3,6,9,16,19,22-Hexa­aza­tri­cyclo[22.2.­2.2^11,14]­tria­conta-11,13,24,26(1),27,29-hexa­ene penta­hydrate

In the title macrocyclic poly­amine, C₂₄H₃₈N₆·5H₂O, the centrosymmetric poly­amine mol­ecules are stacked in rows, and between these mol­ecules there are channels along the a axis. The intermolecular hydrogen bonds formed between the water and poly­amine, together with those formed between water mol­ecules, generate an extensive hydrogen-bonding network.

S1. Comment

Macrocyclic complexes play a key role in the modelling of metallobiosites (Fenton & Ōkawa, 1993), and in the development of systems for activating substrate molecules (Vigato et al., 1990). Our current studies focus on macrocyclic polyamines in which the relative positions of the donor atoms in the ring are deigned to hold pairs of coordinated transition metal ions at specified distances. The distance between these two metal ions is considered to be an important factor in increasing the efficiency in activation of substrates. Recently, it was reported that the title compound, (I), and its analogues can accelerate the hydrolysis of bis(p-nitrophenyl)phosphate and ATP (Ragunathan & Schneider, 1996; Lu et al., 1997). On the other hand, these compounds and their metal complexes are good receptors for inorganic phosphates and RNA (Nation et al., 1996; Li et al., 1997). Therefore, the structure of the title compound may prove useful for understanding the mechanisms of hydrolysis and for the dsign of new compounds. \sch

Fig. 1. is the ORTEP representation of compound (I). The centrosymmetric macrocycle adopts a chair-like conformation, with one diethylene triamine moiety flipped down and the other flipped up. While in its analogue 3,7,11,19,23,27-hexaazatricyclo [27.3.1.1^13,17]tetratriaconta-1(32),13,15,17 (34),29 (33),30-hexaene hexahydrobromide dihydrate, (II), although the molecule is still in the chair conformation, in this case, it is the two phenyl rings that flipped down and flipped up and the two phenyl rings are nearly perpendicular to the plane of the macrocyclic arms (Liobet et al., 1994). These differences may depend both on the different states of protonation and on the different plaing of the aromatic substituents, para in (I) and meta in (II). The C—C and C—N bond lengths in (I) are almost equal to those in (II). In the crystal, the macrocyclic molecules are arranged in stacks (Fig. 2), and the macrocycles of the molecules form an apparent channel along the a axis. The water molecules [O11, O12, O14, O15 and their symmetry-related partners] link different polyamine molecules by hydrogen bonds (Table 2) to form a supermolecule.

S2. Experimental

The title compound was synthesized in a similar procedure used by others (Chen & Martell, 1991). To an MeCN solution of diethylene triamine an equivalent amount of terephthalaldehyde was added slowly at room temperature. Several hours later, a white precipitate was obtained. The white solid was reduced with sodium borohydride in ethanol for 5 h. The solvent was then removed in vacuo, and the residue was extracted with chloroform. The product was purified by recrystallization from MeCN, the pure compound dissolved in an appropriate amount of hot water and prismatic single crystals suitable for crystallographic analysis were obtained by crystallization from water.

S3. Refinement

Hydrogen atoms were found from the difference map and were refined isotropically with fixed isotropic displacement parameters 1.2 × isotropic U_eq of the atoms to which they attached. To make the refinement stable, several restraints were used to fix the O—H and N—H bond distances as well as H—O—H angles. No suitable positions were found from the difference map for the hydrogen atoms attached to the disordered oxygen atoms O15 and O15'.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; 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.

Figures

	Fig. 1. Structure of the title compound showing 50% probability displacement ellipsoids with numbering scheme. The water molecules were omitted for clarity. Symmetry code: (A) 1 − x, 1 − y, 1 − z.
	Fig. 2. The unit cell of the title compound, hydrogen atoms are omitted for clarity.

3,6,9,16,19,22-hexaazatricyclo[22.2.2.2^11,14]triaconta-11,13,24,26,27, 29-hexaene pentahydrate

Crystal data

C24H38N6·5H2O	Dx = 1.218 Mg m^−3
Mr = 500.68	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 29 reflections
a = 7.451 (3) Å	θ = 7.8–9.2°
b = 19.709 (6) Å	µ = 0.09 mm^−1
c = 18.587 (8) Å	T = 293 K
V = 2729.6 (18) Å^3	Prism, colourless
Z = 4	0.40 × 0.20 × 0.20 mm
F(000) = 1096

Data collection

Bruker P4 diffractometer	Rint = 0.034
Radiation source: sealed tube	θmax = 25.0°, θmin = 2.1°
Graphite monochromator	h = −1→8
2θ/ω scans	k = −23→1
3241 measured reflections	l = −1→22
2474 independent reflections	3 standard reflections every 97 reflections
1770 reflections with I > 2σ(I)	intensity decay: 4.9%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.197	Only H-atom coordinates refined
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1131P)^2 + 1.2637P] where P = (Fo^2 + 2Fc^2)/3
2474 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.36 e Å^−3
21 restraints	Δρmin = −0.31 e Å^−3

Special details

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.

Hydrogen atoms were found from different map and were refined isotropically with fixed isotropic thermal parameters 1.2 times equivalent isotropic U_eq of the atoms they attached. To make the refinement stable, several restraints were used to fix the O—H and N—H bond distances as well as H—O—H angles. No suitable positions were found from the different map for the hydrogen atoms attached to the disordered oxygen atoms O15 and O15'.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.7066 (4)	0.65895 (14)	0.38227 (15)	0.0685 (8)
H1N	0.693 (2)	0.6886 (11)	0.3503 (13)	0.082*
N2	1.0172 (3)	0.65199 (11)	0.48594 (13)	0.0505 (6)
H2N	0.928 (3)	0.6762 (14)	0.4981 (17)	0.061*
N3	0.9297 (3)	0.63938 (10)	0.64678 (11)	0.0440 (6)
H3N	0.855 (3)	0.6545 (14)	0.6158 (12)	0.053*
C1	0.8571 (4)	0.61237 (17)	0.37799 (17)	0.0562 (7)
H1A	0.954 (5)	0.6358 (15)	0.3460 (17)	0.067*
H1B	0.815 (5)	0.5718 (18)	0.3541 (18)	0.067*
C2	0.9454 (5)	0.59274 (14)	0.44828 (16)	0.0504 (7)
H2A	0.859 (5)	0.5695 (16)	0.4766 (16)	0.061*
H2B	1.057 (4)	0.5618 (16)	0.4368 (15)	0.061*
C3	1.1400 (4)	0.63528 (15)	0.54497 (15)	0.0496 (7)
H3A	1.191 (4)	0.6785 (16)	0.5635 (16)	0.060*
H3B	1.244 (4)	0.6066 (15)	0.5247 (16)	0.060*
C4	1.0594 (4)	0.59784 (14)	0.60828 (15)	0.0476 (7)
H4A	1.013 (4)	0.5569 (16)	0.5922 (16)	0.057*
H4B	1.156 (4)	0.5842 (15)	0.6424 (16)	0.057*
C5	0.8274 (4)	0.60255 (14)	0.70239 (15)	0.0483 (7)
H5A	0.737 (4)	0.6374 (14)	0.7268 (15)	0.058*
H5B	0.910 (4)	0.5890 (14)	0.7398 (17)	0.058*
C6	0.7235 (4)	0.54177 (13)	0.67558 (13)	0.0427 (6)
C7	0.5920 (4)	0.54929 (14)	0.62383 (14)	0.0486 (7)
H7	0.562 (4)	0.5932 (16)	0.6063 (16)	0.058*
C8	0.5026 (4)	0.49400 (14)	0.59559 (16)	0.0497 (7)
H8	0.411 (4)	0.4990 (15)	0.5556 (16)	0.060*
C9	0.5414 (4)	0.42834 (13)	0.61831 (14)	0.0462 (7)
C10	0.6665 (4)	0.42099 (14)	0.67200 (15)	0.0501 (7)
H10	0.705 (4)	0.3755 (16)	0.6913 (16)	0.060*
C11	0.7579 (4)	0.47635 (14)	0.70054 (15)	0.0485 (7)
H11	0.846 (4)	0.4736 (14)	0.7347 (17)	0.058*
C12	0.4526 (5)	0.36756 (15)	0.58191 (19)	0.0603 (8)
H12A	0.416 (5)	0.3813 (17)	0.5295 (19)	0.072*
H12B	0.545 (5)	0.3269 (17)	0.5794 (18)	0.072*
O11	1.1218 (4)	0.7500	0.70300 (15)	0.0537 (7)
H21	1.056 (3)	0.7145 (3)	0.6875 (15)	0.064*
O12	1.1879 (5)	0.7500	0.39151 (18)	0.0713 (10)
H22	1.131 (4)	0.7145 (3)	0.4118 (16)	0.086*
O13	0.7169 (5)	0.7500	0.53880 (19)	0.0744 (9)
H23	0.623 (4)	0.7500	0.5695 (17)	0.089*
H33	0.663 (5)	0.7500	0.4958 (11)	0.089*
O14	1.4852 (6)	0.7500	0.6552 (2)	0.1123 (16)
H24	1.3667 (19)	0.7500	0.664 (3)	0.135*
H34	1.532 (7)	0.7500	0.6997 (15)	0.135*
O15	0.579 (2)	0.7500	0.2565 (5)	0.107 (3)	0.559 (14)
O15'	0.723 (2)	0.7500	0.2534 (6)	0.096 (4)	0.441 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0705 (17)	0.0521 (15)	0.083 (2)	−0.0111 (14)	−0.0109 (14)	0.0134 (13)
N2	0.0622 (15)	0.0354 (12)	0.0541 (13)	−0.0049 (11)	−0.0059 (12)	−0.0033 (10)
N3	0.0543 (13)	0.0343 (11)	0.0435 (12)	0.0004 (10)	−0.0018 (10)	−0.0047 (9)
C1	0.0555 (17)	0.0534 (17)	0.0596 (17)	−0.0092 (15)	−0.0082 (15)	−0.0043 (14)
C2	0.0559 (17)	0.0383 (14)	0.0571 (17)	−0.0100 (13)	0.0019 (14)	−0.0034 (12)
C3	0.0515 (15)	0.0465 (15)	0.0509 (15)	−0.0103 (14)	0.0002 (13)	−0.0027 (12)
C4	0.0568 (17)	0.0393 (14)	0.0468 (15)	0.0016 (13)	−0.0027 (13)	−0.0026 (12)
C5	0.0579 (16)	0.0482 (15)	0.0386 (13)	−0.0042 (14)	0.0005 (13)	−0.0051 (12)
C6	0.0500 (14)	0.0442 (14)	0.0338 (12)	0.0039 (12)	0.0065 (11)	0.0013 (10)
C7	0.0566 (17)	0.0419 (15)	0.0474 (15)	−0.0001 (13)	−0.0040 (13)	0.0064 (12)
C8	0.0504 (15)	0.0480 (15)	0.0507 (15)	−0.0020 (13)	−0.0053 (14)	0.0026 (13)
C9	0.0430 (15)	0.0435 (14)	0.0521 (15)	0.0023 (12)	0.0053 (12)	−0.0008 (12)
C10	0.0525 (16)	0.0402 (14)	0.0577 (17)	0.0042 (13)	0.0054 (14)	0.0066 (13)
C11	0.0509 (16)	0.0523 (16)	0.0424 (14)	0.0048 (13)	0.0001 (13)	0.0050 (12)
C12	0.0638 (19)	0.0452 (16)	0.072 (2)	−0.0042 (15)	−0.0003 (17)	−0.0124 (15)
O11	0.0656 (18)	0.0370 (14)	0.0585 (16)	0.000	−0.0099 (15)	0.000
O12	0.095 (3)	0.0416 (15)	0.078 (2)	0.000	0.0199 (18)	0.000
O13	0.081 (2)	0.069 (2)	0.073 (2)	0.000	−0.0030 (18)	0.000
O14	0.080 (3)	0.196 (5)	0.061 (2)	0.000	0.003 (2)	0.000
O15	0.162 (9)	0.095 (5)	0.065 (4)	0.000	−0.033 (6)	0.000
O15'	0.161 (10)	0.069 (4)	0.058 (4)	0.000	−0.015 (7)	0.000

Geometric parameters (Å, º)

N1—C1	1.451 (4)	C5—H5B	0.97 (3)
N1—C12^i	1.457 (4)	C6—C7	1.381 (4)
N1—H1N	0.841 (8)	C6—C11	1.394 (4)
N2—C2	1.463 (3)	C7—C8	1.381 (4)
N2—C3	1.466 (4)	C7—H7	0.95 (3)
N2—H2N	0.847 (10)	C8—C9	1.392 (4)
N3—C4	1.455 (4)	C8—H8	1.01 (3)
N3—C5	1.475 (4)	C9—C10	1.373 (4)
N3—H3N	0.853 (10)	C9—C12	1.526 (4)
C1—C2	1.513 (4)	C10—C11	1.391 (4)
C1—H1A	1.04 (3)	C10—H10	1.01 (3)
C1—H1B	0.97 (4)	C11—H11	0.92 (3)
C2—H2A	0.95 (3)	C12—N1^i	1.457 (4)
C2—H2B	1.05 (3)	C12—H12A	1.05 (3)
C3—C4	1.513 (4)	C12—H12B	1.06 (4)
C3—H3A	0.99 (3)	O11—H21	0.902 (10)
C3—H3B	1.03 (3)	O12—H22	0.900 (10)
C4—H4A	0.93 (3)	O13—H23	0.901 (10)
C4—H4B	1.00 (3)	O13—H33	0.895 (10)
C5—C6	1.511 (4)	O14—H24	0.898 (11)
C5—H5A	1.06 (3)	O14—H34	0.899 (10)
C1—N1—C12^i	115.3 (3)	N3—C5—C6	115.1 (2)
C1—N1—H1N	119.7 (11)	N3—C5—H5A	108.0 (15)
C12^i—N1—H1N	118.3 (11)	C6—C5—H5A	109.1 (16)
C2—N2—C3	114.0 (2)	N3—C5—H5B	108.0 (18)
C2—N2—H2N	107 (2)	C6—C5—H5B	110.2 (17)
C3—N2—H2N	114 (2)	H5A—C5—H5B	106 (2)
C4—N3—C5	114.3 (2)	C7—C6—C11	117.5 (3)
C4—N3—H3N	107 (2)	C7—C6—C5	120.6 (2)
C5—N3—H3N	108 (2)	C11—C6—C5	121.9 (3)
N1—C1—C2	116.8 (3)	C6—C7—C8	121.5 (3)
N1—C1—H1A	106.6 (17)	C6—C7—H7	120.1 (18)
C2—C1—H1A	107.7 (18)	C8—C7—H7	118.4 (18)
N1—C1—H1B	107 (2)	C7—C8—C9	121.2 (3)
C2—C1—H1B	109 (2)	C7—C8—H8	121.8 (17)
H1A—C1—H1B	109 (3)	C9—C8—H8	116.9 (17)
N2—C2—C1	111.6 (2)	C10—C9—C8	117.4 (3)
N2—C2—H2A	111.6 (19)	C10—C9—C12	122.2 (3)
C1—C2—H2A	107.8 (19)	C8—C9—C12	120.3 (3)
N2—C2—H2B	105.8 (17)	C9—C10—C11	121.8 (3)
C1—C2—H2B	108.5 (16)	C9—C10—H10	123.1 (17)
H2A—C2—H2B	112 (3)	C11—C10—H10	114.9 (17)
N2—C3—C4	116.4 (2)	C10—C11—C6	120.5 (3)
N2—C3—H3A	107.8 (17)	C10—C11—H11	124.7 (19)
C4—C3—H3A	107.5 (17)	C6—C11—H11	114.7 (19)
N2—C3—H3B	108.6 (17)	N1^i—C12—C9	115.6 (3)
C4—C3—H3B	108.4 (17)	N1^i—C12—H12A	108 (2)
H3A—C3—H3B	108 (2)	C9—C12—H12A	108.8 (19)
N3—C4—C3	111.8 (2)	N1^i—C12—H12B	106.1 (18)
N3—C4—H4A	113 (2)	C9—C12—H12B	109.4 (18)
C3—C4—H4A	108.8 (19)	H12A—C12—H12B	109 (3)
N3—C4—H4B	108.6 (17)	H23—O13—H33	102.6 (15)
C3—C4—H4B	109.9 (18)	H24—O14—H34	102.5 (16)
H4A—C4—H4B	104 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O15	0.84 (2)	2.29 (2)	3.097 (9)	162 (2)
N2—H2N···O13	0.85 (2)	2.27 (3)	3.115 (4)	172 (2)
N3—H3N···O13	0.85 (2)	2.58 (3)	3.361 (4)	153 (2)
O11—H21···N3	0.90 (2)	1.91 (2)	2.810 (3)	175 (2)
O12—H22···N2	0.90 (2)	2.03 (2)	2.903 (4)	162 (2)
O13—H23···O14^ii	0.90 (3)	1.90 (3)	2.768 (6)	162 (3)
O14—H24···O11	0.90 (2)	1.96 (2)	2.850 (5)	169 (5)
O14—H34···O11^iii	0.90 (3)	1.93 (3)	2.825 (5)	177 (5)

Symmetry codes: (ii) x−1, y, z; (iii) x+1/2, −y+3/2, −z+3/2.