Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018932/su6003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018932/su6003Isup2.hkl |
CCDC reference: 222919
The title compound was obtained from Key Organics Ltd and crystals were grown from ethanol solution.
Crystals in this series of compounds, including those not suitable for data collection, are thin plates with weak high angle data and high Rint values have occurred. The crystals of the title compound were extremely thin needles that resulted not only in weak high angle data but also in overall weak data, with the ratio of observed/unique reflections being ca 0.32. Hence, the Rint is very high (0.28) and the data/parameters ratio is low (ca 4). In the previous structures, the number of observed data was sufficiently high to generate data/parameters ratios well above 6. A l l H atoms were included in the refinement at calculated positions, as riding models with C—H set to 0.95 (Ar—H), 0.98 (CH3) and 0.99 Å (CH2). The isotropic displacement parameters were set equal to 1.25(Ueq) of the preceding normal atom except for N—H. The latter was located from a difference synthesis, and both the positional and displacement parameters were refined.
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 the title compound, showing 50% probability ellipsoids. |
C15H17ClN2O2 | F(000) = 616 |
Mr = 292.76 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0693 (8) Å | Cell parameters from 4100 reflections |
b = 13.002 (1) Å | θ = 2.9–27.5° |
c = 13.931 (2) Å | µ = 0.27 mm−1 |
β = 105.623 (4)° | T = 150 K |
V = 1407.6 (3) Å3 | Needle, red |
Z = 4 | 0.20 × 0.03 × 0.02 mm |
Bruker–Nonius KappaCCD area-detector diffractometer | 2439 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 777 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.277 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −15→15 |
Tmin = 0.947, Tmax = 0.995 | l = −15→16 |
9261 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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.176 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0498P)2] where P = (Fo2 + 2Fc2)/3 |
2439 reflections | (Δ/σ)max < 0.001 |
193 parameters | Δρmax = 0.24 e Å−3 |
15 restraints | Δρmin = −0.30 e Å−3 |
C15H17ClN2O2 | V = 1407.6 (3) Å3 |
Mr = 292.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0693 (8) Å | µ = 0.27 mm−1 |
b = 13.002 (1) Å | T = 150 K |
c = 13.931 (2) Å | 0.20 × 0.03 × 0.02 mm |
β = 105.623 (4)° |
Bruker–Nonius KappaCCD area-detector diffractometer | 2439 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 777 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.995 | Rint = 0.277 |
9261 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 15 restraints |
wR(F2) = 0.176 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | Δρmax = 0.24 e Å−3 |
2439 reflections | Δρmin = −0.30 e Å−3 |
193 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.1462 (7) | 0.4164 (5) | −0.1323 (5) | 0.0352 (18) | |
O1 | 0.1206 (5) | 0.4221 (4) | −0.2236 (3) | 0.0492 (14) | |
C2 | 0.2192 (7) | 0.4992 (5) | −0.0652 (5) | 0.0376 (17) | |
Cl2 | 0.2775 (2) | 0.60483 (15) | −0.12583 (13) | 0.0582 (6) | |
C3 | 0.2424 (7) | 0.4965 (5) | 0.0344 (5) | 0.0337 (17) | |
C4 | 0.1840 (7) | 0.4009 (6) | 0.0798 (5) | 0.0371 (17) | |
O4 | 0.2029 (5) | 0.3978 (4) | 0.1697 (3) | 0.0437 (13) | |
C5 | 0.0606 (7) | 0.2258 (5) | 0.0551 (5) | 0.0377 (18) | |
H5 | 0.0643 | 0.2231 | 0.1237 | 0.047* | |
C6 | 0.0033 (8) | 0.1424 (5) | −0.0060 (5) | 0.0429 (19) | |
H6 | −0.0335 | 0.0825 | 0.0214 | 0.054* | |
C7 | −0.0017 (7) | 0.1440 (5) | −0.1060 (5) | 0.043 (2) | |
H7 | −0.0386 | 0.0850 | −0.1463 | 0.054* | |
C8 | 0.0477 (7) | 0.2330 (6) | −0.1472 (5) | 0.0413 (18) | |
H8 | 0.0444 | 0.2350 | −0.2158 | 0.052* | |
C9 | 0.1021 (7) | 0.3193 (6) | −0.0864 (5) | 0.0351 (17) | |
C10 | 0.1128 (7) | 0.3138 (5) | 0.0151 (5) | 0.0308 (16) | |
N31 | 0.3104 (7) | 0.5656 (5) | 0.1056 (5) | 0.0437 (16) | |
H31 | 0.327 (6) | 0.542 (4) | 0.168 (4) | 0.019 (17)* | |
C32 | 0.3885 (7) | 0.6658 (5) | 0.0981 (4) | 0.052 (2) | |
H321 | 0.3130 | 0.7063 | 0.0433 | 0.065* | |
H322 | 0.5010 | 0.6564 | 0.0834 | 0.065* | |
C33A | 0.4137 (11) | 0.7239 (7) | 0.1993 (6) | 0.051 (3) | 0.79 |
H331 | 0.4700 | 0.7905 | 0.1940 | 0.063* | 0.79 |
H332 | 0.2984 | 0.7393 | 0.2077 | 0.063* | 0.79 |
C33B | 0.534 (3) | 0.692 (3) | 0.1913 (12) | 0.049 (9) | 0.21 |
H333 | 0.6372 | 0.6533 | 0.1871 | 0.061* | 0.21 |
H334 | 0.5608 | 0.7661 | 0.1875 | 0.061* | 0.21 |
C34 | 0.5102 (11) | 0.6741 (6) | 0.2867 (6) | 0.081 (3) | |
H341 | 0.5258 | 0.7225 | 0.3432 | 0.101* | |
H342 | 0.6258 | 0.6581 | 0.2788 | 0.101* | |
N35 | 0.4346 (7) | 0.5793 (5) | 0.3119 (4) | 0.0485 (16) | |
C36 | 0.3036 (8) | 0.5979 (6) | 0.3630 (5) | 0.062 (2) | |
H361 | 0.2606 | 0.5320 | 0.3808 | 0.077* | |
H362 | 0.2085 | 0.6365 | 0.3193 | 0.077* | |
H363 | 0.3528 | 0.6378 | 0.4237 | 0.077* | |
C37 | 0.5693 (7) | 0.5165 (5) | 0.3731 (4) | 0.075 (3) | |
H371 | 0.5376 | 0.4438 | 0.3627 | 0.094* | |
H372 | 0.5851 | 0.5342 | 0.4434 | 0.094* | |
H373 | 0.6768 | 0.5289 | 0.3550 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.041 (4) | 0.038 (5) | 0.030 (4) | 0.005 (4) | 0.016 (3) | 0.003 (4) |
O1 | 0.062 (3) | 0.057 (4) | 0.030 (3) | −0.001 (3) | 0.014 (2) | 0.004 (3) |
C2 | 0.048 (4) | 0.029 (5) | 0.037 (5) | 0.003 (4) | 0.016 (4) | 0.011 (4) |
Cl2 | 0.0771 (13) | 0.0474 (14) | 0.0505 (12) | −0.0090 (11) | 0.0179 (10) | 0.0134 (12) |
C3 | 0.042 (4) | 0.028 (5) | 0.030 (5) | 0.006 (3) | 0.008 (3) | −0.003 (4) |
C4 | 0.042 (4) | 0.035 (5) | 0.035 (5) | 0.006 (4) | 0.012 (3) | −0.001 (5) |
O4 | 0.064 (3) | 0.035 (3) | 0.033 (3) | −0.004 (2) | 0.015 (2) | −0.001 (3) |
C5 | 0.046 (4) | 0.035 (5) | 0.036 (4) | 0.003 (4) | 0.018 (4) | 0.004 (4) |
C6 | 0.051 (4) | 0.032 (5) | 0.051 (5) | 0.009 (4) | 0.022 (4) | −0.002 (4) |
C7 | 0.048 (4) | 0.034 (6) | 0.047 (5) | 0.002 (4) | 0.012 (4) | −0.009 (4) |
C8 | 0.043 (4) | 0.048 (6) | 0.033 (4) | 0.001 (4) | 0.010 (3) | −0.001 (5) |
C9 | 0.037 (4) | 0.034 (5) | 0.036 (5) | 0.009 (4) | 0.012 (3) | 0.005 (4) |
C10 | 0.034 (4) | 0.030 (5) | 0.028 (4) | 0.006 (3) | 0.007 (3) | −0.006 (4) |
N31 | 0.064 (4) | 0.028 (4) | 0.037 (4) | −0.001 (3) | 0.009 (3) | 0.007 (4) |
C32 | 0.061 (5) | 0.045 (6) | 0.052 (5) | −0.001 (4) | 0.022 (4) | 0.001 (4) |
C33A | 0.053 (4) | 0.039 (5) | 0.052 (4) | −0.005 (4) | 0.001 (4) | 0.001 (4) |
C33B | 0.048 (10) | 0.049 (11) | 0.049 (10) | −0.004 (5) | 0.014 (5) | 0.000 (5) |
C34 | 0.111 (7) | 0.060 (7) | 0.069 (6) | −0.034 (6) | 0.022 (5) | −0.003 (6) |
N35 | 0.065 (4) | 0.040 (5) | 0.045 (4) | −0.005 (3) | 0.021 (3) | 0.002 (3) |
C36 | 0.067 (5) | 0.060 (6) | 0.060 (5) | 0.003 (5) | 0.018 (4) | −0.004 (5) |
C37 | 0.075 (5) | 0.067 (7) | 0.090 (7) | 0.021 (5) | 0.032 (5) | 0.004 (6) |
C1—O1 | 1.235 (6) | N31—H31 | 0.90 (5) |
C1—C2 | 1.443 (8) | N35—C37 | 1.440 (6) |
C1—C9 | 1.500 (9) | N35—C36 | 1.445 (7) |
C2—C3 | 1.350 (8) | N35—C34 | 1.460 (9) |
C2—Cl2 | 1.742 (6) | C36—H361 | 0.98 |
C3—N31 | 1.341 (8) | C36—H362 | 0.98 |
C3—C4 | 1.526 (9) | C36—H363 | 0.98 |
C4—O4 | 1.220 (6) | C37—H371 | 0.98 |
C4—C10 | 1.465 (8) | C37—H372 | 0.98 |
C5—C10 | 1.385 (8) | C37—H373 | 0.98 |
C5—C6 | 1.378 (8) | C32—C33A | 1.563 (9) |
C5—H5 | 0.95 | C32—H321 | 0.99 |
C6—C7 | 1.383 (8) | C32—H322 | 0.99 |
C6—H6 | 0.95 | C33A—C34 | 1.414 (10) |
C7—C8 | 1.397 (8) | C33A—H331 | 0.99 |
C7—H7 | 0.95 | C33A—H332 | 0.99 |
C8—C9 | 1.404 (8) | C34—H341 | 0.99 |
C8—H8 | 0.95 | C34—H342 | 0.99 |
C9—C10 | 1.396 (8) | C33B—H333 | 0.99 |
N31—C32 | 1.463 (8) | C33B—H334 | 0.99 |
O1—C1—C2 | 123.2 (6) | C37—N35—C34 | 108.9 (6) |
O1—C1—C9 | 119.8 (7) | C36—N35—C34 | 112.7 (6) |
C2—C1—C9 | 117.0 (6) | N35—C36—H361 | 109.5 |
C3—C2—C1 | 124.4 (6) | N35—C36—H362 | 109.5 |
C3—C2—Cl2 | 122.6 (6) | H361—C36—H362 | 109.5 |
C1—C2—Cl2 | 113.0 (5) | N35—C36—H363 | 109.5 |
N31—C3—C2 | 131.2 (7) | H361—C36—H363 | 109.5 |
N31—C3—C4 | 110.5 (6) | H362—C36—H363 | 109.5 |
C2—C3—C4 | 118.3 (6) | N35—C37—H371 | 109.5 |
O4—C4—C10 | 121.7 (7) | N35—C37—H372 | 109.5 |
O4—C4—C3 | 119.0 (7) | H371—C37—H372 | 109.5 |
C10—C4—C3 | 119.3 (6) | N35—C37—H373 | 109.5 |
C10—C5—C6 | 119.3 (6) | H371—C37—H373 | 109.5 |
C10—C5—H5 | 120.4 | H372—C37—H373 | 109.5 |
C6—C5—H5 | 120.4 | N31—C32—C33A | 108.6 (5) |
C5—C6—C7 | 121.6 (7) | N31—C32—H321 | 110.0 |
C5—C6—H6 | 119.2 | C33A—C32—H321 | 110.0 |
C7—C6—H6 | 119.2 | N31—C32—H322 | 110.0 |
C6—C7—C8 | 119.5 (7) | C33A—C32—H322 | 110.0 |
C6—C7—H7 | 120.3 | H321—C32—H322 | 108.3 |
C8—C7—H7 | 120.3 | C34—C33A—C32 | 117.6 (7) |
C7—C8—C9 | 119.5 (6) | C34—C33A—H331 | 107.9 |
C7—C8—H8 | 120.2 | C32—C33A—H331 | 107.9 |
C9—C8—H8 | 120.2 | C34—C33A—H332 | 107.9 |
C10—C9—C8 | 119.6 (7) | C32—C33A—H332 | 107.9 |
C10—C9—C1 | 121.2 (7) | H331—C33A—H332 | 107.2 |
C8—C9—C1 | 119.2 (6) | C33A—C34—N35 | 115.2 (7) |
C5—C10—C9 | 120.5 (6) | C33A—C34—H341 | 108.5 |
C5—C10—C4 | 120.1 (6) | N35—C34—H341 | 108.5 |
C9—C10—C4 | 119.4 (7) | C33A—C34—H342 | 108.5 |
C3—N31—C32 | 129.9 (6) | N35—C34—H342 | 108.5 |
C3—N31—H31 | 115 (3) | H341—C34—H342 | 107.5 |
C32—N31—H31 | 115 (3) | H333—C33B—H334 | 107.0 |
C37—N35—C36 | 109.8 (5) | ||
O1—C1—C2—C3 | 177.4 (6) | O1—C1—C9—C8 | 6.0 (8) |
C9—C1—C2—C3 | −3.2 (9) | C2—C1—C9—C8 | −173.4 (5) |
O1—C1—C2—Cl2 | −3.2 (8) | C6—C5—C10—C9 | 2.1 (9) |
C9—C1—C2—Cl2 | 176.2 (4) | C6—C5—C10—C4 | −176.2 (5) |
C1—C2—C3—N31 | 178.6 (6) | C8—C9—C10—C5 | −3.7 (9) |
Cl2—C2—C3—N31 | −0.8 (10) | C1—C9—C10—C5 | 175.6 (5) |
C1—C2—C3—C4 | −1.6 (9) | C8—C9—C10—C4 | 174.7 (5) |
Cl2—C2—C3—C4 | 179.0 (4) | C1—C9—C10—C4 | −6.0 (8) |
N31—C3—C4—O4 | 0.5 (8) | O4—C4—C10—C5 | 1.7 (9) |
C2—C3—C4—O4 | −179.4 (6) | C3—C4—C10—C5 | 179.3 (5) |
N31—C3—C4—C10 | −177.3 (5) | O4—C4—C10—C9 | −176.7 (6) |
C2—C3—C4—C10 | 2.9 (8) | C3—C4—C10—C9 | 0.9 (8) |
C10—C5—C6—C7 | 0.7 (9) | C2—C3—N31—C32 | −2.8 (11) |
C5—C6—C7—C8 | −1.8 (9) | C4—C3—N31—C32 | 177.4 (5) |
C6—C7—C8—C9 | 0.2 (9) | C3—N31—C32—C33A | 169.0 (6) |
C7—C8—C9—C10 | 2.6 (9) | N31—C32—C33A—C34 | 56.0 (8) |
C7—C8—C9—C1 | −176.8 (5) | C32—C33A—C34—N35 | −64.2 (10) |
O1—C1—C9—C10 | −173.4 (6) | C37—N35—C34—C33A | 156.4 (7) |
C2—C1—C9—C10 | 7.2 (8) | C36—N35—C34—C33A | −81.5 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N31—H31···O4 | 0.90 (5) | 2.13 (5) | 2.593 (8) | 111 (4) |
N31—H31···N35 | 0.90 (5) | 2.01 (5) | 2.783 (8) | 143 (5) |
Experimental details
Crystal data | |
Chemical formula | C15H17ClN2O2 |
Mr | 292.76 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 8.0693 (8), 13.002 (1), 13.931 (2) |
β (°) | 105.623 (4) |
V (Å3) | 1407.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.20 × 0.03 × 0.02 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.947, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9261, 2439, 777 |
Rint | 0.277 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.176, 0.88 |
No. of reflections | 2439 |
No. of parameters | 193 |
No. of restraints | 15 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.30 |
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 |
N31—H31···O4 | 0.90 (5) | 2.13 (5) | 2.593 (8) | 111 (4) |
N31—H31···N35 | 0.90 (5) | 2.01 (5) | 2.783 (8) | 143 (5) |
The title compound, (I), was prepared as part of a series of studies investigating the synthesis and structural properties of 2-substituted 3-chloro-1,4-naphthoquinones. Thus far, our structural investigations have concentrated on cyclic nucleophilic substituents such as morpholine (Lynch & McClenaghan, 2000a), pyrrolidine (Lynch & McClenaghan, 2000b), piperidine (Lynch & McClenaghan, 2001a), piperazine (Lynch & McClenaghan, 2001b). However, we report here the structure of an N-alkyl analogue whose crystallographic parameters typify the difficulties encountered with this series of molecules (see refinement details).
The structure of (I) (Fig. 1) comprises essentially planar molecules slip-stacked along the a axis. The propyl chain has sufficient length to allow an intramolecular hydrogen bond between the N—H and N(CH3)2 groups and the N—H also hydrogen bonds to the adjacent O atom (Table 1), completing a three-centre association. No other intermolecular C—H···O/Cl close contacts are recorded. One C atom in the propyl chain (C33) is unequally disordered (0.79/0.21) over two sites. This disorder may also extend to C34, which has an increased U11 of 0.111 (7), but not enough to be split.