2-Chloro-3-(3-di­methyl­amino­propyl­amino)-1,4-naphtho­quinone

The structure of the title compound, C₁₅H₁₇ClN₂O₂, comprises essentially planar mol­ecules slip-stacked along the a axis. The propyl chain has sufficient length to allow an intramolecular H-bond between the N-H and N(CH₃)₂ groups and the N-H also hydrogen bonds to the adjacent O atom, completing a three-centre association.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.067
• wR factor = 0.176
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level A
RINTA01_ALERT_3_A  The value of Rint is greater than 0.20
            Rint given   0.277
PLAT020_ALERT_3_A The value of Rint is greater than 0.10 .........       0.28
PLAT027_ALERT_3_A _diffrn_reflns_theta_full too Low ..............      24.99 Deg.
PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       5.32 Ratio

Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         32 Perc.
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.98

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.58 Ratio
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        C34
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        N35
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....       C33B
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT333_ALERT_2_C Large Av Benzene C-C Dist. C1     -   C9       =       1.44 Ang.
PLAT335_ALERT_2_C Large Benzene C-C Range    C1     -   C9       =       0.18 Ang.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C3     -   C4       =       1.53 Ang.
PLAT413_ALERT_2_C Short Inter XH3 .. XHn     H331   ..  H371     =       2.14 Ang.

   4 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

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.

S2. Experimental

The title compound was obtained from Key Organics Ltd and crystals were grown from ethanol solution.

S3. Refinement

Crystals in this series of compounds, including those not suitable for data collection, are thin plates with weak high angle data and high R_int 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 R_int 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(U_eq) 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.

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

Figures

Fig. 1. The molecular configuration and atom-numbering scheme for the title compound, showing 50% probability ellipsoids.

2-Chloro-3-(3-dimethylaminopropylamino)-1,4-naphthoquinone

Crystal data

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) Å^3	Needle, red
Z = 4	0.20 × 0.03 × 0.02 mm

Data collection

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

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0498P)^2] where P = (Fo^2 + 2Fc^2)/3
2439 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.24 e Å^−3
15 restraints	Δρmin = −0.30 e Å^−3

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

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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)