1-(4-Chloro­phen­yl)-3-[3-(4-chloro­phen­yl)pyrazol-1-yl]propan-1-one

The title compound, C₁₈H₁₄Cl₂N₂O, is an isomer of the triplet alkyl nitrene decay product formed upon photolysis of β-azido propiophenone complexes. The mol­ecule exhibits an overall twist with dihedral angles of 10.32 (7) and 24.94 (4)° between the pyrazole plane and the planes of the chloro­phenyl rings. The crystal packing of the title compound features stacks of mol­ecules in alternating orientations running along the b axis; the approximate separation distance between the planes of neighboring mol­ecules in the stack is 3.66 Å.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.055
• wR factor = 0.124
• Data-to-parameter ratio = 18.7

checkCIF/PLATON results

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.

1-(4-Chlorophenyl)-3-[3-(4-chlorophenyl)pyrazol-1-yl]propan-1-one

Crystal data

C18H14Cl2N2O	F(000) = 712
Mr = 345.21	Dx = 1.465 Mg m^−3
Monoclinic, P21/c	Melting point: 371 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 19.1362 (5) Å	Cell parameters from 6273 reflections
b = 7.2803 (2) Å	θ = 2.9–32.2°
c = 11.2860 (3) Å	µ = 0.42 mm^−1
β = 95.377 (1)°	T = 150 K
V = 1565.42 (7) Å^3	Block, colorless
Z = 4	0.22 × 0.18 × 0.11 mm

Data collection

Bruker SMART 6000 CCD diffractometer	3889 independent reflections
Radiation source: sealed tube	3188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 0.75 pixels mm^-1	θmax = 28.3°, θmin = 1.1°
ω scans	h = −25→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −9→9
Tmin = 0.822, Tmax = 0.955	l = −15→15
13291 measured reflections

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)] = 0.055	Hydrogen site location: mixed
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 1.3572P] where P = (Fo^2 + 2Fc^2)/3
3889 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. Single crystals were obtained from ethanol. A suitable crystal was mounted on the tip of a glass fiber with paratone-N.

The first 50 frames of data were recollected for a decay correction. The decay correction was applied simultaneously with the absorption correction in SADABS. No formal measure of the extent of decay is printed out by this program.

The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I).

Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely absorption effects and crystal size.

Spectroscopic details for (4): IR (KBr) 2923, 1685, 1589, 1400, 1092 cm^{-16. 1}H NMR (250 MHz, CDCl₃) δ 3.59 (t, 2H, 7 Hz, –CO—CH₂–), 4.51 (t, 2H, 7 Hz, –CH₂—N<), 6.27 (d, 1H, 2 Hz, C-4_pyrazoleH), 7.38–7.43 (m, 6H, aromatic H), 7.53 (d, 1H, 2 Hz, C-3_pyrazoleH), 7.86 (d, 2H, 7.5 Hz, aromatic H) p.p.m. ¹³C NMR (75 MHz, CDCl₃) δ 196.2 (C=O), 142.7 C-5_pyrazoleC), 140.0 (aromatic C), 139.9 (C3-_pyrazoleC), 134.9, 134.7 (aromatic C), 130.3, 129.5, 129.1, 129.0 (aromatic C), 106.5 (C-4_pyrazoleC), 44.3, 38.3 (CH₂) p.p.m. MS (ESI, M⁺) calcd. for C₁₈H₁₄N₂OCl₂, 344.0483, found 344.0477

Spectroscopic details for (5): IR (KBr) 3447, 3132, 1682, 1590, 1098 cm^{-1 1}H NMR (250 MHz, CDCl₃) δ 3.61(t, 2H, 7 Hz, –CO—CH₂–), 4.61 (t, 2H, 7 Hz, –CH₂—N<), 6.47 (d, 1H, 2 Hz, C-4_pyrazoleH), 7.33 (d, 2H, 8 Hz, aromatic H), 7.37 (d, 2H, 8 Hz, aromatic H), 7.51 (d, 1H, 3 Hz, C-5_pyrazoleH), 7.68 (d, 2H, 8 Hz, aromatic H), 7.89 (d, 2H, 8 Hz, aromatic H) p.p.m. ¹³C NMR (75 MHz, CDCl₃) δ 196.3 (C=O), 150.8 (C-3_pyrazoleC), 140.0, 134.7, 132.1 (aromatic C), 131.8 (C-5_pyrazoleC), 129.5, 129.0, 128.8, 126.8 (aromatic C), 102.6 (C-4_pyrazoleC), 46.9, 38.8 (CH₂) p.p.m. MS (ESI, M⁺) calcd. for C₁₈H₁₄N₂OCl₂, 344.0483, found 344.0502

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

-1.5903 (154)x + 6.8634 (21)y + 3.7176 (90)z = 3.5593 (47)

* 0.0013 (0.0014) C1 * 0.0044 (0.0014) C2 * -0.0054 (0.0015) C3 * 0.0005 (0.0015) C4 * 0.0053 (0.0015) C5 * -0.0061 (0.0014) C6

Rms deviation of fitted atoms = 0.0044

-2.3188 (203)x + 7.1421 (15)y + 1.8291 (117)z = 2.8504 (36)

Angle to previous plane (with approximate e.s.d.) = 10.32 (7)

* 0.0010 (0.0012) C7 * 0.0005 (0.0013) C8 * -0.0018 (0.0013) C9 * 0.0025 (0.0012) N10 * -0.0022 (0.0011) N11

Rms deviation of fitted atoms = 0.0018

0.5565 (162)x + 7.0399 (16)y - 2.8757 (96)z = 2.1353 (57)

Angle to previous plane (with approximate e.s.d.) = 24.94 (4)

* -0.0041 (0.0014) C15 * 0.0012 (0.0015) C16 * 0.0046 (0.0015) C17 * -0.0076 (0.0015) C18 * 0.0045 (0.0015) C19 * 0.0013 (0.0015) C20

Rms deviation of fitted atoms = 0.0045

- 2.3188 (203) x + 7.1421 (15) y + 1.8291 (117) z = 2.8504 (36)

* 0.0010 (0.0012) C7 * 0.0025 (0.0012) N10 * 0.0005 (0.0013) C8 * -0.0022 (0.0011) N11 * -0.0018 (0.0013) C9

Rms deviation of fitted atoms = 0.0018

2.1589 (174) x + 7.1466 (32) y - 1.8475 (253) z = 1.9057 (72)

Angle to previous plane (with approximate e.s.d.) = 22.17 (0.07)

* -0.0044 (0.0010) N10 * 0.0254 (0.0013) C14 * -0.0200 (0.0012) C12 * -0.0263 (0.0011) C15 * 0.0252 (0.0015) C13

Rms deviation of fitted atoms = 0.0219

0.5565 (162) x + 7.0399 (16) y - 2.8757 (96) z = 2.1353 (57)

Angle to previous plane (with approximate e.s.d.) = 7.50 (0.10)

* -0.0041 (0.0014) C15 * -0.0076 (0.0015) C18 * 0.0012 (0.0015) C16 * 0.0045 (0.0015) C19 * 0.0046 (0.0015) C17 * 0.0013 (0.0015) C20

Rms deviation of fitted atoms = 0.0045

Refinement. 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
C1	0.22305 (11)	0.4214 (3)	0.27525 (17)	0.0207 (4)
H1	0.1991	0.4564	0.2012	0.025*
C2	0.29563 (11)	0.4303 (3)	0.29067 (19)	0.0235 (4)
H2	0.3213	0.4716	0.2277	0.028*
Cl3	0.42157 (3)	0.38898 (9)	0.41830 (6)	0.03759 (17)
C3	0.33051 (11)	0.3784 (3)	0.3987 (2)	0.0236 (4)
C4	0.29395 (11)	0.3204 (3)	0.49185 (19)	0.0252 (4)
H4	0.3183	0.2861	0.5657	0.030*
C5	0.22148 (11)	0.3127 (3)	0.47622 (18)	0.0229 (4)
H5	0.1962	0.2738	0.5403	0.027*
C6	0.18454 (10)	0.3613 (3)	0.36767 (17)	0.0186 (4)
C7	0.10761 (10)	0.3438 (3)	0.35279 (17)	0.0183 (4)
C8	0.06191 (11)	0.3065 (3)	0.44014 (18)	0.0241 (4)
H8	0.0739	0.2894	0.5230	0.029*
C9	−0.00366 (11)	0.3003 (3)	0.38031 (17)	0.0242 (4)
H9	−0.0465	0.2772	0.4138	0.029*
N10	0.00423 (8)	0.3331 (2)	0.26438 (14)	0.0194 (3)
N11	0.07216 (9)	0.3596 (2)	0.24465 (15)	0.0195 (3)
C12	−0.04835 (10)	0.3203 (3)	0.16175 (17)	0.0207 (4)
H12A	−0.0468	0.1959	0.1267	0.025*
H12B	−0.0370	0.4101	0.1005	0.025*
C13	−0.12186 (10)	0.3578 (3)	0.19656 (17)	0.0200 (4)
H13A	−0.1234	0.4817	0.2324	0.024*
H13B	−0.1336	0.2671	0.2570	0.024*
C14	−0.17585 (10)	0.3464 (3)	0.08904 (18)	0.0204 (4)
O14	−0.15794 (8)	0.3182 (2)	−0.00984 (13)	0.0308 (4)
C15	−0.25147 (10)	0.3671 (3)	0.10904 (18)	0.0199 (4)
C16	−0.27366 (11)	0.4147 (3)	0.21927 (18)	0.0234 (4)
H16	−0.2400	0.4389	0.2847	0.028*
C17	−0.34459 (11)	0.4267 (3)	0.23383 (19)	0.0255 (4)
H17	−0.3596	0.4600	0.3088	0.031*
Cl18	−0.48173 (3)	0.39787 (9)	0.15999 (6)	0.03929 (18)
C18	−0.39355 (11)	0.3898 (3)	0.1383 (2)	0.0252 (4)
C19	−0.37282 (11)	0.3445 (3)	0.0272 (2)	0.0267 (5)
H19	−0.4067	0.3219	−0.0383	0.032*
C20	−0.30176 (11)	0.3330 (3)	0.01395 (18)	0.0227 (4)
H20	−0.2869	0.3013	−0.0614	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0233 (10)	0.0194 (10)	0.0191 (9)	0.0025 (8)	0.0013 (7)	−0.0021 (7)
C2	0.0246 (10)	0.0215 (10)	0.0252 (10)	0.0000 (8)	0.0063 (8)	−0.0015 (8)
Cl3	0.0187 (3)	0.0380 (3)	0.0550 (4)	0.0020 (2)	−0.0017 (2)	−0.0005 (3)
C3	0.0175 (9)	0.0195 (10)	0.0333 (11)	0.0013 (8)	−0.0008 (8)	−0.0038 (8)
C4	0.0277 (11)	0.0231 (10)	0.0230 (10)	0.0011 (8)	−0.0069 (8)	0.0000 (8)
C5	0.0265 (10)	0.0231 (10)	0.0187 (9)	−0.0010 (8)	0.0000 (8)	0.0013 (8)
C6	0.0210 (9)	0.0157 (9)	0.0188 (9)	−0.0007 (7)	0.0008 (7)	−0.0029 (7)
C7	0.0206 (9)	0.0166 (9)	0.0176 (9)	0.0012 (7)	0.0014 (7)	−0.0016 (7)
C8	0.0243 (10)	0.0310 (11)	0.0171 (9)	−0.0013 (9)	0.0022 (8)	0.0014 (8)
C9	0.0235 (10)	0.0312 (11)	0.0184 (9)	−0.0022 (8)	0.0050 (8)	0.0007 (8)
N10	0.0167 (8)	0.0236 (9)	0.0177 (8)	−0.0005 (6)	0.0002 (6)	−0.0002 (7)
N11	0.0175 (8)	0.0212 (8)	0.0197 (8)	−0.0008 (6)	0.0020 (6)	0.0012 (6)
C12	0.0203 (9)	0.0259 (10)	0.0160 (9)	−0.0020 (8)	0.0018 (7)	0.0007 (8)
C13	0.0191 (9)	0.0217 (10)	0.0192 (9)	−0.0011 (7)	0.0014 (7)	0.0013 (7)
C14	0.0203 (9)	0.0188 (9)	0.0218 (9)	−0.0007 (7)	0.0000 (8)	0.0024 (7)
O14	0.0248 (8)	0.0476 (10)	0.0200 (7)	0.0013 (7)	0.0022 (6)	0.0004 (7)
C15	0.0207 (9)	0.0173 (9)	0.0212 (9)	−0.0010 (7)	−0.0002 (7)	0.0038 (7)
C16	0.0231 (10)	0.0238 (10)	0.0227 (10)	−0.0004 (8)	−0.0010 (8)	−0.0012 (8)
C17	0.0260 (10)	0.0255 (11)	0.0255 (10)	0.0022 (9)	0.0056 (8)	−0.0026 (8)
Cl18	0.0203 (3)	0.0497 (4)	0.0485 (4)	0.0002 (2)	0.0062 (2)	−0.0026 (3)
C18	0.0188 (10)	0.0229 (10)	0.0341 (11)	0.0013 (8)	0.0032 (8)	0.0026 (9)
C19	0.0226 (10)	0.0288 (11)	0.0278 (11)	−0.0018 (9)	−0.0023 (8)	0.0012 (9)
C20	0.0246 (10)	0.0228 (10)	0.0205 (9)	−0.0001 (8)	0.0003 (8)	0.0016 (8)

Geometric parameters (Å, º)

C1—C2	1.385 (3)	C12—C13	1.520 (3)
C1—C6	1.402 (3)	C12—H12A	0.9900
C1—H1	0.9500	C12—H12B	0.9900
C2—C3	1.386 (3)	C13—C14	1.521 (3)
C2—H2	0.9500	C13—H13A	0.9900
Cl3—C3	1.738 (2)	C13—H13B	0.9900
C3—C4	1.383 (3)	C14—O14	1.215 (3)
C4—C5	1.382 (3)	C14—C15	1.493 (3)
C4—H4	0.9500	C15—C20	1.395 (3)
C5—C6	1.401 (3)	C15—C16	1.395 (3)
C5—H5	0.9500	C16—C17	1.385 (3)
C6—C7	1.471 (3)	C16—H16	0.9500
C7—N11	1.344 (2)	C17—C18	1.387 (3)
C7—C8	1.404 (3)	C17—H17	0.9500
C8—C9	1.369 (3)	Cl18—C18	1.729 (2)
C8—H8	0.9500	C18—C19	1.390 (3)
C9—N10	1.352 (3)	C19—C20	1.384 (3)
C9—H9	0.9500	C19—H19	0.9500
N10—N11	1.353 (2)	C20—H20	0.9500
N10—C12	1.464 (2)
C2—C1—C6	120.79 (18)	N10—C12—H12A	109.3
C2—C1—H1	119.6	C13—C12—H12A	109.3
C6—C1—H1	119.6	N10—C12—H12B	109.3
C1—C2—C3	119.49 (19)	C13—C12—H12B	109.3
C1—C2—H2	120.3	H12A—C12—H12B	108.0
C3—C2—H2	120.3	C12—C13—C14	111.09 (16)
C4—C3—C2	121.04 (19)	C12—C13—H13A	109.4
C4—C3—Cl3	119.32 (16)	C14—C13—H13A	109.4
C2—C3—Cl3	119.63 (17)	C12—C13—H13B	109.4
C5—C4—C3	119.23 (19)	C14—C13—H13B	109.4
C5—C4—H4	120.4	H13A—C13—H13B	108.0
C3—C4—H4	120.4	O14—C14—C15	121.11 (18)
C4—C5—C6	121.29 (19)	O14—C14—C13	120.88 (18)
C4—C5—H5	119.4	C15—C14—C13	118.00 (17)
C6—C5—H5	119.4	C20—C15—C16	118.98 (19)
C5—C6—C1	118.15 (19)	C20—C15—C14	118.30 (18)
C5—C6—C7	119.69 (18)	C16—C15—C14	122.69 (18)
C1—C6—C7	122.14 (17)	C17—C16—C15	120.32 (19)
N11—C7—C8	111.06 (17)	C17—C16—H16	119.8
N11—C7—C6	120.69 (17)	C15—C16—H16	119.8
C8—C7—C6	128.23 (18)	C16—C17—C18	119.6 (2)
C9—C8—C7	105.22 (17)	C16—C17—H17	120.2
C9—C8—H8	127.4	C18—C17—H17	120.2
C7—C8—H8	127.4	C17—C18—C19	121.2 (2)
N10—C9—C8	106.92 (18)	C17—C18—Cl18	118.70 (17)
N10—C9—H9	126.5	C19—C18—Cl18	120.07 (17)
C8—C9—H9	126.5	C20—C19—C18	118.55 (19)
C9—N10—N11	112.36 (16)	C20—C19—H19	120.7
C9—N10—C12	128.55 (17)	C18—C19—H19	120.7
N11—N10—C12	118.59 (15)	C19—C20—C15	121.3 (2)
C7—N11—N10	104.44 (16)	C19—C20—H20	119.3
N10—C12—C13	111.59 (16)	C15—C20—H20	119.3
C6—C1—C2—C3	0.3 (3)	C9—N10—N11—C7	−0.5 (2)
C1—C2—C3—C4	−0.9 (3)	C12—N10—N11—C7	−173.05 (17)
C1—C2—C3—Cl3	179.87 (15)	C9—N10—C12—C13	28.8 (3)
C2—C3—C4—C5	0.5 (3)	N11—N10—C12—C13	−160.02 (16)
Cl3—C3—C4—C5	179.75 (16)	N10—C12—C13—C14	179.32 (16)
C3—C4—C5—C6	0.5 (3)	C12—C13—C14—O14	−2.9 (3)
C4—C5—C6—C1	−1.1 (3)	C12—C13—C14—C15	175.93 (17)
C4—C5—C6—C7	177.37 (19)	O14—C14—C15—C20	7.1 (3)
C2—C1—C6—C5	0.7 (3)	C13—C14—C15—C20	−171.74 (18)
C2—C1—C6—C7	−177.72 (18)	O14—C14—C15—C16	−174.5 (2)
C5—C6—C7—N11	−168.74 (18)	C13—C14—C15—C16	6.6 (3)
C1—C6—C7—N11	9.7 (3)	C20—C15—C16—C17	0.3 (3)
C5—C6—C7—C8	9.7 (3)	C14—C15—C16—C17	−178.04 (19)
C1—C6—C7—C8	−171.9 (2)	C15—C16—C17—C18	0.5 (3)
N11—C7—C8—C9	−0.1 (2)	C16—C17—C18—C19	−1.3 (3)
C6—C7—C8—C9	−178.6 (2)	C16—C17—C18—Cl18	177.75 (16)
C7—C8—C9—N10	−0.2 (2)	C17—C18—C19—C20	1.3 (3)
C8—C9—N10—N11	0.4 (2)	Cl18—C18—C19—C20	−177.76 (16)
C8—C9—N10—C12	172.1 (2)	C18—C19—C20—C15	−0.5 (3)
C8—C7—N11—N10	0.3 (2)	C16—C15—C20—C19	−0.3 (3)
C6—C7—N11—N10	178.97 (17)	C14—C15—C20—C19	178.10 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O14^i	0.95	2.47	3.418 (3)	173

Symmetry code: (i) x, −y+1/2, z+1/2.