Crystal structure of 4-[(adamantan-1-yl)amino]­naphthalene-1,2-dione

The title compound, an example of a stable 1,2-naphtho­quinone, illustrates steric buttressing of the adamantanyl group.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.056
• wR factor = 0.121
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT414_ALERT_2_B Short Intra D-H..H-X       H1       ..H6               1.83 Ang.
                                                      x,y,z  =      1_555 Check

Alert level C
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C2       - C11      .       1.53 Ang.
PLAT410_ALERT_2_C Short Intra H...H Contact  H3       ..H18A     .       1.94 Ang.
                                                      x,y,z  =      1_555 Check
PLAT420_ALERT_2_C D-H Without Acceptor       N1       --H1       .     Please Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      6.540 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT333_ALERT_2_G Large Aver C6-Ring C-C Dist C2       -C11      .       1.46 Ang.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         17 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011); software used to prepare material for publication: SHELXL (Sheldrick, 2015b).

4-[(Adamantan-1-yl)amino]naphthalene-1,2-dione

Crystal data

C20H21NO2	F(000) = 656
Mr = 307.38	Dx = 1.339 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.8487 (5) Å	Cell parameters from 80 reflections
b = 10.8187 (4) Å	θ = 3.5–20.0°
c = 11.8469 (5) Å	µ = 0.09 mm^−1
β = 112.248 (1)°	T = 100 K
V = 1524.20 (10) Å^3	Block, translucent intense orange-red
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection

Bruker D8 Venture diffractometer	3494 independent reflections
Radiation source: Incoatec Microsource	2412 reflections with I > 2σ(I)
Mirrors monochromator	Rint = 0.075
Detector resolution: 10.4167 pixels mm^-1	θmax = 27.5°, θmin = 2.5°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −14→14
Tmin = 0.702, Tmax = 0.746	l = −15→15
31552 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.826P] where P = (Fo^2 + 2Fc^2)/3
3494 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
O1	0.38228 (11)	0.03240 (12)	0.55184 (12)	0.0167 (3)
O2	0.15850 (11)	0.07574 (12)	0.43684 (12)	0.0174 (3)
N1	0.45787 (13)	0.36387 (14)	0.33029 (14)	0.0130 (3)
H1	0.4241	0.4268	0.2837	0.016*
C2	0.35129 (15)	0.11642 (16)	0.47491 (16)	0.0115 (4)
C3	0.42405 (15)	0.18810 (17)	0.43727 (16)	0.0119 (4)
H3	0.5014	0.1664	0.4668	0.014*
C4	0.38867 (15)	0.28844 (16)	0.35958 (16)	0.0106 (4)
C5	0.26636 (15)	0.32093 (16)	0.30318 (16)	0.0099 (4)
C6	0.22581 (16)	0.41901 (17)	0.22207 (17)	0.0136 (4)
H6	0.2768	0.4671	0.1996	0.016*
C7	0.11207 (16)	0.44738 (17)	0.17363 (17)	0.0145 (4)
H7	0.0861	0.5149	0.1188	0.017*
C8	0.03608 (16)	0.37845 (18)	0.20441 (17)	0.0148 (4)
H8	−0.0416	0.3991	0.172	0.018*
C9	0.07435 (16)	0.27905 (17)	0.28295 (17)	0.0135 (4)
H9	0.0224	0.2304	0.3034	0.016*
C10	0.18809 (15)	0.24991 (16)	0.33209 (16)	0.0107 (4)
C11	0.22506 (16)	0.14264 (16)	0.41573 (16)	0.0114 (4)
C12	0.58113 (15)	0.35926 (16)	0.36293 (16)	0.0105 (4)
C13	0.61093 (15)	0.48247 (17)	0.31748 (17)	0.0131 (4)
H13A	0.5659	0.4918	0.2292	0.016*
H13B	0.5922	0.552	0.3608	0.016*
C14	0.73627 (15)	0.48667 (17)	0.33974 (17)	0.0133 (4)
H14	0.7542	0.567	0.3093	0.016*
C15	0.80594 (16)	0.47438 (18)	0.47649 (17)	0.0156 (4)
H15A	0.8871	0.476	0.4912	0.019*
H15B	0.7896	0.5444	0.521	0.019*
C16	0.77630 (16)	0.35233 (18)	0.52241 (17)	0.0140 (4)
H16	0.8215	0.3441	0.6118	0.017*
C17	0.80384 (16)	0.24419 (18)	0.45448 (17)	0.0145 (4)
H17A	0.8852	0.2441	0.4703	0.017*
H17B	0.7851	0.165	0.4842	0.017*
C18	0.65032 (15)	0.35023 (18)	0.50031 (16)	0.0133 (4)
H18A	0.6318	0.2726	0.5329	0.016*
H18B	0.6321	0.4206	0.543	0.016*
C19	0.61046 (15)	0.25234 (17)	0.29482 (16)	0.0118 (4)
H19A	0.5923	0.1724	0.3238	0.014*
H19B	0.5655	0.2592	0.2063	0.014*
C20	0.76438 (16)	0.37983 (17)	0.27165 (17)	0.0144 (4)
H20A	0.8453	0.382	0.2853	0.017*
H20B	0.7205	0.388	0.183	0.017*
C21	0.73612 (15)	0.25706 (17)	0.31772 (17)	0.0128 (4)
H21	0.7551	0.1872	0.2736	0.015*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0177 (7)	0.0131 (7)	0.0193 (7)	0.0022 (6)	0.0070 (6)	0.0057 (6)
O2	0.0172 (7)	0.0148 (7)	0.0198 (8)	−0.0043 (6)	0.0068 (6)	0.0024 (6)
N1	0.0103 (8)	0.0108 (8)	0.0171 (8)	0.0015 (6)	0.0042 (7)	0.0050 (6)
C2	0.0149 (10)	0.0087 (9)	0.0118 (9)	0.0001 (7)	0.0059 (8)	−0.0028 (7)
C3	0.0101 (10)	0.0113 (9)	0.0140 (10)	0.0008 (8)	0.0041 (8)	−0.0008 (8)
C4	0.0123 (10)	0.0103 (9)	0.0103 (9)	−0.0008 (7)	0.0055 (8)	−0.0043 (7)
C5	0.0121 (9)	0.0091 (9)	0.0091 (9)	−0.0001 (7)	0.0046 (8)	−0.0027 (7)
C6	0.0144 (10)	0.0111 (9)	0.0159 (10)	−0.0012 (8)	0.0065 (8)	−0.0005 (8)
C7	0.0165 (10)	0.0122 (10)	0.0140 (10)	0.0032 (8)	0.0048 (8)	0.0029 (8)
C8	0.0108 (9)	0.0174 (10)	0.0154 (10)	0.0017 (8)	0.0040 (8)	−0.0020 (8)
C9	0.0146 (10)	0.0121 (9)	0.0154 (10)	−0.0025 (8)	0.0076 (8)	−0.0028 (8)
C10	0.0125 (9)	0.0091 (9)	0.0109 (9)	−0.0012 (7)	0.0050 (8)	−0.0038 (7)
C11	0.0157 (10)	0.0103 (9)	0.0091 (9)	−0.0028 (8)	0.0058 (8)	−0.0038 (7)
C12	0.0088 (9)	0.0100 (9)	0.0121 (9)	−0.0004 (7)	0.0034 (7)	0.0003 (7)
C13	0.0137 (10)	0.0084 (9)	0.0172 (10)	−0.0003 (7)	0.0060 (8)	0.0022 (7)
C14	0.0144 (10)	0.0092 (9)	0.0177 (10)	−0.0019 (7)	0.0075 (8)	0.0028 (8)
C15	0.0124 (10)	0.0166 (10)	0.0171 (10)	−0.0040 (8)	0.0050 (8)	−0.0043 (8)
C16	0.0126 (10)	0.0188 (10)	0.0093 (9)	−0.0014 (8)	0.0027 (8)	0.0010 (8)
C17	0.0100 (9)	0.0141 (10)	0.0200 (10)	0.0021 (8)	0.0064 (8)	0.0042 (8)
C18	0.0139 (10)	0.0156 (10)	0.0111 (9)	−0.0027 (8)	0.0055 (8)	−0.0007 (8)
C19	0.0141 (10)	0.0109 (9)	0.0102 (9)	−0.0027 (8)	0.0042 (8)	−0.0003 (7)
C20	0.0141 (10)	0.0169 (10)	0.0139 (10)	−0.0012 (8)	0.0073 (8)	0.0014 (8)
C21	0.0150 (10)	0.0099 (9)	0.0151 (10)	0.0024 (8)	0.0075 (8)	−0.0008 (7)

Geometric parameters (Å, º)

O1—C2	1.241 (2)	C13—C14	1.531 (3)
O2—C11	1.216 (2)	C13—H13A	0.99
N1—C4	1.346 (2)	C13—H13B	0.99
N1—C12	1.482 (2)	C14—C20	1.529 (3)
N1—H1	0.88	C14—C15	1.531 (3)
C2—C3	1.411 (3)	C14—H14	1.0
C2—C11	1.530 (3)	C15—C16	1.530 (3)
C3—C4	1.384 (3)	C15—H15A	0.99
C3—H3	0.95	C15—H15B	0.99
C4—C5	1.498 (3)	C16—C17	1.535 (3)
C5—C6	1.393 (3)	C16—C18	1.539 (3)
C5—C10	1.407 (2)	C16—H16	1.0
C6—C7	1.387 (3)	C17—C21	1.528 (3)
C6—H6	0.95	C17—H17A	0.99
C7—C8	1.383 (3)	C17—H17B	0.99
C7—H7	0.95	C18—H18A	0.99
C8—C9	1.385 (3)	C18—H18B	0.99
C8—H8	0.95	C19—C21	1.533 (2)
C9—C10	1.389 (3)	C19—H19A	0.99
C9—H9	0.95	C19—H19B	0.99
C10—C11	1.482 (3)	C20—C21	1.531 (3)
C12—C18	1.534 (3)	C20—H20A	0.99
C12—C19	1.537 (2)	C20—H20B	0.99
C12—C13	1.539 (2)	C21—H21	1.0
C4—N1—C12	131.11 (16)	C13—C14—C15	109.58 (15)
C4—N1—H1	114.4	C20—C14—H14	109.5
C12—N1—H1	114.4	C13—C14—H14	109.5
O1—C2—C3	124.61 (17)	C15—C14—H14	109.5
O1—C2—C11	117.51 (16)	C16—C15—C14	109.06 (15)
C3—C2—C11	117.87 (16)	C16—C15—H15A	109.9
C4—C3—C2	123.46 (17)	C14—C15—H15A	109.9
C4—C3—H3	118.3	C16—C15—H15B	109.9
C2—C3—H3	118.3	C14—C15—H15B	109.9
N1—C4—C3	124.37 (17)	H15A—C15—H15B	108.3
N1—C4—C5	115.26 (16)	C15—C16—C17	109.47 (15)
C3—C4—C5	120.37 (16)	C15—C16—C18	109.85 (16)
C6—C5—C10	117.95 (17)	C17—C16—C18	109.63 (15)
C6—C5—C4	122.78 (16)	C15—C16—H16	109.3
C10—C5—C4	119.27 (16)	C17—C16—H16	109.3
C7—C6—C5	120.93 (17)	C18—C16—H16	109.3
C7—C6—H6	119.5	C21—C17—C16	109.55 (15)
C5—C6—H6	119.5	C21—C17—H17A	109.8
C8—C7—C6	120.67 (18)	C16—C17—H17A	109.8
C8—C7—H7	119.7	C21—C17—H17B	109.8
C6—C7—H7	119.7	C16—C17—H17B	109.8
C7—C8—C9	119.31 (18)	H17A—C17—H17B	108.2
C7—C8—H8	120.3	C12—C18—C16	109.22 (14)
C9—C8—H8	120.3	C12—C18—H18A	109.8
C8—C9—C10	120.49 (17)	C16—C18—H18A	109.8
C8—C9—H9	119.8	C12—C18—H18B	109.8
C10—C9—H9	119.8	C16—C18—H18B	109.8
C9—C10—C5	120.63 (17)	H18A—C18—H18B	108.3
C9—C10—C11	118.54 (16)	C21—C19—C12	109.46 (14)
C5—C10—C11	120.83 (17)	C21—C19—H19A	109.8
O2—C11—C10	122.06 (17)	C12—C19—H19A	109.8
O2—C11—C2	120.08 (16)	C21—C19—H19B	109.8
C10—C11—C2	117.85 (15)	C12—C19—H19B	109.8
N1—C12—C18	114.32 (15)	H19A—C19—H19B	108.2
N1—C12—C19	109.79 (14)	C14—C20—C21	109.42 (14)
C18—C12—C19	110.51 (15)	C14—C20—H20A	109.8
N1—C12—C13	105.21 (14)	C21—C20—H20A	109.8
C18—C12—C13	107.78 (15)	C14—C20—H20B	109.8
C19—C12—C13	108.98 (14)	C21—C20—H20B	109.8
C14—C13—C12	110.50 (15)	H20A—C20—H20B	108.2
C14—C13—H13A	109.5	C17—C21—C20	109.90 (15)
C12—C13—H13A	109.5	C17—C21—C19	108.87 (14)
C14—C13—H13B	109.5	C20—C21—C19	109.98 (15)
C12—C13—H13B	109.5	C17—C21—H21	109.4
H13A—C13—H13B	108.1	C20—C21—H21	109.4
C20—C14—C13	109.26 (15)	C19—C21—H21	109.4
C20—C14—C15	109.40 (15)
O1—C2—C3—C4	−173.98 (18)	C4—N1—C12—C19	71.4 (2)
C11—C2—C3—C4	6.9 (3)	C4—N1—C12—C13	−171.49 (17)
C12—N1—C4—C3	3.9 (3)	N1—C12—C13—C14	−176.98 (14)
C12—N1—C4—C5	−177.13 (16)	C18—C12—C13—C14	60.65 (19)
C2—C3—C4—N1	174.46 (17)	C19—C12—C13—C14	−59.31 (19)
C2—C3—C4—C5	−4.5 (3)	C12—C13—C14—C20	59.72 (19)
N1—C4—C5—C6	2.6 (2)	C12—C13—C14—C15	−60.13 (19)
C3—C4—C5—C6	−178.38 (17)	C20—C14—C15—C16	−60.95 (19)
N1—C4—C5—C10	−177.72 (15)	C13—C14—C15—C16	58.82 (19)
C3—C4—C5—C10	1.3 (2)	C14—C15—C16—C17	60.51 (19)
C10—C5—C6—C7	1.5 (3)	C14—C15—C16—C18	−59.93 (19)
C4—C5—C6—C7	−178.80 (17)	C15—C16—C17—C21	−59.66 (19)
C5—C6—C7—C8	−0.3 (3)	C18—C16—C17—C21	60.90 (19)
C6—C7—C8—C9	−1.0 (3)	N1—C12—C18—C16	−177.36 (15)
C7—C8—C9—C10	1.1 (3)	C19—C12—C18—C16	58.19 (19)
C8—C9—C10—C5	0.1 (3)	C13—C12—C18—C16	−60.80 (19)
C8—C9—C10—C11	−179.99 (17)	C15—C16—C18—C12	61.65 (19)
C6—C5—C10—C9	−1.4 (3)	C17—C16—C18—C12	−58.69 (19)
C4—C5—C10—C9	178.86 (16)	N1—C12—C19—C21	173.69 (14)
C6—C5—C10—C11	178.73 (16)	C18—C12—C19—C21	−59.31 (19)
C4—C5—C10—C11	−1.0 (2)	C13—C12—C19—C21	58.95 (18)
C9—C10—C11—O2	4.3 (3)	C13—C14—C20—C21	−59.63 (19)
C5—C10—C11—O2	−175.85 (16)	C15—C14—C20—C21	60.33 (19)
C9—C10—C11—C2	−176.47 (16)	C16—C17—C21—C20	59.08 (19)
C5—C10—C11—C2	3.4 (2)	C16—C17—C21—C19	−61.43 (19)
O1—C2—C11—O2	−6.1 (3)	C14—C20—C21—C17	−59.49 (19)
C3—C2—C11—O2	173.12 (16)	C14—C20—C21—C19	60.35 (19)
O1—C2—C11—C10	174.65 (16)	C12—C19—C21—C17	60.33 (19)
C3—C2—C11—C10	−6.1 (2)	C12—C19—C21—C20	−60.13 (18)
C4—N1—C12—C18	−53.4 (3)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1^i	0.95	2.59	3.385 (3)	142
C8—H8···O2^ii	0.95	2.47	3.231 (2)	137
C13—H13A···O1^i	0.99	2.51	3.400 (2)	150
C15—H15B···Cg1^iii	0.99	2.74	3.587 (2)	144

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