3,3′-Dibutanoyl-1,1′-(o-phenyl­ene)dithio­urea

Saeed, A.; Abbas, N.; Rafique, H.; Bolte, M.

doi:10.1107/S1600536810001789

3,3′-Dibutanoyl-1,1′-(o-phenylene)dithiourea

A. Saeed, N. Abbas, H. Rafique and M. Bolte

The molecular conformation of the title compound, C₁₆H₂₂N₄O₂S₂, is stabilized by two intramolecular N—H

O hydrogen bonds. The crystal packing shows N—H

O and N—H

S hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810001789/bg2318sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810001789/bg2318Isup2.hkl Contains datablock I

CCDC reference: 765195

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.036
wR factor = 0.095
Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.82 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.68 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C11     ..       5.11 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          9
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         21

Alert level G
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 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
   0 ALERT type 5 Informative message, check

Comment top

Various bisthiourea derivatives have attracted much attention due to their variety of applications and bioactivities. The presence of multivalent binding sites in bis thioureas provide a multitude of bonding possibilities. Urea and thiourea functionalities, presenting opportunities for the formation of diverse hydrogen bonded networks, represent powerful crystal engineering building blocks (Succaw et al., 2005). The fluorinated bis-thiourea derivative are used as organocatalyst in Morita-Baylis-Hillman reaction (Berkessel et al., 2006). N-alkyl thiourea Cadmium(II) complex as precursor for CdS-nanoparticle synthesis (Moloto et al., 2004). BINOL (1,1'-Bi-2-naphthol) bis thiourea derivatives act as chemosensors (Hu et al.,2009). Bis-thiourea resins have been used for adsorption of silver(I) and gold(II) for application to retrieval of silver ions from processed photo films (Atia et al., 2005). Diisoamyloxydiphenylthioureas are effective anti-tuberculosis agents (Phetsuksiri et al. (2003).

The molecular conformation of the title compound is stabilized by two N—H···O hydrogen bonds. The crystal packing shows N—H···O and N—H···S hydrogen bonds.

Related literature top

For details of the biological activity of bis thioureas, see: Berkessel et al. (2006); Moloto et al. (2004). For their applications, see: Atia et al. (2005); Hu et al. (2009); Phetsuksiri et al. (2003). For the synthesis of the title compound, see: Succaw et al. (2005).

Experimental top

The compound was prepared acc ording to lierature procedure (Succaw et al., 2005) and Recrystallized from methanol as colourless crystals: Anal. calcd.for C₁₆H₂₂N₄O₂S2: C, 52.43; H, 6.05; N, 15.29; S, 17.50%; found: C, 52.31; H, 6.19; N, 15.41; S, 17.62.

Structure description top

The molecular conformation of the title compound is stabilized by two N—H···O hydrogen bonds. The crystal packing shows N—H···O and N—H···S hydrogen bonds.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.

3,3'-Dibutanoyl-1,1'-(o-phenylene)dithiourea top

Crystal data top

C₁₆H₂₂N₄O₂S₂	F(000) = 776
M_r = 366.50	D_x = 1.353 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 20465 reflections
a = 8.8099 (5) Å	θ = 3.4–26.0°
b = 16.4925 (7) Å	µ = 0.31 mm⁻¹
c = 12.3923 (8) Å	T = 173 K
β = 91.949 (5)°	Block, colourless
V = 1799.53 (17) Å³	0.28 × 0.28 × 0.23 mm
Z = 4

Data collection top

Stoe IPDS II two-circle diffractometer	3360 independent reflections
Radiation source: fine-focus sealed tube	2890 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ω scans	θ_max = 25.6°, θ_min = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −10→10
T_min = 0.918, T_max = 0.932	k = −19→18
22483 measured reflections	l = −15→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0595P)² + 0.139P] where P = (F_o² + 2F_c²)/3
3360 reflections	(Δ/σ)_max = 0.001
229 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₆H₂₂N₄O₂S₂	V = 1799.53 (17) Å³
M_r = 366.50	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8099 (5) Å	µ = 0.31 mm⁻¹
b = 16.4925 (7) Å	T = 173 K
c = 12.3923 (8) Å	0.28 × 0.28 × 0.23 mm
β = 91.949 (5)°

Data collection top

Stoe IPDS II two-circle diffractometer	3360 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	2890 reflections with I > 2σ(I)
T_min = 0.918, T_max = 0.932	R_int = 0.087
22483 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.23 e Å⁻³
3360 reflections	Δρ_min = −0.33 e Å⁻³
229 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.07444 (5)	0.68569 (3)	0.35994 (3)	0.02446 (14)
S2	0.47542 (5)	0.79179 (3)	0.52094 (3)	0.02947 (14)
O1	0.38901 (14)	0.53284 (9)	0.57778 (9)	0.0278 (3)
O2	0.83408 (13)	0.59749 (8)	0.58037 (9)	0.0224 (3)
C1	0.42857 (18)	0.65251 (9)	0.31239 (12)	0.0152 (3)
C2	0.57714 (18)	0.67920 (9)	0.33537 (12)	0.0154 (3)
C3	0.66576 (19)	0.70843 (10)	0.25383 (13)	0.0206 (3)
H3	0.7674	0.7249	0.2695	0.025*
C4	0.6054 (2)	0.71355 (11)	0.14871 (13)	0.0228 (4)
H4	0.6654	0.7342	0.0927	0.027*
C5	0.4579 (2)	0.68847 (10)	0.12589 (12)	0.0211 (4)
H5	0.4170	0.6924	0.0542	0.025*
C6	0.36860 (19)	0.65746 (10)	0.20698 (12)	0.0180 (3)
H6	0.2678	0.6399	0.1906	0.022*
N11	0.34909 (15)	0.61572 (8)	0.39740 (10)	0.0160 (3)
H11	0.401 (2)	0.5867 (12)	0.4430 (16)	0.019*
C11	0.20588 (17)	0.62849 (10)	0.42462 (12)	0.0159 (3)
N12	0.16371 (16)	0.58921 (8)	0.51872 (10)	0.0168 (3)
H12	0.072 (2)	0.5945 (12)	0.5357 (15)	0.020*
C12	0.25388 (19)	0.54519 (10)	0.59085 (12)	0.0195 (3)
C13	0.1723 (2)	0.51260 (12)	0.68687 (14)	0.0272 (4)
H13A	0.1316	0.4581	0.6691	0.033*
H13B	0.0852	0.5484	0.7017	0.033*
C14	0.2751 (2)	0.50692 (12)	0.78795 (14)	0.0285 (4)
H14A	0.2206	0.4776	0.8446	0.034*
H14B	0.3663	0.4748	0.7711	0.034*
C15	0.3251 (3)	0.58888 (14)	0.83166 (17)	0.0447 (5)
H15A	0.3912	0.5812	0.8961	0.054*
H15B	0.2357	0.6205	0.8506	0.054*
H15C	0.3809	0.6179	0.7765	0.054*
N21	0.64067 (16)	0.67101 (9)	0.44277 (10)	0.0170 (3)
H21	0.708 (2)	0.6374 (13)	0.4558 (15)	0.020*
C21	0.59630 (17)	0.71486 (10)	0.52676 (12)	0.0171 (3)
N22	0.65944 (15)	0.69253 (8)	0.62711 (11)	0.0172 (3)
H22	0.630 (2)	0.7231 (13)	0.6794 (16)	0.021*
C22	0.77077 (18)	0.63670 (10)	0.65070 (12)	0.0178 (3)
C23	0.8064 (2)	0.62499 (11)	0.76915 (12)	0.0223 (4)
H23A	0.7462	0.6636	0.8114	0.027*
H23B	0.9154	0.6361	0.7847	0.027*
C24	0.7692 (2)	0.53829 (12)	0.80244 (14)	0.0308 (4)
H24A	0.6617	0.5264	0.7825	0.037*
H24B	0.8335	0.5000	0.7627	0.037*
C25	0.7954 (4)	0.52563 (15)	0.92284 (17)	0.0580 (8)
H25A	0.7694	0.4697	0.9415	0.070*
H25B	0.7314	0.5632	0.9623	0.070*
H25C	0.9024	0.5358	0.9424	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0188 (2)	0.0308 (3)	0.0237 (2)	0.00497 (16)	0.00078 (16)	0.01004 (17)
S2	0.0334 (3)	0.0301 (3)	0.0245 (2)	0.01694 (19)	−0.00509 (18)	−0.00387 (18)
O1	0.0216 (6)	0.0399 (8)	0.0223 (6)	0.0105 (5)	0.0046 (5)	0.0104 (5)
O2	0.0225 (6)	0.0264 (7)	0.0184 (6)	0.0085 (5)	−0.0012 (4)	−0.0018 (5)
C1	0.0168 (7)	0.0135 (8)	0.0153 (7)	0.0021 (6)	0.0025 (6)	0.0011 (6)
C2	0.0181 (8)	0.0137 (8)	0.0144 (7)	0.0028 (6)	−0.0005 (6)	−0.0001 (6)
C3	0.0182 (8)	0.0201 (9)	0.0236 (8)	0.0003 (6)	0.0022 (6)	0.0020 (6)
C4	0.0268 (9)	0.0219 (9)	0.0200 (8)	0.0017 (7)	0.0073 (6)	0.0058 (7)
C5	0.0289 (9)	0.0213 (9)	0.0130 (7)	0.0052 (7)	0.0006 (6)	0.0007 (6)
C6	0.0191 (8)	0.0172 (8)	0.0175 (7)	0.0012 (6)	−0.0026 (6)	−0.0011 (6)
N11	0.0152 (6)	0.0189 (7)	0.0138 (6)	0.0005 (5)	−0.0007 (5)	0.0040 (5)
C11	0.0175 (8)	0.0155 (8)	0.0145 (7)	−0.0034 (6)	−0.0010 (6)	−0.0020 (6)
N12	0.0137 (7)	0.0200 (7)	0.0168 (6)	0.0006 (5)	0.0021 (5)	0.0035 (5)
C12	0.0216 (8)	0.0201 (8)	0.0169 (7)	0.0026 (6)	0.0017 (6)	0.0010 (6)
C13	0.0256 (9)	0.0324 (10)	0.0242 (8)	0.0047 (7)	0.0063 (7)	0.0108 (7)
C14	0.0391 (10)	0.0280 (10)	0.0187 (8)	0.0083 (8)	0.0043 (7)	0.0074 (7)
C15	0.0663 (16)	0.0377 (12)	0.0303 (10)	0.0012 (11)	0.0033 (10)	−0.0059 (9)
N21	0.0153 (7)	0.0195 (7)	0.0159 (6)	0.0045 (5)	−0.0027 (5)	−0.0006 (5)
C21	0.0147 (7)	0.0185 (8)	0.0180 (7)	−0.0001 (6)	0.0001 (6)	0.0006 (6)
N22	0.0190 (7)	0.0177 (7)	0.0148 (6)	0.0015 (5)	−0.0010 (5)	−0.0029 (5)
C22	0.0186 (8)	0.0168 (8)	0.0178 (7)	−0.0021 (6)	−0.0028 (6)	0.0003 (6)
C23	0.0296 (9)	0.0203 (9)	0.0167 (8)	0.0036 (7)	−0.0047 (6)	−0.0010 (6)
C24	0.0442 (11)	0.0265 (10)	0.0215 (8)	−0.0072 (8)	0.0001 (8)	0.0024 (7)
C25	0.115 (2)	0.0344 (13)	0.0240 (10)	−0.0185 (14)	−0.0110 (12)	0.0085 (9)

Geometric parameters (Å, º) top

S1—C11	1.6763 (16)	C13—H13A	0.9900
S2—C21	1.6566 (16)	C13—H13B	0.9900
O1—C12	1.224 (2)	C14—C15	1.516 (3)
O2—C22	1.234 (2)	C14—H14A	0.9900
C1—C6	1.395 (2)	C14—H14B	0.9900
C1—C2	1.401 (2)	C15—H15A	0.9800
C1—N11	1.4207 (19)	C15—H15B	0.9800
C2—C3	1.385 (2)	C15—H15C	0.9800
C2—N21	1.4325 (19)	N21—C21	1.337 (2)
C3—C4	1.393 (2)	N21—H21	0.83 (2)
C3—H3	0.9500	C21—N22	1.395 (2)
C4—C5	1.384 (3)	N22—C22	1.370 (2)
C4—H4	0.9500	N22—H22	0.87 (2)
C5—C6	1.394 (2)	C22—C23	1.503 (2)
C5—H5	0.9500	C23—C24	1.527 (3)
C6—H6	0.9500	C23—H23A	0.9900
N11—C11	1.334 (2)	C23—H23B	0.9900
N11—H11	0.86 (2)	C24—C25	1.516 (3)
C11—N12	1.395 (2)	C24—H24A	0.9900
N12—C12	1.382 (2)	C24—H24B	0.9900
N12—H12	0.84 (2)	C25—H25A	0.9800
C12—C13	1.510 (2)	C25—H25B	0.9800
C13—C14	1.524 (3)	C25—H25C	0.9800

C6—C1—C2	119.57 (14)	C15—C14—H14B	108.9
C6—C1—N11	122.61 (14)	C13—C14—H14B	108.9
C2—C1—N11	117.65 (13)	H14A—C14—H14B	107.7
C3—C2—C1	120.47 (14)	C14—C15—H15A	109.5
C3—C2—N21	119.91 (14)	C14—C15—H15B	109.5
C1—C2—N21	119.48 (14)	H15A—C15—H15B	109.5
C2—C3—C4	119.80 (15)	C14—C15—H15C	109.5
C2—C3—H3	120.1	H15A—C15—H15C	109.5
C4—C3—H3	120.1	H15B—C15—H15C	109.5
C5—C4—C3	119.94 (15)	C21—N21—C2	123.85 (14)
C5—C4—H4	120.0	C21—N21—H21	116.0 (13)
C3—C4—H4	120.0	C2—N21—H21	120.1 (13)
C4—C5—C6	120.74 (15)	N21—C21—N22	115.68 (14)
C4—C5—H5	119.6	N21—C21—S2	125.81 (12)
C6—C5—H5	119.6	N22—C21—S2	118.52 (12)
C5—C6—C1	119.45 (15)	C22—N22—C21	128.97 (14)
C5—C6—H6	120.3	C22—N22—H22	117.5 (13)
C1—C6—H6	120.3	C21—N22—H22	113.1 (13)
C11—N11—C1	127.91 (14)	O2—C22—N22	122.64 (14)
C11—N11—H11	114.1 (12)	O2—C22—C23	122.56 (15)
C1—N11—H11	117.4 (13)	N22—C22—C23	114.77 (14)
N11—C11—N12	114.78 (14)	C22—C23—C24	110.15 (14)
N11—C11—S1	127.73 (12)	C22—C23—H23A	109.6
N12—C11—S1	117.49 (11)	C24—C23—H23A	109.6
C12—N12—C11	128.39 (14)	C22—C23—H23B	109.6
C12—N12—H12	115.2 (13)	C24—C23—H23B	109.6
C11—N12—H12	116.3 (13)	H23A—C23—H23B	108.1
O1—C12—N12	122.84 (14)	C25—C24—C23	111.58 (16)
O1—C12—C13	122.44 (15)	C25—C24—H24A	109.3
N12—C12—C13	114.71 (14)	C23—C24—H24A	109.3
C12—C13—C14	112.57 (15)	C25—C24—H24B	109.3
C12—C13—H13A	109.1	C23—C24—H24B	109.3
C14—C13—H13A	109.1	H24A—C24—H24B	108.0
C12—C13—H13B	109.1	C24—C25—H25A	109.5
C14—C13—H13B	109.1	C24—C25—H25B	109.5
H13A—C13—H13B	107.8	H25A—C25—H25B	109.5
C15—C14—C13	113.35 (16)	C24—C25—H25C	109.5
C15—C14—H14A	108.9	H25A—C25—H25C	109.5
C13—C14—H14A	108.9	H25B—C25—H25C	109.5

C6—C1—C2—C3	−1.7 (2)	C11—N12—C12—O1	−2.4 (3)
N11—C1—C2—C3	173.81 (15)	C11—N12—C12—C13	178.22 (16)
C6—C1—C2—N21	−177.47 (14)	O1—C12—C13—C14	31.9 (2)
N11—C1—C2—N21	−2.0 (2)	N12—C12—C13—C14	−148.67 (15)
C1—C2—C3—C4	1.9 (2)	C12—C13—C14—C15	67.2 (2)
N21—C2—C3—C4	177.67 (15)	C3—C2—N21—C21	113.70 (18)
C2—C3—C4—C5	−0.8 (3)	C1—C2—N21—C21	−70.5 (2)
C3—C4—C5—C6	−0.4 (3)	C2—N21—C21—N22	173.38 (14)
C4—C5—C6—C1	0.6 (2)	C2—N21—C21—S2	−6.7 (2)
C2—C1—C6—C5	0.4 (2)	N21—C21—N22—C22	6.5 (2)
N11—C1—C6—C5	−174.83 (15)	S2—C21—N22—C22	−173.42 (13)
C6—C1—N11—C11	−49.1 (2)	C21—N22—C22—O2	1.0 (3)
C2—C1—N11—C11	135.57 (16)	C21—N22—C22—C23	−177.18 (15)
C1—N11—C11—N12	−174.00 (14)	O2—C22—C23—C24	−61.4 (2)
C1—N11—C11—S1	5.6 (2)	N22—C22—C23—C24	116.77 (17)
N11—C11—N12—C12	6.0 (2)	C22—C23—C24—C25	−176.8 (2)
S1—C11—N12—C12	−173.65 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O1	0.86 (2)	1.90 (2)	2.6336 (17)	142.6 (17)
N12—H12···O2ⁱ	0.84 (2)	2.19 (2)	3.0309 (18)	175.3 (19)
N21—H21···O2	0.83 (2)	1.98 (2)	2.6616 (18)	139.1 (18)
N22—H22···S1ⁱⁱ	0.87 (2)	2.75 (2)	3.6147 (14)	172.0 (17)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₂₂N₄O₂S₂
M_r	366.50
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	8.8099 (5), 16.4925 (7), 12.3923 (8)
β (°)	91.949 (5)
V (Å³)	1799.53 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.28 × 0.28 × 0.23

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)
T_min, T_max	0.918, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	22483, 3360, 2890
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.095, 1.04
No. of reflections	3360
No. of parameters	229
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.33

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).