organic compounds
N′′-(4-Methoxyphenyl)-N,N,N′-trimethyl-N′-phenylguanidine
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany, and bInstitut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
*Correspondence e-mail: willi.kantlehner@htw-aalen.de
In the title compound, C17H21N3O, the C—N bond lengths in the guanidine unit are 1.2889 (19), 1.3682 (19) and 1.408 (2) Å, indicating double- and single-bond character. The N—C—N angles are 115.10 (13), 119.29 (15) and 125.61 (14)°, showing a deviation of the CN3 plane from an ideal trigonal–planar geometry. In the crystal, non-classical C—H⋯O hydrogen bonds between methyl H atoms and methoxy O atoms are present, generating centrosymmetric dimers running in the [101] direction.
CCDC reference: 991872
Related literature
For the crystal structures of N-methylated diphenylguanidines, see: Tanatani et al. (1998). For non-classical hydrogen bonds, see: Desiraju & Steiner (1999). For the of N′′-(4-carbazol-9-ylphenyl)-N,N′-diethyl-N,N′-diphenylguanidine, see: Tiritiris & Kantlehner (2013).
Experimental
Crystal data
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Data collection: XSCANS (Siemens, 1996); cell XSCANS; data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 991872
10.1107/S1600536814005819/kp2467sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005819/kp2467Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005819/kp2467Isup3.cml
One equivalent of N,N-dimethyl-N',N'-methylphenyl- chloroformamidinium-chloride (synthesized from N,N-dimethyl- N',N'-methylphenylthiourea and phosgene) was reacted with one equivalent of 4-methoxyaniline (Sigma-Aldrich) in acetonitrile, in the presence of one equivalent of triethylamine, at 273 K. The obtained mixture consisting of the guanidinium chloride and triethylammonium chloride was reacted in the next step with an excess of an aqueous sodium hydroxide solution at 273 K. After extraction of the guanidine with diethyl ether from the water phase, the solvent was evaporated and the title compound was isolated in form of a colourless solid. Single crystals have been obtained by recrystallization from a saturated acetonitrile solution at 273 K.
The hydrogen atoms of the methyl groups were allowed to rotate with a fixed angle around the C–N and C–O bond to best fit the experimental electron density, with Uiso(H) set to 1.5 Ueq(C) and d(C—H) = 0.96 Å. The H atoms in aromatic rings were placed in calculated positions with (C—H) = 0.93 Å. They were included in the
in the riding model approximation, with Uiso(H) set to 1.2Ueq(C).Data collection: XSCANS (Siemens, 1996); cell
XSCANS (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C17H21N3O | F(000) = 1216 |
Mr = 283.37 | Dx = 1.190 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 32 reflections |
a = 26.691 (4) Å | θ = 12.5–17.0° |
b = 7.5135 (7) Å | µ = 0.08 mm−1 |
c = 19.361 (2) Å | T = 293 K |
β = 125.412 (8)° | Block, colourless |
V = 3164.4 (7) Å3 | 0.45 × 0.30 × 0.20 mm |
Z = 8 |
Nicolet P3/F diffractometer | Rint = 0.000 |
Radiation source: sealed tube | θmax = 28.0°, θmin = 1.9° |
Graphite monochromator | h = −35→28 |
Wyckoff–Scan scans | k = 0→9 |
3817 measured reflections | l = 0→25 |
3817 independent reflections | 3 standard reflections every 50 reflections |
2770 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.161 | w = 1/[σ2(Fo2) + (0.0907P)2 + 0.4749P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3817 reflections | Δρmax = 0.21 e Å−3 |
195 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0126 (12) |
C17H21N3O | V = 3164.4 (7) Å3 |
Mr = 283.37 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.691 (4) Å | µ = 0.08 mm−1 |
b = 7.5135 (7) Å | T = 293 K |
c = 19.361 (2) Å | 0.45 × 0.30 × 0.20 mm |
β = 125.412 (8)° |
Nicolet P3/F diffractometer | Rint = 0.000 |
3817 measured reflections | 3 standard reflections every 50 reflections |
3817 independent reflections | intensity decay: 2% |
2770 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.21 e Å−3 |
3817 reflections | Δρmin = −0.16 e Å−3 |
195 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 | ||
N1 | 0.08203 (6) | 0.45184 (19) | 0.19928 (10) | 0.0707 (4) | |
N2 | 0.05887 (6) | 0.71681 (18) | 0.12254 (7) | 0.0580 (3) | |
N3 | −0.01532 (6) | 0.56477 (18) | 0.13348 (9) | 0.0647 (4) | |
C1 | 0.03887 (6) | 0.5790 (2) | 0.15042 (9) | 0.0569 (4) | |
C2 | 0.07023 (9) | 0.3255 (3) | 0.24493 (16) | 0.0970 (7) | |
H2A | 0.0506 | 0.3854 | 0.2671 | 0.146* | |
H2B | 0.1084 | 0.2751 | 0.2908 | 0.146* | |
H2C | 0.0439 | 0.2325 | 0.2071 | 0.146* | |
C3 | 0.12795 (8) | 0.4022 (3) | 0.18495 (13) | 0.0820 (6) | |
H3A | 0.1185 | 0.2864 | 0.1593 | 0.123* | |
H3B | 0.1678 | 0.3999 | 0.2381 | 0.123* | |
H3C | 0.1279 | 0.4875 | 0.1480 | 0.123* | |
C4 | 0.02692 (9) | 0.7432 (3) | 0.03201 (10) | 0.0774 (5) | |
H4A | 0.0262 | 0.8677 | 0.0204 | 0.116* | |
H4B | −0.0145 | 0.7000 | 0.0029 | 0.116* | |
H4C | 0.0478 | 0.6793 | 0.0128 | 0.116* | |
C5 | 0.11327 (6) | 0.8100 (2) | 0.18048 (9) | 0.0525 (3) | |
C6 | 0.13389 (7) | 0.8259 (2) | 0.26485 (9) | 0.0586 (4) | |
H6 | 0.1117 | 0.7736 | 0.2828 | 0.070* | |
C7 | 0.18709 (7) | 0.9188 (2) | 0.32194 (10) | 0.0663 (4) | |
H7 | 0.2004 | 0.9275 | 0.3781 | 0.080* | |
C8 | 0.22101 (8) | 0.9991 (3) | 0.29729 (13) | 0.0744 (5) | |
H8 | 0.2570 | 1.0604 | 0.3363 | 0.089* | |
C9 | 0.20037 (8) | 0.9863 (3) | 0.21424 (13) | 0.0768 (5) | |
H9 | 0.2225 | 1.0410 | 0.1967 | 0.092* | |
C10 | 0.14755 (8) | 0.8943 (2) | 0.15616 (11) | 0.0674 (4) | |
H10 | 0.1345 | 0.8879 | 0.1000 | 0.081* | |
C11 | −0.05759 (6) | 0.7075 (2) | 0.09794 (9) | 0.0570 (4) | |
C12 | −0.11896 (7) | 0.6672 (2) | 0.03552 (11) | 0.0676 (4) | |
H12 | −0.1300 | 0.5498 | 0.0180 | 0.081* | |
C13 | −0.16389 (7) | 0.7981 (3) | −0.00107 (11) | 0.0683 (4) | |
H13 | −0.2044 | 0.7684 | −0.0438 | 0.082* | |
C14 | −0.14870 (7) | 0.9715 (2) | 0.02570 (10) | 0.0607 (4) | |
C15 | −0.08802 (7) | 1.0149 (2) | 0.08889 (10) | 0.0626 (4) | |
H15 | −0.0774 | 1.1321 | 0.1072 | 0.075* | |
C16 | −0.04339 (7) | 0.8840 (2) | 0.12449 (10) | 0.0610 (4) | |
H16 | −0.0030 | 0.9144 | 0.1671 | 0.073* | |
O1 | −0.19000 (6) | 1.11075 (18) | −0.00565 (8) | 0.0812 (4) | |
C17 | −0.25343 (8) | 1.0690 (3) | −0.06419 (12) | 0.0898 (7) | |
H17A | −0.2772 | 1.1766 | −0.0817 | 0.135* | |
H17B | −0.2661 | 0.9915 | −0.0376 | 0.135* | |
H17C | −0.2597 | 1.0108 | −0.1128 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0551 (7) | 0.0659 (8) | 0.0859 (10) | 0.0101 (6) | 0.0379 (7) | 0.0117 (7) |
N2 | 0.0533 (7) | 0.0721 (8) | 0.0512 (6) | 0.0078 (6) | 0.0318 (6) | 0.0042 (6) |
N3 | 0.0481 (6) | 0.0664 (8) | 0.0729 (8) | 0.0038 (6) | 0.0312 (6) | 0.0037 (6) |
C1 | 0.0486 (7) | 0.0594 (8) | 0.0585 (8) | 0.0050 (6) | 0.0286 (6) | 0.0002 (6) |
C2 | 0.0641 (10) | 0.0750 (12) | 0.1319 (18) | 0.0057 (9) | 0.0453 (12) | 0.0345 (12) |
C3 | 0.0589 (9) | 0.0856 (12) | 0.0863 (12) | 0.0236 (9) | 0.0333 (9) | −0.0041 (10) |
C4 | 0.0842 (12) | 0.0862 (12) | 0.0534 (9) | 0.0075 (10) | 0.0350 (9) | 0.0023 (8) |
C5 | 0.0502 (7) | 0.0610 (8) | 0.0559 (7) | 0.0110 (6) | 0.0362 (6) | 0.0060 (6) |
C6 | 0.0544 (7) | 0.0747 (9) | 0.0563 (8) | 0.0062 (7) | 0.0376 (7) | 0.0068 (7) |
C7 | 0.0552 (8) | 0.0834 (11) | 0.0590 (8) | 0.0057 (8) | 0.0323 (7) | −0.0003 (8) |
C8 | 0.0514 (8) | 0.0812 (11) | 0.0880 (12) | 0.0003 (8) | 0.0390 (8) | −0.0004 (9) |
C9 | 0.0654 (10) | 0.0875 (12) | 0.1004 (13) | 0.0015 (9) | 0.0611 (10) | 0.0110 (10) |
C10 | 0.0699 (9) | 0.0834 (11) | 0.0705 (9) | 0.0097 (8) | 0.0531 (8) | 0.0099 (8) |
C11 | 0.0455 (7) | 0.0688 (9) | 0.0574 (8) | 0.0028 (6) | 0.0302 (6) | 0.0023 (7) |
C12 | 0.0486 (8) | 0.0723 (10) | 0.0731 (10) | −0.0024 (7) | 0.0302 (7) | −0.0046 (8) |
C13 | 0.0446 (7) | 0.0873 (12) | 0.0633 (9) | 0.0040 (7) | 0.0257 (7) | −0.0003 (8) |
C14 | 0.0530 (8) | 0.0815 (11) | 0.0567 (8) | 0.0136 (7) | 0.0369 (7) | 0.0079 (7) |
C15 | 0.0586 (8) | 0.0691 (9) | 0.0671 (9) | 0.0028 (7) | 0.0405 (8) | −0.0083 (7) |
C16 | 0.0467 (7) | 0.0763 (10) | 0.0577 (8) | 0.0024 (7) | 0.0290 (6) | −0.0083 (7) |
O1 | 0.0646 (7) | 0.0920 (9) | 0.0876 (8) | 0.0245 (6) | 0.0445 (7) | 0.0114 (7) |
C17 | 0.0629 (10) | 0.1322 (18) | 0.0652 (10) | 0.0366 (11) | 0.0318 (9) | 0.0137 (11) |
N1—C1 | 1.3682 (19) | C7—H7 | 0.9300 |
N1—C2 | 1.450 (3) | C8—C9 | 1.368 (3) |
N1—C3 | 1.453 (2) | C8—H8 | 0.9300 |
N2—C5 | 1.4035 (19) | C9—C10 | 1.376 (3) |
N2—C1 | 1.408 (2) | C9—H9 | 0.9300 |
N2—C4 | 1.4513 (19) | C10—H10 | 0.9300 |
N3—C1 | 1.2889 (19) | C11—C16 | 1.392 (2) |
N3—C11 | 1.4133 (19) | C11—C12 | 1.393 (2) |
C2—H2A | 0.9600 | C12—C13 | 1.386 (2) |
C2—H2B | 0.9600 | C12—H12 | 0.9300 |
C2—H2C | 0.9600 | C13—C14 | 1.374 (3) |
C3—H3A | 0.9600 | C13—H13 | 0.9300 |
C3—H3B | 0.9600 | C14—O1 | 1.3792 (19) |
C3—H3C | 0.9600 | C14—C15 | 1.389 (2) |
C4—H4A | 0.9600 | C15—C16 | 1.382 (2) |
C4—H4B | 0.9600 | C15—H15 | 0.9300 |
C4—H4C | 0.9600 | C16—H16 | 0.9300 |
C5—C6 | 1.394 (2) | O1—C17 | 1.423 (2) |
C5—C10 | 1.399 (2) | C17—H17A | 0.9600 |
C6—C7 | 1.381 (2) | C17—H17B | 0.9600 |
C6—H6 | 0.9300 | C17—H17C | 0.9600 |
C7—C8 | 1.383 (2) | ||
C1—N1—C2 | 119.01 (14) | C8—C7—H7 | 119.3 |
C1—N1—C3 | 120.83 (15) | C9—C8—C7 | 118.47 (17) |
C2—N1—C3 | 116.97 (15) | C9—C8—H8 | 120.8 |
C5—N2—C1 | 120.47 (12) | C7—C8—H8 | 120.8 |
C5—N2—C4 | 120.59 (13) | C8—C9—C10 | 121.32 (15) |
C1—N2—C4 | 118.38 (14) | C8—C9—H9 | 119.3 |
C1—N3—C11 | 121.50 (14) | C10—C9—H9 | 119.3 |
N3—C1—N1 | 119.29 (15) | C9—C10—C5 | 120.83 (15) |
N3—C1—N2 | 125.61 (14) | C9—C10—H10 | 119.6 |
N1—C1—N2 | 115.10 (13) | C5—C10—H10 | 119.6 |
N1—C2—H2A | 109.5 | C16—C11—C12 | 117.32 (14) |
N1—C2—H2B | 109.5 | C16—C11—N3 | 124.97 (13) |
H2A—C2—H2B | 109.5 | C12—C11—N3 | 117.57 (15) |
N1—C2—H2C | 109.5 | C13—C12—C11 | 121.54 (17) |
H2A—C2—H2C | 109.5 | C13—C12—H12 | 119.2 |
H2B—C2—H2C | 109.5 | C11—C12—H12 | 119.2 |
N1—C3—H3A | 109.5 | C14—C13—C12 | 120.06 (15) |
N1—C3—H3B | 109.5 | C14—C13—H13 | 120.0 |
H3A—C3—H3B | 109.5 | C12—C13—H13 | 120.0 |
N1—C3—H3C | 109.5 | C13—C14—O1 | 124.56 (14) |
H3A—C3—H3C | 109.5 | C13—C14—C15 | 119.57 (15) |
H3B—C3—H3C | 109.5 | O1—C14—C15 | 115.87 (16) |
N2—C4—H4A | 109.5 | C16—C15—C14 | 120.01 (16) |
N2—C4—H4B | 109.5 | C16—C15—H15 | 120.0 |
H4A—C4—H4B | 109.5 | C14—C15—H15 | 120.0 |
N2—C4—H4C | 109.5 | C15—C16—C11 | 121.46 (14) |
H4A—C4—H4C | 109.5 | C15—C16—H16 | 119.3 |
H4B—C4—H4C | 109.5 | C11—C16—H16 | 119.3 |
C6—C5—C10 | 117.68 (15) | C14—O1—C17 | 117.52 (16) |
C6—C5—N2 | 120.15 (13) | O1—C17—H17A | 109.5 |
C10—C5—N2 | 122.15 (13) | O1—C17—H17B | 109.5 |
C7—C6—C5 | 120.37 (14) | H17A—C17—H17B | 109.5 |
C7—C6—H6 | 119.8 | O1—C17—H17C | 109.5 |
C5—C6—H6 | 119.8 | H17A—C17—H17C | 109.5 |
C6—C7—C8 | 121.31 (16) | H17B—C17—H17C | 109.5 |
C6—C7—H7 | 119.3 | ||
C11—N3—C1—N1 | 167.43 (14) | C7—C8—C9—C10 | −0.8 (3) |
C11—N3—C1—N2 | −12.8 (2) | C8—C9—C10—C5 | −0.2 (3) |
C2—N1—C1—N3 | −12.6 (2) | C6—C5—C10—C9 | 1.3 (2) |
C3—N1—C1—N3 | 146.64 (17) | N2—C5—C10—C9 | 179.28 (15) |
C2—N1—C1—N2 | 167.62 (17) | C1—N3—C11—C16 | −44.6 (2) |
C3—N1—C1—N2 | −33.2 (2) | C1—N3—C11—C12 | 139.97 (16) |
C5—N2—C1—N3 | 128.72 (16) | C16—C11—C12—C13 | 2.3 (3) |
C4—N2—C1—N3 | −59.8 (2) | N3—C11—C12—C13 | 178.05 (15) |
C5—N2—C1—N1 | −51.48 (19) | C11—C12—C13—C14 | −1.8 (3) |
C4—N2—C1—N1 | 120.04 (16) | C12—C13—C14—O1 | −179.03 (15) |
C1—N2—C5—C6 | −27.5 (2) | C12—C13—C14—C15 | 0.7 (2) |
C4—N2—C5—C6 | 161.16 (15) | C13—C14—C15—C16 | −0.1 (2) |
C1—N2—C5—C10 | 154.51 (14) | O1—C14—C15—C16 | 179.66 (14) |
C4—N2—C5—C10 | −16.8 (2) | C14—C15—C16—C11 | 0.6 (2) |
C10—C5—C6—C7 | −1.4 (2) | C12—C11—C16—C15 | −1.6 (2) |
N2—C5—C6—C7 | −179.44 (14) | N3—C11—C16—C15 | −177.09 (14) |
C5—C6—C7—C8 | 0.4 (2) | C13—C14—O1—C17 | 5.9 (2) |
C6—C7—C8—C9 | 0.6 (3) | C15—C14—O1—C17 | −173.79 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17A···O1i | 0.96 | 2.81 | 3.502 (2) | 130 |
Symmetry code: (i) −x−1/2, −y+5/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17A···O1i | 0.96 | 2.81 | 3.502 (2) | 130 |
Symmetry code: (i) −x−1/2, −y+5/2, −z. |
Acknowledgements
The authors thank Dr B. Iliev (IoLiTec GmbH) for the synthesis of the title compound.
References
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond In Structural Chemistry and Biology, ch. 2. Oxford University Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Tanatani, A., Yamaguchi, K., Azumaya, I., Fukutomi, R., Shudo, K. & Kagechika, H. (1998). J. Am. Chem. Soc. 120, 6433–6442. Web of Science CSD CrossRef CAS Google Scholar
Tiritiris, I. & Kantlehner, W. (2013). Acta Cryst. E69, o1066. CSD CrossRef IUCr Journals Google Scholar
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The here presented title compound is similar to the structurally known compound N''-phenyl-N,N-dimethyl-N',N'-methylphenyl- guanidine (Tanatani et al., 1998). According to the structure analysis, the C1–N3 bond in the guanidine unit is 1.2889 (19) Å, indicating double bond character. The bond lengths C1–N2 = 1.408 (2) Å and C1–N1 = 1.3682 (19) Å are elongated and characteristic for C–N imine single bonds. The N–C1–N angles are 115.10 (13)° (N1–C1–N2), 125.61 (14)° (N2–C1–N3) and 119.29 (15)° (N1–C1–N3), showing a deviation of the CN3 plane from an ideal trigonal planar geometry (Fig. 1). Similar bond lengths and angles of the guanidine CN3 group have been found by structure analysis for N''-(4-carbazol-9-yl-phenyl)- N,N'-diethyl-N,N'-diphenyl-guanidine (Tiritiris & Kantlehner, 2013) and several N-methylated diphenylguanidines (Tanatani et al., 1998). Non-classical C–H···O hydrogen bonds (Desiraju & Steiner, 1999) between methyl hydrogen atoms and oxygen atoms of the methoxy groups are present [d(H···O) = 2.81 Å] (Table 1), generating centrosymmetric dimers (Fig. 2 and Fig. 3) running in the direction [101].