Poly[μ2-aqua-aqua-[μ3-N-butyl-N-(2-hy-droxy-ethyl)di-thio-carbamato-κ(3) O,O':S]sodium].

In the title compound, [Na(C7H14NOS2)(H2O)2] n , the Na(I) cation is coordinated by five O atoms [Na-O = 2.3142 (11)-2.4677 (10) Å] from three aqua and two N-butyl-N-(2-hy-droxy-eth-yl)di-thio-carbamate (L) ligands and one S atom [Na-S = 3.0074 (6) Å] from a third L ligand in a highly distorted octa-hedral geometry. Two aqua ligands related by an inversion center bridge two Na(I) cations, and each L ligand coordinates three Na(I) cations, leading to a layered arrangement aligned parallel to the bc plane. Inter-molecular O-H⋯S hydrogen bonds are observed in the inner part of each polymeric layer; these are packed along the a axis and held together by weak van der Waals forces.

Chemical context

Di­thio­carbamates have recently drawn more attention due to their application in group-transfer radical cyclization reactions (Grainger & Innocenti, 2007 ▸) and as ligands for chelating metals (Greenwood & Earnshaw, 1997 ▸). In recent years, their applications have not only become apparent as pesticides and fungicides, but they have also been widely used as vulcanization accelerators in the rubber industry (Svetlik et al., 1955 ▸). Di­thio­carbamates are also of biological importance due to their anti­cancer, anti­bacterial, anti­tuberculosis and anti­fungal properties (Li et al., 2015 ▸; Sim et al., 2014 ▸; Chauhan et al., 2012 ▸; Byrne et al., 2007 ▸). Their anti-oxidant properties make them even more valuable compounds. As part of our investigations on organotindi­thio complexes (Srivastava et al., 2007 ▸), we herein report the synthesis and structure of the title compound.

Structural commentary

The title compound is a two-dimensional polymer with formula [Na(μ3-C7H14NOS2)(μ2-H2O)(H2O)]. Within this polymer, each NaI ion exhibits a distorted octa­hedral geometry (Fig. 1 ▸) made up from coordination by the S atom of one N-butyl-N-(2-hy­droxy­eth­yl)di­thio­carbamate (L) anion, two hy­droxy O atoms from two L ligands and three aqua ligands, of which two aqua ligands form bridging units between two NaI cations. The di­thio­carbamate anion acts as a triply bridging ligand, where one S atom coordinates one sodium atom and the Ohy­droxy atom coordinates two sodium atoms (Fig. 2 ▸). The aforementioned feature of multiple coord­ination modes leads to the formation of polymeric layers parallel to the bc plane with the hydro­phobic butyl arms protruding up and down. In the L ligand, while the two S atoms are not chemically equivalent as only one is involved in bonding to the Na cation, the C—S bond lengths are identical at 1.726 (1) Å.

Figure 1

A portion of the title crystal structure showing the coordination environment for the NaI cation and the atomic labels [symmetry codes: (A) 1 − x, y − ,  − z; (B) 1 − x, −y, 1 − z]. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2

Diagram showing the triply bridging nature of the di­thio­carbamate anion [symmetry codes: (A) 1 − x, −y, 1 − z; (B) 1 − x, y + ,  − z].

Supra­molecular features

Inter­molecular O—H⋯S hydrogen bonds (Table 1 ▸) are observed in the inner part of each polymeric layer (Fig. 3 ▸). The layers are further packed along the a axis and held together by weak van der Waals forces.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S1i	0.82 (2)	2.41 (2)	3.2227 (10)	167.6 (19)
O1W—H1W1⋯S2	0.82 (2)	2.48 (2)	3.2933 (10)	168 (2)
O1W—H1W2⋯S2ii	0.85 (3)	2.42 (3)	3.2605 (10)	171 (2)
O2W—H2W2⋯S1ii	0.78 (2)	2.48 (2)	3.2624 (11)	173 (2)

Symmetry codes: (i) ; (ii) .

Figure 3

A portion of the crystal packing showing the O—H⋯S hydrogen bonds (dashed lines) in the inner part of the polymeric layer [symmetry codes: (A) 1 − x, 1 − y, 1 − z; (B) 1 − x, y − ,  − z; (C) 1 − x, −y, 1 − z; (D) x,  − y,  + z; (E) x, 1 + y, z; (F) x,  − y,  + x].

Database survey

In a recent publication, Howie et al. (2008 ▸) reported a structurally similar compound where the butyl substituent was replaced by a propyl substituent. The crystal structures of other sodium salts of di­thio­carbamates, Na[S2CN(C2H5)2]·3H2O (Colapietro et al., 1968 ▸), Na[S2CN(CH2)4]·2H2O (Albertsson et al., 1980 ▸; Ymén, 1982 ▸), Na[S2CN(C3H7)2]·5H2O (Ymén, 1983 ▸) and Na[S2CN(CH3)2]·2H2O (Oskarsson & Ymén, 1983 ▸), Na[S2CN(CH2)5]·2H2O (Mafud & Gambardella, 2011 ▸), Na[S2CN(C8H5NS)]·3H2O (Téllez et al., 2004 ▸) have been reported. All these structures are polymeric in nature and contain the μ(H2O)2Na2 unit.

Synthesis and crystallization

The title compound was prepared by the reaction of N-butyl N-hy­droxy­ethyl amine (0.01 mol), carbon di­sulfide (0.01 mol) and sodium hydroxide (0.01 mol) in dry diethyl ether and was stirred for 4 h at 253 K. The crude product was recrystallized from isopropyl alcohol. It was then dissolved in a hexa­ne:diethyl ether (1:1 v/v) mixture and put in a deep freezer overnight. Square transparent crystals suitable for X ray analysis were obtained in 80% yield (m.p.: 430 K). Analysis calculated for C7H18NO3S2 (%) S, 29.78; found: S, 29.84.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All C-bound H atoms were idealized with C—H distances of 0.99 Å for CH2 and 0.98 Å for CH3 groups with atomic displacement parameters of U(H) = 1.5U eq(C) for methyl H atoms and 1.2U(C) for other H atoms. The water and hydroxyl H atoms were freely refined.

Table 2

Experimental details

Crystal data
Chemical formula	[Na(C7H14NOS2)(H2O)2]
M r	251.33
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	120
a, b, c (Å)	15.6223 (3), 5.8379 (1), 14.7114 (3)
β (°)	101.868 (2)
V (Å3)	1313.02 (4)
Z	4
Radiation type	Cu Kα
μ (mm−1)	3.90
Crystal size (mm)	0.39 × 0.31 × 0.24
Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012 ▸)
T min, T max	0.660, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5973, 2731, 2617
R int	0.019
(sin θ/λ)max (Å−1)	0.631
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.029, 0.080, 1.05
No. of reflections	2731
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.29, −0.39

Computer programs: CrysAlis PRO (Agilent, 2012 ▸), SHELXTL (Sheldrick, 2008 ▸) and SHELXL2014 (Sheldrick, 2015 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016000657/cv5500sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016000657/cv5500Isup2.hkl

CCDC reference: 1447132

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

[Na(C7H14NOS2)(H2O)2]	F(000) = 536
Mr = 251.33	Dx = 1.271 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 15.6223 (3) Å	Cell parameters from 4003 reflections
b = 5.8379 (1) Å	θ = 3.1–76.6°
c = 14.7114 (3) Å	µ = 3.90 mm−1
β = 101.868 (2)°	T = 120 K
V = 1313.02 (4) Å3	Chunk, colorless
Z = 4	0.39 × 0.31 × 0.24 mm

Agilent SuperNova Dual Source diffractometer with an Atlas detector	2731 independent reflections
Radiation source: sealed X-ray tube	2617 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm-1	Rint = 0.019
ω scans	θmax = 76.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −19→17
Tmin = 0.660, Tmax = 1.000	k = −7→4
5973 measured reflections	l = −18→17

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.0516P)2 + 0.3898P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.29 e Å−3
2731 reflections	Δρmin = −0.39 e Å−3
149 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0041 (4)

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.

	x	y	z	Uiso*/Ueq
Na1	0.44835 (3)	0.26004 (8)	0.45654 (3)	0.01595 (14)
S1	0.76058 (2)	0.34854 (5)	0.14289 (2)	0.01645 (11)
S2	0.60961 (2)	0.50629 (5)	0.22351 (2)	0.01569 (11)
O1	0.59309 (6)	0.09872 (16)	0.47496 (6)	0.0155 (2)
H1O	0.6306 (14)	0.125 (4)	0.5218 (15)	0.035 (5)*
O1W	0.50061 (6)	0.58495 (17)	0.39025 (6)	0.0172 (2)
H1W1	0.5325 (15)	0.551 (4)	0.3542 (15)	0.039 (6)*
H1W2	0.4670 (16)	0.686 (4)	0.3609 (16)	0.046 (6)*
O2W	0.30199 (7)	0.34773 (19)	0.44462 (7)	0.0220 (2)
H2W1	0.2792 (15)	0.233 (4)	0.4121 (16)	0.041 (6)*
H2W2	0.2843 (15)	0.462 (4)	0.4197 (15)	0.036 (6)*
N1	0.73937 (7)	0.23989 (18)	0.31192 (7)	0.0149 (2)
C1	0.70580 (8)	0.3542 (2)	0.23350 (8)	0.0138 (2)
C2	0.70139 (8)	0.2560 (2)	0.39489 (8)	0.0154 (3)
H2A	0.6735	0.4079	0.3964	0.019*
H2B	0.7485	0.2424	0.4510	0.019*
C3	0.63355 (8)	0.0692 (2)	0.39629 (8)	0.0167 (3)
H3A	0.5884	0.0758	0.3383	0.020*
H3B	0.6621	−0.0828	0.3996	0.020*
C4	0.82101 (9)	0.1072 (2)	0.32374 (9)	0.0197 (3)
H4A	0.8270	0.0440	0.2629	0.024*
H4B	0.8184	−0.0229	0.3662	0.024*
C5	0.90068 (9)	0.2546 (3)	0.36299 (10)	0.0269 (3)
H5A	0.9006	0.3906	0.3228	0.032*
H5B	0.8963	0.3091	0.4256	0.032*
C6	0.98645 (11)	0.1266 (4)	0.36977 (15)	0.0465 (5)
H6A	0.9929	0.0811	0.3067	0.056*
H6B	0.9852	−0.0147	0.4067	0.056*
C7	1.06488 (12)	0.2721 (5)	0.41491 (19)	0.0658 (8)
H7A	1.1185	0.1809	0.4213	0.099*
H7B	1.0576	0.3224	0.4764	0.099*
H7C	1.0689	0.4063	0.3760	0.099*

	U11	U22	U33	U12	U13	U23
Na1	0.0155 (3)	0.0175 (3)	0.0152 (2)	−0.00088 (18)	0.00403 (19)	0.00032 (18)
S1	0.01710 (17)	0.02187 (18)	0.01177 (17)	0.00208 (11)	0.00623 (12)	0.00148 (10)
S2	0.01414 (17)	0.02106 (18)	0.01238 (17)	0.00310 (10)	0.00394 (11)	0.00173 (10)
O1	0.0133 (4)	0.0226 (5)	0.0114 (4)	−0.0007 (3)	0.0044 (3)	0.0013 (3)
O1W	0.0175 (4)	0.0200 (5)	0.0152 (4)	0.0025 (4)	0.0061 (4)	0.0011 (4)
O2W	0.0203 (5)	0.0190 (5)	0.0257 (5)	0.0024 (4)	0.0024 (4)	−0.0033 (4)
N1	0.0121 (5)	0.0214 (5)	0.0118 (5)	0.0007 (4)	0.0040 (4)	0.0013 (4)
C1	0.0136 (6)	0.0157 (6)	0.0118 (5)	−0.0035 (4)	0.0020 (4)	−0.0014 (4)
C2	0.0141 (6)	0.0226 (6)	0.0100 (5)	−0.0014 (5)	0.0036 (4)	0.0014 (4)
C3	0.0174 (6)	0.0211 (6)	0.0130 (6)	−0.0013 (5)	0.0062 (4)	−0.0006 (5)
C4	0.0166 (6)	0.0260 (6)	0.0167 (6)	0.0060 (5)	0.0038 (5)	0.0034 (5)
C5	0.0143 (7)	0.0410 (9)	0.0250 (7)	0.0026 (6)	0.0027 (5)	−0.0022 (6)
C6	0.0172 (8)	0.0670 (13)	0.0528 (11)	0.0100 (8)	0.0015 (7)	−0.0184 (10)
C7	0.0139 (8)	0.0942 (19)	0.0856 (18)	0.0041 (10)	0.0015 (9)	−0.0321 (15)

Na1—O2W	2.3142 (11)	N1—C1	1.3425 (16)
Na1—O1W	2.3544 (11)	N1—C2	1.4658 (15)
Na1—O1Wi	2.4074 (11)	N1—C4	1.4717 (16)
Na1—O1	2.4128 (10)	C2—C3	1.5237 (17)
Na1—O1ii	2.4677 (10)	C2—H2A	0.9900
Na1—S2iii	3.0074 (6)	C2—H2B	0.9900
Na1—Na1i	3.3527 (10)	C3—H3A	0.9900
Na1—Na1ii	3.5509 (10)	C3—H3B	0.9900
Na1—H2W1	2.59 (2)	C4—C5	1.525 (2)
S1—C1	1.7261 (13)	C4—H4A	0.9900
S2—C1	1.7256 (13)	C4—H4B	0.9900
S2—Na1iv	3.0073 (6)	C5—C6	1.519 (2)
O1—C3	1.4386 (14)	C5—H5A	0.9900
O1—Na1ii	2.4677 (10)	C5—H5B	0.9900
O1—H1O	0.82 (2)	C6—C7	1.526 (3)
O1W—Na1i	2.4074 (10)	C6—H6A	0.9900
O1W—H1W1	0.82 (2)	C6—H6B	0.9900
O1W—H1W2	0.85 (3)	C7—H7A	0.9800
O2W—H2W1	0.86 (2)	C7—H7B	0.9800
O2W—H2W2	0.78 (2)	C7—H7C	0.9800
O2W—Na1—O1W	102.22 (4)	Na1i—O1W—H1W2	105.5 (16)
O2W—Na1—O1Wi	96.88 (4)	H1W1—O1W—H1W2	103 (2)
O1W—Na1—O1Wi	90.49 (4)	Na1—O2W—H2W1	99.2 (15)
O2W—Na1—O1	169.54 (4)	Na1—O2W—H2W2	118.2 (16)
O1W—Na1—O1	87.95 (4)	H2W1—O2W—H2W2	110 (2)
O1Wi—Na1—O1	85.37 (4)	C1—N1—C2	122.02 (10)
O2W—Na1—O1ii	83.15 (4)	C1—N1—C4	122.61 (11)
O1W—Na1—O1ii	174.49 (4)	C2—N1—C4	115.15 (10)
O1Wi—Na1—O1ii	90.05 (4)	N1—C1—S2	120.56 (9)
O1—Na1—O1ii	86.64 (3)	N1—C1—S1	119.09 (9)
O2W—Na1—S2iii	85.90 (3)	S2—C1—S1	120.36 (7)
O1W—Na1—S2iii	95.69 (3)	N1—C2—C3	111.54 (10)
O1Wi—Na1—S2iii	172.54 (3)	N1—C2—H2A	109.3
O1—Na1—S2iii	90.69 (3)	C3—C2—H2A	109.3
O1ii—Na1—S2iii	83.39 (3)	N1—C2—H2B	109.3
O2W—Na1—Na1i	103.57 (4)	C3—C2—H2B	109.3
O1W—Na1—Na1i	45.89 (3)	H2A—C2—H2B	108.0
O1Wi—Na1—Na1i	44.60 (3)	O1—C3—C2	110.32 (10)
O1—Na1—Na1i	85.23 (3)	O1—C3—H3A	109.6
O1ii—Na1—Na1i	134.40 (3)	C2—C3—H3A	109.6
S2iii—Na1—Na1i	141.41 (3)	O1—C3—H3B	109.6
O2W—Na1—Na1ii	125.82 (4)	C2—C3—H3B	109.6
O1W—Na1—Na1ii	131.86 (3)	H3A—C3—H3B	108.1
O1Wi—Na1—Na1ii	86.89 (3)	N1—C4—C5	111.56 (12)
O1—Na1—Na1ii	43.93 (2)	N1—C4—H4A	109.3
O1ii—Na1—Na1ii	42.71 (2)	C5—C4—H4A	109.3
S2iii—Na1—Na1ii	85.882 (19)	N1—C4—H4B	109.3
Na1i—Na1—Na1ii	115.45 (3)	C5—C4—H4B	109.3
O2W—Na1—H2W1	19.0 (5)	H4A—C4—H4B	108.0
O1W—Na1—H2W1	111.5 (5)	C6—C5—C4	112.80 (14)
O1Wi—Na1—H2W1	112.5 (5)	C6—C5—H5A	109.0
O1—Na1—H2W1	152.6 (6)	C4—C5—H5A	109.0
O1ii—Na1—H2W1	73.3 (5)	C6—C5—H5B	109.0
S2iii—Na1—H2W1	69.0 (5)	C4—C5—H5B	109.0
Na1i—Na1—H2W1	122.2 (5)	H5A—C5—H5B	107.8
Na1ii—Na1—H2W1	113.8 (5)	C5—C6—C7	111.93 (18)
C1—S2—Na1iv	115.32 (4)	C5—C6—H6A	109.2
C3—O1—Na1	120.87 (7)	C7—C6—H6A	109.2
C3—O1—Na1ii	115.00 (8)	C5—C6—H6B	109.2
Na1—O1—Na1ii	93.36 (3)	C7—C6—H6B	109.2
C3—O1—H1O	109.9 (14)	H6A—C6—H6B	107.9
Na1—O1—H1O	120.7 (14)	C6—C7—H7A	109.5
Na1ii—O1—H1O	91.1 (15)	C6—C7—H7B	109.5
Na1—O1W—Na1i	89.50 (4)	H7A—C7—H7B	109.5
Na1—O1W—H1W1	112.5 (16)	C6—C7—H7C	109.5
Na1i—O1W—H1W1	124.5 (15)	H7A—C7—H7C	109.5
Na1—O1W—H1W2	122.7 (16)	H7B—C7—H7C	109.5
C2—N1—C1—S2	−5.92 (16)	Na1—O1—C3—C2	102.88 (10)
C4—N1—C1—S2	179.80 (9)	Na1ii—O1—C3—C2	−146.38 (8)
C2—N1—C1—S1	173.66 (9)	N1—C2—C3—O1	−176.02 (9)
C4—N1—C1—S1	−0.62 (16)	C1—N1—C4—C5	89.35 (15)
Na1iv—S2—C1—N1	178.00 (8)	C2—N1—C4—C5	−85.29 (13)
Na1iv—S2—C1—S1	−1.57 (9)	N1—C4—C5—C6	−176.06 (13)
C1—N1—C2—C3	91.65 (14)	C4—C5—C6—C7	−176.34 (18)
C4—N1—C2—C3	−93.68 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S1v	0.82 (2)	2.41 (2)	3.2227 (10)	167.6 (19)
O1W—H1W1···S2	0.82 (2)	2.48 (2)	3.2933 (10)	168 (2)
O1W—H1W2···S2iv	0.85 (3)	2.42 (3)	3.2605 (10)	171 (2)
O2W—H2W2···S1iv	0.78 (2)	2.48 (2)	3.2624 (11)	173 (2)