Conformational chirality of chemically symmetric mol­ecules and a superlattice through enantioselective self-assembly: 1,1,1-tris­[(4-cyano­phenoxy)­methyl]­ethane

Xu, W.; Zou, Z.-G.; Guo, P.; Lu, Y.-X.

doi:10.1107/S1600536804029939

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Conformational chirality of chemically symmetric molecules and a superlattice through enantioselective self-assembly: 1,1,1-tris[(4-cyanophenoxy)methyl]ethane

W. Xu, Z.-G. Zou, P. Guo and Y.-X. Lu

The title compound, C₂₆H₂₁N₃O₃, is a chemically symmetrical molecule with one methyl group and three (4-cyanophenoxy)methyl groups bonded to a tetracoordinate C atom. It crystallizes in the centrosymmetric space group P $\overline 1$ . In the crystal structure, there are many non-covalent interactions, including O

N short contacts and antiparallel dipole-dipole interactions. The tetracoordinate C atom of the molecule exhibits central chirality, while the three attached groups exhibit different axial chirality. The enantiomers form homochiral monolayers through enantioselective self-assembly, and the monolayers are packed in the formation of a superlattice based on alternating the two enantiomeric states. The physical image of molecular chirality as well as the concept of a superlattice with respect to chirality may provide a new insight into such a racemic crystal, which is very common in crystallography.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804029939/ww6294sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804029939/ww6294Isup2.hkl Contains datablock I

CCDC reference: 259616

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.052
wR factor = 0.134
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C7     -   C10    ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C14    -   C18    ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C23    -   C26    ...       1.44 Ang.

   0 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

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

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

1,1,1-tris[(4-cyanophenoxy)methyl]ethane top

Crystal data top

C₂₆H₂₁N₃O₃	Z = 2
M_r = 423.46	F(000) = 444
Triclinic, P1	D_x = 1.237 Mg m⁻³
a = 8.248 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.097 (3) Å	Cell parameters from 828 reflections
c = 14.786 (5) Å	θ = 2.7–27.1°
α = 79.404 (5)°	µ = 0.08 mm⁻¹
β = 74.292 (5)°	T = 293 K
γ = 75.089 (4)°	Parallelepiped, colourless
V = 1136.8 (6) Å³	0.45 × 0.40 × 0.35 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3936 independent reflections
Radiation source: fine-focus sealed tube	3350 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
φ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.964, T_max = 0.972	k = −11→11
4780 measured reflections	l = −12→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0533P)² + 0.3456P] where P = (F_o² + 2F_c²)/3
3936 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

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
N1	0.9279 (3)	−0.0993 (2)	0.86727 (19)	0.0883 (7)
N2	−0.9152 (3)	0.7360 (3)	1.09970 (18)	0.0960 (8)
N3	0.4091 (3)	1.3621 (2)	0.43431 (15)	0.0698 (6)
O1	0.24958 (16)	0.36296 (14)	0.75397 (11)	0.0560 (4)
O2	−0.19828 (17)	0.66364 (15)	0.74973 (10)	0.0579 (4)
O3	0.1547 (2)	0.78080 (14)	0.64707 (10)	0.0576 (4)
C1	0.0183 (3)	0.4640 (2)	0.63121 (17)	0.0565 (5)
H1A	−0.0938	0.5104	0.6213	0.085*
H1B	0.0098	0.3808	0.6739	0.085*
H1C	0.0950	0.4416	0.5718	0.085*
C2	0.0884 (2)	0.55825 (19)	0.67348 (14)	0.0443 (5)
C3	0.2673 (2)	0.48579 (19)	0.69009 (15)	0.0466 (5)
H3A	0.3470	0.4629	0.6307	0.056*
H3B	0.3117	0.5459	0.7169	0.056*
C4	0.3945 (2)	0.2748 (2)	0.77336 (15)	0.0465 (5)
C5	0.5600 (3)	0.2951 (2)	0.73465 (16)	0.0538 (5)
H5A	0.5788	0.3737	0.6930	0.065*
C6	0.6968 (3)	0.1964 (2)	0.75896 (17)	0.0594 (6)
H6A	0.8087	0.2088	0.7332	0.071*
C7	0.6700 (3)	0.0795 (2)	0.82093 (16)	0.0555 (5)
C8	0.5035 (3)	0.0606 (2)	0.85917 (17)	0.0566 (5)
H8A	0.4847	−0.0181	0.9008	0.068*
C9	0.3664 (3)	0.1578 (2)	0.83564 (16)	0.0543 (5)
H9A	0.2545	0.1452	0.8614	0.065*
C10	0.8139 (3)	−0.0204 (2)	0.84715 (18)	0.0652 (6)
C11	−0.0320 (2)	0.5954 (2)	0.76736 (14)	0.0474 (5)
H11A	−0.0409	0.5126	0.8119	0.057*
H11B	0.0119	0.6561	0.7940	0.057*
C12	−0.3288 (3)	0.6546 (2)	0.91831 (15)	0.0531 (5)
H12A	−0.2221	0.6295	0.9339	0.064*
C13	−0.4788 (3)	0.6708 (2)	0.98840 (16)	0.0568 (5)
H13A	−0.4729	0.6561	1.0515	0.068*
C14	−0.6374 (3)	0.7086 (2)	0.96607 (16)	0.0526 (5)
C15	−0.6463 (3)	0.7314 (2)	0.87184 (17)	0.0588 (6)
H15A	−0.7529	0.7577	0.8562	0.071*
C16	−0.4965 (3)	0.7147 (2)	0.80180 (16)	0.0581 (6)
H16A	−0.5021	0.7298	0.7386	0.070*
C17	−0.3376 (2)	0.6758 (2)	0.82461 (15)	0.0474 (5)
C18	−0.7936 (3)	0.7242 (2)	1.04004 (18)	0.0658 (6)
C19	0.1116 (3)	0.6853 (2)	0.60234 (15)	0.0493 (5)
H19A	0.2029	0.6597	0.5473	0.059*
H19B	0.0057	0.7269	0.5817	0.059*
C20	0.2010 (2)	0.89694 (19)	0.59648 (14)	0.0470 (5)
C21	0.2234 (3)	0.9298 (2)	0.49932 (15)	0.0505 (5)
H21A	0.2025	0.8718	0.4637	0.061*
C22	0.2770 (3)	1.0495 (2)	0.45589 (15)	0.0521 (5)
H22A	0.2934	1.0714	0.3906	0.062*
C23	0.3066 (2)	1.1372 (2)	0.50814 (15)	0.0481 (5)
C24	0.2804 (3)	1.1041 (2)	0.60568 (16)	0.0563 (5)
H24A	0.2986	1.1630	0.6416	0.068*
C25	0.2280 (3)	0.9855 (2)	0.64909 (15)	0.0570 (6)
H25A	0.2104	0.9642	0.7145	0.068*
C26	0.3646 (3)	1.2616 (2)	0.46505 (16)	0.0541 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0639 (13)	0.0755 (15)	0.113 (2)	0.0130 (12)	−0.0311 (14)	−0.0056 (13)
N2	0.0592 (13)	0.1128 (19)	0.0893 (18)	−0.0155 (13)	0.0153 (13)	0.0002 (15)
N3	0.0659 (12)	0.0580 (12)	0.0741 (14)	−0.0165 (10)	−0.0010 (10)	0.0008 (10)
O1	0.0336 (7)	0.0479 (8)	0.0739 (10)	−0.0037 (6)	−0.0103 (7)	0.0127 (7)
O2	0.0370 (7)	0.0699 (10)	0.0505 (9)	0.0078 (6)	−0.0042 (6)	−0.0042 (7)
O3	0.0745 (10)	0.0447 (8)	0.0487 (8)	−0.0145 (7)	−0.0093 (7)	0.0007 (6)
C1	0.0444 (11)	0.0534 (12)	0.0689 (15)	−0.0032 (9)	−0.0128 (10)	−0.0123 (11)
C2	0.0347 (9)	0.0403 (10)	0.0512 (11)	−0.0019 (8)	−0.0063 (8)	−0.0036 (9)
C3	0.0365 (10)	0.0418 (10)	0.0540 (12)	−0.0045 (8)	−0.0065 (9)	0.0012 (9)
C4	0.0358 (10)	0.0449 (11)	0.0540 (12)	−0.0019 (8)	−0.0106 (9)	−0.0042 (9)
C5	0.0415 (11)	0.0528 (12)	0.0594 (13)	−0.0079 (9)	−0.0101 (10)	0.0057 (10)
C6	0.0351 (10)	0.0643 (14)	0.0712 (15)	−0.0064 (10)	−0.0091 (10)	−0.0008 (12)
C7	0.0442 (11)	0.0497 (12)	0.0662 (14)	0.0028 (9)	−0.0164 (10)	−0.0049 (10)
C8	0.0531 (12)	0.0438 (11)	0.0663 (14)	−0.0050 (9)	−0.0152 (11)	0.0036 (10)
C9	0.0389 (10)	0.0489 (12)	0.0674 (14)	−0.0074 (9)	−0.0076 (10)	0.0019 (10)
C10	0.0502 (13)	0.0575 (14)	0.0795 (17)	0.0033 (11)	−0.0182 (12)	−0.0049 (12)
C11	0.0366 (10)	0.0478 (11)	0.0502 (12)	−0.0003 (8)	−0.0091 (9)	−0.0015 (9)
C12	0.0412 (11)	0.0585 (13)	0.0539 (13)	−0.0019 (9)	−0.0108 (10)	−0.0063 (10)
C13	0.0518 (12)	0.0623 (14)	0.0491 (12)	−0.0064 (10)	−0.0054 (10)	−0.0069 (10)
C14	0.0424 (11)	0.0481 (11)	0.0577 (13)	−0.0071 (9)	0.0010 (10)	−0.0059 (10)
C15	0.0380 (11)	0.0643 (14)	0.0677 (15)	−0.0022 (10)	−0.0110 (10)	−0.0075 (11)
C16	0.0427 (11)	0.0706 (14)	0.0537 (13)	0.0011 (10)	−0.0105 (10)	−0.0101 (11)
C17	0.0388 (10)	0.0441 (11)	0.0505 (12)	0.0002 (8)	−0.0034 (9)	−0.0081 (9)
C18	0.0501 (13)	0.0629 (14)	0.0704 (16)	−0.0100 (11)	0.0019 (12)	−0.0011 (12)
C19	0.0439 (11)	0.0468 (11)	0.0501 (12)	−0.0007 (9)	−0.0088 (9)	−0.0051 (9)
C20	0.0417 (10)	0.0394 (10)	0.0499 (12)	0.0010 (8)	−0.0071 (9)	−0.0002 (9)
C21	0.0513 (12)	0.0469 (11)	0.0498 (12)	−0.0059 (9)	−0.0118 (10)	−0.0040 (9)
C22	0.0507 (12)	0.0520 (12)	0.0446 (11)	−0.0017 (9)	−0.0099 (9)	0.0006 (9)
C23	0.0386 (10)	0.0416 (11)	0.0542 (12)	0.0012 (8)	−0.0074 (9)	−0.0007 (9)
C24	0.0671 (14)	0.0452 (12)	0.0544 (13)	−0.0065 (10)	−0.0152 (11)	−0.0078 (10)
C25	0.0728 (14)	0.0480 (12)	0.0437 (12)	−0.0064 (10)	−0.0131 (11)	−0.0001 (10)
C26	0.0452 (11)	0.0506 (12)	0.0568 (13)	−0.0022 (10)	−0.0054 (10)	−0.0042 (10)

Geometric parameters (Å, º) top

N1—C10	1.134 (3)	C9—H9A	0.9300
N2—C18	1.139 (3)	C11—H11A	0.9700
N3—C26	1.142 (3)	C11—H11B	0.9700
O1—C4	1.359 (2)	C12—C13	1.377 (3)
O1—C3	1.428 (2)	C12—C17	1.381 (3)
O2—C17	1.360 (2)	C12—H12A	0.9300
O2—C11	1.437 (2)	C13—C14	1.378 (3)
O3—C20	1.354 (2)	C13—H13A	0.9300
O3—C19	1.426 (2)	C14—C15	1.388 (3)
C1—C2	1.525 (3)	C14—C18	1.441 (3)
C1—H1A	0.9600	C15—C16	1.375 (3)
C1—H1B	0.9600	C15—H15A	0.9300
C1—H1C	0.9600	C16—C17	1.382 (3)
C2—C11	1.519 (3)	C16—H16A	0.9300
C2—C19	1.519 (3)	C19—H19A	0.9700
C2—C3	1.532 (3)	C19—H19B	0.9700
C3—H3A	0.9700	C20—C25	1.381 (3)
C3—H3B	0.9700	C20—C21	1.386 (3)
C4—C5	1.382 (3)	C21—C22	1.380 (3)
C4—C9	1.387 (3)	C21—H21A	0.9300
C5—C6	1.379 (3)	C22—C23	1.380 (3)
C5—H5A	0.9300	C22—H22A	0.9300
C6—C7	1.381 (3)	C23—C24	1.389 (3)
C6—H6A	0.9300	C23—C26	1.436 (3)
C7—C8	1.385 (3)	C24—C25	1.366 (3)
C7—C10	1.437 (3)	C24—H24A	0.9300
C8—C9	1.371 (3)	C25—H25A	0.9300
C8—H8A	0.9300

C4—O1—C3	118.51 (14)	H11A—C11—H11B	108.5
C17—O2—C11	118.39 (15)	C13—C12—C17	119.59 (19)
C20—O3—C19	120.52 (16)	C13—C12—H12A	120.2
C2—C1—H1A	109.5	C17—C12—H12A	120.2
C2—C1—H1B	109.5	C12—C13—C14	120.7 (2)
H1A—C1—H1B	109.5	C12—C13—H13A	119.6
C2—C1—H1C	109.5	C14—C13—H13A	119.6
H1A—C1—H1C	109.5	C13—C14—C15	119.67 (19)
H1B—C1—H1C	109.5	C13—C14—C18	120.2 (2)
C11—C2—C19	112.11 (16)	C15—C14—C18	120.1 (2)
C11—C2—C1	110.15 (16)	C16—C15—C14	119.6 (2)
C19—C2—C1	108.66 (17)	C16—C15—H15A	120.2
C11—C2—C3	108.82 (16)	C14—C15—H15A	120.2
C19—C2—C3	106.78 (15)	C15—C16—C17	120.5 (2)
C1—C2—C3	110.27 (16)	C15—C16—H16A	119.8
O1—C3—C2	107.68 (15)	C17—C16—H16A	119.8
O1—C3—H3A	110.2	O2—C17—C12	124.64 (18)
C2—C3—H3A	110.2	O2—C17—C16	115.43 (18)
O1—C3—H3B	110.2	C12—C17—C16	119.92 (19)
C2—C3—H3B	110.2	N2—C18—C14	178.8 (3)
H3A—C3—H3B	108.5	O3—C19—C2	108.19 (16)
O1—C4—C5	124.37 (18)	O3—C19—H19A	110.1
O1—C4—C9	114.95 (17)	C2—C19—H19A	110.1
C5—C4—C9	120.67 (18)	O3—C19—H19B	110.1
C6—C5—C4	118.7 (2)	C2—C19—H19B	110.1
C6—C5—H5A	120.6	H19A—C19—H19B	108.4
C4—C5—H5A	120.6	O3—C20—C25	114.88 (18)
C5—C6—C7	121.04 (19)	O3—C20—C21	125.20 (19)
C5—C6—H6A	119.5	C25—C20—C21	119.92 (19)
C7—C6—H6A	119.5	C22—C21—C20	119.4 (2)
C6—C7—C8	119.62 (18)	C22—C21—H21A	120.3
C6—C7—C10	120.2 (2)	C20—C21—H21A	120.3
C8—C7—C10	120.2 (2)	C21—C22—C23	120.8 (2)
C9—C8—C7	120.0 (2)	C21—C22—H22A	119.6
C9—C8—H8A	120.0	C23—C22—H22A	119.6
C7—C8—H8A	120.0	C22—C23—C24	119.12 (19)
C8—C9—C4	119.99 (19)	C22—C23—C26	122.2 (2)
C8—C9—H9A	120.0	C24—C23—C26	118.7 (2)
C4—C9—H9A	120.0	C25—C24—C23	120.4 (2)
N1—C10—C7	179.6 (3)	C25—C24—H24A	119.8
O2—C11—C2	107.68 (15)	C23—C24—H24A	119.8
O2—C11—H11A	110.2	C24—C25—C20	120.4 (2)
C2—C11—H11A	110.2	C24—C25—H25A	119.8
O2—C11—H11B	110.2	C20—C25—H25A	119.8
C2—C11—H11B	110.2	N3—C26—C23	177.3 (2)

C1—C2—C3—O1	−59.9 (2)	C3—O1—C4—C5	−0.6 (3)
C1—C2—C11—O2	−59.3 (2)	C3—O1—C4—C9	−179.73 (18)
C1—C2—C19—O3	172.34 (15)	C11—O2—C17—C12	14.6 (3)
C2—C3—O1—C4	174.57 (16)	C11—O2—C17—C16	−166.65 (18)
C2—C11—O2—C17	163.67 (16)	C19—O3—C20—C21	−4.9 (3)
C2—C19—O3—C20	172.76 (15)	C19—O3—C20—C25	175.73 (17)

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