Semicarbazones can exist in two tautomeric forms. In the solid state, they are found in the keto form. This work presents the synthesis, structures and spectroscopic characterization (IR and NMR spectroscopy) of four such compounds, namely the neutral molecule 4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide, C19H16N4O, (I), abbreviated as HBzPyS, and three different hydrated salts, namely the chloride dihydrate, C19H17N4O+·Cl−·2H2O, (II), the nitrate dihydrate, C19H17N4O+·NO3−·2H2O, (III), and the thiocyanate 2.5-hydrate, C19H17N4O+·SCN−·2.5H2O, (IV), of 2-[phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium, abbreviated as [H2BzPyS]+·X−·nH2O, with X = Cl− and n = 2 for (II), X = NO3− and n = 2 for (III), and X = SCN− and n = 2.5 for (IV), showing the influence of the anionic form in the intermolecular interactions. Water molecules and counter-ions (chloride or nitrate) are involved in the formation of a two-dimensional arrangement by the establishment of hydrogen bonds with the N—H groups of the cation, stabilizing the E isomers in the solid state. The neutral HBzPyS molecule crystallized as the E isomer due to the existence of weak π–π interactions between pairs of molecules. The calculated IR spectrum of the hydrated [H2BzPyS]+ cation is in good agreement with the experimental results.
Supporting information
CCDC references: 1879906; 1879905; 1879904; 1879903
For all structures, data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).
4-Phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide (I)
top
Crystal data top
C19H16N4O | F(000) = 664 |
Mr = 316.36 | Dx = 1.365 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9971 reflections |
a = 5.6126 (3) Å | θ = 2.5–30.5° |
b = 10.0683 (4) Å | µ = 0.09 mm−1 |
c = 27.2349 (12) Å | T = 100 K |
β = 90.095 (2)° | Block, colourless |
V = 1539.02 (12) Å3 | 0.31 × 0.13 × 0.07 mm |
Z = 4 | |
Data collection top
Bruker D8 Venture Photon 100 diffractometer | 3813 reflections with I > 2σ(I) |
Radiation source: microfocus X ray tube | Rint = 0.039 |
φ and ω scans | θmax = 30.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −8→8 |
Tmin = 0.715, Tmax = 0.746 | k = −14→14 |
37458 measured reflections | l = −38→38 |
4693 independent reflections | |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0685P)2 + 0.7078P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
4693 reflections | Δρmax = 0.43 e Å−3 |
217 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.05213 (17) | 0.05900 (9) | 0.62708 (3) | 0.0231 (2) | |
N1 | 0.09296 (18) | 0.44896 (10) | 0.55743 (4) | 0.0173 (2) | |
N2 | 0.58312 (18) | 0.28384 (10) | 0.61287 (3) | 0.0152 (2) | |
N3 | 0.73938 (19) | 0.18385 (10) | 0.60314 (4) | 0.0182 (2) | |
H3A | 0.7275 | 0.14 | 0.5753 | 0.022* | |
N4 | 0.91577 (18) | 0.22644 (10) | 0.67747 (4) | 0.0173 (2) | |
H4A | 0.7922 | 0.2792 | 0.6812 | 0.021* | |
C1 | −0.0760 (2) | 0.53746 (13) | 0.56891 (4) | 0.0199 (2) | |
H1 | −0.1889 | 0.5609 | 0.5444 | 0.024* | |
C2 | −0.0950 (2) | 0.59682 (12) | 0.61466 (4) | 0.0196 (2) | |
H2 | −0.2206 | 0.6573 | 0.6216 | 0.023* | |
C3 | 0.0740 (2) | 0.56568 (12) | 0.65015 (4) | 0.0200 (2) | |
H3 | 0.0673 | 0.6056 | 0.6817 | 0.024* | |
C4 | 0.2517 (2) | 0.47617 (12) | 0.63895 (4) | 0.0181 (2) | |
H4 | 0.3705 | 0.4545 | 0.6625 | 0.022* | |
C5 | 0.2540 (2) | 0.41762 (11) | 0.59223 (4) | 0.0135 (2) | |
C6 | 0.4318 (2) | 0.31515 (11) | 0.57900 (4) | 0.0136 (2) | |
C7 | 0.4285 (2) | 0.25270 (11) | 0.52920 (4) | 0.0135 (2) | |
C8 | 0.2388 (2) | 0.17334 (12) | 0.51455 (4) | 0.0185 (2) | |
H8 | 0.1083 | 0.1594 | 0.5361 | 0.022* | |
C9 | 0.2392 (2) | 0.11422 (12) | 0.46839 (5) | 0.0204 (2) | |
H9 | 0.1087 | 0.0605 | 0.4585 | 0.024* | |
C10 | 0.4293 (2) | 0.13349 (12) | 0.43688 (4) | 0.0191 (2) | |
H10 | 0.4298 | 0.0923 | 0.4055 | 0.023* | |
C11 | 0.6184 (2) | 0.21273 (14) | 0.45113 (4) | 0.0215 (3) | |
H11 | 0.7484 | 0.2264 | 0.4294 | 0.026* | |
C12 | 0.6188 (2) | 0.27252 (13) | 0.49728 (4) | 0.0189 (2) | |
H12 | 0.749 | 0.3269 | 0.507 | 0.023* | |
C13 | 0.9165 (2) | 0.15002 (11) | 0.63625 (4) | 0.0158 (2) | |
C14 | 1.0893 (2) | 0.23100 (12) | 0.71477 (4) | 0.0154 (2) | |
C15 | 1.2864 (2) | 0.14683 (13) | 0.71683 (4) | 0.0183 (2) | |
H15 | 1.3078 | 0.0797 | 0.6927 | 0.022* | |
C16 | 1.4520 (2) | 0.16245 (13) | 0.75474 (4) | 0.0213 (3) | |
H16 | 1.5862 | 0.1051 | 0.7563 | 0.026* | |
C17 | 1.4241 (2) | 0.26024 (14) | 0.79021 (4) | 0.0227 (3) | |
H17 | 1.5396 | 0.271 | 0.8154 | 0.027* | |
C18 | 1.2252 (2) | 0.34212 (13) | 0.78834 (4) | 0.0218 (3) | |
H18 | 1.2029 | 0.4082 | 0.8128 | 0.026* | |
C19 | 1.0589 (2) | 0.32794 (12) | 0.75103 (4) | 0.0188 (2) | |
H19 | 0.9234 | 0.3844 | 0.7501 | 0.023* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0272 (5) | 0.0230 (4) | 0.0191 (4) | 0.0077 (4) | −0.0042 (3) | −0.0028 (3) |
N1 | 0.0197 (5) | 0.0177 (5) | 0.0144 (4) | −0.0005 (4) | −0.0046 (4) | −0.0013 (4) |
N2 | 0.0171 (5) | 0.0149 (4) | 0.0137 (4) | −0.0004 (4) | −0.0020 (3) | 0.0009 (3) |
N3 | 0.0223 (5) | 0.0183 (5) | 0.0138 (4) | 0.0031 (4) | −0.0044 (4) | −0.0035 (4) |
N4 | 0.0169 (5) | 0.0201 (5) | 0.0149 (4) | 0.0040 (4) | −0.0028 (4) | −0.0023 (4) |
C1 | 0.0205 (6) | 0.0214 (6) | 0.0180 (5) | 0.0009 (5) | −0.0049 (4) | −0.0012 (4) |
C2 | 0.0211 (6) | 0.0176 (5) | 0.0199 (5) | 0.0009 (4) | 0.0003 (4) | −0.0016 (4) |
C3 | 0.0257 (6) | 0.0208 (6) | 0.0135 (5) | −0.0007 (5) | −0.0006 (4) | −0.0028 (4) |
C4 | 0.0214 (6) | 0.0209 (5) | 0.0120 (5) | −0.0014 (5) | −0.0036 (4) | −0.0003 (4) |
C5 | 0.0155 (5) | 0.0133 (5) | 0.0118 (4) | −0.0034 (4) | −0.0018 (4) | 0.0012 (4) |
C6 | 0.0157 (5) | 0.0133 (5) | 0.0120 (4) | −0.0038 (4) | −0.0010 (4) | 0.0009 (4) |
C7 | 0.0158 (5) | 0.0129 (5) | 0.0118 (4) | −0.0003 (4) | −0.0021 (4) | 0.0003 (4) |
C8 | 0.0172 (5) | 0.0197 (5) | 0.0186 (5) | −0.0055 (4) | 0.0019 (4) | −0.0029 (4) |
C9 | 0.0207 (6) | 0.0191 (5) | 0.0213 (5) | −0.0056 (5) | −0.0016 (4) | −0.0048 (4) |
C10 | 0.0254 (6) | 0.0178 (5) | 0.0142 (5) | −0.0014 (5) | −0.0015 (4) | −0.0023 (4) |
C11 | 0.0211 (6) | 0.0284 (6) | 0.0150 (5) | −0.0046 (5) | 0.0026 (4) | −0.0013 (5) |
C12 | 0.0163 (5) | 0.0243 (6) | 0.0160 (5) | −0.0061 (5) | −0.0011 (4) | −0.0010 (4) |
C13 | 0.0197 (5) | 0.0155 (5) | 0.0124 (5) | −0.0016 (4) | −0.0003 (4) | 0.0016 (4) |
C14 | 0.0161 (5) | 0.0176 (5) | 0.0124 (5) | −0.0008 (4) | −0.0013 (4) | 0.0027 (4) |
C15 | 0.0175 (5) | 0.0221 (6) | 0.0154 (5) | 0.0023 (4) | −0.0001 (4) | 0.0014 (4) |
C16 | 0.0169 (5) | 0.0286 (6) | 0.0182 (5) | 0.0035 (5) | −0.0014 (4) | 0.0033 (5) |
C17 | 0.0220 (6) | 0.0304 (7) | 0.0157 (5) | −0.0030 (5) | −0.0036 (4) | 0.0012 (5) |
C18 | 0.0272 (6) | 0.0224 (6) | 0.0159 (5) | −0.0020 (5) | −0.0018 (4) | −0.0019 (4) |
C19 | 0.0211 (6) | 0.0189 (5) | 0.0164 (5) | 0.0017 (4) | −0.0016 (4) | 0.0005 (4) |
Geometric parameters (Å, º) top
O1—C13 | 1.2173 (15) | C7—C12 | 1.3926 (16) |
N1—C1 | 1.3385 (16) | C8—C9 | 1.3911 (16) |
N1—C5 | 1.3462 (14) | C8—H8 | 0.95 |
N2—C6 | 1.2919 (14) | C9—C10 | 1.3839 (18) |
N2—N3 | 1.3615 (14) | C9—H9 | 0.95 |
N3—C13 | 1.3839 (15) | C10—C11 | 1.3829 (18) |
N3—H3A | 0.88 | C10—H10 | 0.95 |
N4—C13 | 1.3610 (15) | C11—C12 | 1.3936 (16) |
N4—C14 | 1.4066 (14) | C11—H11 | 0.95 |
N4—H4A | 0.88 | C12—H12 | 0.95 |
C1—C2 | 1.3864 (17) | C14—C15 | 1.3949 (16) |
C1—H1 | 0.95 | C14—C19 | 1.3990 (16) |
C2—C3 | 1.3891 (17) | C15—C16 | 1.3968 (16) |
C2—H2 | 0.95 | C15—H15 | 0.95 |
C3—C4 | 1.3785 (18) | C16—C17 | 1.3883 (18) |
C3—H3 | 0.95 | C16—H16 | 0.95 |
C4—C5 | 1.4024 (15) | C17—C18 | 1.3888 (19) |
C4—H4 | 0.95 | C17—H17 | 0.95 |
C5—C6 | 1.4804 (16) | C18—C19 | 1.3858 (16) |
C6—C7 | 1.4949 (15) | C18—H18 | 0.95 |
C7—C8 | 1.3894 (16) | C19—H19 | 0.95 |
| | | |
C1—N1—C5 | 117.81 (10) | C10—C9—H9 | 119.9 |
C6—N2—N3 | 117.67 (9) | C8—C9—H9 | 119.9 |
N2—N3—C13 | 121.17 (9) | C11—C10—C9 | 119.92 (11) |
N2—N3—H3A | 119.4 | C11—C10—H10 | 120 |
C13—N3—H3A | 119.4 | C9—C10—H10 | 120 |
C13—N4—C14 | 127.66 (10) | C10—C11—C12 | 120.16 (11) |
C13—N4—H4A | 116.2 | C10—C11—H11 | 119.9 |
C14—N4—H4A | 116.2 | C12—C11—H11 | 119.9 |
N1—C1—C2 | 123.55 (11) | C7—C12—C11 | 120.07 (11) |
N1—C1—H1 | 118.2 | C7—C12—H12 | 120 |
C2—C1—H1 | 118.2 | C11—C12—H12 | 120 |
C1—C2—C3 | 118.32 (11) | O1—C13—N4 | 126.70 (11) |
C1—C2—H2 | 120.8 | O1—C13—N3 | 120.02 (10) |
C3—C2—H2 | 120.8 | N4—C13—N3 | 113.28 (10) |
C4—C3—C2 | 119.15 (11) | C15—C14—C19 | 119.53 (11) |
C4—C3—H3 | 120.4 | C15—C14—N4 | 123.87 (10) |
C2—C3—H3 | 120.4 | C19—C14—N4 | 116.59 (10) |
C3—C4—C5 | 118.90 (10) | C14—C15—C16 | 119.22 (11) |
C3—C4—H4 | 120.5 | C14—C15—H15 | 120.4 |
C5—C4—H4 | 120.5 | C16—C15—H15 | 120.4 |
N1—C5—C4 | 122.21 (11) | C17—C16—C15 | 121.23 (12) |
N1—C5—C6 | 116.36 (10) | C17—C16—H16 | 119.4 |
C4—C5—C6 | 121.41 (10) | C15—C16—H16 | 119.4 |
N2—C6—C5 | 116.03 (10) | C16—C17—C18 | 119.14 (11) |
N2—C6—C7 | 123.52 (10) | C16—C17—H17 | 120.4 |
C5—C6—C7 | 120.45 (9) | C18—C17—H17 | 120.4 |
C8—C7—C12 | 119.43 (10) | C19—C18—C17 | 120.40 (12) |
C8—C7—C6 | 120.71 (10) | C19—C18—H18 | 119.8 |
C12—C7—C6 | 119.86 (10) | C17—C18—H18 | 119.8 |
C7—C8—C9 | 120.21 (11) | C18—C19—C14 | 120.45 (11) |
C7—C8—H8 | 119.9 | C18—C19—H19 | 119.8 |
C9—C8—H8 | 119.9 | C14—C19—H19 | 119.8 |
C10—C9—C8 | 120.20 (11) | | |
| | | |
C6—N2—N3—C13 | 175.88 (11) | C7—C8—C9—C10 | 0.36 (19) |
C5—N1—C1—C2 | −0.80 (19) | C8—C9—C10—C11 | −0.59 (19) |
N1—C1—C2—C3 | 1.8 (2) | C9—C10—C11—C12 | 0.42 (19) |
C1—C2—C3—C4 | −0.86 (19) | C8—C7—C12—C11 | −0.19 (18) |
C2—C3—C4—C5 | −0.99 (18) | C6—C7—C12—C11 | 178.94 (11) |
C1—N1—C5—C4 | −1.21 (17) | C10—C11—C12—C7 | −0.03 (19) |
C1—N1—C5—C6 | 177.43 (10) | C14—N4—C13—O1 | 10.2 (2) |
C3—C4—C5—N1 | 2.11 (18) | C14—N4—C13—N3 | −170.32 (11) |
C3—C4—C5—C6 | −176.45 (11) | N2—N3—C13—O1 | 178.95 (11) |
N3—N2—C6—C5 | 175.80 (10) | N2—N3—C13—N4 | −0.52 (16) |
N3—N2—C6—C7 | −3.42 (16) | C13—N4—C14—C15 | −5.38 (19) |
N1—C5—C6—N2 | −178.80 (10) | C13—N4—C14—C19 | 173.74 (11) |
C4—C5—C6—N2 | −0.15 (16) | C19—C14—C15—C16 | −0.99 (18) |
N1—C5—C6—C7 | 0.45 (15) | N4—C14—C15—C16 | 178.09 (11) |
C4—C5—C6—C7 | 179.09 (10) | C14—C15—C16—C17 | −0.18 (19) |
N2—C6—C7—C8 | 113.46 (13) | C15—C16—C17—C18 | 1.3 (2) |
C5—C6—C7—C8 | −65.72 (15) | C16—C17—C18—C19 | −1.2 (2) |
N2—C6—C7—C12 | −65.65 (15) | C17—C18—C19—C14 | 0.00 (19) |
C5—C6—C7—C12 | 115.16 (12) | C15—C14—C19—C18 | 1.09 (18) |
C12—C7—C8—C9 | 0.03 (18) | N4—C14—C19—C18 | −178.07 (11) |
C6—C7—C8—C9 | −179.09 (11) | | |
2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium chloride
dihydrate (II)
top
Crystal data top
C19H17N4O+·Cl−·2H2O | F(000) = 816 |
Mr = 388.85 | Dx = 1.367 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9932 reflections |
a = 9.4452 (19) Å | θ = 2.9–30.5° |
b = 9.5489 (19) Å | µ = 0.23 mm−1 |
c = 21.039 (4) Å | T = 100 K |
β = 95.26 (3)° | Block, yellow |
V = 1889.5 (7) Å3 | 0.28 × 0.23 × 0.13 mm |
Z = 4 | |
Data collection top
Bruker D8 Venture Photon 100 diffractometer | 4889 reflections with I > 2σ(I) |
Radiation source: microfocus X ray tube | Rint = 0.119 |
φ and ω scans | θmax = 30.6°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −13→13 |
Tmin = 0.724, Tmax = 0.745 | k = −13→13 |
66072 measured reflections | l = −30→30 |
5794 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: mixed |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.9098P] where P = (Fo2 + 2Fc2)/3 |
5794 reflections | (Δ/σ)max = 0.001 |
256 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
0 constraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.06783 (3) | 0.09797 (4) | 0.22145 (2) | 0.02280 (9) | |
O1 | −0.17520 (9) | 0.40910 (9) | 0.50096 (4) | 0.01606 (18) | |
N1 | 0.10125 (10) | 0.07050 (10) | 0.43270 (4) | 0.01254 (18) | |
H1A | 0.0284 | 0.1283 | 0.4307 | 0.015* | |
N2 | 0.05449 (10) | 0.24698 (10) | 0.52436 (4) | 0.01189 (18) | |
N3 | 0.01723 (10) | 0.33890 (10) | 0.56830 (4) | 0.01274 (19) | |
H3A | 0.0691 | 0.3502 | 0.6049 | 0.015* | |
N4 | −0.13882 (10) | 0.49480 (11) | 0.60335 (5) | 0.01421 (19) | |
H4A | −0.081 | 0.4876 | 0.6384 | 0.017* | |
C1 | 0.11352 (13) | −0.01729 (13) | 0.38390 (5) | 0.0155 (2) | |
H1 | 0.0446 | −0.0152 | 0.3481 | 0.019* | |
C2 | 0.22502 (13) | −0.11075 (13) | 0.38504 (6) | 0.0164 (2) | |
H2 | 0.2337 | −0.1734 | 0.3505 | 0.02* | |
C3 | 0.32428 (13) | −0.11085 (13) | 0.43795 (6) | 0.0169 (2) | |
H3 | 0.4021 | −0.1742 | 0.44 | 0.02* | |
C4 | 0.30990 (12) | −0.01824 (13) | 0.48798 (5) | 0.0153 (2) | |
H4 | 0.378 | −0.0184 | 0.5241 | 0.018* | |
C5 | 0.19622 (12) | 0.07440 (12) | 0.48516 (5) | 0.0116 (2) | |
C6 | 0.17085 (12) | 0.17684 (12) | 0.53552 (5) | 0.0116 (2) | |
C7 | 0.27603 (12) | 0.19470 (12) | 0.59235 (5) | 0.0125 (2) | |
C8 | 0.30414 (13) | 0.08615 (13) | 0.63600 (6) | 0.0165 (2) | |
H8 | 0.2542 | 0 | 0.6305 | 0.02* | |
C9 | 0.40567 (14) | 0.10438 (14) | 0.68769 (6) | 0.0204 (3) | |
H9 | 0.4248 | 0.0305 | 0.7175 | 0.024* | |
C10 | 0.47906 (13) | 0.22994 (15) | 0.69591 (6) | 0.0201 (3) | |
H10 | 0.5501 | 0.2408 | 0.7305 | 0.024* | |
C11 | 0.44861 (13) | 0.33944 (14) | 0.65360 (6) | 0.0191 (2) | |
H11 | 0.4973 | 0.4261 | 0.6598 | 0.023* | |
C12 | 0.34667 (12) | 0.32249 (13) | 0.60189 (5) | 0.0153 (2) | |
H12 | 0.3253 | 0.3979 | 0.5732 | 0.018* | |
C13 | −0.10673 (12) | 0.41545 (12) | 0.55349 (5) | 0.0118 (2) | |
C14 | −0.25407 (12) | 0.58765 (12) | 0.60569 (5) | 0.0115 (2) | |
C15 | −0.24406 (12) | 0.68459 (12) | 0.65562 (5) | 0.0139 (2) | |
H15 | −0.161 | 0.6875 | 0.6847 | 0.017* | |
C16 | −0.35501 (13) | 0.77650 (12) | 0.66282 (5) | 0.0154 (2) | |
H16 | −0.3471 | 0.8433 | 0.6964 | 0.018* | |
C17 | −0.47787 (13) | 0.77128 (13) | 0.62103 (6) | 0.0169 (2) | |
H17 | −0.5545 | 0.8333 | 0.6264 | 0.02* | |
C18 | −0.48763 (13) | 0.67484 (13) | 0.57150 (6) | 0.0168 (2) | |
H18 | −0.5714 | 0.6714 | 0.5429 | 0.02* | |
C19 | −0.37619 (12) | 0.58294 (12) | 0.56314 (5) | 0.0140 (2) | |
H19 | −0.3834 | 0.5178 | 0.5289 | 0.017* | |
O2 | −0.13582 (10) | 0.21563 (10) | 0.40474 (4) | 0.01835 (18) | |
H1W | −0.144 (2) | 0.278 (2) | 0.4289 (9) | 0.028* | |
H2W | −0.154 (2) | 0.2521 (19) | 0.3676 (10) | 0.028* | |
O3 | −0.17336 (12) | 0.28318 (13) | 0.27789 (5) | 0.0287 (2) | |
H3W | −0.152 (2) | 0.377 (2) | 0.2752 (10) | 0.043* | |
H4W | −0.110 (2) | 0.232 (2) | 0.2630 (11) | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.02539 (17) | 0.02989 (17) | 0.01209 (14) | −0.00797 (12) | −0.00386 (11) | −0.00191 (11) |
O1 | 0.0156 (4) | 0.0207 (4) | 0.0110 (4) | 0.0054 (3) | −0.0033 (3) | −0.0029 (3) |
N1 | 0.0126 (4) | 0.0153 (4) | 0.0097 (4) | 0.0016 (3) | 0.0009 (3) | 0.0000 (3) |
N2 | 0.0118 (4) | 0.0132 (4) | 0.0107 (4) | 0.0017 (3) | 0.0013 (3) | −0.0013 (3) |
N3 | 0.0120 (4) | 0.0165 (5) | 0.0093 (4) | 0.0041 (3) | −0.0016 (3) | −0.0029 (3) |
N4 | 0.0124 (4) | 0.0190 (5) | 0.0104 (4) | 0.0058 (4) | −0.0033 (3) | −0.0034 (3) |
C1 | 0.0179 (5) | 0.0188 (5) | 0.0098 (5) | −0.0007 (4) | 0.0007 (4) | −0.0010 (4) |
C2 | 0.0186 (6) | 0.0188 (6) | 0.0123 (5) | 0.0001 (4) | 0.0036 (4) | −0.0028 (4) |
C3 | 0.0158 (5) | 0.0192 (6) | 0.0161 (5) | 0.0041 (4) | 0.0032 (4) | −0.0026 (4) |
C4 | 0.0133 (5) | 0.0201 (6) | 0.0125 (5) | 0.0030 (4) | 0.0005 (4) | −0.0027 (4) |
C5 | 0.0115 (5) | 0.0143 (5) | 0.0092 (4) | −0.0004 (4) | 0.0015 (4) | −0.0003 (4) |
C6 | 0.0112 (5) | 0.0137 (5) | 0.0097 (4) | 0.0013 (4) | 0.0008 (4) | −0.0003 (4) |
C7 | 0.0093 (5) | 0.0175 (5) | 0.0106 (5) | 0.0034 (4) | 0.0005 (4) | −0.0027 (4) |
C8 | 0.0183 (5) | 0.0169 (5) | 0.0139 (5) | 0.0052 (4) | −0.0005 (4) | −0.0020 (4) |
C9 | 0.0235 (6) | 0.0235 (6) | 0.0133 (5) | 0.0101 (5) | −0.0029 (4) | −0.0015 (4) |
C10 | 0.0149 (5) | 0.0319 (7) | 0.0127 (5) | 0.0060 (5) | −0.0024 (4) | −0.0074 (5) |
C11 | 0.0144 (5) | 0.0277 (6) | 0.0153 (5) | −0.0027 (5) | 0.0017 (4) | −0.0068 (5) |
C12 | 0.0136 (5) | 0.0202 (6) | 0.0123 (5) | −0.0001 (4) | 0.0015 (4) | −0.0015 (4) |
C13 | 0.0110 (5) | 0.0127 (5) | 0.0118 (5) | 0.0015 (4) | 0.0007 (4) | −0.0002 (4) |
C14 | 0.0112 (5) | 0.0132 (5) | 0.0100 (4) | 0.0022 (4) | 0.0009 (4) | 0.0001 (4) |
C15 | 0.0128 (5) | 0.0177 (5) | 0.0109 (5) | −0.0002 (4) | −0.0003 (4) | −0.0025 (4) |
C16 | 0.0175 (5) | 0.0160 (5) | 0.0130 (5) | 0.0010 (4) | 0.0032 (4) | −0.0042 (4) |
C17 | 0.0162 (5) | 0.0166 (5) | 0.0178 (5) | 0.0057 (4) | 0.0015 (4) | −0.0019 (4) |
C18 | 0.0145 (5) | 0.0190 (6) | 0.0160 (5) | 0.0049 (4) | −0.0035 (4) | −0.0020 (4) |
C19 | 0.0141 (5) | 0.0154 (5) | 0.0119 (5) | 0.0029 (4) | −0.0023 (4) | −0.0026 (4) |
O2 | 0.0207 (4) | 0.0202 (4) | 0.0132 (4) | 0.0053 (3) | −0.0034 (3) | −0.0023 (3) |
O3 | 0.0287 (5) | 0.0355 (6) | 0.0213 (5) | 0.0013 (5) | −0.0020 (4) | 0.0026 (4) |
Geometric parameters (Å, º) top
O1—C13 | 1.2298 (14) | C8—H8 | 0.95 |
N1—C1 | 1.3387 (15) | C9—C10 | 1.388 (2) |
N1—C5 | 1.3575 (15) | C9—H9 | 0.95 |
N1—H1A | 0.88 | C10—C11 | 1.3863 (19) |
N2—C6 | 1.2901 (14) | C10—H10 | 0.95 |
N2—N3 | 1.3448 (13) | C11—C12 | 1.3946 (17) |
N3—C13 | 1.3912 (14) | C11—H11 | 0.95 |
N3—H3A | 0.88 | C12—H12 | 0.95 |
N4—C13 | 1.3507 (14) | C14—C19 | 1.3946 (16) |
N4—C14 | 1.4083 (14) | C14—C15 | 1.3968 (15) |
N4—H4A | 0.88 | C15—C16 | 1.3858 (16) |
C1—C2 | 1.3790 (17) | C15—H15 | 0.95 |
C1—H1 | 0.95 | C16—C17 | 1.3911 (17) |
C2—C3 | 1.3881 (17) | C16—H16 | 0.95 |
C2—H2 | 0.95 | C17—C18 | 1.3874 (17) |
C3—C4 | 1.3910 (16) | C17—H17 | 0.95 |
C3—H3 | 0.95 | C18—C19 | 1.3939 (16) |
C4—C5 | 1.3883 (16) | C18—H18 | 0.95 |
C4—H4 | 0.95 | C19—H19 | 0.95 |
C5—C6 | 1.4777 (15) | O2—H1W | 0.79 (2) |
C6—C7 | 1.4926 (16) | O2—H2W | 0.86 (2) |
C7—C8 | 1.3942 (16) | O3—H3W | 0.92 (2) |
C7—C12 | 1.3963 (17) | O3—H4W | 0.85 (2) |
C8—C9 | 1.3935 (17) | | |
| | | |
C1—N1—C5 | 122.92 (10) | C10—C9—H9 | 119.8 |
C1—N1—H1A | 118.5 | C8—C9—H9 | 119.8 |
C5—N1—H1A | 118.5 | C11—C10—C9 | 119.99 (11) |
C6—N2—N3 | 119.08 (10) | C11—C10—H10 | 120 |
N2—N3—C13 | 117.18 (9) | C9—C10—H10 | 120 |
N2—N3—H3A | 121.4 | C10—C11—C12 | 120.08 (12) |
C13—N3—H3A | 121.4 | C10—C11—H11 | 120 |
C13—N4—C14 | 127.56 (10) | C12—C11—H11 | 120 |
C13—N4—H4A | 116.2 | C11—C12—C7 | 120.02 (11) |
C14—N4—H4A | 116.2 | C11—C12—H12 | 120 |
N1—C1—C2 | 120.77 (11) | C7—C12—H12 | 120 |
N1—C1—H1 | 119.6 | O1—C13—N4 | 126.06 (10) |
C2—C1—H1 | 119.6 | O1—C13—N3 | 122.54 (10) |
C1—C2—C3 | 118.23 (11) | N4—C13—N3 | 111.40 (10) |
C1—C2—H2 | 120.9 | C19—C14—C15 | 119.95 (10) |
C3—C2—H2 | 120.9 | C19—C14—N4 | 123.62 (10) |
C2—C3—C4 | 120.06 (11) | C15—C14—N4 | 116.38 (10) |
C2—C3—H3 | 120 | C16—C15—C14 | 120.14 (11) |
C4—C3—H3 | 120 | C16—C15—H15 | 119.9 |
C5—C4—C3 | 120.10 (11) | C14—C15—H15 | 119.9 |
C5—C4—H4 | 120 | C15—C16—C17 | 120.24 (11) |
C3—C4—H4 | 120 | C15—C16—H16 | 119.9 |
N1—C5—C4 | 117.92 (10) | C17—C16—H16 | 119.9 |
N1—C5—C6 | 117.56 (10) | C18—C17—C16 | 119.52 (11) |
C4—C5—C6 | 124.52 (10) | C18—C17—H17 | 120.2 |
N2—C6—C5 | 113.87 (10) | C16—C17—H17 | 120.2 |
N2—C6—C7 | 125.44 (10) | C17—C18—C19 | 120.91 (11) |
C5—C6—C7 | 120.68 (10) | C17—C18—H18 | 119.5 |
C8—C7—C12 | 119.69 (11) | C19—C18—H18 | 119.5 |
C8—C7—C6 | 121.02 (11) | C18—C19—C14 | 119.24 (10) |
C12—C7—C6 | 119.29 (10) | C18—C19—H19 | 120.4 |
C9—C8—C7 | 119.81 (12) | C14—C19—H19 | 120.4 |
C9—C8—H8 | 120.1 | H1W—O2—H2W | 104.9 (18) |
C7—C8—H8 | 120.1 | H3W—O3—H4W | 111 (2) |
C10—C9—C8 | 120.35 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1W···O1 | 0.79 (2) | 2.01 (2) | 2.7906 (13) | 169.6 (19) |
N3—H3A···Cl1i | 0.88 | 2.5 | 3.2698 (12) | 146 |
O3—H3W···Cl1ii | 0.92 (2) | 2.25 (2) | 3.1665 (14) | 171.1 (19) |
N1—H1A···O2 | 0.88 | 1.8 | 2.6531 (14) | 162 |
N4—H4A···Cl1i | 0.88 | 2.29 | 3.1432 (13) | 163 |
O3—H4W···Cl1 | 0.85 (2) | 2.35 (2) | 3.1973 (14) | 178 (2) |
O2—H2W···O3 | 0.86 (2) | 1.90 (2) | 2.7370 (15) | 163.8 (18) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+1/2. |
2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium nitrate
dihydrate (III)
top
Crystal data top
C19H17N4O+·NO3−·2H2O | F(000) = 872 |
Mr = 415.41 | Dx = 1.401 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8565 reflections |
a = 9.5556 (4) Å | θ = 2.7–27.9° |
b = 9.3050 (4) Å | µ = 0.11 mm−1 |
c = 22.2715 (10) Å | T = 100 K |
β = 96.048 (2)° | Block, colourless |
V = 1969.24 (15) Å3 | 0.21 × 0.10 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker D8 Venture Photon 100 diffractometer | 3810 reflections with I > 2σ(I) |
Radiation source: microfocus X ray tube | Rint = 0.068 |
φ and ω scans | θmax = 30.6°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −10→13 |
Tmin = 0.683, Tmax = 0.746 | k = −11→13 |
42340 measured reflections | l = −31→31 |
6023 independent reflections | |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.9729P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
6023 reflections | Δρmax = 0.37 e Å−3 |
293 parameters | Δρmin = −0.54 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.32424 (12) | 0.59204 (13) | 0.50656 (5) | 0.0272 (3) | |
N1 | 0.61087 (14) | 0.92847 (15) | 0.44107 (6) | 0.0235 (3) | |
H1A | 0.538 | 0.8701 | 0.438 | 0.028* | |
N2 | 0.55957 (14) | 0.74698 (14) | 0.52725 (6) | 0.0222 (3) | |
N3 | 0.52299 (14) | 0.65225 (15) | 0.56847 (6) | 0.0231 (3) | |
H3A | 0.5761 | 0.6381 | 0.6027 | 0.028* | |
N4 | 0.36940 (14) | 0.49149 (15) | 0.60069 (6) | 0.0257 (3) | |
H4A | 0.434 | 0.4888 | 0.6319 | 0.031* | |
C1 | 0.62604 (18) | 1.01918 (19) | 0.39554 (8) | 0.0276 (4) | |
H1 | 0.5586 | 1.0192 | 0.361 | 0.033* | |
C2 | 0.73808 (19) | 1.11222 (19) | 0.39826 (8) | 0.0287 (4) | |
H2 | 0.7494 | 1.1762 | 0.3659 | 0.034* | |
C3 | 0.83374 (18) | 1.11048 (19) | 0.44915 (8) | 0.0298 (4) | |
H3 | 0.9118 | 1.1742 | 0.4522 | 0.036* | |
C4 | 0.81631 (17) | 1.01591 (19) | 0.49601 (8) | 0.0278 (4) | |
H4 | 0.8822 | 1.0152 | 0.5311 | 0.033* | |
C5 | 0.70294 (16) | 0.92278 (17) | 0.49155 (7) | 0.0220 (3) | |
C6 | 0.67558 (16) | 0.81803 (17) | 0.53874 (7) | 0.0222 (3) | |
C7 | 0.77787 (16) | 0.80131 (18) | 0.59359 (7) | 0.0232 (3) | |
C8 | 0.79217 (19) | 0.90835 (19) | 0.63769 (8) | 0.0283 (4) | |
H8 | 0.7356 | 0.9924 | 0.6332 | 0.034* | |
C9 | 0.8892 (2) | 0.8918 (2) | 0.68806 (8) | 0.0341 (4) | |
H9 | 0.898 | 0.9643 | 0.7183 | 0.041* | |
C10 | 0.97306 (19) | 0.7707 (2) | 0.69468 (8) | 0.0323 (4) | |
H10 | 1.0416 | 0.7615 | 0.7286 | 0.039* | |
C11 | 0.95692 (18) | 0.6625 (2) | 0.65172 (8) | 0.0313 (4) | |
H11 | 1.013 | 0.5782 | 0.6567 | 0.038* | |
C12 | 0.85883 (18) | 0.6771 (2) | 0.60138 (8) | 0.0281 (4) | |
H12 | 0.8471 | 0.6023 | 0.5723 | 0.034* | |
C13 | 0.39750 (17) | 0.57767 (17) | 0.55469 (7) | 0.0228 (3) | |
C14 | 0.24971 (17) | 0.40541 (17) | 0.60497 (7) | 0.0240 (3) | |
C15 | 0.25362 (19) | 0.31422 (19) | 0.65482 (8) | 0.0304 (4) | |
H15 | 0.3352 | 0.311 | 0.6831 | 0.036* | |
C16 | 0.1394 (2) | 0.2286 (2) | 0.66323 (9) | 0.0344 (4) | |
H16 | 0.1436 | 0.1656 | 0.6969 | 0.041* | |
C17 | 0.0190 (2) | 0.2338 (2) | 0.62299 (9) | 0.0353 (4) | |
H17 | −0.0598 | 0.1755 | 0.6292 | 0.042* | |
C18 | 0.0146 (2) | 0.32443 (19) | 0.57376 (8) | 0.0337 (4) | |
H18 | −0.068 | 0.3281 | 0.5461 | 0.04* | |
C19 | 0.12930 (18) | 0.41061 (18) | 0.56400 (8) | 0.0277 (4) | |
H19 | 0.1254 | 0.4721 | 0.5298 | 0.033* | |
N5 | 0.35984 (18) | 0.7937 (2) | 0.26526 (7) | 0.0420 (4) | |
O3 | 0.27741 (16) | 0.73306 (18) | 0.29534 (6) | 0.0475 (4) | |
O4 | 0.4492 (2) | 0.8758 (3) | 0.28338 (8) | 0.0799 (7) | |
O5A | 0.3005 (3) | 0.8518 (4) | 0.21244 (13) | 0.0435 (11) | 0.448 (4) |
O5B | 0.4115 (4) | 0.7187 (4) | 0.22044 (14) | 0.0774 (15) | 0.552 (4) |
O2 | 0.36998 (14) | 0.78603 (15) | 0.41599 (6) | 0.0318 (3) | |
H1W | 0.359 (2) | 0.721 (3) | 0.4424 (11) | 0.048* | |
H2W | 0.342 (2) | 0.755 (3) | 0.3815 (12) | 0.048* | |
O6 | 0.60636 (15) | 0.95394 (19) | 0.18834 (6) | 0.0431 (4) | |
H3W | 0.563 (3) | 0.907 (3) | 0.2169 (12) | 0.065* | |
H4W | 0.656 (3) | 1.044 (3) | 0.2014 (12) | 0.065* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0320 (6) | 0.0274 (6) | 0.0225 (6) | −0.0074 (5) | 0.0041 (5) | 0.0012 (5) |
N1 | 0.0258 (7) | 0.0223 (7) | 0.0234 (7) | −0.0013 (6) | 0.0079 (5) | −0.0009 (5) |
N2 | 0.0244 (7) | 0.0218 (7) | 0.0217 (6) | 0.0005 (6) | 0.0084 (5) | 0.0006 (5) |
N3 | 0.0235 (7) | 0.0262 (7) | 0.0201 (6) | −0.0013 (6) | 0.0047 (5) | 0.0039 (5) |
N4 | 0.0228 (7) | 0.0290 (7) | 0.0259 (7) | −0.0008 (6) | 0.0055 (5) | 0.0053 (6) |
C1 | 0.0330 (9) | 0.0281 (9) | 0.0230 (8) | 0.0029 (7) | 0.0091 (7) | 0.0030 (7) |
C2 | 0.0355 (9) | 0.0257 (8) | 0.0278 (8) | 0.0033 (7) | 0.0162 (7) | 0.0043 (7) |
C3 | 0.0290 (9) | 0.0285 (9) | 0.0341 (9) | −0.0042 (7) | 0.0136 (7) | 0.0009 (7) |
C4 | 0.0247 (8) | 0.0320 (9) | 0.0276 (8) | −0.0027 (7) | 0.0075 (7) | 0.0005 (7) |
C5 | 0.0235 (8) | 0.0231 (8) | 0.0209 (7) | 0.0018 (6) | 0.0086 (6) | −0.0016 (6) |
C6 | 0.0223 (8) | 0.0241 (8) | 0.0214 (7) | 0.0024 (6) | 0.0079 (6) | −0.0007 (6) |
C7 | 0.0211 (7) | 0.0272 (8) | 0.0227 (8) | −0.0025 (7) | 0.0084 (6) | 0.0020 (6) |
C8 | 0.0330 (9) | 0.0245 (8) | 0.0279 (8) | −0.0027 (7) | 0.0055 (7) | 0.0019 (7) |
C9 | 0.0424 (11) | 0.0338 (10) | 0.0261 (9) | −0.0081 (8) | 0.0026 (8) | −0.0011 (7) |
C10 | 0.0272 (9) | 0.0462 (11) | 0.0239 (8) | −0.0064 (8) | 0.0044 (7) | 0.0073 (8) |
C11 | 0.0272 (8) | 0.0415 (10) | 0.0265 (9) | 0.0067 (8) | 0.0087 (7) | 0.0058 (8) |
C12 | 0.0277 (8) | 0.0340 (9) | 0.0238 (8) | 0.0035 (7) | 0.0082 (7) | −0.0011 (7) |
C13 | 0.0261 (8) | 0.0200 (8) | 0.0237 (8) | 0.0010 (6) | 0.0084 (6) | −0.0015 (6) |
C14 | 0.0283 (8) | 0.0191 (7) | 0.0267 (8) | 0.0006 (6) | 0.0134 (7) | −0.0015 (6) |
C15 | 0.0315 (9) | 0.0308 (9) | 0.0308 (9) | 0.0049 (8) | 0.0126 (7) | 0.0065 (7) |
C16 | 0.0429 (11) | 0.0273 (9) | 0.0367 (10) | 0.0009 (8) | 0.0208 (8) | 0.0051 (8) |
C17 | 0.0423 (11) | 0.0262 (9) | 0.0399 (10) | −0.0122 (8) | 0.0166 (9) | −0.0042 (8) |
C18 | 0.0398 (10) | 0.0280 (9) | 0.0336 (10) | −0.0127 (8) | 0.0056 (8) | −0.0054 (7) |
C19 | 0.0360 (9) | 0.0221 (8) | 0.0259 (8) | −0.0072 (7) | 0.0073 (7) | −0.0038 (7) |
N5 | 0.0413 (9) | 0.0690 (12) | 0.0153 (7) | −0.0250 (9) | 0.0002 (6) | −0.0117 (7) |
O3 | 0.0451 (8) | 0.0632 (10) | 0.0341 (7) | −0.0108 (7) | 0.0034 (6) | 0.0024 (7) |
O4 | 0.0730 (12) | 0.1290 (18) | 0.0398 (9) | −0.0472 (13) | 0.0160 (8) | −0.0220 (11) |
O5A | 0.0423 (19) | 0.060 (2) | 0.0261 (16) | −0.0135 (16) | −0.0057 (13) | 0.0111 (14) |
O5B | 0.109 (3) | 0.082 (3) | 0.0463 (19) | −0.036 (2) | 0.0351 (19) | −0.0313 (17) |
O2 | 0.0369 (7) | 0.0350 (7) | 0.0232 (6) | −0.0070 (6) | 0.0023 (5) | 0.0055 (5) |
O6 | 0.0371 (8) | 0.0598 (10) | 0.0333 (8) | −0.0059 (7) | 0.0082 (6) | −0.0129 (7) |
Geometric parameters (Å, º) top
O1—C13 | 1.224 (2) | C9—H9 | 0.95 |
N1—C1 | 1.339 (2) | C10—C11 | 1.386 (3) |
N1—C5 | 1.354 (2) | C10—H10 | 0.95 |
N1—H1A | 0.88 | C11—C12 | 1.390 (2) |
N2—C6 | 1.293 (2) | C11—H11 | 0.95 |
N2—N3 | 1.3451 (18) | C12—H12 | 0.95 |
N3—C13 | 1.391 (2) | C14—C19 | 1.392 (2) |
N3—H3A | 0.88 | C14—C15 | 1.395 (2) |
N4—C13 | 1.350 (2) | C15—C16 | 1.380 (3) |
N4—C14 | 1.408 (2) | C15—H15 | 0.95 |
N4—H4A | 0.88 | C16—C17 | 1.383 (3) |
C1—C2 | 1.373 (2) | C16—H16 | 0.95 |
C1—H1 | 0.95 | C17—C18 | 1.381 (3) |
C2—C3 | 1.379 (3) | C17—H17 | 0.95 |
C2—H2 | 0.95 | C18—C19 | 1.393 (2) |
C3—C4 | 1.389 (2) | C18—H18 | 0.95 |
C3—H3 | 0.95 | C19—H19 | 0.95 |
C4—C5 | 1.383 (2) | N5—O4 | 1.185 (2) |
C4—H4 | 0.95 | N5—O3 | 1.224 (2) |
C5—C6 | 1.477 (2) | N5—O5B | 1.353 (3) |
C6—C7 | 1.490 (2) | N5—O5A | 1.363 (3) |
C7—C12 | 1.391 (2) | O2—H1W | 0.86 (3) |
C7—C8 | 1.395 (2) | O2—H2W | 0.84 (3) |
C8—C9 | 1.386 (2) | O6—H3W | 0.91 (3) |
C8—H8 | 0.95 | O6—H4W | 0.99 (3) |
C9—C10 | 1.382 (3) | | |
| | | |
C1—N1—C5 | 122.74 (15) | C9—C10—C11 | 119.83 (17) |
C1—N1—H1A | 118.6 | C9—C10—H10 | 120.1 |
C5—N1—H1A | 118.6 | C11—C10—H10 | 120.1 |
C6—N2—N3 | 118.62 (14) | C10—C11—C12 | 120.15 (17) |
N2—N3—C13 | 117.15 (13) | C10—C11—H11 | 119.9 |
N2—N3—H3A | 121.4 | C12—C11—H11 | 119.9 |
C13—N3—H3A | 121.4 | C11—C12—C7 | 120.04 (17) |
C13—N4—C14 | 128.13 (14) | C11—C12—H12 | 120 |
C13—N4—H4A | 115.9 | C7—C12—H12 | 120 |
C14—N4—H4A | 115.9 | O1—C13—N4 | 126.03 (15) |
N1—C1—C2 | 120.68 (16) | O1—C13—N3 | 122.58 (14) |
N1—C1—H1 | 119.7 | N4—C13—N3 | 111.39 (14) |
C2—C1—H1 | 119.7 | C19—C14—C15 | 119.60 (16) |
C1—C2—C3 | 118.35 (16) | C19—C14—N4 | 123.86 (15) |
C1—C2—H2 | 120.8 | C15—C14—N4 | 116.51 (15) |
C3—C2—H2 | 120.8 | C16—C15—C14 | 120.28 (17) |
C2—C3—C4 | 120.23 (16) | C16—C15—H15 | 119.9 |
C2—C3—H3 | 119.9 | C14—C15—H15 | 119.9 |
C4—C3—H3 | 119.9 | C15—C16—C17 | 120.53 (17) |
C5—C4—C3 | 119.88 (16) | C15—C16—H16 | 119.7 |
C5—C4—H4 | 120.1 | C17—C16—H16 | 119.7 |
C3—C4—H4 | 120.1 | C18—C17—C16 | 119.32 (17) |
N1—C5—C4 | 118.10 (15) | C18—C17—H17 | 120.3 |
N1—C5—C6 | 117.94 (14) | C16—C17—H17 | 120.3 |
C4—C5—C6 | 123.96 (15) | C17—C18—C19 | 121.13 (18) |
N2—C6—C5 | 114.14 (14) | C17—C18—H18 | 119.4 |
N2—C6—C7 | 125.70 (14) | C19—C18—H18 | 119.4 |
C5—C6—C7 | 120.16 (14) | C14—C19—C18 | 119.15 (16) |
C12—C7—C8 | 119.55 (16) | C14—C19—H19 | 120.4 |
C12—C7—C6 | 119.81 (15) | C18—C19—H19 | 120.4 |
C8—C7—C6 | 120.64 (15) | O4—N5—O3 | 126.39 (16) |
C9—C8—C7 | 119.86 (17) | O4—N5—O5B | 106.1 (2) |
C9—C8—H8 | 120.1 | O3—N5—O5B | 118.2 (2) |
C7—C8—H8 | 120.1 | O4—N5—O5A | 104.9 (2) |
C10—C9—C8 | 120.50 (17) | O3—N5—O5A | 114.96 (19) |
C10—C9—H9 | 119.7 | H1W—O2—H2W | 109 (2) |
C8—C9—H9 | 119.7 | H3W—O6—H4W | 116 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.88 | 1.81 | 2.6639 (19) | 164 |
N3—H3A···O6i | 0.88 | 2.08 | 2.8794 (19) | 150 |
N4—H4A···O6i | 0.88 | 2.03 | 2.875 (2) | 159 |
O2—H1W···O1 | 0.86 (3) | 1.92 (3) | 2.7756 (17) | 174 (2) |
O2—H2W···O3 | 0.84 (3) | 1.96 (3) | 2.783 (2) | 165 (2) |
O6—H3W···O4 | 0.91 (3) | 1.95 (3) | 2.816 (2) | 159 (2) |
O6—H3W···O5A | 0.91 (3) | 2.55 (3) | 3.172 (3) | 126 (2) |
O6—H3W···O5B | 0.91 (3) | 2.28 (3) | 3.008 (4) | 137 (2) |
O6—H4W···O3ii | 0.99 (3) | 1.87 (3) | 2.833 (2) | 163 (2) |
O6—H4W···O5Bii | 0.99 (3) | 2.51 (3) | 3.210 (4) | 127.0 (19) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium thiocyanate
2.5-hydrate (IV)
top
Crystal data top
C19H17N4O+·NCS−·2.5H2O | F(000) = 884 |
Mr = 420.48 | Dx = 1.387 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9596 reflections |
a = 13.0053 (4) Å | θ = 2.8–30.4° |
b = 7.7965 (2) Å | µ = 0.20 mm−1 |
c = 20.8703 (7) Å | T = 100 K |
β = 107.887 (1)° | Block, colourless |
V = 2013.87 (11) Å3 | 0.24 × 0.10 × 0.05 mm |
Z = 4 | |
Data collection top
Bruker D8 Venture Photon 100 diffractometer | 4590 reflections with I > 2σ(I) |
Radiation source: microfocus X ray tube | Rint = 0.040 |
φ and ω scans | θmax = 30.6°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −18→18 |
Tmin = 0.707, Tmax = 0.746 | k = −9→11 |
31447 measured reflections | l = −29→29 |
6146 independent reflections | |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0561P)2 + 1.2977P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
6146 reflections | Δρmax = 0.4 e Å−3 |
326 parameters | Δρmin = −0.41 e Å−3 |
6 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.47184 (8) | 0.41475 (14) | 0.59764 (5) | 0.0210 (2) | |
N1 | 0.61991 (9) | 0.14483 (15) | 0.45619 (6) | 0.0149 (2) | |
H1A | 0.6215 | 0.203 | 0.4926 | 0.018* | |
N2 | 0.44095 (9) | 0.23927 (15) | 0.48298 (6) | 0.0152 (2) | |
N3 | 0.35678 (9) | 0.30584 (16) | 0.49958 (6) | 0.0177 (2) | |
H3A | 0.29 | 0.2947 | 0.4729 | 0.021* | |
N4 | 0.28807 (9) | 0.44702 (15) | 0.57257 (6) | 0.0174 (2) | |
H4A | 0.2267 | 0.42 | 0.5421 | 0.021* | |
C1 | 0.71372 (11) | 0.09103 (18) | 0.44878 (7) | 0.0180 (3) | |
H1 | 0.7798 | 0.1174 | 0.4824 | 0.022* | |
C2 | 0.71496 (11) | −0.00216 (19) | 0.39290 (7) | 0.0197 (3) | |
H2 | 0.7811 | −0.0414 | 0.3877 | 0.024* | |
C3 | 0.61693 (12) | −0.03710 (19) | 0.34444 (8) | 0.0209 (3) | |
H3 | 0.6155 | −0.1005 | 0.3053 | 0.025* | |
C4 | 0.52099 (11) | 0.02051 (18) | 0.35314 (7) | 0.0182 (3) | |
H4 | 0.454 | −0.0039 | 0.32 | 0.022* | |
C5 | 0.52304 (10) | 0.11323 (17) | 0.40989 (7) | 0.0141 (3) | |
C6 | 0.42486 (10) | 0.17971 (17) | 0.42306 (7) | 0.0143 (2) | |
C7 | 0.32143 (10) | 0.17993 (17) | 0.36716 (7) | 0.0149 (3) | |
C8 | 0.31493 (11) | 0.27020 (19) | 0.30834 (7) | 0.0197 (3) | |
H8 | 0.376 | 0.3318 | 0.3048 | 0.024* | |
C9 | 0.21989 (12) | 0.2705 (2) | 0.25502 (8) | 0.0219 (3) | |
H9 | 0.2161 | 0.3321 | 0.2151 | 0.026* | |
C10 | 0.13050 (12) | 0.18130 (19) | 0.25987 (8) | 0.0209 (3) | |
H10 | 0.0656 | 0.1813 | 0.2232 | 0.025* | |
C11 | 0.13570 (11) | 0.09185 (19) | 0.31826 (8) | 0.0209 (3) | |
H11 | 0.0741 | 0.0316 | 0.3216 | 0.025* | |
C12 | 0.23077 (11) | 0.09030 (18) | 0.37174 (7) | 0.0179 (3) | |
H12 | 0.2343 | 0.0282 | 0.4115 | 0.022* | |
C13 | 0.37967 (11) | 0.39275 (17) | 0.56052 (7) | 0.0162 (3) | |
C14 | 0.28004 (11) | 0.54163 (17) | 0.62831 (7) | 0.0163 (3) | |
C15 | 0.17552 (12) | 0.5914 (2) | 0.62653 (8) | 0.0218 (3) | |
H15 | 0.1152 | 0.5589 | 0.5896 | 0.026* | |
C16 | 0.16016 (13) | 0.6876 (2) | 0.67847 (8) | 0.0252 (3) | |
H16 | 0.0892 | 0.7209 | 0.677 | 0.03* | |
C17 | 0.24754 (13) | 0.7358 (2) | 0.73280 (8) | 0.0243 (3) | |
H17 | 0.2369 | 0.8039 | 0.768 | 0.029* | |
C18 | 0.35041 (13) | 0.68370 (19) | 0.73511 (8) | 0.0231 (3) | |
H18 | 0.4103 | 0.7143 | 0.7727 | 0.028* | |
C19 | 0.36737 (11) | 0.58715 (18) | 0.68315 (7) | 0.0188 (3) | |
H19 | 0.4384 | 0.5526 | 0.6852 | 0.023* | |
S1A | 0.89347 (17) | 0.4590 (5) | 0.6458 (2) | 0.0352 (6) | 0.571 (10) |
C20A | 0.9293 (4) | 0.3324 (9) | 0.5930 (3) | 0.0380 (13) | 0.571 (10) |
N5A | 0.9541 (3) | 0.2489 (9) | 0.5538 (3) | 0.0572 (18) | 0.571 (10) |
O3A | 0.1094 (3) | 0.2788 (8) | 0.4800 (2) | 0.0432 (12) | 0.571 (10) |
H3WA | 0.068 (3) | 0.319 (6) | 0.4430 (14) | 0.065* | 0.571 (10) |
H4WA | 0.077 (3) | 0.204 (5) | 0.496 (2) | 0.065* | 0.571 (10) |
S1B | 0.9023 (2) | 0.4113 (5) | 0.6645 (2) | 0.0313 (5) | 0.429 (10) |
C20B | 0.9362 (5) | 0.2778 (9) | 0.6152 (4) | 0.0328 (13) | 0.429 (10) |
N5B | 0.9595 (5) | 0.1776 (7) | 0.5811 (3) | 0.0436 (13) | 0.429 (10) |
O3B | 0.1309 (4) | 0.3389 (7) | 0.4610 (3) | 0.0346 (11) | 0.429 (10) |
H3WB | 0.110 (4) | 0.407 (5) | 0.4269 (17) | 0.052* | 0.429 (10) |
H4WB | 0.098 (5) | 0.243 (4) | 0.453 (3) | 0.052* | 0.429 (10) |
O2 | 0.65756 (10) | 0.29775 (19) | 0.57474 (6) | 0.0339 (3) | |
H1W | 0.604 (2) | 0.340 (3) | 0.5815 (12) | 0.051* | |
H2W | 0.714 (2) | 0.346 (3) | 0.5973 (13) | 0.051* | |
O4 | −0.0067 (3) | 0.0865 (5) | 0.46176 (17) | 0.0568 (8) | 0.5 |
H5W | −0.0156 | 0.0898 | 0.5085 | 0.085* | 0.5 |
H6W | 0.0065 | −0.036 | 0.4523 | 0.085* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0158 (5) | 0.0269 (5) | 0.0219 (5) | 0.0016 (4) | 0.0084 (4) | −0.0045 (4) |
N1 | 0.0160 (5) | 0.0168 (5) | 0.0135 (5) | 0.0018 (4) | 0.0068 (4) | 0.0022 (4) |
N2 | 0.0157 (5) | 0.0156 (5) | 0.0172 (6) | 0.0024 (4) | 0.0092 (4) | 0.0026 (4) |
N3 | 0.0139 (5) | 0.0215 (6) | 0.0195 (6) | 0.0027 (4) | 0.0080 (4) | −0.0014 (5) |
N4 | 0.0146 (5) | 0.0208 (6) | 0.0185 (6) | 0.0025 (4) | 0.0078 (4) | −0.0007 (5) |
C1 | 0.0149 (6) | 0.0207 (7) | 0.0195 (7) | 0.0034 (5) | 0.0071 (5) | 0.0073 (5) |
C2 | 0.0191 (6) | 0.0208 (7) | 0.0229 (7) | 0.0054 (5) | 0.0122 (6) | 0.0063 (6) |
C3 | 0.0252 (7) | 0.0202 (7) | 0.0219 (7) | 0.0026 (5) | 0.0139 (6) | −0.0008 (6) |
C4 | 0.0185 (6) | 0.0187 (6) | 0.0189 (7) | 0.0002 (5) | 0.0080 (5) | −0.0005 (5) |
C5 | 0.0150 (6) | 0.0131 (6) | 0.0158 (6) | 0.0012 (5) | 0.0069 (5) | 0.0036 (5) |
C6 | 0.0138 (6) | 0.0140 (6) | 0.0167 (6) | 0.0006 (5) | 0.0068 (5) | 0.0031 (5) |
C7 | 0.0145 (6) | 0.0148 (6) | 0.0163 (6) | 0.0014 (5) | 0.0063 (5) | −0.0002 (5) |
C8 | 0.0163 (6) | 0.0220 (7) | 0.0219 (7) | 0.0007 (5) | 0.0073 (5) | 0.0053 (6) |
C9 | 0.0220 (7) | 0.0238 (7) | 0.0192 (7) | 0.0037 (6) | 0.0052 (6) | 0.0065 (6) |
C10 | 0.0186 (6) | 0.0199 (7) | 0.0211 (7) | 0.0024 (5) | 0.0017 (5) | −0.0004 (5) |
C11 | 0.0178 (6) | 0.0194 (7) | 0.0260 (8) | −0.0030 (5) | 0.0076 (6) | −0.0019 (6) |
C12 | 0.0193 (6) | 0.0177 (6) | 0.0183 (7) | −0.0006 (5) | 0.0080 (5) | 0.0012 (5) |
C13 | 0.0185 (6) | 0.0153 (6) | 0.0179 (7) | 0.0018 (5) | 0.0102 (5) | 0.0020 (5) |
C14 | 0.0201 (6) | 0.0144 (6) | 0.0184 (7) | 0.0022 (5) | 0.0119 (5) | 0.0032 (5) |
C15 | 0.0185 (6) | 0.0259 (7) | 0.0243 (8) | 0.0026 (6) | 0.0114 (6) | 0.0020 (6) |
C16 | 0.0242 (7) | 0.0273 (8) | 0.0314 (8) | 0.0043 (6) | 0.0195 (6) | 0.0019 (6) |
C17 | 0.0327 (8) | 0.0204 (7) | 0.0279 (8) | −0.0004 (6) | 0.0214 (7) | −0.0014 (6) |
C18 | 0.0274 (7) | 0.0204 (7) | 0.0249 (8) | −0.0022 (6) | 0.0132 (6) | −0.0019 (6) |
C19 | 0.0202 (6) | 0.0166 (6) | 0.0228 (7) | 0.0014 (5) | 0.0111 (6) | 0.0015 (5) |
S1A | 0.0246 (5) | 0.0454 (12) | 0.0383 (11) | −0.0050 (6) | 0.0136 (6) | −0.0152 (8) |
C20A | 0.0224 (16) | 0.054 (3) | 0.039 (3) | −0.0089 (19) | 0.0109 (18) | −0.016 (2) |
N5A | 0.0403 (19) | 0.076 (4) | 0.058 (3) | −0.007 (2) | 0.0193 (19) | −0.033 (3) |
O3A | 0.0255 (14) | 0.064 (3) | 0.033 (2) | 0.0072 (15) | −0.0012 (12) | −0.0149 (17) |
S1B | 0.0217 (6) | 0.0371 (11) | 0.0338 (11) | −0.0032 (6) | 0.0068 (7) | −0.0009 (8) |
C20B | 0.036 (3) | 0.032 (3) | 0.031 (3) | −0.009 (2) | 0.012 (2) | 0.006 (2) |
N5B | 0.063 (3) | 0.036 (3) | 0.038 (3) | −0.004 (2) | 0.025 (2) | 0.009 (2) |
O3B | 0.0267 (19) | 0.044 (3) | 0.031 (2) | 0.0023 (16) | 0.0051 (15) | −0.0012 (17) |
O2 | 0.0160 (5) | 0.0557 (8) | 0.0280 (6) | 0.0060 (5) | 0.0041 (5) | −0.0176 (6) |
O4 | 0.066 (2) | 0.055 (2) | 0.055 (2) | −0.0040 (17) | 0.0280 (17) | −0.0048 (16) |
Geometric parameters (Å, º) top
O1—C13 | 1.2232 (17) | C10—H10 | 0.95 |
N1—C1 | 1.3431 (17) | C11—C12 | 1.388 (2) |
N1—C5 | 1.3542 (17) | C11—H11 | 0.95 |
N1—H1A | 0.88 | C12—H12 | 0.95 |
N2—C6 | 1.2895 (18) | C14—C19 | 1.388 (2) |
N2—N3 | 1.3492 (15) | C14—C15 | 1.4030 (19) |
N3—C13 | 1.3902 (18) | C15—C16 | 1.382 (2) |
N3—H3A | 0.88 | C15—H15 | 0.95 |
N4—C13 | 1.3585 (17) | C16—C17 | 1.388 (2) |
N4—C14 | 1.4081 (18) | C16—H16 | 0.95 |
N4—H4A | 0.88 | C17—C18 | 1.385 (2) |
C1—C2 | 1.378 (2) | C17—H17 | 0.95 |
C1—H1 | 0.95 | C18—C19 | 1.392 (2) |
C2—C3 | 1.389 (2) | C18—H18 | 0.95 |
C2—H2 | 0.95 | C19—H19 | 0.95 |
C3—C4 | 1.3894 (19) | S1A—C20A | 1.650 (5) |
C3—H3 | 0.95 | C20A—N5A | 1.166 (6) |
C4—C5 | 1.3809 (19) | O3A—H3WA | 0.855 (10) |
C4—H4 | 0.95 | O3A—H4WA | 0.850 (10) |
C5—C6 | 1.4798 (18) | S1B—C20B | 1.616 (8) |
C6—C7 | 1.4855 (18) | C20B—N5B | 1.159 (8) |
C7—C8 | 1.3950 (19) | O3B—H3WB | 0.863 (10) |
C7—C12 | 1.3988 (19) | O3B—H4WB | 0.856 (10) |
C8—C9 | 1.386 (2) | O2—H1W | 0.82 (3) |
C8—H8 | 0.95 | O2—H2W | 0.83 (3) |
C9—C10 | 1.385 (2) | O4—H5W | 1.016 |
C9—H9 | 0.95 | O4—H6W | 1.0012 |
C10—C11 | 1.388 (2) | | |
| | | |
C1—N1—C5 | 122.68 (12) | C9—C10—C11 | 120.07 (13) |
C1—N1—H1A | 118.7 | C9—C10—H10 | 120 |
C5—N1—H1A | 118.7 | C11—C10—H10 | 120 |
C6—N2—N3 | 119.00 (12) | C10—C11—C12 | 120.10 (13) |
N2—N3—C13 | 117.37 (11) | C10—C11—H11 | 119.9 |
N2—N3—H3A | 121.3 | C12—C11—H11 | 119.9 |
C13—N3—H3A | 121.3 | C11—C12—C7 | 120.14 (13) |
C13—N4—C14 | 127.43 (12) | C11—C12—H12 | 119.9 |
C13—N4—H4A | 116.3 | C7—C12—H12 | 119.9 |
C14—N4—H4A | 116.3 | O1—C13—N4 | 125.70 (13) |
N1—C1—C2 | 120.60 (13) | O1—C13—N3 | 122.73 (12) |
N1—C1—H1 | 119.7 | N4—C13—N3 | 111.57 (12) |
C2—C1—H1 | 119.7 | C19—C14—C15 | 119.45 (13) |
C1—C2—C3 | 118.20 (13) | C19—C14—N4 | 124.44 (12) |
C1—C2—H2 | 120.9 | C15—C14—N4 | 116.10 (13) |
C3—C2—H2 | 120.9 | C16—C15—C14 | 120.10 (14) |
C2—C3—C4 | 120.11 (13) | C16—C15—H15 | 119.9 |
C2—C3—H3 | 119.9 | C14—C15—H15 | 119.9 |
C4—C3—H3 | 119.9 | C15—C16—C17 | 120.55 (14) |
C5—C4—C3 | 119.98 (13) | C15—C16—H16 | 119.7 |
C5—C4—H4 | 120 | C17—C16—H16 | 119.7 |
C3—C4—H4 | 120 | C18—C17—C16 | 119.26 (14) |
N1—C5—C4 | 118.41 (12) | C18—C17—H17 | 120.4 |
N1—C5—C6 | 118.07 (12) | C16—C17—H17 | 120.4 |
C4—C5—C6 | 123.52 (12) | C17—C18—C19 | 120.93 (15) |
N2—C6—C5 | 114.46 (12) | C17—C18—H18 | 119.5 |
N2—C6—C7 | 126.82 (12) | C19—C18—H18 | 119.5 |
C5—C6—C7 | 118.65 (12) | C14—C19—C18 | 119.68 (13) |
C8—C7—C12 | 119.19 (13) | C14—C19—H19 | 120.2 |
C8—C7—C6 | 119.16 (12) | C18—C19—H19 | 120.2 |
C12—C7—C6 | 121.65 (12) | N5A—C20A—S1A | 177.1 (5) |
C9—C8—C7 | 120.36 (13) | H3WA—O3A—H4WA | 111 (3) |
C9—C8—H8 | 119.8 | N5B—C20B—S1B | 177.7 (5) |
C7—C8—H8 | 119.8 | H3WB—O3B—H4WB | 111 (3) |
C10—C9—C8 | 120.14 (14) | H1W—O2—H2W | 112 (2) |
C10—C9—H9 | 119.9 | H5W—O4—H6W | 106.9 |
C8—C9—H9 | 119.9 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.88 | 1.79 | 2.6531 (17) | 166 |
N3—H3A···O3A | 0.88 | 2.4 | 3.123 (5) | 139 |
N3—H3A···O3B | 0.88 | 2.04 | 2.809 (5) | 146 |
N4—H4A···O3A | 0.88 | 2 | 2.845 (4) | 160 |
N4—H4A···O3B | 0.88 | 1.88 | 2.718 (4) | 160 |
O2—H1W···O1 | 0.82 (3) | 1.94 (3) | 2.7575 (15) | 174 (2) |
O2—H2W···S1A | 0.83 (3) | 2.40 (3) | 3.225 (2) | 168 (2) |
O2—H2W···S1B | 0.83 (3) | 2.47 (3) | 3.280 (3) | 164 (2) |
O3A—H3WA···S1Ai | 0.86 (1) | 2.69 (3) | 3.319 (5) | 131 (4) |
O3B—H3WB···S1Bi | 0.86 (1) | 2.34 (2) | 3.185 (5) | 166 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Selected geometric parameters (Å, °) for compounds (I)–(IV) topCompound (I) | | | |
O1—C13 | 1.2173 (15) | N3—C13 | 1.3839 (15) |
N1—C1 | 1.3385 (16) | N4—C13 | 1.3610 (15) |
N1—C5 | 1.3462 (14) | N4—C14 | 1.4066 (14) |
N2—C6 | 1.2919 (14) | C5—C6 | 1.4804 (16) |
N2—N3 | 1.3615 (14) | C6—C7 | 1.4949 (15) |
| | | |
C6—N2—N3 | 117.67 (9) | N2—C6—C7 | 123.52 (10) |
N2—N3—C13 | 121.17 (9) | C5—C6—C7 | 120.45 (9) |
C13—N4—C14 | 127.66 (10) | O1—C13—N4 | 126.70 (11) |
N1—C5—C6 | 116.36 (10) | O1—C13—N3 | 120.02 (10) |
N2—C6—C5 | 116.03 (10) | N4—C13—N3 | 113.28 (10) |
| | | |
Compound (II) | | | |
O1—C13 | 1.2298 (14) | N3—C13 | 1.3910 (14) |
N1—C1 | 1.3384 (15) | N4—C13 | 1.3507 (14) |
N1—C5 | 1.3575 (15) | N4—C14 | 1.4081 (14) |
N2—C6 | 1.2902 (15) | C5—C6 | 1.4775 (15) |
N2—N3 | 1.3447 (13) | C6—C7 | 1.4927 (16) |
| | | |
C6—N2—N3 | 119.08 (10) | N2—C6—C7 | 125.44 (10) |
N2—N3—C13 | 117.20 (9) | C5—C6—C7 | 120.68 (10) |
C13—N4—C14 | 127.57 (10) | O1—C13—N4 | 126.05 (10) |
N1—C5—C6 | 117.58 (10) | O1—C13—N3 | 122.53 (10) |
N2—C6—C5 | 113.87 (10) | N4—C13—N3 | 111.42 (10) |
| | | |
Compound (III) | | | |
O1—C13 | 1.224 (2) | N4—C14 | 1.408 (2) |
N1—C1 | 1.339 (2) | C5—C6 | 1.477 (2) |
N1—C5 | 1.354 (2) | C6—C7 | 1.490 (2) |
N2—C6 | 1.293 (2) | N5—O4 | 1.185 (2) |
N2—N3 | 1.3451 (18) | N5—O3 | 1.224 (2) |
N3—C13 | 1.391 (2) | N5—O5B | 1.353 (3) |
N4—C13 | 1.350 (2) | N5—O5A | 1.363 (3) |
| | | |
C6—N2—N3 | 118.62 (14) | O1—C13—N3 | 122.58 (14) |
N2—N3—C13 | 117.15 (13) | N4—C13—N3 | 111.39 (14) |
C13—N4—C14 | 128.13 (14) | O4—N5—O3 | 126.39 (16) |
N1—C5—C6 | 117.94 (14) | O4—N5—O5B | 106.1 (2) |
N2—C6—C5 | 114.14 (14) | O3—N5—O5B | 118.2 (2) |
N2—C6—C7 | 125.70 (14) | O4—N5—O5A | 104.9 (2) |
C5—C6—C7 | 120.16 (14) | O3—N5—O5A | 114.96 (19) |
O1—C13—N4 | 126.03 (15) | | |
| | | |
Compound (IV) | | | |
O1—C13 | 1.2232 (17) | N4—C14 | 1.4081 (18) |
N1—C1 | 1.3431 (17) | C5—C6 | 1.4798 (18) |
N1—C5 | 1.3542 (17) | C6—C7 | 1.4855 (18) |
N2—C6 | 1.2895 (18) | S1A—C20A | 1.650 (5) |
N2—N3 | 1.3492 (15) | C20A—N5A | 1.166 (6) |
N3—C13 | 1.3902 (18) | S1B—C20B | 1.616 (8) |
N4—C13 | 1.3585 (17) | C20B—N5B | 1.159 (8) |
| | | |
C6—N2—N3 | 119.00 (12) | C5—C6—C7 | 118.65 (12) |
N2—N3—C13 | 117.37 (11) | O1—C13—N4 | 125.70 (13) |
C13—N4—C14 | 127.43 (12) | O1—C13—N3 | 122.73 (12) |
N1—C5—C6 | 118.07 (12) | N4—C13—N3 | 111.57 (12) |
N2—C6—C5 | 114.46 (12) | N5A—C20A—S1A | 177.1 (5) |
N2—C6—C7 | 126.82 (12) | N5B—C20B—S1B | 177.7 (5) |
Selected normal modes of vibration for the hydrated [H2BzPyS]+ cation topNormal vibrations | Frequency (cm-1) | Normal vibrations | Frequency (cm-1) |
ν2(O2—H) | 3892.64 | ν1(N3—H) | 3474.86 |
ν1(O2—H) | 3530.41 | ν1(N1—H) | 3329.39 |
ν2(O3—H) | 3883.54 | ν1(C13—O1) | 1733.86 |
ν1(O3—H) | 3763.48 | ν2(C13—N4) | 1585.25 |
ν1(N4—H) | 3552.76 | ν1(C13—N4) | 1581.30 |