1,15:21,35-Bis(oxydiethyl­ene)-5,8,11,18,25,28,31,38-octa­oxa-1,15,21,35-tetra­azacyclo­tetra­decane-16,20,36,40-tetra­one–benzene (1/2): a macrotricyclic tetra­lactam

Smith, G.L.N.; Nguyen, T.; Powell, D.R.; Taylor, R.W.

doi:10.1107/S1600536809026531

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1927

doi:10.1107/S1600536809026531

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1,15:21,35-Bis(oxydiethylene)-5,8,11,18,25,28,31,38-octaoxa-1,15,21,35-tetraazacyclotetradecane-16,20,36,40-tetraone–benzene (1/2): a macrotricyclic tetralactam

Gary L. N. Smith,^a ^* Tam Nguyen,^b Douglas R. Powell ^b and Richard W. Taylor ^b

^aPoint Loma Nazarene University, Department of Chemistry, 3900 Lomaland Dr., Rohr Science 305E, San Diego, CA 92106, USA, and ^bDepartment of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Room 208, Norman, OK 73019-3051, USA
^*Correspondence e-mail: GarySmith@pointloma.edu

(Received 22 June 2009; accepted 7 July 2009; online 18 July 2009)

The macrotricyclic title compound, C₃₆H₆₄N₄O₁₄·2C₆H₆, is located on a crystallographic center of symmetry. The molecule has four tertiary amide bridgehead atoms and consists of two unsymmetrical 20-membered diazatetraoxamacrocycles (N₂O₄ donor atom set) connected through the N atoms by two lateral oxydiethylene bridges. The bridging subunits, together with the short bridging strand (NCCOCCN) from each monocycle, define a 24-membered ring (N₄O₄ donor atom set) that forms a central cavity.

Related literature

For general background to macrotricyclic ligands as receptors for cationic, anionic and neutral guests, see: Lehn (1973 , 1988 ); Lehn et al. (1977 ). For related structures, see: Wiest & Weiss (1973 ); Fischer et al. (1977 ); Pascard et al. (1982 ); Rebizant et al. (1984 ); Groth (1986 ); Cheetham & Harding (1991 ); Bencini et al. (1992 ); Krakowiak et al. (1995 ); Plenio & Diodone (1995 ); Smith et al. (2007 ). For the synthesis, see: Dietrich et al. (1973 ); Cheney et al. (1978 ).

Experimental

Crystal data

C₃₆H₆₄N₄O₁₄·2C₆H₆
M_r = 933.13
Triclinic, $[P \overline 1]$
a = 8.9632 (14) Å
b = 11.988 (2) Å
c = 12.806 (2) Å
α = 72.728 (5)°
β = 71.758 (5)°
γ = 68.443 (6)°
V = 1189.4 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.41 × 0.37 × 0.30 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.954, T_max = 0.978
9363 measured reflections
4603 independent reflections
4198 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.089
S = 1.00
4603 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026531/pk2175sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026531/pk2175Isup2.hkl

checkCIF report

Comment top

Macrotricyclic ligands are of interest as receptors for cationic, anionic and neutral guests (Lehn et al., 1977; Lehn, 1988). The title compound (I) was isolated as the 2 + 2 addition product during the synthesis of the corresponding bicyclic cryptand 3pp1.1. A related macrotricyclic tetraamine has been reported, but with the propylene groups in (I) replaced by benzene rings (Smith et al., 2007). Fig. 1 shows that (I) contains three monocyclic rings: a 24-membered ring, B (N1/O4/N7/O24A/N1A/O4A/N7A/O24) and two 20-membered rings, A (N1/O4/N7/O11/O14/O17) and C (N1A/O4A/N7A/O11A/O14A/O17A). The two 20-membered macrocyclic rings form the ends of the skewed cylinder with two oxydiethylene bridges linking the macrocylic end groups. Each of the 20-membered rings (A and C) has an elliptical shape, with non-bonding distances of 4.495 (2)Å (N1···O11), 6.639 (2)Å (O4···O14), and 7.209 (2)Å (N7···O17). The planes defined by donor atoms (N1/N7/O11/O14/O17) of rings A (and C) (average deviation = 0.1796 Å) are parallel, and form a dihedral angle of 100.7 (2)° with the plane defined by the nitrogen donor atoms in ring B. Thus, the centers of rings A and C do not overlap in the direction defined by the O4···O14 axis. The two 20-membered rings are oriented in an opposing fashion with respect to the plane defined by the N donor atoms in ring B. Similar behavior has been seen with other cylindrical tricyclic cryptands having unsymmetric end groups. (Groth, 1986; Cheetham & Harding, 1991; Plenio & Diodone, 1995). Fig. 2 shows that the nitrogen atoms in the 24-membered ring form the corners of a parallelogram defined by the following non-bonding distances and angles: 4.300 (2)Å (N1···N7); 6.901 (2)Å (N7···N1A); 74.0 (2)° (N1···N7···N1A); 106.0 (2)° (N7···N1···N7A). As a result, the 20-membered rings are also offset along the O24···O24A axis. Analogous macrotricyclic compounds also exhibit a skewed cylindrical shape (Bencini et al., 1992; Pascard et al., 1982; Rebizant et al., 1984: Smith et al., 2007).

Related literature top

For general background to macrotricyclic ligands as receptors for cationic, anionic and neutral guests, see: Lehn (1973, 1988); Lehn et al. (1977). For related structures, see: Wiest & Weiss (1973); Fischer et al. (1977); Pascard et al. (1982); Rebizant et al. (1984); Groth (1986); Cheetham & Harding (1991); Bencini et al. (1992); Krakowiak et al. (1995); Plenio & Diodone (1995); Smith et al. (2007). For the synthesis, see: Dietrich et al. (1973); Cheney et al. (1978).

Experimental top

The 20-membered monocyclic diamine was prepared according to reported methods (Dietrich et al., 1973). The tricyclic tetralactam was obtained as the 2 + 2 cycloaddition product from the reaction of 1,7-diaza-4,11,14,17-tetraoxacycloicosane (3.56 mmole) in 150 ml toluene and 2,2'-oxydiacetyl chloride (3.54 mmole) in 150 ml toluene. These solutions were added synchronously to 800 ml of toluene containing triethylamine (7.80 mmole) over a period of 2 h under high-dilution conditions (Dietrich et al., 1973; Cheney et al., 1978). The crude tetralactam was purified by recrystallization from benzene to give (I) in 10% overall yield. ESI-MS: m/z = 799.5 (M + Na⁺). Crystals suitable for X-ray crystallography were grown by vapor diffusion of heptane into a solution of (I) in benzene.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to their labelled counterparts by (1-x, 1-y, 1-z).
	Fig. 2. A view of the molecular structure of (I), along an axis perpendicular to the plane defined by the donor atoms of the 24-membered ring (B). Atoms marked with the letter A are related to unsubscripted atoms by (1-x, 1-y, 1-z). H atoms have been omitted for clarity.

1,15:21,35-Bis(oxydiethylene)-5,8,11,18,25,28,31,38-octaoxa-1,15,21,35- tetraazacyclotetradecane-16,20,36,40-tetraone–benzene (1/2) top

Crystal data top

C₃₆H₆₄N₄O₁₄·2C₆H₆	Z = 1
M_r = 933.13	F(000) = 504
Triclinic, P1	D_x = 1.303 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9632 (14) Å	Cell parameters from 7833 reflections
b = 11.988 (2) Å	θ = 2.3–28.3°
c = 12.806 (2) Å	µ = 0.10 mm⁻¹
α = 72.728 (5)°	T = 100 K
β = 71.758 (5)°	Block, colorless
γ = 68.443 (6)°	0.41 × 0.37 × 0.30 mm
V = 1189.4 (3) Å³

Data collection top

Bruker APEX CCD diffractometer	4603 independent reflections
Radiation source: fine-focus sealed tube	4198 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −11→11
T_min = 0.954, T_max = 0.978	k = −14→13
9363 measured reflections	l = −15→15

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.04P)² + 0.42P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4603 reflections	Δρ_max = 0.27 e Å⁻³
299 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0145 (16)

Crystal data top

C₃₆H₆₄N₄O₁₄·2C₆H₆	γ = 68.443 (6)°
M_r = 933.13	V = 1189.4 (3) Å³
Triclinic, P1	Z = 1
a = 8.9632 (14) Å	Mo Kα radiation
b = 11.988 (2) Å	µ = 0.10 mm⁻¹
c = 12.806 (2) Å	T = 100 K
α = 72.728 (5)°	0.41 × 0.37 × 0.30 mm
β = 71.758 (5)°

Data collection top

Bruker APEX CCD diffractometer	4603 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	4198 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.978	R_int = 0.018
9363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
4603 reflections	Δρ_min = −0.21 e Å⁻³
299 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.47767 (12)	0.74664 (8)	0.56224 (8)	0.0167 (2)
C2	0.53952 (14)	0.83074 (10)	0.46324 (9)	0.0186 (2)
H2A	0.6567	0.7900	0.4317	0.022*
H2B	0.5341	0.9039	0.4868	0.022*
C3	0.44488 (14)	0.87172 (10)	0.37224 (9)	0.0188 (2)
H3A	0.5076	0.9109	0.3015	0.023*
H3B	0.4303	0.7998	0.3585	0.023*
O4	0.28675 (10)	0.95714 (7)	0.40616 (7)	0.02112 (19)
C5	0.18854 (16)	0.99679 (11)	0.32485 (10)	0.0224 (3)
H5A	0.2614	0.9827	0.2508	0.027*
H5B	0.1317	1.0859	0.3176	0.027*
C6	0.06115 (15)	0.92948 (11)	0.35714 (10)	0.0217 (3)
H6A	−0.0156	0.9479	0.4289	0.026*
H6B	−0.0037	0.9605	0.2989	0.026*
N7	0.13369 (12)	0.79611 (9)	0.36959 (8)	0.0176 (2)
C8	0.12705 (14)	0.72108 (11)	0.48393 (9)	0.0179 (2)
H8A	0.1507	0.7626	0.5304	0.021*
H8B	0.2139	0.6412	0.4809	0.021*
C9	−0.03960 (14)	0.69865 (11)	0.53976 (9)	0.0208 (3)
H9A	−0.1261	0.7780	0.5470	0.025*
H9B	−0.0663	0.6605	0.4919	0.025*
C10	−0.03863 (15)	0.61574 (11)	0.65499 (10)	0.0215 (3)
H10A	−0.1487	0.6043	0.6904	0.026*
H10B	0.0429	0.5344	0.6479	0.026*
O11	0.00290 (10)	0.66990 (7)	0.72305 (6)	0.02062 (19)
C12	−0.04284 (15)	0.61758 (12)	0.83951 (9)	0.0228 (3)
H12A	−0.0026	0.5271	0.8509	0.027*
H12B	−0.1645	0.6429	0.8651	0.027*
C13	0.02910 (15)	0.65877 (12)	0.90752 (10)	0.0236 (3)
H13A	0.0266	0.7453	0.8757	0.028*
H13B	−0.0368	0.6529	0.9860	0.028*
O14	0.19488 (10)	0.58292 (8)	0.90553 (7)	0.0235 (2)
C15	0.26383 (16)	0.59898 (12)	0.98450 (10)	0.0256 (3)
H15A	0.3544	0.5238	1.0025	0.031*
H15B	0.1782	0.6097	1.0548	0.031*
C16	0.32977 (16)	0.70713 (12)	0.94297 (10)	0.0254 (3)
H16A	0.2425	0.7826	0.9204	0.031*
H16B	0.3661	0.7186	1.0035	0.031*
O17	0.46530 (10)	0.68442 (8)	0.84922 (7)	0.0226 (2)
C18	0.50076 (16)	0.79286 (12)	0.77925 (10)	0.0247 (3)
H18A	0.6099	0.7698	0.7272	0.030*
H18B	0.5070	0.8421	0.8267	0.030*
C19	0.37289 (16)	0.87074 (11)	0.71125 (10)	0.0235 (3)
H19A	0.4124	0.9382	0.6575	0.028*
H19B	0.2697	0.9081	0.7628	0.028*
C20	0.33413 (14)	0.80088 (10)	0.64589 (9)	0.0177 (2)
H20A	0.2915	0.7348	0.6996	0.021*
H20B	0.2461	0.8576	0.6072	0.021*
C21	0.54820 (14)	0.62431 (10)	0.56542 (9)	0.0159 (2)
O22	0.66849 (10)	0.58351 (7)	0.49363 (6)	0.01991 (19)
C23	0.46919 (14)	0.53806 (10)	0.66279 (9)	0.0180 (2)
H23A	0.4537	0.5610	0.7345	0.022*
H23B	0.3593	0.5472	0.6537	0.022*
O24	0.56807 (9)	0.41414 (7)	0.66696 (6)	0.01685 (18)
C25	0.70820 (14)	0.38705 (10)	0.71013 (9)	0.0184 (2)
H25A	0.6741	0.4119	0.7833	0.022*
H25B	0.7847	0.4319	0.6574	0.022*
C26	0.79233 (13)	0.24948 (10)	0.72452 (9)	0.0166 (2)
O27	0.79022 (10)	0.18395 (7)	0.81918 (6)	0.02115 (19)
C1S	0.23336 (16)	0.07749 (12)	0.97250 (11)	0.0275 (3)
H1S	0.2265	0.0058	1.0285	0.033*
C2S	0.13507 (16)	0.12252 (12)	0.89521 (10)	0.0258 (3)
H2S	0.0591	0.0824	0.8989	0.031*
C3S	0.14782 (15)	0.22620 (12)	0.81243 (10)	0.0253 (3)
H3S	0.0809	0.2566	0.7593	0.030*
C4S	0.25741 (15)	0.28561 (12)	0.80677 (10)	0.0252 (3)
H4S	0.2665	0.3560	0.7495	0.030*
C5S	0.35382 (15)	0.24199 (12)	0.88490 (11)	0.0257 (3)
H5S	0.4279	0.2833	0.8820	0.031*
C6S	0.34207 (16)	0.13823 (12)	0.96721 (11)	0.0273 (3)
H6S	0.4087	0.1083	1.0204	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0211 (5)	0.0133 (5)	0.0153 (4)	−0.0056 (4)	−0.0043 (4)	−0.0019 (4)
C2	0.0237 (6)	0.0147 (5)	0.0178 (5)	−0.0080 (5)	−0.0051 (4)	−0.0009 (4)
C3	0.0229 (6)	0.0154 (5)	0.0176 (5)	−0.0050 (5)	−0.0048 (4)	−0.0034 (4)
O4	0.0265 (4)	0.0169 (4)	0.0188 (4)	−0.0007 (3)	−0.0096 (3)	−0.0049 (3)
C5	0.0309 (7)	0.0144 (6)	0.0202 (6)	−0.0014 (5)	−0.0122 (5)	−0.0013 (4)
C6	0.0238 (6)	0.0173 (6)	0.0207 (6)	0.0020 (5)	−0.0092 (5)	−0.0054 (5)
N7	0.0191 (5)	0.0153 (5)	0.0165 (5)	−0.0014 (4)	−0.0066 (4)	−0.0027 (4)
C8	0.0190 (6)	0.0196 (6)	0.0149 (5)	−0.0045 (5)	−0.0059 (4)	−0.0030 (4)
C9	0.0199 (6)	0.0238 (6)	0.0203 (6)	−0.0058 (5)	−0.0070 (5)	−0.0056 (5)
C10	0.0228 (6)	0.0219 (6)	0.0224 (6)	−0.0096 (5)	−0.0046 (5)	−0.0053 (5)
O11	0.0266 (4)	0.0225 (4)	0.0148 (4)	−0.0122 (4)	−0.0041 (3)	−0.0017 (3)
C12	0.0212 (6)	0.0262 (6)	0.0169 (6)	−0.0085 (5)	−0.0020 (4)	0.0006 (5)
C13	0.0221 (6)	0.0262 (6)	0.0168 (5)	−0.0020 (5)	−0.0028 (5)	−0.0047 (5)
O14	0.0207 (4)	0.0255 (5)	0.0236 (4)	−0.0031 (4)	−0.0064 (3)	−0.0075 (4)
C15	0.0279 (7)	0.0303 (7)	0.0184 (6)	−0.0102 (5)	−0.0079 (5)	−0.0005 (5)
C16	0.0303 (7)	0.0304 (7)	0.0164 (6)	−0.0111 (5)	−0.0030 (5)	−0.0062 (5)
O17	0.0236 (4)	0.0240 (5)	0.0183 (4)	−0.0061 (4)	−0.0051 (3)	−0.0026 (3)
C18	0.0294 (7)	0.0307 (7)	0.0198 (6)	−0.0161 (5)	−0.0047 (5)	−0.0056 (5)
C19	0.0367 (7)	0.0159 (6)	0.0181 (6)	−0.0090 (5)	−0.0057 (5)	−0.0034 (4)
C20	0.0205 (6)	0.0139 (5)	0.0165 (5)	−0.0020 (4)	−0.0050 (4)	−0.0031 (4)
C21	0.0190 (6)	0.0151 (5)	0.0154 (5)	−0.0044 (4)	−0.0071 (4)	−0.0031 (4)
O22	0.0209 (4)	0.0173 (4)	0.0186 (4)	−0.0047 (3)	−0.0017 (3)	−0.0038 (3)
C23	0.0179 (6)	0.0128 (5)	0.0200 (5)	−0.0026 (4)	−0.0027 (4)	−0.0032 (4)
O24	0.0179 (4)	0.0119 (4)	0.0206 (4)	−0.0031 (3)	−0.0066 (3)	−0.0027 (3)
C25	0.0217 (6)	0.0172 (6)	0.0181 (5)	−0.0054 (5)	−0.0076 (4)	−0.0039 (4)
C26	0.0160 (5)	0.0174 (6)	0.0185 (5)	−0.0051 (4)	−0.0074 (4)	−0.0028 (4)
O27	0.0256 (4)	0.0196 (4)	0.0169 (4)	−0.0050 (3)	−0.0081 (3)	−0.0009 (3)
C1S	0.0335 (7)	0.0196 (6)	0.0252 (6)	−0.0047 (5)	−0.0063 (5)	−0.0032 (5)
C2S	0.0256 (6)	0.0269 (7)	0.0273 (6)	−0.0102 (5)	−0.0033 (5)	−0.0092 (5)
C3S	0.0212 (6)	0.0309 (7)	0.0215 (6)	−0.0039 (5)	−0.0061 (5)	−0.0060 (5)
C4S	0.0230 (6)	0.0242 (6)	0.0227 (6)	−0.0059 (5)	−0.0008 (5)	−0.0029 (5)
C5S	0.0193 (6)	0.0302 (7)	0.0291 (6)	−0.0077 (5)	−0.0013 (5)	−0.0125 (5)
C6S	0.0246 (6)	0.0299 (7)	0.0256 (6)	0.0006 (5)	−0.0104 (5)	−0.0096 (5)

Geometric parameters (Å, º) top

N1—C21	1.3606 (15)	C15—H15B	0.9900
N1—C2	1.4639 (14)	C16—O17	1.4245 (14)
N1—C20	1.4702 (14)	C16—H16A	0.9900
C2—C3	1.5137 (15)	C16—H16B	0.9900
C2—H2A	0.9900	O17—C18	1.4240 (14)
C2—H2B	0.9900	C18—C19	1.5163 (18)
C3—O4	1.4347 (14)	C18—H18A	0.9900
C3—H3A	0.9900	C18—H18B	0.9900
C3—H3B	0.9900	C19—C20	1.5281 (16)
O4—C5	1.4344 (14)	C19—H19A	0.9900
C5—C6	1.5196 (18)	C19—H19B	0.9900
C5—H5A	0.9900	C20—H20A	0.9900
C5—H5B	0.9900	C20—H20B	0.9900
C6—N7	1.4677 (15)	C21—O22	1.2272 (14)
C6—H6A	0.9900	C21—C23	1.5314 (15)
C6—H6B	0.9900	C23—O24	1.4178 (13)
N7—C26ⁱ	1.3473 (15)	C23—H23A	0.9900
N7—C8	1.4695 (14)	C23—H23B	0.9900
C8—C9	1.5254 (16)	O24—C25	1.4202 (13)
C8—H8A	0.9900	C25—C26	1.5216 (16)
C8—H8B	0.9900	C25—H25A	0.9900
C9—C10	1.5153 (16)	C25—H25B	0.9900
C9—H9A	0.9900	C26—O27	1.2321 (14)
C9—H9B	0.9900	C26—N7ⁱ	1.3473 (15)
C10—O11	1.4270 (14)	C1S—C2S	1.3879 (18)
C10—H10A	0.9900	C1S—C6S	1.3910 (19)
C10—H10B	0.9900	C1S—H1S	0.9500
O11—C12	1.4271 (13)	C2S—C3S	1.3884 (18)
C12—C13	1.5030 (17)	C2S—H2S	0.9500
C12—H12A	0.9900	C3S—C4S	1.3842 (19)
C12—H12B	0.9900	C3S—H3S	0.9500
C13—O14	1.4257 (15)	C4S—C5S	1.3856 (18)
C13—H13A	0.9900	C4S—H4S	0.9500
C13—H13B	0.9900	C5S—C6S	1.3848 (19)
O14—C15	1.4269 (14)	C5S—H5S	0.9500
C15—C16	1.5066 (18)	C6S—H6S	0.9500
C15—H15A	0.9900

C21—N1—C2	117.64 (9)	O14—C15—H15B	108.9
C21—N1—C20	124.81 (9)	C16—C15—H15B	108.9
C2—N1—C20	117.31 (9)	H15A—C15—H15B	107.7
N1—C2—C3	113.65 (9)	O17—C16—C15	108.46 (10)
N1—C2—H2A	108.8	O17—C16—H16A	110.0
C3—C2—H2A	108.8	C15—C16—H16A	110.0
N1—C2—H2B	108.8	O17—C16—H16B	110.0
C3—C2—H2B	108.8	C15—C16—H16B	110.0
H2A—C2—H2B	107.7	H16A—C16—H16B	108.4
O4—C3—C2	109.78 (9)	C18—O17—C16	113.39 (9)
O4—C3—H3A	109.7	O17—C18—C19	112.94 (10)
C2—C3—H3A	109.7	O17—C18—H18A	109.0
O4—C3—H3B	109.7	C19—C18—H18A	109.0
C2—C3—H3B	109.7	O17—C18—H18B	109.0
H3A—C3—H3B	108.2	C19—C18—H18B	109.0
C5—O4—C3	112.59 (8)	H18A—C18—H18B	107.8
O4—C5—C6	112.06 (9)	C18—C19—C20	114.43 (10)
O4—C5—H5A	109.2	C18—C19—H19A	108.7
C6—C5—H5A	109.2	C20—C19—H19A	108.7
O4—C5—H5B	109.2	C18—C19—H19B	108.7
C6—C5—H5B	109.2	C20—C19—H19B	108.7
H5A—C5—H5B	107.9	H19A—C19—H19B	107.6
N7—C6—C5	113.36 (10)	N1—C20—C19	113.30 (10)
N7—C6—H6A	108.9	N1—C20—H20A	108.9
C5—C6—H6A	108.9	C19—C20—H20A	108.9
N7—C6—H6B	108.9	N1—C20—H20B	108.9
C5—C6—H6B	108.9	C19—C20—H20B	108.9
H6A—C6—H6B	107.7	H20A—C20—H20B	107.7
C26ⁱ—N7—C6	117.95 (9)	O22—C21—N1	122.34 (10)
C26ⁱ—N7—C8	124.07 (9)	O22—C21—C23	120.75 (10)
C6—N7—C8	117.93 (9)	N1—C21—C23	116.91 (9)
N7—C8—C9	112.88 (9)	O24—C23—C21	111.41 (9)
N7—C8—H8A	109.0	O24—C23—H23A	109.3
C9—C8—H8A	109.0	C21—C23—H23A	109.3
N7—C8—H8B	109.0	O24—C23—H23B	109.3
C9—C8—H8B	109.0	C21—C23—H23B	109.3
H8A—C8—H8B	107.8	H23A—C23—H23B	108.0
C10—C9—C8	111.23 (9)	C23—O24—C25	112.15 (8)
C10—C9—H9A	109.4	O24—C25—C26	107.45 (9)
C8—C9—H9A	109.4	O24—C25—H25A	110.2
C10—C9—H9B	109.4	C26—C25—H25A	110.2
C8—C9—H9B	109.4	O24—C25—H25B	110.2
H9A—C9—H9B	108.0	C26—C25—H25B	110.2
O11—C10—C9	109.22 (9)	H25A—C25—H25B	108.5
O11—C10—H10A	109.8	O27—C26—N7ⁱ	122.37 (10)
C9—C10—H10A	109.8	O27—C26—C25	120.34 (10)
O11—C10—H10B	109.8	N7ⁱ—C26—C25	117.29 (10)
C9—C10—H10B	109.8	C2S—C1S—C6S	119.43 (12)
H10A—C10—H10B	108.3	C2S—C1S—H1S	120.3
C10—O11—C12	111.42 (9)	C6S—C1S—H1S	120.3
O11—C12—C13	110.40 (10)	C1S—C2S—C3S	119.94 (12)
O11—C12—H12A	109.6	C1S—C2S—H2S	120.0
C13—C12—H12A	109.6	C3S—C2S—H2S	120.0
O11—C12—H12B	109.6	C4S—C3S—C2S	120.43 (12)
C13—C12—H12B	109.6	C4S—C3S—H3S	119.8
H12A—C12—H12B	108.1	C2S—C3S—H3S	119.8
O14—C13—C12	109.13 (10)	C3S—C4S—C5S	119.77 (12)
O14—C13—H13A	109.9	C3S—C4S—H4S	120.1
C12—C13—H13A	109.9	C5S—C4S—H4S	120.1
O14—C13—H13B	109.9	C6S—C5S—C4S	119.96 (12)
C12—C13—H13B	109.9	C6S—C5S—H5S	120.0
H13A—C13—H13B	108.3	C4S—C5S—H5S	120.0
C13—O14—C15	113.38 (9)	C5S—C6S—C1S	120.47 (12)
O14—C15—C16	113.48 (10)	C5S—C6S—H6S	119.8
O14—C15—H15A	108.9	C1S—C6S—H6S	119.8
C16—C15—H15A	108.9

C21—N1—C2—C3	92.67 (12)	O17—C18—C19—C20	−50.94 (14)
C20—N1—C2—C3	−81.95 (12)	C21—N1—C20—C19	115.78 (12)
N1—C2—C3—O4	73.21 (12)	C2—N1—C20—C19	−70.02 (12)
C2—C3—O4—C5	−178.20 (9)	C18—C19—C20—N1	−61.35 (13)
C3—O4—C5—C6	100.21 (11)	C2—N1—C21—O22	6.07 (15)
O4—C5—C6—N7	−59.09 (13)	C20—N1—C21—O22	−179.75 (10)
C5—C6—N7—C26ⁱ	−75.20 (13)	C2—N1—C21—C23	−173.17 (9)
C5—C6—N7—C8	102.34 (11)	C20—N1—C21—C23	1.00 (15)
C26ⁱ—N7—C8—C9	−102.18 (12)	O22—C21—C23—O24	10.07 (15)
C6—N7—C8—C9	80.43 (12)	N1—C21—C23—O24	−170.67 (9)
N7—C8—C9—C10	177.10 (9)	C21—C23—O24—C25	75.22 (11)
C8—C9—C10—O11	57.98 (13)	C23—O24—C25—C26	172.99 (8)
C9—C10—O11—C12	162.03 (9)	O24—C25—C26—O27	−110.47 (11)
C10—O11—C12—C13	169.66 (10)	O24—C25—C26—N7ⁱ	68.94 (12)
O11—C12—C13—O14	−83.13 (12)	C6S—C1S—C2S—C3S	1.05 (19)
C12—C13—O14—C15	−168.70 (9)	C1S—C2S—C3S—C4S	−0.38 (19)
C13—O14—C15—C16	−82.55 (13)	C2S—C3S—C4S—C5S	−0.64 (18)
O14—C15—C16—O17	−65.05 (13)	C3S—C4S—C5S—C6S	0.98 (18)
C15—C16—O17—C18	159.12 (10)	C4S—C5S—C6S—C1S	−0.31 (19)
C16—O17—C18—C19	−71.92 (12)	C2S—C1S—C6S—C5S	−0.71 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₃₆H₆₄N₄O₁₄·2C₆H₆
M_r	933.13
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.9632 (14), 11.988 (2), 12.806 (2)
α, β, γ (°)	72.728 (5), 71.758 (5), 68.443 (6)
V (Å³)	1189.4 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.41 × 0.37 × 0.30

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.954, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	9363, 4603, 4198
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.00
No. of reflections	4603
No. of parameters	299
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.21

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Oklahoma Center for the Advancement of Science and Technology (grant HR06–113). The authors also thank the National Science Foundation (CHE-0130835) and the University of Oklahoma for funds to acquire the diffractometer and computers used in this work.

References

Bencini, A., Bianchi, A., Ciampolini, M., Dapporto, P., Fusi, V., Micheloni, M., Nardi, N., Paoli, P. & Valtancoli, B. (1992). J. Chem. Soc. Dalton Trans. pp. 2049–2054. CSD CrossRef Web of Science Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheetham, G. M. T. & Harding, M. M. (1991). Acta Cryst. C47, 2478–2479. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Cheney, J., Kintzinger, J. P. & Lehn, J. M. (1978). Nouv. J. Chim. 2, 411–418. CAS Google Scholar
Dietrich, B., Lehn, J. M., Sauvage, J. P. & Blanzat, J. (1973). Tetrahedron, 29, 1629–1645. CrossRef CAS Web of Science Google Scholar
Fischer, J., Mellinger, M. & Weiss, R. (1977). Inorg. Chim. Acta, 21, 259–263. CSD CrossRef CAS Web of Science Google Scholar
Groth, P. (1986). Acta Chem. Scand. Ser. A, 40, 154–156. CrossRef Web of Science Google Scholar
Krakowiak, K. E., Bradshaw, J. S., Kou, X. & Dalley, N. K. (1995). J. Heterocycl. Chem. 32, 931–935. CrossRef CAS Google Scholar
Lehn, J. M. (1973). Struct. Bond. 16, 1–69. CrossRef CAS Google Scholar
Lehn, J. M. (1988). Angew. Chem. Int. Ed. Engl. 27, 89–112. CrossRef Web of Science Google Scholar
Lehn, J. M., Simon, J. & Wagner, J. (1977). Nouv. J. Chim. 1, 77–84. CAS Google Scholar
Pascard, C., Riche, C., Cesario, M., Kotzyba-Hibert, F. & Lehn, J. M. (1982). J. Chem. Soc. Chem. Commun. pp. 557–560. CrossRef Web of Science Google Scholar
Plenio, H. & Diodone, R. (1995). J. Organomet. Chem. 492, 73–80. CSD CrossRef CAS Web of Science Google Scholar
Rebizant, J., Spirlet, M. R., Barthelemy, P. & Desreux, J. F. (1984). Acta Cryst. C40, 484–486. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G. L. N., Rocher, N. M., Powell, D. R. & Taylor, R. W. (2007). Acta Cryst. E63, o1253–o1255. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wiest, R. & Weiss, R. (1973). J. Chem. Soc. Chem. Commun. pp. 678–679. CrossRef Web of Science Google Scholar

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