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In the title mol­ecule, C15H15ClN2O2, the piperazine ring adopts a chair conformation and the mean plane through that ring forms a dihedral angle of 43.66 (6)° with the planar naphtho­quinone moiety. The structure contains two intramolecular C—H...X short contacts to the Cl atom and one of the O atoms, and one intermolecular short contact to the same O atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003634/ci6012sup1.cif
Contains datablocks I, default

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003634/ci6012Isup2.hkl
Contains datablock I

CCDC reference: 159875

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.042
  • wR factor = 0.116
  • Data-to-parameter ratio = 16.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

The title compound, (I), is a derivative of 2,3-dichloro-1,4-naphthoquinone (Dichlone; Metras, 1961; Ikemoto et al., 1977). In Dichlone, both Cl atoms can equally be displaced by nucleophiles, but once one Cl is replaced then the substituent deactivates the second Cl, thus additional replacement by a second nucleophile is much slower. Dichlone and its derivatives display both herbicidal and pesticidal activity (Merck Index, 1996), for which reasons we have instigated a program of research to investigate the biological properties of a range of new Dichlone derivatives. A search of the Cambridge Structural Database (Allen & Kennard, 1993; Fletcher et al., 1996) indicated that there are nine previously reported monosubstituted derivatives of Dichlone, of which six were prepared by nucleophilic replacement of one Cl atom. We report here the single-crystal structure of the 4-methylpiperazino analogue, (I), which is in addition to our recently reported structures of the morpholino (Lynch & McClenaghan, 2000a), pyrrolidin-1-yl (Lynch & McClenaghan, 2000b) and 4-(ethoxycarbonyl)-1-piperidyl (Lynch & McClenaghan, 2001) derivatives of Dichlone.

Experimental top

The title compound, (I), was prepared by Spa Contract Synthesis. Crystals of (I) formed when the reaction solution N-methylpyrrolidone was pored into excess water.

Refinement top

All H atoms were included in the refinement at calculated positions as riding models, with C—H distances of 0.95 (Ar—H), 0.98 Å (CH3) and 0.99 Å (CH2).

Computing details top

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); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level.
2-Chloro-3-(4-methylpiperizino)-1,4-naphthoquinone top
Crystal data top
C15H15ClN2O2Dx = 1.430 Mg m3
Mr = 290.74Melting point: 387-400 K K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.379 (3) ÅCell parameters from 7161 reflections
b = 9.389 (2) Åθ = 2.9–27.5°
c = 12.995 (3) ŵ = 0.29 mm1
β = 116.60 (3)°T = 150 K
V = 1350.6 (5) Å3Prism, red
Z = 40.20 × 0.14 × 0.14 mm
F(000) = 608
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
3067 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode2322 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 1514
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 012
Tmin = 0.945, Tmax = 0.961l = 016
11054 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0685P)2]
where P = (Fo2 + 2Fc2)/3
3067 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C15H15ClN2O2V = 1350.6 (5) Å3
Mr = 290.74Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.379 (3) ŵ = 0.29 mm1
b = 9.389 (2) ÅT = 150 K
c = 12.995 (3) Å0.20 × 0.14 × 0.14 mm
β = 116.60 (3)°
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
3067 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
2322 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.961Rint = 0.057
11054 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.03Δρmax = 0.23 e Å3
3067 reflectionsΔρmin = 0.46 e Å3
182 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.89909 (14)0.03254 (17)0.23676 (13)0.0240 (4)
O10.79363 (10)0.01992 (14)0.16625 (10)0.0383 (3)
C20.99739 (14)0.03580 (16)0.22078 (12)0.0211 (3)
Cl20.94716 (4)0.15460 (5)0.10630 (3)0.03148 (16)
C31.11721 (13)0.01831 (16)0.29166 (12)0.0185 (3)
N311.21129 (12)0.06901 (14)0.27450 (10)0.0220 (3)
C321.20713 (15)0.08709 (19)0.16036 (12)0.0248 (4)
H3211.19180.18820.13670.031*
H3221.14060.02930.10290.031*
C331.32618 (15)0.04042 (18)0.16517 (13)0.0245 (4)
H3311.33740.06280.18230.031*
H3321.32420.05600.08900.031*
N341.42799 (12)0.11799 (14)0.25238 (10)0.0209 (3)
C351.43165 (14)0.09283 (17)0.36551 (12)0.0220 (4)
H3511.50030.14560.42530.027*
H3521.44390.00990.38430.027*
C361.31504 (14)0.14127 (17)0.36517 (12)0.0213 (4)
H3611.31750.12040.44090.027*
H3621.30620.24550.35270.027*
C371.54101 (15)0.06948 (18)0.25506 (14)0.0262 (4)
H3711.60820.12480.31210.033*
H3721.53790.08260.17900.033*
H3731.55290.03160.27590.033*
C41.15166 (14)0.07536 (16)0.39713 (12)0.0190 (3)
O41.25679 (9)0.10712 (12)0.45637 (8)0.0258 (3)
C51.08581 (15)0.20685 (17)0.52433 (12)0.0248 (4)
H51.16840.21930.57740.031*
C60.99591 (17)0.26450 (19)0.54739 (14)0.0306 (4)
H61.01710.31610.61670.038*
C70.87551 (15)0.24747 (18)0.47035 (14)0.0286 (4)
H70.81450.28800.48660.036*
C80.84372 (15)0.17140 (18)0.36950 (14)0.0260 (4)
H80.76100.15960.31670.032*
C90.93340 (14)0.11219 (16)0.34565 (13)0.0209 (3)
C101.05473 (14)0.13066 (16)0.42324 (12)0.0190 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0193 (8)0.0227 (9)0.0287 (8)0.0012 (6)0.0097 (7)0.0001 (6)
O10.0167 (6)0.0484 (8)0.0409 (7)0.0000 (6)0.0048 (5)0.0138 (6)
C20.0222 (8)0.0209 (8)0.0193 (7)0.0015 (6)0.0085 (6)0.0021 (6)
Cl20.0256 (3)0.0350 (3)0.0296 (2)0.00451 (18)0.00853 (18)0.01337 (17)
C30.0195 (8)0.0190 (8)0.0190 (7)0.0010 (6)0.0105 (6)0.0028 (6)
N310.0186 (7)0.0308 (8)0.0177 (6)0.0061 (6)0.0090 (5)0.0026 (5)
C320.0239 (9)0.0338 (10)0.0173 (7)0.0052 (7)0.0097 (7)0.0013 (6)
C330.0280 (9)0.0296 (9)0.0192 (7)0.0063 (7)0.0135 (7)0.0024 (6)
N340.0200 (7)0.0248 (7)0.0207 (6)0.0027 (5)0.0116 (6)0.0004 (5)
C350.0205 (8)0.0262 (9)0.0195 (7)0.0016 (7)0.0093 (7)0.0002 (6)
C360.0208 (8)0.0242 (9)0.0195 (7)0.0053 (6)0.0097 (6)0.0037 (6)
C370.0247 (9)0.0294 (9)0.0295 (8)0.0001 (7)0.0165 (7)0.0010 (7)
C40.0188 (8)0.0208 (8)0.0182 (7)0.0003 (6)0.0089 (6)0.0031 (6)
O40.0170 (6)0.0353 (7)0.0244 (6)0.0015 (5)0.0087 (5)0.0042 (5)
C50.0246 (9)0.0274 (9)0.0229 (8)0.0007 (7)0.0111 (7)0.0005 (6)
C60.0364 (10)0.0336 (10)0.0290 (8)0.0029 (8)0.0211 (8)0.0024 (7)
C70.0287 (10)0.0292 (10)0.0378 (9)0.0057 (7)0.0237 (8)0.0036 (7)
C80.0192 (8)0.0262 (9)0.0358 (9)0.0018 (7)0.0153 (7)0.0064 (7)
C90.0199 (8)0.0191 (8)0.0261 (8)0.0007 (6)0.0123 (7)0.0029 (6)
C100.0199 (8)0.0196 (8)0.0212 (7)0.0007 (6)0.0124 (6)0.0026 (6)
Geometric parameters (Å, º) top
C1—O11.2193 (19)C35—H3520.99
C1—C21.470 (2)C36—H3610.99
C1—C91.484 (2)C36—H3620.99
C2—C31.361 (2)C37—H3710.98
C2—Cl21.7365 (15)C37—H3720.98
C3—N311.3657 (19)C37—H3730.98
C3—C41.520 (2)C4—O41.2157 (19)
N31—C361.464 (2)C4—C101.480 (2)
N31—C321.4708 (18)C5—C61.386 (2)
C32—C331.512 (2)C5—C101.390 (2)
C32—H3210.99C5—H50.95
C32—H3220.99C6—C71.383 (2)
C33—N341.457 (2)C6—H60.95
C33—H3310.99C7—C81.386 (2)
C33—H3320.99C7—H70.95
N34—C371.457 (2)C8—C91.395 (2)
N34—C351.4695 (19)C8—H80.95
C35—C361.512 (2)C9—C101.395 (2)
C35—H3510.99
O1—C1—C2121.79 (14)N31—C36—C35110.82 (13)
O1—C1—C9121.22 (15)N31—C36—H361109.5
C2—C1—C9116.92 (13)C35—C36—H361109.5
C3—C2—C1124.88 (13)N31—C36—H362109.5
C3—C2—Cl2121.40 (12)C35—C36—H362109.5
C1—C2—Cl2113.56 (11)H361—C36—H362108.1
C2—C3—N31126.73 (13)N34—C37—H371109.5
C2—C3—C4117.44 (13)N34—C37—H372109.5
N31—C3—C4115.69 (13)H371—C37—H372109.5
C3—N31—C36122.35 (12)N34—C37—H373109.5
C3—N31—C32123.89 (12)H371—C37—H373109.5
C36—N31—C32112.34 (12)H372—C37—H373109.5
N31—C32—C33109.37 (13)O4—C4—C10121.12 (13)
N31—C32—H321109.8O4—C4—C3120.10 (14)
C33—C32—H321109.8C10—C4—C3118.74 (13)
N31—C32—H322109.8C6—C5—C10119.74 (15)
C33—C32—H322109.8C6—C5—H5120.1
H321—C32—H322108.2C10—C5—H5120.1
N34—C33—C32112.01 (13)C7—C6—C5120.52 (15)
N34—C33—H331109.2C7—C6—H6119.7
C32—C33—H331109.2C5—C6—H6119.7
N34—C33—H332109.2C6—C7—C8120.11 (15)
C32—C33—H332109.2C6—C7—H7119.9
H331—C33—H332107.9C8—C7—H7119.9
C37—N34—C33110.43 (13)C7—C8—C9119.89 (16)
C37—N34—C35109.07 (12)C7—C8—H8120.1
C33—N34—C35109.03 (12)C9—C8—H8120.1
N34—C35—C36110.31 (12)C10—C9—C8119.76 (14)
N34—C35—H351109.6C10—C9—C1120.50 (14)
C36—C35—H351109.6C8—C9—C1119.74 (14)
N34—C35—H352109.6C5—C10—C9119.98 (14)
C36—C35—H352109.6C5—C10—C4119.17 (14)
H351—C35—H352108.1C9—C10—C4120.79 (13)
O1—C1—C2—C3175.21 (15)N31—C3—C4—O44.0 (2)
C9—C1—C2—C37.7 (2)C2—C3—C4—C105.8 (2)
O1—C1—C2—Cl29.2 (2)N31—C3—C4—C10178.19 (12)
C9—C1—C2—Cl2167.87 (11)C10—C5—C6—C70.3 (2)
C1—C2—C3—N31173.57 (14)C5—C6—C7—C80.5 (2)
Cl2—C2—C3—N3111.2 (2)C6—C7—C8—C90.1 (2)
C1—C2—C3—C41.9 (2)C7—C8—C9—C100.4 (2)
Cl2—C2—C3—C4173.27 (10)C7—C8—C9—C1179.13 (14)
C2—C3—N31—C36133.54 (16)O1—C1—C9—C10177.34 (15)
C4—C3—N31—C3650.89 (19)C2—C1—C9—C105.5 (2)
C2—C3—N31—C3231.8 (2)O1—C1—C9—C81.4 (2)
C4—C3—N31—C32143.77 (14)C2—C1—C9—C8175.74 (14)
C3—N31—C32—C33139.34 (15)C6—C5—C10—C90.2 (2)
C36—N31—C32—C3354.02 (17)C6—C5—C10—C4177.20 (14)
N31—C32—C33—N3456.84 (17)C8—C9—C10—C50.5 (2)
C32—C33—N34—C37179.58 (12)C1—C9—C10—C5179.27 (14)
C32—C33—N34—C3559.75 (17)C8—C9—C10—C4176.81 (14)
C37—N34—C35—C36179.62 (12)C1—C9—C10—C41.9 (2)
C33—N34—C35—C3658.95 (16)O4—C4—C10—C57.3 (2)
C3—N31—C36—C35138.07 (14)C3—C4—C10—C5174.89 (13)
C32—N31—C36—C3555.05 (17)O4—C4—C10—C9170.04 (14)
N34—C35—C36—N3157.04 (16)C3—C4—C10—C97.8 (2)
C2—C3—C4—O4172.01 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C32—H321···O4i0.992.503.369 (2)146
C32—H322···Cl20.992.693.038 (2)101
C36—H361···O40.992.302.851 (2)114
Symmetry code: (i) x+5/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC15H15ClN2O2
Mr290.74
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)12.379 (3), 9.389 (2), 12.995 (3)
β (°) 116.60 (3)
V3)1350.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.20 × 0.14 × 0.14
Data collection
DiffractometerEnraf Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.945, 0.961
No. of measured, independent and
observed [I > 2σ(I)] reflections
11054, 3067, 2322
Rint0.057
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.116, 1.03
No. of reflections3067
No. of parameters182
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.46

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON97 (Spek, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C32—H321···O4i0.992.503.369 (2)146
C32—H322···Cl20.992.693.038 (2)101
C36—H361···O40.992.302.851 (2)114
Symmetry code: (i) x+5/2, y+1/2, z+1/2.
 

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