4,8,9,10-Tetrakis(4-methoxy­phenyl)-1,3-di­aza­adamantan-6-one benzene solvate

Krishnakumar, R.V.; Vijayakumar, V.; Sundaravadivelu, M.; Natarajan, S.; Perumal, S.; Selvaraj, S.

doi:10.1107/S1600536801003956

4,8,9,10-Tetrakis(4-methoxyphenyl)-1,3-diazaadamantan-6-one benzene solvate

R. V. Krishnakumar, V. Vijayakumar, M. Sundaravadivelu, S. Natarajan, S. Perumal and S. Selvaraj

Mirror symmetry is retained in the crystals of the title compound, C₃₆H₃₆N₂O₅·C₆H₆. The trapping of the solvent (benzene) molecule in the crystal lattice as space filler with no strong interactions with the solute molecule presumably plays an important role in the retention of molecular site symmetry. The crystal structure is stabilized by van der Waals interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003956/na6059sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003956/na6059Isup2.hkl Contains datablock I

CCDC reference: 162809

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.009 Å
R factor = 0.066
wR factor = 0.191
Data-to-parameter ratio = 14.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_731  Alert C Bond    Calc     1.31(3), Rep   1.305(13) ....       2.31 s.u-Ratio
                     C1B  -C2B     1.555   1.555

PLAT_731  Alert C Bond    Calc     1.33(3), Rep   1.332(13) ....       2.31 s.u-Ratio
                     C1B  -C3B     1.555   5.665

PLAT_731  Alert C Bond    Calc     1.30(4), Rep   1.303(13) ....       3.08 s.u-Ratio
                     C2B  -C3B     1.555   1.555

PLAT_731  Alert C Bond    Calc     1.33(3), Rep   1.332(13) ....       2.31 s.u-Ratio
                     C3B  -C1B     1.555   5.665


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 4 Alert Level C = Please check

Comment top

Crystallographic studies on symmetrically shaped molecules, with a view to understand the nature and strength of intermolecular interactions, are expected to provide information regarding their role in effecting symmetry carry-over from the free state to the solid and obtain information about specific interactions. The symmetry of a molecule in the solid state is often found reduced than that observed in the free state as the molecules tend to pack as closely as possible upon crystallization (Kitaigorodskii, 1973), giving rise to a variety of intermolecular interactions. While inversion centre is often carried over into the crystal, the retention of mirror or twofold symmetry by molecules seems to depend on the presence, nature and strength of the intermolecular interactions. The present crystal structure (I) is a good example of the retention of mirror symmetry by a molecule in the crystal state.

Fig. 1 shows the crystallographic numbering scheme adopted. All four six-membered rings which constitute the diazaadamantanone cage adopt the chair conformation which is the most preferred conformation for adamantanes, irrespective of substitution. The molecule is bisected by a mirror plane passing through atoms C2, N1, N3, C10 and O11 of the diazaadamantanone cage. The solvent benzene molecule is trapped in the crystal lattice and held inside the channel running along the c axis by van der Waals interactions (Fig. 2). In the absence of C—H···X-type hydrogen bonds, the solvent molecule presumably plays a role in optimizing packing efficiency within the lattice. The absence of C—H···X-type interactions may be attributed to the deficiency of acceptors compared to donors (phenyl C—H) whose presence otherwise might have had a considerable influence on the molecular conformation.

Experimental top

Colourless single crystals were obtained as transparent needles by slow evaporation of a benzene solution at room temperature.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. ORTEP diagram (PLATON; Spek, 1999) with displacement ellipsoids drawn at the 40% probability level showing the numbering scheme adopted.
	Fig. 2. Figure showing the solvent benzene molecule trapped inside channels running along the c axis.

4,8,9,10-Tetra(4-methoxyphenyl)-1,3-diazaadamantan-6-one-benzene solvate top

Crystal data top

C₃₆H₃₆N₂O₅·C₆H₆	F(000) = 1392
M_r = 654.78	D_x = 1.224 Mg m⁻³
Orthorhombic, Pnma	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 16.6240 (5) Å	θ = 16–26°
b = 26.0007 (16) Å	µ = 0.64 mm⁻¹
c = 8.2207 (7) Å	T = 293 K
V = 3553.3 (4) Å³	Needles, colourless
Z = 4	0.33 × 0.22 × 0.18 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	2226 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.010
Graphite monochromator	θ_max = 70.0°, θ_min = 3.4°
/w–2/q scans	h = 0→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→31
T_min = 0.864, T_max = 0.892	l = 0→10
3401 measured reflections	2 standard reflections every 200 reflections
3401 independent reflections	intensity decay: 0.1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.191	w = 1/[σ²(F_o²) + (0.0399P)² + 6.1627P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
3401 reflections	Δρ_max = 0.29 e Å⁻³
230 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00090 (11)

Crystal data top

C₃₆H₃₆N₂O₅·C₆H₆	V = 3553.3 (4) Å³
M_r = 654.78	Z = 4
Orthorhombic, Pnma	Cu Kα radiation
a = 16.6240 (5) Å	µ = 0.64 mm⁻¹
b = 26.0007 (16) Å	T = 293 K
c = 8.2207 (7) Å	0.33 × 0.22 × 0.18 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	2226 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.010
T_min = 0.864, T_max = 0.892	2 standard reflections every 200 reflections
3401 measured reflections	intensity decay: 0.1%
3401 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.13	Δρ_max = 0.29 e Å⁻³
3401 reflections	Δρ_min = −0.20 e Å⁻³
230 parameters

Special details top

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.3199 (2)	0.2500	−0.2382 (5)	0.0376 (9)
C2	0.4080 (3)	0.2500	−0.2495 (6)	0.0397 (11)
H2A	0.4248	0.2801	−0.3103	0.048*	0.50
H2B	0.4248	0.2199	−0.3103	0.048*	0.50
N3	0.4496 (2)	0.2500	−0.0909 (5)	0.0386 (9)
C4	0.42588 (19)	0.29796 (13)	−0.0049 (4)	0.0378 (8)
H4	0.4367	0.3259	−0.0817	0.045*
C5	0.33314 (19)	0.29789 (13)	0.0201 (4)	0.0399 (8)
H5	0.3161	0.3286	0.0800	0.048*
C6	0.2918 (2)	0.29584 (13)	−0.1496 (4)	0.0395 (8)
H6	0.2341	0.2912	−0.1302	0.047*
C10	0.3093 (3)	0.2500	0.1103 (6)	0.0402 (11)
O11	0.2731 (2)	0.2500	0.2391 (4)	0.0513 (9)
C41	0.4747 (2)	0.31038 (12)	0.1447 (4)	0.0367 (8)
C42	0.5587 (2)	0.31181 (14)	0.1355 (5)	0.0460 (9)
H42	0.5837	0.3029	0.0384	0.055*
C43	0.6051 (2)	0.32602 (14)	0.2657 (5)	0.0474 (9)
H43	0.6609	0.3256	0.2569	0.057*
C44	0.5693 (2)	0.34093 (13)	0.4101 (4)	0.0432 (8)
C45	0.4865 (2)	0.34060 (14)	0.4229 (4)	0.0453 (9)
H45	0.4616	0.3509	0.5188	0.054*
C46	0.4408 (2)	0.32464 (14)	0.2903 (4)	0.0450 (9)
H46	0.3851	0.3236	0.3007	0.054*
O47	0.62036 (15)	0.35496 (11)	0.5339 (3)	0.0570 (7)
C48	0.5862 (3)	0.3659 (2)	0.6866 (5)	0.0822 (16)
H48A	0.6279	0.3751	0.7619	0.123*
H48B	0.5583	0.3360	0.7260	0.123*
H48C	0.5490	0.3939	0.6761	0.123*
C61	0.3010 (2)	0.34442 (13)	−0.2511 (4)	0.0412 (8)
C62	0.2767 (2)	0.34370 (14)	−0.4137 (4)	0.0462 (9)
H62	0.2599	0.3129	−0.4602	0.055*
C63	0.2771 (2)	0.38790 (15)	−0.5065 (5)	0.0522 (10)
H63	0.2597	0.3868	−0.6139	0.063*
C64	0.3032 (2)	0.43397 (15)	−0.4404 (5)	0.0560 (10)
C65	0.3290 (3)	0.43554 (15)	−0.2823 (5)	0.0632 (12)
H65	0.3477	0.4661	−0.2377	0.076*
C66	0.3270 (3)	0.39082 (15)	−0.1889 (5)	0.0579 (11)
H66	0.3438	0.3923	−0.0811	0.070*
O67	0.3004 (2)	0.47552 (11)	−0.5421 (4)	0.0791 (10)
C68	0.3254 (4)	0.52372 (18)	−0.4764 (8)	0.109 (2)
H68A	0.3209	0.5498	−0.5585	0.164*
H68B	0.3802	0.5213	−0.4410	0.164*
H68C	0.2917	0.5325	−0.3856	0.164*
C1B	0.4342 (9)	0.4969 (12)	0.090 (2)	0.162 (5)
H1B	0.3884	0.4947	0.1547	0.195*
C2B	0.4424 (14)	0.5339 (7)	−0.016 (3)	0.161 (5)
H2B1	0.4014	0.5578	−0.0283	0.193*
C3B	0.5072 (19)	0.5378 (5)	−0.1042 (16)	0.155 (5)
H3B	0.5125	0.5649	−0.1773	0.186*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.038 (2)	0.038 (2)	0.036 (2)	0.000	0.0003 (18)	0.000
C2	0.049 (3)	0.034 (2)	0.036 (3)	0.000	0.006 (2)	0.000
N3	0.037 (2)	0.042 (2)	0.036 (2)	0.000	0.0059 (18)	0.000
C4	0.0393 (18)	0.0388 (18)	0.0352 (18)	0.0017 (15)	0.0019 (15)	−0.0007 (15)
C5	0.0375 (18)	0.0435 (19)	0.0388 (19)	0.0024 (15)	0.0008 (15)	−0.0006 (16)
C6	0.0386 (18)	0.0428 (19)	0.0370 (18)	0.0045 (15)	0.0012 (15)	−0.0017 (16)
C10	0.028 (2)	0.051 (3)	0.042 (3)	0.000	0.002 (2)	0.000
O11	0.044 (2)	0.068 (2)	0.042 (2)	0.000	0.0075 (17)	0.000
C41	0.0383 (17)	0.0350 (17)	0.0367 (18)	−0.0006 (14)	0.0002 (15)	0.0005 (14)
C42	0.0423 (19)	0.047 (2)	0.048 (2)	0.0005 (16)	0.0041 (17)	−0.0048 (17)
C43	0.0369 (18)	0.052 (2)	0.053 (2)	−0.0029 (16)	0.0000 (17)	−0.0016 (19)
C44	0.045 (2)	0.0388 (19)	0.046 (2)	−0.0040 (16)	−0.0088 (17)	0.0047 (17)
C45	0.045 (2)	0.053 (2)	0.0376 (19)	−0.0032 (17)	0.0028 (16)	−0.0031 (17)
C46	0.0379 (18)	0.055 (2)	0.042 (2)	−0.0020 (16)	0.0024 (16)	−0.0022 (17)
O47	0.0518 (15)	0.0679 (18)	0.0512 (16)	−0.0067 (13)	−0.0122 (13)	−0.0066 (14)
C48	0.070 (3)	0.120 (4)	0.056 (3)	−0.012 (3)	−0.012 (2)	−0.015 (3)
C61	0.0420 (18)	0.0389 (18)	0.0429 (19)	0.0036 (15)	0.0023 (17)	−0.0034 (17)
C62	0.051 (2)	0.044 (2)	0.044 (2)	0.0034 (17)	−0.0015 (18)	−0.0032 (17)
C63	0.057 (2)	0.056 (2)	0.044 (2)	0.0047 (19)	−0.0063 (19)	0.0026 (19)
C64	0.060 (2)	0.049 (2)	0.059 (3)	0.0022 (19)	−0.003 (2)	0.009 (2)
C65	0.086 (3)	0.038 (2)	0.065 (3)	−0.002 (2)	−0.016 (2)	−0.002 (2)
C66	0.076 (3)	0.049 (2)	0.048 (2)	0.003 (2)	−0.013 (2)	−0.0018 (19)
O67	0.111 (3)	0.0510 (17)	0.075 (2)	−0.0044 (17)	−0.015 (2)	0.0179 (16)
C68	0.159 (6)	0.046 (3)	0.123 (5)	−0.015 (3)	−0.031 (5)	0.023 (3)
C1B	0.134 (9)	0.240 (15)	0.112 (9)	−0.055 (10)	0.019 (7)	−0.069 (9)
C2B	0.188 (13)	0.125 (9)	0.170 (12)	0.071 (9)	−0.088 (9)	−0.071 (8)
C3B	0.281 (16)	0.082 (6)	0.103 (7)	−0.064 (9)	−0.048 (10)	0.021 (5)

Geometric parameters (Å, º) top

N1—C2	1.467 (6)	C44—O47	1.375 (4)
N1—C6	1.473 (4)	C44—C45	1.381 (5)
N1—C6ⁱ	1.473 (4)	C45—C46	1.392 (5)
C2—N3	1.476 (6)	O47—C48	1.407 (5)
N3—C4	1.487 (4)	C61—C66	1.379 (5)
N3—C4ⁱ	1.487 (4)	C61—C62	1.397 (5)
C4—C41	1.509 (4)	C62—C63	1.379 (5)
C4—C5	1.555 (4)	C63—C64	1.385 (5)
C5—C10	1.503 (4)	C64—O67	1.367 (5)
C5—C6	1.556 (5)	C64—C65	1.370 (6)
C6—C61	1.521 (5)	C65—C66	1.394 (5)
C10—O11	1.217 (6)	O67—C68	1.426 (5)
C10—C5ⁱ	1.503 (4)	C1B—C2B	1.305 (13)
C41—C46	1.374 (5)	C1B—C3Bⁱⁱ	1.332 (13)
C41—C42	1.398 (5)	C2B—C3B	1.303 (13)
C42—C43	1.370 (5)	C3B—C1Bⁱⁱ	1.332 (13)
C43—C44	1.384 (5)

C2—N1—C6	110.4 (2)	C43—C42—C41	121.8 (3)
C2—N1—C6ⁱ	110.4 (2)	C42—C43—C44	120.2 (3)
C6—N1—C6ⁱ	108.0 (4)	O47—C44—C45	124.1 (3)
N1—C2—N3	114.3 (4)	O47—C44—C43	116.3 (3)
C2—N3—C4	107.2 (2)	C45—C44—C43	119.6 (3)
C2—N3—C4ⁱ	107.2 (2)	C44—C45—C46	119.1 (3)
C4—N3—C4ⁱ	114.0 (4)	C41—C46—C45	122.5 (3)
N3—C4—C41	115.1 (3)	C44—O47—C48	117.7 (3)
N3—C4—C5	109.0 (3)	C66—C61—C62	117.2 (3)
C41—C4—C5	115.2 (3)	C66—C61—C6	123.7 (3)
C10—C5—C4	109.1 (3)	C62—C61—C6	119.0 (3)
C10—C5—C6	107.3 (3)	C63—C62—C61	121.1 (4)
C4—C5—C6	108.6 (3)	C62—C63—C64	120.4 (4)
N1—C6—C61	111.6 (3)	O67—C64—C65	124.6 (4)
N1—C6—C5	109.3 (3)	O67—C64—C63	115.7 (4)
C61—C6—C5	114.7 (3)	C65—C64—C63	119.7 (4)
O11—C10—C5ⁱ	124.0 (2)	C64—C65—C66	119.4 (4)
O11—C10—C5	124.0 (2)	C61—C66—C65	122.2 (4)
C5ⁱ—C10—C5	111.9 (4)	C64—O67—C68	117.0 (4)
C46—C41—C42	116.7 (3)	C2B—C1B—C3Bⁱⁱ	118.7 (10)
C46—C41—C4	123.1 (3)	C3B—C2B—C1B	121.1 (10)
C42—C41—C4	119.9 (3)	C2B—C3B—C1Bⁱⁱ	120.2 (10)

C6—N1—C2—N3	59.7 (2)	C4—C41—C42—C43	175.9 (3)
C6ⁱ—N1—C2—N3	−59.7 (2)	C41—C42—C43—C44	−1.9 (6)
N1—C2—N3—C4	−61.4 (2)	C42—C43—C44—O47	−179.5 (3)
N1—C2—N3—C4ⁱ	61.4 (2)	C42—C43—C44—C45	1.0 (6)
C2—N3—C4—C41	−168.3 (3)	O47—C44—C45—C46	−178.7 (3)
C4ⁱ—N3—C4—C41	73.3 (4)	C43—C44—C45—C46	0.7 (6)
C2—N3—C4—C5	60.6 (4)	C42—C41—C46—C45	0.9 (5)
C4ⁱ—N3—C4—C5	−57.9 (4)	C4—C41—C46—C45	−173.9 (3)
N3—C4—C5—C10	56.2 (4)	C44—C45—C46—C41	−1.8 (6)
C41—C4—C5—C10	−74.9 (4)	C45—C44—O47—C48	5.0 (6)
N3—C4—C5—C6	−60.5 (4)	C43—C44—O47—C48	−174.4 (4)
C41—C4—C5—C6	168.4 (3)	N1—C6—C61—C66	−139.3 (4)
C2—N1—C6—C61	72.4 (4)	C5—C6—C61—C66	−14.3 (5)
C6ⁱ—N1—C6—C61	−166.9 (2)	N1—C6—C61—C62	45.5 (4)
C2—N1—C6—C5	−55.6 (4)	C5—C6—C61—C62	170.5 (3)
C6ⁱ—N1—C6—C5	65.1 (4)	C66—C61—C62—C63	−1.4 (5)
C10—C5—C6—N1	−60.7 (3)	C6—C61—C62—C63	174.1 (3)
C4—C5—C6—N1	57.2 (4)	C61—C62—C63—C64	1.2 (6)
C10—C5—C6—C61	173.0 (3)	C62—C63—C64—O67	−179.4 (4)
C4—C5—C6—C61	−69.1 (4)	C62—C63—C64—C65	0.2 (6)
C4—C5—C10—O11	122.5 (4)	O67—C64—C65—C66	178.2 (4)
C6—C5—C10—O11	−120.0 (5)	C63—C64—C65—C66	−1.4 (7)
C4—C5—C10—C5ⁱ	−59.2 (5)	C62—C61—C66—C65	0.3 (6)
C6—C5—C10—C5ⁱ	58.3 (4)	C6—C61—C66—C65	−175.0 (4)
N3—C4—C41—C46	−133.1 (3)	C64—C65—C66—C61	1.1 (7)
C5—C4—C41—C46	−4.9 (5)	C65—C64—O67—C68	−0.9 (7)
N3—C4—C41—C42	52.3 (4)	C63—C64—O67—C68	178.7 (4)
C5—C4—C41—C42	−179.6 (3)	C3Bⁱⁱ—C1B—C2B—C3B	−1.5 (17)
C46—C41—C42—C43	0.9 (5)	C1B—C2B—C3B—C1Bⁱⁱ	1.5 (18)

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

Experimental details

Crystal data
Chemical formula	C₃₆H₃₆N₂O₅·C₆H₆
M_r	654.78
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	16.6240 (5), 26.0007 (16), 8.2207 (7)
V (Å³)	3553.3 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.33 × 0.22 × 0.18

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.864, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	3401, 3401, 2226
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.191, 1.13
No. of reflections	3401
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.20

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.

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		CIF
		SGML
		Text
		Plain Text

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4,8,9,10-Tetrakis(4-methoxy­phenyl)-1,3-di­aza­adamantan-6-one benzene solvate

Supporting information

Key indicators

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4,8,9,10-Tetrakis(4-methoxyphenyl)-1,3-diazaadamantan-6-one benzene solvate