2,6-Bis­(butyl­amino)-4,8-di­hydroxy-1,5-naphthalene­dione

The title compound, C₁₈H₂₄N₂O₄, is an amino­naphtho­quinone derivative that exhibits a large third-order non-linear optical susceptibility. The centrosymmetric naphtho­quinone moieties are connected by bifurcated N—H...O hydrogen bonds to form a ribbon structure along [10]. The mol­ecules are stacked along the c axis, with overlap occurring only at the periphery of the naphtho­quinone skeleton.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.117
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.91

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           68.19
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               1429
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         1584
           Completeness (_total/calc)             90.21%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.90
PLAT127_ALERT_1_C Implicit Hall Symbol Inconsistent with Expl ....       P -1
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.38 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C4     -   C5       =       5.84 su
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O2     -   H1       =       1.06 Ang.

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C18H24N2O4	Z = 1
Mr = 332.40	F(000) = 178.0
Triclinic, P1	Dx = 1.275 Mg m^−3
Hall symbol: P -1	Cu Kα radiation, λ = 1.5418 Å
a = 5.2257 (7) Å	Cell parameters from 3066 reflections
b = 6.8930 (9) Å	θ = 3.7–68.1°
c = 12.162 (1) Å	µ = 0.74 mm^−1
α = 97.72 (1)°	T = 93 K
β = 91.93 (1)°	Platelet, black
γ = 93.66 (1)°	0.35 × 0.20 × 0.03 mm
V = 432.83 (9) Å^3

Data collection

Rigaku RAXIS-RAPID Imaging Plate diffractometer	775 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.038
48 frames, delta ω = 15 deg scans	θmax = 68.2°
Absorption correction: multi-scan (Higashi, 1995)	h = −6→6
Tmin = 0.738, Tmax = 0.978	k = −8→8
3858 measured reflections	l = −14→14
1429 independent reflections

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.05[Max(Fo^2,0) + 2Fc^2]/3)^2]
wR(F^2) = 0.117	(Δ/σ)max = 0.016
S = 1.06	Δρmax = 0.26 e Å^−3
1421 reflections	Δρmin = −0.31 e Å^−3
112 parameters

Special details

Refinement. Refinement using reflections with F² > -3.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
O1	0.1064 (3)	0.7748 (2)	0.9472 (1)	0.0563 (5)
O2	0.9064 (3)	0.5406 (2)	1.1846 (1)	0.0604 (5)
N1	0.3045 (3)	1.0093 (3)	1.1258 (1)	0.0515 (5)
C1	0.7098 (4)	0.5954 (3)	1.1259 (2)	0.0466 (6)
C2	0.6123 (4)	0.7753 (3)	1.1603 (2)	0.0506 (7)
C3	0.4082 (4)	0.8379 (3)	1.1003 (2)	0.0463 (6)
C4	0.2937 (4)	0.7116 (3)	1.0013 (2)	0.0455 (6)
C5	0.3957 (3)	0.5312 (3)	0.9694 (2)	0.0418 (6)
C6	0.3796 (4)	1.1551 (3)	1.2203 (2)	0.0536 (7)
C7	0.2453 (5)	1.1212 (3)	1.3246 (2)	0.0681 (8)
C8	0.3248 (6)	1.2774 (4)	1.4211 (2)	0.097 (1)
C9	0.2008 (7)	1.2514 (5)	1.5269 (2)	0.141 (1)
H1	0.9361	0.4043	1.1369	0.1101*
H2	0.6846	0.8559	1.2248	0.0607*
H3	0.1692	1.0381	1.0777	0.0618*
H4	0.5593	1.1534	1.2344	0.0643*
H5	0.3411	1.2802	1.2022	0.0643*
H6	0.2858	0.9973	1.3438	0.0818*
H7	0.0654	1.1212	1.3107	0.0818*
H8	0.5053	1.2776	1.4336	0.1166*
H9	0.2831	1.4006	1.4012	0.1166*
H10	0.2470	1.1317	1.5502	0.1688*
H11	0.0197	1.2479	1.5158	0.1688*
H12	0.2565	1.3577	1.5822	0.1688*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0558 (10)	0.055 (1)	0.0578 (9)	0.0151 (8)	−0.0072 (8)	0.0029 (8)
O2	0.061 (1)	0.059 (1)	0.0589 (10)	0.0158 (8)	−0.0146 (8)	−0.0021 (8)
N1	0.059 (1)	0.045 (1)	0.049 (1)	0.0101 (9)	−0.0041 (9)	−0.0021 (8)
C1	0.048 (1)	0.044 (1)	0.047 (1)	0.005 (1)	0.001 (1)	0.005 (1)
C2	0.057 (1)	0.047 (1)	0.046 (1)	0.003 (1)	−0.001 (1)	−0.001 (1)
C3	0.051 (1)	0.041 (1)	0.047 (1)	0.004 (1)	0.008 (1)	0.003 (1)
C4	0.045 (1)	0.046 (1)	0.045 (1)	0.002 (1)	0.0043 (10)	0.004 (1)
C5	0.042 (1)	0.039 (1)	0.044 (1)	0.005 (1)	0.0027 (9)	0.0044 (9)
C6	0.058 (1)	0.046 (1)	0.054 (1)	0.006 (1)	0.001 (1)	−0.001 (1)
C7	0.077 (2)	0.064 (2)	0.059 (1)	−0.004 (1)	0.007 (1)	−0.003 (1)
C8	0.126 (2)	0.095 (2)	0.059 (2)	−0.024 (2)	0.013 (2)	−0.018 (2)
C9	0.196 (4)	0.144 (3)	0.067 (2)	−0.050 (3)	0.030 (2)	−0.019 (2)

Geometric parameters (Å, º)

O1—C4	1.292 (2)	C6—C7	1.509 (3)
O2—C1	1.334 (2)	C6—H4	0.950
O2—H1	1.059	C6—H5	0.950
N1—C3	1.334 (2)	C7—C8	1.509 (3)
N1—C6	1.447 (3)	C7—H6	0.950
N1—H3	0.950	C7—H7	0.950
C1—C2	1.388 (3)	C8—C9	1.487 (4)
C1—C5^i	1.426 (3)	C8—H8	0.950
C2—C3	1.395 (3)	C8—H9	0.950
C2—H2	0.950	C9—H10	0.951
C3—C4	1.474 (3)	C9—H11	0.950
C4—C5	1.396 (3)	C9—H12	0.950
C5—C5^i	1.421 (4)
O1···N1^ii	2.872 (2)	N1···H1^vii	3.424
O1···C6^ii	3.302 (3)	N1···C3^iv	3.433 (3)
O1···C1^iii	3.354 (2)	C1···C4^vi	3.546 (3)
O1···O1^ii	3.463 (3)	C4···H1^iii	3.367
O1···C6^iv	3.473 (3)	C4···C6^iv	3.434 (3)
O1···C5^v	3.523 (2)	C5···H1^iii	3.350
O1···N1^iv	3.526 (2)	C5···C6^iv	3.546 (3)
O2···C4^vi	3.341 (2)	C6···H1^vii	3.189
O2···C3^vi	3.491 (2)	C6···H1^viii	3.531
N1···C4^iv	3.317 (2)
C1—O2—H1	99.8	C7—C6—H4	108.4
C3—N1—C6	125.8 (2)	C7—C6—H5	108.4
C3—N1—H3	117.1	H4—C6—H5	109.5
C6—N1—H3	117.1	C6—C7—C8	112.3 (2)
O2—C1—C2	118.6 (2)	C6—C7—H6	108.8
O2—C1—C5^i	119.7 (2)	C6—C7—H7	108.8
C2—C1—C5^i	121.7 (2)	C8—C7—H6	108.7
C1—C2—C3	120.1 (2)	C8—C7—H7	108.8
C1—C2—H2	120.0	H6—C7—H7	109.5
C3—C2—H2	120.0	C7—C8—C9	114.9 (2)
N1—C3—C2	124.4 (2)	C7—C8—H8	108.1
N1—C3—C4	115.7 (2)	C7—C8—H9	108.1
C2—C3—C4	119.9 (2)	C9—C8—H8	108.1
O1—C4—C3	118.2 (2)	C9—C8—H9	108.1
O1—C4—C5	123.3 (2)	H8—C8—H9	109.5
C3—C4—C5	118.5 (2)	C8—C9—H10	109.5
C1^i—C5—C4	120.2 (2)	C8—C9—H11	109.5
C1^i—C5—C5^i	118.5 (2)	C8—C9—H12	109.5
C4—C5—C5^i	121.3 (2)	H10—C9—H11	109.4
N1—C6—C7	113.6 (2)	H10—C9—H12	109.4
N1—C6—H4	108.4	H11—C9—H12	109.5
N1—C6—H5	108.4

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+2, −z+2; (iii) x−1, y, z; (iv) −x+1, −y+2, −z+2; (v) −x, −y+1, −z+2; (vi) x+1, y, z; (vii) x−1, y+1, z; (viii) x, y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O1^i	1.06	1.49	2.517 (2)	161
N1—H3···O1	0.95	2.24	2.664 (2)	106
N1—H3···O1^ii	0.95	2.04	2.871 (2)	146

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+2, −z+2.