Diammonium tetra­kis­(iso­thio­cyanato)­zincate–1,4,10,13,16-hexa­oxa­cyclo­octa­deca­ne–water (1/2/1)

Showrilu, K.; Rajarajan, K.; NizamMohideen, M.

doi:10.1107/S1600536813019739

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m469-m470

doi:10.1107/S1600536813019739

Open

access

Diammonium tetrakis(isothiocyanato)zincate–1,4,10,13,16-hexaoxacyclooctadecane–water (1/2/1)

K. Showrilu,^a K. Rajarajan ^b ^* and M. NizamMohideen ^c ^*

^aResearch and Development Centre, Bharathiyar University, Coimbatore 641 046, India, ^bDepartment of Physics, Rajeswari Vedachalam Government Arts College, Chengalpet 603 001, India, and ^cDepartment of Physics, The New College (Autonomous), Chennai 600 014, India
^*Correspondence e-mail: drkrr2007@gmail.com, mnizam_new@yahoo.in

(Received 24 June 2013; accepted 16 July 2013; online 24 July 2013)

The title compound, (NH₄)₂[Zn(NCS)₄]·2C₁₂H₂₄O₆·H₂O, the result of the reaction of ammonium thiocyanate, 18-crown-6 and zinc(II) chloride in aqueous solution, exhibits an unusual supramolecular structure. The Zn atom, two of the thiocyanate chains and a water molecule, disordered over two positions, lie on a mirror plane. The macrocycle adopts a conformation with approximate D_3d symmetry. The ammonium molecules are contained within the bowl of the macrocycle via extensive N—H⋯O hydrogen bonds and the complex molecules are linked via N—H⋯S hydrogen bonds, forming chains along the c-axis direction. The macrocycle is disordered over two positions [refined occupancy ratio = 0.666 (8):0.334 (8)]. The S atoms of two isothiocyanate ligands are disordered within and about the mirror plane.

Related literature

For background to crown ether/ammonium ion complexes, see: Fender et al. (2002 ); Kryatova et al. (2004 ); Akutagawa et al. (2002 ); Ramesh et al. (2012 ).

Experimental

Crystal data

(NH₄)₂[Zn(NCS)₄]·2C₁₂H₂₄O₆·H₂O
M_r = 880.41
Orthorhombic, P n m a
a = 22.7875 (12) Å
b = 23.6254 (12) Å
c = 8.5593 (5) Å
V = 4608.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.802, T_max = 0.861
24101 measured reflections
4641 independent reflections
2467 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.175
S = 1.00
4641 reflections
454 parameters
276 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4H⋯O1	0.88 (1)	2.44 (4)	3.069 (8)	129 (4)
N4—H4E⋯O2	0.87 (1)	2.06 (1)	2.934 (8)	176 (5)
N4—H4G⋯O4	0.88 (1)	1.97 (2)	2.829 (7)	166 (4)
N4—H4G⋯O5	0.88 (1)	2.53 (4)	3.010 (8)	115 (3)
N4—H4H⋯O6	0.88 (1)	2.05 (3)	2.850 (8)	150 (5)
N4—H4F⋯S1ⁱ	0.87 (1)	2.63 (2)	3.441 (4)	156 (4)
Symmetry code: (i) x, y, z-1.

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: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019739/su2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019739/su2617Isup2.hkl

checkCIF report

Comment top

There is currently significant interest in crown ethers because of their ability to form non-covalent, hydrogen bonding complexes with ammonium cations both in the solid state and in solution (Fender et al., 2002; Kryatova et al., 2004; Akutagawa et al., 2002). Recently, the crystal structure of catena-Poly[ammonium(cadmium-tri-lthiocyanato κ⁴S:N; κ²N:S) -1,4,10,13,16- hexaoxacyclooctadecane (1/1)] (I), obtained in our laboratory, has been reported (Ramesh et al., 2012). In continuation of our studies of compounds containing 18-crown-6 macrocycles and ammonium cations NH₄⁺, we describe herein the crystal structure of the title compound (II), which is isostructural with (I).

The reaction of ammonium thiocyanate, 18-crown-6 and Zinc (II) chloride in aqueous solution yields the title compound, Fig. 1. All bond lengths and angles are normal and correspond to those reported for (I) (Ramesh et al., 2012). The C—S [average value of 1.658 (2) Å] and C—N [average value of 1.116 (2) Å] bond lengths indicate the presence of double-bond character. The zinc atom, Zn1, two of the thiocyanate chains [N2—C2—S2 and N3—C3—S3; symmetry code: x, -y + 1/2, z] and the water molecule lie in a mirror plane, except one of the disordered component sulfur atoms, which is inclined at quite an angle to the ac plane. The thiocyanate (N1—C1—S1 = 178.2 (4) °) ligands are almost linear.

The macrocycle adopts a conformation with approximate D_3d symmetry, with all O—C—C—O torsion angles being gauche and alternating in sign, and all C—O—C—C torsion angles being anti.

The sulfur atoms (S2 and S3) of the thiocyanate chains are disordered with large displacement parameters for the S atoms and short C—S bond lengths. The disorder over two positions was modelled and the site occupancies refined to 0.39 (9) and 0.61 (9) for atom S2 and 0.376 (9) and 0.248 (18) for atom S3. The entire crown either molecule is disordered, as detectable from the large displacement parameters for C and O atoms and short C—C and C—O bond lengths. The disorder over two positions was modelled and the site occupancies refined to 0.666 (9) and 0.334 (9) for carbon and oxygen atoms. The water molecule is disordered, as detectable from the large displacement parameters for the O atoms. The disorder over two positions was modelled and the site occupancies refined to 0.425 (15) and 0.575 (15). for carbon and oxygen atoms. The geometry was regularized by soft restraints.

The ammonium cations are contained within the bowl of the macrocycle via extensive N—H···O hydrogen bonding. The N—H···O [2.830 (7) to 3.074 (7) Å] and N—H···S [3.442 (4) Å] hydrogen bond lengths are within the usual range (Table 1 and Fig. 2).

In the crystal, the complex molecules are linked via N—H···S hydrogen bonds forming chains along the c axis (Table 1 and Fig. 2).

Related literature top

For background to crown ether/ammonium ion complexes, see: Fender et al. (2002); Kryatova et al. (2004); Akutagawa et al. (2002); Ramesh et al. (2012).

Experimental top

A mixture of 18-crown-6, ammonium thiocyanate and Zinc (II) chloride were dissolved in an aqueous solution in the molar ratio 2:4:1 and thoroughly mixed for two hours to obtain a homogeneous mixture. The solution was allowed to evaporate slowly at ambient temperature. Colourless single crystals suitable for single-crystal X-ray diffraction analysis were obtained in a week.

Computing details top

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Crystal structure of the title compound with atom labelling. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (a) x, -y+1/2, z; the disordered fraction is shown with dashed bonds and atom labels with prefix '].
	Fig. 2. A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

Diammonium tetrakis(isothiocyanato)zincate–1,4,10,13,16-hexaoxacyclooctadecane–water (1/2/1) top

Crystal data top

(NH₄)₂[Zn(NCS)₄]·2C₁₂H₂₄O₆·H₂O	F(000) = 1864
M_r = 880.41	D_x = 1.269 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5119 reflections
a = 22.7875 (12) Å	θ = 2.6–26.7°
b = 23.6254 (12) Å	µ = 0.77 mm⁻¹
c = 8.5593 (5) Å	T = 293 K
V = 4608.0 (4) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4641 independent reflections
Radiation source: fine-focus sealed tube	2467 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω and ϕ scan	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −24→28
T_min = 0.802, T_max = 0.861	k = −19→29
24101 measured reflections	l = −10→9

Refinement top

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0932P)² + 0.2607P] where P = (F_o² + 2F_c²)/3
4641 reflections	(Δ/σ)_max = 0.001
454 parameters	Δρ_max = 0.72 e Å⁻³
276 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

(NH₄)₂[Zn(NCS)₄]·2C₁₂H₂₄O₆·H₂O	V = 4608.0 (4) Å³
M_r = 880.41	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 22.7875 (12) Å	µ = 0.77 mm⁻¹
b = 23.6254 (12) Å	T = 293 K
c = 8.5593 (5) Å	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4641 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2467 reflections with I > 2σ(I)
T_min = 0.802, T_max = 0.861	R_int = 0.058
24101 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	276 restraints
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.72 e Å⁻³
4641 reflections	Δρ_min = −0.24 e Å⁻³
454 parameters

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	U_iso*/U_eq	Occ. (<1)
C1	0.51074 (15)	0.13492 (16)	0.9699 (5)	0.0534 (10)
C2	0.6728 (3)	0.2500	0.7518 (7)	0.0668 (16)
C3	0.4978 (4)	0.2500	0.4932 (11)	0.094 (2)
O1	0.6093 (3)	0.0412 (3)	0.5640 (8)	0.086 (2)	0.666 (8)
O2	0.6025 (4)	−0.0710 (3)	0.4650 (8)	0.082 (2)	0.666 (8)
O3	0.6681 (3)	−0.1007 (3)	0.1940 (9)	0.079 (2)	0.666 (8)
O4	0.6950 (3)	−0.0163 (3)	−0.0249 (8)	0.0798 (19)	0.666 (8)
O5	0.6998 (3)	0.0974 (4)	0.0798 (7)	0.083 (2)	0.666 (8)
O6	0.6318 (3)	0.1232 (3)	0.3415 (9)	0.092 (2)	0.666 (8)
C4	0.6209 (4)	0.1375 (4)	0.4993 (11)	0.103 (3)	0.666 (8)
H4A	0.6025	0.1744	0.5053	0.124*	0.666 (8)
H4B	0.6576	0.1388	0.5567	0.124*	0.666 (8)
C5	0.5811 (4)	0.0935 (4)	0.5696 (12)	0.106 (3)	0.666 (8)
H5A	0.5721	0.1034	0.6770	0.127*	0.666 (8)
H5B	0.5446	0.0918	0.5115	0.127*	0.666 (8)
C6	0.5761 (5)	0.0013 (5)	0.6449 (14)	0.097 (4)	0.666 (8)
H6A	0.5363	0.0007	0.6046	0.116*	0.666 (8)
H6B	0.5745	0.0110	0.7549	0.116*	0.666 (8)
C7	0.6040 (4)	−0.0556 (5)	0.6243 (9)	0.102 (3)	0.666 (8)
H7A	0.6443	−0.0544	0.6603	0.122*	0.666 (8)
H7B	0.5831	−0.0835	0.6859	0.122*	0.666 (8)
C8	0.6256 (5)	−0.1260 (4)	0.4391 (12)	0.103 (3)	0.666 (8)
H8A	0.6009	−0.1539	0.4898	0.123*	0.666 (8)
H8B	0.6646	−0.1286	0.4840	0.123*	0.666 (8)
C9	0.6284 (4)	−0.1378 (4)	0.2670 (12)	0.094 (3)	0.666 (8)
H9A	0.6407	−0.1766	0.2500	0.113*	0.666 (8)
H9B	0.5897	−0.1331	0.2214	0.113*	0.666 (8)
C10	0.6751 (5)	−0.1127 (5)	0.0337 (12)	0.093 (4)	0.666 (8)
H10A	0.6377	−0.1093	−0.0199	0.111*	0.666 (8)
H10B	0.6895	−0.1510	0.0198	0.111*	0.666 (8)
C11	0.7185 (4)	−0.0709 (4)	−0.0321 (10)	0.091 (3)	0.666 (8)
H11A	0.7547	−0.0724	0.0273	0.109*	0.666 (8)
H11B	0.7273	−0.0805	−0.1397	0.109*	0.666 (8)
C12	0.7343 (5)	0.0238 (5)	−0.0886 (15)	0.094 (4)	0.666 (8)
H12A	0.7426	0.0148	−0.1969	0.113*	0.666 (8)
H12B	0.7709	0.0237	−0.0308	0.113*	0.666 (8)
C13	0.7052 (4)	0.0806 (5)	−0.0767 (10)	0.098 (3)	0.666 (8)
H13A	0.7282	0.1084	−0.1333	0.118*	0.666 (8)
H13B	0.6666	0.0788	−0.1241	0.118*	0.666 (8)
C14	0.6687 (5)	0.1489 (5)	0.0924 (14)	0.107 (4)	0.666 (8)
H14A	0.6296	0.1447	0.0488	0.129*	0.666 (8)
H14B	0.6889	0.1785	0.0351	0.129*	0.666 (8)
C15	0.6647 (5)	0.1645 (4)	0.2617 (13)	0.107 (3)	0.666 (8)
H15A	0.7038	0.1669	0.3062	0.128*	0.666 (8)
H15B	0.6460	0.2012	0.2726	0.128*	0.666 (8)
O1'	0.6101 (6)	0.0748 (7)	0.5055 (18)	0.095 (4)	0.334 (8)
O2'	0.5880 (8)	−0.0418 (7)	0.489 (2)	0.094 (4)	0.334 (8)
O3'	0.6481 (6)	−0.1061 (6)	0.2641 (16)	0.073 (4)	0.334 (8)
O4'	0.6913 (5)	−0.0500 (6)	0.0013 (14)	0.062 (3)	0.334 (8)
O5'	0.7128 (6)	0.0659 (6)	0.0284 (19)	0.082 (4)	0.334 (8)
O6'	0.6437 (7)	0.1284 (6)	0.2342 (19)	0.103 (5)	0.334 (8)
C4'	0.6350 (10)	0.1591 (9)	0.373 (2)	0.115 (6)	0.334 (8)
H4'1	0.6223	0.1974	0.3495	0.138*	0.334 (8)
H4'2	0.6714	0.1613	0.4319	0.138*	0.334 (8)
C5'	0.5891 (10)	0.1293 (8)	0.468 (3)	0.118 (7)	0.334 (8)
H5'1	0.5809	0.1504	0.5623	0.142*	0.334 (8)
H5'2	0.5531	0.1263	0.4079	0.142*	0.334 (8)
C6'	0.5720 (9)	0.0449 (9)	0.604 (2)	0.103 (6)	0.334 (8)
H6'1	0.5334	0.0432	0.5563	0.124*	0.334 (8)
H6'2	0.5683	0.0649	0.7024	0.124*	0.334 (8)
C7'	0.5935 (12)	−0.0141 (10)	0.634 (2)	0.098 (7)	0.334 (8)
H7'1	0.6340	−0.0137	0.6686	0.118*	0.334 (8)
H7'2	0.5697	−0.0326	0.7132	0.118*	0.334 (8)
C8'	0.6053 (10)	−0.0980 (7)	0.513 (2)	0.094 (6)	0.334 (8)
H8'1	0.5787	−0.1159	0.5865	0.113*	0.334 (8)
H8'2	0.6444	−0.0987	0.5586	0.113*	0.334 (8)
C9'	0.6055 (9)	−0.1305 (8)	0.363 (2)	0.093 (6)	0.334 (8)
H9'1	0.6148	−0.1699	0.3822	0.112*	0.334 (8)
H9'2	0.5671	−0.1285	0.3139	0.112*	0.334 (8)
C10'	0.6499 (6)	−0.1330 (6)	0.1179 (19)	0.071 (4)	0.334 (8)
H10C	0.6134	−0.1267	0.0621	0.085*	0.334 (8)
H10D	0.6553	−0.1735	0.1312	0.085*	0.334 (8)
C11'	0.7003 (6)	−0.1085 (6)	0.028 (3)	0.058 (4)	0.334 (8)
H11C	0.7365	−0.1139	0.0858	0.070*	0.334 (8)
H11D	0.7041	−0.1279	−0.0716	0.070*	0.334 (8)
C12'	0.7390 (6)	−0.0224 (7)	−0.0687 (18)	0.080 (4)	0.334 (8)
H12C	0.7514	−0.0431	−0.1608	0.096*	0.334 (8)
H12D	0.7717	−0.0209	0.0038	0.096*	0.334 (8)
C13'	0.7211 (12)	0.0367 (9)	−0.114 (2)	0.082 (6)	0.334 (8)
H13C	0.7515	0.0547	−0.1755	0.098*	0.334 (8)
H13D	0.6850	0.0362	−0.1738	0.098*	0.334 (8)
C14'	0.6902 (10)	0.1195 (6)	−0.007 (3)	0.105 (6)	0.334 (8)
H14C	0.6521	0.1152	−0.0563	0.125*	0.334 (8)
H14D	0.7160	0.1382	−0.0809	0.125*	0.334 (8)
C15'	0.6838 (11)	0.1560 (10)	0.135 (3)	0.105 (7)	0.334 (8)
H15C	0.7213	0.1605	0.1871	0.127*	0.334 (8)
H15D	0.6692	0.1932	0.1067	0.127*	0.334 (8)
N1	0.52011 (15)	0.18067 (14)	0.9297 (4)	0.0703 (10)
N2	0.6247 (3)	0.2500	0.7865 (7)	0.0768 (16)
N3	0.5010 (3)	0.2500	0.6166 (7)	0.0796 (16)
N4	0.61488 (17)	0.01292 (18)	0.2144 (5)	0.0594 (9)
S1	0.49673 (5)	0.07035 (4)	1.02060 (15)	0.0704 (4)
S2	0.7443 (4)	0.2500	0.740 (7)	0.100 (6)	0.39 (9)
S2A	0.7397 (6)	0.2500	0.684 (5)	0.098 (5)	0.61 (9)
S3	0.5017 (4)	0.2703 (4)	0.3036 (5)	0.138 (3)	0.376 (9)
S3A	0.4660 (14)	0.2500	0.3119 (17)	0.161 (7)	0.248 (18)
Zn1	0.54016 (3)	0.2500	0.82110 (8)	0.0587 (3)
O1W	0.3179 (18)	0.2500	0.361 (5)	0.328 (15)	0.425 (15)
O2W	0.3443 (14)	0.2500	0.199 (3)	0.328 (15)	0.575 (15)
H1W	0.31 (2)	0.2500	0.258 (11)	0.492*	0.425 (15)
H2W	0.289 (15)	0.2500	0.43 (4)	0.492*	0.425 (15)
H3W	0.327 (15)	0.2500	0.29 (2)	0.492*	0.575 (15)
H4W	0.384 (3)	0.2500	0.19 (5)	0.492*	0.575 (15)
H4E	0.609 (2)	−0.0122 (17)	0.288 (4)	0.11 (2)*
H4F	0.5826 (12)	0.016 (2)	0.160 (5)	0.099 (18)*
H4G	0.6438 (14)	0.0081 (19)	0.148 (4)	0.097 (17)*
H4H	0.624 (2)	0.0393 (16)	0.282 (5)	0.11 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.048 (2)	0.053 (2)	0.059 (3)	0.0033 (18)	0.0027 (18)	0.004 (2)
C2	0.089 (5)	0.043 (3)	0.069 (4)	0.000	0.003 (4)	0.000
C3	0.110 (6)	0.090 (5)	0.083 (6)	0.000	−0.001 (5)	0.000
O1	0.080 (4)	0.112 (5)	0.067 (4)	0.007 (4)	0.016 (3)	−0.017 (4)
O2	0.097 (5)	0.083 (5)	0.065 (4)	−0.013 (4)	−0.009 (3)	0.026 (4)
O3	0.085 (5)	0.073 (4)	0.081 (5)	0.002 (3)	−0.018 (4)	−0.011 (4)
O4	0.061 (4)	0.113 (5)	0.065 (4)	0.007 (4)	0.013 (3)	−0.003 (4)
O5	0.082 (4)	0.087 (5)	0.080 (5)	−0.003 (4)	−0.014 (3)	0.031 (4)
O6	0.110 (4)	0.070 (4)	0.097 (6)	0.012 (3)	−0.008 (4)	−0.008 (4)
C4	0.108 (7)	0.098 (7)	0.102 (7)	0.038 (6)	−0.010 (6)	−0.047 (6)
C5	0.094 (6)	0.137 (8)	0.086 (7)	0.031 (7)	0.011 (5)	−0.042 (7)
C6	0.096 (8)	0.139 (10)	0.056 (6)	−0.014 (7)	0.023 (5)	−0.013 (6)
C7	0.114 (6)	0.133 (8)	0.059 (6)	−0.031 (6)	0.004 (5)	0.023 (6)
C8	0.120 (8)	0.084 (6)	0.105 (8)	−0.019 (6)	−0.026 (6)	0.030 (6)
C9	0.105 (7)	0.057 (5)	0.119 (9)	0.002 (5)	−0.032 (6)	−0.006 (6)
C10	0.092 (9)	0.089 (7)	0.097 (7)	0.030 (6)	−0.022 (7)	−0.033 (6)
C11	0.078 (6)	0.131 (9)	0.063 (5)	0.038 (7)	0.002 (5)	−0.034 (6)
C12	0.061 (6)	0.155 (10)	0.068 (7)	−0.007 (6)	0.017 (5)	0.000 (8)
C13	0.085 (6)	0.138 (9)	0.072 (6)	−0.023 (6)	0.007 (5)	0.022 (7)
C14	0.122 (7)	0.075 (7)	0.124 (9)	−0.010 (6)	−0.040 (7)	0.036 (7)
C15	0.129 (7)	0.058 (5)	0.133 (9)	0.009 (5)	−0.017 (7)	0.012 (6)
O1'	0.087 (7)	0.101 (10)	0.097 (10)	0.023 (8)	0.017 (7)	−0.039 (8)
O2'	0.098 (9)	0.108 (11)	0.075 (8)	−0.022 (8)	−0.004 (7)	0.019 (8)
O3'	0.072 (8)	0.053 (6)	0.094 (10)	−0.012 (6)	−0.007 (6)	0.004 (7)
O4'	0.047 (6)	0.076 (8)	0.063 (7)	0.009 (6)	0.018 (5)	−0.014 (7)
O5'	0.086 (8)	0.095 (9)	0.066 (8)	−0.023 (7)	−0.022 (7)	0.027 (8)
O6'	0.123 (10)	0.056 (7)	0.129 (14)	0.007 (6)	−0.046 (9)	−0.009 (8)
C4'	0.141 (13)	0.061 (10)	0.143 (16)	0.026 (10)	−0.024 (12)	−0.034 (11)
C5'	0.112 (12)	0.095 (11)	0.147 (15)	0.034 (11)	−0.015 (12)	−0.051 (11)
C6'	0.106 (12)	0.123 (14)	0.081 (11)	−0.001 (12)	0.026 (10)	−0.014 (11)
C7'	0.102 (13)	0.123 (14)	0.070 (12)	−0.014 (12)	0.020 (10)	0.002 (12)
C8'	0.104 (11)	0.094 (12)	0.084 (12)	−0.036 (10)	0.006 (10)	0.031 (10)
C9'	0.113 (12)	0.075 (10)	0.091 (13)	−0.040 (9)	−0.017 (10)	0.024 (10)
C10'	0.063 (8)	0.051 (7)	0.099 (11)	0.007 (6)	−0.011 (8)	−0.016 (8)
C11'	0.044 (9)	0.058 (8)	0.074 (9)	0.003 (7)	−0.007 (7)	−0.024 (7)
C12'	0.087 (10)	0.102 (11)	0.052 (9)	−0.019 (9)	0.017 (7)	−0.023 (9)
C13'	0.083 (12)	0.114 (13)	0.049 (10)	−0.023 (11)	0.004 (9)	0.022 (9)
C14'	0.124 (12)	0.084 (11)	0.106 (13)	−0.024 (10)	−0.035 (11)	0.035 (11)
C15'	0.140 (13)	0.057 (9)	0.120 (16)	−0.020 (10)	−0.046 (12)	0.011 (10)
N1	0.087 (2)	0.0477 (19)	0.076 (3)	−0.0038 (17)	0.0057 (19)	0.0091 (19)
N2	0.069 (3)	0.063 (3)	0.099 (5)	0.000	0.015 (3)	0.000
N3	0.110 (5)	0.068 (3)	0.060 (4)	0.000	0.009 (4)	0.000
N4	0.061 (3)	0.067 (2)	0.051 (3)	0.007 (2)	−0.001 (2)	−0.002 (2)
S1	0.0688 (7)	0.0521 (6)	0.0903 (9)	−0.0072 (5)	−0.0075 (6)	0.0253 (6)
S2	0.080 (5)	0.099 (5)	0.121 (17)	0.000	0.029 (5)	0.000
S2A	0.070 (3)	0.104 (3)	0.121 (12)	0.000	0.025 (4)	0.000
S3	0.149 (6)	0.198 (9)	0.067 (3)	−0.007 (4)	−0.005 (3)	0.016 (3)
S3A	0.234 (17)	0.175 (14)	0.076 (7)	0.000	0.019 (11)	0.000
Zn1	0.0725 (5)	0.0362 (3)	0.0674 (5)	0.000	0.0085 (4)	0.000
O1W	0.39 (3)	0.34 (2)	0.25 (3)	0.000	−0.20 (3)	0.000
O2W	0.39 (3)	0.34 (2)	0.25 (3)	0.000	−0.20 (3)	0.000

Geometric parameters (Å, º) top

C1—N1	1.154 (4)	O2'—C7'	1.410 (10)
C1—S1	1.618 (4)	O3'—C10'	1.405 (10)
C2—N2	1.136 (7)	O3'—C9'	1.410 (10)
C2—S2A	1.631 (9)	O4'—C12'	1.403 (9)
C2—S2	1.632 (10)	O4'—C11'	1.414 (10)
C3—N3	1.058 (8)	O5'—C14'	1.403 (10)
C3—S3ⁱ	1.695 (10)	O5'—C13'	1.409 (10)
C3—S3	1.695 (10)	O6'—C15'	1.406 (10)
C3—S3A	1.714 (12)	O6'—C4'	1.409 (10)
O1—C6	1.393 (9)	C4'—C5'	1.497 (10)
O1—C5	1.394 (8)	C4'—H4'1	0.9700
O2—C7	1.411 (8)	C4'—H4'2	0.9700
O2—C8	1.420 (8)	C5'—H5'1	0.9700
O3—C9	1.406 (8)	C5'—H5'2	0.9700
O3—C10	1.410 (8)	C6'—C7'	1.501 (10)
O4—C11	1.398 (7)	C6'—H6'1	0.9700
O4—C12	1.411 (9)	C6'—H6'2	0.9700
O5—C13	1.402 (8)	C7'—H7'1	0.9700
O5—C14	1.413 (9)	C7'—H7'2	0.9700
O6—C15	1.407 (8)	C8'—C9'	1.500 (10)
O6—C4	1.414 (8)	C8'—H8'1	0.9700
C4—C5	1.504 (8)	C8'—H8'2	0.9700
C4—H4A	0.9700	C9'—H9'1	0.9700
C4—H4B	0.9700	C9'—H9'2	0.9700
C5—H5A	0.9700	C10'—C11'	1.500 (10)
C5—H5B	0.9700	C10'—H10C	0.9700
C6—C7	1.499 (9)	C10'—H10D	0.9700
C6—H6A	0.9700	C11'—H11C	0.9700
C6—H6B	0.9700	C11'—H11D	0.9700
C7—H7A	0.9700	C12'—C13'	1.506 (10)
C7—H7B	0.9700	C12'—H12C	0.9700
C8—C9	1.501 (8)	C12'—H12D	0.9700
C8—H8A	0.9700	C13'—H13C	0.9700
C8—H8B	0.9700	C13'—H13D	0.9700
C9—H9A	0.9700	C14'—C15'	1.499 (10)
C9—H9B	0.9700	C14'—H14C	0.9700
C10—C11	1.507 (8)	C14'—H14D	0.9700
C10—H10A	0.9700	C15'—H15C	0.9700
C10—H10B	0.9700	C15'—H15D	0.9700
C11—H11A	0.9700	N1—Zn1	1.938 (3)
C11—H11B	0.9700	N2—Zn1	1.948 (6)
C12—C13	1.501 (8)	N3—Zn1	1.964 (7)
C12—H12A	0.9700	N4—H4E	0.873 (10)
C12—H12B	0.9700	N4—H4F	0.874 (10)
C13—H13A	0.9700	N4—H4G	0.878 (10)
C13—H13B	0.9700	N4—H4H	0.878 (10)
C14—C15	1.497 (9)	S3—S3ⁱ	0.957 (17)
C14—H14A	0.9700	Zn1—N1ⁱ	1.938 (3)
C14—H14B	0.9700	O1W—H1W	0.900 (11)
C15—H15A	0.9700	O1W—H2W	0.899 (10)
C15—H15B	0.9700	O1W—H3W	0.61 (7)
O1'—C6'	1.401 (10)	O2W—H1W	0.9 (5)
O1'—C5'	1.411 (10)	O2W—H3W	0.900 (10)
O2'—C8'	1.401 (10)	O2W—H4W	0.898 (11)

N1—C1—S1	178.1 (4)	O6'—C4'—H4'1	110.1
N2—C2—S2A	174.3 (16)	C5'—C4'—H4'1	110.1
N2—C2—S2	168 (2)	O6'—C4'—H4'2	110.1
N3—C3—S3ⁱ	162.2 (5)	C5'—C4'—H4'2	110.1
N3—C3—S3	162.2 (5)	H4'1—C4'—H4'2	108.4
N3—C3—S3A	158.9 (13)	O1'—C5'—C4'	108.5 (17)
C6—O1—C5	109.4 (8)	O1'—C5'—H5'1	110.0
C7—O2—C8	112.2 (8)	C4'—C5'—H5'1	110.0
C9—O3—C10	112.3 (7)	O1'—C5'—H5'2	110.0
C11—O4—C12	111.0 (8)	C4'—C5'—H5'2	110.0
C13—O5—C14	111.2 (9)	H5'1—C5'—H5'2	108.4
C15—O6—C4	113.1 (9)	O1'—C6'—C7'	112 (2)
O6—C4—C5	108.9 (7)	O1'—C6'—H6'1	109.3
O6—C4—H4A	109.9	C7'—C6'—H6'1	109.3
C5—C4—H4A	109.9	O1'—C6'—H6'2	109.3
O6—C4—H4B	109.9	C7'—C6'—H6'2	109.3
C5—C4—H4B	109.9	H6'1—C6'—H6'2	108.0
H4A—C4—H4B	108.3	O2'—C7'—C6'	104.5 (18)
O1—C5—C4	108.7 (9)	O2'—C7'—H7'1	110.8
O1—C5—H5A	110.0	C6'—C7'—H7'1	110.8
C4—C5—H5A	110.0	O2'—C7'—H7'2	110.8
O1—C5—H5B	110.0	C6'—C7'—H7'2	110.8
C4—C5—H5B	110.0	H7'1—C7'—H7'2	108.9
H5A—C5—H5B	108.3	O2'—C8'—C9'	110.9 (17)
O1—C6—C7	108.6 (8)	O2'—C8'—H8'1	109.5
O1—C6—H6A	110.0	C9'—C8'—H8'1	109.5
C7—C6—H6A	110.0	O2'—C8'—H8'2	109.5
O1—C6—H6B	110.0	C9'—C8'—H8'2	109.5
C7—C6—H6B	110.0	H8'1—C8'—H8'2	108.0
H6A—C6—H6B	108.4	O3'—C9'—C8'	107.9 (14)
O2—C7—C6	109.5 (9)	O3'—C9'—H9'1	110.1
O2—C7—H7A	109.8	C8'—C9'—H9'1	110.1
C6—C7—H7A	109.8	O3'—C9'—H9'2	110.1
O2—C7—H7B	109.8	C8'—C9'—H9'2	110.1
C6—C7—H7B	109.8	H9'1—C9'—H9'2	108.4
H7A—C7—H7B	108.2	O3'—C10'—C11'	107.8 (15)
O2—C8—C9	109.8 (7)	O3'—C10'—H10C	110.1
O2—C8—H8A	109.7	C11'—C10'—H10C	110.1
C9—C8—H8A	109.7	O3'—C10'—H10D	110.1
O2—C8—H8B	109.7	C11'—C10'—H10D	110.1
C9—C8—H8B	109.7	H10C—C10'—H10D	108.5
H8A—C8—H8B	108.2	O4'—C11'—C10'	110.3 (12)
O3—C9—C8	110.4 (8)	O4'—C11'—H11C	109.6
O3—C9—H9A	109.6	C10'—C11'—H11C	109.6
C8—C9—H9A	109.6	O4'—C11'—H11D	109.6
O3—C9—H9B	109.6	C10'—C11'—H11D	109.6
C8—C9—H9B	109.6	H11C—C11'—H11D	108.1
H9A—C9—H9B	108.1	O4'—C12'—C13'	109.3 (18)
O3—C10—C11	107.8 (8)	O4'—C12'—H12C	109.8
O3—C10—H10A	110.2	C13'—C12'—H12C	109.8
C11—C10—H10A	110.2	O4'—C12'—H12D	109.8
O3—C10—H10B	110.2	C13'—C12'—H12D	109.8
C11—C10—H10B	110.2	H12C—C12'—H12D	108.3
H10A—C10—H10B	108.5	O5'—C13'—C12'	105.6 (15)
O4—C11—C10	109.8 (9)	O5'—C13'—H13C	110.6
O4—C11—H11A	109.7	C12'—C13'—H13C	110.6
C10—C11—H11A	109.7	O5'—C13'—H13D	110.6
O4—C11—H11B	109.7	C12'—C13'—H13D	110.6
C10—C11—H11B	109.7	H13C—C13'—H13D	108.8
H11A—C11—H11B	108.2	O5'—C14'—C15'	112 (2)
O4—C12—C13	107.1 (9)	O5'—C14'—H14C	109.1
O4—C12—H12A	110.3	C15'—C14'—H14C	109.1
C13—C12—H12A	110.3	O5'—C14'—H14D	109.1
O4—C12—H12B	110.3	C15'—C14'—H14D	109.1
C13—C12—H12B	110.3	H14C—C14'—H14D	107.9
H12A—C12—H12B	108.6	O6'—C15'—C14'	106.6 (19)
O5—C13—C12	110.9 (11)	O6'—C15'—H15C	110.4
O5—C13—H13A	109.5	C14'—C15'—H15C	110.4
C12—C13—H13A	109.5	O6'—C15'—H15D	110.4
O5—C13—H13B	109.5	C14'—C15'—H15D	110.4
C12—C13—H13B	109.5	H15C—C15'—H15D	108.6
H13A—C13—H13B	108.0	C1—N1—Zn1	168.0 (4)
O5—C14—C15	108.4 (9)	C2—N2—Zn1	173.6 (6)
O5—C14—H14A	110.0	C3—N3—Zn1	157.0 (7)
C15—C14—H14A	110.0	H4E—N4—H4F	109 (5)
O5—C14—H14B	110.0	H4E—N4—H4G	119 (5)
C15—C14—H14B	110.0	H4F—N4—H4G	107 (5)
H14A—C14—H14B	108.4	H4E—N4—H4H	92 (5)
O6—C15—C14	109.4 (11)	H4F—N4—H4H	120 (5)
O6—C15—H15A	109.8	H4G—N4—H4H	110 (5)
C14—C15—H15A	109.8	S3ⁱ—S3—C3	73.6 (3)
O6—C15—H15B	109.8	N1—Zn1—N1ⁱ	115.4 (2)
C14—C15—H15B	109.8	N1—Zn1—N2	107.82 (13)
H15A—C15—H15B	108.2	N1ⁱ—Zn1—N2	107.82 (13)
C6'—O1'—C5'	112.8 (17)	N1—Zn1—N3	108.70 (13)
C8'—O2'—C7'	106.5 (15)	N1ⁱ—Zn1—N3	108.70 (13)
C10'—O3'—C9'	111.7 (14)	N2—Zn1—N3	108.2 (2)
C12'—O4'—C11'	114.2 (14)	H1W—O1W—H2W	120 (2)
C14'—O5'—C13'	107.7 (17)	H2W—O1W—H3W	152 (10)
C15'—O6'—C4'	111.2 (18)	H1W—O2W—H4W	152 (10)
O6'—C4'—C5'	108 (2)	H3W—O2W—H4W	121 (2)

C15—O6—C4—C5	174.9 (8)	O1'—C6'—C7'—O2'	−68 (3)
C6—O1—C5—C4	173.1 (8)	C7'—O2'—C8'—C9'	−175.8 (18)
O6—C4—C5—O1	61.5 (10)	C10'—O3'—C9'—C8'	−178.1 (15)
C5—O1—C6—C7	174.5 (8)	O2'—C8'—C9'—O3'	64 (2)
C8—O2—C7—C6	−176.9 (8)	C9'—O3'—C10'—C11'	−174.2 (15)
O1—C6—C7—O2	−63.5 (11)	C12'—O4'—C11'—C10'	174.0 (14)
C7—O2—C8—C9	−174.4 (8)	O3'—C10'—C11'—O4'	−62.7 (18)
C10—O3—C9—C8	176.1 (8)	C11'—O4'—C12'—C13'	171.2 (15)
O2—C8—C9—O3	64.5 (10)	C14'—O5'—C13'—C12'	−174.0 (16)
C9—O3—C10—C11	−179.8 (8)	O4'—C12'—C13'—O5'	68 (2)
C12—O4—C11—C10	−178.8 (9)	C13'—O5'—C14'—C15'	−175.8 (19)
O3—C10—C11—O4	−65.3 (10)	C4'—O6'—C15'—C14'	179.3 (18)
C11—O4—C12—C13	179.6 (8)	O5'—C14'—C15'—O6'	−62 (2)
C14—O5—C13—C12	−175.7 (9)	S3ⁱ—C3—N3—Zn1	67 (3)
O4—C12—C13—O5	67.7 (11)	S3—C3—N3—Zn1	−67 (3)
C13—O5—C14—C15	−179.8 (8)	S3A—C3—N3—Zn1	180.0
C4—O6—C15—C14	−174.1 (8)	N3—C3—S3—S3ⁱ	156 (3)
O5—C14—C15—O6	−63.7 (11)	S3A—C3—S3—S3ⁱ	−62.2 (12)
C15'—O6'—C4'—C5'	176.4 (18)	C1—N1—Zn1—N1ⁱ	170.5 (15)
C6'—O1'—C5'—C4'	175.5 (17)	C1—N1—Zn1—N2	−69.0 (17)
O6'—C4'—C5'—O1'	62 (2)	C1—N1—Zn1—N3	48.1 (17)
C5'—O1'—C6'—C7'	176.4 (18)	C3—N3—Zn1—N1	−116.85 (12)
C8'—O2'—C7'—C6'	−177.5 (18)	C3—N3—Zn1—N1ⁱ	116.85 (12)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4H···O1	0.88 (1)	2.44 (4)	3.069 (8)	129 (4)
N4—H4E···O2	0.87 (1)	2.06 (1)	2.934 (8)	176 (5)
N4—H4G···O4	0.88 (1)	1.97 (2)	2.829 (7)	166 (4)
N4—H4G···O5	0.88 (1)	2.53 (4)	3.010 (8)	115 (3)
N4—H4H···O6	0.88 (1)	2.05 (3)	2.850 (8)	150 (5)
N4—H4F···S1ⁱⁱ	0.87 (1)	2.63 (2)	3.441 (4)	156 (4)

Symmetry code: (ii) x, y, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4H···O1	0.878 (10)	2.44 (4)	3.069 (8)	129 (4)
N4—H4E···O2	0.873 (10)	2.062 (14)	2.934 (8)	176 (5)
N4—H4G···O4	0.878 (10)	1.971 (17)	2.829 (7)	166 (4)
N4—H4G···O5	0.878 (10)	2.53 (4)	3.010 (8)	115 (3)
N4—H4H···O6	0.878 (10)	2.05 (3)	2.850 (8)	150 (5)
N4—H4F···S1ⁱ	0.874 (10)	2.63 (2)	3.441 (4)	156 (4)

Symmetry code: (i) x, y, z−1.

Acknowledgements

The authors are thankful to the SAIF, IIT Madras, for the data collection. KR thanks the University Grants Commission, Government of India, for financial support granted under a Major Research Project [F. No.41–1008/2012 (SR)].

References

Akutagawa, T., Hashimoto, A., Nishihara, S., Hasegawa, T. & Nakamura, T. (2002). J. Supramol. Chem. 2, 175–186. CSD CrossRef CAS Google Scholar
Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fender, N. S., Kahwa, I. A. & Fronczek, F. R. (2002). J. Solid State Chem. 163, 286–293. Web of Science CSD CrossRef CAS Google Scholar
Kryatova, O. P., Korendovych, I. V. & Rybak-Akimova, E. V. (2004). Tetrahedron, 60, 4579–4588. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ramesh, V., Rajarajan, K., Kumar, K. S., Subashini, A. & NizamMohideen, M. (2012). Acta Cryst. E68, m335–m336. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2004). 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m469-m470

doi:10.1107/S1600536813019739

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­ammonium tetra­kis­(iso­thio­cyanato)­zincate–1,4,10,13,16-hexa­oxa­cyclo­octa­deca­ne–water (1/2/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Diammonium tetrakis(isothiocyanato)zincate–1,4,10,13,16-hexaoxacyclooctadecane–water (1/2/1)