2-But-oxy-N-[2-(diethyl-amino)-eth-yl]quinoline-4-carboxamide (dibucaine).

The mol-ecular conformation of the title compound, C(20)H(29)N(3)O(2), is stabilized by an intra-molecular C-H⋯O hydrogen bond. The orientation of the amide group to the ring system is characterized by a C-C-C-O dihedral angle of 137.5 (3)°. In the crystal, inter-molecular N-H⋯O hydrogen bonds between the amide groups form C(4) chains running parallel to the a axis.

Related literature

For a monograph on dibucaine, see: Sweetman (2009 ▶). For a comparison of the vasoactivity of dibucaine with other amide and ester local anaesthetics, see: Willatts & Reynolds (1985 ▶). For the initial crystal structure determination of dibucaine hydro­chloride monohydrate, see: Hayward & Donohue (1977 ▶). For the subsequent revision of parameters, bond distances and bond angles, see Donohue & Hayward (1980 ▶). Outlier data were removed using a local program based on the method of Prince & Nicholson (1983 ▶).

Experimental

Crystal data

C20H29N3O2

M = 343.47

Triclinic,

a = 4.9323 (1) Å

b = 7.2044 (1) Å

c = 26.9914 (19) Å

α = 94.080 (7)°

β = 90.611 (6)°

γ = 94.728 (7)°

V = 953.30 (7) Å3

Z = 2

Cu Kα radiation

μ = 0.62 mm−1

T = 150 K

0.20 × 0.20 × 0.06 mm

Data collection

Rigaku Rapid II diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2001 ▶) T min = 0.845, T max = 0.966

22671 measured reflections

2786 independent reflections

1829 reflections with I > 2σ(I)

R int = 0.096

Refinement

R[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.168

S = 1.05

2786 reflections

234 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and local programs.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045460/rz2498sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045460/rz2498Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1

C20H29N3O2	Z = 2
Mr = 343.47	F(000) = 372
Triclinic, P1	Dx = 1.197 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 4.9323 (1) Å	Cell parameters from 22671 reflections
b = 7.2044 (1) Å	θ = 6–66°
c = 26.9914 (19) Å	µ = 0.62 mm−1
α = 94.080 (7)°	T = 150 K
β = 90.611 (6)°	Plate, colourless
γ = 94.728 (7)°	0.20 × 0.20 × 0.06 mm
V = 953.30 (7) Å3

Rigaku Rapid II diffractometer	1829 reflections with I > 2σ(I)
confocal optics	Rint = 0.096
ω scans	θmax = 66.6°, θmin = 6.5°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2001)	h = −5→5
Tmin = 0.845, Tmax = 0.966	k = −8→8
22671 measured reflections	l = −32→32
2786 independent reflections

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0819P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.064	(Δ/σ)max < 0.001
wR(F2) = 0.168	Δρmax = 0.28 e Å−3
S = 1.05	Δρmin = −0.22 e Å−3
2786 reflections	Extinction correction: (SHELXL97; Sheldrick 2008)
234 parameters	Extinction coefficient: 0.32E-02
0 restraints

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Outlier data were removed using a local program based on the method of Prince and Nicholson (1983).Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O11	0.7912 (3)	0.4509 (2)	0.20477 (6)	0.0463 (5)
O31	−0.0013 (3)	0.4421 (2)	0.36166 (6)	0.0469 (5)
N4	0.2537 (4)	0.1888 (3)	0.34861 (7)	0.0416 (6)
N12	0.3625 (5)	0.5263 (3)	0.19137 (7)	0.0382 (6)
N15	0.2615 (4)	0.8145 (3)	0.08439 (7)	0.0409 (6)
C1	0.4443 (5)	0.3476 (3)	0.26107 (8)	0.0362 (7)
C2	0.2628 (5)	0.4293 (3)	0.29099 (8)	0.0388 (7)
C3	0.1742 (5)	0.3452 (3)	0.33440 (9)	0.0399 (7)
C5	0.4357 (5)	0.1009 (3)	0.31830 (8)	0.0392 (7)
C6	0.5198 (5)	−0.0696 (3)	0.33278 (9)	0.0460 (8)
C7	0.7017 (5)	−0.1636 (3)	0.30513 (9)	0.0484 (8)
C8	0.8064 (5)	−0.0917 (3)	0.26159 (9)	0.0473 (8)
C9	0.7263 (5)	0.0726 (3)	0.24632 (8)	0.0430 (7)
C10	0.5402 (5)	0.1733 (3)	0.27428 (8)	0.0370 (7)
C11	0.5499 (6)	0.4428 (3)	0.21690 (9)	0.0384 (7)
C13	0.4394 (4)	0.6311 (3)	0.14897 (8)	0.0392 (7)
C14	0.1956 (5)	0.7230 (3)	0.13009 (8)	0.0447 (8)
C16	0.2090 (5)	0.6808 (3)	0.04102 (8)	0.0456 (8)
C17	0.3601 (5)	0.7366 (4)	−0.00472 (8)	0.0515 (8)
C18	0.1034 (5)	0.9769 (3)	0.08026 (8)	0.0489 (8)
C19	0.2050 (6)	1.1414 (3)	0.11548 (9)	0.0644 (9)
C32	−0.0885 (5)	0.3722 (4)	0.40823 (8)	0.0475 (8)
C33	−0.2632 (5)	0.5140 (4)	0.43239 (9)	0.0491 (8)
C34	−0.1155 (5)	0.7061 (4)	0.44398 (9)	0.0528 (8)
C35	−0.2952 (5)	0.8435 (4)	0.47007 (9)	0.0603 (9)
H2	0.1951	0.5431	0.2828	0.047*
H6	0.4492	−0.1197	0.3621	0.055*
H7	0.7576	−0.2782	0.3154	0.058*
H8	0.9337	−0.1576	0.2426	0.057*
H9	0.7967	0.1193	0.2166	0.052*
H12	0.180 (5)	0.502 (3)	0.1994 (7)	0.043 (8)*
H13A	0.5062	0.5461	0.1222	0.047*
H13B	0.5883	0.7278	0.1588	0.047*
H14A	0.0410	0.6274	0.1235	0.054*
H14B	0.1401	0.8165	0.1558	0.054*
H16A	0.0113	0.6679	0.0333	0.055*
H16B	0.2619	0.5571	0.0495	0.055*
H17A	0.3099	0.8593	−0.0133	0.077*
H17B	0.3120	0.6441	−0.0325	0.077*
H17C	0.5565	0.7427	0.0019	0.077*
H18A	−0.0895	0.9409	0.0873	0.059*
H18B	0.1126	1.0150	0.0458	0.059*
H19A	0.1885	1.1064	0.1498	0.097*
H19B	0.0961	1.2467	0.1107	0.097*
H19C	0.3962	1.1776	0.1087	0.097*
H32A	0.0708	0.3571	0.4298	0.057*
H32B	−0.1943	0.2495	0.4024	0.057*
H33A	−0.3349	0.4670	0.4637	0.059*
H33B	−0.4205	0.5264	0.4101	0.059*
H34A	−0.0502	0.7562	0.4126	0.063*
H34B	0.0456	0.6940	0.4653	0.063*
H35A	−0.4621	0.8485	0.4504	0.090*
H35B	−0.1972	0.9678	0.4736	0.090*
H35C	−0.3419	0.8026	0.5030	0.090*

	U11	U22	U33	U12	U13	U23
O11	0.0350 (13)	0.0471 (12)	0.0590 (11)	0.0077 (10)	0.0081 (9)	0.0141 (9)
O31	0.0541 (13)	0.0469 (12)	0.0426 (10)	0.0170 (10)	0.0117 (9)	0.0061 (8)
N4	0.0475 (16)	0.0351 (13)	0.0434 (13)	0.0079 (12)	0.0037 (10)	0.0048 (10)
N12	0.0306 (15)	0.0407 (14)	0.0451 (13)	0.0037 (12)	0.0073 (11)	0.0138 (10)
N15	0.0500 (16)	0.0332 (13)	0.0413 (12)	0.0107 (11)	0.0057 (10)	0.0062 (10)
C1	0.0364 (18)	0.0312 (15)	0.0414 (14)	0.0040 (13)	0.0002 (12)	0.0035 (12)
C2	0.0416 (19)	0.0334 (16)	0.0425 (15)	0.0088 (14)	0.0002 (13)	0.0038 (12)
C3	0.0433 (18)	0.0366 (16)	0.0405 (15)	0.0098 (14)	0.0054 (12)	−0.0001 (12)
C5	0.0443 (19)	0.0334 (16)	0.0402 (15)	0.0069 (14)	−0.0013 (13)	0.0022 (12)
C6	0.058 (2)	0.0334 (16)	0.0485 (16)	0.0103 (15)	0.0027 (14)	0.0082 (13)
C7	0.056 (2)	0.0331 (16)	0.0567 (18)	0.0077 (15)	−0.0021 (14)	0.0067 (13)
C8	0.051 (2)	0.0371 (17)	0.0542 (17)	0.0118 (15)	0.0030 (14)	−0.0003 (13)
C9	0.0460 (19)	0.0375 (16)	0.0471 (16)	0.0110 (14)	0.0042 (13)	0.0054 (13)
C10	0.0361 (18)	0.0312 (15)	0.0439 (15)	0.0059 (13)	−0.0032 (12)	0.0014 (12)
C11	0.0392 (19)	0.0321 (16)	0.0449 (15)	0.0077 (14)	0.0025 (13)	0.0029 (12)
C13	0.0326 (17)	0.0407 (16)	0.0457 (15)	0.0032 (13)	0.0047 (12)	0.0115 (13)
C14	0.0450 (19)	0.0412 (16)	0.0509 (16)	0.0121 (14)	0.0054 (13)	0.0128 (13)
C16	0.051 (2)	0.0357 (16)	0.0503 (17)	0.0066 (15)	0.0008 (14)	0.0038 (13)
C17	0.064 (2)	0.0452 (18)	0.0468 (16)	0.0125 (16)	0.0016 (14)	0.0019 (13)
C18	0.058 (2)	0.0378 (17)	0.0535 (17)	0.0161 (16)	0.0037 (14)	0.0078 (14)
C19	0.095 (3)	0.0378 (18)	0.0614 (19)	0.0118 (18)	0.0086 (17)	−0.0013 (15)
C32	0.054 (2)	0.0491 (18)	0.0405 (15)	0.0085 (16)	0.0092 (13)	0.0054 (13)
C33	0.050 (2)	0.0524 (19)	0.0454 (16)	0.0082 (16)	0.0104 (13)	−0.0003 (14)
C34	0.052 (2)	0.0502 (19)	0.0555 (18)	0.0071 (17)	0.0013 (14)	−0.0036 (15)
C35	0.061 (2)	0.056 (2)	0.0640 (18)	0.0135 (17)	0.0046 (15)	−0.0045 (15)

O11—C11	1.236 (2)	C13—H13B	0.9900
O31—C3	1.348 (2)	C14—H14A	0.9900
O31—C32	1.444 (2)	C14—H14B	0.9900
N4—C3	1.304 (3)	C16—C17	1.511 (3)
N4—C5	1.383 (3)	C16—H16A	0.9900
N12—C11	1.352 (3)	C16—H16B	0.9900
N12—C13	1.452 (3)	C17—H17A	0.9800
N12—H12	0.94 (2)	C17—H17B	0.9800
N15—C14	1.466 (3)	C17—H17C	0.9800
N15—C18	1.469 (2)	C18—C19	1.513 (3)
N15—C16	1.469 (3)	C18—H18A	0.9900
C1—C2	1.354 (3)	C18—H18B	0.9900
C1—C10	1.444 (3)	C19—H19A	0.9800
C1—C11	1.494 (3)	C19—H19B	0.9800
C2—C3	1.414 (3)	C19—H19C	0.9800
C2—H2	0.9500	C32—C33	1.508 (3)
C5—C6	1.408 (3)	C32—H32A	0.9900
C5—C10	1.417 (3)	C32—H32B	0.9900
C6—C7	1.365 (3)	C33—C34	1.520 (3)
C6—H6	0.9500	C33—H33A	0.9900
C7—C8	1.404 (3)	C33—H33B	0.9900
C7—H7	0.9500	C34—C35	1.523 (3)
C8—C9	1.368 (3)	C34—H34A	0.9900
C8—H8	0.9500	C34—H34B	0.9900
C9—C10	1.409 (3)	C35—H35A	0.9800
C9—H9	0.9500	C35—H35B	0.9800
C13—C14	1.520 (3)	C35—H35C	0.9800
C13—H13A	0.9900
C3—O31—C32	117.98 (18)	H14A—C14—H14B	108.10
C3—N4—C5	116.6 (2)	N15—C16—C17	113.6 (2)
C11—N12—C13	120.9 (2)	N15—C16—H16A	108.90
C11—N12—H12	117.6 (13)	C17—C16—H16A	108.90
C13—N12—H12	121.0 (13)	N15—C16—H16B	108.90
C14—N15—C18	110.81 (18)	C17—C16—H16B	108.90
C14—N15—C16	109.95 (18)	H16A—C16—H16B	107.70
C18—N15—C16	110.41 (18)	C16—C17—H17A	109.50
C2—C1—C10	118.5 (2)	C16—C17—H17B	109.50
C2—C1—C11	119.8 (2)	H17A—C17—H17B	109.50
C10—C1—C11	121.6 (2)	C16—C17—H17C	109.50
C1—C2—C3	120.0 (2)	H17A—C17—H17C	109.50
C1—C2—H2	120.00	H17B—C17—H17C	109.50
C3—C2—H2	120.00	N15—C18—C19	112.7 (2)
N4—C3—O31	121.0 (2)	N15—C18—H18A	109.10
N4—C3—C2	124.6 (2)	C19—C18—H18A	109.10
O31—C3—C2	114.4 (2)	N15—C18—H18B	109.10
N4—C5—C6	117.2 (2)	C19—C18—H18B	109.10
N4—C5—C10	123.7 (2)	H18A—C18—H18B	107.80
C6—C5—C10	119.2 (2)	C18—C19—H19A	109.50
C7—C6—C5	120.6 (2)	C18—C19—H19B	109.50
C7—C6—H6	119.70	H19A—C19—H19B	109.50
C5—C6—H6	119.70	C18—C19—H19C	109.50
C6—C7—C8	120.3 (2)	H19A—C19—H19C	109.50
C6—C7—H7	119.90	H19B—C19—H19C	109.50
C8—C7—H7	119.90	O31—C32—C33	106.61 (19)
C9—C8—C7	120.4 (2)	O31—C32—H32A	110.40
C9—C8—H8	119.80	C33—C32—H32A	110.40
C7—C8—H8	119.80	O31—C32—H32B	110.40
C8—C9—C10	120.6 (2)	C33—C32—H32B	110.40
C8—C9—H9	119.70	H32A—C32—H32B	108.60
C10—C9—H9	119.70	C32—C33—C34	114.2 (2)
C9—C10—C5	118.9 (2)	C32—C33—H33A	108.70
C9—C10—C1	124.4 (2)	C34—C33—H33A	108.70
C5—C10—C1	116.6 (2)	C32—C33—H33B	108.70
O11—C11—N12	121.4 (2)	C34—C33—H33B	108.70
O11—C11—C1	123.5 (2)	H33A—C33—H33B	107.60
N12—C11—C1	115.1 (2)	C33—C34—C35	112.7 (2)
N12—C13—C14	109.85 (19)	C33—C34—H34A	109.10
N12—C13—H13A	109.70	C35—C34—H34A	109.10
C14—C13—H13A	109.70	C33—C34—H34B	109.10
N12—C13—H13B	109.70	C35—C34—H34B	109.10
C14—C13—H13B	109.70	H34A—C34—H34B	107.80
H13A—C13—H13B	108.20	C34—C35—H35A	109.50
N15—C14—C13	110.76 (19)	C34—C35—H35B	109.50
N15—C14—H14A	109.50	H35A—C35—H35B	109.50
C13—C14—H14A	109.50	C34—C35—H35C	109.50
N15—C14—H14B	109.50	H35A—C35—H35C	109.50
C13—C14—H14B	109.50	H35B—C35—H35C	109.50
C10—C1—C2—C3	0.8 (4)	C2—C1—C10—C9	179.3 (2)
C11—C1—C2—C3	−176.4 (2)	C11—C1—C10—C9	−3.5 (4)
C5—N4—C3—O31	−179.5 (2)	C2—C1—C10—C5	−0.2 (3)
C5—N4—C3—C2	−0.5 (4)	C11—C1—C10—C5	176.9 (2)
C32—O31—C3—N4	2.9 (4)	C13—N12—C11—O11	−0.8 (4)
C32—O31—C3—C2	−176.12 (19)	C13—N12—C11—C1	177.23 (19)
C1—C2—C3—N4	−0.5 (4)	C2—C1—C11—O11	137.5 (3)
C1—C2—C3—O31	178.5 (2)	C10—C1—C11—O11	−39.6 (4)
C3—N4—C5—C6	−179.0 (2)	C2—C1—C11—N12	−40.5 (3)
C3—N4—C5—C10	1.2 (4)	C10—C1—C11—N12	142.4 (2)
N4—C5—C6—C7	−179.2 (2)	C11—N12—C13—C14	−175.3 (2)
C10—C5—C6—C7	0.6 (4)	C18—N15—C14—C13	−149.9 (2)
C5—C6—C7—C8	−0.4 (4)	C16—N15—C14—C13	87.7 (2)
C6—C7—C8—C9	−0.3 (4)	N12—C13—C14—N15	−174.54 (18)
C7—C8—C9—C10	0.8 (4)	C14—N15—C16—C17	−159.16 (19)
C8—C9—C10—C5	−0.5 (4)	C18—N15—C16—C17	78.3 (2)
C8—C9—C10—C1	180.0 (2)	C14—N15—C18—C19	74.0 (3)
N4—C5—C10—C9	179.6 (2)	C16—N15—C18—C19	−164.0 (2)
C6—C5—C10—C9	−0.2 (4)	C3—O31—C32—C33	175.6 (2)
N4—C5—C10—C1	−0.8 (4)	O31—C32—C33—C34	−61.5 (3)
C6—C5—C10—C1	179.4 (2)	C32—C33—C34—C35	−177.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O11	0.95	2.43	3.015 (3)	119
N12—H12···O11i	0.93 (2)	1.93 (2)	2.857 (3)	170.9 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O11	0.95	2.43	3.015 (3)	119
N12—H12⋯O11i	0.93 (2)	1.93 (2)	2.857 (3)	171 (2)

Symmetry code: (i) .