The title compound, C40H40N4O4, contains a 1,4,8,11-tetraazacyclotetradecane ring, with four benzyl and two methylene substituents and also four carbonyl groups. This molecule is only the second reported structure of the 1,4,8,11-tetraazacyclotetradecane ring with four carbonyl groups on C atoms 2, 3, 9 and 10. Large-ring nitrogen heterocycles are often useful for their ability to selectively coordinate with certain metal ions, and are also sometimes used as precursors to new energetic materials. In the crystal structure the molecule is centrosymmetric.
Supporting information
CCDC reference: 221681
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.048
- wR factor = 0.139
- Data-to-parameter ratio = 13.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 67.21
From the CIF: _reflns_number_total 2938
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 3124
Completeness (_total/calc) 94.05%
Alert C: < 95% complete
PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C2 - C3 = 1.53 Ang.
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 67.21
From the CIF: _reflns_number_total 2938
From the CIF: _diffrn_reflns_limit_ max hkl 11. 9. 20.
From the CIF: _diffrn_reflns_limit_ min hkl -11. -11. -20.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 11. 11. 22.
Calculated minimum hkl -11. -11. -22.
ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
1,4,8,11-Tetrabenzyl-6,13-dimethylene-1,4,8,11-tetraazacyclotetradecane-
2,3,9,10-tetraone
top
Crystal data top
C40H40N4O4 | F(000) = 680 |
Mr = 640.76 | Dx = 1.221 Mg m−3 |
Monoclinic, P21/c | Melting point: 284 K |
Hall symbol: -P 2ybc | Cu Kα radiation, λ = 1.54178 Å |
a = 9.9969 (3) Å | Cell parameters from 3915 reflections |
b = 9.3366 (3) Å | θ = 4.4–60.6° |
c = 18.6720 (6) Å | µ = 0.64 mm−1 |
β = 90.758 (2)° | T = 295 K |
V = 1742.64 (9) Å3 | Thin plate, colorless |
Z = 2 | 0.18 × 0.16 × 0.03 mm |
Data collection top
Bruker SMART-CCD diffractometer | 2938 independent reflections |
Radiation source: fine-focus sealed tube | 1764 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.096 |
ω scans | θmax = 67.2°, θmin = 4.4° |
Absorption correction: integration (Wuensch & Prewitt, 1965) | h = −11→11 |
Tmin = 0.897, Tmax = 0.981 | k = −11→9 |
10138 measured reflections | l = −20→20 |
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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0773P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.91 | (Δ/σ)max < 0.001 |
2938 reflections | Δρmax = 0.15 e Å−3 |
218 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0048 (7) |
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 | Uiso*/Ueq | |
N1 | 0.43480 (18) | 0.57576 (16) | 0.37534 (8) | 0.0671 (5) | |
C1 | 0.4346 (2) | 0.4562 (2) | 0.32461 (10) | 0.0699 (6) | |
H1A | 0.3605 | 0.3929 | 0.3352 | 0.084* | |
H1B | 0.5168 | 0.4021 | 0.3306 | 0.084* | |
C11 | 0.4222 (2) | 0.50611 (19) | 0.24751 (10) | 0.0680 (5) | |
C12 | 0.3032 (3) | 0.5540 (3) | 0.22025 (13) | 0.1025 (8) | |
H12A | 0.2281 | 0.5552 | 0.2491 | 0.123* | |
C13 | 0.2927 (3) | 0.6010 (4) | 0.14983 (16) | 0.1212 (10) | |
H13A | 0.2110 | 0.6340 | 0.1321 | 0.145* | |
C14 | 0.4004 (4) | 0.5990 (3) | 0.10686 (14) | 0.1005 (8) | |
H14A | 0.3930 | 0.6287 | 0.0594 | 0.121* | |
C15 | 0.5189 (3) | 0.5533 (3) | 0.13369 (13) | 0.0946 (8) | |
H15A | 0.5941 | 0.5538 | 0.1049 | 0.114* | |
C16 | 0.5296 (3) | 0.5057 (2) | 0.20349 (12) | 0.0815 (6) | |
H16A | 0.6117 | 0.4728 | 0.2208 | 0.098* | |
C2 | 0.3407 (2) | 0.5960 (2) | 0.42418 (12) | 0.0716 (6) | |
O2 | 0.34354 (17) | 0.69188 (17) | 0.46907 (9) | 0.0979 (5) | |
C3 | 0.2166 (2) | 0.5004 (2) | 0.42217 (11) | 0.0736 (6) | |
O3 | 0.11917 (16) | 0.53828 (17) | 0.38595 (9) | 0.0941 (5) | |
N4 | 0.21932 (17) | 0.38257 (19) | 0.46380 (8) | 0.0730 (5) | |
C4 | 0.0989 (2) | 0.2916 (3) | 0.46770 (11) | 0.0853 (7) | |
H4A | 0.0201 | 0.3504 | 0.4595 | 0.102* | |
H4B | 0.0931 | 0.2513 | 0.5155 | 0.102* | |
C41 | 0.0996 (2) | 0.1717 (2) | 0.41389 (11) | 0.0740 (6) | |
C42 | 0.1216 (3) | 0.0308 (3) | 0.43390 (16) | 0.1037 (8) | |
H42A | 0.1392 | 0.0079 | 0.4816 | 0.124* | |
C43 | 0.1170 (3) | −0.0788 (3) | 0.3811 (2) | 0.1207 (11) | |
H43A | 0.1307 | −0.1741 | 0.3938 | 0.145* | |
C44 | 0.0921 (3) | −0.0422 (4) | 0.3116 (2) | 0.1213 (10) | |
H44A | 0.0895 | −0.1138 | 0.2770 | 0.146* | |
C45 | 0.0716 (3) | 0.0930 (4) | 0.29184 (16) | 0.1091 (9) | |
H45A | 0.0546 | 0.1150 | 0.2440 | 0.131* | |
C46 | 0.0755 (2) | 0.1994 (3) | 0.34209 (12) | 0.0867 (7) | |
H46A | 0.0614 | 0.2935 | 0.3275 | 0.104* | |
C5 | 0.3372 (2) | 0.3398 (2) | 0.50508 (10) | 0.0706 (6) | |
H5A | 0.4153 | 0.3843 | 0.4843 | 0.085* | |
H5B | 0.3480 | 0.2369 | 0.5010 | 0.085* | |
C6 | 0.3325 (2) | 0.3789 (3) | 0.58343 (11) | 0.0783 (6) | |
C6A | 0.2368 (3) | 0.4524 (4) | 0.61191 (15) | 0.1319 (12) | |
H6AA | 0.2399 | 0.4741 | 0.6605 | 0.172* | |
H6AB | 0.1651 | 0.4834 | 0.5837 | 0.172* | |
C7 | 0.4506 (2) | 0.3262 (2) | 0.62656 (11) | 0.0818 (7) | |
H7A | 0.4239 | 0.3133 | 0.6759 | 0.098* | |
H7B | 0.4779 | 0.2336 | 0.6083 | 0.098* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0690 (12) | 0.0625 (9) | 0.0696 (10) | −0.0066 (8) | −0.0103 (9) | 0.0018 (7) |
C1 | 0.0723 (15) | 0.0644 (11) | 0.0729 (12) | 0.0017 (9) | −0.0029 (10) | 0.0052 (9) |
C11 | 0.0692 (15) | 0.0634 (11) | 0.0712 (12) | −0.0034 (10) | −0.0053 (11) | 0.0010 (9) |
C12 | 0.0785 (18) | 0.149 (2) | 0.0801 (15) | 0.0167 (16) | −0.0056 (13) | 0.0159 (14) |
C13 | 0.101 (2) | 0.168 (3) | 0.0947 (19) | 0.027 (2) | −0.0203 (18) | 0.0248 (18) |
C14 | 0.123 (3) | 0.1004 (18) | 0.0778 (15) | −0.0090 (16) | −0.0046 (17) | 0.0174 (12) |
C15 | 0.101 (2) | 0.0948 (16) | 0.0887 (17) | −0.0179 (14) | 0.0166 (15) | 0.0054 (13) |
C16 | 0.0814 (17) | 0.0831 (14) | 0.0798 (14) | −0.0038 (12) | 0.0017 (12) | 0.0009 (11) |
C2 | 0.0701 (15) | 0.0692 (12) | 0.0750 (13) | 0.0049 (10) | −0.0169 (11) | −0.0049 (10) |
O2 | 0.1027 (13) | 0.0892 (10) | 0.1012 (11) | 0.0022 (9) | −0.0141 (9) | −0.0309 (9) |
C3 | 0.0681 (15) | 0.0809 (14) | 0.0715 (12) | 0.0074 (11) | −0.0078 (10) | −0.0152 (11) |
O3 | 0.0702 (11) | 0.1008 (11) | 0.1105 (11) | 0.0114 (8) | −0.0259 (9) | −0.0032 (9) |
N4 | 0.0608 (11) | 0.0905 (12) | 0.0676 (10) | −0.0069 (9) | −0.0060 (8) | −0.0020 (9) |
C4 | 0.0648 (15) | 0.1153 (17) | 0.0758 (13) | −0.0159 (13) | 0.0012 (11) | −0.0012 (12) |
C41 | 0.0538 (13) | 0.0864 (14) | 0.0817 (13) | −0.0106 (10) | −0.0036 (10) | 0.0083 (11) |
C42 | 0.0755 (18) | 0.114 (2) | 0.122 (2) | −0.0129 (15) | −0.0022 (15) | 0.0334 (17) |
C43 | 0.088 (2) | 0.0759 (17) | 0.198 (4) | −0.0028 (14) | 0.011 (2) | 0.006 (2) |
C44 | 0.094 (2) | 0.117 (3) | 0.153 (3) | −0.0125 (18) | 0.000 (2) | −0.034 (2) |
C45 | 0.106 (2) | 0.118 (2) | 0.1024 (18) | −0.0018 (17) | −0.0093 (16) | −0.0230 (17) |
C46 | 0.0836 (17) | 0.0946 (15) | 0.0817 (15) | −0.0022 (12) | −0.0109 (12) | −0.0050 (12) |
C5 | 0.0641 (14) | 0.0818 (13) | 0.0657 (12) | −0.0034 (10) | −0.0034 (10) | 0.0008 (9) |
C6 | 0.0681 (15) | 0.1042 (16) | 0.0625 (12) | −0.0161 (13) | −0.0021 (11) | −0.0026 (11) |
C6A | 0.082 (2) | 0.232 (4) | 0.0810 (16) | 0.009 (2) | 0.0021 (14) | −0.045 (2) |
C7 | 0.0910 (17) | 0.0835 (14) | 0.0705 (12) | −0.0232 (12) | −0.0126 (11) | 0.0142 (10) |
Geometric parameters (Å, º) top
N1—C2 | 1.332 (3) | C4—H4A | 0.9700 |
N1—C1 | 1.464 (2) | C4—H4B | 0.9700 |
N1—C7i | 1.467 (3) | C41—C46 | 1.384 (3) |
C1—C11 | 1.517 (3) | C41—C42 | 1.384 (3) |
C1—H1A | 0.9700 | C42—C43 | 1.421 (4) |
C1—H1B | 0.9700 | C42—H42A | 0.9300 |
C11—C16 | 1.360 (3) | C43—C44 | 1.362 (4) |
C11—C12 | 1.364 (3) | C43—H43A | 0.9300 |
C12—C13 | 1.389 (4) | C44—C45 | 1.331 (4) |
C12—H12A | 0.9300 | C44—H44A | 0.9300 |
C13—C14 | 1.351 (4) | C45—C46 | 1.367 (3) |
C13—H13A | 0.9300 | C45—H45A | 0.9300 |
C14—C15 | 1.349 (4) | C46—H46A | 0.9300 |
C14—H14A | 0.9300 | C5—C6 | 1.509 (3) |
C15—C16 | 1.380 (3) | C5—H5A | 0.9700 |
C15—H15A | 0.9300 | C5—H5B | 0.9700 |
C16—H16A | 0.9300 | C6—C6A | 1.297 (4) |
C2—O2 | 1.227 (2) | C6—C7 | 1.504 (3) |
C2—C3 | 1.529 (3) | C6A—H6AA | 0.9300 |
C3—O3 | 1.230 (2) | C6A—H6AB | 0.9300 |
C3—N4 | 1.347 (3) | C7—N1i | 1.467 (3) |
N4—C5 | 1.455 (2) | C7—H7A | 0.9700 |
N4—C4 | 1.476 (3) | C7—H7B | 0.9700 |
C4—C41 | 1.504 (3) | | |
| | | |
C2—N1—C1 | 123.77 (17) | N4—C4—H4B | 109.1 |
C2—N1—C7i | 119.12 (17) | C41—C4—H4B | 109.1 |
C1—N1—C7i | 117.05 (18) | H4A—C4—H4B | 107.8 |
N1—C1—C11 | 112.30 (15) | C46—C41—C42 | 117.7 (2) |
N1—C1—H1A | 109.1 | C46—C41—C4 | 120.4 (2) |
C11—C1—H1A | 109.1 | C42—C41—C4 | 121.9 (2) |
N1—C1—H1B | 109.1 | C41—C42—C43 | 119.6 (3) |
C11—C1—H1B | 109.1 | C41—C42—H42A | 120.2 |
H1A—C1—H1B | 107.9 | C43—C42—H42A | 120.2 |
C16—C11—C12 | 117.8 (2) | C44—C43—C42 | 119.0 (3) |
C16—C11—C1 | 121.20 (19) | C44—C43—H43A | 120.5 |
C12—C11—C1 | 121.0 (2) | C42—C43—H43A | 120.5 |
C11—C12—C13 | 120.8 (3) | C45—C44—C43 | 121.9 (3) |
C11—C12—H12A | 119.6 | C45—C44—H44A | 119.1 |
C13—C12—H12A | 119.6 | C43—C44—H44A | 119.1 |
C14—C13—C12 | 120.5 (3) | C44—C45—C46 | 119.8 (3) |
C14—C13—H13A | 119.8 | C44—C45—H45A | 120.1 |
C12—C13—H13A | 119.8 | C46—C45—H45A | 120.1 |
C15—C14—C13 | 119.1 (2) | C45—C46—C41 | 122.2 (2) |
C15—C14—H14A | 120.4 | C45—C46—H46A | 118.9 |
C13—C14—H14A | 120.4 | C41—C46—H46A | 118.9 |
C14—C15—C16 | 120.6 (3) | N4—C5—C6 | 114.31 (18) |
C14—C15—H15A | 119.7 | N4—C5—H5A | 108.7 |
C16—C15—H15A | 119.7 | C6—C5—H5A | 108.7 |
C11—C16—C15 | 121.2 (2) | N4—C5—H5B | 108.7 |
C11—C16—H16A | 119.4 | C6—C5—H5B | 108.7 |
C15—C16—H16A | 119.4 | H5A—C5—H5B | 107.6 |
O2—C2—N1 | 124.1 (2) | C6A—C6—C7 | 122.1 (2) |
O2—C2—C3 | 117.0 (2) | C6A—C6—C5 | 123.9 (2) |
N1—C2—C3 | 118.73 (17) | C7—C6—C5 | 113.9 (2) |
O3—C3—N4 | 124.2 (2) | C6—C6A—H6AA | 120.0 |
O3—C3—C2 | 118.8 (2) | C6—C6A—H6AB | 120.0 |
N4—C3—C2 | 116.89 (18) | H6AA—C6A—H6AB | 120.0 |
C3—N4—C5 | 122.67 (18) | N1i—C7—C6 | 113.02 (16) |
C3—N4—C4 | 119.22 (18) | N1i—C7—H7A | 109.0 |
C5—N4—C4 | 118.11 (17) | C6—C7—H7A | 109.0 |
N4—C4—C41 | 112.57 (18) | N1i—C7—H7B | 109.0 |
N4—C4—H4A | 109.1 | C6—C7—H7B | 109.0 |
C41—C4—H4A | 109.1 | H7A—C7—H7B | 107.8 |
| | | |
C6i—C7i—N1—C2 | 93.3 (2) | C3—N4—C5—C6 | 100.4 (2) |
C7i—N1—C2—C3 | 175.43 (17) | N4—C5—C6—C7 | 176.35 (17) |
N1—C2—C3—N4 | 93.9 (2) | C5—C6—C7—N1i | 85.5 (2) |
C2—C3—N4—C5 | −4.6 (3) | O2—C2—C3—O3 | 86.9 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14A···O2ii | 0.93 | 2.42 | 3.274 (3) | 152 |
Symmetry code: (ii) x, −y+3/2, z−1/2. |