2,2′-(Quinoxaline-2,3-di­yl)diphenol dimethyl­formamide solvate

You, Z.-L.

doi:10.1107/S1600536809054385

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o395

https://doi.org/10.1107/S1600536809054385

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2,2′-(Quinoxaline-2,3-diyl)diphenol dimethylformamide solvate

Zhong-Lu You ^a ^*

^aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, People's Republic of China
^*Correspondence e-mail: youzhonglu@lnnu.edu.cn

(Received 14 December 2009; accepted 16 December 2009; online 16 January 2010)

In the title compound, C₂₀H₁₄N₂O₂·C₃H₇NO, the quinoxaline ring forms dihedral angles of 64.9 (2) and 30.9 (2)° with the two substituted benzene rings, which are themselves inclined at 58.4 (2)°. An intramolecular O—H⋯N hydrogen bond occurs. In the crystal, molecules are linked through intermolecular O—H⋯O hydrogen bonds.

Related literature

For details of cyanide-catalysed cyclizations via aldimine coupling, see: Reich et al. (2004 ).

Experimental

Crystal data

C₂₀H₁₄N₂O₂·C₃H₇NO
M_r = 387.43
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.759 (2) Å
b = 10.672 (2) Å
c = 19.049 (4) Å
V = 1983.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.23 × 0.21 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.980, T_max = 0.983
11593 measured reflections
4322 independent reflections
3434 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.102
S = 1.05
4322 reflections
266 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.82	1.81	2.6172 (19)	168
O1—H1⋯N1	0.82	1.94	2.647 (2)	144
Symmetry code: (i) x+1, y+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809054385/sj2713sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809054385/sj2713Isup2.hkl

checkCIF report

Comment top

Reich and co-workers have reported a series of compounds with the cyanide-catalyzed cyclizations via aldimine coupling (Reich et al., 2004), including the crystal structure of 2,2'-(quinoxaline-2,3-diyl)diphenol. In this paper, the title compound, Fig. 1, 2,2'-(quinoxaline-2,3-diyl)diphenol as the N,Ndimethylformamide solvate is formed in an aldimine coupling reaction and its structure is reported here.

In the compound, the dimethylformamide molecule is linked to the 2,2'-(quinoxaline-2,3-diyl)diphenol molecule through an intermolecular O2—H2···O3 hydrogen bond (Table 1 and Fig. 2). The quinoxaline ring forms dihedral angles of 64.9 (2) and 30.9 (2)°, respectively, with the two substituted benzene rings C9-C14 and C15-C20. The dihedral angle between the two substituted benzene rings is 58.4 (2)°. An intramolecular O1—H1···N1 hydrogen bond (Table 1) is observed in the 2,2'-(quinoxaline-2,3-diyl)diphenol molecule.

Related literature top

For details of cyanide-catalysed cyclizations via aldimine coupling, see: Reich et al. (2004).

Experimental top

The compound was prepared according to a literature procedure (Reich et al., 2004). Yellow block-shaped crystals suitable for X-ray structural determination were obtained by slow diffusion of diethyl ether into a N,Ndimethylformamide solution.

Structure description top

For details of cyanide-catalysed cyclizations via aldimine coupling, see: Reich et al. (2004).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. The molecular packing of the title compound, viewed along the c axis. Hydrogen bonds are drawn as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted.

2,2'-(Quinoxaline-2,3-diyl)diphenol dimethylformamide solvate top

Crystal data top

C₂₀H₁₄N₂O₂·C₃H₇NO	F(000) = 816
M_r = 387.43	D_x = 1.297 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4283 reflections
a = 9.759 (2) Å	θ = 2.2–25.9°
b = 10.672 (2) Å	µ = 0.09 mm⁻¹
c = 19.049 (4) Å	T = 298 K
V = 1983.9 (7) Å³	Block, yellow
Z = 4	0.23 × 0.21 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4322 independent reflections
Radiation source: fine-focus sealed tube	3434 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.980, T_max = 0.983	k = −13→10
11593 measured reflections	l = −24→19

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0529P)² + 0.0554P] where P = (F_o² + 2F_c²)/3
4322 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₁₄N₂O₂·C₃H₇NO	V = 1983.9 (7) Å³
M_r = 387.43	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.759 (2) Å	µ = 0.09 mm⁻¹
b = 10.672 (2) Å	T = 298 K
c = 19.049 (4) Å	0.23 × 0.21 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4322 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3434 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.983	R_int = 0.028
11593 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.05	Δρ_max = 0.17 e Å⁻³
4322 reflections	Δρ_min = −0.22 e Å⁻³
266 parameters

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. 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 > 2sigma(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	0.87527 (15)	0.67113 (14)	0.14671 (8)	0.0496 (3)
N2	0.61529 (14)	0.78228 (13)	0.14710 (8)	0.0494 (4)
N3	0.22105 (17)	0.28969 (17)	0.15246 (8)	0.0639 (4)
O1	1.13645 (14)	0.73589 (16)	0.15603 (8)	0.0771 (4)
H1	1.0673	0.6979	0.1681	0.116*
O2	0.83600 (16)	1.05141 (12)	0.16631 (7)	0.0695 (4)
H2	0.8792	1.1162	0.1731	0.104*
O3	0.00473 (16)	0.23971 (15)	0.18290 (9)	0.0795 (5)
C1	0.76781 (19)	0.61476 (16)	0.18052 (9)	0.0483 (4)
C2	0.63779 (19)	0.66962 (16)	0.18002 (9)	0.0486 (4)
C3	0.5287 (2)	0.61110 (19)	0.21599 (11)	0.0639 (5)
H3	0.4419	0.6472	0.2163	0.077*
C4	0.5521 (3)	0.5016 (2)	0.25004 (11)	0.0711 (6)
H4	0.4808	0.4635	0.2744	0.085*
C5	0.6807 (2)	0.4452 (2)	0.24920 (11)	0.0721 (6)
H5	0.6935	0.3691	0.2721	0.087*
C6	0.7878 (2)	0.49954 (18)	0.21537 (11)	0.0641 (5)
H6	0.8735	0.4613	0.2152	0.077*
C7	0.85364 (16)	0.77757 (15)	0.11304 (8)	0.0430 (4)
C8	0.71927 (17)	0.83557 (15)	0.11509 (8)	0.0433 (4)
C9	0.68921 (17)	0.96032 (16)	0.08390 (9)	0.0464 (4)
C10	0.75162 (19)	1.06703 (16)	0.11096 (9)	0.0528 (5)
C11	0.7215 (2)	1.18364 (17)	0.08143 (11)	0.0638 (5)
H11	0.7619	1.2557	0.0994	0.077*
C12	0.6323 (2)	1.1920 (2)	0.02580 (12)	0.0684 (6)
H12	0.6153	1.2697	0.0055	0.082*
C13	0.5678 (2)	1.0874 (2)	−0.00042 (12)	0.0676 (5)
H13	0.5062	1.0943	−0.0375	0.081*
C14	0.59580 (18)	0.97191 (18)	0.02901 (11)	0.0550 (5)
H14	0.5517	0.9009	0.0119	0.066*
C15	0.97327 (16)	0.83049 (16)	0.07577 (9)	0.0453 (4)
C16	1.10760 (18)	0.80861 (18)	0.09958 (9)	0.0529 (4)
C17	1.2185 (2)	0.8622 (2)	0.06566 (11)	0.0625 (5)
H17	1.3065	0.8496	0.0830	0.075*
C18	1.1996 (2)	0.9338 (2)	0.00648 (10)	0.0633 (5)
H18	1.2746	0.9701	−0.0157	0.076*
C19	1.0700 (2)	0.95219 (19)	−0.02002 (10)	0.0615 (5)
H19	1.0576	0.9991	−0.0607	0.074*
C20	0.95835 (19)	0.90080 (18)	0.01386 (9)	0.0523 (4)
H20	0.8712	0.9130	−0.0047	0.063*
C21	0.2074 (3)	0.4182 (2)	0.17613 (15)	0.0940 (8)
H21A	0.2527	0.4731	0.1436	0.141*
H21B	0.2483	0.4268	0.2217	0.141*
H21C	0.1120	0.4399	0.1787	0.141*
C22	0.3494 (2)	0.2530 (3)	0.11988 (14)	0.0951 (8)
H22A	0.3473	0.1649	0.1095	0.143*
H22B	0.4238	0.2704	0.1514	0.143*
H22C	0.3619	0.2993	0.0772	0.143*
C23	0.1181 (2)	0.2123 (2)	0.15743 (10)	0.0660 (5)
H23	0.1303	0.1311	0.1408	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0505 (8)	0.0416 (8)	0.0568 (8)	−0.0064 (7)	−0.0007 (7)	0.0007 (7)
N2	0.0512 (8)	0.0368 (8)	0.0601 (8)	−0.0058 (6)	0.0123 (7)	−0.0042 (6)
N3	0.0591 (10)	0.0707 (11)	0.0620 (9)	0.0009 (9)	0.0025 (8)	−0.0038 (8)
O1	0.0513 (8)	0.0915 (11)	0.0886 (10)	−0.0128 (8)	−0.0080 (7)	0.0264 (9)
O2	0.0955 (11)	0.0479 (8)	0.0652 (8)	−0.0194 (7)	−0.0054 (7)	−0.0031 (6)
O3	0.0707 (10)	0.0683 (10)	0.0996 (11)	−0.0145 (8)	0.0137 (9)	−0.0173 (8)
C1	0.0572 (10)	0.0390 (8)	0.0486 (9)	−0.0130 (8)	0.0007 (8)	−0.0009 (7)
C2	0.0576 (10)	0.0378 (9)	0.0504 (9)	−0.0130 (9)	0.0080 (8)	−0.0041 (7)
C3	0.0657 (12)	0.0562 (12)	0.0697 (12)	−0.0169 (10)	0.0190 (10)	0.0010 (9)
C4	0.0841 (16)	0.0620 (13)	0.0673 (13)	−0.0310 (12)	0.0107 (12)	0.0086 (10)
C5	0.0904 (17)	0.0550 (13)	0.0709 (12)	−0.0213 (12)	−0.0100 (12)	0.0199 (10)
C6	0.0700 (12)	0.0502 (11)	0.0721 (12)	−0.0085 (10)	−0.0075 (11)	0.0112 (10)
C7	0.0475 (9)	0.0362 (8)	0.0454 (8)	−0.0051 (7)	0.0043 (7)	−0.0075 (7)
C8	0.0478 (8)	0.0343 (8)	0.0478 (8)	−0.0065 (7)	0.0088 (8)	−0.0061 (7)
C9	0.0470 (9)	0.0364 (8)	0.0559 (9)	−0.0021 (7)	0.0157 (8)	−0.0025 (7)
C10	0.0645 (11)	0.0408 (9)	0.0530 (10)	−0.0061 (8)	0.0175 (9)	−0.0023 (8)
C11	0.0821 (13)	0.0348 (9)	0.0747 (13)	−0.0040 (10)	0.0253 (11)	−0.0012 (9)
C12	0.0776 (14)	0.0490 (12)	0.0786 (14)	0.0106 (11)	0.0244 (12)	0.0142 (10)
C13	0.0598 (12)	0.0668 (14)	0.0762 (13)	0.0110 (11)	0.0068 (10)	0.0094 (11)
C14	0.0470 (10)	0.0502 (11)	0.0679 (11)	0.0005 (8)	0.0102 (9)	−0.0015 (9)
C15	0.0478 (9)	0.0362 (9)	0.0519 (9)	−0.0041 (7)	0.0088 (8)	−0.0068 (7)
C16	0.0544 (10)	0.0481 (10)	0.0564 (10)	−0.0085 (8)	0.0057 (8)	−0.0063 (8)
C17	0.0482 (10)	0.0697 (13)	0.0696 (12)	−0.0101 (10)	0.0085 (10)	−0.0117 (10)
C18	0.0584 (12)	0.0635 (13)	0.0681 (12)	−0.0121 (10)	0.0250 (10)	−0.0117 (10)
C19	0.0715 (13)	0.0592 (12)	0.0539 (10)	−0.0016 (10)	0.0217 (9)	−0.0018 (9)
C20	0.0548 (10)	0.0509 (10)	0.0513 (10)	0.0036 (9)	0.0120 (8)	−0.0033 (8)
C21	0.0760 (15)	0.0876 (18)	0.119 (2)	−0.0221 (15)	0.0046 (15)	−0.0334 (16)
C22	0.0715 (15)	0.128 (2)	0.0853 (16)	0.0205 (16)	0.0133 (12)	0.0106 (16)
C23	0.0809 (15)	0.0573 (13)	0.0598 (12)	0.0019 (11)	0.0001 (11)	−0.0042 (9)

Geometric parameters (Å, º) top

N1—C7	1.321 (2)	C9—C14	1.393 (3)
N1—C1	1.370 (2)	C10—C11	1.397 (3)
N2—C8	1.313 (2)	C11—C12	1.374 (3)
N2—C2	1.374 (2)	C11—H11	0.9300
N3—C23	1.304 (3)	C12—C13	1.376 (3)
N3—C21	1.450 (3)	C12—H12	0.9300
N3—C22	1.452 (3)	C13—C14	1.381 (3)
O1—C16	1.356 (2)	C13—H13	0.9300
O1—H1	0.8200	C14—H14	0.9300
O2—C10	1.348 (2)	C15—C20	1.405 (2)
O2—H2	0.8200	C15—C16	1.407 (3)
O3—C23	1.243 (2)	C16—C17	1.384 (3)
C1—C2	1.398 (3)	C17—C18	1.375 (3)
C1—C6	1.411 (3)	C17—H17	0.9300
C2—C3	1.412 (2)	C18—C19	1.376 (3)
C3—C4	1.356 (3)	C18—H18	0.9300
C3—H3	0.9300	C19—C20	1.380 (3)
C4—C5	1.393 (3)	C19—H19	0.9300
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.358 (3)	C21—H21A	0.9600
C5—H5	0.9300	C21—H21B	0.9600
C6—H6	0.9300	C21—H21C	0.9600
C7—C8	1.451 (2)	C22—H22A	0.9600
C7—C15	1.479 (2)	C22—H22B	0.9600
C8—C9	1.487 (2)	C22—H22C	0.9600
C9—C10	1.391 (2)	C23—H23	0.9300

C7—N1—C1	118.91 (15)	C11—C12—H12	119.4
C8—N2—C2	117.87 (15)	C13—C12—H12	119.4
C23—N3—C21	120.37 (19)	C12—C13—C14	119.1 (2)
C23—N3—C22	121.7 (2)	C12—C13—H13	120.5
C21—N3—C22	117.9 (2)	C14—C13—H13	120.5
C16—O1—H1	109.5	C13—C14—C9	120.89 (19)
C10—O2—H2	109.5	C13—C14—H14	119.6
N1—C1—C2	120.52 (15)	C9—C14—H14	119.6
N1—C1—C6	119.86 (18)	C20—C15—C16	117.11 (15)
C2—C1—C6	119.61 (17)	C20—C15—C7	121.67 (15)
N2—C2—C1	120.99 (15)	C16—C15—C7	121.18 (15)
N2—C2—C3	119.22 (18)	O1—C16—C17	116.38 (17)
C1—C2—C3	119.74 (17)	O1—C16—C15	122.97 (16)
C4—C3—C2	119.1 (2)	C17—C16—C15	120.65 (17)
C4—C3—H3	120.4	C18—C17—C16	120.49 (19)
C2—C3—H3	120.4	C18—C17—H17	119.8
C3—C4—C5	121.28 (19)	C16—C17—H17	119.8
C3—C4—H4	119.4	C17—C18—C19	120.25 (18)
C5—C4—H4	119.4	C17—C18—H18	119.9
C6—C5—C4	121.0 (2)	C19—C18—H18	119.9
C6—C5—H5	119.5	C18—C19—C20	119.84 (19)
C4—C5—H5	119.5	C18—C19—H19	120.1
C5—C6—C1	119.3 (2)	C20—C19—H19	120.1
C5—C6—H6	120.4	C19—C20—C15	121.53 (18)
C1—C6—H6	120.4	C19—C20—H20	119.2
N1—C7—C8	119.88 (14)	C15—C20—H20	119.2
N1—C7—C15	115.80 (15)	N3—C21—H21A	109.5
C8—C7—C15	124.31 (15)	N3—C21—H21B	109.5
N2—C8—C7	121.74 (15)	H21A—C21—H21B	109.5
N2—C8—C9	114.88 (15)	N3—C21—H21C	109.5
C7—C8—C9	123.34 (14)	H21A—C21—H21C	109.5
C10—C9—C14	119.49 (17)	H21B—C21—H21C	109.5
C10—C9—C8	119.91 (16)	N3—C22—H22A	109.5
C14—C9—C8	120.57 (15)	N3—C22—H22B	109.5
O2—C10—C9	117.14 (15)	H22A—C22—H22B	109.5
O2—C10—C11	123.62 (17)	N3—C22—H22C	109.5
C9—C10—C11	119.22 (18)	H22A—C22—H22C	109.5
C12—C11—C10	120.10 (19)	H22B—C22—H22C	109.5
C12—C11—H11	120.0	O3—C23—N3	124.4 (2)
C10—C11—H11	120.0	O3—C23—H23	117.8
C11—C12—C13	121.16 (19)	N3—C23—H23	117.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.82	1.81	2.6172 (19)	168
O1—H1···N1	0.82	1.94	2.647 (2)	144

Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₄N₂O₂·C₃H₇NO
M_r	387.43
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	9.759 (2), 10.672 (2), 19.049 (4)
V (Å³)	1983.9 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.980, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	11593, 4322, 3434
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.102, 1.05
No. of reflections	4322
No. of parameters	266
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.22

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.82	1.81	2.6172 (19)	168.1
O1—H1···N1	0.82	1.94	2.647 (2)	144.1

Symmetry code: (i) x+1, y+1, z.

Acknowledgements

The author acknowledges Dalian University of Technology for financial support.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Reich, B. J. E., Justice, A. K., Beckstead, B. T., Reibenspies, J. H. & Miller, S. A. (2004). J. Org. Chem. 69, 1357–1359. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar