2-[Carbamo­thio­yl(2-hy­dr­oxy­eth­yl)amino]­ethyl benzoate: crystal structure, Hirshfeld surface analysis and computational study

The title di-substituted thio­urea, C₁₂H₁₆N₂O₃S, has the hy­droxy­lethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the N_amine—C—C—O_{(hydroxyl, carbon­yl)} torsion angles of 49.39 (13) and 59.09 (12)°, respectively; the dihedral angle between the almost planar CN₂S core and the pendent benzene ring is 69.26 (4)°. In the crystal, supra­molecular layers propagating in the ac plane are formed via a combination of hydroxyl-O—H⋯S(thione), amine-N—H⋯O(hydroxyl, carbon­yl) hydrogen-bonds. The layers stack along the b axis with inter-digitation of the benzene rings allowing the formation of π–π stacking [inter-centroid separation = 3.8722 (7) Å] and parallel C=O⋯π inter­actions. A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are also apparent, notably through the inter­actions involving the benzene residue.

1. Chemical context

The title compound, (I), was characterized crystallographically in a continuation of recent structural studies of tri-substituted thio­urea derivatives formulated as (HOCH₂CH₂)₂NC(=S)N(H)C(=O)C₆H₄-R-4 for R = Me (Tan, Azizan et al., 2019) and R = NO₂ (Tan et al., 2020): these mol­ecules are known for their various applications including biological activity (Saeed et al., 2014). A convenient synthesis for these mol­ecules is via the reaction of NH₄(NCS), R₂NH and ArC(=O)Cl to yield R₂NC(=S)N(H)C(=O)Ar. In an experiment with R = CH₂CH₂OH and Ar = C₆H₅, the solution was also heated resulting in an apparent rearrangement with deprotonation of one hy­droxy­ethyl group followed by nucleophilic attachment at the carbonyl-C atom along with protonation of the primary amine and cleavage of the original N—C(=O) bond to yield (I), formulated as H₂NC(=S)N(CH₂CH₂OH)CH₂CH₂OC(=O)C₆H₅. The mol­ecular structure of (I) was determined by X-ray crystallography and the supra­molecular association investigated by Hirshfeld surface analysis and computational chemistry.

2. Structural commentary

The mol­ecule of (I) is shown in Fig. 1 and comprises a di-substituted thio­urea mol­ecule with both substitutions occurring at the same amine atom. The CN₂S atoms of the thio­urea core are almost planar, exhibiting a r.m.s. deviation = 0.0054 Å, with the appended C2 and C4 atoms lying 0.0236 (18) and 0.0216 (16) Å to either side of the plane. The conformation of the C2-hy­droxy­lethyl residue is (+)syn-clinal as indicated by the N2—C2—C3—O1 torsion angle of 49.39 (13)°. The CO₂ residue is close to co-planar with the (C7–C12)-benzene ring to which it is connected, forming a dihedral angle of 4.83 (9)°. The dihedral angle between the least-squares planes through the CN₂S core and the benzene ring is 69.26 (4)°, indicating the mol­ecule is highly twisted. Finally, the N2—C4—C5—O2 torsion angle of 59.09 (12)° is indicative of a (+)syn-clinal configuration about the C—C bond, thereby confirming the twisted nature of the mol­ecule.

Figure 1 The mol­ecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

3. Supra­molecular features

As anti­cipated, hydrogen bonding plays a key role in the supra­molecular assembly of (I); see Table 1 for geometrical data. The combination of hydroxyl-O—H⋯S(thione) and amine-N—H⋯O(hydrox­yl) hydrogen bonds connect mol­ecules into a supra­molecular tape propagating along the a-axis direction, Fig. 2(a). These hydrogen bonds also lead to the formation of 12-membered {⋯HO⋯HNCS}₂ and 14-membered {⋯OC₂NCNH}₂ synthons, each disposed about a centre of inversion, and linked via the edges defined by the amine-N—H⋯O(hydrox­yl) hydrogen bonds. The tape has a step-ladder topology and projecting laterally to either side of the tape are the remaining amine-H and carbonyl-O atoms, which form the donors and acceptors of amine-N—H⋯O(carbon­yl) hydrogen bonds to link the tapes into a layer in the ac plane, Fig. 2(b). The directional links between layers are twofold, namely π–π stacking between the centrosymmetrically related benzene rings [inter-centroid separation = 3.8722 (7)° for symmetry operation 2 − x, 1 − y, 1 − z] and parallel C=O⋯π inter­actions, Table 1 and Fig. 2(c). These inter­actions are possible owing to the inter-digitation of the benzene rings along the b-axis direction, as highlighted in Fig. 2(d).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the (C7–C12) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S1^i	0.84 (1)	2.35 (1)	3.1746 (9)	169 (2)
N1—H2N⋯O1^ii	0.88 (1)	2.04 (1)	2.8582 (13)	155 (1)
N1—H1N⋯O3^iii	0.88 (1)	2.30 (1)	3.1218 (13)	158 (1)
C6—O3⋯Cg1^iv	1.21 (1)	3.66 (1)	3.5026 (12)	73 (1)
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z+2; (iii) -x+1, -y, -z+1; (iv) -x+1, -y+1, -z+1.

Figure 2 Mol­ecular packing in the crystal of (I): (a) supra­molecular tape along the a axis mediated by hydroxyl-O—H⋯S(thione) and amine-N—H⋯O(hydrox­yl) hydrogen bonding shown as orange and blue dashed lines, respectively, (b) supra­molecular layer where the tapes of (a) are connected by amine-N—H⋯O(carbon­yl) hydrogen bonds shown as green dashed lines, (c) detail of C—O⋯π(benzene) inter­actions shown as red dashed lines and (d) a view of the unit-cell contents down the b axis with π(benzene)–π(benzene) inter­actions shown as purple dashed lines.

4. Hirshfeld surface analysis

Structure (I) was subjected to a Hirshfeld surface analysis in order to gain further understanding into the mol­ecular inter­actions existing within the crystal. This was achieved through Crystal Explorer 17 (Turner et al., 2017) using established methods (Tan, Jotani et al., 2019). A list of d_norm contact distances for all identified inter­actions is given in Table 2. As noted from Fig. 3, several red spots of variable intensity were identified on the Hirshfeld surface of (I), being indicative of close inter­actions with contact distances shorter than the sum of the respective van der Waals (vdW) radii (Spackman & Jayatilaka, 2009). In particular, the most intense red spot is observed for the amine-N1—H2N⋯O1(hydrox­yl) hydrogen bond with a d_norm distance of 1.92 Å, which is significantly shorter, by 0.69 Å [= Δ|(d_norm – ΣvdW)_H⋯O| in Table 2], than the vdW value of 2.61 Å (adjusted to neutron values). Other prominent features are due to the hydroxyl-O1—H1O⋯S1(thione) and amine-N1—H1N⋯O3(carbon­yl) hydrogen bonds. Less intense features on the d_norm maps of Fig. 3 are due to benzene-C9—H9⋯C1(thione) and methyl­ene-C3—H3B⋯H8(benzene) inter­actions, and the diminutive spots arise from weaker methyl­ene-C5⋯O3(carbon­yl), methyl­ene-C2—H2A⋯S1(thione) and benzene-C9—H9⋯S1(thione) contacts at distances just shorter or approximately equivalent to the values of the respective ΣvdW radii. Apart from the conventional hydrogen bonds and other inter­actions involving hydrogen, several inter­actions involving the aromatic ring are apparent.

Table 2
A summary of short inter­atomic contacts (Å) for (I)^a

Contact	Distance	ΣvdW	Δ|(dnorm −ΣvdW)|	Symmetry operation
H2N⋯O1^b	1.92	2.61	0.69	1 − x, −y, 2 − z
H1O⋯S1^b	2.21	2.89	0.68	1 + x, y, z
H1N⋯O3^b	2.17	2.61	0.44	1 − x, −y, 1 − z
H3B⋯H8	2.08	2.18	0.10	x, y, 1 + z
H9⋯C1	2.60	2.79	0.19	1 − x, 1 − y, 1 − z
C5⋯O3	3.17	3.22	0.05	1 − x, − y, 1 − z
H2A⋯S1	2.87	2.89	0.02	1 − x, 1 − y, 2 − z
H9⋯S1	2.89	2.89	0.00	1 − x, 1 − y, 1 − z
Notes: (a) The inter­atomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values; (b) these inter­actions correspond to conventional hydrogen bonds.

Figure 3 The two views of the dnorm maps for (I), showing the relevant short contacts indicated by the red spots on the Hirshfeld surface with varying intensities within the range −0.0322 to 1.1699 arbitrary units for (a) H1B⋯O1, H1O⋯S1, H1A⋯O3, C5⋯O3 and H3B⋯H8 and (b) H9⋯C1, H9⋯S1 as well as H2A⋯S1 (not connected for clarity). All H⋯O/O⋯H inter­actions are indicated in green, H⋯S/S⋯H in black, H⋯C/C⋯H in light blue, C⋯O/O⋯C in pink and H⋯H in orange.

Thus, π(benzene)–π(benzene) inter­actions, with an inter-centroid separation = 3.8722 (7) Å, as well as parallel C6=O3⋯Cg(C7–C11) inter­actions, occurring on either side of a reference benzene ring, are validated through further Hirshfeld surface analysis. The presence of π–π inter­actions are supported by the shape complementarity between the aromatic rings as evidenced from the planar stacking arrangement illustrated through the Hirshfeld surface mapped with curvedness in Fig. 4(a). As for the C=O⋯π inter­action, the shape-index on the Hirshfeld surface reveals that there are complementary concave and convex shapes indicated by the red and blue regions around the centre of aromatic ring and ester-C6 atom, respectively, in Fig. 4(b). This suggests the inter­action could involve a significant contribution from the C6 atom; the C6⋯Cg(benzene) separation is 3.5026 (11) Å as opposed to the O3⋯Cg(benzene) separation of 3.6604 (10) Å, Table 1.

Figure 4 (a) The Hirshfeld surface mapped with curvedness (property range: −4.0 to +0.4 arbitrary units) for the benzoate fragments of (I), showing the shape complementarity for the π–π stacking between the fragments and (b) the shape-index (property range: −1.0 to +1.0 arbitrary units) on the Hirshfeld surface of (I), showing the concave (red) and convex (blue) regions indicating the C⋯O shape complementary inter­action (circled).

In order to confirm the above findings, particularly the short contacts as well as the inter­actions involving the aromatic ring, electrostatic potential (ESP) mapping was also performed on the Hirshfeld surface using the DFT-B3LYP quantum level of theory and 6-31G(d,p) basis set as available in Crystal Explorer 17 (Turner et al., 2017). The ESP charge for each H-atom donor and acceptor of the relevant close contacts are tabulated in Table 3. As expected for the conventional hydrogen bonds detected through PLATON (Spek, 2020), significant differences are observed in the electrostatic potentials of the hydrogen-bond donor and acceptor atoms, indicating a strong attraction. Similar observations are noted for the other identified contacts but with smaller differences with the notable exception of the methyl­ene-C3—H3B⋯H8(benzene) contact, for which both inter­acting hydrogen atoms exhibit a positive electrostatic potential signifying that the inter­action is dispersive in nature. As for the π–π inter­action, it has already been established that the contacts arise to charge complementarity between the rings. Concerning the C=O3⋯π contact, occurring between benzene rings separated by an inter-centroid separation of 4.5890 (7) Å, the ester-C6 atom exhibits positive ESP of +0.0127 a.u. on one side to complement the negative ESP of −0.0114 a.u. at the centre of the aromatic ring it inter­acts with, Fig. 5(a). At the same time it has an ESP charge of +0.0223 a.u. on the reverse side that complements the other side of a symmetry related aromatic ring, involved in the π–π contact with an inter-centroid distance of 3.8722 (7) Å, with the ESP charge of −0.0091 a.u., Fig. 5(b).

Table 3
Electrostatic potential charge (V_ESP) for each hydrogen atom donor and acceptor in (I) participating in a close contact identified through Hirshfeld surface analysis

Contact	Electrostatic potential, VESP (a.u.)		Δ|VESP|
	H-donor	H-acceptor
H2N⋯O1	0.1446	−0.0654	0.2100
H1O⋯S1	0.1488	−0.0607	0.2095
H1N⋯O3	0.1248	−0.0601	0.1849
H9⋯C1	0.0441	−0.0119	0.0560
H3B⋯H8	0.0066	0.0229	0.0163
C5⋯O3	0.0581	−0.0562	0.1143
H2A⋯S1	0.0239	−0.0589	0.0828
H9⋯S1	0.0219	−0.0458	0.0677

Figure 5 The electrostatic potential mapped onto the Hirshfeld surface for (I) within the range −0.0672 to 0.0620 atomic units for (a) the upper side of the ester group (circled blue region) and π-ring system (circled red region) and (b) the reverse sides of the ester group (circled faint-blue region) and π-ring system (circled faint-red region). The images highlight the charge complementarity between the specified inter­actions.

The close contacts were also investigated through fingerprint plot analysis, shown in the upper views of Fig. 6. The d_norm-mapped Hirshfeld surfaces for the most prominent point-to-point inter­actions, giving rise to the most discernible peaks in the fingerprint plots, are shown in the lower views of Fig. 6. In general, (I) exhibits a paw-like, overall fingerprint profile, Fig. 6(a), which can be mainly delineated into H⋯H (51.1%), H⋯O/ O⋯H (14.6%), H⋯S/ S⋯H (14.5%), H⋯C/ C⋯H (7.2%), C⋯C (6.0%) contacts, Fig. 6(b)–(e), as well as other minor contacts which constitute about 6.0% of the remaining contacts. A further analysis on the respective fingerprint plots shows that the distribution for the (inter­nal)-O⋯H-(external), (inter­nal)-S⋯H-(external) and (inter­nal)-C⋯H-(external) are slightly more dominant than the (inter­nal)-H⋯X-(external) counterparts (X = O, S, and C), with the distribution being 8.0, 9.3 and 4.0% as against 6.6, 5.2 and 3.2%, respectively. These results tally with the fact that (I) has more hydrogen-bond acceptors than hydrogen-bond donor atoms. Nonetheless, both (inter­nal)-X⋯H-(external) and (inter­nal)-H⋯X-(external) exhibit equivalent contact distances that are tipped at the minimum d_i + d_e values, which correspond to the specified contacts in Table 2.

Figure 6 Upper view: (a) The overall two-dimensional fingerprint plot for (I) and those delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯S/S⋯H and (e) H⋯C/C⋯H, (e) contacts, with the percentage contributions to the overall surface specified within each plot. Lower views: dnorm maps where the tip of the delineated fingerprint plot corresponds to the relevant contact on the Hirshfeld surface and identified through the red cursors.

5. Computational chemistry

The calculation of the inter­action energy for all pairwise mol­ecules in (I) was performed through Crystal Explorer 17 (Turner et al., 2017) with the purpose of studying the strength of each inter­action/set of inter­actions identified from the Hirshfeld surface analysis. Hence, the electrostatic (E_ele), polarization (E_pol), dispersion (E_dis) and exchange-repulsion (E_rep) terms were calculated with the results tabulated in Table 4.

Table 4
A summary of inter­action energies (kJ mol⁻¹) calculated for (I)

Contact	Eele	Epol	Edis	Erep	Etot	Symmetry operation
{N1—H2N⋯O1}2	−91.6	−13.5	−39.5	59.1	−85.6	1 − x, − y, 2 − z
{N1—H1N⋯O3}2 + {C5⋯O3}2	−56.9	−10.1	−26.5	27.4	−66.1	1 − x, − y, 1 − z
C6⋯π(benzene) +
{C9—H9⋯S1}2 +
{C9—H9⋯C1}2	−21.6	−3.0	−57.1	33.2	−48.3	1 − x, 1 − y, 1 − z
O1—H1O⋯S1	−47.2	−7.5	−10.6	36.5	−28.8	1 + x, y, z
π(benzene)–π(benzene)	−0.4	−1.6	−43.2	17.0	−28.3	2 − x, 1 − y, 1 − z
{C2—H2A⋯S1}2	−14.6	−5.1	−14.7	11.3	−23.1	1 − x, 1 − y, 2 − z
C3—H3B⋯H8	1.1	−1.8	−12.7	9.1	−4.3	x, y, 1 + z

Among all the inter­actions, it is the amine-N1—H2N⋯O1(hydrox­yl) hydrogen bond, that closes the connected 12-membered {⋯HO⋯HNCS}₂ and 14-membered {⋯OC₂NCNH}₂ synthons, that has the greatest inter­action energy, E_int = −85.6 kJ mol⁻¹. Next most stabil­izing are the amine-N1—H1N⋯O3(carbon­yl) and methyl­ene-C5⋯O3(carbon­yl) contacts between centrosym­metrically related mol­ecules [−66.1 kJ mol⁻¹], the ester-C6⋯π(benzene), benzene-C9—H9⋯S1(thione) and benzene-C9–H9⋯C1(thione) contacts with a combined E_int of −48.3 kJ mol⁻¹ and hydroxyl-O1–H1O⋯S1(thione) [−28.8 kJ mol⁻¹]. Close in energy to latter is that due to π–π [Cg1⋯Cg1 = 3.8722 (7) Å] with E_int = −28.3 kJ mol⁻¹. Next most significant are the pairwise ethyl­ene-C2—H2A⋯S1(thione) inter­actions (E_int = −23.1 kJ mol⁻¹) then methyl­ene-C3—H3B⋯H8(benzene) (E_int = −4.3 kJ mol⁻¹).

The crystal of (I) is mainly sustained by electrostatic forces owing to the presence of the relatively strong hydrogen-bonding inter­actions, viz. amine-N1—H1N⋯O3(carbon­yl) that propagates along the c axis together with amine-N1—H2N⋯O1(hydrox­yl) and hydroxyl-O1—H1O⋯S1(thione), which extend along the a axis, thereby forming a step-ladder framework as shown in Fig. 7(a). On the other hand, significant dispersion force is also present as evidenced from the wire mesh-like dispersion energy framework predominantly governed by the π–π inter­actions, with contributions from the inter­actions involving the benzene-C9 atom, Fig. 7(b). Overall, the combination of electrostatic and dispersion forces leads to a cuboid-like framework shown in Fig. 7(c).

Figure 7 Perspective views of the energy frameworks of (I), showing the (a) electrostatic force, (b) dispersion force and (c) total energy. The radii of the cylinders are proportional to the relative strength of the corresponding energies and were adjusted to the same scale factor of 100 with a cut-off value of 8 kJ mol^−1 within a 2 × 2 × 2 unit cells.

6. Database survey

Crystal-structure determinations of organic mol­ecules of the general formula R(R′)NC(=S)NH₂ are comparatively rare with the simplest derivative being the R = R′ = Me species, the almost planar mol­ecule being first reported in 1994 (WIFKOL; Pathirana et al., 1994). Similarly, derivatives bearing hydroxyl groups are uncommon and include the relatively simple derivatives shown in Fig. 8, i.e. acyclic (II) (IYAYAJ; Griffiths et al., 2010) and cyclic imidazolidine-2-thione (III) (DOJSUT; Lee et al., 2018).

Figure 8 Chemical diagrams for (II) and (III).

7. Synthesis and crystallization

Compound (I) was synthesized by gently heating an acetone mixture (30 ml) containing ammonium thio­cyanate (Fisher, 1 mmol), benzoyl chloride (Acros, 1 mmol) and bis­(hy­droxy­eth­yl)amine (Acros, 1 mmol). The solution was concentrated to half of the initial volume under heating and a white precipitate was obtained upon cooling the solution to room temperature. Colourless blocks were formed through recrystallization of the crude product from acetone solution. M.p. 388.6–390.1 K. IR (cm⁻¹): 3419 ν(OH), 3323 ν(NH₂)_asym, 3222 ν(NH₂)_sym, 3058 ν(CH)_arom, 3002–2881 ν(CH), 1706 ν(COO), 1647 ν(C=O), 1600 δ(NH), 1523 ν(C=C), 1270 ν(CN), 1053 ν(C=S), 711 δ(CH).

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C). The oxygen- and nitro­gen-bound H atoms were located from a difference-Fourier map and refined with O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with U_iso(H) set to 1.5U_eq(O) or 1.2U_eq(N).

Table 5
Experimental details

Crystal data
Chemical formula	C12H16N2O3S
Mr	268.33
Crystal system, space group	Triclinic, P
Temperature (K)	100
a, b, c (Å)	7.1608 (2), 8.8771 (2), 10.0728 (2)
α, β, γ (°)	96.815 (2), 96.057 (2), 95.990 (2)
V (Å^3)	627.78 (3)
Z	2
Radiation type	Cu Kα
μ (mm^−1)	2.33
Crystal size (mm)	0.14 × 0.10 × 0.09
Data collection
Diffractometer	XtaLAB Synergy, Dualflex, AtlasS2
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2018)
Tmin, Tmax	0.656, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15863, 2608, 2530
Rint	0.028
(sin θ/λ)max (Å^−1)	0.631
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.027, 0.072, 1.02
No. of reflections	2608
No. of parameters	172
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	0.28, −0.29
Computer programs: CrysAlis PRO (Rigaku OD, 2018), SHELXS (Sheldrick, 2015a), SHELXL2018/3 (Sheldrick, 2015b), ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006) andpublCIF (Westrip, 2010).

Supporting information

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

2-[Carbamothioyl(2-hydroxyethyl)amino]ethyl benzoate

Crystal data

C12H16N2O3S	Z = 2
Mr = 268.33	F(000) = 284
Triclinic, P1	Dx = 1.420 Mg m^−3
a = 7.1608 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.8771 (2) Å	Cell parameters from 11731 reflections
c = 10.0728 (2) Å	θ = 5.0–76.3°
α = 96.815 (2)°	µ = 2.33 mm^−1
β = 96.057 (2)°	T = 100 K
γ = 95.990 (2)°	Block, colourless
V = 627.78 (3) Å^3	0.14 × 0.10 × 0.09 mm

Data collection

XtaLAB Synergy, Dualflex, AtlasS2 diffractometer	2608 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2530 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.028
Detector resolution: 5.2558 pixels mm^-1	θmax = 76.6°, θmin = 4.5°
ω scans	h = −8→9
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2018)	k = −11→11
Tmin = 0.656, Tmax = 1.000	l = −12→11
15863 measured reflections

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)] = 0.027	Hydrogen site location: mixed
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 0.2837P] where P = (Fo^2 + 2Fc^2)/3
2608 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.28 e Å^−3
3 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
S1	0.37572 (4)	0.27008 (3)	1.03290 (3)	0.01701 (9)
O1	0.95223 (11)	0.15258 (9)	1.06895 (9)	0.02017 (19)
H1O	1.0641 (15)	0.1717 (19)	1.0521 (17)	0.030*
O2	0.70466 (11)	0.26850 (9)	0.61989 (8)	0.01658 (17)
O3	0.60618 (13)	0.20970 (10)	0.39867 (8)	0.02231 (19)
N1	0.35269 (14)	0.03143 (11)	0.84534 (10)	0.0167 (2)
H1N	0.396 (2)	−0.0360 (14)	0.7896 (13)	0.020*
H2N	0.2480 (16)	0.0025 (16)	0.8779 (14)	0.020*
N2	0.63866 (13)	0.18528 (10)	0.87909 (9)	0.01420 (19)
C1	0.46322 (16)	0.15473 (12)	0.91223 (11)	0.0146 (2)
C2	0.76658 (16)	0.31983 (13)	0.94513 (12)	0.0169 (2)
H2A	0.692935	0.407323	0.960760	0.020*
H2B	0.861614	0.347207	0.884739	0.020*
C3	0.86760 (16)	0.29131 (13)	1.07870 (12)	0.0183 (2)
H3A	0.966872	0.377706	1.111775	0.022*
H3B	0.775824	0.287765	1.145528	0.022*
C4	0.71451 (16)	0.08514 (13)	0.77635 (11)	0.0158 (2)
H4A	0.676376	−0.022672	0.787412	0.019*
H4B	0.854379	0.103147	0.790497	0.019*
C5	0.64657 (16)	0.11088 (13)	0.63421 (11)	0.0170 (2)
H5A	0.702102	0.042030	0.568493	0.020*
H5B	0.507114	0.088915	0.617061	0.020*
C6	0.67210 (15)	0.30367 (13)	0.49377 (11)	0.0162 (2)
C7	0.72974 (15)	0.46730 (13)	0.48446 (11)	0.0158 (2)
C8	0.70318 (16)	0.51705 (14)	0.35804 (12)	0.0180 (2)
H8	0.641338	0.448875	0.282694	0.022*
C9	0.76728 (17)	0.66610 (14)	0.34284 (12)	0.0214 (2)
H9	0.752018	0.699503	0.256588	0.026*
C10	0.85375 (17)	0.76653 (14)	0.45357 (13)	0.0218 (3)
H10	0.899045	0.868220	0.442592	0.026*
C11	0.87453 (17)	0.71919 (14)	0.58064 (13)	0.0212 (2)
H11	0.930722	0.789112	0.656580	0.025*
C12	0.81286 (16)	0.56950 (13)	0.59597 (12)	0.0182 (2)
H12	0.827287	0.536650	0.682476	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01619 (15)	0.01550 (15)	0.01948 (15)	0.00207 (10)	0.00422 (10)	0.00084 (10)
O1	0.0143 (4)	0.0183 (4)	0.0283 (5)	0.0016 (3)	0.0032 (3)	0.0041 (3)
O2	0.0206 (4)	0.0148 (4)	0.0137 (4)	−0.0014 (3)	0.0016 (3)	0.0025 (3)
O3	0.0282 (5)	0.0199 (4)	0.0162 (4)	−0.0027 (3)	−0.0008 (3)	−0.0003 (3)
N1	0.0162 (5)	0.0147 (5)	0.0184 (5)	−0.0008 (4)	0.0025 (4)	0.0015 (4)
N2	0.0149 (4)	0.0131 (4)	0.0141 (4)	0.0001 (3)	0.0018 (3)	0.0012 (3)
C1	0.0162 (5)	0.0140 (5)	0.0144 (5)	0.0020 (4)	0.0001 (4)	0.0057 (4)
C2	0.0170 (5)	0.0127 (5)	0.0203 (5)	−0.0024 (4)	0.0030 (4)	0.0017 (4)
C3	0.0170 (5)	0.0157 (5)	0.0203 (6)	−0.0002 (4)	0.0005 (4)	−0.0021 (4)
C4	0.0172 (5)	0.0146 (5)	0.0160 (5)	0.0027 (4)	0.0033 (4)	0.0019 (4)
C5	0.0203 (5)	0.0136 (5)	0.0163 (5)	−0.0011 (4)	0.0030 (4)	0.0007 (4)
C6	0.0139 (5)	0.0201 (6)	0.0147 (5)	0.0019 (4)	0.0024 (4)	0.0019 (4)
C7	0.0134 (5)	0.0176 (6)	0.0169 (5)	0.0030 (4)	0.0029 (4)	0.0028 (4)
C8	0.0178 (5)	0.0207 (6)	0.0160 (5)	0.0057 (4)	0.0015 (4)	0.0017 (4)
C9	0.0234 (6)	0.0233 (6)	0.0206 (6)	0.0095 (5)	0.0048 (5)	0.0085 (5)
C10	0.0209 (6)	0.0164 (5)	0.0301 (6)	0.0050 (4)	0.0058 (5)	0.0061 (5)
C11	0.0202 (6)	0.0190 (6)	0.0231 (6)	0.0024 (4)	0.0001 (5)	−0.0007 (5)
C12	0.0180 (5)	0.0204 (6)	0.0162 (5)	0.0027 (4)	0.0009 (4)	0.0028 (4)

Geometric parameters (Å, º)

S1—C1	1.7082 (11)	C4—C5	1.5141 (15)
O1—C3	1.4259 (14)	C4—H4A	0.9900
O1—H1O	0.840 (9)	C4—H4B	0.9900
O2—C6	1.3462 (14)	C5—H5A	0.9900
O2—C5	1.4460 (13)	C5—H5B	0.9900
O3—C6	1.2121 (14)	C6—C7	1.4847 (16)
N1—C1	1.3454 (15)	C7—C12	1.3941 (16)
N1—H1N	0.874 (9)	C7—C8	1.3974 (16)
N1—H2N	0.876 (9)	C8—C9	1.3859 (17)
N2—C1	1.3424 (15)	C8—H8	0.9500
N2—C2	1.4706 (14)	C9—C10	1.3876 (18)
N2—C4	1.4688 (14)	C9—H9	0.9500
C2—C3	1.5203 (16)	C10—C11	1.3919 (18)
C2—H2A	0.9900	C10—H10	0.9500
C2—H2B	0.9900	C11—C12	1.3876 (17)
C3—H3A	0.9900	C11—H11	0.9500
C3—H3B	0.9900	C12—H12	0.9500
C3—O1—H1O	108.6 (12)	H4A—C4—H4B	107.8
C6—O2—C5	114.66 (8)	O2—C5—C4	108.15 (9)
C1—N1—H1N	122.3 (10)	O2—C5—H5A	110.1
C1—N1—H2N	117.4 (10)	C4—C5—H5A	110.1
H1N—N1—H2N	117.2 (14)	O2—C5—H5B	110.1
C1—N2—C2	121.80 (9)	C4—C5—H5B	110.1
C1—N2—C4	121.91 (9)	H5A—C5—H5B	108.4
C2—N2—C4	116.29 (9)	O3—C6—O2	122.83 (10)
N2—C1—N1	118.46 (10)	O3—C6—C7	124.38 (10)
N2—C1—S1	121.95 (8)	O2—C6—C7	112.78 (9)
N1—C1—S1	119.57 (9)	C12—C7—C8	119.92 (11)
N2—C2—C3	112.00 (9)	C12—C7—C6	122.18 (10)
N2—C2—H2A	109.2	C8—C7—C6	117.88 (10)
C3—C2—H2A	109.2	C9—C8—C7	119.84 (11)
N2—C2—H2B	109.2	C9—C8—H8	120.1
C3—C2—H2B	109.2	C7—C8—H8	120.1
H2A—C2—H2B	107.9	C8—C9—C10	120.01 (11)
O1—C3—C2	112.86 (9)	C8—C9—H9	120.0
O1—C3—H3A	109.0	C10—C9—H9	120.0
C2—C3—H3A	109.0	C11—C10—C9	120.41 (11)
O1—C3—H3B	109.0	C11—C10—H10	119.8
C2—C3—H3B	109.0	C9—C10—H10	119.8
H3A—C3—H3B	107.8	C12—C11—C10	119.75 (11)
N2—C4—C5	112.81 (9)	C12—C11—H11	120.1
N2—C4—H4A	109.0	C10—C11—H11	120.1
C5—C4—H4A	109.0	C11—C12—C7	120.01 (11)
N2—C4—H4B	109.0	C11—C12—H12	120.0
C5—C4—H4B	109.0	C7—C12—H12	120.0
C2—N2—C1—N1	178.51 (9)	O3—C6—C7—C12	−177.03 (11)
C4—N2—C1—N1	−2.38 (15)	O2—C6—C7—C12	1.55 (15)
C2—N2—C1—S1	0.22 (15)	O3—C6—C7—C8	1.20 (17)
C4—N2—C1—S1	179.33 (8)	O2—C6—C7—C8	179.78 (9)
C1—N2—C2—C3	82.67 (13)	C12—C7—C8—C9	2.89 (17)
C4—N2—C2—C3	−96.49 (11)	C6—C7—C8—C9	−175.38 (10)
N2—C2—C3—O1	49.39 (13)	C7—C8—C9—C10	−1.46 (17)
C1—N2—C4—C5	80.00 (13)	C8—C9—C10—C11	−0.84 (18)
C2—N2—C4—C5	−100.85 (11)	C9—C10—C11—C12	1.71 (18)
C6—O2—C5—C4	172.96 (9)	C10—C11—C12—C7	−0.26 (18)
N2—C4—C5—O2	59.09 (12)	C8—C7—C12—C11	−2.03 (17)
C5—O2—C6—O3	−2.74 (15)	C6—C7—C12—C11	176.17 (10)
C5—O2—C6—C7	178.64 (9)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the (C7–C12) ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S1^i	0.84 (1)	2.35 (1)	3.1746 (9)	169 (2)
N1—H2N···O1^ii	0.88 (1)	2.04 (1)	2.8582 (13)	155 (1)
N1—H1N···O3^iii	0.88 (1)	2.30 (1)	3.1218 (13)	158 (1)
C6—O3···Cg1^iv	1.21 (1)	3.66 (1)	3.5026 (12)	73 (1)

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