5,5,7,12,12,14-Hexamethyl-1,8-bis-(4-nitro-benz-yl)-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne.

The asymmetric unit of the title compound, C30H46N6O4, contains one half-mol-ecule. The C(benzene)-C(CH2)-N-C(-Me) torsion angle is -79.89 (13)° suggesting a synclinal orientation of the nitro-benzene ring with respect to the macrocycle. The conformation of the macrocycle is stabilized by intra-molecular N-H⋯N hydrogen bonds.

Related literature

For the biological activity of cyclam derivatives, see: Cronin et al. (1999 ▶); Fzerov et al. (2005 ▶). For related structures, see: Xie et al. (2008 ▶); Feng et al. (2009 ▶).

Experimental

Crystal data

C30H46N6O4

M = 554.73

Triclinic,

a = 8.6407 (4) Å

b = 9.1433 (3) Å

c = 11.0008 (5) Å

α = 107.742 (2)°

β = 104.898 (2)°

γ = 102.372 (2)°

V = 758.45 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.08 mm−1

T = 273 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.972, T max = 0.980

18201 measured reflections

4819 independent reflections

3340 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.185

S = 0.96

4819 reflections

185 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813031164/vm2199sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813031164/vm2199Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813031164/vm2199Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C30H46N6O4	V = 758.45 (6) Å3
Mr = 554.73	Z = 1
Triclinic, P1	F(000) = 300
Hall symbol: -P 1	Dx = 1.215 Mg m−3
a = 8.6407 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1433 (3) Å	θ = 1.0–31.1°
c = 11.0008 (5) Å	µ = 0.08 mm−1
α = 107.742 (2)°	T = 273 K
β = 104.898 (2)°	Block, colourless
γ = 102.372 (2)°	0.35 × 0.30 × 0.25 mm

Bruker Kappa APEXII CCD diffractometer	4819 independent reflections
Radiation source: fine-focus sealed tube	3340 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω and φ scan	θmax = 31.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→12
Tmin = 0.972, Tmax = 0.980	k = −13→11
18201 measured reflections	l = −15→15

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.185	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ2(Fo2) + (0.1167P)2 + 0.0862P] where P = (Fo2 + 2Fc2)/3
4819 reflections	(Δ/σ)max < 0.001
185 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.17573 (15)	0.33128 (15)	0.19940 (12)	0.0405 (3)
H1	0.1959	0.3975	0.2942	0.049*
C2	0.26370 (18)	0.93648 (14)	0.50435 (14)	0.0469 (3)
C3	0.19243 (17)	0.89974 (15)	0.36661 (14)	0.0466 (3)
H3	0.1203	0.9525	0.3346	0.056*
C4	0.23154 (16)	0.78245 (15)	0.27817 (13)	0.0431 (3)
H4	0.1849	0.7554	0.1850	0.052*
C5	0.33941 (14)	0.70422 (13)	0.32604 (12)	0.0384 (3)
C6	0.40708 (17)	0.74400 (16)	0.46470 (13)	0.0469 (3)
H6	0.4791	0.6915	0.4974	0.056*
C7	0.37823 (15)	0.57761 (15)	0.22457 (13)	0.0441 (3)
H7A	0.4292	0.6259	0.1712	0.053*
H7B	0.4584	0.5366	0.2724	0.053*
C8	0.2822 (2)	0.2174 (2)	0.20329 (19)	0.0615 (4)
H8A	0.3998	0.2799	0.2438	0.092*
H8B	0.2596	0.1444	0.1123	0.092*
H8C	0.2537	0.1565	0.2562	0.092*
C9	−0.01195 (16)	0.23196 (14)	0.13605 (14)	0.0427 (3)
H9A	−0.0295	0.1501	0.1746	0.051*
H9B	−0.0366	0.1755	0.0396	0.051*
C10	0.22706 (16)	0.36646 (14)	−0.00178 (12)	0.0395 (3)
H10A	0.1226	0.2776	−0.0545	0.047*
H10B	0.3190	0.3208	0.0056	0.047*
C11	0.24794 (16)	0.47711 (16)	−0.07869 (14)	0.0439 (3)
H11A	0.3646	0.5463	−0.0422	0.053*
H11B	0.2231	0.4118	−0.1735	0.053*
C12	0.14282 (15)	0.68065 (14)	−0.15082 (13)	0.0403 (3)
C13	0.31661 (18)	0.81153 (19)	−0.08704 (18)	0.0604 (4)
H13A	0.4025	0.7614	−0.0944	0.091*
H13B	0.3368	0.8705	0.0072	0.091*
H13C	0.3193	0.8845	−0.1339	0.091*
C14	0.1105 (2)	0.5867 (2)	−0.30121 (15)	0.0606 (4)
H14A	0.0017	0.5051	−0.3412	0.091*
H14B	0.1962	0.5363	−0.3088	0.091*
H14C	0.1135	0.6599	−0.3479	0.091*
C15	0.36900 (19)	0.86074 (17)	0.55532 (13)	0.0512 (3)
H15	0.4139	0.8870	0.6485	0.061*
N1	0.2281 (2)	1.06532 (16)	0.59985 (15)	0.0653 (4)
N2	0.22416 (11)	0.44428 (11)	0.13438 (9)	0.0347 (2)
N3	0.13852 (12)	0.57798 (12)	−0.07040 (10)	0.0348 (2)
O1	0.1657 (2)	1.15487 (16)	0.55712 (16)	0.0867 (4)
O2	0.2633 (3)	1.0778 (2)	0.71694 (15)	0.1117 (6)
H3A	0.0333 (19)	0.5159 (18)	−0.0954 (14)	0.044 (4)*

	U11	U22	U33	U12	U13	U23
C1	0.0390 (6)	0.0426 (6)	0.0402 (6)	0.0128 (5)	0.0113 (5)	0.0180 (5)
C2	0.0518 (7)	0.0350 (6)	0.0468 (7)	0.0052 (5)	0.0239 (6)	0.0065 (5)
C3	0.0470 (7)	0.0391 (6)	0.0524 (7)	0.0137 (5)	0.0168 (6)	0.0159 (5)
C4	0.0444 (7)	0.0404 (6)	0.0378 (6)	0.0096 (5)	0.0113 (5)	0.0112 (5)
C5	0.0322 (5)	0.0337 (5)	0.0386 (6)	0.0031 (4)	0.0095 (4)	0.0070 (4)
C6	0.0462 (7)	0.0452 (6)	0.0417 (6)	0.0120 (5)	0.0087 (5)	0.0134 (5)
C7	0.0316 (5)	0.0425 (6)	0.0463 (7)	0.0077 (5)	0.0113 (5)	0.0059 (5)
C8	0.0553 (9)	0.0637 (9)	0.0778 (11)	0.0282 (7)	0.0172 (8)	0.0418 (8)
C9	0.0419 (6)	0.0371 (5)	0.0501 (7)	0.0102 (5)	0.0157 (5)	0.0198 (5)
C10	0.0407 (6)	0.0396 (6)	0.0391 (6)	0.0187 (5)	0.0156 (5)	0.0107 (5)
C11	0.0428 (6)	0.0531 (7)	0.0473 (7)	0.0237 (5)	0.0248 (5)	0.0209 (5)
C12	0.0388 (6)	0.0420 (6)	0.0438 (6)	0.0101 (5)	0.0189 (5)	0.0194 (5)
C13	0.0415 (7)	0.0556 (8)	0.0866 (11)	0.0069 (6)	0.0256 (7)	0.0333 (8)
C14	0.0729 (10)	0.0772 (10)	0.0474 (8)	0.0301 (8)	0.0322 (7)	0.0305 (7)
C15	0.0579 (8)	0.0488 (7)	0.0362 (6)	0.0087 (6)	0.0126 (6)	0.0107 (5)
N1	0.0779 (9)	0.0465 (6)	0.0655 (8)	0.0149 (6)	0.0370 (7)	0.0067 (6)
N2	0.0322 (4)	0.0321 (4)	0.0349 (5)	0.0084 (3)	0.0110 (4)	0.0082 (3)
N3	0.0325 (5)	0.0385 (5)	0.0371 (5)	0.0123 (4)	0.0163 (4)	0.0152 (4)
O1	0.1035 (11)	0.0574 (7)	0.0994 (10)	0.0386 (7)	0.0451 (9)	0.0127 (7)
O2	0.1857 (18)	0.0998 (11)	0.0652 (9)	0.0661 (12)	0.0679 (10)	0.0175 (8)

C1—N2	1.4742 (15)	C9—H9B	0.9700
C1—C9	1.5305 (17)	C10—N2	1.4588 (15)
C1—C8	1.5328 (19)	C10—C11	1.5145 (17)
C1—H1	0.9800	C10—H10A	0.9700
C2—C15	1.366 (2)	C10—H10B	0.9700
C2—C3	1.382 (2)	C11—N3	1.4559 (16)
C2—N1	1.4675 (18)	C11—H11A	0.9700
C3—C4	1.3781 (18)	C11—H11B	0.9700
C3—H3	0.9300	C12—N3	1.4743 (15)
C4—C5	1.3859 (18)	C12—C9i	1.5317 (18)
C4—H4	0.9300	C12—C14	1.5318 (19)
C5—C6	1.3831 (17)	C12—C13	1.5349 (18)
C5—C7	1.5067 (17)	C13—H13A	0.9600
C6—C15	1.383 (2)	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—N2	1.4598 (14)	C14—H14A	0.9600
C7—H7A	0.9700	C14—H14B	0.9600
C7—H7B	0.9700	C14—H14C	0.9600
C8—H8A	0.9600	C15—H15	0.9300
C8—H8B	0.9600	N1—O2	1.208 (2)
C8—H8C	0.9600	N1—O1	1.214 (2)
C9—C12i	1.5317 (18)	N3—H3A	0.883 (15)
C9—H9A	0.9700
N2—C1—C9	112.95 (9)	C11—C10—H10A	108.6
N2—C1—C8	113.69 (11)	N2—C10—H10B	108.6
C9—C1—C8	109.55 (11)	C11—C10—H10B	108.6
N2—C1—H1	106.7	H10A—C10—H10B	107.5
C9—C1—H1	106.7	N3—C11—C10	112.80 (10)
C8—C1—H1	106.7	N3—C11—H11A	109.0
C15—C2—C3	122.80 (12)	C10—C11—H11A	109.0
C15—C2—N1	118.71 (13)	N3—C11—H11B	109.0
C3—C2—N1	118.47 (14)	C10—C11—H11B	109.0
C4—C3—C2	117.93 (13)	H11A—C11—H11B	107.8
C4—C3—H3	121.0	N3—C12—C9i	107.94 (9)
C2—C3—H3	121.0	N3—C12—C14	113.61 (11)
C3—C4—C5	120.98 (12)	C9i—C12—C14	110.55 (11)
C3—C4—H4	119.5	N3—C12—C13	108.11 (11)
C5—C4—H4	119.5	C9i—C12—C13	106.91 (11)
C6—C5—C4	119.18 (11)	C14—C12—C13	109.47 (11)
C6—C5—C7	122.20 (12)	C12—C13—H13A	109.5
C4—C5—C7	118.62 (11)	C12—C13—H13B	109.5
C15—C6—C5	120.86 (13)	H13A—C13—H13B	109.5
C15—C6—H6	119.6	C12—C13—H13C	109.5
C5—C6—H6	119.6	H13A—C13—H13C	109.5
N2—C7—C5	110.45 (9)	H13B—C13—H13C	109.5
N2—C7—H7A	109.6	C12—C14—H14A	109.5
C5—C7—H7A	109.6	C12—C14—H14B	109.5
N2—C7—H7B	109.6	H14A—C14—H14B	109.5
C5—C7—H7B	109.6	C12—C14—H14C	109.5
H7A—C7—H7B	108.1	H14A—C14—H14C	109.5
C1—C8—H8A	109.5	H14B—C14—H14C	109.5
C1—C8—H8B	109.5	C2—C15—C6	118.25 (12)
H8A—C8—H8B	109.5	C2—C15—H15	120.9
C1—C8—H8C	109.5	C6—C15—H15	120.9
H8A—C8—H8C	109.5	O2—N1—O1	123.36 (15)
H8B—C8—H8C	109.5	O2—N1—C2	118.46 (16)
C1—C9—C12i	118.88 (10)	O1—N1—C2	118.18 (15)
C1—C9—H9A	107.6	C10—N2—C7	113.41 (9)
C12i—C9—H9A	107.6	C10—N2—C1	114.37 (9)
C1—C9—H9B	107.6	C7—N2—C1	111.66 (10)
C12i—C9—H9B	107.6	C11—N3—C12	115.96 (9)
H9A—C9—H9B	107.0	C11—N3—H3A	109.2 (10)
N2—C10—C11	114.82 (10)	C12—N3—H3A	108.6 (9)
N2—C10—H10A	108.6
C15—C2—C3—C4	−0.6 (2)	C3—C2—N1—O2	166.54 (16)
N1—C2—C3—C4	177.77 (11)	C15—C2—N1—O1	164.41 (15)
C2—C3—C4—C5	−0.19 (19)	C3—C2—N1—O1	−14.0 (2)
C3—C4—C5—C6	0.62 (18)	C11—C10—N2—C7	−60.07 (13)
C3—C4—C5—C7	−179.70 (11)	C11—C10—N2—C1	170.32 (10)
C4—C5—C6—C15	−0.30 (19)	C5—C7—N2—C10	149.14 (10)
C7—C5—C6—C15	−179.97 (12)	C5—C7—N2—C1	−79.89 (13)
C6—C5—C7—N2	118.14 (13)	C9—C1—N2—C10	−71.93 (13)
C4—C5—C7—N2	−61.53 (15)	C8—C1—N2—C10	53.70 (14)
N2—C1—C9—C12i	−66.10 (14)	C9—C1—N2—C7	157.59 (10)
C8—C1—C9—C12i	166.07 (12)	C8—C1—N2—C7	−76.78 (13)
N2—C10—C11—N3	−45.97 (15)	C10—C11—N3—C12	−175.81 (10)
C3—C2—C15—C6	0.9 (2)	C9i—C12—N3—C11	176.37 (10)
N1—C2—C15—C6	−177.46 (12)	C14—C12—N3—C11	53.40 (15)
C5—C6—C15—C2	−0.4 (2)	C13—C12—N3—C11	−68.32 (14)
C15—C2—N1—O2	−15.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2i	0.883 (17)	2.284 (17)	2.9770 (15)	135.3 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2i	0.883 (17)	2.284 (17)	2.9770 (15)	135.3 (15)

Symmetry code: (i) .