N′′-(4-Meth­oxy­phen­yl)-N,N,N′-trimethyl-N′-phenyl­guanidine

Tiritiris, I.; Frey, W.; Kantlehner, W.

doi:10.1107/S1600536814005819

organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o460

doi:10.1107/S1600536814005819

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N′′-(4-Methoxyphenyl)-N,N,N′-trimethyl-N′-phenylguanidine

Ioannis Tiritiris,^a Wolfgang Frey ^b and Willi Kantlehner ^a ^*

^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

(Received 11 March 2014; accepted 14 March 2014; online 22 March 2014)

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 crystal structure of N′′-(4-carbazol-9-ylphenyl)-N,N′-diethyl-N,N′-diphenylguanidine, see: Tiritiris & Kantlehner (2013 ).

Experimental

Crystal data

C₁₇H₂₁N₃O
M_r = 283.37
Monoclinic, C 2/c
a = 26.691 (4) Å
b = 7.5135 (7) Å
c = 19.361 (2) Å
β = 125.412 (8)°
V = 3164.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.45 × 0.30 × 0.20 mm

Data collection

Nicolet P3/F diffractometer
3817 measured reflections
3817 independent reflections
2770 reflections with I > 2σ(I)
3 standard reflections every 50 reflections intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.161
S = 1.04
3817 reflections
195 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ .

Data collection: XSCANS (Siemens, 1996 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814005819/kp2467sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814005819/kp2467Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814005819/kp2467Isup3.cml

checkCIF report

Comment top

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].

Related literature top

For the crystal structures of N-methylated diphenylguanidines, see: Tanatani et al. (1998). For non-classical hydrogen bonds, see: Desiraju & Steiner (1999). For the crystal structure of N''-(4-carbazol-9-ylphenyl)-N,N'-diethyl-N,N'-diphenylguanidine, see: Tiritiris & Kantlehner (2013).

Experimental top

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.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: 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).

Figures top

	Fig. 1. The structure of the title compound with atom labels and 50% probability displacement ellipsoids.
	Fig. 2. Non-classical C–H···O hydrogen bonds (indicated by dashed lines) between the methyl hydrogen atoms (H17A) and oxygen atoms (O1) of the methoxy groups, forming a centrosymmetric dimer.
	Fig. 3. Packing diagram of the title compound in ac-plane. The hydrogen bonds are indicated by dashed lines.

N''-(4-Methoxyphenyl)-N,N,N'-trimethyl-N'-phenylguanidine top

Crystal data top

C₁₇H₂₁N₃O	F(000) = 1216
M_r = 283.37	D_x = 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

Data collection top

Nicolet P3/F diffractometer	R_int = 0.000
Radiation source: sealed tube	θ_max = 28.0°, θ_min = 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 top

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(F_o²) + (0.0907P)² + 0.4749P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3817 reflections	Δρ_max = 0.21 e Å⁻³
195 parameters	Δρ_min = −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)

Crystal data top

C₁₇H₂₁N₃O	V = 3164.4 (7) Å³
M_r = 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)°

Data collection top

Nicolet P3/F diffractometer	R_int = 0.000
3817 measured reflections	3 standard reflections every 50 reflections
3817 independent reflections	intensity decay: 2%
2770 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.04	Δρ_max = 0.21 e Å⁻³
3817 reflections	Δρ_min = −0.16 e Å⁻³
195 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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

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