4-(Dimethyl­amino)phenyl phenyl ketone

Fun, H.-K.; Jebas, S.R.

doi:10.1107/S1600536808020953

organic compounds

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Volume 64| Part 8| August 2008| Page o1466

doi:10.1107/S1600536808020953

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4-(Dimethylamino)phenyl phenyl ketone

Hoong-Kun Fun ^a ^* and Samuel Robinson Jebas ^a ‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 27 June 2008; accepted 7 July 2008; online 12 July 2008)

In the crystal structure of the title compound, C₁₅H₁₅NO, the two benzene rings are twisted from each other by a dihedral angle of 47.97 (4)°. The crystal structure is stabilized by weak intermolecular C—H⋯O and C—H⋯π interactions, and π–π interactions with a centroid–centroid distance of 3.8493 (5) Å are observed.

Related literature

For related literature on non-linear optical properties of benzophenone, see: Arivanandhan et al. (2006 ); Szyrszyng et al. (2004 ); Vijayan et al. (2002 ) & Wang et al., (2007 ). For bond-length data see: Allen et al. (1987 )

Experimental

Crystal data

C₁₅H₁₅NO
M_r = 225.28
Monoclinic, P 2₁ /c
a = 13.0575 (3) Å
b = 7.7456 (2) Å
c = 12.4931 (3) Å
β = 111.717 (1)°
V = 1173.85 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100.0 (1) K
0.60 × 0.43 × 0.28 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.939, T_max = 0.977
22302 measured reflections
5156 independent reflections
4138 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.138
S = 1.06
5156 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.42 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
C4—H4⋯O1ⁱ	0.93	2.46	3.3730 (12)	168
C10—H10⋯Cg2ⁱⁱ	0.93	2.98	3.6452 (9)	130
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg2 is the centroid of atoms C8–C13.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020953/at2585sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020953/at2585Isup2.hkl

checkCIF report

Comment top

Benzophenone and its derivatives exhibits non-linear optical properties (Wang et al., 2007; Vijayan et al., 2002 & Arivanandhan et al., 2006) and are good candidates for the non-linear optical applications (Szyrszyng et al., 2004). In view of the importance of the benzophenone derivatives, the crystal structure of the title compound (I) has been elucidated.

The asymmetric unit of (I) consists of one molecule of 4-(dimethylamino)benzophenone. Bond lengths and angles in the molecule are found to have normal values (Allen et al., 1987) The dihedral angle formed by the rings (C1–C6) and (C8–C13) is 47.97 (4)° indicating that the rings are twisted from each other. The crystal packing (Fig.2) is consolidated by intermolecular C—H···O hydrogen bonds and C—H···π interactions. π–π interactions with the centroid to centroid distance of 3.8493 (5)Å are observed.

Related literature top

For related literature on non–linear optical properties of benzophenone, see: Arivanandhan et al. (2006); Szyrszyng et al. (2004); Vijayan et al. (2002) & Wang et al., (2007). For bond-length data see: Allen et al. (1987)

Experimental top

4-(Dimethylamino)benzophenone was purchased from Aldrich and dissolved in ethanol. The solution was allowed to evaporate slowly. Colourless crystals were obtained after a month.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

4-(Dimethylamino)phenyl phenyl ketone top

Crystal data top

C₁₅H₁₅NO	F(000) = 480
M_r = 225.28	D_x = 1.275 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8685 reflections
a = 13.0575 (3) Å	θ = 3.1–38.7°
b = 7.7456 (2) Å	µ = 0.08 mm⁻¹
c = 12.4931 (3) Å	T = 100 K
β = 111.717 (1)°	Block, colourless
V = 1173.85 (5) Å³	0.60 × 0.43 × 0.28 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5156 independent reflections
Radiation source: fine-focus sealed tube	4138 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 35.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −21→19
T_min = 0.939, T_max = 0.977	k = −10→12
22302 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0744P)² + 0.1876P] where P = (F_o² + 2F_c²)/3
5156 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₅H₁₅NO	V = 1173.85 (5) Å³
M_r = 225.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.0575 (3) Å	µ = 0.08 mm⁻¹
b = 7.7456 (2) Å	T = 100 K
c = 12.4931 (3) Å	0.60 × 0.43 × 0.28 mm
β = 111.717 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5156 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4138 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.977	R_int = 0.028
22302 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.06	Δρ_max = 0.42 e Å⁻³
5156 reflections	Δρ_min = −0.25 e Å⁻³
156 parameters

Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.26958 (5)	0.42158 (10)	0.20400 (5)	0.02533 (15)
N1	−0.10640 (5)	0.34279 (10)	0.40740 (6)	0.01934 (14)
C1	0.43352 (6)	0.31796 (11)	0.49440 (7)	0.01861 (15)
H1	0.3933	0.3765	0.5308	0.022*
C2	0.53797 (7)	0.25436 (12)	0.55889 (7)	0.02153 (16)
H2	0.5677	0.2714	0.6382	0.026*
C3	0.59761 (7)	0.16567 (12)	0.50493 (8)	0.02318 (17)
H3	0.6668	0.1215	0.5484	0.028*
C4	0.55457 (7)	0.14235 (12)	0.38612 (8)	0.02373 (17)
H4	0.5948	0.0833	0.3500	0.028*
C5	0.45115 (7)	0.20786 (11)	0.32186 (7)	0.02078 (16)
H5	0.4228	0.1942	0.2423	0.025*
C6	0.38907 (6)	0.29412 (10)	0.37532 (7)	0.01685 (14)
C7	0.27935 (6)	0.36465 (10)	0.29960 (7)	0.01733 (14)
C8	0.18415 (6)	0.36068 (10)	0.33575 (6)	0.01575 (14)
C9	0.08856 (6)	0.44970 (10)	0.26790 (7)	0.01806 (15)
H9	0.0897	0.5141	0.2055	0.022*
C10	−0.00688 (6)	0.44473 (11)	0.29074 (7)	0.01847 (15)
H10	−0.0687	0.5052	0.2436	0.022*
C11	−0.01199 (6)	0.34866 (10)	0.38509 (6)	0.01540 (14)
C12	0.08462 (6)	0.25969 (10)	0.45427 (6)	0.01625 (14)
H12	0.0843	0.1963	0.5174	0.019*
C13	0.17938 (6)	0.26547 (10)	0.42967 (6)	0.01610 (14)
H13	0.2414	0.2051	0.4763	0.019*
C14	−0.11461 (7)	0.24089 (12)	0.50120 (7)	0.02242 (16)
H14A	−0.0465	0.2479	0.5664	0.034*
H14B	−0.1292	0.1227	0.4773	0.034*
H14C	−0.1735	0.2846	0.5220	0.034*
C15	−0.20773 (7)	0.41652 (14)	0.32699 (8)	0.02666 (19)
H15A	−0.1986	0.5387	0.3213	0.040*
H15B	−0.2666	0.3950	0.3538	0.040*
H15C	−0.2250	0.3646	0.2526	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0234 (3)	0.0354 (4)	0.0184 (3)	−0.0007 (2)	0.0091 (2)	0.0074 (2)
N1	0.0154 (3)	0.0231 (3)	0.0193 (3)	0.0014 (2)	0.0062 (2)	0.0022 (2)
C1	0.0176 (3)	0.0211 (3)	0.0172 (3)	−0.0011 (3)	0.0065 (3)	−0.0014 (3)
C2	0.0176 (3)	0.0274 (4)	0.0181 (3)	−0.0012 (3)	0.0049 (3)	0.0009 (3)
C3	0.0168 (3)	0.0271 (4)	0.0261 (4)	0.0013 (3)	0.0086 (3)	0.0050 (3)
C4	0.0208 (3)	0.0280 (4)	0.0262 (4)	0.0017 (3)	0.0133 (3)	0.0007 (3)
C5	0.0204 (3)	0.0254 (4)	0.0190 (3)	−0.0013 (3)	0.0102 (3)	−0.0012 (3)
C6	0.0162 (3)	0.0185 (3)	0.0166 (3)	−0.0019 (2)	0.0070 (2)	0.0003 (2)
C7	0.0183 (3)	0.0180 (3)	0.0156 (3)	−0.0021 (2)	0.0062 (3)	0.0002 (2)
C8	0.0162 (3)	0.0163 (3)	0.0143 (3)	−0.0005 (2)	0.0051 (2)	0.0006 (2)
C9	0.0195 (3)	0.0184 (3)	0.0152 (3)	0.0006 (2)	0.0052 (3)	0.0031 (2)
C10	0.0176 (3)	0.0193 (3)	0.0167 (3)	0.0026 (2)	0.0042 (3)	0.0029 (3)
C11	0.0154 (3)	0.0149 (3)	0.0148 (3)	−0.0003 (2)	0.0043 (2)	−0.0019 (2)
C12	0.0170 (3)	0.0169 (3)	0.0148 (3)	0.0006 (2)	0.0058 (2)	0.0016 (2)
C13	0.0158 (3)	0.0164 (3)	0.0154 (3)	0.0013 (2)	0.0049 (2)	0.0016 (2)
C14	0.0229 (3)	0.0252 (4)	0.0216 (4)	−0.0004 (3)	0.0112 (3)	0.0007 (3)
C15	0.0158 (3)	0.0350 (5)	0.0267 (4)	0.0032 (3)	0.0049 (3)	0.0048 (3)

Geometric parameters (Å, º) top

O1—C7	1.2346 (10)	C8—C9	1.4031 (10)
N1—C11	1.3615 (10)	C8—C13	1.4066 (11)
N1—C14	1.4494 (11)	C9—C10	1.3781 (11)
N1—C15	1.4499 (11)	C9—H9	0.9300
C1—C2	1.3924 (11)	C10—C11	1.4163 (11)
C1—C6	1.3947 (11)	C10—H10	0.9300
C1—H1	0.9300	C11—C12	1.4165 (10)
C2—C3	1.3862 (12)	C12—C13	1.3816 (11)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.3907 (13)	C13—H13	0.9300
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.3868 (12)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C5—C6	1.3965 (11)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—C7	1.4976 (11)	C15—H15C	0.9600
C7—C8	1.4716 (11)

C11—N1—C14	121.81 (7)	C10—C9—C8	122.12 (7)
C11—N1—C15	120.55 (7)	C10—C9—H9	118.9
C14—N1—C15	116.94 (7)	C8—C9—H9	118.9
C2—C1—C6	120.15 (8)	C9—C10—C11	120.77 (7)
C2—C1—H1	119.9	C9—C10—H10	119.6
C6—C1—H1	119.9	C11—C10—H10	119.6
C3—C2—C1	120.02 (8)	N1—C11—C10	120.86 (7)
C3—C2—H2	120.0	N1—C11—C12	121.89 (7)
C1—C2—H2	120.0	C10—C11—C12	117.25 (7)
C2—C3—C4	120.36 (8)	C13—C12—C11	121.14 (7)
C2—C3—H3	119.8	C13—C12—H12	119.4
C4—C3—H3	119.8	C11—C12—H12	119.4
C5—C4—C3	119.52 (8)	C12—C13—C8	121.49 (7)
C5—C4—H4	120.2	C12—C13—H13	119.3
C3—C4—H4	120.2	C8—C13—H13	119.3
C4—C5—C6	120.76 (8)	N1—C14—H14A	109.5
C4—C5—H5	119.6	N1—C14—H14B	109.5
C6—C5—H5	119.6	H14A—C14—H14B	109.5
C1—C6—C5	119.17 (7)	N1—C14—H14C	109.5
C1—C6—C7	123.28 (7)	H14A—C14—H14C	109.5
C5—C6—C7	117.47 (7)	H14B—C14—H14C	109.5
O1—C7—C8	120.51 (7)	N1—C15—H15A	109.5
O1—C7—C6	118.26 (7)	N1—C15—H15B	109.5
C8—C7—C6	121.18 (7)	H15A—C15—H15B	109.5
C9—C8—C13	117.23 (7)	N1—C15—H15C	109.5
C9—C8—C7	117.90 (7)	H15A—C15—H15C	109.5
C13—C8—C7	124.76 (7)	H15B—C15—H15C	109.5

C6—C1—C2—C3	−0.63 (13)	C6—C7—C8—C13	−12.54 (12)
C1—C2—C3—C4	1.18 (13)	C13—C8—C9—C10	−0.33 (12)
C2—C3—C4—C5	−0.29 (14)	C7—C8—C9—C10	175.94 (7)
C3—C4—C5—C6	−1.15 (13)	C8—C9—C10—C11	0.20 (12)
C2—C1—C6—C5	−0.79 (12)	C14—N1—C11—C10	177.99 (7)
C2—C1—C6—C7	−177.50 (7)	C15—N1—C11—C10	7.82 (12)
C4—C5—C6—C1	1.69 (12)	C14—N1—C11—C12	−1.90 (12)
C4—C5—C6—C7	178.59 (8)	C15—N1—C11—C12	−172.07 (8)
C1—C6—C7—O1	141.72 (9)	C9—C10—C11—N1	−179.62 (7)
C5—C6—C7—O1	−35.04 (11)	C9—C10—C11—C12	0.27 (11)
C1—C6—C7—C8	−40.56 (11)	N1—C11—C12—C13	179.28 (7)
C5—C6—C7—C8	142.68 (8)	C10—C11—C12—C13	−0.61 (11)
O1—C7—C8—C9	−10.84 (12)	C11—C12—C13—C8	0.49 (12)
C6—C7—C8—C9	171.49 (7)	C9—C8—C13—C12	−0.02 (11)
O1—C7—C8—C13	165.13 (8)	C7—C8—C13—C12	−176.00 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.46	3.3730 (12)	168
C10—H10···Cg2ⁱⁱ	0.93	2.98	3.6452 (9)	130

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO
M_r	225.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.0575 (3), 7.7456 (2), 12.4931 (3)
β (°)	111.717 (1)
V (Å³)	1173.85 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.60 × 0.43 × 0.28

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.939, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	22302, 5156, 4138
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.138, 1.06
No. of reflections	5156
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.25

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.46	3.3730 (12)	168
C10—H10···Cg2ⁱⁱ	0.93	2.98	3.6452 (9)	130

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

Footnotes

‡Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

References

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