Crystal structures of crotonaldehyde semicarbazone and crotonaldehyde thiosemicarbazone from X-ray powder diffraction data

Crotonaldehyde semicarbazone and crotonaldehyde thio­semicarbazone show the same E conformation around the imine C=N bond. Each mol­ecule has an intra­molecular N—H...N hydrogen bond, which generates an S(5) ring. Inter­molecular N—H...O hydrogen bonds in the semicarbazone link the mol­ecules into layers parallel to the bc plane, while weak inter­molecular N—H...S hydrogen bonds in the thio­semicarbazone link the mol­ecules into chains propagating in [110].

Key indicators

• Powder X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.020 Å
• Mean [sigma](C-C) = 0.020 Å
• R factor = 0.000
• wR factor = 0.000
• Data-to-parameter ratio = 0.0

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
PLAT340_ALERT_3_B Low Bond Precision on  C-C Bonds ...............     0.0197 Ang.

Author Response: Our data are from Powder X-Ray diffraction

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
PLAT981_ALERT_1_G No non-zero f" Anomalous Scattering Values Found     Please Check
PLAT986_ALERT_1_G No non-zero f' Anomalous Scattering Values Found     Please Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: II


Alert level B
PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem...        c/2 Check

Author Response: There is not any pseudo translation. There is a one molecule in asymmetry unit with triclinic systsm in P-1 space group

PLAT340_ALERT_3_B Low Bond Precision on  C-C Bonds ...............     0.0197 Ang.

Author Response: Our data are from Powder X-Ray diffraction

Alert level C
PLAT213_ALERT_2_C Atom S1              has ADP max/min Ratio .....        3.4 prolat

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.13 Ratio
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT981_ALERT_1_G No non-zero f" Anomalous Scattering Values Found     Please Check
PLAT986_ALERT_1_G No non-zero f' Anomalous Scattering Values Found     Please Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Chemical context

The chemistry of semicarbazones and thio­semicarbazones is especially inter­esting due to their special role in biological applications such as anti-proliferative, anti-tumoral, anti-convulsant, anti-trypanosomal, herbicidal and biocidal activities (Beraldo et al., 2002; Kasuga et al., 2003; Teixeira et al., 2003; Beraldo & Gambino, 2004; Mikhaleva et al., 2008; de Oliveira et al., 2008; Alomar et al., 2012; Gan et al., 2014). They are also important inter­mediates in organic synthesis, mainly for obtaining heterocyclic rings, such as thia­zolidones, oxa­diazo­les, pyrazolidones, and thia­diazo­les (Greenbaum et al., 2004; Küçükgüzel et al., 2006). Semicarbazones and thio­semicarbazones have received considerable attention in view of their simplicity of preparation, various complexing abilities and coordination behavior that can be used in analytical applications (Garg & Jain, 1988; Casas et al., 2000). They are of inter­est from a supra­molecular point of view since they can be functionalized to give different supra­molecular arrays.

S2. Structural commentary

Compounds (I) and (II) crystallize in centrosymmetric space groups P2₁/c and P1, respectively, with one molecule in the asymmetric unit. Each molecule has an intra­molecular N—H···N hydrogen bond (Tables 1 and 2), which forms an S(5) ring. The semicarbazone and thio­semicarbazone fragments in the compounds show an E conformation around the imine C=N bond. The molecules (Fig. 1) are approximately planar, with a dihedral angle of 2.59 (5)° between the C1/C2/C3 crotonaldehyde plane and the mean plane of the C4/N1/N2/C5/O1/N3 semicarbazone fragment for (I), and of 9.12 (5)° between the C1/C2/C3 crotonaldehyde plane and the mean plane of the C4/N1/N2/C5/S1/N3 thio­semicarbazone fragment for (II). All bond lengths and angles in (I) and (II) are normal and correspond well to those observed in the crystal structures of related semi- and thio­semicarbazone derivatives, viz. acetone semicarbazone and benzaldehyde­semicarbazone (Naik & Palenik, 1974), 3,4- methyl­ene­dioxy­benzaldehyde­semicarbazone (Wang et al., 2004), isatin 3-semicarbazone and 1-methyl­isatin 3-semicarbazone (Pelosi et al., 2005), 4- (methyl­sulfanyl)benzaldehyde­thio­semicarbazone (Yathirajan et al., 2006), 4-(methyl­sulfanyl)benzaldehyde­semicarbazone (Sarojini et al., 2007), 5-hy­droxy-2-nitro­benzaldehyde thio­semicarbazone (Reddy et al., 2014) and 1-(4-formyl­benzyl­idene) thio­semicarbazone (Carballo et al., 2014).

S3. Supra­molecular features

As a result of the presence of potential hydrogen-donor sites in molecules (I) and (II), supra­molecular hydrogen-bonding inter­actions are observed in both compounds (Tables 1 and 2). In the crystal of (I), molecules are linked by pairs of N—H···O hydrogen bonds, forming inversion dimers with R²₂(8) ring motifs (Fig. 2a). The resulting dimers are connected through N—H···O hydrogen bonds, forming layers parallel to bc plane. In the crystal of (II), molecules are linked by weak N—H···S hydrogen bonds, forming chains propagating in [110] (Fig. 2b).

S4. Synthesis and crystallization

All reactions and manipulations were carried out in air with reagent grade solvents. The IR spectra were recorded on a Jasco FT–IR 300E instrument. ¹H and ¹³C{¹H} NMR spectra were recorded on a Bruker Bio spin 400 spectrometer. Microanalysis was performed using EURO EA. Powder X-ray diffraction data were collected with Stoe Transmission diffractometer (Stadi P).

For the synthesis of (I), a mixture of semicarbazide hydro­chloride (CH₅N₃O·HCl; 0.5 g, 4.5 mmol) and sodium acetate (CH₃COONa; 0.75 g, 9.1 mmol) in 10 ml water was agitated well and crotonaldehyde (0.5 g, 7.1 mmol) was added slowly with stirring. On completion of the addition, the reaction mixture was agitated for 24 h at room temperature. The solid product which formed was separated by filtration and washed with water and finally recrystallized from absolute ethanol to produce the product (I) (white powder; m.p. 481–482 K) in 55.5 % yield.

IR (KBr, ν, cm^-1): 3456, 3281, 3192 (NH₂), (1668–1638) (C═O); ¹H NMR (400 MHz, CD₃OD) δ p.p.m. 1.76 (d, J = 4.42 Hz, 3H, –CH₃), 6.43–5.46 (m, 2H, –HC═CH–), 7.39 (d, J = 7.19 Hz, 1H, HC═N–).¹³C NMR (100 MHz, CD₃OD) δ p.p.m. 18.52 (CH₃), 130.01 (–HC═CH–), 137.62 (–HC═CH–), 145.64 (N═C) , 160.19 (C═O). Analysis calculated for (I): C, 47.23; H, 7.13; N, 33.05, 12.58 O%. Found: C, 46.43; H, 6.08; N, 34.69%

For the synthesis of (II), crotonaldehyde (0.5 g, 7.1 mmol) was added to thio­semicarbazide (CH₅N₃S; 0.65 g, 7.1 mmol) in 5 ml water and the mixture was stirred at room temperature for 24 h. The product was separated by filtration and recrystallized from absolute ethanol to produce the product (II) (white powder; m.p. 435–436 K) in 72.5% yield.

IR (KBr, ν, cm^-1): 3323, 3244, 3164 (NH₂), 1650(C═S). ¹H NMR (400 MHz, CDCl₃) δ p.p.m. 1.90 (d, J = 5.86 Hz, 3H, –CH₃), 6.07–6.27 (m, 2H, –HC═CH–), 6.49 (sb, 1H), 7.10 (sb, 1H) 7.60 (d, J = 8.57 Hz, 1H, HC═N–), 10.10 (sb, 2H). ¹³C NMR (100.6 MHz, CDCl₃) 18.73 (CH₃), 127.70 (–HC═CH–), 140.58 (–HC═CH–), 146.21 (N═C), 177.95 (C═S). Analysis calculated for (II): C, 41.93; H, 6.33; N, 29.34.05, 22.39 S%. Found: C, 41.89; H, 6.25; N, 31.88%.

S5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. Compounds (I) and (II) crystallized in the form of a very fine white powder. Since no single crystals of sufficient size and quality could be obtained, the crystal structures of both compounds were determined from X-ray powder diffraction patterns. The powder samples of (I) and (II) were lightly ground in a mortar, loaded into two Mylar foils and fixed onto the sample holder with a mask of suitable inter­nal diameter (8.0 mm). The powder X-ray diffraction data were collected at room temperature with a STOE transmission STADI-P diffractometer using monochromatic Cu K_a1 radiation (λ= 1.54060 Å) selected with an incident beam curved-crystal germanium Ge(111) monochromator with a linear position-sensitive detector (PSD). The patterns were scanned over the angular range 5.0–80.0° (2θ). For pattern indexing, the extraction of the peak positions was carried out with the program WinPLOTR (Roisnel & Rodríguez-Carvajal, 2000). Pattern indexing was performed with the program DICVOL4.0 (Boultif & Louër, 2004). The first 20 lines of the powder pattern were indexed completely on the basis of a monoclinic cell for (I) and a triclinic cell for (II). The figures of merit (de Wolff et al., 1968; Smith & Snyder, 1979) are sufficiently acceptable to support the obtained indexing results [M(20) = 50.5, F(20) = 71.9 (0.0034, 83)] for (I) and [M(20) = 61.8, F(20) = 96.0 (0.0051, 41)] for (II). The best estimated space groups were P2₁/c in the monoclinic system for (I) and P1 in the triclinic system for (II).

The whole powder diffraction patterns from 5 to 80° (2θ) for the two compounds (I) and (II) were subsequently refined with cell and resolution constraints (Le Bail et al., 1988) using the profile-matching option of the program FULLPROF (Rodríguez-Carvajal, 2001). The number of molecules per unit cell was estimated to be Z = 4 for (I) and Z = 2 for (II). The initial crystal structures for (I) and (II) were determined by direct methods using the program EXPO2014 (Altomare et al., 2013). The models found by this program were introduced into the program GSAS (Larson & Von Dreele, 2004) implemented in EXPGUI (Toby, 2001) for Rietveld refinement. During the Rietveld refinements, the background was refined using a shifted Chebyshev polynomial with 20 coefficients. The effect of asymmetry of low-order peaks was corrected using a pseudo-Voigt description of the peak shape (Thompson et al., 1987), which allows for angle-dependent asymmetry with axial divergence (Finger et al., 1994) and microstrain broadening, as described by Stephens (1999). The two asymmetry parameters of this function, S/L and D/L, were both fixed at 0.022 during this refinement. Intensities were corrected from absorption effects with a function for a plate sample in transmission geometry with a µ·d value of 0.15 for (I) and 0.72 for (II) (µ is the absorption coefficient and d is the sample thickness). These µ·d values were determined experimentally.

Before the final refinement, all H atoms were introduced in geometrically calculated positions. The coordinates of these H atoms were refined with strict restraints on bond lengths and angles until a suitable geometry was obtained, after that they were fixed in the final stage of the refinement. No soft restraints were imposed for (I), while for (II) the bond CH₃—CH was a clearly stretched (close to1.6 Å), therefore a single soft restraint was carried out to obtain a normal value (1.49 Å). The final refinement cycles were performed using isotropic atomic displacement parameters for the C, N and O atoms, an anisotropic atomic displacement parameter for S atom in (II) and a fixed global isotropic atomic displacement parameter for the H atoms. The preferred orientation was modelled with 12 coefficients using a spherical harmonics correction (Von Dreele, 1997) of intensities in the final refinement. The use of the preferred orientation correction leads to a better molecular geometry with better agreement factors. The final Rietveld plots of the X-ray diffraction patterns for both (I) and (II) are given in Fig. 3.

Related literature

For related literature, see: Allen et al. (1987); Alomar et al. (2012); Altomare et al. (2013); Beraldo & Gambino (2004); Beraldo et al. (2002); Boultif & Louër (2004); Carballo et al. (2014); Casas et al. (2000); Gan et al. (2014); Greenbaum et al. (2004); Finger et al. (1994); Garg & Jain (1988); Kasuga et al. (2003); Küçükgüzel et al. (2006); Larson & Von Dreele (2004); Le Bail, Duroy & Fourquet (1988); Macrae et al. (2006); Mikhaleva et al. (2008); Naik & Palenik (1974); Oliveira et al. (2008); Pelosi et al. (2005); Reddy et al. (2014); Roisnel, T. & Rodríguez-Carvajal (2001); Roisnel & Roisnel, T. & Rodríguez-Carvajal (2001); Sarojini et al. (2007); Smith & Snyder (1979); Stephens (1999); Teixeira et al. (2003); Thompson et al. (1987); Toby (2001); Von Dreele (1997); Wang et al. (2004); Yathirajan et al. (2006); de Wolff et al. (1968).

Computing details

For both compounds, data collection: WinXPOW (Stoe & Cie, 1999). Data reduction: WinXPOW (Stoe & Cie, 1999) for (I). For both compounds, program(s) used to solve structure: EXPO2014 (Altomare et al., 2013); program(s) used to refine structure: GSAS (Larson & Von Dreele, 2004); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structures of (a) (I) and (b) (II), showing the atom-labelling schemes. Displacement spheres (and the ellipsoid for S1) are drawn at the 50% probability level.
	Fig. 2. (a) A portion of the crystal packing of (I) viewed down the b axis (parallel to the hydrogen-bonded layer). (b) A portion of the crystal packing of (II), showing the hydrogen-bonded chain of the molecules. Thin dotted lines denote intermolecular hydrogen bonds.
	Fig. 3. The final Rietveld plots for (a) (I) and (b) (II). Experimental intensities are indicated by dots and the best-fit profile (upper trace) and difference pattern (lower trace) are shown as solid lines. The vertical bars indicate the calculated positions of the Bragg peaks.

(I) (E)-2-[(E)-But-2-en-1-ylidene]hydrazinecarboxamide

Crystal data

C5H9N3O	Z = 4
Mr = 127.15	F(000) = 272
Monoclinic, P21/c	Dx = 1.222 Mg m^−3
Hall symbol: -P 2ybc	Cu Kα1 radiation, λ = 1.5406 Å
a = 11.1646 (3) Å	µ = 0.74 mm^−1
b = 5.13891 (9) Å	T = 298 K
c = 13.0301 (2) Å	Particle morphology: fine powder
β = 112.3496 (11)°	white
V = 691.43 (3) Å^3	flat sheet, 8 × 8 mm

Data collection

Stoe transmission Stadi-P diffractometer	Data collection mode: transmission
Radiation source: sealed X-ray tube	Scan method: step
Ge 111 monochromator	2θmin = 5°, 2θmax = 80°, 2θstep = 0.02°
Specimen mounting: Powder loaded into two Mylar foils

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in (Thompson et al., 1987) Asymmetry correction of Finger et al., 1994. Microstrain broadening by P.W. Stephens, (1999. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 10.054 #4(GP) = 0.000 #5(LX) = 2.972 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0220 #11(H/L) = 0.0220 #12(eta) = 0.6000 #13(S400 ) = 2.1E-01 #14(S040 ) = 3.3E-01 #15(S004 ) = 4.2E-02 #16(S220 ) = 2.1E-02 #17(S202 ) = 4.8E-03 #18(S022 ) = 8.7E-02 #19(S301 ) = -3.5E-03 #20(S103 ) = 5.2E-02 #21(S121 ) = 5.4E-02 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.027	121 parameters
Rwp = 0.036	0 restraints
Rexp = 0.029	H-atom parameters not refined
R(F^2) = 0.02795	Weighting scheme based on measured s.u.'s
χ^2 = 1.613	(Δ/σ)max = 0.03
3750 data points	Background function: GSAS Background function number 1 with 20 terms. Shifted Chebyshev function of 1st kind 1: 983.478 2: -916.772 3: 421.914 4: -92.3775 5: -9.18321 6: 30.2365 7: -2.25826 8: -10.7421 9: -19.9256 10: 25.6982 11: -24.5216 12: 4.20376 13: 6.93721 14: -3.88406 15: -7.36711 16: 7.71847 17: -1.82508 18: -0.259371 19: -0.220296 20: 0.765767

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

	x	y	z	Uiso*/Ueq
C1	0.935 (2)	0.8319 (18)	0.3282 (11)	0.057 (5)*
H1a	0.88432	0.92372	0.25964	0.075*
H1b	0.96701	0.95714	0.38819	0.075*
H1c	1.00844	0.74948	0.31821	0.075*
C2	0.855 (2)	0.6310 (16)	0.3552 (13)	0.052 (4)*
H2	0.8297	0.48475	0.30627	0.075*
C3	0.8056 (15)	0.6448 (14)	0.4352 (9)	0.033 (4)*
H3	0.80211	0.8092	0.46492	0.05*
C4	0.7367 (18)	0.4405 (17)	0.4558 (11)	0.032 (4)*
H4	0.73987	0.27746	0.42622	0.075*
N1	0.7027 (14)	0.4632 (13)	0.5417 (7)	0.025 (3)*
N2	0.6313 (12)	0.2520 (15)	0.5530 (7)	0.031 (3)*
H1n2	0.60928	0.12885	0.50191	0.05*
C5	0.5708 (15)	0.252 (2)	0.6285 (11)	0.029 (4)*
O1	0.5060 (12)	0.0728 (12)	0.6388 (6)	0.029 (3)*
N3	0.6041 (15)	0.4651 (13)	0.6956 (9)	0.024 (3)*
H1n3	0.55477	0.51321	0.73425	0.05*
H2n3	0.67532	0.55182	0.70648	0.05*

Geometric parameters (Å, º)

C1—C2	1.493 (17)	C4—H4	0.928
C1—H1a	0.978	N1—N2	1.387 (11)
C1—H1b	0.970	N2—H1n2	0.883
C1—H1c	0.975	N2—C5	1.390 (10)
C2—C3	1.353 (11)	C5—O1	1.210 (11)
C2—H2	0.956	C5—N3	1.361 (11)
C3—C4	1.387 (13)	N3—H1n3	0.911
C3—H3	0.936	N3—H2n3	0.875
C4—N1	1.317 (11)
H1a—C1—H1b	108.9	C3—C4—N1	117.2 (12)
H1a—C1—H1c	108.1	H4—C4—N1	120.1
H1a—C1—C2	111.0	C4—N1—N2	112.5 (9)
H1b—C1—H1c	109.0	N1—N2—H1n2	119.2
H1b—C1—C2	109.9	N1—N2—C5	121.9 (9)
H1c—C1—C2	109.9	H1n2—N2—C5	117.6
C1—C2—H2	115.9	N2—C5—O1	123.3 (11)
C1—C2—C3	126.9 (9)	N2—C5—N3	111.6 (11)
H2—C2—C3	116.9	O1—C5—N3	124.8 (11)
C2—C3—H3	117.3	C5—N3—H1n3	119.9
C2—C3—C4	121.8 (10)	C5—N3—H2n3	121.6
H3—C3—C4	119.4	H1n3—N3—H2n3	118.4
C3—C4—H4	119.5
C4—N1—N2—C5	−171.0 (13)	N1—N2—C5—N3	−7.4 (18)
N2—N1—C4—C3	178.3 (13)	C1—C2—C3—C4	−177.3 (16)
N1—N2—C5—O1	178.6 (13)	C2—C3—C4—N1	174.0 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N1	0.87	2.33	2.629 (19)	100
N2—H1N2···O1^i	0.88	2.07	2.910 (11)	158
N3—H1N3···O1^ii	0.91	2.04	2.914 (18)	162

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

(II) (E)-2-[(E)-But-2-en-1-yldene]hydrazinecarbothioamide

Crystal data

C5H9N3S	V = 382.15 (2) Å^3
Mr = 143.21	Z = 2
Triclinic, P1	F(000) = 152
Hall symbol: -P 1	Dx = 1.245 Mg m^−3
a = 5.86650 (17) Å	Cu Kα1 radiation, λ = 1.5406 Å
b = 8.0313 (2) Å	µ = 3.11 mm^−1
c = 9.0795 (4) Å	T = 298 K
α = 104.1407 (18)°	Particle morphology: fine powder
β = 101.0403 (19)°	white
γ = 106.3511 (17)°	flat sheet, 8 × 8 mm

Data collection

Stoe transmission Stadi-P diffractometer	Data collection mode: transmission
Radiation source: sealed X-ray tube	Scan method: step
Ge 111 monochromator	2θmin = 4.980°, 2θmax = 79.960°, 2θstep = 0.02°
Specimen mounting: Powder loaded into two Mylar foils

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in (Thompson et al., 1987) Asymmetry correction of Finger et al., 1994. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 2.793 #4(GP) = 0.000 #5(LX) = 5.477 #6(ptec) = 2.45 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0220 #11(H/L) = 0.0220 #12(eta) = 0.6000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.033	114 parameters
Rwp = 0.043	1 restraint
Rexp = 0.034	H-atom parameters not refined
R(F^2) = 0.02670	(Δ/σ)max = 0.03
χ^2 = 1.664	Background function: GSAS Background function number 1 with 20 terms. Shifted Chebyshev function of 1st kind 1: 590.360 2: -469.557 3: 198.126 4: -45.2586 5: -2.75624 6: 13.8508 7: 4.35563 8: -5.95029 9: -12.8815 10: 35.6051 11: -12.9276 12: -11.1488 13: 8.85293 14: -2.01034 15: -0.496121 16: 8.39616 17: -2.33367 18: -5.14527 19: 10.5079 20: -3.85249
3750 data points

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

	x	y	z	Uiso*/Ueq
C1	0.184 (2)	0.841 (2)	0.515 (2)	0.103 (6)*
H1A	0.15342	0.79934	0.39748	0.12*
H1B	0.2323	0.97016	0.55142	0.12*
H1C	0.02574	0.78525	0.53491	0.12*
C2	0.370 (2)	0.7688 (17)	0.5865 (18)	0.054 (5)*
H2	0.53963	0.83335	0.59455	0.055*
C3	0.325 (2)	0.6393 (16)	0.6524 (15)	0.034 (5)*
H3	0.14582	0.56255	0.63049	0.055*
C4	0.487 (3)	0.5747 (19)	0.7264 (19)	0.039 (5)*
H4	0.66632	0.65671	0.74816	0.055*
N1	0.4514 (17)	0.4461 (12)	0.7878 (15)	0.035 (4)*
N2	0.6486 (16)	0.4005 (12)	0.8462 (13)	0.021 (4)*
H1n2	0.79218	0.45838	0.841	0.05*
C5	0.611 (3)	0.2572 (16)	0.907 (2)	0.034 (4)*
N3	0.3681 (15)	0.1560 (12)	0.8849 (13)	0.017 (4)*
H1n3	0.34725	0.13246	0.97116	0.05*
H2n3	0.26401	0.20773	0.84645	0.05*
S1	0.8446 (6)	0.1980 (5)	0.9772 (6)	0.04081

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.032 (4)	0.039 (5)	0.082 (8)	0.026 (4)	0.043 (5)	0.035 (5)

Geometric parameters (Å, º)

C1—H1A	0.999	C4—N1	1.274 (12)
C1—H1B	0.946	N1—N2	1.361 (10)
C1—H1C	0.983	N2—H1n2	0.856
C1—C2	1.49 (2)	N2—C5	1.377 (13)
C2—H2	0.963	C5—N3	1.376 (13)
C2—C3	1.311 (13)	C5—S1	1.638 (13)
C3—H3	1.008	N3—C5	1.376 (13)
C3—C4	1.352 (14)	N3—H1n3	0.872
C4—H4	1.024	N3—H2n3	0.894
H1A—C1—H1B	109.0	C3—C4—N1	130.8 (16)
H1A—C1—H1C	106.2	H4—C4—N1	116.8
H1A—C1—C2	108.5	C4—N1—N2	118.6 (11)
H1B—C1—H1C	110.2	N1—N2—H1n2	119.6
H1B—C1—C2	113.8	N1—N2—C5	119.2 (10)
H1C—C1—C2	108.8	H1n2—N2—C5	121.2
C1—C2—H2	115.8	N2—C5—N3	115.6 (12)
C1—C2—C3	125.6 (13)	N2—C5—S1	120.4 (11)
H2—C2—C3	118.2	N3—C5—S1	123.5 (9)
C2—C3—H3	116.8	C5—N3—H1n3	110.5
C2—C3—C4	128.4 (15)	C5—N3—H2n3	112.2
H3—C3—C4	113.9	H1n3—N3—H2n3	113.2
C3—C4—H4	111.8
C4—N1—N2—C5	−177.4 (14)	N1—N2—C5—N3	8.0 (19)
N2—N1—C4—C3	175.6 (15)	C1—C2—C3—C4	−176.2 (15)
N1—N2—C5—S1	179.6 (11)	C2—C3—C4—N1	−177.6 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N1	0.89	2.17	2.641 (14)	112
N2—H1N2···S1^i	0.86	2.83	3.473 (11)	133
N3—H1N3···S1^ii	0.87	2.77	3.398 (11)	130

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