4-(Diethyl­amino)­salicyl­aldehyde azine

Qiu, J.-B.; Yin, B.-Z.

doi:10.1107/S1600536811013237

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1092

doi:10.1107/S1600536811013237

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4-(Diethylamino)salicylaldehyde azine

Jing-Bo Qiu ^a and Bing-Zhu Yin ^a ^*

^aKey Laboratory of Natural Resources of Changbai Mountain & Functional Molecules (Yanbian University), Ministry of Eduction, Yanji 133002, People's Republic of China
^*Correspondence e-mail: zqcong@ybu.edu.cn

(Received 7 April 2011; accepted 8 April 2011; online 13 April 2011)

The title compound, C₂₂H₃₀N₄O₂, has a crystallographic inversion center located at the mid-point of the N—N single bond. Apart from the four ethyl C atoms, the non-H atoms are nearly coplanar with a mean deviation of 0.0596 (2) Å. An intramolecular O—H⋯N hydrogen bond occurs. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into layers parallel to (100).

Related literature

For the synthesis, see Tang et al. (2009 ). For a related structure, see Gil et al. (2010 ). For applications of photochromic aromatic Schiff base molecules as molecular memories and switches, see Sliwa et al. (2005 ).

Experimental

Crystal data

C₂₂H₃₀N₄O₂
M_r = 382.50
Monoclinic, P 2₁ /c
a = 8.736 (5) Å
b = 7.809 (5) Å
c = 16.122 (10) Å
β = 103.57 (2)°
V = 1069.1 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 290 K
0.15 × 0.14 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.988, T_max = 0.991
9903 measured reflections
2431 independent reflections
1227 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.228
S = 1.10
2431 reflections
129 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O1ⁱ	0.97	2.64	3.481 (5)	145
O1—H1⋯N1	0.85	1.88	2.640 (3)	149
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku Corporation, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013237/ng5147sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013237/ng5147Isup2.hkl

checkCIF report

Comment top

Salicylaldehyde azine belongs to the photochromic aromatic schiff base molecules with two intramolecular hydrogen bonds (Gil et al., 2010). The photochromism of the molecules, owing to enol-keto intramolecular tautomerism, attracts much interest because of possible applications, for example, in molecular memories and switches (Sliwa et al., 2005). Herein, we report the crystal structure of the title compound.

The title compound, as shown in Fig. 1, all bond lengths and angles are in the normal ranges. Except for four carbon atoms, all the other non-hydrogen atoms nearly lie on the same plane. The intramolecular O—H···N and intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into layers prallel to (100).

Related literature top

For the synthesis, see Tang et al. (2009). For a related structure, see Gil et al. (2010). For applications of photochromic aromatic Schiff base molecules as molecular memories and switches, see Sliwa et al. (2005).

Experimental top

The title compound was prepared according to the literature (Tang et al., 2009). Single crystals suitable for X-ray diffraction were prepared by slow evaporation a mixture of dichloromethane and petroleum (60–90 °C) at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The crystal structure of the title compound, with the atom numbering. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level. [Symmetry code: A: 1 - x, 1 - y, 1 - z]

4-(Diethylamino)-2-hydroxybenzaldehyde azine top

Crystal data top

C₂₂H₃₀N₄O₂	F(000) = 412
M_r = 382.50	D_x = 1.188 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5162 reflections
a = 8.736 (5) Å	θ = 3.1–27.7°
b = 7.809 (5) Å	µ = 0.08 mm⁻¹
c = 16.122 (10) Å	T = 290 K
β = 103.57 (2)°	Block, yellow
V = 1069.1 (11) Å³	0.15 × 0.14 × 0.12 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	2431 independent reflections
Radiation source: fine-focus sealed tube	1227 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.988, T_max = 0.991	k = −10→10
9903 measured reflections	l = −20→20

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.228	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0919P)² + 0.3133P] where P = (F_o² + 2F_c²)/3
2431 reflections	(Δ/σ)_max = 0.003
129 parameters	Δρ_max = 0.45 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₂H₃₀N₄O₂	V = 1069.1 (11) Å³
M_r = 382.50	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.736 (5) Å	µ = 0.08 mm⁻¹
b = 7.809 (5) Å	T = 290 K
c = 16.122 (10) Å	0.15 × 0.14 × 0.12 mm
β = 103.57 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2431 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1227 reflections with I > 2σ(I)
T_min = 0.988, T_max = 0.991	R_int = 0.046
9903 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	1 restraint
wR(F²) = 0.228	H-atom parameters constrained
S = 1.10	Δρ_max = 0.45 e Å⁻³
2431 reflections	Δρ_min = −0.25 e Å⁻³
129 parameters

Special details top

Experimental. (See detailed section in the paper)

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
O1	0.2021 (2)	0.6394 (3)	0.57469 (13)	0.0809 (8)
H1	0.2663	0.6244	0.5433	0.121*
C1	0.4983 (3)	0.4599 (4)	0.60317 (18)	0.0556 (7)
H1A	0.5914	0.3972	0.6165	0.067*
C2	0.4129 (3)	0.4858 (3)	0.66828 (16)	0.0489 (7)
C3	0.4698 (3)	0.4235 (4)	0.75059 (18)	0.0602 (8)
H3	0.5638	0.3624	0.7625	0.072*
C4	0.3937 (3)	0.4480 (4)	0.81492 (18)	0.0653 (9)
H4	0.4360	0.4031	0.8688	0.078*
C5	0.2503 (3)	0.5418 (4)	0.79966 (18)	0.0575 (7)
C6	0.1898 (3)	0.5998 (4)	0.71712 (17)	0.0558 (7)
H6	0.0939	0.6573	0.7048	0.067*
C7	0.2678 (3)	0.5745 (4)	0.65257 (17)	0.0537 (7)
C8	0.2343 (5)	0.5030 (6)	0.9510 (2)	0.0878 (11)
H8A	0.3481	0.5128	0.9679	0.105*
H8B	0.1906	0.5672	0.9915	0.105*
C9	0.1893 (5)	0.3226 (6)	0.9530 (3)	0.1028 (14)
H9A	0.0770	0.3142	0.9441	0.154*
H9B	0.2387	0.2742	1.0074	0.154*
H9C	0.2226	0.2614	0.9086	0.154*
C10	0.0357 (4)	0.6857 (5)	0.8511 (2)	0.0735 (9)
H10A	0.0461	0.7776	0.8123	0.088*
H10B	0.0312	0.7373	0.9052	0.088*
C11	−0.1157 (4)	0.5939 (5)	0.8161 (2)	0.0858 (11)
H11A	−0.1144	0.5460	0.7615	0.129*
H11B	−0.2018	0.6729	0.8100	0.129*
H11C	−0.1283	0.5038	0.8545	0.129*
N1	0.4511 (3)	0.5198 (3)	0.52728 (15)	0.0589 (7)
N2	0.1766 (3)	0.5765 (4)	0.86429 (15)	0.0752 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0839 (14)	0.1066 (19)	0.0616 (13)	0.0420 (13)	0.0362 (11)	0.0333 (12)
C1	0.0554 (15)	0.0532 (17)	0.0651 (18)	0.0019 (13)	0.0280 (13)	0.0001 (13)
C2	0.0482 (14)	0.0504 (16)	0.0521 (15)	−0.0016 (12)	0.0197 (11)	0.0012 (12)
C3	0.0454 (14)	0.076 (2)	0.0619 (18)	0.0117 (13)	0.0182 (13)	0.0085 (15)
C4	0.0519 (15)	0.097 (2)	0.0484 (16)	0.0105 (16)	0.0142 (12)	0.0101 (15)
C5	0.0505 (14)	0.0707 (19)	0.0569 (17)	0.0039 (13)	0.0242 (13)	0.0042 (14)
C6	0.0525 (14)	0.0620 (18)	0.0581 (16)	0.0110 (13)	0.0235 (13)	0.0091 (14)
C7	0.0560 (15)	0.0550 (17)	0.0549 (16)	0.0075 (13)	0.0227 (13)	0.0111 (13)
C8	0.084 (2)	0.115 (3)	0.074 (2)	0.002 (2)	0.0365 (19)	−0.009 (2)
C9	0.101 (3)	0.114 (4)	0.103 (3)	0.019 (3)	0.043 (2)	0.009 (2)
C10	0.075 (2)	0.083 (2)	0.072 (2)	0.0104 (18)	0.0374 (17)	−0.0018 (17)
C11	0.079 (2)	0.091 (3)	0.094 (3)	0.009 (2)	0.0336 (19)	0.007 (2)
N1	0.0643 (14)	0.0606 (15)	0.0616 (15)	0.0027 (12)	0.0345 (11)	0.0032 (12)
N2	0.0708 (16)	0.108 (2)	0.0548 (15)	0.0222 (15)	0.0301 (12)	0.0097 (14)

Geometric parameters (Å, º) top

O1—C7	1.351 (3)	C8—C9	1.465 (6)
O1—H1	0.8461	C8—N2	1.486 (4)
C1—N1	1.284 (4)	C8—H8A	0.9700
C1—C2	1.438 (4)	C8—H8B	0.9700
C1—H1A	0.9300	C9—H9A	0.9600
C2—C3	1.391 (4)	C9—H9B	0.9600
C2—C7	1.414 (4)	C9—H9C	0.9600
C3—C4	1.371 (4)	C10—N2	1.471 (4)
C3—H3	0.9300	C10—C11	1.494 (5)
C4—C5	1.422 (4)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
C5—N2	1.374 (3)	C11—H11A	0.9600
C5—C6	1.387 (4)	C11—H11B	0.9600
C6—C7	1.386 (3)	C11—H11C	0.9600
C6—H6	0.9300	N1—N1ⁱ	1.397 (4)

C7—O1—H1	107.9	C9—C8—H8B	109.4
N1—C1—C2	122.6 (3)	N2—C8—H8B	109.4
N1—C1—H1A	118.7	H8A—C8—H8B	108.0
C2—C1—H1A	118.7	C8—C9—H9A	109.5
C3—C2—C7	116.6 (2)	C8—C9—H9B	109.5
C3—C2—C1	121.1 (2)	H9A—C9—H9B	109.5
C7—C2—C1	122.3 (2)	C8—C9—H9C	109.5
C4—C3—C2	123.0 (3)	H9A—C9—H9C	109.5
C4—C3—H3	118.5	H9B—C9—H9C	109.5
C2—C3—H3	118.5	N2—C10—C11	114.4 (3)
C3—C4—C5	120.3 (3)	N2—C10—H10A	108.7
C3—C4—H4	119.8	C11—C10—H10A	108.7
C5—C4—H4	119.8	N2—C10—H10B	108.7
N2—C5—C6	121.5 (2)	C11—C10—H10B	108.7
N2—C5—C4	121.4 (3)	H10A—C10—H10B	107.6
C6—C5—C4	117.1 (2)	C10—C11—H11A	109.5
C7—C6—C5	122.0 (2)	C10—C11—H11B	109.5
C7—C6—H6	119.0	H11A—C11—H11B	109.5
C5—C6—H6	119.0	C10—C11—H11C	109.5
O1—C7—C6	117.9 (2)	H11A—C11—H11C	109.5
O1—C7—C2	121.2 (2)	H11B—C11—H11C	109.5
C6—C7—C2	120.9 (2)	C1—N1—N1ⁱ	114.3 (3)
C9—C8—N2	111.0 (3)	C5—N2—C10	122.0 (2)
C9—C8—H8A	109.4	C5—N2—C8	121.4 (3)
N2—C8—H8A	109.4	C10—N2—C8	116.6 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱⁱ	0.97	2.64	3.481 (5)	145
O1—H1···N1	0.85	1.88	2.640 (3)	149

Symmetry code: (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₃₀N₄O₂
M_r	382.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	8.736 (5), 7.809 (5), 16.122 (10)
β (°)	103.57 (2)
V (Å³)	1069.1 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.15 × 0.14 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.988, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	9903, 2431, 1227
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.228, 1.10
No. of reflections	2431
No. of parameters	129
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.25

Computer programs: RAPID-AUTO (Rigaku Corporation, 1998), CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱ	0.97	2.64	3.481 (5)	145
O1—H1···N1	0.85	1.88	2.640 (3)	149

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 21062022) and the Open Project of the State Key Laboratory of Supramolecular Structure and Materials, Jilin University.

References

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