2-Chloro-3-[4-(ethoxy­carbonyl)-1-piperidyl]-1,4-naphtho­quinone

The structure of the title compound, C₁₈H₁₈ClNO₄, (I), comprises twisted mol­ecules that associate by an intermolecular C—H...O close contact to one of the naphtho­quinone O atoms. The other naphtho­quinone O atom and the Cl atom are involved in intramolecular C—H close contacts, while no similar interactions are observed to the carbethoxy O atoms. The ethyl C atoms are disordered over two sites.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.055
• wR factor = 0.154
• Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.118

PLAT_301  Alert C Main residue disorder ........................       8.00 Perc.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

NO COMMENT

S2. Experimental

The title compound, (I), was prepared by Spa Contract Synthesis. Crystals of (I) were grown from a methanol solution.

S3. Refinement

X-ray intensity data were measured with the maximum possible exposure time per frame (120 s) without overloading the detector due to background scatter. In addition, due to the very small size of the crystal, the rotating anode generator was operated at full power and equipped with a capillary lined collimator in order to increase incident X-ray intensity at the crystal position. However, even with this configuration the number of observed data was low and the resultant data(observed)/parameter ratio is 4.75. The large R_int value (> 0.10) may be due to a slight misalignment of the crystal in the X-ray beam. There is a positional disorder of the ethyl C atoms. A split-site model was applicable and it was assumed that there are two possible sets of positions C39A/C40A and C39B/C40B with 50% probability each. The geometry of O38—C39A—C40A and O38—C39B—C40B was restrained to be similar by the SAME instruction, and the displacement parameters of C39 and C40 (both A and B) were restrained to be nearly isotropic by the ISOR instraction of SHELXL97 (Sheldrick, 1997). All H atoms were included in the refinement at calculated positions as riding models with C—H set to 0.93 (Ar—H), 0.96 (CH₃), 0.97 Å (CH₂) and 0.98 Å (CH).

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular configuration and atom numbering scheme for (I), showing 50% probability ellipsoids. There is positional disorder of the ethyl group, C39 and C40.

2-Chloro-3-[4-(ethoxycarbonyl)-1-piperidyl]-1,4-naphthoquinone

Crystal data

C18H18ClNO4	F(000) = 728
Mr = 347.78	Dx = 1.389 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.780 (3) Å	Cell parameters from 1591 reflections
b = 16.931 (3) Å	θ = 1.0–27.5°
c = 7.8532 (16) Å	µ = 0.25 mm^−1
β = 101.85 (3)°	T = 298 K
V = 1663.1 (6) Å^3	Needle, orange
Z = 4	0.45 × 0.02 × 0.01 mm

Data collection

Enraf Nonius KappaCCD area-detector diffractometer	2802 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	1040 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.118
Detector resolution: 9.091 pixels mm^-1	θmax = 25.0°, θmin = 2.0°
ϕ and ω scans	h = −14→15
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −20→19
Tmin = 0.895, Tmax = 0.998	l = −9→9
9954 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.0586P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.92	(Δ/σ)max < 0.001
2802 reflections	Δρmax = 0.19 e Å^−3
238 parameters	Δρmin = −0.22 e Å^−3
27 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0073 (15)

Special details

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.8680 (3)	0.0461 (3)	0.2380 (6)	0.0584 (13)
O1	0.8973 (2)	0.0793 (2)	0.1157 (4)	0.0865 (11)
C2	0.8018 (3)	0.0873 (3)	0.3404 (6)	0.0537 (12)
Cl2	0.77616 (10)	0.18514 (8)	0.27846 (17)	0.0864 (5)
C3	0.7683 (3)	0.0558 (3)	0.4778 (6)	0.0533 (12)
C4	0.8034 (3)	−0.0272 (3)	0.5313 (6)	0.0565 (12)
O4	0.7686 (3)	−0.0615 (2)	0.6433 (4)	0.0873 (11)
C5	0.9145 (3)	−0.1432 (3)	0.4887 (6)	0.0690 (14)
H5	0.8970	−0.1658	0.5872	0.083*
C6	0.9781 (3)	−0.1847 (3)	0.3958 (7)	0.0746 (15)
H6	1.0022	−0.2353	0.4299	0.089*
C7	1.0047 (4)	−0.1496 (4)	0.2524 (7)	0.0795 (16)
H7	1.0476	−0.1768	0.1898	0.095*
C8	0.9694 (3)	−0.0755 (3)	0.2000 (6)	0.0683 (14)
H8	0.9883	−0.0527	0.1028	0.082*
C9	0.9047 (3)	−0.0341 (3)	0.2935 (6)	0.0522 (12)
C10	0.8766 (3)	−0.0682 (3)	0.4364 (6)	0.0514 (12)
N31	0.6976 (3)	0.0888 (2)	0.5680 (5)	0.0612 (10)
C32	0.7219 (3)	0.0921 (3)	0.7569 (6)	0.0666 (13)
H321	0.7486	0.1443	0.7942	0.080*
H322	0.7776	0.0541	0.8015	0.080*
C33	0.6247 (3)	0.0745 (3)	0.8309 (6)	0.0715 (15)
H331	0.6426	0.0801	0.9564	0.086*
H332	0.6025	0.0203	0.8042	0.086*
C34	0.5335 (3)	0.1298 (3)	0.7565 (6)	0.0620 (13)
H341	0.5556	0.1840	0.7895	0.074*
C35	0.5119 (3)	0.1232 (3)	0.5603 (6)	0.0748 (15)
H351	0.4557	0.1600	0.5108	0.090*
H352	0.4865	0.0703	0.5267	0.090*
C36	0.6100 (3)	0.1402 (3)	0.4858 (6)	0.0744 (14)
H361	0.5939	0.1311	0.3612	0.089*
H362	0.6308	0.1950	0.5062	0.089*
C37	0.4365 (4)	0.1107 (4)	0.8269 (7)	0.0769 (16)
O37	0.3804 (3)	0.0549 (3)	0.7853 (5)	0.1216 (16)
O38	0.4212 (3)	0.1606 (2)	0.9450 (6)	0.1123 (14)
C39A	0.3515 (8)	0.1423 (7)	1.0760 (16)	0.087 (4)	0.50
H39A	0.3222	0.0893	1.0613	0.104*	0.50
H39B	0.3900	0.1493	1.1950	0.104*	0.50
C40A	0.2664 (8)	0.2043 (8)	1.0238 (17)	0.097 (4)	0.50
H40A	0.2962	0.2556	1.0556	0.145*	0.50
H40B	0.2086	0.1946	1.0822	0.145*	0.50
H40C	0.2401	0.2023	0.9002	0.145*	0.50
C39B	0.3094 (8)	0.1473 (7)	0.9773 (15)	0.072 (3)	0.50
H39C	0.2553	0.1562	0.8729	0.086*	0.50
H39D	0.3014	0.0944	1.0205	0.086*	0.50
C40B	0.3047 (9)	0.2091 (7)	1.1144 (14)	0.076 (4)	0.50
H40D	0.3655	0.2034	1.2083	0.114*	0.50
H40E	0.2403	0.2023	1.1578	0.114*	0.50
H40F	0.3052	0.2607	1.0642	0.114*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.061 (3)	0.070 (4)	0.047 (3)	−0.002 (3)	0.016 (2)	0.000 (3)
O1	0.097 (2)	0.099 (3)	0.072 (2)	0.010 (2)	0.0381 (19)	0.021 (2)
C2	0.065 (3)	0.044 (3)	0.052 (3)	−0.005 (2)	0.012 (2)	0.002 (2)
Cl2	0.1009 (9)	0.0642 (10)	0.0989 (11)	0.0039 (8)	0.0319 (7)	0.0184 (9)
C3	0.055 (3)	0.056 (3)	0.049 (3)	−0.003 (2)	0.010 (2)	−0.004 (3)
C4	0.059 (3)	0.055 (4)	0.058 (3)	−0.005 (2)	0.019 (2)	0.002 (3)
O4	0.110 (2)	0.074 (3)	0.095 (3)	0.0127 (19)	0.060 (2)	0.023 (2)
C5	0.066 (3)	0.069 (4)	0.073 (4)	−0.004 (3)	0.017 (3)	−0.004 (3)
C6	0.067 (3)	0.058 (4)	0.097 (4)	0.013 (3)	0.012 (3)	0.005 (4)
C7	0.068 (3)	0.088 (5)	0.085 (4)	−0.001 (3)	0.022 (3)	−0.015 (4)
C8	0.058 (3)	0.085 (5)	0.065 (4)	−0.006 (3)	0.018 (2)	−0.003 (3)
C9	0.051 (2)	0.055 (4)	0.053 (3)	0.002 (2)	0.015 (2)	−0.003 (3)
C10	0.046 (2)	0.050 (3)	0.059 (3)	0.000 (2)	0.011 (2)	−0.002 (3)
N31	0.065 (2)	0.073 (3)	0.048 (3)	0.017 (2)	0.0171 (19)	−0.001 (2)
C32	0.068 (3)	0.076 (4)	0.059 (4)	0.004 (3)	0.019 (2)	−0.006 (3)
C33	0.064 (3)	0.093 (4)	0.060 (3)	0.000 (3)	0.019 (2)	−0.009 (3)
C34	0.062 (3)	0.055 (3)	0.075 (4)	−0.004 (2)	0.028 (2)	−0.008 (3)
C35	0.063 (3)	0.084 (4)	0.079 (4)	0.013 (3)	0.018 (3)	−0.001 (3)
C36	0.081 (3)	0.076 (4)	0.068 (3)	0.024 (3)	0.020 (3)	0.008 (3)
C37	0.068 (3)	0.076 (5)	0.090 (4)	−0.003 (3)	0.027 (3)	−0.009 (4)
O37	0.107 (3)	0.133 (4)	0.136 (4)	−0.056 (3)	0.053 (2)	−0.044 (3)
O38	0.113 (3)	0.095 (3)	0.157 (4)	−0.018 (2)	0.093 (3)	−0.034 (3)
C39A	0.084 (5)	0.093 (6)	0.086 (6)	0.004 (4)	0.023 (4)	0.007 (4)
C40A	0.091 (6)	0.097 (6)	0.102 (6)	0.002 (4)	0.020 (4)	−0.002 (5)
C39B	0.069 (5)	0.077 (5)	0.075 (5)	−0.006 (4)	0.025 (4)	−0.004 (4)
C40B	0.077 (5)	0.083 (5)	0.075 (5)	0.008 (4)	0.031 (4)	0.001 (4)

Geometric parameters (Å, º)

C1—O1	1.235 (5)	C33—H332	0.97
C1—C2	1.459 (6)	C34—C37	1.493 (6)
C1—C9	1.471 (6)	C34—C35	1.513 (5)
C2—C3	1.350 (5)	C34—H341	0.98
C2—Cl2	1.739 (4)	C35—C36	1.517 (5)
C3—N31	1.376 (5)	C35—H351	0.97
C3—C4	1.509 (6)	C35—H352	0.97
C4—O4	1.212 (5)	C36—H361	0.97
C4—C10	1.483 (5)	C36—H362	0.97
C5—C6	1.389 (6)	C37—O37	1.190 (6)
C5—C10	1.391 (6)	C37—O38	1.299 (6)
C5—H5	0.93	O38—C39A	1.525 (9)
C6—C7	1.377 (6)	O38—C39B	1.518 (9)
C6—H6	0.93	C39A—C40A	1.506 (11)
C7—C8	1.367 (6)	C39A—H39A	0.97
C7—H7	0.93	C39A—H39B	0.97
C8—C9	1.402 (6)	C40A—H40A	0.96
C8—H8	0.93	C40A—H40B	0.96
C9—C10	1.374 (5)	C40A—H40C	0.96
N31—C32	1.453 (5)	C39B—C40B	1.512 (11)
N31—C36	1.458 (5)	C39B—H39C	0.97
C32—C33	1.505 (5)	C39B—H39D	0.97
C32—H321	0.97	C40B—H40D	0.96
C32—H322	0.97	C40B—H40E	0.96
C33—C34	1.515 (5)	C40B—H40F	0.96
C33—H331	0.97
O1—C1—C2	120.8 (5)	C34—C33—H332	109.4
O1—C1—C9	121.4 (4)	H331—C33—H332	108.0
C2—C1—C9	117.6 (4)	C37—C34—C35	111.6 (4)
C3—C2—C1	124.5 (4)	C37—C34—C33	110.8 (4)
C3—C2—Cl2	121.8 (4)	C35—C34—C33	108.2 (4)
C1—C2—Cl2	113.5 (3)	C37—C34—H341	108.7
C2—C3—N31	126.9 (4)	C35—C34—H341	108.7
C2—C3—C4	117.7 (4)	C33—C34—H341	108.7
N31—C3—C4	115.1 (4)	C34—C35—C36	112.7 (4)
O4—C4—C10	120.3 (4)	C34—C35—H351	109.1
O4—C4—C3	121.0 (4)	C36—C35—H351	109.1
C10—C4—C3	118.6 (4)	C34—C35—H352	109.1
C6—C5—C10	120.8 (5)	C36—C35—H352	109.1
C6—C5—H5	119.6	H351—C35—H352	107.8
C10—C5—H5	119.6	N31—C36—C35	109.7 (4)
C7—C6—C5	118.7 (5)	N31—C36—H361	109.7
C7—C6—H6	120.6	C35—C36—H361	109.7
C5—C6—H6	120.6	N31—C36—H362	109.7
C8—C7—C6	121.4 (5)	C35—C36—H362	109.7
C8—C7—H7	119.3	H361—C36—H362	108.2
C6—C7—H7	119.3	O37—C37—O38	122.8 (5)
C7—C8—C9	119.7 (5)	O37—C37—C34	124.7 (5)
C7—C8—H8	120.2	O38—C37—C34	112.5 (5)
C9—C8—H8	120.2	C37—O38—C39A	122.9 (6)
C10—C9—C8	119.9 (4)	C40A—C39A—O38	99.4 (8)
C10—C9—C1	120.6 (4)	O38—C39A—H39A	111.9
C8—C9—C1	119.5 (5)	O38—C39A—H39B	111.9
C9—C10—C5	119.5 (4)	C40A—C39A—H39A	111.9
C9—C10—C4	120.8 (4)	C40A—C39A—H39B	111.9
C5—C10—C4	119.7 (4)	H39A—C39A—H39B	109.6
C3—N31—C32	121.0 (3)	C40B—C39B—O38	101.1 (8)
C3—N31—C36	122.6 (4)	O38—C39B—H39C	111.5
C32—N31—C36	114.4 (3)	O38—C39B—H39D	111.5
N31—C32—C33	111.5 (3)	C40B—C39B—H39C	111.5
N31—C32—H321	109.3	C40B—C39B—H39D	111.5
C33—C32—H321	109.3	H39C—C39B—H39D	109.4
N31—C32—H322	109.3	C39B—C40B—H40D	109.5
C33—C32—H322	109.3	C39B—C40B—H40E	109.5
H321—C32—H322	108.0	H40D—C40B—H40E	109.5
C32—C33—C34	111.0 (4)	C39B—C40B—H40F	109.5
C32—C33—H331	109.4	H40D—C40B—H40F	109.5
C34—C33—H331	109.4	H40E—C40B—H40F	109.5
C32—C33—H332	109.4
O1—C1—C2—C3	−178.6 (4)	C6—C5—C10—C4	176.2 (4)
C9—C1—C2—C3	−2.8 (6)	O4—C4—C10—C9	170.8 (4)
O1—C1—C2—Cl2	−2.8 (5)	C3—C4—C10—C9	−5.5 (6)
C9—C1—C2—Cl2	173.0 (3)	O4—C4—C10—C5	−6.9 (6)
C1—C2—C3—N31	−173.2 (4)	C3—C4—C10—C5	176.8 (4)
Cl2—C2—C3—N31	11.4 (6)	C2—C3—N31—C32	−131.7 (5)
C1—C2—C3—C4	1.1 (6)	C4—C3—N31—C32	53.9 (5)
Cl2—C2—C3—C4	−174.3 (3)	C2—C3—N31—C36	31.7 (6)
C2—C3—C4—O4	−173.3 (4)	C4—C3—N31—C36	−142.7 (4)
N31—C3—C4—O4	1.6 (6)	C3—N31—C32—C33	−139.9 (4)
C2—C3—C4—C10	2.9 (6)	C36—N31—C32—C33	55.4 (5)
N31—C3—C4—C10	177.9 (3)	N31—C32—C33—C34	−55.8 (5)
C10—C5—C6—C7	1.2 (7)	C32—C33—C34—C37	178.6 (4)
C5—C6—C7—C8	−0.4 (7)	C32—C33—C34—C35	55.8 (5)
C6—C7—C8—C9	0.0 (7)	C37—C34—C35—C36	−178.5 (4)
C7—C8—C9—C10	−0.3 (6)	C33—C34—C35—C36	−56.3 (5)
C7—C8—C9—C1	179.2 (4)	C3—N31—C36—C35	141.7 (4)
O1—C1—C9—C10	176.0 (4)	C32—N31—C36—C35	−53.9 (5)
C2—C1—C9—C10	0.2 (6)	C34—C35—C36—N31	54.8 (5)
O1—C1—C9—C8	−3.6 (6)	C35—C34—C37—O37	46.9 (7)
C2—C1—C9—C8	−179.3 (4)	C33—C34—C37—O37	−73.8 (7)
C8—C9—C10—C5	1.1 (6)	C35—C34—C37—O38	−135.4 (5)
C1—C9—C10—C5	−178.4 (4)	C33—C34—C37—O38	103.9 (5)
C8—C9—C10—C4	−176.6 (4)	O37—C37—O38—C39A	17.3 (10)
C1—C9—C10—C4	3.9 (6)	C34—C37—O38—C39A	−160.5 (6)
C6—C5—C10—C9	−1.6 (6)	C37—O38—C39A—C40A	−117.0 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1^i	0.93	2.51	3.285 (6)	141
C32—H322···O4	0.97	2.31	2.852 (6)	115
C36—H361···Cl2	0.97	2.70	3.026 (5)	100

Symmetry code: (i) −x+2, −y, −z.