A Variable Temperature X-ray Diffraction Investigation of [PPN+][S4N5−]: Supramolecular Interactions Governing an Order/Disorder Transformation and the First High Resolution X-ray Structure of the Anion
Abstract
:1. Introduction
2. Results and Discussion
2.1. Sample Preparation and X-ray Diffraction Experiments
2.1.1. The structure of [PPN+][S4N5−]∙CH3CN
2.1.2. S4N5− Disorder as a Function of Temperature
Parameter, Å or ° | 100 K a | 120 K a | 172 K a | Flues et al. b | Martan et al. c | DFT d |
---|---|---|---|---|---|---|
S3∙∙∙S7 | 2.695(1) | 2.697(2) | 2.724(6) | 2.71(1) | 2.657(10) | 2.8417 |
S1∙∙∙S5 | 2.769(1) | 2.763(3) | 2.760(6) | 2.75(1) | 2.795 | 2.7913 |
S1–N2 | 1.657(2) | 1.657(3) | 1.690(8) | 1.62(2) | 1.67(1) | 1.6667 |
S1–N8 | 1.666(2) | 1.668(3) | 1.655(6) | 1.65(2) | 1.67(1) g | 1.6688 |
S5–N4 | 1.677(2) | 1.676(4) | 1.703(8) | 1.63(2) | 1.67(2) | 1.6687 |
S5–N6 | 1.6710(17) | 1.670(3) | 1.683(8) | 1.66(2) | 1.67(2) g | 1.6667 |
S3–N2 | 1.614(2) | 1.619(3) | 1.605(9) | 1.61(2) | 1.61(1) | 1.6171 |
S3–N4 | 1.604(2) | 1.599(4) | 1.574(8) | 1.63(2) | 1.61(1) | 1.6164 |
S7–N6 | 1.6080(17) | 1.608(3) | 1.581(6) | 1.60(2) | 1.61(1) g | 1.6172 |
S7–N8 | 1.6170(18) | 1.615(3) | 1.610(6) | 1.57(2) | 1.61(1) g | 1.6164 |
S1–N9 | 1.6450(17 | 1.640(4) | 1.664(5) | 1.68(2) | 1.64(2) | 1.6484 |
S5–N9 | 1.6446(19) | 1.621(5) | 1.665(5) | 1.64(2) | 1.64(2) | 1.6485 |
P1–N1 | 1.5855(11) | 1.5838(14) | 1.5803(12) | — | — | — |
P2–N1 | 1.5824(11) | 1.5794(14) | 1.5788(13) | — | — | — |
S1–N2–S3 | 114.15(12) | 114.06(15) | 115.1(5) | 113(1) | 113.2(8) | 114.80 |
N2–S3–N4 | 115.20(12) | 114.32(17) | 112.9(4) | 114(1) | 113.5(8) | 114.21 |
S3–N4–S5 | 113.03(11) | 113.3(2) | 113.8(6) | 114(1) | 113.7(9) | 114.82 |
N4–S5–N6 | 99.33(10) | 99.14(18) | 100.0(4) | 100(1) | 101(1) | 101.69 |
S5–N6–S7 | 113.57(10) | 113.51(19) | 114.5(4) | 115(1) | 113.7(9) g | 114.80 |
N6–S7–N8 | 113.82(9) | 113.83(16) | 113.6(4) | 114(1) | 113.5(8) g | 114.21 |
S7–N8–S1 | 113.13(10) | 112.76(18) | 112.7(4) | 114(1) | 113.2(8) g | 114.81 |
N8–S1–N2 | 99.65(11) | 100.91(17) | 101.3(4) | 101(1) | 100(1) g | 101.68 |
N2–S1–N9 | 109.47(11) | 108.7(3) | 107.6(4 | 110(1) | 117(1) | 108.49 |
N8–S1–N9 | 109.34(9) | 108.6(2) | 111.1(3) | 111(1) | 108.3(6) g | 108.41 |
N4–S5–N9 | 109.62(11) | 110.0(3) | 108.2(4) | 110(1) | 107.7(6) | 108.41 |
N6–S5–N9 | 109.52(11) | 108.8(2) | 110.3(3) | 109(1) | 107.7(6) g | 108.49 |
S1–N9–S5 | 114.68(10) | 115.8(3) | 112.1(2) | 112(1) | 117(1) | 115.70 |
∠S1N8N6S5:S1N9S5 e | 49.51(9) | 50.7(4) | 47.6(2) | — | 50.2 | 50.86 |
∠S1N2N4S5:S1N9S5 e | 50.01(9) | 49.3(3) | 53.1(3) | — | 50.2 g | 50.86 |
P1–N1–P2 | 137.81(7) | 138.16(10) | 138.98(9) | — | — | — |
Ct1–P1–P2–Ct2 f | −32.99 | −33.05 | −33.33 | — | — | — |
Parameter, b Å or ° | 100 K | 120 K | 172 K | Flues et al. c | Martan et al. d | DFT e |
---|---|---|---|---|---|---|
S3∙∙∙S7 | 2.695(1) | 2.697(2) | 2.724(6) | 2.71(1) | 2.667(10) | 2.8427 |
S3–N2 | 1.611(6) | 1.610(9) | 1.593(18) | 1.60(3) | 1.61(1) | 1.6166 |
S1–N2 | 1.668(8) | 1.668(8) | 1.68(2) | 1.640(18) | 1.67(1) | 1.6675 |
S1–N9 | 1.6448(3) | 1.631(13) | 1.665(1) | 1.66(3) | 1.64(1) | 1.6486 |
S1∙∙∙S5 | 2.769(1) | 2.763(3) | 2.760(6) | 2.75(1) | 2.795 | 2.7914 |
S1–N2–S3 | 113.5(5) | 113.4(5) | 114.0(10) | 113.5(10) | 113(2) | 114.81 |
N2–S3–N4 | 114.5(10) | 114.4(3) | 113.3(5) | 113.5(10) | 113.5(10) | 114.21 |
N2–S1–N8 | 99. 5(2) | 100.0(13) | 100.7(9) | 100.5(10) | 100(1) | 101.69 |
N2–S1–N9 | 109.49(12) | 109.0(7) | 109.3(17) | 110.1(10) | 110(3) | 108.45 |
S1–N9–S5 | 114.68(10) | 115.8(3) | 112.1(2) | 112(1) | 117 | 115.70 |
2.1.3. On the Structure of PPN+
2.1.4. Supramolecular Interactions in the [PPN+][S4N5−] Lattice
Component | Atom1 | Atom2 | Symm. op. 1 | Symm. op. 2 | Length | d−∑rvdW | d−Wk | Type |
---|---|---|---|---|---|---|---|---|
100K Main | N6 | H2 | x,y,z | 1−x,1−y,−z | 2.479 | −0.271 | −0.051 | n.c. H-bond |
100K Main | N6 | H15 | x,y,z | x,1+y,z | 2.481 | −0.269 | −0.049 | n.c. H-bond |
100K Main | N1S | H35 | 1−x,1/2+y,1/2−z | x,1.5−y,1/2+z | 2.531 | −0.219 | 0.001 | n.c. H-bond |
100K Main | S5 | H15 | x,y,z | x,1+y,z | 2.796 | −0.204 | −0.104 | n.c. H-bond |
100K Main | S7 | H8 | x,y,z | 1−x,1−y,−z | 2.865 | −0.135 | −0.035 | n.c. H-bond |
100K Main | S5 | C15 | x,y,z | x,1+y,z | 3.376 | −0.124 | n/a | n.c. H-bond |
100K Main | N2 | C2S | x,y,z | 1−x,1/2+y,1/2−z | 3.143 | −0.107 | n/a | N≡C carbon π |
100K Minor | N6A | H27 | x,y,z | −x,1/2+y,1/2−z | 2.35 | −0.400 | −0.180 | n.c. H-bond |
100K Minor | N9A | H30 | x,y,z | 1−x,1/2+y,1/2−z | 2.365 | −0.385 | −0.165 | n.c. H-bond |
100K Minor | N2A | H2 | x,y,z | 1−x,1−y,−z | 2.432 | −0.318 | −0.098 | n.c. H-bond |
100K Minor | N6A | C27 | x,y,z | −x,1/2+y,1/2−z | 3.022 | −0.228 | n/a | n.c. H-bond |
100K Minor | N8A | H5 | x,y,z | 1−x,1/2+y,1/2−z | 2.524 | −0.226 | −0.006 | n.c. H-bond |
100K Minor | S5A | H4 | x,y,z | −1+x,1+y,z | 2.801 | −0.199 | −0.099 | n.c. H-bond |
100K Minor | S1A | H6 | x,y,z | 1−x,1/2+y,1/2−z | 2.807 | −0.193 | −0.093 | n.c. H-bond |
100K Minor | N4A | H4 | x,y,z | −1+x,1+y,z | 2.62 | −0.130 | 0.090 | n.c. H-bond |
100K Minor | N6A | C1S | x,y,z | 1−x,1/2+y,1/2−z | 3.126 | −0.124 | n/a | N≡C carbon π |
100K Minor | S3A | H15 | x,y,z | x,1+y,z | 2.893 | −0.107 | −0.007 | n.c. H-bond |
100K Minor | N9A | C30 | x,y,z | 1−x,1/2+y,1/2−z | 3.15 | −0.100 | n/a | n.c. H-bond |
280K Single | N10 | H30 | x,y,z | 1−x,1/2+y,1/2−z | 2.511 | −0.239 | −0.019 | n.c. H-bond |
280K Single | N6 | H2 | x,y,z | 1−x,1/2+y,1/2−z | 2.531 | −0.219 | 0.001 | n.c. H-bond |
280K Single | N8 | H5 | x,y,z | 1−x,1/2+y,1/2−z | 2.617 | −0.133 | 0.087 | n.c. H-bond |
280K Single | N1S | H35 | 1−x,1/2+y,1/2−z | x,1.5−y,1/2+z | 2.625 | −0.125 | 0.095 | n.c. H-bond |
2.2. Density Functional Theory Study of the Geometry of S4N5− in the Gas Phase
2.3. Confirmation and Assignment of the Bands in Infra-red Spectra of S4N5−
Mode | DFT calc. cm−1 a | Calc. rel. intensity a | Ave. exptl. cm−1 b | PPN+ c nujol/CsI | Li+ d nujol/CsI | NH4+ d nujol/CsI | PipNH2+ e nujol/CsI | Na+ f KBr |
---|---|---|---|---|---|---|---|---|
1b2 | 940 | 1.00 | 946, vs | 955, s | 940, vs | 940, vs | 945, vs | 950, vs |
1a1 | 897 | 0.50 | 906, vs | 916, s | 910, vs | 910, vs | 910, vs | 885, sh |
1a2 | 798 | 0.00 | not obs. | — | — | — | — | — |
2a1 | 706 | 0.01 | 744, m | 757, m | 750, m | 735, s | 735, s | 745, s |
2b2 | 688 | 0.01 | 731, m g | 747, m | — | 725, s | 725, s | 725, w |
1b1 | 688 | 0.27 | 693, s g | — | 700,s s | 685, s | 685, s | 700, s |
3a1 | 659 | 0.18 | 667, m | 666, w | 670, s | 663, s | 670, s | 665, vs |
3b2 | 631 | 0.11 | 645, w | 647, w | — | — | 652, m | 635, w |
2b1 | 620 | 0.07 | 623, w | — | 625, w | 620, w | 625, m | — |
4a1 | 597 | 0.02 | not obs. | — | — | — | — | — |
3b1 | 573 | 0.23 | 600, s | 598, m | 600, s | 600, s | 600, s | 600, vs |
2a2 | 562 | 0.00 | not obs. | — | — | — | — | — |
5a1 | 516 | 0.10 | 531, s | — | 530, s | 530, s | 532, s | 530, vs |
4b2 | 489 | 0.04 | 505, s | — | 510, m | 500, s | 503, s | 505, s |
4b1 | 423 | 0.10 | 436, s | 428, m | 440, s | 435, m | 435, s | 440, vs |
6a1 | 387 | 0.01 | 406, m | — | 410, m | 405, m | 400, m | 410, s |
3a2 | 322 | 0.00 | 338, w | — | 345, w | 335, w | 335, w | 335, w |
5b2 | 314 | 0.00 | not obs. | — | — | — | — | — |
5b1 | 286 | 0.06 | 304, w | 300, vw | 310, m | 300, w | 305, m | 305, m |
4a2 | 252 | 0.00 | not obs. | — | — | — | — | |
7a1 | 155 | 0.00 | not obs. | Beyond range of experiments. |
3. Experimental
CAUTION: salts of S4N5− and other binary sulfur-nitrides are notorious contact explosives. Any attempts to prepare or handle them must only be undertaken by appropriately qualified personnel, properly supervised, and taking all necessary precautionary measures.
Parameter | 100 K | 120 K | 140 K | 172 K | 200 K | 240 K | 280 K |
---|---|---|---|---|---|---|---|
a, Å | 10.8717(5) | 10.8904(6) | 10.9331(5) | 10.9878(6) | 11.0218(5) | 11.0664(7) | 11.131(18) |
b, Å | 17.7722(8) | 17.7756(10) | 17.8025(8) | 17.8189(10) | 17.8463(8) | 17.8745(11) | 17.92(3) |
c, Å | 18.8902(8) | 18.8948(11) | 18.9084(9) | 18.9099(11) | 18.9487(9) | 18.9951(11) | 19.14(3) |
β, ° | 95.0291(5)° | 95.0132(7) | 94.9623(5) | 94.8670(10) | 94.8131(5) | 94.7601(7) | 94.601(19) |
Volume, Å3 | 3635.8(3) | 3643.7(4) | 3666.5(3) | 3689.0(4) | 3714.0(3) | 3744.4(4) | 3805(11) |
Dcalc, g cm−1 | 1.421 | 1.418 | 1.409 | 1.401 | 1.391 | 1.380 | 1.358 |
μ, mm−1 | 0.390 | 0.389 | 0.387 | 0.384 | 0.382 | 0.378 | 0.372 |
Tmin | 0.7456 | 0.4305 | 0.7456 | 0.4309 | 0.7456 | 0.7456 | 0.7456 |
Tmax | 0.6942 | 0.3780 | 0.6971 | 0.3928 | 0.7059 | 0.6858 | 0.5867 |
Cr. max, mm | 0.41 | 0.21 | 0.41 | 0.35 | 0.41 | 0.41 | 0.41 |
mid, mm | 0.20 | 0.11 | 0.20 | 0.22 | 0.20 | 0.20 | 0.20 |
min, mm | 0.17 | 0.10 | 0.17 | 0.15 | 0.17 | 0.17 | 0.17 |
Rfl. Measured | 51759 | 41490 | 41636 | 38803 | 52563 | 42717 | 41322 |
Index ranges: h | −14, 14 | −14, 14 | −14, 14 | −13, 13 | −14, 14 | −14, 14 | −14, 14 |
k | −23, 23 | −23, 23 | −23, 23 | −22, 22 | −23, 23 | −23, 23 | −23, 23 |
l | −24, 24 | −24, 24 | −24, 24 | −23, 23 | −24, 24 | −24, 24 | −24, 24 |
θ limit, ° | 27.480 | 27.437 | 27.427 | 26.373 | 27.388 | 27.440 | 27.448 |
Unique data | 8283 | 8298 | 8302 | 7522 | 8381 | 8517 | 8594 |
Restraints | 34 | 64 | 46 | 170 | 62 | 0 | 0 |
Parameters | 516 | 536 | 542 | 542 | 542 | 470 | 470 |
G.O.F. on F2 | 1.038 | 1.051 | 1.041 | 1.027 | 1.026 | 1.055 | 1.051 |
R1 | 0.0298 | 0.0361 | 0.0357 | 0.0326 | 0.0339 | 0.0467 | 0.0492 |
wR2 [I ≥ 2σ(I)] | 0.0765 | 0.0800 | 0.0935 | 0.0853 | 0.0903 | 0.1216 | 0.1287 |
Largest pk, eÅ−3 | 0.422 | 0.391 | 0.584 | 0.378 | 0.359 | 0.529 | 0.548 |
Largest hl, eÅ−3 | −0.297 | −0.333 | −0.281 | −0.287 | −0.289 | −0.565 | −0.497 |
4. Conclusions
Supplementary Materials
Acknowledgments
Conflicts of Interest
References
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Boeré, R.T.; Roemmele, T.L.; Krall, M.K. A Variable Temperature X-ray Diffraction Investigation of [PPN+][S4N5−]: Supramolecular Interactions Governing an Order/Disorder Transformation and the First High Resolution X-ray Structure of the Anion. Molecules 2014, 19, 1956-1975. https://doi.org/10.3390/molecules19021956
Boeré RT, Roemmele TL, Krall MK. A Variable Temperature X-ray Diffraction Investigation of [PPN+][S4N5−]: Supramolecular Interactions Governing an Order/Disorder Transformation and the First High Resolution X-ray Structure of the Anion. Molecules. 2014; 19(2):1956-1975. https://doi.org/10.3390/molecules19021956
Chicago/Turabian StyleBoeré, René T., Tracey L. Roemmele, and Maria K. Krall. 2014. "A Variable Temperature X-ray Diffraction Investigation of [PPN+][S4N5−]: Supramolecular Interactions Governing an Order/Disorder Transformation and the First High Resolution X-ray Structure of the Anion" Molecules 19, no. 2: 1956-1975. https://doi.org/10.3390/molecules19021956