(1S,4R)-1,11,11-Trimethyl-1,2,3,4-tetra­hydro-1,4-methano­phenazine N5-oxide

Quirion, K.; Crundwell, G.; Glagovich, N.M.

doi:10.1107/S241431461800531X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 4| April 2018| x180531

https://doi.org/10.1107/S241431461800531X

Open

access

(1S,4R)-1,11,11-Trimethyl-1,2,3,4-tetrahydro-1,4-methanophenazine N⁵-oxide

Kevin Quirion,^a Guy Crundwell ^a ^* and Neil M. Glagovich ^a

^aDepartment of Chemistry & Biochemistry, Central Connecticut State University, New Britain, CT 06053, USA
^*Correspondence e-mail: crundwellg@mail.ccsu.edu

Edited by M. Zeller, Purdue University, USA (Received 23 March 2018; accepted 3 April 2018; online 17 April 2018)

The title compound, C₁₆H₁₈N₂O, was synthesized via reaction of (1S,4R)-1,2,3,4-tetrahydro-1,11,11-trimethyl-1,4-methanophenazine with 3-chloroperbenzoic acid in dichloromethane. The absolute configuration for the product was assigned based on the stereochemistry of the camphorquinone reactant.

Keywords: crystal structure; N⁵-oxide.

CCDC reference: 1834618

Structure description

In the molecule (Fig. 1), all bond lengths and angles are within expected values. The conformation of the product was assigned based upon the stereochemistry of the camphorquinone reactant. No classical hydrogen bonds are present.

Figure 1
A view of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Glisic et al. (2016 ) crystallized several chiral 1,2,3,4-tetrahydro-1,11,11-trimethyl-1,4-methanophenazine ligands with Au⁺³. Steel & Fitchett (2000 , 2006 ) illustrate the use of stereochemically active quinoxalines in extended metal–ligand networks.

Synthesis and crystallization

(1S,4R)-1,2,3,4-Tetrahydro-1,11,11-trimethyl-1,4-methanophenazine was synthesized by the condensation reaction of a diketone with a diamine in acid. To a 50 mL round-bottom flask were added (1S)-(+)-camphorquinone (3.1 g, 18.5 mmol), o-phenylenediamine (2.0 g, 18.5 mmol), and 20 ml of glacial acetic acid. This solution was then heated to boiling and held at reflux for 16 h. The resulting brown-colored solution was poured over 550 ml of cold water, neutralized with sodium carbonate, and isolated via vacuum filtration, which produced a light-brown solid. A hot gravity filtration with petroleum ether and activated charcoal, after evaporation of the petroleum ether, yielded 3.3 g of (1S,4R)-1,2,3,4-tetrahydro-1,11,11-trimethyl-1,4-methanophenazine (75%).

(1S,4R)-1,2,3,4-Tetrahydro-1,11,11-trimethyl-1,4-methanophenazine (3.3 g, 13.8 mmol) and 3-chloroperbenzoic acid (4.8 g, 27.6 mmol) were dissolved in dichloromethane and stirred at room temperature for 24 h. Several spots were observed during TLC, suggesting the other possible oxide was also formed. The product was isolated via column chromatography (SiO₂, 50% dichloromethane/50% ethyl acetate, R_f = 0.5) to yield 1.77 g of the title compound (50%), m.p. 433.2 K. ATR–IR (cm⁻¹): 2971, 1496, 780; ¹H NMR (300 MHz, CDCl₃): δ 8.653 (dd, 1H, J = 8.3 Hz, 1.5 Hz), 8.113 (dd, 1H, J = 7.7 Hz, 1.7 Hz), 7.763 (dt, 1H, J = 7.6 Hz, 1.8 Hz), 7.701 (dt, 1H, J = 7.6 Hz, 1.8 Hz), 3.674 (d, 1H, J = 4.17 Hz), 2.310 (m, 1H), 2.087 (m, 1H), 1.498 (m, 2H), 1.459 (s, 3H), 1.142 (s, 3H), 0.756 (s, 3H); ¹³C NMR (300 MHz, CDCl₃): δ 168.06, 144.26, 130.15, 129.30, 128.40, 118.71, 77.23, 76.51, 55.00, 54.71, 47.92, 32.37, 23.78, 20.32, 18.40, 10.14; UV/Vis (CH₂Cl₂; λ_max) 315 nm.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Reflections affected by the beam stop were omitted from the refinement.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₂O
M_r	254.32
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	10.6779 (3), 10.7120 (3), 11.5207 (3)
V (Å³)	1317.76 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.34 × 0.28 × 0.15

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.801, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	33091, 4925, 4043
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.779

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.132, 0.93
No. of reflections	4925
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.14
Absolute structure	Flack x determined using 1516 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.1 (4)
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and OLEX2 (Bourhis et al., 2015 ).

Structural data

CCDC reference: 1834618

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461800531X/zl4024sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461800531X/zl4024Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: OLEX2 (Bourhis et al., 2015).

(1S,4R)-1,11,11-Trimethyl-1,2,3,4-tetrahydro-1,4-methanophenazine N⁵-oxide top

Crystal data top

C₁₆H₁₈N₂O	D_x = 1.282 Mg m⁻³
M_r = 254.32	Melting point: 433.2 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 10.6779 (3) Å	Cell parameters from 9304 reflections
b = 10.7120 (3) Å	θ = 5.1–31.4°
c = 11.5207 (3) Å	µ = 0.08 mm⁻¹
V = 1317.76 (6) Å³	T = 298 K
Z = 4	Plate, yellow
F(000) = 544	0.34 × 0.28 × 0.15 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	4925 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4043 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 16.1790 pixels mm^-1	θ_max = 33.6°, θ_min = 5.2°
ω scans	h = −16→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −16→16
T_min = 0.801, T_max = 1.000	l = −17→17
33091 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.0978P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.132	(Δ/σ)_max < 0.001
S = 0.93	Δρ_max = 0.24 e Å⁻³
4925 reflections	Δρ_min = −0.14 e Å⁻³
175 parameters	Absolute structure: Flack x determined using 1516 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.1 (4)

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.

Refinement. H atoms were included in calculated positions with C—H distances of 0.93 Å, 0.96 Å, 0.97 Å, and 0.98 Å based upon type of carbon and were included in the refinement in riding motion approximation with U_iso = 1.2 U_eq for CH and CH₂ and 1.5 U_eq for CH₃ groups, respectively. of the carrier atom.

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

	x	y	z	U_iso*/U_eq
C1	0.39348 (13)	0.85071 (12)	0.83151 (13)	0.0297 (3)
C2	0.20009 (13)	0.95167 (14)	0.82727 (14)	0.0332 (3)
C3	0.07772 (15)	0.96131 (18)	0.78408 (17)	0.0435 (4)
H3	0.0479	0.9039	0.7302	0.052*
C4	0.00214 (16)	1.0572 (2)	0.82275 (19)	0.0510 (4)
H4	−0.0782	1.0660	0.7926	0.061*
C5	0.04485 (18)	1.14087 (18)	0.9064 (2)	0.0499 (4)
H5	−0.0086	1.2027	0.9339	0.060*
C6	0.16511 (17)	1.13333 (16)	0.94883 (18)	0.0439 (4)
H6	0.1926	1.1901	1.0044	0.053*
C7	0.24709 (14)	1.03897 (13)	0.90783 (14)	0.0343 (3)
C8	0.43617 (13)	0.94590 (12)	0.90722 (13)	0.0301 (3)
C9	0.56940 (13)	0.91155 (13)	0.93723 (14)	0.0312 (3)
C10	0.55122 (17)	0.79711 (15)	1.01944 (15)	0.0401 (3)
H10A	0.6299	0.7736	1.0555	0.048*
H10B	0.4906	0.8158	1.0797	0.048*
C11	0.50284 (17)	0.69165 (14)	0.93913 (15)	0.0400 (3)
H11A	0.4211	0.6624	0.9637	0.048*
H11B	0.5606	0.6217	0.9377	0.048*
C12	0.49567 (13)	0.75654 (13)	0.81835 (12)	0.0308 (3)
H12	0.4898	0.7012	0.7508	0.037*
C13	0.61140 (13)	0.84520 (13)	0.82243 (13)	0.0316 (3)
C14	0.61709 (19)	0.93181 (18)	0.71758 (16)	0.0450 (4)
H14A	0.6400	0.8847	0.6500	0.068*
H14B	0.6783	0.9958	0.7311	0.068*
H14C	0.5365	0.9695	0.7057	0.068*
C15	0.73576 (16)	0.77619 (18)	0.8335 (2)	0.0483 (4)
H15A	0.7303	0.7162	0.8953	0.073*
H15B	0.8012	0.8349	0.8503	0.073*
H15C	0.7540	0.7340	0.7620	0.073*
C16	0.64970 (16)	1.01615 (17)	0.98404 (18)	0.0445 (4)
H16A	0.6561	1.0811	0.9269	0.067*
H16B	0.7318	0.9848	1.0016	0.067*
H16C	0.6123	1.0491	1.0534	0.067*
N1	0.27666 (11)	0.85118 (11)	0.79122 (11)	0.0314 (3)
N2	0.36923 (12)	1.03772 (12)	0.94822 (12)	0.0356 (3)
O1	0.23308 (12)	0.76566 (11)	0.72480 (12)	0.0454 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0288 (6)	0.0278 (6)	0.0326 (6)	−0.0004 (5)	−0.0027 (5)	−0.0014 (5)
C2	0.0283 (6)	0.0345 (7)	0.0368 (7)	0.0008 (5)	0.0002 (5)	0.0076 (6)
C3	0.0321 (7)	0.0500 (9)	0.0484 (9)	0.0001 (7)	−0.0059 (6)	0.0099 (8)
C4	0.0306 (7)	0.0597 (11)	0.0628 (11)	0.0084 (7)	−0.0004 (7)	0.0196 (9)
C5	0.0402 (8)	0.0477 (10)	0.0619 (11)	0.0136 (8)	0.0118 (8)	0.0140 (8)
C6	0.0418 (8)	0.0401 (9)	0.0498 (9)	0.0100 (7)	0.0081 (7)	0.0017 (7)
C7	0.0329 (6)	0.0318 (6)	0.0382 (7)	0.0030 (6)	0.0032 (6)	0.0030 (5)
C8	0.0287 (6)	0.0277 (6)	0.0341 (6)	−0.0005 (5)	−0.0021 (5)	−0.0030 (5)
C9	0.0280 (6)	0.0299 (6)	0.0356 (7)	0.0004 (5)	−0.0046 (5)	−0.0040 (5)
C10	0.0475 (8)	0.0399 (7)	0.0330 (7)	0.0005 (7)	−0.0067 (6)	0.0036 (6)
C11	0.0495 (9)	0.0295 (6)	0.0409 (8)	−0.0024 (6)	−0.0027 (7)	0.0049 (6)
C12	0.0331 (6)	0.0254 (6)	0.0341 (6)	−0.0002 (5)	−0.0021 (5)	−0.0032 (5)
C13	0.0295 (6)	0.0298 (6)	0.0355 (6)	0.0002 (5)	0.0003 (5)	−0.0022 (5)
C14	0.0498 (9)	0.0449 (8)	0.0404 (8)	−0.0058 (7)	0.0075 (7)	0.0051 (7)
C15	0.0342 (7)	0.0510 (10)	0.0598 (11)	0.0100 (7)	−0.0009 (7)	−0.0119 (8)
C16	0.0372 (7)	0.0410 (8)	0.0553 (10)	−0.0044 (6)	−0.0104 (7)	−0.0125 (7)
N1	0.0298 (5)	0.0319 (6)	0.0324 (6)	−0.0039 (4)	−0.0026 (4)	0.0014 (5)
N2	0.0346 (6)	0.0318 (6)	0.0404 (6)	0.0032 (5)	−0.0012 (5)	−0.0060 (5)
O1	0.0430 (6)	0.0453 (6)	0.0480 (6)	−0.0082 (5)	−0.0101 (5)	−0.0100 (6)

Geometric parameters (Å, º) top

C1—N1	1.3310 (17)	C10—C11	1.549 (2)
C1—C8	1.4172 (19)	C10—H10A	0.9700
C1—C12	1.4937 (19)	C10—H10B	0.9700
C2—C3	1.402 (2)	C11—C12	1.557 (2)
C2—C7	1.410 (2)	C11—H11A	0.9700
C2—N1	1.4142 (19)	C11—H11B	0.9700
C3—C4	1.380 (3)	C12—C13	1.559 (2)
C3—H3	0.9300	C12—H12	0.9800
C4—C5	1.393 (3)	C13—C14	1.524 (2)
C4—H4	0.9300	C13—C15	1.525 (2)
C5—C6	1.376 (3)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.418 (2)	C14—H14C	0.9600
C6—H6	0.9300	C15—H15A	0.9600
C7—N2	1.385 (2)	C15—H15B	0.9600
C8—N2	1.3045 (18)	C15—H15C	0.9600
C8—C9	1.5095 (19)	C16—H16A	0.9600
C9—C16	1.510 (2)	C16—H16B	0.9600
C9—C10	1.561 (2)	C16—H16C	0.9600
C9—C13	1.567 (2)	N1—O1	1.2811 (15)

N1—C1—C8	120.89 (12)	C12—C11—H11A	111.2
N1—C1—C12	130.68 (13)	C10—C11—H11B	111.2
C8—C1—C12	108.26 (11)	C12—C11—H11B	111.2
C3—C2—C7	121.10 (15)	H11A—C11—H11B	109.1
C3—C2—N1	119.38 (15)	C1—C12—C11	104.29 (12)
C7—C2—N1	119.50 (12)	C1—C12—C13	99.47 (11)
C4—C3—C2	119.03 (18)	C11—C12—C13	101.89 (12)
C4—C3—H3	120.5	C1—C12—H12	116.3
C2—C3—H3	120.5	C11—C12—H12	116.3
C3—C4—C5	120.72 (16)	C13—C12—H12	116.3
C3—C4—H4	119.6	C14—C13—C15	109.07 (14)
C5—C4—H4	119.6	C14—C13—C12	112.23 (12)
C6—C5—C4	120.90 (17)	C15—C13—C12	113.41 (12)
C6—C5—H5	119.6	C14—C13—C9	113.84 (12)
C4—C5—H5	119.6	C15—C13—C9	113.47 (13)
C5—C6—C7	119.96 (18)	C12—C13—C9	94.29 (11)
C5—C6—H6	120.0	C13—C14—H14A	109.5
C7—C6—H6	120.0	C13—C14—H14B	109.5
N2—C7—C2	123.37 (13)	H14A—C14—H14B	109.5
N2—C7—C6	118.45 (15)	C13—C14—H14C	109.5
C2—C7—C6	118.18 (15)	H14A—C14—H14C	109.5
N2—C8—C1	126.10 (13)	H14B—C14—H14C	109.5
N2—C8—C9	128.12 (13)	C13—C15—H15A	109.5
C1—C8—C9	105.59 (11)	C13—C15—H15B	109.5
C8—C9—C16	115.85 (12)	H15A—C15—H15B	109.5
C8—C9—C10	102.30 (12)	C13—C15—H15C	109.5
C16—C9—C10	115.88 (14)	H15A—C15—H15C	109.5
C8—C9—C13	100.78 (11)	H15B—C15—H15C	109.5
C16—C9—C13	118.38 (13)	C9—C16—H16A	109.5
C10—C9—C13	101.04 (11)	C9—C16—H16B	109.5
C11—C10—C9	104.58 (12)	H16A—C16—H16B	109.5
C11—C10—H10A	110.8	C9—C16—H16C	109.5
C9—C10—H10A	110.8	H16A—C16—H16C	109.5
C11—C10—H10B	110.8	H16B—C16—H16C	109.5
C9—C10—H10B	110.8	O1—N1—C1	123.09 (12)
H10A—C10—H10B	108.9	O1—N1—C2	120.65 (12)
C10—C11—C12	102.98 (12)	C1—N1—C2	116.25 (12)
C10—C11—H11A	111.2	C8—N2—C7	113.68 (13)

C7—C2—C3—C4	−0.9 (2)	C10—C11—C12—C1	−67.26 (15)
N1—C2—C3—C4	177.78 (15)	C10—C11—C12—C13	35.86 (15)
C2—C3—C4—C5	−2.2 (3)	C1—C12—C13—C14	−66.52 (15)
C3—C4—C5—C6	2.8 (3)	C11—C12—C13—C14	−173.42 (13)
C4—C5—C6—C7	−0.3 (3)	C1—C12—C13—C15	169.31 (15)
C3—C2—C7—N2	−176.30 (15)	C11—C12—C13—C15	62.41 (16)
N1—C2—C7—N2	5.0 (2)	C1—C12—C13—C9	51.42 (12)
C3—C2—C7—C6	3.2 (2)	C11—C12—C13—C9	−55.48 (13)
N1—C2—C7—C6	−175.42 (14)	C8—C9—C13—C14	65.83 (15)
C5—C6—C7—N2	176.95 (16)	C16—C9—C13—C14	−61.56 (18)
C5—C6—C7—C2	−2.6 (2)	C10—C9—C13—C14	170.79 (13)
N1—C1—C8—N2	2.7 (2)	C8—C9—C13—C15	−168.62 (13)
C12—C1—C8—N2	−173.03 (15)	C16—C9—C13—C15	63.99 (18)
N1—C1—C8—C9	177.97 (13)	C10—C9—C13—C15	−63.66 (15)
C12—C1—C8—C9	2.21 (16)	C8—C9—C13—C12	−50.78 (12)
N2—C8—C9—C16	−24.0 (2)	C16—C9—C13—C12	−178.17 (13)
C1—C8—C9—C16	160.86 (15)	C10—C9—C13—C12	54.18 (12)
N2—C8—C9—C10	102.99 (17)	C8—C1—N1—O1	−178.35 (13)
C1—C8—C9—C10	−72.13 (14)	C12—C1—N1—O1	−3.7 (2)
N2—C8—C9—C13	−153.07 (15)	C8—C1—N1—C2	0.7 (2)
C1—C8—C9—C13	31.82 (14)	C12—C1—N1—C2	175.35 (14)
C8—C9—C10—C11	69.77 (15)	C3—C2—N1—O1	−3.8 (2)
C16—C9—C10—C11	−163.24 (14)	C7—C2—N1—O1	174.85 (13)
C13—C9—C10—C11	−33.97 (15)	C3—C2—N1—C1	177.13 (14)
C9—C10—C11—C12	−0.94 (17)	C7—C2—N1—C1	−4.19 (19)
N1—C1—C12—C11	−105.67 (18)	C1—C8—N2—C7	−2.1 (2)
C8—C1—C12—C11	69.52 (14)	C9—C8—N2—C7	−176.23 (14)
N1—C1—C12—C13	149.38 (16)	C2—C7—N2—C8	−1.8 (2)
C8—C1—C12—C13	−35.42 (14)	C6—C7—N2—C8	178.64 (14)

Funding information

This research was funded by a CCSU–AAUP research grant.

References

Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Glisic, B. D., Hoffmann, M., Warzajtis, B., Gencic, M. S., Blagojevic, P. D., Radulovic, N. S., Rychlewska, U. & Djuran, M. I. (2016). Polyhedron, 105, 137–149. CAS Google Scholar
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Steel, P. J. & Fitchett, C. M. (2000). New J. Chem. 24, 945–947. Google Scholar
Steel, P. J. & Fitchett, C. M. (2006). Dalton Trans. pp. 4886–4888. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.