1-(2-Chloro­benzo­yl)-3-(2,3-dimethyl­phen­yl)thio­urea

Rauf, M.K.; Ebihara, M.; Badshah, A.

doi:10.1107/S1600536812048209

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3483

doi:10.1107/S1600536812048209

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1-(2-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea

M. Khawar Rauf,^a ^* Masahiro Ebihara ^b and Amin Badshah ^a ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Faculty of Engineering, Gifu University Yanagido, Gifu 501-1193, Japan
^*Correspondence e-mail: mkhawarrauf@yahoo.co.uk, aminbadshah@yahoo.com

(Received 17 November 2012; accepted 23 November 2012; online 30 November 2012)

The dihedral angle between the two phenyl groups in the title compound, C₁₆H₁₅ClN₂OS, is 14.88 (4)°. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, pairs of N—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For background and a related structure, see: Rauf et al. (2012 ). For a description of the Cambridge Structural Database, see: Allen et al. (2002 ).

Experimental

Crystal data

C₁₆H₁₅ClN₂OS
M_r = 318.81
Triclinic, $[P \overline 1]$
a = 7.489 (3) Å
b = 9.338 (4) Å
c = 13.274 (5) Å
α = 65.674 (13)°
β = 69.975 (16)°
γ = 73.639 (17)°
V = 783.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 123 K
0.50 × 0.35 × 0.28 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
6180 measured reflections
3506 independent reflections
3373 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.090
S = 1.08
3506 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.88	2.46	3.3104 (15)	164
N2—H2⋯O1	0.88	2.00	2.6866 (17)	134
Symmetry code: (i) -x, -y, -z+1.

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: Yadokari-XG (Wakita, 2001 ; Kabuto et al., 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812048209/hg5274sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048209/hg5274Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812048209/hg5274Isup3.cml

checkCIF report

Comment top

The background to this study has been set out in our previous work for the structural chemistry of N,N'-disubstituted thiourea (Rauf et al., 2012) and their coordination chemistry. Herein, as a continuation of these crytallographic studies, the structure of the title compound (I) is described, Fig. 1. Compared to N-benzoyl-N'-phenylthioureas [Cambridge Structural Database (Mogul Version 1.7; Allen, 2002], the methyl substitutions at C(10) and C(11)on phenyl ring, implies no significant effect on these bond lengths. and show the molecule to exist in the thione form with typical thiourea C—S and C—O bonds, as well as shortened C—N bond lengths. The dihedral angles to the O(1) C(1) N(1) C(2) N(2)S(1) plane are 79.89 (2)° for the ring formed by C(3) to C(8) and 65.32 (2)° for the ring formed by C(9) to C(14). An intramolecular N—H···O H–bond is present (Table 1), forming a six-membered ring commonly observed in this class of compounds (Rauf et al., 2012). In the crystal packing of (I), intermolecular N—H···S H–bonds link the molecules into centrosymmetric dimers (Fig.2).

Related literature top

For backgrounfd and a related structure, see: Rauf et al. (2012). For a description of the Cambridge Structural Database, see: Allen et al. (2002).

Experimental top

Freshly prepared 2-chlorobenzoylisothiocyanate (1.98 g, 10 mmol) was dissolved in acetone (30 ml) and stirred for 30 minutes. Afterwards neat 2,3-dimethylaniline(1.21 g, 10 mmol) was added and the resulting mixture was stirred for 2 h. The reaction mixture was then poured into acidified water and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from methanol/ 1,1-dichloromethane (1:1 v/v) to give fine crystals of the title compound (I), with an overall yield of 95% (3.02 g). M.P; 180–181°C Anal. calcd. for C₁₆ H₁₅Cl N₂ O S; C, 60.28 H, 4.74 N, 8.79 S, 10.06 Found: C, 60.22 H, 4.73 N, 8.78 S, 10.01.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: Yadokari-XG (Wakita, 2001; Kabuto et al., 2009).

Figures top

	Fig. 1. ORTEP of (I). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds shown as dashed lines.
	Fig. 2. Packing diagram of (I). Hydrogen bonds shown as dashed lines.

1-(2-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea top

Crystal data top

C₁₆H₁₅ClN₂OS	Z = 2
M_r = 318.81	F(000) = 332
Triclinic, P1	D_x = 1.351 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 7.489 (3) Å	Cell parameters from 2732 reflections
b = 9.338 (4) Å	θ = 3.0–27.5°
c = 13.274 (5) Å	µ = 0.38 mm⁻¹
α = 65.674 (13)°	T = 123 K
β = 69.975 (16)°	Prism, colorless
γ = 73.639 (17)°	0.50 × 0.35 × 0.28 mm
V = 783.9 (5) Å³

Data collection top

Rigaku/MSC Mercury CCD diffractometer	3373 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.062
Graphite Monochromator monochromator	θ_max = 27.5°, θ_min = 3.5°
Detector resolution: 14.62 pixels mm^-1	h = −6→9
ω scans	k = −9→12
6180 measured reflections	l = −10→17
3506 independent reflections

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) = 0.090	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0371P)² + 0.4197P] where P = (F_o² + 2F_c²)/3
3506 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₆H₁₅ClN₂OS	γ = 73.639 (17)°
M_r = 318.81	V = 783.9 (5) Å³
Triclinic, P1	Z = 2
a = 7.489 (3) Å	Mo Kα radiation
b = 9.338 (4) Å	µ = 0.38 mm⁻¹
c = 13.274 (5) Å	T = 123 K
α = 65.674 (13)°	0.50 × 0.35 × 0.28 mm
β = 69.975 (16)°

Data collection top

Rigaku/MSC Mercury CCD diffractometer	3373 reflections with I > 2σ(I)
6180 measured reflections	R_int = 0.062
3506 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	Δρ_max = 0.32 e Å⁻³
3506 reflections	Δρ_min = −0.31 e Å⁻³
192 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
C1	0.38592 (19)	0.07516 (15)	0.27734 (11)	0.0162 (3)
O1	0.44634 (15)	0.17028 (13)	0.18262 (9)	0.0245 (2)
N1	0.20232 (16)	0.09731 (13)	0.34511 (9)	0.0170 (2)
H1	0.1791	0.0275	0.4152	0.020*
C2	0.04854 (19)	0.21635 (15)	0.31664 (11)	0.0151 (2)
S1	−0.15915 (5)	0.22091 (4)	0.41821 (3)	0.01758 (10)
N2	0.07877 (16)	0.31921 (13)	0.20967 (9)	0.0172 (2)
H2	0.1972	0.3159	0.1655	0.021*
C3	0.51000 (18)	−0.07725 (15)	0.32976 (11)	0.0157 (3)
C4	0.48935 (19)	−0.22203 (16)	0.33182 (11)	0.0175 (3)
C5	0.6119 (2)	−0.36192 (17)	0.37358 (12)	0.0234 (3)
H5	0.5988	−0.4597	0.3728	0.028*
C6	0.7535 (2)	−0.35614 (18)	0.41627 (13)	0.0269 (3)
H6	0.8371	−0.4512	0.4460	0.032*
C7	0.7751 (2)	−0.21271 (19)	0.41617 (13)	0.0258 (3)
H7	0.8721	−0.2102	0.4462	0.031*
C8	0.6538 (2)	−0.07287 (17)	0.37186 (12)	0.0211 (3)
H8	0.6695	0.0255	0.3704	0.025*
Cl1	0.30905 (5)	−0.22869 (5)	0.28008 (3)	0.02652 (11)
C9	−0.07073 (18)	0.43554 (16)	0.16191 (10)	0.0155 (3)
C10	−0.06255 (19)	0.59756 (16)	0.12305 (11)	0.0166 (3)
C11	−0.2070 (2)	0.70696 (16)	0.07143 (11)	0.0188 (3)
C12	−0.3533 (2)	0.65092 (18)	0.06365 (11)	0.0206 (3)
H12	−0.4519	0.7251	0.0304	0.025*
C13	−0.3589 (2)	0.48910 (18)	0.10335 (11)	0.0213 (3)
H13	−0.4604	0.4533	0.0973	0.026*
C14	−0.2158 (2)	0.38012 (17)	0.15185 (11)	0.0191 (3)
H14	−0.2166	0.2690	0.1779	0.023*
C15	0.0930 (2)	0.65647 (18)	0.13585 (13)	0.0236 (3)
H15C	0.1687	0.5671	0.1833	0.035*
H15A	0.0342	0.7369	0.1724	0.035*
H15B	0.1773	0.7038	0.0602	0.035*
C16	−0.2044 (2)	0.88359 (18)	0.02548 (14)	0.0299 (3)
H16C	−0.3084	0.9405	−0.0127	0.045*
H16A	−0.0802	0.9059	−0.0295	0.045*
H16B	−0.2229	0.9192	0.0888	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0165 (6)	0.0149 (6)	0.0178 (6)	−0.0008 (5)	−0.0061 (5)	−0.0059 (5)
O1	0.0191 (5)	0.0235 (5)	0.0202 (5)	−0.0012 (4)	−0.0032 (4)	−0.0004 (4)
N1	0.0172 (5)	0.0141 (5)	0.0143 (5)	0.0016 (4)	−0.0037 (4)	−0.0030 (4)
C2	0.0173 (6)	0.0126 (5)	0.0161 (6)	−0.0001 (5)	−0.0061 (5)	−0.0059 (5)
S1	0.01736 (17)	0.01515 (16)	0.01454 (16)	0.00274 (11)	−0.00288 (12)	−0.00425 (12)
N2	0.0138 (5)	0.0177 (5)	0.0152 (5)	0.0010 (4)	−0.0040 (4)	−0.0031 (4)
C3	0.0140 (6)	0.0156 (6)	0.0149 (6)	0.0003 (5)	−0.0025 (5)	−0.0055 (5)
C4	0.0149 (6)	0.0193 (6)	0.0183 (6)	−0.0020 (5)	−0.0018 (5)	−0.0092 (5)
C5	0.0230 (7)	0.0174 (6)	0.0253 (7)	0.0014 (5)	−0.0021 (6)	−0.0095 (5)
C6	0.0234 (7)	0.0227 (7)	0.0270 (7)	0.0076 (6)	−0.0087 (6)	−0.0070 (6)
C7	0.0185 (7)	0.0310 (8)	0.0285 (7)	0.0027 (6)	−0.0112 (6)	−0.0111 (6)
C8	0.0191 (6)	0.0216 (7)	0.0245 (7)	−0.0018 (5)	−0.0078 (5)	−0.0094 (5)
Cl1	0.02276 (19)	0.0319 (2)	0.0347 (2)	−0.00257 (14)	−0.00959 (15)	−0.02058 (16)
C9	0.0147 (6)	0.0169 (6)	0.0111 (5)	0.0013 (5)	−0.0037 (4)	−0.0037 (5)
C10	0.0157 (6)	0.0184 (6)	0.0138 (5)	−0.0011 (5)	−0.0029 (5)	−0.0057 (5)
C11	0.0184 (6)	0.0181 (6)	0.0153 (6)	0.0013 (5)	−0.0038 (5)	−0.0046 (5)
C12	0.0162 (6)	0.0260 (7)	0.0146 (6)	0.0025 (5)	−0.0055 (5)	−0.0048 (5)
C13	0.0167 (6)	0.0297 (7)	0.0170 (6)	−0.0045 (5)	−0.0050 (5)	−0.0069 (5)
C14	0.0206 (6)	0.0184 (6)	0.0160 (6)	−0.0037 (5)	−0.0041 (5)	−0.0040 (5)
C15	0.0229 (7)	0.0225 (7)	0.0283 (7)	−0.0031 (5)	−0.0097 (6)	−0.0096 (6)
C16	0.0303 (8)	0.0173 (7)	0.0344 (8)	0.0012 (6)	−0.0100 (7)	−0.0037 (6)

Geometric parameters (Å, º) top

C1—O1	1.2211 (17)	C8—H8	0.9500
C1—N1	1.3743 (17)	C9—C14	1.392 (2)
C1—C3	1.5017 (18)	C9—C10	1.395 (2)
N1—C2	1.3912 (17)	C10—C11	1.4115 (19)
N1—H1	0.8800	C10—C15	1.504 (2)
C2—N2	1.3299 (17)	C11—C12	1.389 (2)
C2—S1	1.6770 (14)	C11—C16	1.508 (2)
N2—C9	1.4385 (17)	C12—C13	1.388 (2)
N2—H2	0.8800	C12—H12	0.9500
C3—C8	1.389 (2)	C13—C14	1.385 (2)
C3—C4	1.3917 (19)	C13—H13	0.9500
C4—C5	1.390 (2)	C14—H14	0.9500
C4—Cl1	1.7367 (15)	C15—H15C	0.9800
C5—C6	1.385 (2)	C15—H15A	0.9800
C5—H5	0.9500	C15—H15B	0.9800
C6—C7	1.393 (2)	C16—H16C	0.9800
C6—H6	0.9500	C16—H16A	0.9800
C7—C8	1.393 (2)	C16—H16B	0.9800
C7—H7	0.9500

O1—C1—N1	123.81 (12)	C14—C9—C10	122.26 (13)
O1—C1—C3	121.86 (12)	C14—C9—N2	117.73 (12)
N1—C1—C3	114.33 (11)	C10—C9—N2	119.95 (12)
C1—N1—C2	128.06 (11)	C9—C10—C11	117.91 (13)
C1—N1—H1	116.0	C9—C10—C15	121.91 (13)
C2—N1—H1	116.0	C11—C10—C15	120.18 (13)
N2—C2—N1	116.79 (11)	C12—C11—C10	119.49 (13)
N2—C2—S1	124.85 (10)	C12—C11—C16	119.89 (13)
N1—C2—S1	118.37 (10)	C10—C11—C16	120.61 (13)
C2—N2—C9	123.85 (11)	C13—C12—C11	121.55 (13)
C2—N2—H2	118.1	C13—C12—H12	119.2
C9—N2—H2	118.1	C11—C12—H12	119.2
C8—C3—C4	119.39 (12)	C14—C13—C12	119.64 (13)
C8—C3—C1	119.55 (12)	C14—C13—H13	120.2
C4—C3—C1	120.99 (12)	C12—C13—H13	120.2
C5—C4—C3	121.20 (13)	C13—C14—C9	119.12 (13)
C5—C4—Cl1	119.12 (11)	C13—C14—H14	120.4
C3—C4—Cl1	119.67 (11)	C9—C14—H14	120.4
C6—C5—C4	118.81 (14)	C10—C15—H15C	109.5
C6—C5—H5	120.6	C10—C15—H15A	109.5
C4—C5—H5	120.6	H15C—C15—H15A	109.5
C5—C6—C7	120.82 (14)	C10—C15—H15B	109.5
C5—C6—H6	119.6	H15C—C15—H15B	109.5
C7—C6—H6	119.6	H15A—C15—H15B	109.5
C6—C7—C8	119.76 (14)	C11—C16—H16C	109.5
C6—C7—H7	120.1	C11—C16—H16A	109.5
C8—C7—H7	120.1	H16C—C16—H16A	109.5
C3—C8—C7	119.99 (14)	C11—C16—H16B	109.5
C3—C8—H8	120.0	H16C—C16—H16B	109.5
C7—C8—H8	120.0	H16A—C16—H16B	109.5

O1—C1—N1—C2	7.9 (2)	C1—C3—C8—C7	−177.24 (12)
C3—C1—N1—C2	−172.60 (12)	C6—C7—C8—C3	1.1 (2)
C1—N1—C2—N2	2.5 (2)	C2—N2—C9—C14	−64.20 (17)
C1—N1—C2—S1	−177.20 (11)	C2—N2—C9—C10	118.53 (15)
N1—C2—N2—C9	171.32 (12)	C14—C9—C10—C11	−0.39 (19)
S1—C2—N2—C9	−8.96 (19)	N2—C9—C10—C11	176.76 (11)
O1—C1—C3—C8	74.09 (18)	C14—C9—C10—C15	179.07 (12)
N1—C1—C3—C8	−105.46 (15)	N2—C9—C10—C15	−3.78 (19)
O1—C1—C3—C4	−102.77 (16)	C9—C10—C11—C12	1.59 (19)
N1—C1—C3—C4	77.68 (16)	C15—C10—C11—C12	−177.88 (12)
C8—C3—C4—C5	−1.0 (2)	C9—C10—C11—C16	−178.78 (12)
C1—C3—C4—C5	175.84 (12)	C15—C10—C11—C16	1.75 (19)
C8—C3—C4—Cl1	179.64 (10)	C10—C11—C12—C13	−1.4 (2)
C1—C3—C4—Cl1	−3.49 (17)	C16—C11—C12—C13	178.98 (13)
C3—C4—C5—C6	1.6 (2)	C11—C12—C13—C14	−0.1 (2)
Cl1—C4—C5—C6	−179.05 (11)	C12—C13—C14—C9	1.29 (19)
C4—C5—C6—C7	−0.9 (2)	C10—C9—C14—C13	−1.1 (2)
C5—C6—C7—C8	−0.5 (2)	N2—C9—C14—C13	−178.27 (11)
C4—C3—C8—C7	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.88	2.46	3.3104 (15)	164
N2—H2···O1	0.88	2.00	2.6866 (17)	134

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅ClN₂OS
M_r	318.81
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	7.489 (3), 9.338 (4), 13.274 (5)
α, β, γ (°)	65.674 (13), 69.975 (16), 73.639 (17)
V (Å³)	783.9 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.50 × 0.35 × 0.28

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6180, 3506, 3373
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.090, 1.08
No. of reflections	3506
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.31

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976), Yadokari-XG (Wakita, 2001; Kabuto et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.88	2.46	3.3104 (15)	163.6
N2—H2···O1	0.88	2.00	2.6866 (17)	134.3

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

MR is grateful to The Quaid-i-Azam University, Islamabad, for financial support for a postdoctoral fellowship.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Kabuto, C., Akine, S., Nemoto, T. & Kwon, E. (2009). J. Cryst. Soc. Jpn, 51, 218–224. CrossRef Google Scholar
Molecular Structure Corporation & Rigaku (2001). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Rauf, M. K, Ebihara, M., Badshah, A. & Imtiaz-ud-Din, (2012). Acta Cryst. E68, o119. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wakita, K. (2001). Yadokari-XG. http://www.hat.hi-ho.ne .jp/k-wakita/yadokari Google Scholar