The hydrogen-bonded adduct 7,16-diazonia-18-crown-6-4-aminobenzenesulfonate-water (1/2/2)

In the title hydrated adduct, 1,4,10,13-tetraoxa-7,16-diazo­nia­cyclo­octa­decane bis(4-amino­benzene­sulfonate) dihydrate, C₁₂H₂₈N₂O₄²⁺·2C₆H₆NO₃S^-·2H₂O, formed between 7,16-di­aza-18-crown-6 and the dihydrate of 4-amino­benzene­sulfonic acid, the macrocyclic cations lie across centres of inversion in the orthorhombic space group Pbca. The anions alone form zigzag chains, and the cations and anions together form sheets that are linked via water mol­ecules and anions to form a three-dimensional grid.

S1. Comment

N-containing crown ethers merit considerable attention for their host behaviour as receptors for anions and neutral organic molecules (Goldberg, 1984; Lehn, 1995; Vögtle & Weber, 1985). These receptors are capable of being included in the extended supramolecular networks formed by self-assembled organic molecules, rich in both hydrogen-donor and -acceptor centres, with partial preservation or rearrangement of the hydrogen bonds which sustain the supramolecular architecture.

Diaza-18-crown-6 has attracted our attention as a suitable macrocycle to provide hydrogen-bonded frameworks. A search of the Cambridge Structural Database (CSD, April 2002 release; Allen, 2002) yielded a list of 17 entries covering complexes of 7,16-diazonia-18-crown-6 with different anions and water molecules with extended hydrogen-bonded architectures. The closest crown environment that includes both water molecules and anions in an inversion symmetry-related fashion is found in the 7,16-diazonia-18-crown-6 hydrates with tetrahydroxypentaborate (Chekhlov & Martynov, 1998), a 1,10-dioate derivative (Chekhlov, 2000) and hydrogen sulfate (Chekhlov, 1995). Another route for macrocyclic cation coordination also exists when the anions (formate, tartrate, hydrogen tartrate, sulfate) are bound directly to the macrocycle via hydrogen bonds, while the water molecules are not involved in direct contacts with the macrocycle but bridge the anions in the chains (Chekhlov 1999; Chekhlov & Martynov, 1999a,b; Chekhlov, 1996). 7,16-Diaza-18-crown-6 and the dihydrate of 4-aminobenzenesulfonic acid form the title hydrated salt, (I), and its structure is presented here. \sch

The centrosymmetric formula unit of (I) is shown in Fig. 1. This salt crystallizes in space group Pbca with Z = 4. The macrocyclic cation adopts a C_i conformation and lies across a centre of inversion. The water molecule acts as a double donor, using O—H···O hydrogen bonds between the crown cation and the anion (Table 1), and as a single acceptor, in N—H···O hydrogen bonds with the crown cation. The 4-aminobenzenesulfonate anion and the macrocyclic cation are arranged in a T-shaped mode, with the dihedral angle between the mean planes of the aromatic ring and the six-membered set of N and O atoms of the crown ether being 80.63 (6)°.

It is possible to identify one-component hydrogen-bonded zigzag chains built from the anions running along the [100] direction. The amino atom N11 of the anion at the original position forms a weak hydrogen bond with atom O11 of the anion at (1/2 + x, y, 1/2 − z), with N11···O11 3.052 (5) Å and the angle subtended at the H atom being 168 (3)°.

Each anion in the self-assembled chain interacts with the macrocyclic cation via the same atom O11, with N1···O11 2.920 (3) Å [the angle subtended at the H atom is 175 (3)°]. The anionic chains and cations attached to them generate sheets running parallel to the (101) plane (Fig. 2). The sheets are built from the centrosymmetric six-membered fused rings that combine two cations and four anions, each component being shared between two neighbouring rings.

The water molecules are located 1.702 (2) Å above and below the macrocyclic cavity and are bound to the macrocycle via the above-mentioned O—H···O and N—H···O hydrogen bonds (Table 1). The water molecule acts as a hydrogen-bond donor to sulfonate atom O12 of the anion related to the basic one by a twofold screw axis, with O1W···O12(3/2 − x, y − 1/2, z) 2.764 (3) Å [the angle subtended at the H atom is 161 (3)°], and functions as a bridge between adjacent sheets, consolidating them into three-dimensional network. The architecture of (I) strictly resembles that of 7,16-diazonia-18-crown-6 bis(hydrogen sulfate) dihydrate (Chekhlov, 1995).

S2. Experimental

Diaza-18-crown-6 (52.4 mg, 0.02 mmol) and 4-H₂NC₆H₄SO₃H (83.6 mg, 0.04 mmol) were dissolved in a mixture of water (1.5 ml), methanol (2 ml) and n-butanol (4 ml). The resulting clear solution was slowly reduced in volume by evaporating the solvents at room temperature. Crystals of (I) suitable for X-ray analysis were selected in a yield of 85% (110 mg) [m.p. 498–500 K] directly from the analytical sample. Analysis, found: C 44.73, H 6.85, N 8.74%; C₂₄H₄₄N₄O₁₂S₂ requires: C 44.71, H 6.88, N 8.69%.

S3. Refinement

Anisotropic displacement parameters were used for all non-H atoms except for the O atoms of the SO₃-group minor site. This group was found to be disordered over two sites rotated about the C—S axis, with occupancy factors of 0.932 and 0.068. The major site was refined with anisotropic displacement parameters and the minor site was treated with SADI restraints for three S—O distances and a group value isotropic displacement parameter. The coordinates of the H atoms on atoms N1, N11 and O1W were determined from a difference map and were then allowed to refine isotropically subject to a DFIX restraint. All other H atoms were riding, with C—H distances in the range 0.93–0.97 Å. Is this added text OK? The final difference Fourier map did not show positions for disordered H atoms on the water molecule. The hydrogen-bonding system is the same for the two positions of the SO₃ group, as shown in Table 1.

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1997); software used to prepare material for publication: SHELXS97.

Figures

	Fig. 1. The structure of (I) in the crystal. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only the asymmetric unit is numbered. The minor site of the disordered SO3 group has been omitted for clarity.
	Fig. 2. Part of the crystal structure of (I) showing the (101) sheets formed by the hydrogen-bonded anions and cations. For the sake of clarity, H atoms bonded to C atoms have been omitted.

1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane bis(4-aminobenzenesulfonate) dihydrate

Crystal data

C12H28N2O4^+·2C6H6NO3S^−·2H2O	Dx = 1.388 Mg m^−3
Mr = 644.75	Melting point = 498–500 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p_2ac_2ab	Cell parameters from 5186 reflections
a = 12.319 (2) Å	θ = 1.0–25.0°
b = 10.976 (2) Å	µ = 0.24 mm^−1
c = 22.826 (4) Å	T = 293 K
V = 3086.4 (9) Å^3	Plate, white
Z = 4	0.25 × 0.15 × 0.10 mm
F(000) = 1376

Data collection

Nonius KappaCCD area-detector diffractometer	1821 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 25.2°, θmin = 2.4°
ϕ scans	h = −14→14
5052 measured reflections	k = −13→13
2730 independent reflections	l = −26→26

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0638P)^2 + 0.3407P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2730 reflections	Δρmax = 0.35 e Å^−3
226 parameters	Δρmin = −0.24 e Å^−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (9)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.72444 (16)	0.6113 (2)	0.02047 (10)	0.0453 (5)
H1N	0.764 (2)	0.610 (3)	0.0554 (11)	0.077 (10)*
H2N	0.679 (2)	0.542 (2)	0.0238 (13)	0.080 (10)*
C2	0.6608 (2)	0.7257 (2)	0.01781 (13)	0.0554 (7)
H2A	0.6120	0.7226	−0.0155	0.066*
H2B	0.7098	0.7939	0.0122	0.066*
C3	0.5961 (2)	0.7452 (3)	0.07269 (13)	0.0606 (8)
H3A	0.6436	0.7444	0.1066	0.073*
H3B	0.5596	0.8235	0.0712	0.073*
O4	0.51844 (13)	0.64981 (16)	0.07710 (8)	0.0529 (5)
C5	0.4553 (2)	0.6534 (3)	0.12921 (11)	0.0544 (7)
H5A	0.4060	0.7223	0.1280	0.065*
H5B	0.5024	0.6629	0.1629	0.065*
C6	0.3923 (2)	0.5379 (3)	0.13451 (11)	0.0533 (7)
H6A	0.4414	0.4689	0.1360	0.064*
H6B	0.3497	0.5388	0.1703	0.064*
O7	0.32289 (13)	0.52767 (16)	0.08528 (7)	0.0548 (5)
C8	0.2563 (2)	0.4221 (3)	0.08743 (11)	0.0564 (7)
H8A	0.2032	0.4300	0.1186	0.068*
H8B	0.3004	0.3507	0.0952	0.068*
C9	0.19985 (19)	0.4085 (3)	0.02967 (12)	0.0543 (7)
H9A	0.1501	0.3401	0.0320	0.065*
H9B	0.1573	0.4812	0.0222	0.065*
O1W	0.61296 (16)	0.39191 (18)	0.02816 (10)	0.0546 (5)
H1W	0.571 (2)	0.367 (3)	0.0546 (12)	0.077 (11)*
H2W	0.581 (3)	0.386 (3)	−0.0040 (12)	0.087 (12)*
S11	0.96272 (5)	0.63706 (6)	0.11872 (3)	0.0431 (2)
O11	0.84996 (15)	0.6252 (3)	0.12877 (11)	0.0979 (12)	0.932 (4)
O12	0.9957 (2)	0.7636 (2)	0.11429 (11)	0.0810 (10)	0.932 (4)
O13	0.9996 (2)	0.5714 (3)	0.06842 (9)	0.0930 (10)	0.932 (4)
O11A	0.8944 (17)	0.5414 (18)	0.0977 (10)	0.039 (6)*	0.068 (4)
O12A	0.9154 (19)	0.7489 (18)	0.1330 (10)	0.039 (6)*	0.068 (4)
O13A	1.0212 (16)	0.699 (2)	0.0786 (10)	0.039 (6)*	0.068 (4)
N11	1.2052 (2)	0.4267 (3)	0.31961 (12)	0.0724 (8)
H11N	1.179 (2)	0.364 (3)	0.3380 (15)	0.075 (11)*
H12N	1.249 (3)	0.471 (3)	0.3357 (14)	0.086 (12)*
C10	1.03092 (17)	0.5781 (2)	0.17995 (9)	0.0382 (6)
C11	1.11695 (18)	0.6415 (2)	0.20552 (11)	0.0456 (6)
H11A	1.1359	0.7180	0.1913	0.055*
C12	1.17405 (19)	0.5923 (2)	0.25158 (11)	0.0506 (7)
H12A	1.2309	0.6361	0.2681	0.061*
C13	1.14794 (18)	0.4781 (2)	0.27369 (11)	0.0469 (6)
C14	1.0615 (2)	0.4148 (2)	0.24816 (11)	0.0513 (7)
H14	1.0425	0.3383	0.2624	0.062*
C15	1.00432 (19)	0.4642 (2)	0.20221 (10)	0.0460 (6)
H15	0.9471	0.4207	0.1858	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0368 (11)	0.0460 (14)	0.0532 (14)	−0.0027 (10)	−0.0047 (9)	0.0033 (10)
C2	0.0424 (13)	0.0415 (15)	0.082 (2)	−0.0025 (12)	−0.0035 (12)	0.0070 (14)
C3	0.0454 (14)	0.0547 (17)	0.082 (2)	−0.0050 (14)	−0.0037 (13)	−0.0165 (15)
O4	0.0471 (10)	0.0577 (11)	0.0539 (11)	−0.0084 (8)	0.0026 (8)	−0.0152 (9)
C5	0.0539 (15)	0.0623 (18)	0.0470 (16)	0.0141 (13)	−0.0047 (12)	−0.0130 (13)
C6	0.0550 (15)	0.0649 (18)	0.0399 (15)	0.0065 (14)	−0.0002 (11)	0.0001 (13)
O7	0.0522 (10)	0.0637 (12)	0.0484 (11)	−0.0099 (9)	−0.0069 (8)	0.0080 (9)
C8	0.0536 (15)	0.0589 (18)	0.0568 (17)	−0.0089 (14)	0.0084 (13)	0.0059 (14)
C9	0.0398 (13)	0.0579 (17)	0.0651 (18)	−0.0064 (12)	0.0026 (12)	0.0003 (14)
O1W	0.0604 (12)	0.0535 (12)	0.0500 (13)	−0.0092 (9)	0.0023 (11)	0.0068 (10)
S11	0.0453 (4)	0.0437 (4)	0.0402 (4)	−0.0008 (3)	−0.0034 (3)	0.0014 (3)
O11	0.0345 (11)	0.180 (3)	0.0788 (18)	−0.0026 (14)	−0.0015 (10)	0.0677 (19)
O12	0.111 (2)	0.0483 (14)	0.0837 (18)	−0.0205 (13)	−0.0390 (16)	0.0212 (13)
O13	0.121 (2)	0.115 (2)	0.0426 (13)	0.0538 (17)	−0.0126 (13)	−0.0254 (14)
N11	0.0637 (16)	0.089 (2)	0.0646 (18)	−0.0112 (16)	−0.0225 (14)	0.0201 (17)
C10	0.0384 (12)	0.0412 (14)	0.0351 (13)	0.0010 (10)	−0.0003 (9)	−0.0029 (11)
C11	0.0450 (13)	0.0442 (15)	0.0476 (15)	−0.0059 (11)	0.0021 (11)	0.0034 (12)
C12	0.0414 (13)	0.0619 (17)	0.0484 (16)	−0.0091 (13)	−0.0059 (11)	−0.0012 (14)
C13	0.0421 (13)	0.0611 (18)	0.0373 (14)	0.0022 (12)	−0.0030 (11)	0.0028 (12)
C14	0.0550 (15)	0.0494 (15)	0.0495 (16)	−0.0054 (13)	−0.0050 (12)	0.0087 (13)
C15	0.0467 (13)	0.0463 (16)	0.0449 (15)	−0.0079 (12)	−0.0064 (11)	0.0020 (12)

Geometric parameters (Å, º)

N1—C2	1.481 (3)	C9—H9B	0.9700
N1—C9^i	1.492 (3)	O1W—H1W	0.84 (2)
N1—H1N	0.94 (2)	O1W—H2W	0.83 (2)
N1—H2N	0.95 (2)	S11—O11	1.414 (2)
C2—C3	1.500 (4)	S11—O12	1.450 (2)
C2—H2A	0.9700	S11—O13	1.430 (2)
C2—H2B	0.9700	S11—O11A	1.429 (16)
C3—O4	1.422 (3)	S11—O12A	1.397 (16)
C3—H3A	0.9700	S11—O13A	1.349 (17)
C3—H3B	0.9700	S11—C10	1.754 (2)
O4—C5	1.422 (3)	N11—C13	1.384 (4)
C5—C6	1.491 (4)	N11—H11N	0.87 (3)
C5—H5A	0.9700	N11—H12N	0.82 (4)
C5—H5B	0.9700	C10—C11	1.396 (3)
C6—O7	1.416 (3)	C10—C15	1.389 (3)
C6—H6A	0.9700	C11—C12	1.376 (3)
C6—H6B	0.9700	C11—H11A	0.9300
O7—C8	1.420 (3)	C12—C13	1.389 (4)
C8—C9	1.498 (3)	C12—H12A	0.9300
C8—H8A	0.9700	C13—C14	1.399 (3)
C8—H8B	0.9700	C14—C15	1.375 (3)
C9—N1^i	1.492 (3)	C14—H14	0.9300
C9—H9A	0.9700	C15—H15	0.9300
C2—N1—C9^i	115.0 (2)	N1^i—C9—H9A	108.9
C2—N1—H1N	108.8 (18)	C8—C9—H9A	108.9
C9^i—N1—H1N	108.8 (18)	N1^i—C9—H9B	108.9
C2—N1—H2N	112.1 (17)	C8—C9—H9B	108.9
C9^i—N1—H2N	108.0 (18)	H9A—C9—H9B	107.7
H1N—N1—H2N	103 (2)	H1W—O1W—H2W	109 (3)
N1—C2—C3	111.6 (2)	O11A—S11—O12A	118.5 (14)
N1—C2—H2A	109.3	O11A—S11—O13A	117.3 (15)
C3—C2—H2A	109.3	O12A—S11—O13A	86.3 (15)
N1—C2—H2B	109.3	O11—S11—O12	112.01 (18)
C3—C2—H2B	109.3	O11—S11—O13	113.32 (18)
H2A—C2—H2B	108.0	O12—S11—O13	109.73 (17)
O4—C3—C2	108.1 (2)	O13A—S11—C10	118.1 (9)
O4—C3—H3A	110.1	O12A—S11—C10	109.8 (9)
C2—C3—H3A	110.1	O11—S11—C10	107.90 (12)
O4—C3—H3B	110.1	O11A—S11—C10	106.2 (9)
C2—C3—H3B	110.1	O13—S11—C10	107.57 (12)
H3A—C3—H3B	108.4	O12—S11—C10	105.92 (12)
C5—O4—C3	114.0 (2)	C13—N11—H11N	120 (2)
O4—C5—C6	109.2 (2)	C13—N11—H12N	116 (2)
O4—C5—H5A	109.8	H11N—N11—H12N	120 (3)
C6—C5—H5A	109.8	C15—C10—C11	118.4 (2)
O4—C5—H5B	109.8	C15—C10—S11	120.69 (17)
C6—C5—H5B	109.8	C11—C10—S11	120.87 (19)
H5A—C5—H5B	108.3	C12—C11—C10	120.8 (2)
O7—C6—C5	108.5 (2)	C12—C11—H11A	119.6
O7—C6—H6A	110.0	C10—C11—H11A	119.6
C5—C6—H6A	110.0	C11—C12—C13	120.9 (2)
O7—C6—H6B	110.0	C11—C12—H12A	119.5
C5—C6—H6B	110.0	C13—C12—H12A	119.5
H6A—C6—H6B	108.4	N11—C13—C12	121.7 (3)
C6—O7—C8	112.71 (19)	N11—C13—C14	120.1 (3)
O7—C8—C9	108.6 (2)	C12—C13—C14	118.3 (2)
O7—C8—H8A	110.0	C15—C14—C13	120.8 (2)
C9—C8—H8A	110.0	C15—C14—H14	119.6
O7—C8—H8B	110.0	C13—C14—H14	119.6
C9—C8—H8B	110.0	C14—C15—C10	120.9 (2)
H8A—C8—H8B	108.3	C14—C15—H15	119.6
N1^i—C9—C8	113.5 (2)	C10—C15—H15	119.6
N1—C2—C3—O4	−64.1 (3)	C6—O7—C8—C9	−170.9 (2)
C2—C3—O4—C5	176.6 (2)	O7—C8—C9—N1^i	62.9 (3)
C3—O4—C5—C6	−169.5 (2)	C8—C9—N1^i—C2^i	63.9 (3)
O4—C5—C6—O7	−60.5 (3)	C9—N1^i—C2^i—C3^i	173.8 (2)
C5—C6—O7—C8	−177.9 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O11	0.94 (2)	1.99 (2)	2.920 (3)	175 (3)
N1—H1N···O11A	0.94 (2)	2.02 (3)	2.84 (2)	146 (3)
N1—H2N···O1W	0.95 (2)	1.84 (2)	2.778 (3)	170 (3)
O1W—H2W···O4^i	0.83 (2)	2.11 (3)	2.933 (3)	170 (3)
O1W—H2W···O7^i	0.83 (2)	2.39 (3)	2.848 (3)	115 (3)
O1W—H1W···O12^ii	0.84 (2)	1.95 (2)	2.764 (3)	161 (3)
O1W—H1W···O12A^ii	0.84 (2)	2.21 (4)	2.88 (2)	136 (3)
N11—H11N···O12^iii	0.87 (3)	2.66 (3)	3.407 (5)	146 (3)
N11—H11N···O12A^iii	0.87 (3)	1.84 (4)	2.682 (17)	162 (3)
N11—H12N···O11^iv	0.82 (4)	2.25 (4)	3.052 (5)	168 (3)
N11—H12N···O11A^iv	0.82 (4)	2.47 (4)	3.25 (2)	161 (3)

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