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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H-atoms were geometrically positioned and refined using a riding model, with C—H = 0.93 Å (aromatic), 0.98 Å (CH₃) and O–H = 0.82 Å, and U_iso(H) = 1.2U_eq (C) for aromatic and 1.5U_eq for O and C_methyl.

Figures

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.

Crystal data

C7H10N2·C7H6O2	Z = 2
Mr = 244.29	F(000) = 260
Triclinic, P1	Dx = 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

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

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.049	w = 1/[σ2(Fo2) + (0.0815P)2 + 0.0644P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.163	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.20 e Å−3
2913 reflections	Δρmin = −0.15 e Å−3
166 parameters

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.