Two mononuclear Tc complexes: [2,2′-(3-phenyl­propyl­imino)- and [2,2′-(propyl­imino)bis­(ethanethiol­ato)](4-methoxy­benzene­thiol­ato)­oxido­technate(V)

The mol­ecular structures of the two mononuclear title complexes, namely (4-methoxy­benzene­thiol­ato-κS)oxido[2,2′-(3-phenyl­propyl­imino)bis­(ethanethiol­ato)-κ³S,N,S′]technetium(V), [Tc(C₁₄H₂₁NS₂)(C₇H₇OS)O], (I), and (4-methoxy­benzene­thiol­ato-κS)oxido[2,2′-(propyl­imino)bis­(ethanethiol­ato)-κ³S,N,S′]technetium(V), [Tc(C₇H₁₅NS₂)(C₇H₇OS)O], (II), exhibit the same coordination environment for the central Tc atoms. The atoms are five-coordinated (TcNOS₃) with a square-pyramidal geometry comprising a tridentate 2,2′-(3-phenyl­prop­ylimino)bis­(ethanethiolate) or 2,2′-(propyl­imino)­bis­(ethanethiolate) ligand, a 4-methoxy­benzene­thiolate ligand and an additional oxide O atom. Inter­molecular C—H...O and C—H...S hydrogen bonds between the monomeric units result in two-dimensional layers with a parallel arrangement.

S1. Comment

Recently a new method has been described that allows the use of metal complexes as a prosthetic group in ¹⁸F labelling of biologically relevant molecules (Noll et al., 2002). The principle is based on labelling a tridentate dithiole ligand with ¹⁸F and combining it with a monodentate thiole ligand to form mixed-ligand technetium complexes (see scheme). To understand the reaction route, a non-radioactive fluorine model compound was prepared and all by-products obtained were characterized by X-ray crystal structure analysis. Here we describe only the metal complexes of the by-products, the title compounds, (I) and (II).

The molecular structures of (I) and (II) reveal that they are neutral square-pyramidal mononuclear complexes, depicted in Figs. 1 and 2. Similar Re complexes are currently under study for various applications (Bouziotis et al., 1999; Chelminiak et al., 2005; Femia et al., 2000; Friebe et al., 2000; Heimbold et al., 2002; Jung et al., 2002; Maresca et al., 2002; Marsh, 2005; Nock, Maina, Tisato, Papadopoulos et al., 1999; Nock, Maina, Tisato, Raptopoulou et al., 1999; Papadopoulos et al., 1999; Tsoukalas et al., 1999). In the case of the title compounds, the Tc atom is coordinated by two S atoms and an N atom from the tridentate ligand, another S atom provided by the 4-methoxybenzenethiol ligand and an additional O atom to complete the coordination environment. The cation environments in both structures are comparable, with axial Tc—O distances of 1.657 (6) Å in (I) and 1.671 (3) Å in (II), Tc—N distances of 2.213 (6) Å in (I) and 2.201 (4) Å in (II), and Tc—S bond lengths in the range 2.241 (3)–2.308 (3) Å in (I) and 2.2801 (19)–2.3093 (19) Å in (II). The values mentioned above are in good agreement with those reported in the Cambridge Structural Database (Version?; Allen, 2002) (TC—O = 1.654–1.670 Å, mean 1.663 Å; Tc—N = 1.996–2.259 Å, mean 2.194 Å; Tc—S = 2.280–2.359 Å, mean 2.304 Å). The Tc1—S3—C5 angles between the methoxyphenyl moiety and the central Tc atom are nearly similar [109.6 (3)° in (I) and 109.2 (2)° in (II)], whereas the S2—Tc1—S3—C5 torsion angles of -164.02 (35) and 45.49 (21)° in (I) and (II), respectively, indicate the opposite positions of the methoxyphenyl moiety.

The analysis of the crystal packing of the title complexes reveals that the monomeric units are linked via non-classical C—H···O hydrogen bonds in complexes (I) and (II) and C—H···S hydrogen bonds in complex (II) only, to result in a two-dimensional layer structure. Thus, each complex is linked to four others, forming a sheet parallel to (110). The relevant hydrogen-bonding geometries and symmetry codes are listed in Tables 2 and 4.

As illustrated in Figs. 3 and 4, the head-to-tail arrangement of the molecules within the layers leads to a zigzag formation of the Tc atoms, along the a axis in the crystal structure of compound (I) and along the b axis in case of compound (II), with Tc···Tc distances of 6.760 (13) Å and 7.042 (16) Å and 6.102 (4) Å, respectively. [Three values for two compounds - please clarify which applies to which] Due to the larger phenyl propylimine ligand, the distance between adjacent sheets is larger in (I) than in (II); in either case, no π–π interactions are observed.

Related literature

For related literature, see: Allen (2002); Bouziotis et al. (1999); Chelminiak et al. (2005); Femia et al. (2000); Flack (1983); Friebe et al. (2000); Heimbold et al. (2002); Jung et al. (2002); Maresca et al. (2002); Marsh (2005); Nock, Maina, Tisato, Papadopoulos, Raptopoulou, Terzis & Chiotellis (1999); Nock, Maina, Tisato, Raptopoulou, Terzis, Papadopoulos, Refosco & Chiotellis (1999); Noll et al. (2002); Papadopoulos et al. (1999); Tsoukalas et al. (1999).

S2. Experimental

The synthesis starts with the preparation of the tridentate ligand containing both the sulfur protecting groups and tosyl as leaving group. In the next step, the fluorine is introduced by nucleophilic substitution in acetonitrile with Kryptofix 2.2.2 at 413 K. Subsequently, both sulfur benzyl protecting groups were split off by reductive cleavage in liquid ammonia and metallic sodium. This reaction is accompanied by rearrangement of the ligand molecule, and besides the favoured fluorinated species two by-products are formed (see reaction scheme). Without further purification, the fluorinated tridentate ligand is combined with the monodentate p-methoxybenzenethiol ligand as model compound and Re or Tc in the oxidation state +5 to give a `3 + 1' complex (see reaction scheme). The Re [Tc here?] complexes were separated out by column chromatography on silica gel with dichloromethane as eluent. The fractions were collected and evaporated to dryness. Crystals of the metal complexes were grown from ethanol. Here we describe only the metal complexes of the by-products.

S3. Refinement

Compound (I) crystallizes in the non-centrosymetric spacegroup P2₁ and was refined as an inversion twin with a Flack parameter (Flack, 1983) of 0.48 (3). Restraints were used for the thermal vibration parameters of four C atoms (C13–C16).

For compound (II), the low N(obs)/N(tot) ratio is the inescapable result of the poor quality of the crystals available; in various trials no better crystals nor resulting data sets could be obtained. This result was unexpected, since comparable Tc compounds investigated by our group tend to build good quality crystals.

All H atoms in both structures were included using a riding model, with C—H = 0.93–0.97 Å and with U_iso(H) = 1.2–1.5U_eq(C).

Computing details

For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. The molecular structure of the `3 + 1' Tc complex (I), showing the atomic labelling of the asymmetric unit and the coordination environment. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of the `3 + 1' Tc complex (II), showing the atomic labelling of the asymmetric unit and the coordination environment. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The two-dimensional supramolecular structure of complex (I), formed via C—H···O hydrogen bonds (dashed lines) between the molecules.
	Fig. 4. The two-dimensional supramolecular structure of complex (II), formed via C—H···O and C—H···S hydrogen bonds (dashed lines) between the molecules.

(I) (4-methoxybenzenethiolato-κS)oxido[2,2'-(3- phenylpropylimino)bis(ethanethiolato)-κ³S,N,S']technetium(V)

Crystal data

[Tc(C14H21NS2)(C7H7OS)O]	F(000) = 536
Mr = 520.62	Dx = 1.500 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 775 reflections
a = 10.885 (7) Å	θ = 3.1–29.6°
b = 7.247 (4) Å	µ = 0.91 mm^−1
c = 14.885 (7) Å	T = 273 K
β = 100.913 (8)°	Plate, brown
V = 1152.9 (11) Å^3	0.45 × 0.39 × 0.15 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	4523 independent reflections
Radiation source: fine-focus sealed tube	3581 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.656, Tmax = 0.872	k = −9→9
6818 measured reflections	l = −14→19

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)] = 0.065	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0606P)^2 + 3.45P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
4523 reflections	Δρmax = 1.57 e Å^−3
236 parameters	Δρmin = −0.81 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.49 (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.

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

	x	y	z	Uiso*/Ueq
Tc1	0.27773 (5)	−0.00001 (10)	0.07540 (4)	0.03687 (17)
S1	0.0771 (2)	0.1056 (4)	0.04157 (16)	0.0558 (6)
S2	0.3154 (3)	−0.3036 (4)	0.07132 (16)	0.0578 (6)
S3	0.2418 (2)	−0.0742 (4)	0.21897 (16)	0.0542 (6)
O1	0.3972 (6)	0.1457 (9)	0.0925 (4)	0.0532 (16)
O2	−0.0126 (7)	0.5290 (13)	0.3822 (5)	0.077 (2)
N1	0.2584 (5)	−0.0152 (14)	−0.0751 (4)	0.0382 (14)
C1	0.0427 (8)	0.1003 (15)	−0.0836 (6)	0.053 (2)
H1B	−0.0451	0.0727	−0.1051	0.064*
H1C	0.0601	0.2200	−0.1075	0.064*
C2	0.1233 (7)	−0.0470 (13)	−0.1178 (6)	0.049 (3)
H2A	0.0975	−0.1686	−0.1015	0.059*
H2B	0.1128	−0.0406	−0.1839	0.059*
C3	0.3137 (10)	−0.3489 (12)	−0.0494 (7)	0.056 (3)
H3A	0.3777	−0.4390	−0.0552	0.067*
H3B	0.2332	−0.3999	−0.0776	0.067*
C4	0.3377 (10)	−0.1700 (16)	−0.0992 (7)	0.048 (3)
H4A	0.4253	−0.1365	−0.0822	0.057*
H4B	0.3190	−0.1903	−0.1648	0.057*
C5	0.1585 (9)	0.1125 (14)	0.2619 (6)	0.051 (2)
C6	0.0598 (9)	0.0655 (14)	0.3056 (6)	0.057 (3)
H6A	0.0344	−0.0569	0.3067	0.069*
C7	−0.0010 (10)	0.2015 (17)	0.3478 (6)	0.062 (3)
H7A	−0.0666	0.1711	0.3771	0.075*
C8	0.0393 (9)	0.3838 (14)	0.3449 (6)	0.054 (3)
C9	0.1339 (8)	0.4258 (14)	0.2979 (6)	0.053 (2)
H9A	0.1577	0.5482	0.2936	0.063*
C10	0.1920 (9)	0.2946 (14)	0.2585 (6)	0.052 (2)
H10A	0.2562	0.3273	0.2284	0.063*
C11	−0.1076 (10)	0.478 (3)	0.4361 (7)	0.090 (4)
H11A	−0.1392	0.5876	0.4601	0.135*
H11B	−0.0706	0.3993	0.4858	0.135*
H11C	−0.1751	0.4141	0.3977	0.135*
C12	0.3049 (10)	0.1596 (13)	−0.1091 (7)	0.042 (2)
H12A	0.3900	0.1798	−0.0768	0.050*
H12B	0.2543	0.2605	−0.0934	0.050*
C13	0.3038 (11)	0.1675 (13)	−0.2140 (6)	0.0618 (14)
H13A	0.3632	0.0786	−0.2294	0.074*
H13B	0.2213	0.1345	−0.2472	0.074*
C14	0.3382 (11)	0.3619 (14)	−0.2432 (6)	0.0618 (14)
H14A	0.2720	0.4474	−0.2363	0.074*
H14B	0.4144	0.4024	−0.2033	0.074*
C15	0.3572 (12)	0.3658 (14)	−0.3430 (6)	0.0618 (14)
H15A	0.4310	0.2933	−0.3465	0.074*
H15B	0.2864	0.3040	−0.3803	0.074*
C16	0.3715 (11)	0.5485 (12)	−0.3850 (6)	0.0618 (14)
C17	0.4528 (11)	0.6806 (15)	−0.3383 (7)	0.065 (3)
H17A	0.4935	0.6584	−0.2785	0.078*
C18	0.4728 (10)	0.8443 (16)	−0.3809 (8)	0.067 (3)
H18A	0.5270	0.9315	−0.3493	0.081*
C19	0.4142 (12)	0.8802 (16)	−0.4688 (8)	0.074 (3)
H19A	0.4290	0.9907	−0.4967	0.088*
C20	0.3337 (13)	0.753 (2)	−0.5152 (8)	0.086 (4)
H20A	0.2932	0.7769	−0.5748	0.103*
C21	0.3121 (11)	0.5863 (18)	−0.4737 (7)	0.075 (3)
H21A	0.2574	0.5002	−0.5058	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tc1	0.0352 (3)	0.0389 (3)	0.0380 (3)	−0.0005 (4)	0.0106 (2)	−0.0010 (4)
S1	0.0489 (13)	0.0742 (16)	0.0469 (13)	0.0193 (13)	0.0157 (10)	−0.0044 (12)
S2	0.0740 (16)	0.0541 (14)	0.0492 (14)	−0.0093 (13)	0.0218 (12)	0.0071 (11)
S3	0.0599 (14)	0.0586 (14)	0.0472 (13)	0.0035 (12)	0.0182 (11)	0.0076 (10)
O1	0.056 (4)	0.055 (4)	0.051 (4)	−0.028 (3)	0.014 (3)	−0.010 (3)
O2	0.070 (4)	0.081 (7)	0.079 (5)	0.020 (5)	0.011 (4)	−0.032 (5)
N1	0.033 (3)	0.035 (4)	0.048 (3)	0.001 (4)	0.012 (3)	−0.002 (4)
C1	0.043 (5)	0.077 (6)	0.038 (5)	0.007 (5)	0.004 (4)	−0.001 (5)
C2	0.039 (4)	0.066 (8)	0.044 (4)	−0.006 (4)	0.011 (4)	−0.007 (4)
C3	0.069 (6)	0.038 (5)	0.069 (7)	0.004 (5)	0.035 (5)	−0.005 (4)
C4	0.048 (6)	0.054 (7)	0.048 (5)	0.014 (5)	0.025 (4)	0.003 (5)
C5	0.059 (6)	0.058 (6)	0.038 (5)	0.002 (5)	0.015 (4)	−0.005 (4)
C6	0.069 (6)	0.058 (7)	0.052 (5)	−0.005 (5)	0.029 (5)	0.006 (4)
C7	0.062 (6)	0.082 (8)	0.047 (6)	0.001 (6)	0.021 (5)	0.010 (5)
C8	0.051 (6)	0.060 (7)	0.047 (5)	0.014 (5)	−0.001 (4)	−0.004 (4)
C9	0.046 (5)	0.061 (6)	0.047 (5)	−0.001 (4)	−0.002 (4)	−0.006 (4)
C10	0.045 (5)	0.060 (6)	0.051 (5)	−0.015 (5)	0.005 (4)	0.002 (4)
C11	0.085 (7)	0.126 (12)	0.064 (6)	0.033 (10)	0.028 (5)	−0.008 (9)
C12	0.042 (5)	0.034 (6)	0.051 (6)	−0.004 (4)	0.015 (4)	−0.001 (4)
C13	0.097 (4)	0.048 (3)	0.045 (3)	−0.015 (3)	0.026 (3)	−0.001 (2)
C14	0.097 (4)	0.048 (3)	0.045 (3)	−0.015 (3)	0.026 (3)	−0.001 (2)
C15	0.097 (4)	0.048 (3)	0.045 (3)	−0.015 (3)	0.026 (3)	−0.001 (2)
C16	0.097 (4)	0.048 (3)	0.045 (3)	−0.015 (3)	0.026 (3)	−0.001 (2)
C17	0.084 (8)	0.058 (6)	0.051 (6)	−0.012 (6)	0.009 (5)	0.002 (5)
C18	0.055 (6)	0.058 (6)	0.092 (8)	0.002 (5)	0.020 (6)	0.016 (6)
C19	0.085 (8)	0.064 (8)	0.080 (8)	−0.004 (7)	0.039 (7)	0.017 (6)
C20	0.105 (10)	0.096 (10)	0.057 (7)	0.020 (9)	0.017 (7)	0.033 (7)
C21	0.086 (8)	0.091 (8)	0.050 (6)	−0.009 (7)	0.015 (6)	−0.002 (6)

Geometric parameters (Å, º)

Tc1—O1	1.657 (6)	C9—C10	1.337 (13)
Tc1—N1	2.213 (6)	C9—H9A	0.9300
Tc1—S2	2.241 (3)	C10—H10A	0.9300
Tc1—S1	2.279 (3)	C11—H11A	0.9600
Tc1—S3	2.308 (3)	C11—H11B	0.9600
S1—C1	1.830 (9)	C11—H11C	0.9600
S2—C3	1.824 (10)	C12—C13	1.561 (13)
S3—C5	1.812 (10)	C12—H12A	0.9700
O2—C8	1.361 (12)	C12—H12B	0.9700
O2—C11	1.471 (13)	C13—C14	1.541 (13)
N1—C12	1.488 (13)	C13—H13A	0.9700
N1—C4	1.500 (13)	C13—H13B	0.9700
N1—C2	1.505 (10)	C14—C15	1.539 (12)
C1—C2	1.529 (12)	C14—H14A	0.9700
C1—H1B	0.9700	C14—H14B	0.9700
C1—H1C	0.9700	C15—C16	1.484 (13)
C2—H2A	0.9700	C15—H15A	0.9700
C2—H2B	0.9700	C15—H15B	0.9700
C3—C4	1.540 (14)	C16—C21	1.383 (14)
C3—H3A	0.9700	C16—C17	1.396 (14)
C3—H3B	0.9700	C17—C18	1.381 (14)
C4—H4A	0.9700	C17—H17A	0.9300
C4—H4B	0.9700	C18—C19	1.367 (15)
C5—C10	1.373 (13)	C18—H18A	0.9300
C5—C6	1.400 (12)	C19—C20	1.368 (16)
C6—C7	1.400 (14)	C19—H19A	0.9300
C6—H6A	0.9300	C20—C21	1.395 (17)
C7—C8	1.395 (15)	C20—H20A	0.9300
C7—H7A	0.9300	C21—H21A	0.9300
C8—C9	1.385 (13)
O1—Tc1—N1	96.3 (3)	C9—C8—C7	119.5 (9)
O1—Tc1—S2	119.2 (3)	C10—C9—C8	121.6 (10)
N1—Tc1—S2	84.6 (3)	C10—C9—H9A	119.2
O1—Tc1—S1	120.8 (3)	C8—C9—H9A	119.2
N1—Tc1—S1	83.65 (16)	C9—C10—C5	121.1 (9)
S2—Tc1—S1	119.76 (10)	C9—C10—H10A	119.4
O1—Tc1—S3	105.8 (2)	C5—C10—H10A	119.4
N1—Tc1—S3	157.8 (2)	O2—C11—H11A	109.5
S2—Tc1—S3	81.96 (9)	O2—C11—H11B	109.5
S1—Tc1—S3	87.69 (9)	H11A—C11—H11B	109.5
C1—S1—Tc1	102.7 (3)	O2—C11—H11C	109.5
C3—S2—Tc1	103.6 (3)	H11A—C11—H11C	109.5
C5—S3—Tc1	109.6 (3)	H11B—C11—H11C	109.5
C8—O2—C11	114.7 (10)	N1—C12—C13	115.6 (8)
C12—N1—C4	107.9 (6)	N1—C12—H12A	108.4
C12—N1—C2	110.8 (7)	C13—C12—H12A	108.4
C4—N1—C2	110.2 (8)	N1—C12—H12B	108.4
C12—N1—Tc1	109.2 (6)	C13—C12—H12B	108.4
C4—N1—Tc1	109.3 (5)	H12A—C12—H12B	107.4
C2—N1—Tc1	109.5 (4)	C14—C13—C12	111.1 (7)
C2—C1—S1	109.5 (6)	C14—C13—H13A	109.4
C2—C1—H1B	109.8	C12—C13—H13A	109.4
S1—C1—H1B	109.8	C14—C13—H13B	109.4
C2—C1—H1C	109.8	C12—C13—H13B	109.4
S1—C1—H1C	109.8	H13A—C13—H13B	108.0
H1B—C1—H1C	108.2	C15—C14—C13	111.9 (8)
N1—C2—C1	109.2 (7)	C15—C14—H14A	109.2
N1—C2—H2A	109.8	C13—C14—H14A	109.2
C1—C2—H2A	109.8	C15—C14—H14B	109.2
N1—C2—H2B	109.8	C13—C14—H14B	109.2
C1—C2—H2B	109.8	H14A—C14—H14B	107.9
H2A—C2—H2B	108.3	C16—C15—C14	117.8 (8)
C4—C3—S2	110.6 (7)	C16—C15—H15A	107.9
C4—C3—H3A	109.5	C14—C15—H15A	107.9
S2—C3—H3A	109.5	C16—C15—H15B	107.9
C4—C3—H3B	109.5	C14—C15—H15B	107.9
S2—C3—H3B	109.5	H15A—C15—H15B	107.2
H3A—C3—H3B	108.1	C21—C16—C17	118.5 (9)
N1—C4—C3	110.9 (7)	C21—C16—C15	120.7 (9)
N1—C4—H4A	109.5	C17—C16—C15	120.6 (9)
C3—C4—H4A	109.5	C18—C17—C16	120.0 (10)
N1—C4—H4B	109.5	C18—C17—H17A	120.0
C3—C4—H4B	109.5	C16—C17—H17A	120.0
H4A—C4—H4B	108.0	C19—C18—C17	121.2 (12)
C10—C5—C6	118.9 (9)	C19—C18—H18A	119.4
C10—C5—S3	123.4 (8)	C17—C18—H18A	119.4
C6—C5—S3	117.5 (8)	C18—C19—C20	119.5 (11)
C5—C6—C7	120.5 (10)	C18—C19—H19A	120.2
C5—C6—H6A	119.8	C20—C19—H19A	120.2
C7—C6—H6A	119.8	C19—C20—C21	120.4 (11)
C8—C7—C6	118.3 (9)	C19—C20—H20A	119.8
C8—C7—H7A	120.8	C21—C20—H20A	119.8
C6—C7—H7A	120.8	C16—C21—C20	120.4 (12)
O2—C8—C9	116.3 (10)	C16—C21—H21A	119.8
O2—C8—C7	124.2 (9)	C20—C21—H21A	119.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···S1^i	0.97	2.78	3.650 (9)	150
C4—H4A···O1^ii	0.97	2.52	3.164 (13)	124

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

(II) (4-methoxybenzenethiolato-κS)oxido[2,2'-(propylimino)bis(ethanethiolato)- κ³S,N,S']technetium(V)

Crystal data

[Tc(C7H15NS2)(C7H7OS)O]	F(000) = 880
Mr = 430.51	Dx = 1.597 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 907 reflections
a = 10.610 (7) Å	θ = 3.0–24.4°
b = 10.356 (7) Å	µ = 1.16 mm^−1
c = 16.296 (11) Å	T = 273 K
β = 90.574 (15)°	Plate, brown
V = 1790 (2) Å^3	0.15 × 0.09 × 0.02 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4031 independent reflections
Radiation source: fine-focus sealed tube	1809 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −13→11
Tmin = 0.879, Tmax = 0.978	k = −13→13
10232 measured reflections	l = −20→17

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0371P)^2] where P = (Fo^2 + 2Fc^2)/3
4031 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.92 e Å^−3
2 restraints	Δρmin = −0.60 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.

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

	x	y	z	Uiso*/Ueq
Tc1	0.76655 (4)	0.24888 (5)	0.15162 (3)	0.05211 (17)
S1	0.89303 (16)	0.08218 (15)	0.11159 (12)	0.0775 (5)
S2	0.60719 (13)	0.21855 (13)	0.24244 (10)	0.0629 (4)
S3	0.63174 (15)	0.16995 (16)	0.05143 (10)	0.0729 (5)
O1	0.8032 (3)	0.3985 (3)	0.1219 (2)	0.0648 (10)
O2	0.1240 (4)	0.4098 (5)	0.0654 (3)	0.0811 (13)
N1	0.8856 (4)	0.2457 (4)	0.2630 (3)	0.0565 (11)
C1	0.9964 (5)	0.0625 (6)	0.2008 (5)	0.083 (2)
H1B	1.0166	−0.0282	0.2082	0.099*
H1C	1.0744	0.1091	0.1922	0.099*
C2	0.9322 (5)	0.1132 (6)	0.2764 (4)	0.0718 (18)
H2A	0.8622	0.0573	0.2901	0.086*
H2B	0.9913	0.1127	0.3222	0.086*
C3	0.6871 (5)	0.2281 (6)	0.3424 (3)	0.0665 (17)
H3A	0.6345	0.2753	0.3804	0.080*
H3B	0.6993	0.1417	0.3640	0.080*
C4	0.8121 (5)	0.2941 (6)	0.3358 (4)	0.0701 (17)
H4A	0.8607	0.2790	0.3857	0.084*
H4B	0.7991	0.3864	0.3305	0.084*
C5	0.4808 (5)	0.2437 (6)	0.0622 (3)	0.0604 (14)
C6	0.4681 (5)	0.3750 (6)	0.0706 (4)	0.0656 (17)
H6A	0.5402	0.4257	0.0751	0.079*
C7	0.3506 (6)	0.4341 (6)	0.0726 (4)	0.0668 (17)
H7A	0.3445	0.5230	0.0794	0.080*
C8	0.2429 (5)	0.3597 (7)	0.0644 (3)	0.0586 (15)
C9	0.2546 (6)	0.2278 (6)	0.0560 (4)	0.0670 (17)
H9A	0.1824	0.1774	0.0508	0.080*
C10	0.3700 (7)	0.1698 (6)	0.0552 (3)	0.0673 (17)
H10A	0.3755	0.0806	0.0500	0.081*
C11	0.1083 (5)	0.5442 (7)	0.0804 (4)	0.088 (2)
H11A	0.0201	0.5652	0.0790	0.132*
H11B	0.1511	0.5927	0.0390	0.132*
H11C	0.1429	0.5653	0.1334	0.132*
C12	0.9946 (5)	0.3386 (5)	0.2497 (3)	0.0617 (16)
H12A	1.0377	0.3149	0.1997	0.074*
H12B	0.9612	0.4251	0.2423	0.074*
C13	1.0879 (6)	0.3397 (6)	0.3194 (4)	0.096 (2)
H13A	1.0699	0.4143	0.3534	0.115*
H13B	1.0730	0.2636	0.3526	0.115*
C14	1.2210 (6)	0.3429 (12)	0.2996 (5)	0.181 (5)
H14A	1.2701	0.3413	0.3494	0.271*
H14B	1.2392	0.4204	0.2697	0.271*
H14C	1.2416	0.2691	0.2667	0.271*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tc1	0.0671 (3)	0.0422 (3)	0.0469 (3)	0.0030 (3)	−0.0028 (2)	−0.0003 (3)
S1	0.0841 (11)	0.0586 (10)	0.0901 (14)	0.0114 (9)	0.0079 (10)	−0.0129 (9)
S2	0.0671 (9)	0.0645 (11)	0.0569 (10)	−0.0041 (7)	−0.0024 (8)	−0.0008 (8)
S3	0.0894 (11)	0.0705 (11)	0.0586 (11)	0.0107 (9)	−0.0136 (9)	−0.0207 (9)
O1	0.092 (3)	0.046 (2)	0.056 (3)	−0.005 (2)	−0.005 (2)	0.008 (2)
O2	0.063 (3)	0.102 (4)	0.078 (3)	−0.002 (3)	−0.003 (2)	−0.006 (3)
N1	0.066 (3)	0.050 (3)	0.053 (3)	−0.004 (3)	−0.003 (2)	0.008 (3)
C1	0.068 (4)	0.057 (4)	0.123 (7)	0.011 (3)	−0.001 (4)	0.009 (4)
C2	0.072 (4)	0.061 (4)	0.082 (5)	0.005 (3)	−0.003 (4)	0.024 (4)
C3	0.074 (4)	0.077 (5)	0.049 (4)	−0.005 (3)	−0.002 (3)	0.011 (3)
C4	0.078 (4)	0.080 (4)	0.052 (4)	−0.003 (3)	−0.006 (3)	0.003 (3)
C5	0.073 (4)	0.060 (4)	0.047 (3)	−0.008 (4)	−0.012 (3)	−0.007 (3)
C6	0.062 (4)	0.063 (4)	0.071 (5)	−0.007 (3)	−0.017 (3)	−0.005 (3)
C7	0.074 (4)	0.063 (4)	0.063 (5)	0.002 (3)	−0.016 (3)	−0.009 (3)
C8	0.062 (4)	0.080 (5)	0.033 (4)	−0.001 (3)	−0.005 (3)	0.002 (3)
C9	0.073 (4)	0.070 (5)	0.057 (4)	−0.022 (4)	−0.005 (3)	−0.005 (3)
C10	0.102 (5)	0.057 (4)	0.042 (4)	−0.013 (4)	−0.003 (4)	−0.005 (3)
C11	0.071 (4)	0.109 (6)	0.084 (5)	0.020 (4)	0.000 (4)	0.002 (5)
C12	0.073 (4)	0.058 (4)	0.054 (4)	−0.010 (3)	−0.008 (3)	0.007 (3)
C13	0.122 (6)	0.076 (5)	0.090 (6)	−0.036 (4)	−0.028 (5)	0.012 (4)
C14	0.100 (6)	0.323 (15)	0.120 (8)	−0.076 (8)	−0.026 (6)	0.035 (9)

Geometric parameters (Å, º)

Tc1—O1	1.671 (3)	C5—C6	1.373 (7)
Tc1—N1	2.201 (4)	C5—C10	1.406 (7)
Tc1—S2	2.2801 (19)	C6—C7	1.389 (7)
Tc1—S1	2.2856 (19)	C6—H6A	0.9300
Tc1—S3	2.3093 (19)	C7—C8	1.383 (7)
S1—C1	1.824 (7)	C7—H7A	0.9300
S2—C3	1.831 (6)	C8—C9	1.379 (8)
S3—C5	1.785 (6)	C9—C10	1.364 (7)
O2—C8	1.364 (6)	C9—H9A	0.9300
O2—C11	1.424 (7)	C10—H10A	0.9300
N1—C2	1.474 (6)	C11—H11A	0.9600
N1—C4	1.512 (7)	C11—H11B	0.9600
N1—C12	1.521 (6)	C11—H11C	0.9600
C1—C2	1.508 (8)	C12—C13	1.499 (6)
C1—H1B	0.9700	C12—H12A	0.9700
C1—H1C	0.9700	C12—H12B	0.9700
C2—H2A	0.9700	C13—C14	1.452 (5)
C2—H2B	0.9700	C13—H13A	0.9700
C3—C4	1.497 (7)	C13—H13B	0.9700
C3—H3A	0.9700	C14—H14A	0.9600
C3—H3B	0.9700	C14—H14B	0.9600
C4—H4A	0.9700	C14—H14C	0.9600
C4—H4B	0.9700
O1—Tc1—N1	96.88 (17)	H4A—C4—H4B	107.9
O1—Tc1—S2	119.49 (14)	C6—C5—C10	117.6 (5)
N1—Tc1—S2	83.45 (13)	C6—C5—S3	121.5 (4)
O1—Tc1—S1	118.61 (15)	C10—C5—S3	120.6 (5)
N1—Tc1—S1	83.70 (13)	C5—C6—C7	121.8 (5)
S2—Tc1—S1	121.50 (7)	C5—C6—H6A	119.1
O1—Tc1—S3	105.52 (14)	C7—C6—H6A	119.1
N1—Tc1—S3	157.51 (13)	C8—C7—C6	119.6 (6)
S2—Tc1—S3	87.25 (8)	C8—C7—H7A	120.2
S1—Tc1—S3	83.81 (7)	C6—C7—H7A	120.2
C1—S1—Tc1	102.0 (2)	O2—C8—C9	117.5 (6)
C3—S2—Tc1	103.31 (19)	O2—C8—C7	123.4 (6)
C5—S3—Tc1	109.2 (2)	C9—C8—C7	119.1 (6)
C8—O2—C11	118.9 (5)	C10—C9—C8	121.2 (5)
C2—N1—C4	111.5 (5)	C10—C9—H9A	119.4
C2—N1—C12	110.8 (4)	C8—C9—H9A	119.4
C4—N1—C12	107.5 (4)	C9—C10—C5	120.7 (5)
C2—N1—Tc1	109.0 (3)	C9—C10—H10A	119.7
C4—N1—Tc1	110.3 (3)	C5—C10—H10A	119.7
C12—N1—Tc1	107.7 (3)	O2—C11—H11A	109.5
C2—C1—S1	109.8 (4)	O2—C11—H11B	109.5
C2—C1—H1B	109.7	H11A—C11—H11B	109.5
S1—C1—H1B	109.7	O2—C11—H11C	109.5
C2—C1—H1C	109.7	H11A—C11—H11C	109.5
S1—C1—H1C	109.7	H11B—C11—H11C	109.5
H1B—C1—H1C	108.2	C13—C12—N1	113.2 (5)
N1—C2—C1	110.9 (5)	C13—C12—H12A	108.9
N1—C2—H2A	109.5	N1—C12—H12A	108.9
C1—C2—H2A	109.5	C13—C12—H12B	108.9
N1—C2—H2B	109.5	N1—C12—H12B	108.9
C1—C2—H2B	109.5	H12A—C12—H12B	107.7
H2A—C2—H2B	108.1	C14—C13—C12	117.9 (6)
C4—C3—S2	111.3 (4)	C14—C13—H13A	107.8
C4—C3—H3A	109.4	C12—C13—H13A	107.8
S2—C3—H3A	109.4	C14—C13—H13B	107.8
C4—C3—H3B	109.4	C12—C13—H13B	107.8
S2—C3—H3B	109.4	H13A—C13—H13B	107.2
H3A—C3—H3B	108.0	C13—C14—H14A	109.5
C3—C4—N1	111.7 (4)	C13—C14—H14B	109.5
C3—C4—H4A	109.3	H14A—C14—H14B	109.5
N1—C4—H4A	109.3	C13—C14—H14C	109.5
C3—C4—H4B	109.3	H14A—C14—H14C	109.5
N1—C4—H4B	109.3	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1^i	0.97	2.53	3.464 (7)	162
C12—H12A···O2^ii	0.97	2.58	3.396 (7)	142

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