Molecules of the title compounds
N2-(benzoyloxy)benzamidine, C
14H
12N
2O
2, (I),
N2-(2-hydroxybenzoyloxy)benzamidine, C
14H
12N
2O
3, (II), and
N2-benzoyloxy-2-hydroxybenzamidine, C
14H
12N
2O
3, (III), all have extended chain conformations, with the aryl groups remote from one another. In (I), the molecules are linked into chains by a single N-H
N hydrogen bond [H
N = 2.15 Å, N
N = 3.029 (2) Å and N-H
N = 153°] and these chains are linked into sheets by means of aromatic
-
stacking interactions. There is one intramolecular O-H
O hydrogen bond in (II), and a combination of one three-centre N-H
(N,O) hydrogen bond [H
N = 2.46 Å, H
O = 2.31 Å, N
N = 3.190 (2) Å, N
O = 3.146 (2) Å, N-H
N = 138° and N-H
O = 154°] and one two-centre C-H
O hydrogen bond [H
O = 2.46 Å, C
O = 3.405 (2) Å and C-H
O = 173°] links the molecules into sheets. In (III), an intramolecular O-H
N hydrogen bond and two N-H
O hydrogen bonds [H
O = 2.26 and 2.10 Å, N
O = 2.975 (2) and 2.954 (2) Å, and N-H
O = 138 and 163°] link the molecules into sheets.
Supporting information
CCDC references: 231059; 231060; 231061
Samples of (I)–(III) were prepared by heating, under reflux for 1 h, a mixture containing equimolar quantities of the appropriate acyl chloride and the appropriate benzamidoxime in dry tetrahydrofuran solution, in the presence of triethylamine. After removal of triethylammonium chloride and evaporation of the solvent, the solid products were crystallized from acetonitrile
For compounds (I) and (III), space group P21/n was uniquely assigned from the systematic absences; space group Pbca was likewise assigned for (II). All H atoms were located from difference maps, which showed clearly that the NH2 groups were all pyramidal; all H atoms were then treated as riding atoms with C—H distances of 0.95 Å, N—H distances of 0.88–0.95 Å and O—H distances of 0.84 Å.
For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003). Software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999) for (I), (II); SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999) for (III).
(I)
N2-(Benzoyloxy)benzamidine
top
Crystal data top
C14H12N2O2 | F(000) = 504 |
Mr = 240.26 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2614 reflections |
a = 7.0415 (2) Å | θ = 3.2–27.5° |
b = 21.4704 (7) Å | µ = 0.09 mm−1 |
c = 8.0570 (3) Å | T = 120 K |
β = 108.4804 (16)° | Plate, colourless |
V = 1155.27 (7) Å3 | 0.25 × 0.20 × 0.08 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 2614 independent reflections |
Radiation source: rotating anode | 1708 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −9→9 |
Tmin = 0.967, Tmax = 0.993 | k = −27→27 |
10316 measured reflections | l = −10→10 |
Refinement top
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0719P)2 + 0.0022P] where P = (Fo2 + 2Fc2)/3 |
2614 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C14H12N2O2 | V = 1155.27 (7) Å3 |
Mr = 240.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.0415 (2) Å | µ = 0.09 mm−1 |
b = 21.4704 (7) Å | T = 120 K |
c = 8.0570 (3) Å | 0.25 × 0.20 × 0.08 mm |
β = 108.4804 (16)° | |
Data collection top
Nonius KappaCCD diffractometer | 2614 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 1708 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.993 | Rint = 0.056 |
10316 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.21 e Å−3 |
2614 reflections | Δρmin = −0.27 e Å−3 |
165 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.68674 (18) | 0.20793 (5) | 1.03591 (14) | 0.0222 (3) | |
O5 | 0.62128 (19) | 0.11800 (5) | 0.87945 (15) | 0.0265 (3) | |
N2 | 0.6429 (2) | 0.23953 (6) | 0.86857 (17) | 0.0220 (3) | |
N4 | 0.8343 (2) | 0.31800 (7) | 1.05407 (17) | 0.0218 (3) | |
C3 | 0.7286 (2) | 0.29369 (7) | 0.8972 (2) | 0.0186 (4) | |
C5 | 0.6621 (2) | 0.14541 (8) | 1.0169 (2) | 0.0189 (4) | |
C11 | 0.6990 (2) | 0.33248 (7) | 0.7376 (2) | 0.0180 (4) | |
C12 | 0.6842 (2) | 0.30402 (8) | 0.5786 (2) | 0.0216 (4) | |
C13 | 0.6554 (2) | 0.33948 (8) | 0.4299 (2) | 0.0252 (4) | |
C14 | 0.6435 (3) | 0.40380 (8) | 0.4378 (2) | 0.0263 (4) | |
C15 | 0.6600 (3) | 0.43238 (8) | 0.5957 (2) | 0.0254 (4) | |
C16 | 0.6863 (2) | 0.39696 (8) | 0.7450 (2) | 0.0214 (4) | |
C21 | 0.6908 (2) | 0.11529 (7) | 1.1906 (2) | 0.0182 (4) | |
C22 | 0.7371 (2) | 0.14931 (8) | 1.3457 (2) | 0.0207 (4) | |
C23 | 0.7585 (3) | 0.11870 (8) | 1.5029 (2) | 0.0244 (4) | |
C24 | 0.7311 (3) | 0.05492 (8) | 1.5044 (2) | 0.0270 (4) | |
C25 | 0.6868 (3) | 0.02098 (8) | 1.3499 (2) | 0.0283 (4) | |
C26 | 0.6678 (3) | 0.05123 (8) | 1.1937 (2) | 0.0230 (4) | |
H12 | 0.6939 | 0.2600 | 0.5725 | 0.026* | |
H13 | 0.6437 | 0.3198 | 0.3216 | 0.030* | |
H14 | 0.6240 | 0.4281 | 0.3353 | 0.032* | |
H15 | 0.6534 | 0.4765 | 0.6017 | 0.030* | |
H16 | 0.6957 | 0.4168 | 0.8527 | 0.026* | |
H22 | 0.7540 | 0.1932 | 1.3441 | 0.025* | |
H23 | 0.7919 | 0.1416 | 1.6092 | 0.029* | |
H24 | 0.7426 | 0.0342 | 1.6114 | 0.032* | |
H25 | 0.6696 | −0.0229 | 1.3515 | 0.034* | |
H26 | 0.6388 | 0.0280 | 1.0883 | 0.028* | |
H41 | 0.8959 | 0.2907 | 1.1487 | 0.026* | |
H42 | 0.9223 | 0.3516 | 1.0544 | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0294 (6) | 0.0216 (7) | 0.0139 (6) | −0.0021 (5) | 0.0044 (5) | 0.0035 (5) |
O5 | 0.0353 (7) | 0.0260 (7) | 0.0171 (6) | 0.0000 (5) | 0.0068 (5) | −0.0015 (5) |
N4 | 0.0255 (8) | 0.0222 (7) | 0.0150 (7) | −0.0020 (6) | 0.0028 (6) | 0.0002 (6) |
N2 | 0.0276 (8) | 0.0231 (8) | 0.0126 (7) | −0.0019 (6) | 0.0026 (6) | 0.0054 (5) |
C3 | 0.0188 (8) | 0.0208 (9) | 0.0162 (8) | 0.0012 (6) | 0.0057 (7) | 0.0006 (6) |
C5 | 0.0154 (8) | 0.0222 (9) | 0.0185 (9) | −0.0008 (6) | 0.0044 (6) | 0.0020 (7) |
C11 | 0.0151 (8) | 0.0220 (9) | 0.0163 (8) | −0.0013 (6) | 0.0039 (7) | 0.0013 (6) |
C12 | 0.0229 (9) | 0.0217 (9) | 0.0195 (8) | −0.0009 (7) | 0.0056 (7) | 0.0000 (7) |
C13 | 0.0255 (9) | 0.0316 (10) | 0.0183 (9) | −0.0023 (7) | 0.0068 (7) | −0.0020 (7) |
C14 | 0.0258 (9) | 0.0308 (10) | 0.0196 (9) | −0.0030 (7) | 0.0032 (7) | 0.0092 (7) |
C15 | 0.0258 (9) | 0.0207 (9) | 0.0258 (9) | −0.0016 (7) | 0.0029 (8) | 0.0038 (7) |
C16 | 0.0194 (8) | 0.0239 (9) | 0.0199 (9) | −0.0009 (7) | 0.0045 (7) | −0.0014 (7) |
C21 | 0.0134 (7) | 0.0231 (9) | 0.0168 (8) | 0.0020 (6) | 0.0030 (6) | 0.0017 (6) |
C22 | 0.0204 (8) | 0.0208 (9) | 0.0203 (8) | −0.0003 (7) | 0.0054 (7) | 0.0026 (7) |
C23 | 0.0252 (9) | 0.0299 (10) | 0.0164 (8) | 0.0026 (7) | 0.0042 (7) | −0.0005 (7) |
C24 | 0.0317 (10) | 0.0275 (10) | 0.0222 (9) | 0.0036 (8) | 0.0090 (8) | 0.0094 (7) |
C25 | 0.0366 (10) | 0.0188 (9) | 0.0294 (10) | 0.0018 (8) | 0.0104 (8) | 0.0048 (8) |
C26 | 0.0252 (9) | 0.0216 (9) | 0.0219 (9) | 0.0002 (7) | 0.0071 (7) | −0.0014 (7) |
Geometric parameters (Å, º) top
O1—C5 | 1.356 (2) | C14—H14 | 0.95 |
O1—N2 | 1.452 (2) | C15—C16 | 1.385 (2) |
O5—C5 | 1.206 (2) | C15—H15 | 0.95 |
N4—C3 | 1.352 (2) | C16—H16 | 0.95 |
N4—H41 | 0.95 | C21—C26 | 1.386 (2) |
N4—H42 | 0.95 | C21—C22 | 1.394 (2) |
N2—C3 | 1.297 (2) | C22—C23 | 1.392 (2) |
C3—C11 | 1.490 (2) | C22—H22 | 0.95 |
C5—C21 | 1.496 (2) | C23—C24 | 1.383 (2) |
C11—C16 | 1.390 (2) | C23—H23 | 0.95 |
C11—C12 | 1.393 (2) | C24—C25 | 1.389 (3) |
C12—C13 | 1.379 (2) | C24—H24 | 0.95 |
C12—H12 | 0.95 | C25—C26 | 1.384 (2) |
C13—C14 | 1.386 (3) | C25—H25 | 0.95 |
C13—H13 | 0.95 | C26—H26 | 0.95 |
C14—C15 | 1.383 (3) | | |
| | | |
C5—O1—N2 | 112.07 (12) | C16—C15—H15 | 119.9 |
C3—N4—H41 | 119.2 | C14—C15—H15 | 119.9 |
C3—N4—H42 | 117.4 | C15—C16—C11 | 120.16 (16) |
H41—N4—H42 | 109.5 | C15—C16—H16 | 119.9 |
C3—N2—O1 | 107.69 (12) | C11—C16—H16 | 119.9 |
N2—C3—N4 | 126.84 (14) | C26—C21—C22 | 119.93 (15) |
N2—C3—C11 | 114.70 (14) | C26—C21—C5 | 117.66 (14) |
N4—C3—C11 | 118.43 (14) | C22—C21—C5 | 122.41 (15) |
O5—C5—O1 | 124.86 (14) | C23—C22—C21 | 119.71 (16) |
O5—C5—C21 | 124.77 (15) | C23—C22—H22 | 120.1 |
O1—C5—C21 | 110.37 (13) | C21—C22—H22 | 120.1 |
C16—C11—C12 | 119.28 (15) | C24—C23—C22 | 119.98 (16) |
C16—C11—C3 | 120.87 (15) | C24—C23—H23 | 120.0 |
C12—C11—C3 | 119.84 (14) | C22—C23—H23 | 120.0 |
C13—C12—C11 | 120.28 (16) | C25—C24—C23 | 120.26 (16) |
C13—C12—H12 | 119.9 | C25—C24—H24 | 119.9 |
C11—C12—H12 | 119.9 | C23—C24—H24 | 119.9 |
C12—C13—C14 | 120.28 (16) | C24—C25—C26 | 119.84 (16) |
C12—C13—H13 | 119.9 | C24—C25—H25 | 120.1 |
C14—C13—H13 | 119.9 | C26—C25—H25 | 120.1 |
C15—C14—C13 | 119.72 (16) | C25—C26—C21 | 120.26 (16) |
C15—C14—H14 | 120.1 | C25—C26—H26 | 119.9 |
C13—C14—H14 | 120.1 | C21—C26—H26 | 119.9 |
C16—C15—C14 | 120.27 (16) | | |
| | | |
C5—O1—N2—C3 | −160.0 (2) | C12—C11—C16—C15 | −0.2 (2) |
O1—N2—C3—N4 | −2.1 (2) | C3—C11—C16—C15 | 179.58 (15) |
O1—N2—C3—C11 | 179.8 (2) | O5—C5—C21—C26 | −0.4 (2) |
N2—O1—C5—O5 | 4.5 (2) | O1—C5—C21—C26 | 179.11 (14) |
N2—O1—C5—C21 | −175.0 (2) | O5—C5—C21—C22 | −179.73 (15) |
N2—C3—C11—C16 | 146.99 (15) | O1—C5—C21—C22 | −0.2 (2) |
N4—C3—C11—C16 | −31.2 (2) | C26—C21—C22—C23 | −0.5 (2) |
N2—C3—C11—C12 | −33.2 (2) | C5—C21—C22—C23 | 178.86 (15) |
N4—C3—C11—C12 | 148.57 (16) | C21—C22—C23—C24 | −0.9 (2) |
C16—C11—C12—C13 | −0.6 (2) | C22—C23—C24—C25 | 1.5 (3) |
C3—C11—C12—C13 | 179.58 (15) | C23—C24—C25—C26 | −0.7 (3) |
C11—C12—C13—C14 | 0.8 (3) | C24—C25—C26—C21 | −0.6 (3) |
C12—C13—C14—C15 | −0.2 (3) | C22—C21—C26—C25 | 1.2 (2) |
C13—C14—C15—C16 | −0.7 (3) | C5—C21—C26—C25 | −178.13 (16) |
C14—C15—C16—C11 | 0.9 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···N2i | 0.95 | 2.15 | 3.029 (2) | 153 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
(II)
N2-(2-Hydroxybenzoyloxy)benzamidine
top
Crystal data top
C14H12N2O3 | F(000) = 1072 |
Mr = 256.26 | Dx = 1.408 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2758 reflections |
a = 9.3808 (1) Å | θ = 3.1–27.5° |
b = 24.9553 (4) Å | µ = 0.10 mm−1 |
c = 10.3277 (1) Å | T = 120 K |
V = 2417.72 (5) Å3 | Block, colourless |
Z = 8 | 0.55 × 0.32 × 0.28 mm |
Data collection top
Nonius KappaCCD diffractometer | 2758 independent reflections |
Radiation source: rotating anode | 2308 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −12→9 |
Tmin = 0.966, Tmax = 0.972 | k = −32→32 |
17440 measured reflections | l = −13→12 |
Refinement top
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0581P)2 + 1.0166P] where P = (Fo2 + 2Fc2)/3 |
2758 reflections | (Δ/σ)max = 0.001 |
175 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C14H12N2O3 | V = 2417.72 (5) Å3 |
Mr = 256.26 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.3808 (1) Å | µ = 0.10 mm−1 |
b = 24.9553 (4) Å | T = 120 K |
c = 10.3277 (1) Å | 0.55 × 0.32 × 0.28 mm |
Data collection top
Nonius KappaCCD diffractometer | 2758 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 2308 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.972 | Rint = 0.065 |
17440 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.23 e Å−3 |
2758 reflections | Δρmin = −0.28 e Å−3 |
175 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.16042 (9) | 0.57063 (3) | 0.07061 (8) | 0.0186 (2) | |
O5 | 0.08972 (10) | 0.58517 (3) | 0.27676 (8) | 0.0219 (2) | |
O22 | −0.11487 (11) | 0.65582 (4) | 0.31260 (9) | 0.0254 (2) | |
N2 | 0.24819 (12) | 0.52822 (4) | 0.12648 (10) | 0.0185 (2) | |
N4 | 0.18746 (12) | 0.48525 (4) | −0.07198 (10) | 0.0200 (2) | |
C3 | 0.25882 (13) | 0.48989 (5) | 0.04147 (11) | 0.0162 (3) | |
C5 | 0.09289 (13) | 0.59851 (4) | 0.16295 (12) | 0.0164 (2) | |
C11 | 0.35734 (13) | 0.44605 (5) | 0.08089 (11) | 0.0157 (2) | |
C12 | 0.48275 (13) | 0.45869 (5) | 0.14659 (12) | 0.0183 (3) | |
C13 | 0.57522 (15) | 0.41826 (5) | 0.18447 (12) | 0.0214 (3) | |
C14 | 0.54277 (15) | 0.36493 (5) | 0.15761 (13) | 0.0221 (3) | |
C15 | 0.41747 (15) | 0.35224 (5) | 0.09349 (13) | 0.0222 (3) | |
C16 | 0.32460 (14) | 0.39244 (5) | 0.05472 (12) | 0.0193 (3) | |
C21 | 0.01932 (13) | 0.64654 (4) | 0.11252 (12) | 0.0168 (3) | |
C22 | −0.08237 (14) | 0.67216 (5) | 0.19139 (12) | 0.0185 (3) | |
C23 | −0.15664 (14) | 0.71658 (5) | 0.14315 (13) | 0.0227 (3) | |
C24 | −0.12627 (15) | 0.73610 (5) | 0.02098 (14) | 0.0235 (3) | |
C25 | −0.02321 (15) | 0.71186 (5) | −0.05625 (13) | 0.0232 (3) | |
C26 | 0.04785 (14) | 0.66696 (5) | −0.01138 (12) | 0.0203 (3) | |
H22 | −0.0593 | 0.6311 | 0.3347 | 0.038* | |
H41 | 0.1309 | 0.5129 | −0.0956 | 0.024* | |
H42 | 0.2302 | 0.4665 | −0.1366 | 0.024* | |
H12 | 0.5049 | 0.4950 | 0.1654 | 0.022* | |
H13 | 0.6609 | 0.4270 | 0.2288 | 0.026* | |
H14 | 0.6065 | 0.3373 | 0.1832 | 0.027* | |
H15 | 0.3950 | 0.3158 | 0.0760 | 0.027* | |
H16 | 0.2390 | 0.3836 | 0.0105 | 0.023* | |
H23 | −0.2280 | 0.7333 | 0.1945 | 0.027* | |
H24 | −0.1764 | 0.7665 | −0.0107 | 0.028* | |
H25 | −0.0018 | 0.7261 | −0.1394 | 0.028* | |
H26 | 0.1165 | 0.6498 | −0.0649 | 0.024* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0240 (5) | 0.0150 (4) | 0.0166 (4) | 0.0062 (3) | −0.0012 (3) | 0.0003 (3) |
O5 | 0.0300 (5) | 0.0184 (4) | 0.0174 (5) | 0.0056 (4) | 0.0018 (4) | 0.0019 (3) |
O22 | 0.0324 (5) | 0.0234 (5) | 0.0204 (5) | 0.0085 (4) | 0.0038 (4) | 0.0003 (4) |
N2 | 0.0233 (6) | 0.0145 (5) | 0.0178 (5) | 0.0062 (4) | −0.0019 (4) | 0.0015 (4) |
N4 | 0.0230 (6) | 0.0195 (5) | 0.0175 (5) | 0.0036 (4) | −0.0025 (4) | −0.0027 (4) |
C3 | 0.0168 (6) | 0.0161 (5) | 0.0156 (5) | −0.0015 (5) | 0.0024 (5) | 0.0012 (4) |
C5 | 0.0187 (6) | 0.0133 (5) | 0.0174 (6) | −0.0013 (4) | −0.0008 (5) | −0.0010 (4) |
C11 | 0.0180 (6) | 0.0149 (5) | 0.0141 (5) | 0.0008 (4) | 0.0027 (4) | 0.0000 (4) |
C12 | 0.0222 (6) | 0.0155 (5) | 0.0171 (6) | −0.0019 (5) | 0.0003 (5) | −0.0009 (4) |
C13 | 0.0222 (6) | 0.0211 (6) | 0.0209 (6) | −0.0004 (5) | −0.0042 (5) | 0.0005 (5) |
C14 | 0.0263 (7) | 0.0174 (6) | 0.0227 (6) | 0.0042 (5) | 0.0010 (5) | 0.0019 (5) |
C15 | 0.0269 (7) | 0.0138 (5) | 0.0257 (7) | −0.0007 (5) | 0.0018 (5) | −0.0021 (5) |
C16 | 0.0204 (6) | 0.0174 (6) | 0.0199 (6) | −0.0019 (5) | 0.0003 (5) | −0.0025 (5) |
C21 | 0.0190 (6) | 0.0128 (5) | 0.0185 (6) | −0.0009 (4) | −0.0034 (5) | −0.0014 (4) |
C22 | 0.0225 (6) | 0.0143 (5) | 0.0188 (6) | −0.0012 (5) | −0.0034 (5) | −0.0024 (4) |
C23 | 0.0246 (7) | 0.0161 (6) | 0.0274 (7) | 0.0038 (5) | −0.0040 (5) | −0.0053 (5) |
C24 | 0.0278 (7) | 0.0125 (5) | 0.0303 (7) | 0.0015 (5) | −0.0101 (6) | −0.0004 (5) |
C25 | 0.0297 (7) | 0.0177 (6) | 0.0222 (6) | −0.0021 (5) | −0.0048 (6) | 0.0041 (5) |
C26 | 0.0224 (6) | 0.0181 (6) | 0.0202 (6) | −0.0018 (5) | −0.0006 (5) | 0.0005 (5) |
Geometric parameters (Å, º) top
O1—C5 | 1.340 (2) | C13—H13 | 0.95 |
O1—N2 | 1.460 (2) | C14—C15 | 1.3858 (19) |
O5—C5 | 1.222 (2) | C14—H14 | 0.95 |
O22—C22 | 1.3514 (15) | C15—C16 | 1.3876 (18) |
O22—H22 | 0.84 | C15—H15 | 0.95 |
N2—C3 | 1.302 (2) | C16—H16 | 0.95 |
N4—C3 | 1.354 (2) | C21—C26 | 1.4030 (17) |
N4—H41 | 0.90 | C21—C22 | 1.4080 (18) |
N4—H42 | 0.91 | C22—C23 | 1.4008 (17) |
C3—C11 | 1.4890 (16) | C23—C24 | 1.382 (2) |
C5—C21 | 1.4780 (16) | C23—H23 | 0.95 |
C11—C12 | 1.3942 (17) | C24—C25 | 1.392 (2) |
C11—C16 | 1.3992 (16) | C24—H24 | 0.95 |
C12—C13 | 1.3868 (18) | C25—C26 | 1.3837 (18) |
C12—H12 | 0.95 | C25—H25 | 0.95 |
C13—C14 | 1.3932 (17) | C26—H26 | 0.95 |
| | | |
C5—O1—N2 | 111.21 (9) | C16—C15—C14 | 120.36 (11) |
C22—O22—H22 | 109.5 | C16—C15—H15 | 119.8 |
C3—N2—O1 | 108.01 (9) | C14—C15—H15 | 119.8 |
C3—N4—H41 | 117.3 | C15—C16—C11 | 119.84 (12) |
C3—N4—H42 | 117.5 | C15—C16—H16 | 120.1 |
H41—N4—H42 | 117.0 | C11—C16—H16 | 120.1 |
N2—C3—N4 | 127.46 (11) | C26—C21—C22 | 119.47 (11) |
N2—C3—C11 | 113.76 (10) | C26—C21—C5 | 121.79 (11) |
N4—C3—C11 | 118.72 (10) | C22—C21—C5 | 118.74 (11) |
O5—C5—O1 | 123.69 (11) | O22—C22—C23 | 117.13 (11) |
O5—C5—C21 | 123.27 (11) | O22—C22—C21 | 123.48 (11) |
O1—C5—C21 | 113.02 (10) | C23—C22—C21 | 119.38 (11) |
C12—C11—C16 | 119.70 (11) | C24—C23—C22 | 120.07 (12) |
C12—C11—C3 | 119.39 (10) | C24—C23—H23 | 120.0 |
C16—C11—C3 | 120.90 (11) | C22—C23—H23 | 120.0 |
C13—C12—C11 | 120.04 (11) | C23—C24—C25 | 120.87 (12) |
C13—C12—H12 | 120.0 | C23—C24—H24 | 119.6 |
C11—C12—H12 | 120.0 | C25—C24—H24 | 119.6 |
C12—C13—C14 | 120.14 (12) | C26—C25—C24 | 119.65 (12) |
C12—C13—H13 | 119.9 | C26—C25—H25 | 120.2 |
C14—C13—H13 | 119.9 | C24—C25—H25 | 120.2 |
C15—C14—C13 | 119.91 (12) | C25—C26—C21 | 120.51 (12) |
C15—C14—H14 | 120.0 | C25—C26—H26 | 119.7 |
C13—C14—H14 | 120.0 | C21—C26—H26 | 119.7 |
| | | |
C5—O1—N2—C3 | 152.4 (2) | C3—C11—C16—C15 | −179.40 (11) |
O1—N2—C3—N4 | −8.37 (17) | O5—C5—C21—C26 | 166.77 (12) |
O1—N2—C3—C11 | 174.47 (9) | O1—C5—C21—C26 | −14.64 (16) |
N2—O1—C5—O5 | −9.63 (16) | O5—C5—C21—C22 | −13.45 (18) |
N2—O1—C5—C21 | 171.77 (9) | O1—C5—C21—C22 | 165.14 (11) |
N2—C3—C11—C12 | −38.13 (16) | C26—C21—C22—O22 | −178.88 (11) |
N4—C3—C11—C12 | 144.44 (12) | C5—C21—C22—O22 | 1.33 (18) |
N2—C3—C11—C16 | 140.84 (12) | C26—C21—C22—C23 | 2.06 (18) |
N4—C3—C11—C16 | −36.59 (17) | C5—C21—C22—C23 | −177.73 (11) |
C16—C11—C12—C13 | 0.70 (18) | O22—C22—C23—C24 | 178.54 (12) |
C3—C11—C12—C13 | 179.69 (11) | C21—C22—C23—C24 | −2.34 (19) |
C11—C12—C13—C14 | −0.32 (19) | C22—C23—C24—C25 | 0.7 (2) |
C12—C13—C14—C15 | −0.3 (2) | C23—C24—C25—C26 | 1.3 (2) |
C13—C14—C15—C16 | 0.6 (2) | C24—C25—C26—C21 | −1.59 (19) |
C14—C15—C16—C11 | −0.23 (19) | C22—C21—C26—C25 | −0.09 (18) |
C12—C11—C16—C15 | −0.43 (18) | C5—C21—C26—C25 | 179.69 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O5 | 0.84 | 1.90 | 2.632 (2) | 144 |
N4—H42···O5i | 0.91 | 2.31 | 3.146 (2) | 154 |
N4—H42···N2i | 0.91 | 2.46 | 3.190 (2) | 138 |
C12—H12···O5ii | 0.95 | 2.46 | 3.405 (2) | 173 |
C16—H16···Cg1iii | 0.95 | 2.68 | 3.529 (2) | 149 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x+1/2, y, −z+1/2; (iii) −x, −y+1, −z. |
(III)
N2-Benzoyloxy-2-hydroxybenzamidine
top
Crystal data top
C14H12N2O3 | F(000) = 536 |
Mr = 256.26 | Dx = 1.403 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2549 reflections |
a = 4.6463 (3) Å | θ = 3.3–27.5° |
b = 22.1280 (13) Å | µ = 0.10 mm−1 |
c = 11.9551 (9) Å | T = 120 K |
β = 99.202 (3)° | Plate, colourless |
V = 1213.33 (14) Å3 | 0.25 × 0.10 × 0.01 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 2549 independent reflections |
Radiation source: rotating anode | 1412 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −5→5 |
Tmin = 0.970, Tmax = 0.998 | k = −27→28 |
8910 measured reflections | l = −15→15 |
Refinement top
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0626P)2] where P = (Fo2 + 2Fc2)/3 |
2549 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C14H12N2O3 | V = 1213.33 (14) Å3 |
Mr = 256.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.6463 (3) Å | µ = 0.10 mm−1 |
b = 22.1280 (13) Å | T = 120 K |
c = 11.9551 (9) Å | 0.25 × 0.10 × 0.01 mm |
β = 99.202 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 2549 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 1412 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.998 | Rint = 0.065 |
8910 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.32 e Å−3 |
2549 reflections | Δρmin = −0.22 e Å−3 |
173 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.3688 (3) | 0.18366 (6) | 0.20049 (11) | 0.0294 (4) | |
O5 | 0.2346 (3) | 0.15005 (7) | 0.02115 (12) | 0.0383 (4) | |
O121 | 0.7525 (3) | 0.28621 (7) | 0.00167 (11) | 0.0359 (4) | |
N2 | 0.5570 (4) | 0.22553 (8) | 0.15460 (14) | 0.0289 (5) | |
N4 | 0.6513 (4) | 0.25484 (8) | 0.34554 (14) | 0.0301 (5) | |
C3 | 0.6859 (4) | 0.25965 (9) | 0.23640 (17) | 0.0240 (5) | |
C5 | 0.2209 (4) | 0.14696 (9) | 0.12101 (18) | 0.0268 (5) | |
C11 | 0.8891 (4) | 0.30561 (9) | 0.20344 (16) | 0.0241 (5) | |
C12 | 0.9117 (4) | 0.31623 (9) | 0.09000 (17) | 0.0252 (5) | |
C13 | 1.1034 (5) | 0.35978 (10) | 0.06161 (17) | 0.0314 (6) | |
C14 | 1.2743 (4) | 0.39237 (9) | 0.14485 (18) | 0.0302 (5) | |
C15 | 1.2559 (5) | 0.38254 (9) | 0.25700 (18) | 0.0305 (5) | |
C16 | 1.0651 (4) | 0.33982 (10) | 0.28583 (16) | 0.0289 (5) | |
C21 | 0.0454 (4) | 0.10209 (9) | 0.17318 (17) | 0.0270 (5) | |
C22 | 0.0324 (5) | 0.10087 (10) | 0.28767 (18) | 0.0315 (6) | |
C23 | −0.1280 (5) | 0.05619 (10) | 0.33122 (18) | 0.0356 (6) | |
C24 | −0.2764 (5) | 0.01349 (10) | 0.2605 (2) | 0.0344 (6) | |
C25 | −0.2657 (5) | 0.01489 (10) | 0.1465 (2) | 0.0397 (6) | |
C26 | −0.1052 (5) | 0.05889 (10) | 0.10217 (17) | 0.0358 (6) | |
H121 | 0.6558 | 0.2587 | 0.0267 | 0.054* | |
H41 | 0.5067 | 0.2317 | 0.3590 | 0.045* | |
H42 | 0.7089 | 0.2848 | 0.3922 | 0.045* | |
H13 | 1.1162 | 0.3670 | −0.0158 | 0.038* | |
H14 | 1.4057 | 0.4218 | 0.1248 | 0.036* | |
H15 | 1.3744 | 0.4051 | 0.3144 | 0.037* | |
H16 | 1.0528 | 0.3334 | 0.3635 | 0.035* | |
H22 | 0.1330 | 0.1305 | 0.3366 | 0.038* | |
H23 | −0.1353 | 0.0551 | 0.4101 | 0.043* | |
H24 | −0.3862 | −0.0169 | 0.2907 | 0.041* | |
H25 | −0.3689 | −0.0145 | 0.0978 | 0.048* | |
H26 | −0.0978 | 0.0596 | 0.0232 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0340 (9) | 0.0321 (9) | 0.0235 (8) | −0.0059 (7) | 0.0090 (7) | 0.0010 (7) |
O5 | 0.0509 (10) | 0.0413 (11) | 0.0231 (9) | −0.0070 (8) | 0.0071 (7) | 0.0016 (7) |
O121 | 0.0408 (9) | 0.0445 (11) | 0.0235 (9) | −0.0131 (8) | 0.0087 (7) | −0.0048 (7) |
N2 | 0.0319 (11) | 0.0298 (11) | 0.0271 (11) | −0.0067 (8) | 0.0114 (9) | 0.0013 (8) |
N4 | 0.0347 (10) | 0.0327 (11) | 0.0237 (11) | −0.0038 (8) | 0.0072 (8) | 0.0001 (8) |
C3 | 0.0241 (12) | 0.0258 (13) | 0.0228 (12) | 0.0087 (9) | 0.0058 (10) | 0.0014 (9) |
C5 | 0.0280 (12) | 0.0285 (13) | 0.0234 (12) | 0.0044 (10) | 0.0027 (9) | 0.0021 (10) |
C11 | 0.0236 (11) | 0.0265 (12) | 0.0231 (12) | 0.0057 (9) | 0.0062 (9) | 0.0003 (9) |
C12 | 0.0250 (12) | 0.0287 (13) | 0.0224 (12) | 0.0025 (9) | 0.0051 (9) | −0.0028 (10) |
C13 | 0.0369 (13) | 0.0361 (14) | 0.0228 (12) | −0.0016 (11) | 0.0101 (10) | 0.0027 (10) |
C14 | 0.0308 (13) | 0.0285 (13) | 0.0330 (14) | −0.0015 (10) | 0.0105 (10) | 0.0014 (10) |
C15 | 0.0316 (12) | 0.0308 (14) | 0.0283 (13) | 0.0003 (10) | 0.0023 (10) | −0.0047 (10) |
C16 | 0.0338 (13) | 0.0326 (13) | 0.0207 (11) | 0.0046 (10) | 0.0056 (10) | 0.0014 (10) |
C21 | 0.0267 (12) | 0.0261 (13) | 0.0279 (13) | 0.0045 (10) | 0.0038 (10) | 0.0021 (10) |
C22 | 0.0382 (13) | 0.0271 (13) | 0.0306 (13) | 0.0003 (10) | 0.0100 (10) | −0.0010 (10) |
C23 | 0.0450 (14) | 0.0328 (14) | 0.0324 (13) | 0.0042 (11) | 0.0164 (11) | 0.0040 (11) |
C24 | 0.0321 (13) | 0.0286 (14) | 0.0442 (15) | −0.0003 (10) | 0.0110 (11) | 0.0062 (11) |
C25 | 0.0408 (14) | 0.0344 (15) | 0.0408 (16) | −0.0078 (11) | −0.0035 (12) | 0.0009 (12) |
C26 | 0.0420 (14) | 0.0385 (15) | 0.0258 (13) | −0.0031 (11) | 0.0019 (11) | 0.0035 (11) |
Geometric parameters (Å, º) top
O1—C5 | 1.351 (2) | C14—C15 | 1.374 (3) |
O1—N2 | 1.442 (2) | C14—H14 | 0.95 |
O5—C5 | 1.208 (2) | C15—C16 | 1.377 (3) |
O121—C12 | 1.361 (2) | C15—H15 | 0.95 |
O121—H121 | 0.84 | C16—H16 | 0.95 |
N2—C3 | 1.303 (2) | C21—C22 | 1.380 (3) |
N4—C3 | 1.344 (2) | C21—C26 | 1.391 (3) |
N4—H41 | 0.88 | C22—C23 | 1.388 (3) |
N4—H42 | 0.88 | C22—H22 | 0.95 |
C3—C11 | 1.483 (3) | C23—C24 | 1.377 (3) |
C5—C21 | 1.484 (3) | C23—H23 | 0.95 |
C11—C12 | 1.397 (3) | C24—C25 | 1.373 (3) |
C11—C16 | 1.398 (3) | C24—H24 | 0.95 |
C12—C13 | 1.391 (3) | C25—C26 | 1.382 (3) |
C13—C14 | 1.374 (3) | C25—H25 | 0.95 |
C13—H13 | 0.95 | C26—H26 | 0.95 |
| | | |
C5—O1—N2 | 112.95 (15) | C14—C15—C16 | 119.72 (19) |
C12—O121—H121 | 109.5 | C14—C15—H15 | 120.1 |
C3—N2—O1 | 108.71 (16) | C16—C15—H15 | 120.1 |
C3—N4—H41 | 115.9 | C15—C16—C11 | 121.52 (19) |
C3—N4—H42 | 119.0 | C15—C16—H16 | 119.2 |
H41—N4—H42 | 119.1 | C11—C16—H16 | 119.2 |
N2—C3—N4 | 124.81 (19) | C22—C21—C26 | 119.6 (2) |
N2—C3—C11 | 115.69 (18) | C22—C21—C5 | 122.96 (19) |
N4—C3—C11 | 119.48 (18) | C26—C21—C5 | 117.39 (19) |
O5—C5—O1 | 124.06 (19) | C21—C22—C23 | 119.8 (2) |
O5—C5—C21 | 124.93 (19) | C21—C22—H22 | 120.1 |
O1—C5—C21 | 111.00 (18) | C23—C22—H22 | 120.1 |
C12—C11—C16 | 117.83 (19) | C24—C23—C22 | 120.3 (2) |
C12—C11—C3 | 121.54 (18) | C24—C23—H23 | 119.8 |
C16—C11—C3 | 120.63 (19) | C22—C23—H23 | 119.8 |
O121—C12—C13 | 116.01 (18) | C25—C24—C23 | 120.0 (2) |
O121—C12—C11 | 123.73 (19) | C25—C24—H24 | 120.0 |
C13—C12—C11 | 120.26 (19) | C23—C24—H24 | 120.0 |
C14—C13—C12 | 120.36 (19) | C24—C25—C26 | 120.3 (2) |
C14—C13—H13 | 119.8 | C24—C25—H25 | 119.9 |
C12—C13—H13 | 119.8 | C26—C25—H25 | 119.9 |
C13—C14—C15 | 120.3 (2) | C25—C26—C21 | 120.0 (2) |
C13—C14—H14 | 119.8 | C25—C26—H26 | 120.0 |
C15—C14—H14 | 119.8 | C21—C26—H26 | 120.0 |
| | | |
C5—O1—N2—C3 | 178.82 (16) | C13—C14—C15—C16 | 0.0 (3) |
O1—N2—C3—N4 | 1.5 (3) | C14—C15—C16—C11 | 0.4 (3) |
O1—N2—C3—C11 | 179.97 (15) | C12—C11—C16—C15 | −0.2 (3) |
N2—O1—C5—O5 | −2.7 (3) | C3—C11—C16—C15 | 179.77 (18) |
N2—O1—C5—C21 | 176.26 (14) | O5—C5—C21—C22 | −178.9 (2) |
N2—C3—C11—C12 | 7.6 (3) | O1—C5—C21—C22 | 2.1 (3) |
N4—C3—C11—C12 | −173.83 (17) | O5—C5—C21—C26 | 2.7 (3) |
N2—C3—C11—C16 | −172.38 (18) | O1—C5—C21—C26 | −176.26 (17) |
N4—C3—C11—C16 | 6.2 (3) | C26—C21—C22—C23 | 0.7 (3) |
C16—C11—C12—O121 | −179.81 (18) | C5—C21—C22—C23 | −177.65 (19) |
C3—C11—C12—O121 | 0.2 (3) | C21—C22—C23—C24 | −0.6 (3) |
C16—C11—C12—C13 | −0.3 (3) | C22—C23—C24—C25 | 0.1 (3) |
C3—C11—C12—C13 | 179.74 (19) | C23—C24—C25—C26 | 0.3 (3) |
O121—C12—C13—C14 | −179.80 (19) | C24—C25—C26—C21 | −0.2 (3) |
C11—C12—C13—C14 | 0.6 (3) | C22—C21—C26—C25 | −0.3 (3) |
C12—C13—C14—C15 | −0.5 (3) | C5—C21—C26—C25 | 178.17 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···O121i | 0.88 | 2.26 | 2.975 (2) | 138 |
N4—H42···O5ii | 0.88 | 2.10 | 2.954 (2) | 163 |
O121—H121···N2 | 0.84 | 1.82 | 2.550 (2) | 144 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x+1/2, −y+1/2, z+1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C14H12N2O2 | C14H12N2O3 | C14H12N2O3 |
Mr | 240.26 | 256.26 | 256.26 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca | Monoclinic, P21/n |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 7.0415 (2), 21.4704 (7), 8.0570 (3) | 9.3808 (1), 24.9553 (4), 10.3277 (1) | 4.6463 (3), 22.1280 (13), 11.9551 (9) |
α, β, γ (°) | 90, 108.4804 (16), 90 | 90, 90, 90 | 90, 99.202 (3), 90 |
V (Å3) | 1155.27 (7) | 2417.72 (5) | 1213.33 (14) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 | 0.10 |
Crystal size (mm) | 0.25 × 0.20 × 0.08 | 0.55 × 0.32 × 0.28 | 0.25 × 0.10 × 0.01 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.967, 0.993 | 0.966, 0.972 | 0.970, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10316, 2614, 1708 | 17440, 2758, 2308 | 8910, 2549, 1412 |
Rint | 0.056 | 0.065 | 0.065 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.129, 0.96 | 0.039, 0.105, 0.97 | 0.056, 0.133, 0.98 |
No. of reflections | 2614 | 2758 | 2549 |
No. of parameters | 165 | 175 | 173 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.27 | 0.23, −0.28 | 0.32, −0.22 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···N2i | 0.95 | 2.15 | 3.029 (2) | 153 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O5 | 0.84 | 1.90 | 2.632 (2) | 144 |
N4—H42···O5i | 0.91 | 2.31 | 3.146 (2) | 154 |
N4—H42···N2i | 0.91 | 2.46 | 3.190 (2) | 138 |
C12—H12···O5ii | 0.95 | 2.46 | 3.405 (2) | 173 |
C16—H16···Cg1iii | 0.95 | 2.68 | 3.529 (2) | 149 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x+1/2, y, −z+1/2; (iii) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···O121i | 0.88 | 2.26 | 2.975 (2) | 138 |
N4—H42···O5ii | 0.88 | 2.10 | 2.954 (2) | 163 |
O121—H121···N2 | 0.84 | 1.82 | 2.550 (2) | 144 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x+1/2, −y+1/2, z+1/2. |
Selected geometric parameters (Å, °) for compounds (I) - (III) topParameter | (I) | (II) | (III) |
C3-N2 | 1.297 (2) | 1.302 (2) | 1.303 (2) |
C3-N4 | 1.352 (2) | 1.354 (2) | 1.344 (2) |
N2-O1 | 1.452 (2) | 1.460 (2) | 1.442 (2) |
O1-C5 | 1.356 (2) | 1.340 (2) | 1.351 (2) |
C5-O5 | 1.206 (2) | 1.222 (2) | 1.208 (2) |
C11-C3-N2-O1 | 179.8 (2) | 174.47 (9) | 180.0 (2) |
C3-N2-O1-C5 | -160.0 (2) | 152.4 (2) | 178.8 (2) |
N2-O1-C5-C21 | -175.0 (2) | 171.77 (9) | 176.3 (2) |
Acyloxyarylamidines, Ar1C(O)ON=C(NH2)Ar2, can in principle adopt a wide range of conformations, depending on both the configuration at the C═N double bond, and the rotational freedom about the C—O and N—O single bonds. On the basis of ab initio calculations on the simple model compound HC(O)ON=CHNH2 and qualitative estimates of 1,4 interactions in the aryl analogues Ar1C(O)ON=C(NH2)Ar2, it has been suggested (Tucker et al., 2000) that the two most stable conformers, at least in the vapour phase, are those with chain-extended C(Ar)—C—O—N=C—C(Ar) spacer units. Consistent with this prediction, the structures of three derivatives [Ar1 is 1-naphthyl and Ar2 is 2-methylphenyl, Cambridge Structural Database (CSD; Allen, 2002) refcode QUNMER; Ar1 is 1-naphthyl and Ar2 is 2,6-dichlorophenyl, CSD refcode QUNMOB; Ar1 is 2-methylphenyl and Ar2 is 2,4-dichlorophenyl, CSD refcode QUNMIV] were all found to adopt nearly planar chain-extended conformations, with the aryl groups remote from one another. In this paper, we report the structure of three more compounds of this type, including the unsubstituted parent compound, N-benzoyloxybenzamidine, (I), and two isomeric hydroxy compounds, N-(2-hydroxybenzoyloxy)benzamidine, (II), and N-benzoyloxy-2-hydroxybenzamidine, (III). In these three compounds, there exists the possibility that the overall conformation may be influenced by intermolecular hydrogen bonding involving the substituted aryl rings.
The molecules of (I)–(III) (Figs. 1–3) all have chain-extended conformations, with the aryl groups remote from one another. In (III), the non-H atoms in the central spacer unit between atoms C11 and C21 are almost coplanar, as shown by the key torsion angles (Table 1), whereas in both (I) and (III), there is a modest twist about the central N2—O1 bond. The C—N and C—O distances in the spacer unit distinguish clearly between the formal single and double bonds; the C—N distances are, in addition, fully consistent with the location of the H atoms bonded to atom N4, as deduced from a difference map. The remaining bond distances and interbond angles show no unusual features.
Despite their very similar constitutions and their similar molecular geometries, the supramolecular structures of (I)–(III) are all different, with significant differences even between the isomeric compounds (II) and (III). No two structures employ the same combination of hard and soft (Desiraju & Steiner, 1999) interactions between the molecules.
In (I) (Fig. 1), where both aryl rings are unsubstituted, there are no intramolecular hydrogen bonds and only a single intermolecular hydrogen bond (N—H···O; Table 2). Amino atom N4 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H41, to imino atom N2 in the molecule at (0.5 + x, 0.5 − y, 0.5 + z), so producing a zigzag C(4) chain (Bernstein et al., 1995) running parallel to the [101] direction and generated by the n-glide plane at y = 0.25 (Fig. 4). The second N—H bond plays no role in the supramolecular aggregation, forming neither a hard N—H···O hydrogen bond nor a soft N—H···π(arene) hydrogen bond. Neither of the two O atoms plays any role in the supramolecular structure.
However, the chains in (I) are weakly linked into sheets by a single aromatic π···π stacking interaction. Phenyl rings C11–C16 and C21–C26 in the molecules at (x, y, z) and (0.5 + x, 0.5 − y, −0.5 + z), respectively, are nearly parallel, with an interplanar angle of only 5.1 (2)°; the ring-centroid separation is 3.852 (2) Å and the interplanar spacing is ca 3.50 Å, giving a centroid offset of ca 1.61 Å. Propagation of this interaction thus generates a chain running parallel to the [10–1] direction (Fig. 5), and the combination of [101] and [10–1] chains generates a (010) sheet. Two sheets pass through each unit cell, in the domains −0.02 < y < 0.52 and 0.48 < y < 1.02, but there are no direction-specific interactions between adjacent sheets.
There is an intramolecular hydrogen bond in (II) (Fig. 2) and there are two intermolecular hydrogen bonds, viz. one three-centred N—H···(N,O) bond and one two-centred C—H···O bond, both of which utilize the same O acceptor atom (Table 3). Amino atom N4 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H42, to imino atom N2 and to carbonyl atom O5, both in the molecule at (0.5 − x, 1 − y, −0.5 + z), thereby producing a C(4) C(7)[R21(5)] chain of rings running parallel to the [001] direction and generated by the 21 screw axis along (1/4, 1/2, z) (Fig. 6). At the same time, atom C12 at (x, y, z) acts as a hydrogen-bond donor to atom O5 in the molecule at (0.5 + x, y, 0.5 − z), so producing a zigzag C(8) chain parallel to [100] and generated by the a-glide plane at z = 0.25 (Fig. 7). The combination of the [100] and [001] chains generates a (010) sheet, two of which pass through each unit cell in the domains 0.26 < y < 0.74 and 0.76 < y < 1.24, respectively. There are no direction-specific interactions between adjacent sheets, although there is a single C—H···π(arene) hydrogen bond within the sheet (Table 3).
In (III), which is isomeric with (II), an intramolecular O—H···N hydrogen bond (Fig. 3) forms an S(6) motif and the supramolecular aggregation is dominated by two intermolecular N—H···O hydrogen bonds (Table 4). Amino atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atoms H1A and H1B, respectively, to phenol atom O1 in the molecule at (−0.5 + x, 0.5 − y, 0.5 + z) and to carbonyl atom O3 in the molecule at (0.5 + x, 0.5 − y, 0.5 + z), thereby producing C(6) and C(7) chains running parallel to the [−101] and [101] directions, respectively. The combination of these two chains produces a (010) sheet in the form of a (4,4)-net (Batten & Robson, 1998) containing equal numbers of S(6) and R45(22) rings (Fig. 8). This sheet, which is generated by the n-glide plane at y = 1/4, lies in the domain −0.02 < y < 0.52. A second such sheet, related to the first by inversion, lies in the domain 0.48 < y 1.02, this sheet being generated by the n-glide plane at y = 0.75. However, there are no direction-specific interactions between adjacent sheets; in particular, there are neither X—H···π(arene) hydrogen bonds (X = C, N or O) nor aromatic π···π stacking interactions in the structure.
In summary, the overall conformations adopted by (I)–(III) are similar to those of the analogues reported previously; this conformation appears to be independent of the presence or absence of intermolecular hydrogen bonding involving the carbonyl O atom, previously suggested as a contributory factor in the determination of molecular conformation (Tucker et al., 2000).