4-(Dimethyl­amino)benzaldehyde

Gao, B.; Zhu, J.-L.

doi:10.1107/S160053680801581X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1182

doi:10.1107/S160053680801581X

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4-(Dimethylamino)benzaldehyde

Bo Gao ^a ^* and Jian-Liang Zhu ^a

^aMarine College, Zhejiang Institute of Communications, Hangzhou 311112, People's Republic of China
^*Correspondence e-mail: bgao_zjvtit@126.com

(Received 23 May 2008; accepted 26 May 2008; online 7 June 2008)

The title compound, C₉H₁₁NO, crystallizes with two independent but essentially identical molecules in the asymmetric unit, which are linked via a C—H⋯π interaction. In both molecules, the aldehyde and dimethylamine groups are essentially coplanar with the attached benzene ring. In the crystal structure, C—H⋯O hydrogen bonds link one type of independent molecules into a chain along the a axis. In addition, the structure is stabilized by π–π stacking interactions involving the benzene rings [centroid-to-centroid distance = 3.697 (2) Å].

Related literature

For synthesis, see: Wu & Zhou (2005 ). For general background, see: Kawski et al. (2007 ). For related structures, see: Reffner & McCrone (1959 ); Dattagupta & Saha (1973 ); Herbstein et al. (1984 ); Mahadevan et al. (1982 ); Habibi et al. (2007 ).

Experimental

Crystal data

C₉H₁₁NO
M_r = 149.19
Monoclinic, P 2₁ /n
a = 10.356 (6) Å
b = 7.686 (4) Å
c = 20.8434 (13) Å
β = 96.808 (13)°
V = 1647.4 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 123 (2) K
0.27 × 0.23 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.979, T_max = 0.981
9835 measured reflections
2869 independent reflections
1826 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.160
S = 1.01
2869 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O1ⁱ	0.96	2.57	3.459 (3)	155
C3—H3⋯Cg1	0.93	2.78	3.593 (3)	146
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801581X/ci2602sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801581X/ci2602Isup2.hkl

checkCIF report

Comment top

4-Dimethylaminobenzaldehyde (DMABA) is an important intermediate of dyes and medicine. It belongs to the same family as 4-(dimethylamino)benzonitrile (DMABN) which exhibits dual fluorescence and was a subject of extensive investigations (Kawski et al., 2007). Although the unit-cell parameters of DMABA have been reported (Reffner & McCrone, 1959), to our knowledge there is no report on the crystal structure of DMABA. The crystal structures of DMABA hydrobromide (Dattagupta & Saha, 1973), a 1:1 complex in which DMABA acts as a guest molecule in channels (Herbstein et al., 1984), a tin complex in which DMABA serves as a ligand coordinating through its O atom (Mahadevan et al., 1982), and of a 1:1 cocrystal of DMABA and 6-phenyl-1,3,5-triazine-2,4-diamine (Habibi et al., 2007) have been reported. We report here the crystal structure of the title compound.

The title compound crystallizes with two independent but essentially identical molecules in the asymmetric unit (Fig. 1). In both molecules, the aldehyde and dimethylamino groups are essentially coplanar with the attached benzene ring, similar to those observed in above crystal structures. The mean planes through the non-hydrogen atoms of two independent molecules form a dihedral angle of 76.42 (5)°. The two independent molecules are linked via a C—H···π interaction involving the C3—H3 group and C11–C16 benzene ring (Table 1).

In the crystal structure, C—H···O hydrogen bonds (Table 1) link one type of independent molecules into a chain along the a axis. In addition, the structure is stabilized by stacking interactions between the inversion related C11–C16 benzene rings [centroid–centroid distance is 3.697 (2) Å].

Related literature top

For synthesis, see: Wu & Zhou (2005). For general background, see: Kawski et al. (2007). For related structures, see: Reffner & McCrone (1959); Dattagupta & Saha (1973); Herbstein et al. (1984); Mahadevan et al. (1982); Habibi et al. (2007).

Experimental top

The title compound was prepared according to the literature method (Wu & Zhou, 2005). Crystals suitable for X-ray analysis were obtained by slow evaporation of a isoproanol solution at room temperature (m.p. 343–347 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

4-(Dimethylamino)benzaldehyde top

Crystal data top

C₉H₁₁NO	F(000) = 640
M_r = 149.19	D_x = 1.203 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2869 reflections
a = 10.356 (6) Å	θ = 2–25.0°
b = 7.686 (4) Å	µ = 0.08 mm⁻¹
c = 20.8434 (13) Å	T = 123 K
β = 96.808 (13)°	Block, colourless
V = 1647.4 (12) Å³	0.27 × 0.23 × 0.20 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	2869 independent reflections
Radiation source: fine-focus sealed tube	1826 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
T_min = 0.979, T_max = 0.981	k = −9→9
9835 measured reflections	l = −22→24

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0934P)²] where P = (F_o² + 2F_c²)/3
2869 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₉H₁₁NO	V = 1647.4 (12) Å³
M_r = 149.19	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.356 (6) Å	µ = 0.08 mm⁻¹
b = 7.686 (4) Å	T = 123 K
c = 20.8434 (13) Å	0.27 × 0.23 × 0.20 mm
β = 96.808 (13)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2869 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1826 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.981	R_int = 0.058
9835 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.01	Δρ_max = 0.22 e Å⁻³
2869 reflections	Δρ_min = −0.31 e Å⁻³
199 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
O1	1.26881 (13)	0.5751 (2)	0.18550 (9)	0.1025 (6)
O2	1.37916 (14)	0.2647 (3)	0.04689 (9)	0.1088 (6)
C9	0.57238 (17)	0.7676 (3)	0.21132 (10)	0.0742 (6)
H9A	0.4815	0.7498	0.1976	0.111*
H9B	0.5939	0.8876	0.2055	0.111*
H9C	0.5912	0.7373	0.2561	0.111*
C8	0.57965 (16)	0.5577 (3)	0.12110 (9)	0.0653 (5)
H8A	0.4876	0.5723	0.1213	0.098*
H8B	0.6017	0.4370	0.1271	0.098*
H8C	0.6040	0.5968	0.0805	0.098*
C18	0.69062 (19)	0.0550 (3)	0.08262 (11)	0.0809 (6)
H18A	0.5991	0.0674	0.0694	0.121*
H18B	0.7102	0.0920	0.1267	0.121*
H18C	0.7151	−0.0647	0.0789	0.121*
C17	0.68913 (18)	0.2440 (3)	−0.01380 (10)	0.0776 (6)
H17A	0.5978	0.2267	−0.0120	0.116*
H17B	0.7132	0.1938	−0.0528	0.116*
H17C	0.7079	0.3664	−0.0132	0.116*
C5	0.78138 (15)	0.66025 (19)	0.18319 (8)	0.0453 (4)
C2	1.05546 (16)	0.6610 (2)	0.20311 (9)	0.0524 (5)
N1	0.64859 (12)	0.65921 (18)	0.17319 (7)	0.0542 (4)
C4	0.85497 (16)	0.5535 (2)	0.14644 (8)	0.0508 (4)
H4	0.8126	0.4817	0.1147	0.061*
C3	0.98899 (16)	0.5538 (2)	0.15671 (8)	0.0528 (5)
H3	1.0356	0.4810	0.1322	0.063*
C6	0.84982 (16)	0.7670 (2)	0.23045 (8)	0.0529 (5)
H6	0.8042	0.8385	0.2559	0.063*
C7	0.98356 (16)	0.7666 (2)	0.23942 (8)	0.0559 (5)
H7	1.0268	0.8391	0.2706	0.067*
C1	1.19714 (19)	0.6632 (3)	0.21338 (11)	0.0716 (6)
H1	1.2358	0.7399	0.2444	0.086*
C14	0.89524 (16)	0.1659 (2)	0.05031 (8)	0.0500 (4)
N2	0.76244 (14)	0.1612 (2)	0.04153 (8)	0.0629 (5)
C13	0.96580 (17)	0.2560 (2)	0.00770 (8)	0.0567 (5)
H13	0.9217	0.3114	−0.0281	0.068*
C11	1.16899 (17)	0.1858 (2)	0.07077 (10)	0.0583 (5)
C15	0.96619 (17)	0.0836 (2)	0.10370 (9)	0.0581 (5)
H15	0.9226	0.0210	0.1327	0.070*
C16	1.09953 (17)	0.0953 (2)	0.11309 (9)	0.0609 (5)
H16	1.1446	0.0410	0.1488	0.073*
C12	1.09922 (18)	0.2640 (2)	0.01775 (9)	0.0612 (5)
H12	1.1437	0.3234	−0.0117	0.073*
C10	1.3101 (2)	0.1939 (3)	0.08206 (12)	0.0812 (6)
H10	1.3506	0.1406	0.1192	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0548 (8)	0.1082 (13)	0.1464 (15)	0.0050 (8)	0.0195 (9)	−0.0127 (11)
O2	0.0684 (10)	0.1282 (15)	0.1327 (15)	−0.0202 (9)	0.0242 (10)	−0.0258 (12)
C9	0.0562 (11)	0.0765 (14)	0.0926 (15)	−0.0019 (10)	0.0201 (11)	−0.0170 (12)
C8	0.0548 (10)	0.0758 (13)	0.0633 (12)	−0.0026 (9)	−0.0012 (9)	−0.0029 (10)
C18	0.0624 (12)	0.0841 (15)	0.0979 (16)	−0.0089 (11)	0.0168 (11)	0.0110 (13)
C17	0.0652 (12)	0.0777 (15)	0.0868 (15)	0.0094 (11)	−0.0045 (11)	0.0036 (12)
C5	0.0497 (10)	0.0397 (9)	0.0472 (10)	−0.0017 (7)	0.0080 (8)	0.0049 (7)
C2	0.0497 (10)	0.0492 (10)	0.0580 (11)	−0.0017 (8)	0.0049 (8)	0.0099 (8)
N1	0.0462 (8)	0.0562 (9)	0.0601 (9)	−0.0013 (6)	0.0062 (7)	−0.0077 (7)
C4	0.0564 (10)	0.0476 (10)	0.0486 (10)	−0.0012 (8)	0.0065 (8)	−0.0038 (8)
C3	0.0554 (10)	0.0489 (10)	0.0562 (11)	0.0040 (8)	0.0159 (8)	0.0011 (8)
C6	0.0556 (10)	0.0487 (10)	0.0548 (11)	0.0015 (8)	0.0084 (8)	−0.0069 (9)
C7	0.0593 (11)	0.0507 (11)	0.0565 (11)	−0.0054 (8)	0.0019 (9)	−0.0047 (9)
C1	0.0550 (12)	0.0716 (14)	0.0876 (15)	−0.0007 (10)	0.0052 (11)	0.0053 (11)
C14	0.0566 (10)	0.0416 (9)	0.0516 (11)	0.0016 (8)	0.0052 (8)	−0.0036 (8)
N2	0.0534 (9)	0.0632 (10)	0.0714 (11)	0.0016 (7)	0.0046 (8)	0.0081 (8)
C13	0.0640 (11)	0.0527 (11)	0.0532 (11)	0.0016 (9)	0.0059 (9)	0.0043 (9)
C11	0.0556 (11)	0.0541 (11)	0.0653 (12)	−0.0026 (8)	0.0073 (9)	−0.0135 (9)
C15	0.0649 (12)	0.0516 (11)	0.0584 (11)	−0.0029 (9)	0.0098 (9)	0.0045 (9)
C16	0.0658 (12)	0.0564 (11)	0.0576 (11)	0.0019 (9)	−0.0045 (9)	0.0019 (9)
C12	0.0679 (12)	0.0585 (12)	0.0601 (12)	−0.0068 (9)	0.0189 (9)	−0.0022 (10)
C10	0.0660 (13)	0.0821 (15)	0.0966 (17)	−0.0098 (11)	0.0147 (12)	−0.0188 (13)

Geometric parameters (Å, º) top

O1—C1	1.204 (2)	C2—C3	1.389 (2)
O2—C10	1.212 (3)	C2—C1	1.457 (3)
C9—N1	1.448 (2)	C4—C3	1.379 (2)
C9—H9A	0.96	C4—H4	0.93
C9—H9B	0.96	C3—H3	0.93
C9—H9C	0.96	C6—C7	1.375 (2)
C8—N1	1.454 (2)	C6—H6	0.93
C8—H8A	0.96	C7—H7	0.93
C8—H8B	0.96	C1—H1	0.93
C8—H8C	0.96	C14—N2	1.366 (2)
C18—N2	1.450 (2)	C14—C13	1.399 (2)
C18—H18A	0.96	C14—C15	1.409 (2)
C18—H18B	0.96	C13—C12	1.374 (3)
C18—H18C	0.96	C13—H13	0.93
C17—N2	1.451 (2)	C11—C12	1.384 (3)
C17—H17A	0.96	C11—C16	1.389 (3)
C17—H17B	0.96	C11—C10	1.454 (3)
C17—H17C	0.96	C15—C16	1.374 (2)
C5—N1	1.366 (2)	C15—H15	0.93
C5—C4	1.407 (2)	C16—H16	0.93
C5—C6	1.407 (2)	C12—H12	0.93
C2—C7	1.386 (2)	C10—H10	0.93

N1—C9—H9A	109.5	C4—C3—C2	121.02 (16)
N1—C9—H9B	109.5	C4—C3—H3	119.5
H9A—C9—H9B	109.5	C2—C3—H3	119.5
N1—C9—H9C	109.5	C7—C6—C5	120.61 (16)
H9A—C9—H9C	109.5	C7—C6—H6	119.7
H9B—C9—H9C	109.5	C5—C6—H6	119.7
N1—C8—H8A	109.5	C6—C7—C2	121.65 (16)
N1—C8—H8B	109.5	C6—C7—H7	119.2
H8A—C8—H8B	109.5	C2—C7—H7	119.2
N1—C8—H8C	109.5	O1—C1—C2	126.2 (2)
H8A—C8—H8C	109.5	O1—C1—H1	116.9
H8B—C8—H8C	109.5	C2—C1—H1	116.9
N2—C18—H18A	109.5	N2—C14—C13	121.43 (16)
N2—C18—H18B	109.5	N2—C14—C15	121.09 (16)
H18A—C18—H18B	109.5	C13—C14—C15	117.46 (16)
N2—C18—H18C	109.5	C14—N2—C18	120.96 (15)
H18A—C18—H18C	109.5	C14—N2—C17	121.23 (15)
H18B—C18—H18C	109.5	C18—N2—C17	117.37 (15)
N2—C17—H17A	109.5	C12—C13—C14	121.13 (17)
N2—C17—H17B	109.5	C12—C13—H13	119.4
H17A—C17—H17B	109.5	C14—C13—H13	119.4
N2—C17—H17C	109.5	C12—C11—C16	117.64 (17)
H17A—C17—H17C	109.5	C12—C11—C10	122.03 (19)
H17B—C17—H17C	109.5	C16—C11—C10	120.32 (19)
N1—C5—C4	120.93 (15)	C16—C15—C14	120.27 (17)
N1—C5—C6	121.63 (15)	C16—C15—H15	119.9
C4—C5—C6	117.44 (15)	C14—C15—H15	119.9
C7—C2—C3	118.28 (16)	C15—C16—C11	121.97 (17)
C7—C2—C1	120.65 (17)	C15—C16—H16	119.0
C3—C2—C1	121.07 (17)	C11—C16—H16	119.0
C5—N1—C9	121.13 (15)	C13—C12—C11	121.50 (17)
C5—N1—C8	120.89 (14)	C13—C12—H12	119.3
C9—N1—C8	117.86 (14)	C11—C12—H12	119.3
C3—C4—C5	120.99 (16)	O2—C10—C11	125.1 (2)
C3—C4—H4	119.5	O2—C10—H10	117.4
C5—C4—H4	119.5	C11—C10—H10	117.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱ	0.96	2.57	3.459 (3)	155
C3—H3···Cg1	0.93	2.78	3.593 (3)	146

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO
M_r	149.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	10.356 (6), 7.686 (4), 20.8434 (13)
β (°)	96.808 (13)
V (Å³)	1647.4 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.27 × 0.23 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.979, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	9835, 2869, 1826
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.160, 1.01
No. of reflections	2869
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.31

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱ	0.96	2.57	3.459 (3)	155
C3—H3···Cg1	0.93	2.78	3.593 (3)	146

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors thank Zhejiang Institute of Communications, People's Republic of China, for financial support.

References

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dattagupta, J. K. & Saha, N. N. (1973). Acta Cryst. B29, 1228–1233. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Habibi, M. H., Zendehdel, M., Barati, K., Harrington, R. W. & Clegg, W. (2007). Acta Cryst. C63, o474–o476. Web of Science CSD CrossRef IUCr Journals Google Scholar
Herbstein, F. H., Kapon, M., Reisner, G. M. & Rubin, G. M. (1984). J. Inclusion Phenom. Macrocycl. Chem. 1, 233–250. CSD CrossRef CAS Google Scholar
Kawski, A., Kuklinski, B. & Bojarski, P. (2007). Chem. Phys. Lett. 448, 208–212. Web of Science CrossRef CAS Google Scholar
Mahadevan, C., Seshasayee, M. & Kothiwal, A. S. (1982). Cryst. Struct. Commun. 11, 1725–1730. CAS Google Scholar
Reffner, J. & McCrone, W. C. (1959). Anal. Chem. 31, 1119–1120. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, Y. X. & Zhou, J. H. (2005). Yunnan Chem. Technol. 32(3), 20–22. Web of Science CrossRef Google Scholar