H1A—N1—H1C | 109.5 | C6—C5—H5 | 120.2 |
H1B—N1—H1C | 109.5 | C1—C6—C5 | 119.1 (3) |
C6—C1—C2 | 121.6 (2) | C1—C6—H6 | 120.4 |
C6—C1—N1 | 119.9 (2) | C5—C6—H6 | 120.4 |
C6—C1—C2—C3 | −0.6 (4) | C3—C4—C5—C6 | 0.3 (5) |
N1—C1—C2—C3 | 179.3 (2) | Cl1—C4—C5—C6 | 179.0 (2) |
C1—C2—C3—C4 | 0.9 (4) | C2—C1—C6—C5 | 0.1 (4) |
C2—C3—C4—C5 | −0.7 (5) | N1—C1—C6—C5 | −179.8 (2) |
C2—C3—C4—Cl1 | −179.4 (2) | C4—C5—C6—C1 | 0.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.89 | 1.80 | 2.689 (3) | 176 |
N1—H1B···O3 | 0.89 | 1.97 | 2.862 (3) | 175 |
N1—H1C···O3ii | 0.89 | 2.09 | 2.951 (3) | 162 |
O1—H1D···O4iii | 0.82 | 1.79 | 2.540 (3) | 152 |
O2—H2D···O3iv | 0.82 | 1.82 | 2.585 (3) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, z; (iii) −x+3/2, y−1/2, z; (iv) −x+1, −y, −z+1. |
Experimental details
(2CADHP) | (4CADHP) | |
Crystal data | ||
Chemical formula | C6H7ClN+·H2PO4− | C6H7ClN+·H2PO4− |
Mr | 225.56 | 225.56 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca |
Temperature (K) | 292 | 292 |
a, b, c (Å) | 11.3143 (6), 4.7466 (2), 17.5024 (9) | 9.7371 (19), 7.8756 (16), 25.141 (5) |
α, β, γ (°) | 90, 108.540 (3), 90 | 90, 90, 90 |
V (Å3) | 891.17 (8) | 1927.9 (7) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.59 | 0.55 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 | 0.25 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | Bruker Kappa APEX2 CCD area-detector diffractometer | Bruker Kappa APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker 1999) | Multi-scan (SADABS; Bruker 1999) |
Tmin, Tmax | 0.867, 0.917 | 0.876, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9738, 2044, 1902 | 8591, 1687, 1483 |
Rint | 0.018 | 0.037 |
(sin θ/λ)max (Å−1) | 0.650 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.084, 1.05 | 0.040, 0.127, 1.07 |
No. of reflections | 2044 | 1687 |
No. of parameters | 122 | 123 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.47 | 0.50, −0.31 |
Computer programs: , APEX2 (Bruker, 2004) and SAINT (Bruker, 2004), SAINT (Bruker, 2004) and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4 | 0.89 | 1.95 | 2.8348 (19) | 169.9 |
N1—H1B···O1i | 0.89 | 2.17 | 3.0509 (18) | 168.5 |
N1—H1C···O4ii | 0.89 | 1.87 | 2.7515 (18) | 172.2 |
O1—H1D···O3iii | 0.82 | 1.78 | 2.6017 (17) | 174.4 |
O2—H2D···O3ii | 0.82 | 1.77 | 2.5411 (17) | 157.0 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.89 | 1.80 | 2.689 (3) | 176.1 |
N1—H1B···O3 | 0.89 | 1.97 | 2.862 (3) | 174.9 |
N1—H1C···O3ii | 0.89 | 2.09 | 2.951 (3) | 162.3 |
O1—H1D···O4iii | 0.82 | 1.79 | 2.540 (3) | 152.0 |
O2—H2D···O3iv | 0.82 | 1.82 | 2.585 (3) | 154.6 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, z; (iii) −x+3/2, y−1/2, z; (iv) −x+1, −y, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The construction of organic–inorganic hybrid compounds has been of considerable interest and importance in recent years, not only because they are a powerful means of generating interesting supramolecular frameworks but also due to their potential for providing new materials with magnetic, semiconducting, optical and electrolytic properties (Doyle et al., 2002; Zaccaro & Ibanez, 2000; Chisholm & Haile, 2000). The supramolecular frameworks of these organic–inorganic compounds are generated by hydrogen-bond interactions between donor (D) and acceptor (A) moieties. Orthophosphoric acid (H3PO4), an inorganic oxy-acid, forms dihydrogen phosphate salts with organic amines, resulting in organic–inorganic hybrid systems with potentially powerful hydrogen-bonded D/A moieties. The dihydrogen phosphate anions (H2PO4-) form substructures in these compounds, generating anionic networks via O—H···O hydrogen bonds which act as a template for the assembly of cations (Shylaja et al., 2008). A considerable number of dihydrogen phosphate salts are recorded in the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002). In the crystal structure of N-benzyl ammonium dihydrogen phosphate monohydrate (Elaoud et al., 1998), the H2PO4- anions form a one-dimensional chain network, while in 3-amino-2-chloropyridinium dihydrogen phosphate (Hamed et al., 2007) they form chains of fused R22(8) ring motifs [for graph-set analysis, see Bernstein et al. (1995)]. Two-dimensional nets of anionic substructures were also observed in dimethylammonium dihydrogen phosphate (Pietraszko et al., 1999) and 2-methylpiperazinediium dihydrogen phosphate (Choudhury et al., 2000). Interestingly, in the structure of imidazolinium dihydrogen phosphate (Blessing, 1986), the H2PO4- anions form a three-dimensional cage-type framework inside which the imidazolinium cations are trapped. We have prepared the dihydrogen phosphate salts 2-chloroanilinium dihydrogen phosphate (2CADHP) and 4-chloroanilinium dihydrogen phosphate (4CADHP), and have determined their structures and studied the supramolecular networks in these salts.
The salt 2CADHP crystallizes in the space group P21/n, whereas 4CADHP crystallizes in Pbca. The asymmetric units of both 2CADHP and 4CADHP contain a dihydrogen phosphate anion, and a singly protonated 2- or 4-chloroanilinium cation, respectively. In the tetrahedral dihydrogen phosphate group of both 2CADHP and 4CADHP, the protonated P—O bond distances are P1—O1 = 1.570 (1) Å and P1—O2 = 1.553 (1) Å for 2CADHP, and P1—O1 = 1.541 (2) Å and P1—O2 = 1.557 (2) Å for 4CADHP. These values are as expected and are longer than the other two P—O bonds, P1—O3 = 1.504 (1) Å and P1—O4 = 1.503 (1) Å for 2CADHP, and P1—O3 = 1.517 (2) Å and P1—O4 = 1.496 (2) Å for 4CADHP. The identical P1—O3 and P1—O4 bond distances observed in 2CADHP indicate delocalization of negative charge between them (Demir et al., 2006). The geometries of the 2- and 4-chloroanilinium cations show characteristic values compared with other reported structures (Muthamizhchelvan et al., 2005; Glidewell et al., 2005). The C—N distances of the 2- and 4-chloroanilinium cations, C1—N1 = 1.455 (2) and 1.467 (3) Å, respectively, are longer than the normal value and this lengthening is due to the transfer of an H atom to the N atom from the orthophosphoric acid.
The hydrogen-bonded organic–inorganic supramolecular frameworks of 2CADHP and 4CADHP are determined primarily by a combination of O—H···O and N—H···O hydrogen bonds (Tables 1 and 2).
In 2CADHP, the inversion-related H2PO4- anions are linked through an O1—H1D···O3iii hydrogen bond [symmetry code: (iii) -x + 1, -y + 1, -z + 1], forming an O—H···O dimer with a ring motif of R22(8) with its centroid occupying the inversion centre. These dimers are interlinked through an O2—H2D···O3ii hydrogen bond [symmetry code: (ii) x, y + 1, z] to form a ring motif of type R42(12). The alternately fused R22(8) and R42(12) supramolecular motifs in turn generate a double-stranded inorganic H2PO4- chain made of P—OH···O═P hydrogen bonds extending infinitely along the [010] direction (Fig. 3). The 2-chloroanilinium cations are linked to the anionic substructure through three N—H···O hydrogen bonds and a Cl···O short contact [Cl···O = 3.170 (1) Å]. The N1—H1A···O4 and N1—H1C···O4ii hydrogen bonds [symmetry code: (ii) x, y + 1, z], with O2—H2D···O3ii, form a chain of edge-fused R33(10) ring motifs extending along the [010] direction, as observed in the structure of 3-acetylanilinium dihydrogen phosphate (Cinčić & Kaitner, 2008). The Cl···O1 interaction, which acts as a pseudo hydrogen bond (Bryant et al., 1998; Kubicki & Wagner, 2007), with the Cl atom at (x, y, z) as donor and atom O1 at (-x + 1/2, y + 1/2, -z + 1/2) as acceptor, along with the N—H···O hydrogen bonds, forms a chain of fused R42(10) motifs extending along the [010] direction. The 21 screw-related chains of R33(10) and R42(10) motifs along (1/4, y, 1/4) (Fig. 4) link the anionic substructure, resulting in the formation of an organic–inorganic sheet framework parallel to (101) (Fig. 5).
In 4CADHP, the H2PO4- anions form dimers through an O2—H2D···O3iv hydrogen bond [symmetry code: (iv) -x + 1,-y, -z + 1], with the characteristic ring motif of R22(8), in which the centroid of the dimer occupies the crystallographic inversion centre. The O1—H1D···O4iii hydrogen bond [symmetry code: (iii) -x + 3/2, y - 1/2, z] generates a C4 chain which connects the glide-related anionic dimers with the glide plane perpendicular to the [100] direction, the glide component of which is [0, 1/2, 0]. This forms an infinite two-dimensional layer in the form of a net extending parallel to the (001) plane. This inorganic supramolecular net of H2PO4- anions is built from R22(8) and R66(24)-type ring motifs (Fig. 6). The 4-chloroanilinium cations are anchored to the H2PO4- anionic net through N1—H1A···O4i [symmetry code: -x + 1, -y + 1, -z + 1], N1—H1B···O3 and N1—H1C···O3ii [symmetry code: -x + 3/2, y + 1/2, z] hydrogen bonds, forming fused ring motifs of R53(14) and R53(12) types with O—H···O hydrogen bonds (Fig. 7). The 4-chloroanilinium cations are pendant on both faces of the anionic net, thus resulting in the formation of two-dimensional sheet of an organic–inorganic supramolecular framework (Fig. 8) extending infinitely parallel to the crystallographic (001) plane.
It is of interest to note that in both the title compounds, although they form different types of anionic substructures, the overall anionic–cationic supramolecular framework results in the formation of infinite two-dimensional sheets. In 2CADHP the formation of an anionic double-stranded substructure and the linking of the cations to it is analogous with other reported structures. In the crystal structures of 2,4-dimethylanilinium dihydrogen phosphate (Fábry et al., 2001), 2-(methoxy carbonyl)anilinium dihydrogen phosphate (Shafiq et al., 2009) and 3,5-dimethoxyanilinium dihydrogen phosphate (Kaabi et al., 2004) (Z' = 2Z), the respective cations bound to the anionic substructures form two-dimensional sheets. In the last compound the substructure was formed with different ring motifs than the other two structures. A three-dimensional hydrogen-bonded framework was observed for 1,3-propanediammonium bis(dihydrogen phosphate) (Marsh, 2004), in which the cation contains an additional three N—H bonds involved in hydrogen bonding. The crystal structure of 4CADHP is isomorphous with 4-bromoanilinium dihydrogen phosphate (CSD refcode UGISEI; Zhang et al., 2001) but no H atoms are reported in CSD. In 4CADHP, the hydrogen-bonded anionic substructure formation and the linking of cation pendants from the supramolecular net are analogous with the structures of 4-methylanilinium dihydrogen phosphate (Smirani et al., 2004) and 4-ethylanilinium dihydrogen phosphate (Kaabi et al., 2003), but has markedly different cell dimensions from 4-bromoanilinium dihydrogen phosphate, even though they belong to the same Pbca space group.