4-tert-Butyl-γ-chloro­butyrophenone

The title compound, C₁₄H₁₉ClO, possesses C_s symmetry with all but two C atoms of the tert-butyl group lying in the mirror plane. In the crystal structure, the mol­ecules stack along the b axis and are connected by weak C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.065
• wR factor = 0.140
• Data-to-parameter ratio = 9.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.73
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  CG1     ..       2.92 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The title compound, 4-tert-butyl-γ-chloro-butyrophenone (or 4'-tert-butyl-4-chlorobutyrophenone), (I), belongs to the chemical class of butyrophenones, which are used as tranquillizers and act as antipsychotics through their action as dopamine antagonists (Brea et al., 2003). As part of our continuing interest in the solid-state studies on molecules of pharmaceutical interest, in this report we discuss the structure and crystal packing of compound (I).

The molecular structure of compound (I) is illustrated in Fig. 1. The molecule possesses C_s symmetry, with atoms Cl1 and C1–C12 lying in the mirror plane.

In the crystal structure, symmetry-related molecules stack along the b axis and this arrangement is stabilized by C—H···π interactions (Fig. 2 and Table 1) with typical dimensions (Nishio et al., 1998). The rest of the packing is governed by van der Waals forces.

S2. Experimental

Crystals of compound (I) (obtained from Arvee Pharma, Mysore, India) were grown by evaporation of a hexane solution.

S3. Refinement

H atoms were located from the difference electron-density maps and were refined isotropically. Distance and angle restraints were applied to C12—H12B and C11—C12—H12B, respectively. The refined distances are in the ranges: C_ar—H = 0.87 (3)–0.99 (3) Å, methyl C—H = 0.95 (3)–1.00 (3) Å, and methylene C—H = 0.95 (3)–1.00 (3) Å.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of compound (I), with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (#) x, −y + 1/2, z.]
	Fig. 2. The crystal packing in (I), viewed along the b axis, showing the co-operative association of the molecules, forming dimers via putative C—H···π interactions. Cg1 is the centroid of the C5–C10 ring. The atoms labeled with asterisks (*) and hashes (#) are at the symmetry positions (1 − x, −1/2 + y, 1 − z) and (x, −y + 1/2, z), respectively. Color key: C, black, H white, Cl green, O red.

4-tert-Butyl-γ-chlorobutyrophenone

Crystal data

C14H19ClO	F(000) = 256
Mr = 238.76	Dx = 1.179 Mg m^−3
Monoclinic, P21/m	Melting point: 321 K
Hall symbol: -P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.247 (1) Å	Cell parameters from 1047 reflections
b = 7.242 (1) Å	θ = 5–26°
c = 11.414 (2) Å	µ = 0.26 mm^−1
β = 99.548 (3)°	T = 293 K
V = 672.3 (2) Å^3	Cube, colorless
Z = 2	0.33 × 0.31 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1333 independent reflections
Radiation source: fine-focus sealed tube	948 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 25.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.90, Tmax = 0.94	k = −8→8
3612 measured reflections	l = −13→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: difference Fourier map
wR(F^2) = 0.140	All H-atom parameters refined
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0613P)^2 + 0.014P] where P = (Fo^2 + 2Fc^2)/3
1333 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.15 e Å^−3
2 restraints	Δρmin = −0.24 e Å^−3

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.32876 (14)	0.2500	0.94524 (9)	0.0775 (5)
O1	0.3410 (3)	0.2500	0.4744 (2)	0.0752 (9)
C1	0.4802 (5)	0.2500	0.8498 (4)	0.0623 (12)
C2	0.4065 (4)	0.2500	0.7199 (3)	0.0443 (9)
C3	0.5428 (5)	0.2500	0.6461 (3)	0.0472 (9)
C4	0.4865 (5)	0.2500	0.5144 (3)	0.0460 (9)
C5	0.6117 (4)	0.2500	0.4339 (3)	0.0375 (8)
C6	0.5605 (4)	0.2500	0.3121 (3)	0.0436 (9)
C7	0.6723 (4)	0.2500	0.2347 (3)	0.0434 (9)
C8	0.8414 (4)	0.2500	0.2756 (3)	0.0387 (8)
C9	0.8913 (5)	0.2500	0.3979 (3)	0.0524 (10)
C10	0.7794 (4)	0.2500	0.4751 (3)	0.0528 (11)
C11	0.9699 (4)	0.2500	0.1929 (3)	0.0444 (9)
C12	0.8920 (6)	0.2500	0.0614 (3)	0.0607 (12)
C13	1.0771 (4)	0.0775 (5)	0.2172 (3)	0.0590 (8)
H1	0.539 (3)	0.143 (4)	0.875 (2)	0.075 (9)*
H2	0.335 (3)	0.139 (3)	0.7025 (18)	0.047 (6)*
H3	0.610 (3)	0.145 (3)	0.665 (2)	0.056 (7)*
H6	0.441 (4)	0.2500	0.281 (3)	0.053 (10)*
H7	0.632 (4)	0.2500	0.152 (3)	0.048 (10)*
H9	1.009 (4)	0.2500	0.429 (3)	0.056 (10)*
H10	0.815 (4)	0.2500	0.551 (3)	0.038 (9)*
H12A	0.820 (3)	0.147 (4)	0.041 (2)	0.087 (10)*
H12B	0.973 (2)	0.2500	0.0113 (11)	0.097 (15)*
H13A	1.133 (3)	0.071 (4)	0.297 (3)	0.073 (9)*
H13B	1.156 (3)	0.078 (4)	0.164 (2)	0.070 (8)*
H13C	1.013 (3)	−0.040 (4)	0.206 (2)	0.060 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0746 (8)	0.1051 (10)	0.0590 (7)	0.000	0.0293 (6)	0.000
O1	0.0373 (16)	0.136 (3)	0.0518 (16)	0.000	0.0053 (12)	0.000
C1	0.054 (3)	0.083 (4)	0.053 (3)	0.000	0.018 (2)	0.000
C2	0.041 (2)	0.048 (2)	0.044 (2)	0.000	0.0085 (17)	0.000
C3	0.041 (2)	0.054 (3)	0.047 (2)	0.000	0.0079 (18)	0.000
C4	0.040 (2)	0.049 (2)	0.049 (2)	0.000	0.0060 (17)	0.000
C5	0.0351 (19)	0.0373 (19)	0.0403 (19)	0.000	0.0071 (15)	0.000
C6	0.034 (2)	0.047 (2)	0.047 (2)	0.000	−0.0019 (17)	0.000
C7	0.046 (2)	0.045 (2)	0.037 (2)	0.000	−0.0003 (17)	0.000
C8	0.0372 (19)	0.0366 (19)	0.0411 (19)	0.000	0.0028 (15)	0.000
C9	0.035 (2)	0.079 (3)	0.042 (2)	0.000	0.0029 (17)	0.000
C10	0.043 (2)	0.081 (3)	0.033 (2)	0.000	0.0012 (18)	0.000
C11	0.039 (2)	0.053 (2)	0.0406 (19)	0.000	0.0045 (16)	0.000
C12	0.053 (3)	0.090 (4)	0.039 (2)	0.000	0.010 (2)	0.000
C13	0.0541 (19)	0.065 (2)	0.059 (2)	0.0112 (17)	0.0118 (16)	−0.0029 (17)

Geometric parameters (Å, º)

Cl1—C1	1.788 (4)	C7—H7	0.95 (3)
O1—C4	1.210 (4)	C8—C9	1.389 (5)
C1—C2	1.506 (5)	C8—C11	1.532 (4)
C1—H1	0.93 (2)	C9—C10	1.377 (5)
C2—C3	1.512 (5)	C9—H9	0.98 (3)
C2—H2	1.00 (2)	C10—H10	0.87 (3)
C3—C4	1.499 (5)	C11—C13^i	1.529 (3)
C3—H3	0.94 (2)	C11—C13	1.529 (3)
C4—C5	1.492 (4)	C11—C12	1.531 (5)
C5—C6	1.384 (4)	C12—H12A	0.96 (3)
C5—C10	1.385 (5)	C12—H12B	0.949 (10)
C6—C7	1.379 (5)	C13—H13A	0.95 (3)
C6—H6	0.99 (3)	C13—H13B	0.96 (3)
C7—C8	1.395 (5)	C13—H13C	1.00 (3)
C2—C1—Cl1	113.0 (3)	C7—C8—C11	123.3 (3)
C2—C1—H1	113.9 (17)	C10—C9—C8	121.6 (3)
Cl1—C1—H1	101.2 (17)	C10—C9—H9	120.1 (19)
C1—C2—C3	109.4 (3)	C8—C9—H9	118.3 (19)
C1—C2—H2	108.9 (13)	C9—C10—C5	121.4 (3)
C3—C2—H2	111.1 (12)	C9—C10—H10	119 (2)
C4—C3—C2	115.1 (3)	C5—C10—H10	120 (2)
C4—C3—H3	107.7 (14)	C13^i—C11—C13	109.6 (3)
C2—C3—H3	109.4 (15)	C13^i—C11—C12	108.3 (2)
O1—C4—C5	120.8 (3)	C13—C11—C12	108.3 (2)
O1—C4—C3	120.0 (3)	C13^i—C11—C8	109.1 (2)
C5—C4—C3	119.2 (3)	C13—C11—C8	109.1 (2)
C6—C5—C10	117.5 (3)	C12—C11—C8	112.5 (3)
C6—C5—C4	119.4 (3)	C11—C12—H12A	112.6 (17)
C10—C5—C4	123.0 (3)	C11—C12—H12B	111.6 (11)
C7—C6—C5	121.2 (3)	H12A—C12—H12B	108.9 (19)
C7—C6—H6	120.3 (18)	C11—C13—H13A	112.7 (17)
C5—C6—H6	118.5 (18)	C11—C13—H13B	108.4 (15)
C6—C7—C8	121.6 (3)	H13A—C13—H13B	109 (2)
C6—C7—H7	118.5 (19)	C11—C13—H13C	113.1 (13)
C8—C7—H7	119.9 (19)	H13A—C13—H13C	104 (2)
C9—C8—C7	116.7 (3)	H13B—C13—H13C	109 (2)
C9—C8—C11	120.0 (3)
Cl1—C1—C2—C3	180	C6—C7—C8—C11	180.0
C1—C2—C3—C4	180	C7—C8—C9—C10	0.0
C2—C3—C4—O1	0.0	C11—C8—C9—C10	180.0
C2—C3—C4—C5	180.0	C8—C9—C10—C5	0.0
O1—C4—C5—C6	0.0	C6—C5—C10—C9	0.0
C3—C4—C5—C6	180.0	C4—C5—C10—C9	180.0
O1—C4—C5—C10	180.0	C9—C8—C11—C13^i	−59.8 (2)
C3—C4—C5—C10	0.0	C7—C8—C11—C13^i	120.2 (2)
C10—C5—C6—C7	0.0	C9—C8—C11—C13	59.8 (2)
C4—C5—C6—C7	180.0	C7—C8—C11—C13	−120.2 (2)
C5—C6—C7—C8	0.0	C9—C8—C11—C12	180.0
C6—C7—C8—C9	0.0	C7—C8—C11—C12	0.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg1^ii	1.00 (2)	2.92 (2)	3.837 (1)	154 (2)

Symmetry code: (ii) −x+1, y−1/2, −z+1.