Salicyl­aldehyde–4-(dimethyl­amino)­pyridine (1/1)

Phurat, C.; Teerawatananond, T.; Muangsin, N.

doi:10.1107/S1600536810034185

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2423

https://doi.org/10.1107/S1600536810034185

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Salicylaldehyde–4-(dimethylamino)pyridine (1/1)

Chuttree Phurat,^a Thapong Teerawatananond ^a and Nongnuj Muangsin ^a ^*

^aResearch Centre of Bioorganic Chemistry, Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand
^*Correspondence e-mail: nongnuj.j@chula.ac.th

(Received 21 August 2010; accepted 24 August 2010; online 28 August 2010)

In the title compound, C₇H₁₀N₂·C₇H₆O₂, the components are linked by an O—H⋯N hydrogen bond. The mean planes of two molecules form a dihedral angle of 78.68 (5)°. The crystal packing exhibits weak non-classical C—H⋯O contacts.

Related literature

For background to hydrogen bonding in crystal engineering, see: Bosch (2010 ); Desiraju (1989 ); Lehn (1995 ). For related structures, see: Bosch (2010); Vembu et al. (2003 ); Lo & Ng (2009 ).

Experimental

Crystal data

C₇H₁₀N₂·C₇H₆O₂
M_r = 244.29
Triclinic, $[P \overline 1]$
a = 7.540 (3) Å
b = 8.473 (3) Å
c = 10.413 (4) Å
α = 85.370 (11)°
β = 77.371 (10)°
γ = 87.203 (10)°
V = 646.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.4 × 0.4 × 0.38 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.967, T_max = 0.968
4199 measured reflections
2913 independent reflections
1882 reflections with I > 2σ(I)
R_int = 0.02

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.163
S = 1.01
2913 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1	0.82	1.82	2.637 (2)	174
C9—H9⋯O1ⁱ	0.93	2.69	3.456 (3)	140
C5—H5⋯O1ⁱⁱ	0.93	2.7	3.583 (3)	158
Symmetry codes: (i) -x+2, -y-1, -z; (ii) -x+2, -y, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810034185/cv2756sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810034185/cv2756Isup2.hkl

checkCIF report

Comment top

Hydrogen bonding is the most important and the essential tool for both crystal engineering and supramolecular chemistry (Bosch, 2010; Desiraju, 1989 & Lehn, 1995). The non-classical C—H···N hydrogen bonds in pyridine and pyrimidine derivatives have remarkable potentials and patterns (Bosch, 2010; Desiraju, 1989; Lehn, 1995; Lo & Ng, 2009 & Vembu et al., 2003;). In order to investigate the hydrogen bonding patterns of 4-(dimethylamino)pyridine, the co-crystals with various derivatives of benzaldehyde were prepared.

We report here the structure of the title co-crystal compound (Fig.1), formed from salicylaldehyde and 4-(dimethylamino)pyridine. The asymmetric unit contains one molecule of salicylaldehyde and one molecule of 4-(dimethylamino)pyridine linked by O—H···N hydrogen bond (Table 1). The mean planes of two molecules form a dihedral angle of 78.68 (5)°. The crystal packing exhibits weak non-classical C—H···O contacts (Table 1).

Related literature top

For background to hydrogen bonding in crystal engineering, see: Bosch (2010); Desiraju (1989); Lehn (1995). For related structures, see: Bosch (2010); Vembu et al. (2003); Lo & Ng (2009).

Experimental top

The title cocrystal was crystallized by slow evaporation from the refluxed mixture of an equimolar solution of salicylaldehyde and 4-(dimethylamino)pyridine in a solution of methanol.

Structure description top

For background to hydrogen bonding in crystal engineering, see: Bosch (2010); Desiraju (1989); Lehn (1995). For related structures, see: Bosch (2010); Vembu et al. (2003); Lo & Ng (2009).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXS97 (Sheldrick, 2008).

Figures top

Fig. 1. The content of asymmetric unit of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as a dashed line.

2-Hydroxybenzaldehyde–4-(dimethylamino)pyridine (1/1) top

Crystal data top

C₇H₁₀N₂·C₇H₆O₂	Z = 2
M_r = 244.29	F(000) = 260
Triclinic, P1	D_x = 1.255 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.540 (3) Å	Cell parameters from 1563 reflections
b = 8.473 (3) Å	θ = 2.8–27.8°
c = 10.413 (4) Å	µ = 0.09 mm⁻¹
α = 85.370 (11)°	T = 296 K
β = 77.371 (10)°	Prism, yellow
γ = 87.203 (10)°	0.4 × 0.4 × 0.38 mm
V = 646.7 (4) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2913 independent reflections
Radiation source: Mo Kα	1882 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.02
φ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→9
T_min = 0.967, T_max = 0.968	k = −5→11
4199 measured reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.049	w = 1/[σ²(F_o²) + (0.0815P)² + 0.0644P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.163	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.20 e Å⁻³
2913 reflections	Δρ_min = −0.15 e Å⁻³
166 parameters

Crystal data top

C₇H₁₀N₂·C₇H₆O₂	γ = 87.203 (10)°
M_r = 244.29	V = 646.7 (4) Å³
Triclinic, P1	Z = 2
a = 7.540 (3) Å	Mo Kα radiation
b = 8.473 (3) Å	µ = 0.09 mm⁻¹
c = 10.413 (4) Å	T = 296 K
α = 85.370 (11)°	0.4 × 0.4 × 0.38 mm
β = 77.371 (10)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2913 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1882 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.968	R_int = 0.02
4199 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.01	Δρ_max = 0.20 e Å⁻³
2913 reflections	Δρ_min = −0.15 e Å⁻³
166 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.

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

	x	y	z	U_iso*/U_eq
C1	0.8429 (3)	0.2372 (2)	0.5097 (2)	0.0720 (5)
H1	0.868	0.1401	0.5513	0.086*
C2	0.7810 (3)	0.3587 (2)	0.58701 (17)	0.0638 (5)
H2	0.7635	0.3422	0.6782	0.077*
C3	0.7433 (2)	0.5084 (2)	0.52993 (15)	0.0521 (4)
C4	0.7680 (2)	0.5182 (2)	0.39168 (16)	0.0604 (4)
H4	0.7426	0.6132	0.3469	0.072*
C5	0.8288 (3)	0.3893 (3)	0.32350 (18)	0.0693 (5)
H5	0.8428	0.4003	0.2323	0.083*
C6	0.6562 (3)	0.6217 (3)	0.74452 (19)	0.0879 (7)
H6A	0.5548	0.5552	0.7795	0.132*
H6B	0.6298	0.725	0.777	0.132*
H6C	0.7624	0.5762	0.7717	0.132*
C7	0.6590 (3)	0.7888 (3)	0.5390 (2)	0.0798 (6)
H7A	0.7616	0.8131	0.4686	0.12*
H7B	0.6445	0.8672	0.6024	0.12*
H7C	0.5513	0.7885	0.5041	0.12*
C8	0.9510 (2)	−0.18638 (19)	0.10290 (14)	0.0500 (4)
C9	0.8248 (3)	−0.2663 (2)	0.05460 (16)	0.0603 (5)
H9	0.8641	−0.3511	0.0029	0.072*
C10	0.6437 (3)	−0.2223 (3)	0.08184 (19)	0.0724 (5)
H10	0.5604	−0.2764	0.0493	0.087*
C11	0.5875 (3)	−0.0964 (3)	0.1584 (2)	0.0754 (6)
H11	0.4652	−0.065	0.1763	0.09*
C12	0.7082 (2)	−0.0158 (2)	0.20895 (18)	0.0654 (5)
H12	0.6669	0.0687	0.2605	0.078*
C13	0.8914 (2)	−0.06070 (19)	0.18288 (14)	0.0515 (4)
C14	1.1435 (3)	−0.2309 (2)	0.06846 (17)	0.0631 (5)
H14	1.2235	−0.1669	0.0951	0.076*
N1	0.8703 (2)	0.2475 (2)	0.37777 (17)	0.0724 (5)
N2	0.6887 (2)	0.63491 (19)	0.60206 (13)	0.0636 (4)
O1	1.2084 (2)	−0.34318 (19)	0.00855 (16)	0.0891 (5)
O2	1.01269 (17)	0.01257 (16)	0.23295 (13)	0.0670 (4)
H2A	0.961	0.0844	0.2765	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0818 (13)	0.0592 (12)	0.0816 (13)	−0.0101 (9)	−0.0299 (10)	−0.0061 (9)
C2	0.0763 (12)	0.0654 (12)	0.0532 (9)	−0.0126 (9)	−0.0203 (8)	−0.0007 (8)
C3	0.0488 (8)	0.0622 (11)	0.0477 (8)	−0.0119 (7)	−0.0121 (7)	−0.0073 (7)
C4	0.0678 (10)	0.0654 (11)	0.0503 (9)	−0.0068 (8)	−0.0163 (8)	−0.0055 (8)
C5	0.0764 (12)	0.0813 (15)	0.0542 (10)	−0.0080 (10)	−0.0162 (9)	−0.0188 (9)
C6	0.1038 (16)	0.1054 (19)	0.0546 (11)	0.0003 (13)	−0.0119 (10)	−0.0232 (11)
C7	0.0877 (14)	0.0677 (14)	0.0813 (13)	0.0053 (10)	−0.0114 (11)	−0.0126 (10)
C8	0.0633 (10)	0.0484 (9)	0.0393 (7)	−0.0072 (7)	−0.0137 (7)	0.0023 (6)
C9	0.0776 (12)	0.0578 (11)	0.0483 (9)	−0.0128 (8)	−0.0154 (8)	−0.0085 (7)
C10	0.0688 (12)	0.0883 (15)	0.0667 (11)	−0.0241 (10)	−0.0209 (9)	−0.0136 (10)
C11	0.0588 (11)	0.0952 (16)	0.0755 (12)	−0.0095 (10)	−0.0163 (9)	−0.0173 (11)
C12	0.0636 (11)	0.0681 (12)	0.0668 (11)	−0.0022 (9)	−0.0141 (8)	−0.0187 (9)
C13	0.0615 (10)	0.0502 (9)	0.0455 (8)	−0.0089 (7)	−0.0170 (7)	−0.0008 (7)
C14	0.0698 (11)	0.0637 (12)	0.0600 (10)	−0.0001 (9)	−0.0218 (8)	−0.0105 (8)
N1	0.0745 (10)	0.0704 (12)	0.0794 (11)	−0.0065 (8)	−0.0232 (8)	−0.0264 (8)
N2	0.0734 (9)	0.0667 (10)	0.0507 (8)	−0.0049 (7)	−0.0103 (7)	−0.0114 (7)
O1	0.0889 (10)	0.0822 (11)	0.1002 (11)	0.0161 (8)	−0.0239 (8)	−0.0325 (8)
O2	0.0665 (8)	0.0665 (9)	0.0756 (8)	−0.0047 (6)	−0.0244 (6)	−0.0235 (6)

Geometric parameters (Å, º) top

C1—N1	1.340 (3)	C7—H7B	0.96
C1—C2	1.359 (3)	C7—H7C	0.96
C1—H1	0.93	C8—C9	1.394 (2)
C2—C3	1.400 (3)	C8—C13	1.401 (2)
C2—H2	0.93	C8—C14	1.455 (3)
C3—N2	1.355 (2)	C9—C10	1.372 (3)
C3—C4	1.407 (2)	C9—H9	0.93
C4—C5	1.357 (3)	C10—C11	1.378 (3)
C4—H4	0.93	C10—H10	0.93
C5—N1	1.339 (3)	C11—C12	1.378 (3)
C5—H5	0.93	C11—H11	0.93
C6—N2	1.446 (2)	C12—C13	1.389 (3)
C6—H6A	0.96	C12—H12	0.93
C6—H6B	0.96	C13—O2	1.3452 (18)
C6—H6C	0.96	C14—O1	1.205 (2)
C7—N2	1.442 (3)	C14—H14	0.93
C7—H7A	0.96	O2—H2A	0.82

N1—C1—C2	124.69 (19)	C9—C8—C13	119.44 (16)
N1—C1—H1	117.7	C9—C8—C14	120.36 (16)
C2—C1—H1	117.7	C13—C8—C14	120.19 (14)
C1—C2—C3	120.29 (17)	C10—C9—C8	121.25 (17)
C1—C2—H2	119.9	C10—C9—H9	119.4
C3—C2—H2	119.9	C8—C9—H9	119.4
N2—C3—C2	122.62 (15)	C9—C10—C11	118.68 (17)
N2—C3—C4	122.36 (16)	C9—C10—H10	120.7
C2—C3—C4	115.02 (16)	C11—C10—H10	120.7
C5—C4—C3	120.10 (18)	C10—C11—C12	121.63 (19)
C5—C4—H4	120	C10—C11—H11	119.2
C3—C4—H4	120	C12—C11—H11	119.2
N1—C5—C4	124.86 (17)	C11—C12—C13	119.98 (18)
N1—C5—H5	117.6	C11—C12—H12	120
C4—C5—H5	117.6	C13—C12—H12	120
N2—C6—H6A	109.5	O2—C13—C12	121.78 (16)
N2—C6—H6B	109.5	O2—C13—C8	119.24 (15)
H6A—C6—H6B	109.5	C12—C13—C8	118.99 (15)
N2—C6—H6C	109.5	O1—C14—C8	125.87 (17)
H6A—C6—H6C	109.5	O1—C14—H14	117.1
H6B—C6—H6C	109.5	C8—C14—H14	117.1
N2—C7—H7A	109.5	C5—N1—C1	114.99 (16)
N2—C7—H7B	109.5	C3—N2—C7	120.92 (15)
H7A—C7—H7B	109.5	C3—N2—C6	121.81 (17)
N2—C7—H7C	109.5	C7—N2—C6	117.26 (16)
H7A—C7—H7C	109.5	C13—O2—H2A	109.5
H7B—C7—H7C	109.5

N1—C1—C2—C3	−1.0 (3)	C9—C8—C13—O2	177.74 (14)
C1—C2—C3—N2	−177.17 (16)	C14—C8—C13—O2	−3.5 (2)
C1—C2—C3—C4	2.3 (2)	C9—C8—C13—C12	−1.9 (2)
N2—C3—C4—C5	177.77 (16)	C14—C8—C13—C12	176.90 (16)
C2—C3—C4—C5	−1.7 (2)	C9—C8—C14—O1	−6.8 (3)
C3—C4—C5—N1	−0.3 (3)	C13—C8—C14—O1	174.44 (18)
C13—C8—C9—C10	1.3 (2)	C4—C5—N1—C1	1.7 (3)
C14—C8—C9—C10	−177.51 (16)	C2—C1—N1—C5	−1.1 (3)
C8—C9—C10—C11	0.1 (3)	C2—C3—N2—C7	177.21 (17)
C9—C10—C11—C12	−0.8 (3)	C4—C3—N2—C7	−2.2 (3)
C10—C11—C12—C13	0.2 (3)	C2—C3—N2—C6	−3.3 (3)
C11—C12—C13—O2	−178.43 (16)	C4—C3—N2—C6	177.28 (17)
C11—C12—C13—C8	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1	0.82	1.82	2.637 (2)	174
C9—H9···O1ⁱ	0.93	2.69	3.456 (3)	140
C5—H5···O1ⁱⁱ	0.93	2.7	3.583 (3)	158

Symmetry codes: (i) −x+2, −y−1, −z; (ii) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₇H₁₀N₂·C₇H₆O₂
M_r	244.29
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.540 (3), 8.473 (3), 10.413 (4)
α, β, γ (°)	85.370 (11), 77.371 (10), 87.203 (10)
V (Å³)	646.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.4 × 0.4 × 0.38

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.967, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	4199, 2913, 1882
R_int	0.02
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.163, 1.01
No. of reflections	2913
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.15

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1	0.82	1.82	2.637 (2)	173.6
C9—H9···O1ⁱ	0.93	2.69	3.456 (3)	140.1
C5—H5···O1ⁱⁱ	0.93	2.7	3.583 (3)	158.1

Symmetry codes: (i) −x+2, −y−1, −z; (ii) −x+2, −y, −z.

Acknowledgements

This work was supported by the Research Funds from the Faculty of Science (A1B1), the Thailand Research Fund (RSA4680016) to NM, and the Thai Government Stimulus Package 2 (TKK2555) under the Project for Establishment of Comprehensive Center for Innovative Food, Health Products and Agrigulture and Center for Petroleum Petrochemicals and Advanced Materials.

References

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