Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003634/ci6012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003634/ci6012Isup2.hkl |
CCDC reference: 159875
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.
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).
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.
Fig. 1. The molecular configuration and atom-numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level. |
C15H15ClN2O2 | Dx = 1.430 Mg m−3 |
Mr = 290.74 | Melting point: 387-400 K K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.379 (3) Å | Cell parameters from 7161 reflections |
b = 9.389 (2) Å | θ = 2.9–27.5° |
c = 12.995 (3) Å | µ = 0.29 mm−1 |
β = 116.60 (3)° | T = 150 K |
V = 1350.6 (5) Å3 | Prism, red |
Z = 4 | 0.20 × 0.14 × 0.14 mm |
F(000) = 608 |
Enraf Nonius KappaCCD area-detector diffractometer | 3067 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 2322 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −15→14 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = 0→12 |
Tmin = 0.945, Tmax = 0.961 | l = 0→16 |
11054 measured reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-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 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
C15H15ClN2O2 | V = 1350.6 (5) Å3 |
Mr = 290.74 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.379 (3) Å | µ = 0.29 mm−1 |
b = 9.389 (2) Å | T = 150 K |
c = 12.995 (3) Å | 0.20 × 0.14 × 0.14 mm |
β = 116.60 (3)° |
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 = 0.961 | Rint = 0.057 |
11054 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.23 e Å−3 |
3067 reflections | Δρmin = −0.46 e Å−3 |
182 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.89909 (14) | −0.03254 (17) | 0.23676 (13) | 0.0240 (4) | |
O1 | 0.79363 (10) | −0.01992 (14) | 0.16625 (10) | 0.0383 (3) | |
C2 | 0.99739 (14) | 0.03580 (16) | 0.22078 (12) | 0.0211 (3) | |
Cl2 | 0.94716 (4) | 0.15460 (5) | 0.10630 (3) | 0.03148 (16) | |
C3 | 1.11721 (13) | 0.01831 (16) | 0.29166 (12) | 0.0185 (3) | |
N31 | 1.21129 (12) | 0.06901 (14) | 0.27450 (10) | 0.0220 (3) | |
C32 | 1.20713 (15) | 0.08709 (19) | 0.16036 (12) | 0.0248 (4) | |
H321 | 1.1918 | 0.1882 | 0.1367 | 0.031* | |
H322 | 1.1406 | 0.0293 | 0.1029 | 0.031* | |
C33 | 1.32618 (15) | 0.04042 (18) | 0.16517 (13) | 0.0245 (4) | |
H331 | 1.3374 | −0.0628 | 0.1823 | 0.031* | |
H332 | 1.3242 | 0.0560 | 0.0890 | 0.031* | |
N34 | 1.42799 (12) | 0.11799 (14) | 0.25238 (10) | 0.0209 (3) | |
C35 | 1.43165 (14) | 0.09283 (17) | 0.36551 (12) | 0.0220 (4) | |
H351 | 1.5003 | 0.1456 | 0.4253 | 0.027* | |
H352 | 1.4439 | −0.0099 | 0.3843 | 0.027* | |
C36 | 1.31504 (14) | 0.14127 (17) | 0.36517 (12) | 0.0213 (4) | |
H361 | 1.3175 | 0.1204 | 0.4409 | 0.027* | |
H362 | 1.3062 | 0.2455 | 0.3527 | 0.027* | |
C37 | 1.54101 (15) | 0.06948 (18) | 0.25506 (14) | 0.0262 (4) | |
H371 | 1.6082 | 0.1248 | 0.3121 | 0.033* | |
H372 | 1.5379 | 0.0826 | 0.1790 | 0.033* | |
H373 | 1.5529 | −0.0316 | 0.2759 | 0.033* | |
C4 | 1.15166 (14) | −0.07536 (16) | 0.39713 (12) | 0.0190 (3) | |
O4 | 1.25679 (9) | −0.10712 (12) | 0.45637 (8) | 0.0258 (3) | |
C5 | 1.08581 (15) | −0.20685 (17) | 0.52433 (12) | 0.0248 (4) | |
H5 | 1.1684 | −0.2193 | 0.5774 | 0.031* | |
C6 | 0.99591 (17) | −0.26450 (19) | 0.54739 (14) | 0.0306 (4) | |
H6 | 1.0171 | −0.3161 | 0.6167 | 0.038* | |
C7 | 0.87551 (15) | −0.24747 (18) | 0.47035 (14) | 0.0286 (4) | |
H7 | 0.8145 | −0.2880 | 0.4866 | 0.036* | |
C8 | 0.84372 (15) | −0.17140 (18) | 0.36950 (14) | 0.0260 (4) | |
H8 | 0.7610 | −0.1596 | 0.3167 | 0.032* | |
C9 | 0.93340 (14) | −0.11219 (16) | 0.34565 (13) | 0.0209 (3) | |
C10 | 1.05473 (14) | −0.13066 (16) | 0.42324 (12) | 0.0190 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0193 (8) | 0.0227 (9) | 0.0287 (8) | 0.0012 (6) | 0.0097 (7) | −0.0001 (6) |
O1 | 0.0167 (6) | 0.0484 (8) | 0.0409 (7) | 0.0000 (6) | 0.0048 (5) | 0.0138 (6) |
C2 | 0.0222 (8) | 0.0209 (8) | 0.0193 (7) | 0.0015 (6) | 0.0085 (6) | 0.0021 (6) |
Cl2 | 0.0256 (3) | 0.0350 (3) | 0.0296 (2) | 0.00451 (18) | 0.00853 (18) | 0.01337 (17) |
C3 | 0.0195 (8) | 0.0190 (8) | 0.0190 (7) | −0.0010 (6) | 0.0105 (6) | −0.0028 (6) |
N31 | 0.0186 (7) | 0.0308 (8) | 0.0177 (6) | −0.0061 (6) | 0.0090 (5) | −0.0026 (5) |
C32 | 0.0239 (9) | 0.0338 (10) | 0.0173 (7) | −0.0052 (7) | 0.0097 (7) | 0.0013 (6) |
C33 | 0.0280 (9) | 0.0296 (9) | 0.0192 (7) | −0.0063 (7) | 0.0135 (7) | −0.0024 (6) |
N34 | 0.0200 (7) | 0.0248 (7) | 0.0207 (6) | −0.0027 (5) | 0.0116 (6) | −0.0004 (5) |
C35 | 0.0205 (8) | 0.0262 (9) | 0.0195 (7) | −0.0016 (7) | 0.0093 (7) | −0.0002 (6) |
C36 | 0.0208 (8) | 0.0242 (9) | 0.0195 (7) | −0.0053 (6) | 0.0097 (6) | −0.0037 (6) |
C37 | 0.0247 (9) | 0.0294 (9) | 0.0295 (8) | −0.0001 (7) | 0.0165 (7) | 0.0010 (7) |
C4 | 0.0188 (8) | 0.0208 (8) | 0.0182 (7) | 0.0003 (6) | 0.0089 (6) | −0.0031 (6) |
O4 | 0.0170 (6) | 0.0353 (7) | 0.0244 (6) | 0.0015 (5) | 0.0087 (5) | 0.0042 (5) |
C5 | 0.0246 (9) | 0.0274 (9) | 0.0229 (8) | −0.0007 (7) | 0.0111 (7) | −0.0005 (6) |
C6 | 0.0364 (10) | 0.0336 (10) | 0.0290 (8) | −0.0029 (8) | 0.0211 (8) | 0.0024 (7) |
C7 | 0.0287 (10) | 0.0292 (10) | 0.0378 (9) | −0.0057 (7) | 0.0237 (8) | −0.0036 (7) |
C8 | 0.0192 (8) | 0.0262 (9) | 0.0358 (9) | −0.0018 (7) | 0.0153 (7) | −0.0064 (7) |
C9 | 0.0199 (8) | 0.0191 (8) | 0.0261 (8) | −0.0007 (6) | 0.0123 (7) | −0.0029 (6) |
C10 | 0.0199 (8) | 0.0196 (8) | 0.0212 (7) | −0.0007 (6) | 0.0124 (6) | −0.0026 (6) |
C1—O1 | 1.2193 (19) | C35—H352 | 0.99 |
C1—C2 | 1.470 (2) | C36—H361 | 0.99 |
C1—C9 | 1.484 (2) | C36—H362 | 0.99 |
C2—C3 | 1.361 (2) | C37—H371 | 0.98 |
C2—Cl2 | 1.7365 (15) | C37—H372 | 0.98 |
C3—N31 | 1.3657 (19) | C37—H373 | 0.98 |
C3—C4 | 1.520 (2) | C4—O4 | 1.2157 (19) |
N31—C36 | 1.464 (2) | C4—C10 | 1.480 (2) |
N31—C32 | 1.4708 (18) | C5—C6 | 1.386 (2) |
C32—C33 | 1.512 (2) | C5—C10 | 1.390 (2) |
C32—H321 | 0.99 | C5—H5 | 0.95 |
C32—H322 | 0.99 | C6—C7 | 1.383 (2) |
C33—N34 | 1.457 (2) | C6—H6 | 0.95 |
C33—H331 | 0.99 | C7—C8 | 1.386 (2) |
C33—H332 | 0.99 | C7—H7 | 0.95 |
N34—C37 | 1.457 (2) | C8—C9 | 1.395 (2) |
N34—C35 | 1.4695 (19) | C8—H8 | 0.95 |
C35—C36 | 1.512 (2) | C9—C10 | 1.395 (2) |
C35—H351 | 0.99 | ||
O1—C1—C2 | 121.79 (14) | N31—C36—C35 | 110.82 (13) |
O1—C1—C9 | 121.22 (15) | N31—C36—H361 | 109.5 |
C2—C1—C9 | 116.92 (13) | C35—C36—H361 | 109.5 |
C3—C2—C1 | 124.88 (13) | N31—C36—H362 | 109.5 |
C3—C2—Cl2 | 121.40 (12) | C35—C36—H362 | 109.5 |
C1—C2—Cl2 | 113.56 (11) | H361—C36—H362 | 108.1 |
C2—C3—N31 | 126.73 (13) | N34—C37—H371 | 109.5 |
C2—C3—C4 | 117.44 (13) | N34—C37—H372 | 109.5 |
N31—C3—C4 | 115.69 (13) | H371—C37—H372 | 109.5 |
C3—N31—C36 | 122.35 (12) | N34—C37—H373 | 109.5 |
C3—N31—C32 | 123.89 (12) | H371—C37—H373 | 109.5 |
C36—N31—C32 | 112.34 (12) | H372—C37—H373 | 109.5 |
N31—C32—C33 | 109.37 (13) | O4—C4—C10 | 121.12 (13) |
N31—C32—H321 | 109.8 | O4—C4—C3 | 120.10 (14) |
C33—C32—H321 | 109.8 | C10—C4—C3 | 118.74 (13) |
N31—C32—H322 | 109.8 | C6—C5—C10 | 119.74 (15) |
C33—C32—H322 | 109.8 | C6—C5—H5 | 120.1 |
H321—C32—H322 | 108.2 | C10—C5—H5 | 120.1 |
N34—C33—C32 | 112.01 (13) | C7—C6—C5 | 120.52 (15) |
N34—C33—H331 | 109.2 | C7—C6—H6 | 119.7 |
C32—C33—H331 | 109.2 | C5—C6—H6 | 119.7 |
N34—C33—H332 | 109.2 | C6—C7—C8 | 120.11 (15) |
C32—C33—H332 | 109.2 | C6—C7—H7 | 119.9 |
H331—C33—H332 | 107.9 | C8—C7—H7 | 119.9 |
C37—N34—C33 | 110.43 (13) | C7—C8—C9 | 119.89 (16) |
C37—N34—C35 | 109.07 (12) | C7—C8—H8 | 120.1 |
C33—N34—C35 | 109.03 (12) | C9—C8—H8 | 120.1 |
N34—C35—C36 | 110.31 (12) | C10—C9—C8 | 119.76 (14) |
N34—C35—H351 | 109.6 | C10—C9—C1 | 120.50 (14) |
C36—C35—H351 | 109.6 | C8—C9—C1 | 119.74 (14) |
N34—C35—H352 | 109.6 | C5—C10—C9 | 119.98 (14) |
C36—C35—H352 | 109.6 | C5—C10—C4 | 119.17 (14) |
H351—C35—H352 | 108.1 | C9—C10—C4 | 120.79 (13) |
O1—C1—C2—C3 | −175.21 (15) | N31—C3—C4—O4 | −4.0 (2) |
C9—C1—C2—C3 | 7.7 (2) | C2—C3—C4—C10 | −5.8 (2) |
O1—C1—C2—Cl2 | 9.2 (2) | N31—C3—C4—C10 | 178.19 (12) |
C9—C1—C2—Cl2 | −167.87 (11) | C10—C5—C6—C7 | 0.3 (2) |
C1—C2—C3—N31 | 173.57 (14) | C5—C6—C7—C8 | −0.5 (2) |
Cl2—C2—C3—N31 | −11.2 (2) | C6—C7—C8—C9 | 0.1 (2) |
C1—C2—C3—C4 | −1.9 (2) | C7—C8—C9—C10 | 0.4 (2) |
Cl2—C2—C3—C4 | 173.27 (10) | C7—C8—C9—C1 | 179.13 (14) |
C2—C3—N31—C36 | 133.54 (16) | O1—C1—C9—C10 | 177.34 (15) |
C4—C3—N31—C36 | −50.89 (19) | C2—C1—C9—C10 | −5.5 (2) |
C2—C3—N31—C32 | −31.8 (2) | O1—C1—C9—C8 | −1.4 (2) |
C4—C3—N31—C32 | 143.77 (14) | C2—C1—C9—C8 | 175.74 (14) |
C3—N31—C32—C33 | −139.34 (15) | C6—C5—C10—C9 | 0.2 (2) |
C36—N31—C32—C33 | 54.02 (17) | C6—C5—C10—C4 | −177.20 (14) |
N31—C32—C33—N34 | −56.84 (17) | C8—C9—C10—C5 | −0.5 (2) |
C32—C33—N34—C37 | 179.58 (12) | C1—C9—C10—C5 | −179.27 (14) |
C32—C33—N34—C35 | 59.75 (17) | C8—C9—C10—C4 | 176.81 (14) |
C37—N34—C35—C36 | −179.62 (12) | C1—C9—C10—C4 | −1.9 (2) |
C33—N34—C35—C36 | −58.95 (16) | O4—C4—C10—C5 | 7.3 (2) |
C3—N31—C36—C35 | 138.07 (14) | C3—C4—C10—C5 | −174.89 (13) |
C32—N31—C36—C35 | −55.05 (17) | O4—C4—C10—C9 | −170.04 (14) |
N34—C35—C36—N31 | 57.04 (16) | C3—C4—C10—C9 | 7.8 (2) |
C2—C3—C4—O4 | 172.01 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C32—H321···O4i | 0.99 | 2.50 | 3.369 (2) | 146 |
C32—H322···Cl2 | 0.99 | 2.69 | 3.038 (2) | 101 |
C36—H361···O4 | 0.99 | 2.30 | 2.851 (2) | 114 |
Symmetry code: (i) −x+5/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H15ClN2O2 |
Mr | 290.74 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 12.379 (3), 9.389 (2), 12.995 (3) |
β (°) | 116.60 (3) |
V (Å3) | 1350.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.20 × 0.14 × 0.14 |
Data collection | |
Diffractometer | Enraf Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.945, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11054, 3067, 2322 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.116, 1.03 |
No. of reflections | 3067 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
C32—H321···O4i | 0.99 | 2.50 | 3.369 (2) | 146 |
C32—H322···Cl2 | 0.99 | 2.69 | 3.038 (2) | 101 |
C36—H361···O4 | 0.99 | 2.30 | 2.851 (2) | 114 |
Symmetry code: (i) −x+5/2, y+1/2, −z+1/2. |
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.