Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017277/fg3290sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017277/fg3290Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017277/fg3290IIsup3.hkl |
CCDC references: 962897; 962898
Chalcogenides have become increasingly important in recent years for their fascinating architectures and potential applications in photocatalysis, fast-ion conductivity, adsorption or ion exchange, and tunable electronic and optical properties (Zhou et al., 2009). These materials are usually made by flux methods at high temperature, such as AgGaS2 and LiGaS2 (Nikogosyan, 2005). Since the cobalt thioantimonate complex [Co(en)3][CoSb4S8] was prepared in ethylenediamine (en) under mild solvothermal conditions in 1996, solvothermal reactions in polyamine solutions have become a versatile route for synthesizing ternary main-group chalcogenidometallates containing transition metal complexes (Stephan & Kanatzidis, 1996). More importantly, the optical and magnetic properties of the transition metal complexes may integrate with the specific properties of the inorganic main-group element chalcogenide network, which can be expected to give rise to unusual physical properties (Liu et al., 2012).
Among these chalcogenides, research on thioantimonates has been very fruitful in the past few decades due to the stereochemical effect of the lone pair of electrons and the wide range of coordination numbers of Sb, from 3 to 6. Now, a large number of thioantimonates have been synthesized using transition metal complexes as structural directors under solvothermal conditions. Many types of [SbxSy] anionic oligomers, chains, layers and nets have been found in these compounds. For example, [M(en)3][Sb2S5] (M = Mn, Fe, Ni) contain [Sb2S5]4- dimers composed of two [SbS3] pyramids (Lees & Powell, 2005). [M(en)3][Sb2S4] (M = Co, Ni) and [M(en)3][Sb4S7] (M = Fe, Ni) feature one-dimensional [SbS2]- and [Sb4S7]2- chains composed of [SbS3] pyramids sharing corners, respectively (Stephan & Kanatzidis, 1997). [Co(en)3][Sb12S19] contains a three-dimensional [Sb12S19]2- framework composed of [SbIIIS3] pyramids and [SbIIIS4] units (Vaqueiro et al., 2004). In most of the thioantimonates, the antimony element always occurs as SbIII, and only a few compounds containing SbV have been synthesized. Here, we report two new polymorphic transition metal thioantimonates, [Co(en)3][SbS4], (I) and (II), composed of tetrahedral [SbVS4]3- anions and synthesized under solvothermal conditions in ethylenediamine.
polymorph (I) was obtained from a solvothermal reaction. A mixture of Co(CH3COO)2.4H2O powder (0.1245 g, 0.5 mmol), Sb powder (0.0608 g, 0.5 mmol), S powder (0.0641 g, 2 mmol), ethanolamine (5 ml) and H2O (1 ml) was sealed in a stainless steel reactor with a 20 ml Teflon liner and kept at 400 K for 5 d, and then cooled to room temperature. Orange prism-shaped crystals of (I), along with undefined amorphous black powders, were obtained by filtration [How were crystals of (I) separated from the black powders?], washed with ethanol and air-dried. polymorph (II) was obtained from the reaction of Co(CH3COO)2.4H2O powder (0.1245 g, 0.5 mmol), Sb2S3 powder (0.0849 g, 0.25 mmol), S powder (0.0401 g, 1.25 mmol), ethanolamine (5 ml) and H2O (1 ml) under similar conditions. Elemental analysis, calculated (%) for (I): C 14.73, H 4.94, N 17.18; found: C 14.83, H 4.85, N 17.30. Elemental analysis, calculated (%) for (II): C 14.73, H 4.94, N 17.18; found: C 14.79, H 4.99, N 17.10.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions, with C—H = 0.97 Å and N—H = 0.90 Å, and refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).
polymorph (I) crystallizes in the orthorhombic system (space group Pna21) and the asymmetric unit contains a discrete tetrahedral [SbS4]3- anion, with a [Co(en)3]3+ cation for charge compensation (Fig. 1). The Co3+ cation is coordinated by six N atoms from three en ligands, with octahedral axial trans-N—Co—N angles varying from 175.02 (11) to 176.16 (10)°. The Co—N bond lengths are in the range 1.948 (3)–1.969 (2) Å, comparable with those reported in many chalcogenides containing a CoIII complex with an amine ligand, such as [Co(en)3][AsS4] (Hu et al., 2006). In the [SbS4]3- anion, atom Sb1 is coordinated by four S atoms in a slightly distorted tetrahedral coordination environment. The S—Sb—S angles are in the range 106.71 (3)–110.41 (3)° and the Sb—S bond lengths are between 2.3249 (7) and 2.3380 (9) Å. Both bond lengths and angles are close to those observed in other compounds containing the tetrahedral [SbS4]3- anion, such as [Ni(en)3(Hen)][SbS4], [Cr(en)3][SbS3] and [Ni(en)3]2[SbS4](NO3) (Jia et al., 2004; Schur et al., 1999; Schur & Bensch, 2000).
In polymorph (I), all the S atoms of the [SbS4]3- anion are involved in hydrogen bonding with the NH2 groups of en ligands. The unique [SbS4]3- anion forms contacts with five [Co(en)3]3+ cations via weak N—H···S hydrogen bonds (Fig. 2 and Table 1), which are in accordance with those between [SbS4]3- and [M(en)3]n+ units in analogous compounds, such as [Ni(en)3(Hen)][SbS4] [2.539 (2)–2.89 (4) Å; Jia et al., 2004] and [Cr(en)3]SbS3 (2.438–2.585 Å; Schur et al., 1999). The [Co(en)3]3+ cations and [SbS4]3- anions are interlinked via N—H···S hydrogen-bonding interactions to form a three-dimensional network (Fig. 3).
polymorph (II) crystallizes in the the tetragonal system (space group P42bc) and is isomorphous with the [Co(en)3][AsS4] structure (Hu et al., 2006). The asymmetric unit of (II) contains a discrete tetrahedral [SbS4]3- anion and an octahedral [Co(en)3]3+ cation (Fig. 4). The Co—N bond lengths vary from 1.967 (3) to 1.981 (3) Å and the N—Co—N angles range from 173.99 (15) to 176.03 (15)°, in agreement with those of polymorph (I). In the tetrahedral [SbS4]3- anion, the Sb—S bond lengths and S—Sb—S angles are in the ranges 2.3130 (10)–2.3341 (11) Å and 105.55 (4)–114.00 (4)°, respectively, which are also close to those of polymorph (I).
In polymorph (II), the unique [SbS4]3- anion makes contacts with five [Co(en)3]3+ cations via weak N—H···S hydrogen bonds (Fig. 5 and Table 2). These [SbS4]3- and [Co(en)3]3+ units are interlinked to form another three-dimensional network (Fig. 6).
In summary, two new polymorphs of tris(ethylenediamine)cobalt(III) tetrathioantimonate(V), [Co(en)3][SbS4], have been synthesized and characterized. They both contain [Co(en)3]3+ cations and tetrahedral [SbS4]3- anions. These units are interlinked via hydrogen bonds to form two different types of three-dimensional network. It should be noted that the different reacting materials in the syntheses result in the distinct results for polymorphs (I) and (II). This may introduce a new strategy in the design of new chalcogenides. Further exploration in this field is in progress by our group.
For both compounds, data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Co(C2H8N2)3][SbS4] | Z = 4 |
Mr = 489.23 | F(000) = 976 |
Orthorhombic, Pna21 | Dx = 1.995 Mg m−3 |
Hall symbol: P 2c -2n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.1821 (8) Å | µ = 3.18 mm−1 |
b = 8.3971 (5) Å | T = 296 K |
c = 13.6799 (8) Å | Block, orange |
V = 1629.12 (16) Å3 | 0.12 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 3732 independent reflections |
Radiation source: fine-focus sealed tube | 3516 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (North et al., 1968) | h = −18→18 |
Tmin = 0.701, Tmax = 0.741 | k = −10→10 |
18071 measured reflections | l = −17→17 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.0148P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.038 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.38 e Å−3 |
3732 reflections | Δρmin = −0.26 e Å−3 |
163 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008) |
1 restraint | Extinction coefficient: 0 |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 1774 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.009 (13) |
[Co(C2H8N2)3][SbS4] | V = 1629.12 (16) Å3 |
Mr = 489.23 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 14.1821 (8) Å | µ = 3.18 mm−1 |
b = 8.3971 (5) Å | T = 296 K |
c = 13.6799 (8) Å | 0.12 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 3732 independent reflections |
Absorption correction: multi-scan (North et al., 1968) | 3516 reflections with I > 2σ(I) |
Tmin = 0.701, Tmax = 0.741 | Rint = 0.033 |
18071 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.038 | Δρmax = 0.38 e Å−3 |
S = 1.03 | Δρmin = −0.26 e Å−3 |
3732 reflections | Absolute structure: Flack (1983), with 1774 Friedel pairs |
163 parameters | Absolute structure parameter: 0.009 (13) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Sb1 | 0.025359 (12) | 0.03333 (2) | 0.011795 (14) | 0.02007 (5) | |
Co1 | 0.37507 (3) | −0.01764 (4) | 0.21870 (3) | 0.01623 (8) | |
S4 | 0.05554 (6) | 0.01213 (9) | 0.17931 (6) | 0.02814 (17) | |
S3 | 0.00305 (6) | −0.22462 (9) | −0.04611 (7) | 0.03080 (18) | |
S2 | −0.11059 (5) | 0.18379 (10) | −0.01030 (6) | 0.0348 (2) | |
S1 | 0.15377 (6) | 0.15135 (11) | −0.06531 (7) | 0.0374 (2) | |
N4 | 0.48017 (18) | 0.0083 (3) | 0.12756 (19) | 0.0238 (6) | |
H1 | 0.4862 | −0.0796 | 0.0905 | 0.029* | |
H2 | 0.4693 | 0.0918 | 0.0878 | 0.029* | |
N6 | 0.28411 (18) | −0.0045 (3) | 0.11235 (19) | 0.0253 (6) | |
H3 | 0.2272 | 0.0228 | 0.1362 | 0.030* | |
H4 | 0.3022 | 0.0710 | 0.0696 | 0.030* | |
N2 | 0.27095 (17) | −0.0289 (3) | 0.31290 (18) | 0.0232 (5) | |
H5 | 0.2174 | −0.0565 | 0.2819 | 0.028* | |
H6 | 0.2835 | −0.1036 | 0.3582 | 0.028* | |
N5 | 0.37140 (16) | −0.2484 (3) | 0.19882 (17) | 0.0245 (6) | |
H7 | 0.4246 | −0.2808 | 0.1689 | 0.029* | |
H8 | 0.3673 | −0.2983 | 0.2569 | 0.029* | |
N3 | 0.47201 (18) | −0.0457 (3) | 0.3193 (2) | 0.0243 (6) | |
H9 | 0.4736 | 0.0404 | 0.3584 | 0.029* | |
H10 | 0.4582 | −0.1313 | 0.3563 | 0.029* | |
N1 | 0.36874 (16) | 0.2143 (3) | 0.23858 (18) | 0.0234 (5) | |
H11 | 0.4169 | 0.2464 | 0.2766 | 0.028* | |
H12 | 0.3731 | 0.2648 | 0.1807 | 0.028* | |
C4 | 0.5675 (2) | 0.0353 (4) | 0.1840 (3) | 0.0357 (8) | |
H13 | 0.5719 | 0.1463 | 0.2032 | 0.043* | |
H14 | 0.6221 | 0.0094 | 0.1444 | 0.043* | |
C6 | 0.2774 (2) | −0.1597 (4) | 0.0620 (2) | 0.0325 (8) | |
H15 | 0.3267 | −0.1687 | 0.0131 | 0.039* | |
H16 | 0.2169 | −0.1694 | 0.0296 | 0.039* | |
C5 | 0.2882 (2) | −0.2888 (4) | 0.1376 (3) | 0.0338 (8) | |
H17 | 0.2320 | −0.2951 | 0.1778 | 0.041* | |
H18 | 0.2976 | −0.3910 | 0.1060 | 0.041* | |
C3 | 0.5650 (2) | −0.0679 (4) | 0.2721 (3) | 0.0369 (8) | |
H19 | 0.5735 | −0.1785 | 0.2537 | 0.044* | |
H20 | 0.6151 | −0.0383 | 0.3168 | 0.044* | |
C2 | 0.2585 (2) | 0.1277 (4) | 0.3609 (2) | 0.0313 (8) | |
H21 | 0.3018 | 0.1381 | 0.4155 | 0.038* | |
H22 | 0.1946 | 0.1382 | 0.3854 | 0.038* | |
C1 | 0.2781 (2) | 0.2535 (3) | 0.2860 (2) | 0.0308 (7) | |
H23 | 0.2279 | 0.2561 | 0.2378 | 0.037* | |
H24 | 0.2818 | 0.3573 | 0.3169 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sb1 | 0.01940 (9) | 0.01702 (8) | 0.02379 (9) | 0.00013 (7) | −0.00056 (10) | 0.00062 (11) |
Co1 | 0.01599 (18) | 0.01574 (18) | 0.01696 (18) | 0.00035 (15) | −0.00010 (15) | −0.00115 (16) |
S4 | 0.0250 (4) | 0.0349 (4) | 0.0245 (4) | 0.0002 (3) | −0.0010 (3) | 0.0012 (3) |
S3 | 0.0375 (4) | 0.0200 (4) | 0.0349 (4) | −0.0023 (3) | 0.0095 (4) | −0.0061 (3) |
S2 | 0.0318 (4) | 0.0323 (4) | 0.0404 (6) | 0.0136 (3) | −0.0112 (3) | −0.0108 (4) |
S1 | 0.0298 (4) | 0.0421 (5) | 0.0404 (5) | −0.0110 (4) | −0.0026 (4) | 0.0207 (4) |
N4 | 0.0241 (14) | 0.0217 (13) | 0.0257 (14) | 0.0033 (10) | 0.0036 (11) | 0.0024 (10) |
N6 | 0.0228 (15) | 0.0300 (15) | 0.0230 (13) | 0.0025 (11) | −0.0009 (11) | −0.0011 (10) |
N2 | 0.0240 (13) | 0.0227 (12) | 0.0229 (13) | 0.0010 (11) | 0.0027 (11) | −0.0016 (10) |
N5 | 0.0246 (13) | 0.0206 (12) | 0.0285 (15) | 0.0010 (10) | 0.0035 (11) | −0.0034 (11) |
N3 | 0.0249 (15) | 0.0219 (13) | 0.0262 (14) | 0.0001 (11) | −0.0040 (11) | 0.0001 (11) |
N1 | 0.0227 (13) | 0.0216 (13) | 0.0258 (14) | −0.0002 (10) | −0.0008 (10) | −0.0008 (10) |
C4 | 0.0175 (17) | 0.0362 (19) | 0.053 (2) | −0.0025 (14) | 0.0023 (16) | 0.0080 (17) |
C6 | 0.0231 (16) | 0.044 (2) | 0.0302 (17) | 0.0070 (14) | −0.0086 (14) | −0.0196 (16) |
C5 | 0.0240 (17) | 0.0264 (17) | 0.051 (2) | −0.0050 (13) | 0.0014 (16) | −0.0195 (15) |
C3 | 0.0237 (17) | 0.040 (2) | 0.047 (2) | 0.0044 (15) | −0.0063 (16) | 0.0009 (17) |
C2 | 0.0257 (17) | 0.037 (2) | 0.0312 (18) | −0.0002 (15) | 0.0070 (13) | −0.0152 (14) |
C1 | 0.0250 (16) | 0.0252 (16) | 0.0423 (19) | 0.0060 (13) | −0.0009 (15) | −0.0114 (15) |
Sb1—S2 | 2.3249 (7) | N3—C3 | 1.480 (4) |
Sb1—S1 | 2.3262 (8) | N3—H9 | 0.9000 |
Sb1—S3 | 2.3279 (8) | N3—H10 | 0.9000 |
Sb1—S4 | 2.3380 (9) | N1—C1 | 1.477 (4) |
Co1—N6 | 1.948 (3) | N1—H11 | 0.9000 |
Co1—N4 | 1.955 (3) | N1—H12 | 0.9000 |
Co1—N5 | 1.958 (2) | C4—C3 | 1.484 (5) |
Co1—N3 | 1.960 (3) | C4—H13 | 0.9700 |
Co1—N2 | 1.962 (2) | C4—H14 | 0.9700 |
Co1—N1 | 1.969 (2) | C6—C5 | 1.506 (5) |
N4—C4 | 1.477 (4) | C6—H15 | 0.9700 |
N4—H1 | 0.9000 | C6—H16 | 0.9700 |
N4—H2 | 0.9000 | C5—H17 | 0.9700 |
N6—C6 | 1.477 (4) | C5—H18 | 0.9700 |
N6—H3 | 0.9000 | C3—H19 | 0.9700 |
N6—H4 | 0.9000 | C3—H20 | 0.9700 |
N2—C2 | 1.480 (4) | C2—C1 | 1.499 (4) |
N2—H5 | 0.9000 | C2—H21 | 0.9700 |
N2—H6 | 0.9000 | C2—H22 | 0.9700 |
N5—C5 | 1.486 (4) | C1—H23 | 0.9700 |
N5—H7 | 0.9000 | C1—H24 | 0.9700 |
N5—H8 | 0.9000 | ||
S2—Sb1—S1 | 111.03 (3) | Co1—N3—H9 | 109.8 |
S2—Sb1—S3 | 110.41 (3) | C3—N3—H10 | 109.8 |
S1—Sb1—S3 | 110.40 (3) | Co1—N3—H10 | 109.8 |
S2—Sb1—S4 | 108.70 (3) | H9—N3—H10 | 108.2 |
S1—Sb1—S4 | 109.48 (3) | C1—N1—Co1 | 108.71 (17) |
S3—Sb1—S4 | 106.71 (3) | C1—N1—H11 | 109.9 |
N6—Co1—N4 | 91.28 (11) | Co1—N1—H11 | 109.9 |
N6—Co1—N5 | 86.26 (10) | C1—N1—H12 | 109.9 |
N4—Co1—N5 | 92.41 (10) | Co1—N1—H12 | 109.9 |
N6—Co1—N3 | 175.02 (11) | H11—N1—H12 | 108.3 |
N4—Co1—N3 | 85.79 (11) | N4—C4—C3 | 108.3 (3) |
N5—Co1—N3 | 89.84 (10) | N4—C4—H13 | 110.0 |
N6—Co1—N2 | 89.71 (10) | C3—C4—H13 | 110.0 |
N4—Co1—N2 | 176.16 (10) | N4—C4—H14 | 110.0 |
N5—Co1—N2 | 91.35 (10) | C3—C4—H14 | 110.0 |
N3—Co1—N2 | 93.49 (11) | H13—C4—H14 | 108.4 |
N6—Co1—N1 | 90.96 (10) | N6—C6—C5 | 108.0 (2) |
N4—Co1—N1 | 90.71 (10) | N6—C6—H15 | 110.1 |
N5—Co1—N1 | 175.86 (10) | C5—C6—H15 | 110.1 |
N3—Co1—N1 | 93.10 (10) | N6—C6—H16 | 110.1 |
N2—Co1—N1 | 85.56 (10) | C5—C6—H16 | 110.1 |
C4—N4—Co1 | 108.8 (2) | H15—C6—H16 | 108.4 |
C4—N4—H1 | 109.9 | N5—C5—C6 | 107.7 (2) |
Co1—N4—H1 | 109.9 | N5—C5—H17 | 110.2 |
C4—N4—H2 | 109.9 | C6—C5—H17 | 110.2 |
Co1—N4—H2 | 109.9 | N5—C5—H18 | 110.2 |
H1—N4—H2 | 108.3 | C6—C5—H18 | 110.2 |
C6—N6—Co1 | 109.92 (19) | H17—C5—H18 | 108.5 |
C6—N6—H3 | 109.7 | N3—C3—C4 | 107.6 (3) |
Co1—N6—H3 | 109.7 | N3—C3—H19 | 110.2 |
C6—N6—H4 | 109.7 | C4—C3—H19 | 110.2 |
Co1—N6—H4 | 109.7 | N3—C3—H20 | 110.2 |
H3—N6—H4 | 108.2 | C4—C3—H20 | 110.2 |
C2—N2—Co1 | 109.79 (18) | H19—C3—H20 | 108.5 |
C2—N2—H5 | 109.7 | N2—C2—C1 | 107.5 (2) |
Co1—N2—H5 | 109.7 | N2—C2—H21 | 110.2 |
C2—N2—H6 | 109.7 | C1—C2—H21 | 110.2 |
Co1—N2—H6 | 109.7 | N2—C2—H22 | 110.2 |
H5—N2—H6 | 108.2 | C1—C2—H22 | 110.2 |
C5—N5—Co1 | 108.99 (18) | H21—C2—H22 | 108.5 |
C5—N5—H7 | 109.9 | N1—C1—C2 | 107.7 (2) |
Co1—N5—H7 | 109.9 | N1—C1—H23 | 110.2 |
C5—N5—H8 | 109.9 | C2—C1—H23 | 110.2 |
Co1—N5—H8 | 109.9 | N1—C1—H24 | 110.2 |
H7—N5—H8 | 108.3 | C2—C1—H24 | 110.2 |
C3—N3—Co1 | 109.46 (19) | H23—C1—H24 | 108.5 |
C3—N3—H9 | 109.8 | ||
N6—Co1—N4—C4 | 169.42 (19) | N6—Co1—N3—C3 | 41.7 (13) |
N5—Co1—N4—C4 | −104.27 (19) | N4—Co1—N3—C3 | −12.23 (19) |
N3—Co1—N4—C4 | −14.61 (19) | N5—Co1—N3—C3 | 80.2 (2) |
N2—Co1—N4—C4 | 64.6 (16) | N2—Co1—N3—C3 | 171.55 (19) |
N1—Co1—N4—C4 | 78.44 (19) | N1—Co1—N3—C3 | −102.7 (2) |
N4—Co1—N6—C6 | 80.3 (2) | N6—Co1—N1—C1 | 73.6 (2) |
N5—Co1—N6—C6 | −12.0 (2) | N4—Co1—N1—C1 | 164.9 (2) |
N3—Co1—N6—C6 | 26.6 (14) | N5—Co1—N1—C1 | 25.9 (16) |
N2—Co1—N6—C6 | −103.4 (2) | N3—Co1—N1—C1 | −109.2 (2) |
N1—Co1—N6—C6 | 171.1 (2) | N2—Co1—N1—C1 | −16.0 (2) |
N6—Co1—N2—C2 | −102.5 (2) | Co1—N4—C4—C3 | 38.5 (3) |
N4—Co1—N2—C2 | 2.3 (17) | Co1—N6—C6—C5 | 35.7 (3) |
N5—Co1—N2—C2 | 171.23 (19) | Co1—N5—C5—C6 | 37.7 (3) |
N3—Co1—N2—C2 | 81.3 (2) | N6—C6—C5—N5 | −47.8 (3) |
N1—Co1—N2—C2 | −11.53 (19) | Co1—N3—C3—C4 | 36.3 (3) |
N6—Co1—N5—C5 | −14.7 (2) | N4—C4—C3—N3 | −48.9 (3) |
N4—Co1—N5—C5 | −105.8 (2) | Co1—N2—C2—C1 | 36.2 (3) |
N3—Co1—N5—C5 | 168.4 (2) | Co1—N1—C1—C2 | 39.9 (3) |
N2—Co1—N5—C5 | 74.9 (2) | N2—C2—C1—N1 | −49.7 (3) |
N1—Co1—N5—C5 | 33.2 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H1···S3i | 0.90 | 2.50 | 3.380 (3) | 165.9 |
N4—H2···S2ii | 0.90 | 2.58 | 3.449 (3) | 163.7 |
N6—H3···S4 | 0.90 | 2.51 | 3.371 (3) | 161.2 |
N6—H4···S2ii | 0.90 | 2.64 | 3.507 (3) | 162.3 |
N2—H5···S4 | 0.90 | 2.75 | 3.577 (3) | 152.9 |
N2—H6···S1iii | 0.90 | 2.47 | 3.335 (3) | 160.5 |
N5—H7···S4i | 0.90 | 2.69 | 3.434 (2) | 140.6 |
N5—H8···S1iii | 0.90 | 2.49 | 3.354 (2) | 161.8 |
N3—H9···S3iv | 0.90 | 2.39 | 3.284 (3) | 172.8 |
N3—H10···S1iii | 0.90 | 2.65 | 3.485 (3) | 155.3 |
N1—H11···S3iv | 0.90 | 2.69 | 3.499 (3) | 150.3 |
N1—H12···S2ii | 0.90 | 2.66 | 3.523 (3) | 161.3 |
Symmetry codes: (i) x+1/2, −y−1/2, z; (ii) x+1/2, −y+1/2, z; (iii) −x+1/2, y−1/2, z+1/2; (iv) −x+1/2, y+1/2, z+1/2. |
[Co(C2H8N2)3][SbS4] | F(000) = 1952 |
Mr = 489.23 | Dx = 1.987 Mg m−3 |
Tetragonal, P42bc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 4c -2ab | µ = 3.17 mm−1 |
a = 15.4909 (11) Å | T = 296 K |
c = 13.6285 (9) Å | Block, orange |
V = 3270.4 (4) Å3 | 0.15 × 0.1 × 0.1 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 3783 independent reflections |
Radiation source: fine-focus sealed tube | 3449 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 27.6°, θmin = 1.9° |
Absorption correction: multi-scan (North et al., 1968) | h = −20→20 |
Tmin = 0.648, Tmax = 0.742 | k = −20→20 |
35970 measured reflections | l = −17→17 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.021 | w = 1/[σ2(Fo2) + (0.013P)2 + 3.5797P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.045 | (Δ/σ)max = 0.002 |
S = 1.08 | Δρmax = 0.32 e Å−3 |
3783 reflections | Δρmin = −0.31 e Å−3 |
163 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008) |
1 restraint | Extinction coefficient: 0 |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 1808 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.328 (17) |
[Co(C2H8N2)3][SbS4] | Z = 8 |
Mr = 489.23 | Mo Kα radiation |
Tetragonal, P42bc | µ = 3.17 mm−1 |
a = 15.4909 (11) Å | T = 296 K |
c = 13.6285 (9) Å | 0.15 × 0.1 × 0.1 mm |
V = 3270.4 (4) Å3 |
Bruker SMART CCD area-detector diffractometer | 3783 independent reflections |
Absorption correction: multi-scan (North et al., 1968) | 3449 reflections with I > 2σ(I) |
Tmin = 0.648, Tmax = 0.742 | Rint = 0.047 |
35970 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.045 | Δρmax = 0.32 e Å−3 |
S = 1.08 | Δρmin = −0.31 e Å−3 |
3783 reflections | Absolute structure: Flack (1983), with 1808 Friedel pairs |
163 parameters | Absolute structure parameter: 0.328 (17) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.74447 (3) | 0.52138 (3) | 0.60043 (4) | 0.01911 (10) | |
N1 | 0.7917 (2) | 0.4074 (2) | 0.6331 (2) | 0.0266 (7) | |
H13 | 0.7489 | 0.3680 | 0.6342 | 0.032* | |
H14 | 0.8305 | 0.3912 | 0.5876 | 0.032* | |
N2 | 0.8247 (2) | 0.5655 (2) | 0.7009 (2) | 0.0301 (8) | |
H15 | 0.8559 | 0.6093 | 0.6759 | 0.036* | |
H16 | 0.7946 | 0.5857 | 0.7525 | 0.036* | |
N3 | 0.65204 (19) | 0.5041 (2) | 0.6961 (2) | 0.0254 (7) | |
H17 | 0.6264 | 0.4528 | 0.6855 | 0.030* | |
H18 | 0.6740 | 0.5039 | 0.7572 | 0.030* | |
N4 | 0.6954 (2) | 0.6376 (2) | 0.5831 (2) | 0.0278 (7) | |
H19 | 0.7379 | 0.6771 | 0.5803 | 0.033* | |
H20 | 0.6655 | 0.6399 | 0.5265 | 0.033* | |
N5 | 0.82859 (19) | 0.53845 (18) | 0.4944 (3) | 0.0257 (7) | |
H21 | 0.8303 | 0.5947 | 0.4779 | 0.031* | |
H22 | 0.8815 | 0.5230 | 0.5153 | 0.031* | |
N6 | 0.67249 (19) | 0.47311 (19) | 0.4957 (3) | 0.0281 (7) | |
H23 | 0.6682 | 0.4156 | 0.5035 | 0.034* | |
H24 | 0.6190 | 0.4956 | 0.4997 | 0.034* | |
C1 | 0.7094 (3) | 0.4917 (3) | 0.3987 (3) | 0.0349 (10) | |
H11 | 0.6920 | 0.5488 | 0.3770 | 0.042* | |
H12 | 0.6893 | 0.4498 | 0.3511 | 0.042* | |
C2 | 0.8058 (3) | 0.4871 (3) | 0.4083 (3) | 0.0341 (9) | |
H9 | 0.8242 | 0.4278 | 0.4168 | 0.041* | |
H10 | 0.8333 | 0.5103 | 0.3501 | 0.041* | |
C3 | 0.5875 (2) | 0.5750 (3) | 0.6865 (3) | 0.0274 (8) | |
H7 | 0.5541 | 0.5805 | 0.7464 | 0.033* | |
H8 | 0.5482 | 0.5631 | 0.6327 | 0.033* | |
C4 | 0.6371 (2) | 0.6570 (2) | 0.6670 (3) | 0.0284 (9) | |
H5 | 0.5980 | 0.7037 | 0.6504 | 0.034* | |
H6 | 0.6703 | 0.6735 | 0.7243 | 0.034* | |
C5 | 0.8831 (3) | 0.4955 (3) | 0.7333 (3) | 0.0407 (11) | |
H3 | 0.9035 | 0.5069 | 0.7993 | 0.049* | |
H4 | 0.9327 | 0.4920 | 0.6900 | 0.049* | |
C6 | 0.8337 (3) | 0.4129 (3) | 0.7308 (3) | 0.0383 (10) | |
H1 | 0.8723 | 0.3643 | 0.7403 | 0.046* | |
H2 | 0.7906 | 0.4121 | 0.7823 | 0.046* | |
Sb1 | 0.942464 (13) | 0.756304 (13) | 0.506129 (18) | 0.02129 (5) | |
S1 | 1.02219 (7) | 0.86780 (7) | 0.43621 (8) | 0.0339 (2) | |
S2 | 1.02036 (6) | 0.62934 (6) | 0.51957 (11) | 0.0416 (3) | |
S3 | 0.88830 (7) | 0.78789 (7) | 0.66187 (8) | 0.0341 (2) | |
S4 | 0.82224 (6) | 0.73910 (7) | 0.40527 (8) | 0.0328 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0178 (2) | 0.0206 (2) | 0.0189 (2) | −0.0003 (2) | −0.0008 (2) | 0.0000 (2) |
N1 | 0.0246 (16) | 0.0255 (17) | 0.0298 (18) | 0.0051 (13) | 0.0030 (13) | 0.0011 (13) |
N2 | 0.0284 (18) | 0.0329 (18) | 0.0290 (18) | −0.0026 (14) | −0.0032 (14) | −0.0029 (14) |
N3 | 0.0235 (17) | 0.0284 (17) | 0.0243 (16) | 0.0031 (14) | −0.0010 (13) | 0.0035 (13) |
N4 | 0.0306 (18) | 0.0255 (16) | 0.0274 (17) | 0.0011 (13) | 0.0014 (14) | 0.0039 (13) |
N5 | 0.0250 (14) | 0.0256 (15) | 0.0266 (19) | −0.0015 (11) | 0.0029 (15) | 0.0054 (15) |
N6 | 0.0263 (15) | 0.0298 (15) | 0.0283 (18) | −0.0034 (12) | −0.0066 (16) | −0.0031 (16) |
C1 | 0.041 (3) | 0.040 (2) | 0.024 (2) | −0.0006 (19) | −0.0029 (19) | −0.0051 (18) |
C2 | 0.041 (2) | 0.038 (2) | 0.023 (2) | 0.0064 (19) | 0.0063 (18) | −0.0028 (18) |
C3 | 0.0227 (19) | 0.035 (2) | 0.0244 (19) | 0.0058 (16) | 0.0052 (15) | −0.0029 (17) |
C4 | 0.032 (2) | 0.028 (2) | 0.026 (2) | 0.0083 (16) | −0.0037 (17) | −0.0059 (16) |
C5 | 0.025 (2) | 0.062 (3) | 0.035 (2) | 0.010 (2) | −0.0125 (19) | −0.009 (2) |
C6 | 0.041 (3) | 0.049 (3) | 0.025 (2) | 0.019 (2) | −0.0039 (18) | 0.0057 (19) |
Sb1 | 0.01989 (10) | 0.02054 (11) | 0.02346 (10) | 0.00045 (8) | −0.00092 (12) | 0.00065 (14) |
S1 | 0.0354 (5) | 0.0388 (6) | 0.0273 (5) | −0.0161 (5) | −0.0035 (4) | 0.0052 (5) |
S2 | 0.0293 (5) | 0.0308 (5) | 0.0648 (8) | 0.0106 (4) | −0.0106 (6) | −0.0025 (6) |
S3 | 0.0399 (6) | 0.0360 (6) | 0.0264 (5) | 0.0024 (5) | 0.0060 (5) | −0.0012 (4) |
S4 | 0.0257 (5) | 0.0392 (6) | 0.0335 (5) | −0.0057 (4) | −0.0090 (4) | 0.0104 (5) |
Co1—N3 | 1.955 (3) | N6—H23 | 0.9000 |
Co1—N6 | 1.960 (3) | N6—H24 | 0.9001 |
Co1—N1 | 1.963 (3) | C1—C2 | 1.500 (6) |
Co1—N5 | 1.964 (3) | C1—H11 | 0.9700 |
Co1—N4 | 1.968 (3) | C1—H12 | 0.9700 |
Co1—N2 | 1.971 (3) | C2—H9 | 0.9700 |
N1—C6 | 1.484 (5) | C2—H10 | 0.9700 |
N1—H13 | 0.9001 | C3—C4 | 1.508 (5) |
N1—H14 | 0.8999 | C3—H7 | 0.9700 |
N2—C5 | 1.480 (5) | C3—H8 | 0.9700 |
N2—H15 | 0.8999 | C4—H5 | 0.9700 |
N2—H16 | 0.9000 | C4—H6 | 0.9700 |
N3—C3 | 1.492 (5) | C5—C6 | 1.492 (6) |
N3—H17 | 0.9001 | C5—H3 | 0.9700 |
N3—H18 | 0.9001 | C5—H4 | 0.9700 |
N4—C4 | 1.487 (5) | C6—H1 | 0.9700 |
N4—H19 | 0.9001 | C6—H2 | 0.9700 |
N4—H20 | 0.9000 | Sb1—S2 | 2.3147 (10) |
N5—C2 | 1.461 (5) | Sb1—S1 | 2.3273 (10) |
N5—H21 | 0.9000 | Sb1—S4 | 2.3300 (10) |
N5—H22 | 0.9000 | Sb1—S3 | 2.3342 (11) |
N6—C1 | 1.468 (5) | ||
N3—Co1—N6 | 90.96 (13) | Co1—N6—H23 | 109.4 |
N3—Co1—N1 | 89.89 (13) | C1—N6—H24 | 109.7 |
N6—Co1—N1 | 91.94 (13) | Co1—N6—H24 | 109.3 |
N3—Co1—N5 | 174.39 (14) | H23—N6—H24 | 108.0 |
N6—Co1—N5 | 83.84 (14) | N6—C1—C2 | 107.4 (3) |
N1—Co1—N5 | 92.35 (13) | N6—C1—H11 | 110.2 |
N3—Co1—N4 | 85.56 (13) | C2—C1—H11 | 110.2 |
N6—Co1—N4 | 92.37 (13) | N6—C1—H12 | 110.2 |
N1—Co1—N4 | 173.78 (13) | C2—C1—H12 | 110.2 |
N5—Co1—N4 | 92.57 (13) | H11—C1—H12 | 108.5 |
N3—Co1—N2 | 92.67 (14) | N5—C2—C1 | 106.6 (3) |
N6—Co1—N2 | 175.51 (14) | N5—C2—H9 | 110.4 |
N1—Co1—N2 | 85.41 (13) | C1—C2—H9 | 110.4 |
N5—Co1—N2 | 92.63 (13) | N5—C2—H10 | 110.4 |
N4—Co1—N2 | 90.56 (14) | C1—C2—H10 | 110.4 |
C6—N1—Co1 | 108.4 (2) | H9—C2—H10 | 108.6 |
C6—N1—H13 | 110.3 | N3—C3—C4 | 107.1 (3) |
Co1—N1—H13 | 109.8 | N3—C3—H7 | 110.3 |
C6—N1—H14 | 109.9 | C4—C3—H7 | 110.3 |
Co1—N1—H14 | 110.0 | N3—C3—H8 | 110.3 |
H13—N1—H14 | 108.4 | C4—C3—H8 | 110.3 |
C5—N2—Co1 | 109.8 (2) | H7—C3—H8 | 108.6 |
C5—N2—H15 | 109.7 | N4—C4—C3 | 106.0 (3) |
Co1—N2—H15 | 109.8 | N4—C4—H5 | 110.5 |
C5—N2—H16 | 109.7 | C3—C4—H5 | 110.5 |
Co1—N2—H16 | 109.6 | N4—C4—H6 | 110.5 |
H15—N2—H16 | 108.2 | C3—C4—H6 | 110.5 |
C3—N3—Co1 | 109.4 (2) | H5—C4—H6 | 108.7 |
C3—N3—H17 | 109.9 | N2—C5—C6 | 108.0 (3) |
Co1—N3—H17 | 109.7 | N2—C5—H3 | 110.1 |
C3—N3—H18 | 109.7 | C6—C5—H3 | 110.1 |
Co1—N3—H18 | 109.9 | N2—C5—H4 | 110.1 |
H17—N3—H18 | 108.2 | C6—C5—H4 | 110.1 |
C4—N4—Co1 | 109.1 (2) | H3—C5—H4 | 108.4 |
C4—N4—H19 | 109.9 | N1—C6—C5 | 107.2 (3) |
Co1—N4—H19 | 110.1 | N1—C6—H1 | 110.3 |
C4—N4—H20 | 109.8 | C5—C6—H1 | 110.3 |
Co1—N4—H20 | 109.7 | N1—C6—H2 | 110.3 |
H19—N4—H20 | 108.3 | C5—C6—H2 | 110.3 |
C2—N5—Co1 | 110.9 (2) | H1—C6—H2 | 108.5 |
C2—N5—H21 | 109.5 | S2—Sb1—S1 | 112.73 (4) |
Co1—N5—H21 | 109.5 | S2—Sb1—S4 | 111.48 (4) |
C2—N5—H22 | 109.3 | S1—Sb1—S4 | 105.52 (4) |
Co1—N5—H22 | 109.6 | S2—Sb1—S3 | 107.07 (4) |
H21—N5—H22 | 108.1 | S1—Sb1—S3 | 114.05 (4) |
C1—N6—Co1 | 111.1 (2) | S4—Sb1—S3 | 105.85 (4) |
C1—N6—H23 | 109.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H13···S3i | 0.90 | 2.49 | 3.369 (3) | 166 |
N1—H14···S2ii | 0.90 | 2.51 | 3.346 (3) | 155 |
N2—H15···S3 | 0.90 | 2.82 | 3.622 (3) | 150 |
N2—H16···S4iii | 0.90 | 2.58 | 3.429 (3) | 158 |
N3—H17···S3i | 0.90 | 2.58 | 3.439 (3) | 159 |
N3—H18···S1iii | 0.90 | 2.56 | 3.312 (3) | 142 |
N4—H19···S4 | 0.90 | 2.88 | 3.494 (3) | 126 |
N4—H20···S1iv | 0.90 | 2.54 | 3.348 (3) | 150 |
N5—H21···S4 | 0.90 | 2.45 | 3.338 (3) | 170 |
N5—H22···S2 | 0.90 | 2.71 | 3.305 (3) | 125 |
N5—H22···S2ii | 0.90 | 2.81 | 3.514 (3) | 136 |
N6—H24···S1iv | 0.90 | 2.73 | 3.486 (3) | 142 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+2, −y+1, z; (iii) −y+3/2, −x+3/2, z+1/2; (iv) x−1/2, −y+3/2, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Co(C2H8N2)3][SbS4] | [Co(C2H8N2)3][SbS4] |
Mr | 489.23 | 489.23 |
Crystal system, space group | Orthorhombic, Pna21 | Tetragonal, P42bc |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 14.1821 (8), 8.3971 (5), 13.6799 (8) | 15.4909 (11), 15.4909 (11), 13.6285 (9) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 1629.12 (16) | 3270.4 (4) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 3.18 | 3.17 |
Crystal size (mm) | 0.12 × 0.10 × 0.10 | 0.15 × 0.1 × 0.1 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (North et al., 1968) | Multi-scan (North et al., 1968) |
Tmin, Tmax | 0.701, 0.741 | 0.648, 0.742 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18071, 3732, 3516 | 35970, 3783, 3449 |
Rint | 0.033 | 0.047 |
(sin θ/λ)max (Å−1) | 0.651 | 0.651 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.038, 1.03 | 0.021, 0.045, 1.08 |
No. of reflections | 3732 | 3783 |
No. of parameters | 163 | 163 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.26 | 0.32, −0.31 |
Absolute structure | Flack (1983), with 1774 Friedel pairs | Flack (1983), with 1808 Friedel pairs |
Absolute structure parameter | 0.009 (13) | 0.328 (17) |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H1···S3i | 0.90 | 2.50 | 3.380 (3) | 165.9 |
N4—H2···S2ii | 0.90 | 2.58 | 3.449 (3) | 163.7 |
N6—H3···S4 | 0.90 | 2.51 | 3.371 (3) | 161.2 |
N6—H4···S2ii | 0.90 | 2.64 | 3.507 (3) | 162.3 |
N2—H5···S4 | 0.90 | 2.75 | 3.577 (3) | 152.9 |
N2—H6···S1iii | 0.90 | 2.47 | 3.335 (3) | 160.5 |
N5—H7···S4i | 0.90 | 2.69 | 3.434 (2) | 140.6 |
N5—H8···S1iii | 0.90 | 2.49 | 3.354 (2) | 161.8 |
N3—H9···S3iv | 0.90 | 2.39 | 3.284 (3) | 172.8 |
N3—H10···S1iii | 0.90 | 2.65 | 3.485 (3) | 155.3 |
N1—H11···S3iv | 0.90 | 2.69 | 3.499 (3) | 150.3 |
N1—H12···S2ii | 0.90 | 2.66 | 3.523 (3) | 161.3 |
Symmetry codes: (i) x+1/2, −y−1/2, z; (ii) x+1/2, −y+1/2, z; (iii) −x+1/2, y−1/2, z+1/2; (iv) −x+1/2, y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H13···S3i | 0.90 | 2.49 | 3.369 (3) | 165.5 |
N1—H14···S2ii | 0.90 | 2.51 | 3.346 (3) | 154.9 |
N2—H15···S3 | 0.90 | 2.82 | 3.622 (3) | 149.5 |
N2—H16···S4iii | 0.90 | 2.58 | 3.429 (3) | 158.2 |
N3—H17···S3i | 0.90 | 2.58 | 3.439 (3) | 158.6 |
N3—H18···S1iii | 0.90 | 2.56 | 3.312 (3) | 142.0 |
N4—H19···S4 | 0.90 | 2.88 | 3.494 (3) | 126.4 |
N4—H20···S1iv | 0.90 | 2.54 | 3.348 (3) | 149.6 |
N5—H21···S4 | 0.90 | 2.45 | 3.338 (3) | 169.6 |
N5—H22···S2 | 0.90 | 2.71 | 3.305 (3) | 124.6 |
N5—H22···S2ii | 0.90 | 2.81 | 3.514 (3) | 136.3 |
N6—H24···S1iv | 0.90 | 2.73 | 3.486 (3) | 141.7 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+2, −y+1, z; (iii) −y+3/2, −x+3/2, z+1/2; (iv) x−1/2, −y+3/2, z. |