A second monoclinic polymorph of 6-amino-1,3-dimethyl-5-[(E)-2-(methyl-sulfan-yl)benzyl-idene-amino]-pyrimidine-2,4(1H,3H)-dione.

A new monoclinic form of the title compound, C(14)H(16)N(4)O(2)S, has been identified unexpectedly during an attempt to synthesize a coordination compound. The heterocyclic ring is essentially planar (r.m.s. deviation = 0.005 Å) and makes a dihedral angle of 8.77 (5)° with the benzene ring. This is in contrast to 12.24 (7)° reported for the first monoclinic polymorph [Booysen et al. (2011 ▶). Acta Cryst. E67, o1592]. An intra-molecular N-H⋯S hydrogen bond is observed. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into zigzag chains along the b axis. The closest distance between the centroids of symmetry-related heterocyclic rings is 3.5161 (6) Å.

Related literature

For background to chelating ligands, see: Gade (1998 ▶). For the crystal structure of the title compound in the same space group but different cell parameters, see: Booysen et al. (2011 ▶). For the crystal structures of other Schiff-bases derived from ortho-(thio­meth­yl)-benzaldehyde, see: Yan et al. (2007 ▶); Baidina et al. (1987 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C14H16N4O2S

M = 304.37

Monoclinic,

a = 13.5230 (2) Å

b = 13.8520 (3) Å

c = 7.5180 (1) Å

β = 101.068 (1)°

V = 1382.08 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 100 K

0.46 × 0.29 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer

13030 measured reflections

3420 independent reflections

3112 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.081

S = 1.02

3420 reflections

201 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027322/ci5192sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811027322/ci5192Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027322/ci5192Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811027322/ci5192Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H16N4O2S	F(000) = 640
Mr = 304.37	Dx = 1.463 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 9061 reflections
a = 13.5230 (2) Å	θ = 3.1–28.3°
b = 13.8520 (3) Å	µ = 0.25 mm−1
c = 7.5180 (1) Å	T = 100 K
β = 101.068 (1)°	Rod, orange
V = 1382.08 (4) Å3	0.46 × 0.29 × 0.14 mm
Z = 4

Bruker APEXII CCD diffractometer	3112 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
graphite	θmax = 28.4°, θmin = 2.1°
φ and ω scans	h = −17→18
13030 measured reflections	k = −18→18
3420 independent reflections	l = −10→10

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0421P)2 + 0.5901P] where P = (Fo2 + 2Fc2)/3
3420 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

	x	y	z	Uiso*/Ueq
S1	0.78695 (2)	−0.045540 (19)	0.18639 (4)	0.01558 (9)
O1	0.51894 (6)	0.21801 (5)	0.44986 (11)	0.01675 (17)
O2	0.23379 (6)	0.03778 (6)	0.29316 (11)	0.01758 (17)
N1	0.37683 (7)	0.12677 (6)	0.36962 (12)	0.01399 (18)
N2	0.38044 (7)	−0.02607 (7)	0.23551 (12)	0.01352 (18)
N3	0.63701 (7)	0.06360 (7)	0.31269 (12)	0.01372 (18)
N4	0.52995 (7)	−0.08772 (7)	0.17260 (13)	0.01549 (19)
H741	0.5910 (12)	−0.0762 (11)	0.181 (2)	0.023 (4)*
H742	0.5004 (12)	−0.1407 (12)	0.134 (2)	0.026 (4)*
C1	0.53409 (8)	0.06569 (7)	0.31391 (14)	0.0131 (2)
C2	0.48115 (8)	0.14156 (8)	0.38191 (14)	0.0131 (2)
C3	0.32410 (8)	0.04571 (8)	0.29933 (14)	0.0140 (2)
C4	0.48168 (8)	−0.01659 (8)	0.23983 (13)	0.0128 (2)
C5	0.69984 (8)	0.12764 (8)	0.38818 (14)	0.0144 (2)
H5	0.6751	0.1802	0.4481	0.017*
C6	0.80731 (8)	0.12361 (8)	0.38633 (14)	0.0145 (2)
C7	0.85605 (8)	0.05250 (8)	0.29813 (14)	0.0147 (2)
C8	0.95997 (9)	0.06045 (8)	0.30539 (16)	0.0182 (2)
H8	0.9931	0.0137	0.2453	0.022*
C9	1.01545 (9)	0.13518 (9)	0.39841 (16)	0.0203 (2)
H9	1.0858	0.1393	0.4006	0.024*
C10	0.96888 (9)	0.20383 (9)	0.48817 (16)	0.0195 (2)
H10	1.0070	0.2545	0.5535	0.023*
C11	0.86603 (8)	0.19752 (8)	0.48140 (15)	0.0170 (2)
H11	0.8342	0.2447	0.5430	0.020*
C12	0.31814 (9)	0.20105 (8)	0.44153 (16)	0.0183 (2)
H121	0.2763	0.2358	0.3408	0.027*
H122	0.3640	0.2465	0.5159	0.027*
H123	0.2748	0.1705	0.5160	0.027*
C13	0.32800 (8)	−0.11442 (8)	0.16217 (15)	0.0166 (2)
H131	0.3329	−0.1216	0.0345	0.025*
H132	0.2569	−0.1104	0.1722	0.025*
H133	0.3591	−0.1703	0.2309	0.025*
C14	0.87950 (9)	−0.10803 (9)	0.08635 (16)	0.0199 (2)
H141	0.9071	−0.0639	0.0063	0.030*
H142	0.8478	−0.1632	0.0160	0.030*
H143	0.9340	−0.1310	0.1823	0.030*

	U11	U22	U33	U12	U13	U23
S1	0.01406 (14)	0.01421 (14)	0.01947 (14)	0.00057 (9)	0.00576 (10)	−0.00138 (9)
O1	0.0172 (4)	0.0118 (4)	0.0220 (4)	−0.0002 (3)	0.0056 (3)	−0.0008 (3)
O2	0.0121 (4)	0.0204 (4)	0.0200 (4)	0.0009 (3)	0.0026 (3)	−0.0007 (3)
N1	0.0130 (4)	0.0124 (4)	0.0173 (4)	0.0021 (3)	0.0048 (3)	−0.0002 (3)
N2	0.0126 (4)	0.0124 (4)	0.0154 (4)	0.0001 (3)	0.0024 (3)	−0.0008 (3)
N3	0.0132 (4)	0.0141 (4)	0.0145 (4)	0.0015 (3)	0.0042 (3)	0.0026 (3)
N4	0.0138 (4)	0.0127 (4)	0.0203 (4)	0.0006 (4)	0.0041 (4)	−0.0022 (3)
C1	0.0129 (5)	0.0127 (5)	0.0140 (4)	0.0013 (4)	0.0035 (4)	0.0017 (4)
C2	0.0136 (5)	0.0130 (5)	0.0131 (4)	0.0017 (4)	0.0036 (4)	0.0030 (4)
C3	0.0144 (5)	0.0147 (5)	0.0127 (5)	0.0025 (4)	0.0018 (4)	0.0024 (4)
C4	0.0138 (5)	0.0132 (5)	0.0114 (4)	0.0026 (4)	0.0026 (4)	0.0026 (4)
C5	0.0151 (5)	0.0133 (5)	0.0156 (5)	0.0013 (4)	0.0049 (4)	0.0016 (4)
C6	0.0148 (5)	0.0137 (5)	0.0152 (5)	−0.0004 (4)	0.0041 (4)	0.0036 (4)
C7	0.0149 (5)	0.0139 (5)	0.0157 (5)	−0.0001 (4)	0.0038 (4)	0.0032 (4)
C8	0.0156 (5)	0.0189 (5)	0.0214 (5)	0.0011 (4)	0.0066 (4)	0.0034 (4)
C9	0.0135 (5)	0.0243 (6)	0.0235 (5)	−0.0030 (4)	0.0044 (4)	0.0054 (5)
C10	0.0181 (5)	0.0198 (5)	0.0200 (5)	−0.0058 (4)	0.0019 (4)	0.0023 (4)
C11	0.0171 (5)	0.0152 (5)	0.0192 (5)	−0.0011 (4)	0.0045 (4)	0.0005 (4)
C12	0.0178 (5)	0.0158 (5)	0.0233 (5)	0.0044 (4)	0.0088 (4)	−0.0008 (4)
C13	0.0147 (5)	0.0141 (5)	0.0205 (5)	−0.0019 (4)	0.0021 (4)	−0.0022 (4)
C14	0.0185 (5)	0.0208 (5)	0.0216 (5)	0.0046 (4)	0.0065 (4)	−0.0021 (4)

S1—C7	1.7669 (11)	C6—C11	1.4041 (15)
S1—C14	1.8008 (11)	C6—C7	1.4184 (15)
O1—C2	1.2423 (13)	C7—C8	1.4003 (15)
O2—C3	1.2182 (13)	C8—C9	1.3863 (17)
N1—C3	1.3799 (14)	C8—H8	0.95
N1—C2	1.4108 (13)	C9—C10	1.3856 (17)
N1—C12	1.4648 (13)	C9—H9	0.95
N2—C4	1.3694 (13)	C10—C11	1.3847 (15)
N2—C3	1.3927 (13)	C10—H10	0.95
N2—C13	1.4679 (13)	C11—H11	0.95
N3—C5	1.2829 (14)	C12—H121	0.98
N3—C1	1.3940 (13)	C12—H122	0.98
N4—C4	1.3339 (14)	C12—H123	0.98
N4—H741	0.832 (16)	C13—H131	0.98
N4—H742	0.859 (16)	C13—H132	0.98
C1—C4	1.3999 (14)	C13—H133	0.98
C1—C2	1.4209 (14)	C14—H141	0.98
C5—C6	1.4572 (15)	C14—H142	0.98
C5—H5	0.95	C14—H143	0.98
C7—S1—C14	102.80 (5)	C6—C7—S1	120.35 (8)
C3—N1—C2	125.45 (9)	C9—C8—C7	121.35 (10)
C3—N1—C12	115.86 (9)	C9—C8—H8	119.3
C2—N1—C12	118.66 (9)	C7—C8—H8	119.3
C4—N2—C3	122.27 (9)	C10—C9—C8	120.37 (10)
C4—N2—C13	119.84 (9)	C10—C9—H9	119.8
C3—N2—C13	117.89 (9)	C8—C9—H9	119.8
C5—N3—C1	124.05 (9)	C11—C10—C9	119.08 (11)
C4—N4—H741	112.5 (11)	C11—C10—H10	120.5
C4—N4—H742	122.0 (10)	C9—C10—H10	120.5
H741—N4—H742	125.4 (15)	C10—C11—C6	122.05 (10)
N3—C1—C4	114.23 (9)	C10—C11—H11	119.0
N3—C1—C2	126.19 (10)	C6—C11—H11	119.0
C4—C1—C2	119.58 (10)	N1—C12—H121	109.5
O1—C2—N1	118.55 (9)	N1—C12—H122	109.5
O1—C2—C1	125.63 (10)	H121—C12—H122	109.5
N1—C2—C1	115.82 (9)	N1—C12—H123	109.5
O2—C3—N1	121.91 (10)	H121—C12—H123	109.5
O2—C3—N2	122.23 (10)	H122—C12—H123	109.5
N1—C3—N2	115.86 (9)	N2—C13—H131	109.5
N4—C4—N2	118.68 (10)	N2—C13—H132	109.5
N4—C4—C1	120.32 (10)	H131—C13—H132	109.5
N2—C4—C1	121.00 (9)	N2—C13—H133	109.5
N3—C5—C6	123.11 (10)	H131—C13—H133	109.5
N3—C5—H5	118.4	H132—C13—H133	109.5
C6—C5—H5	118.4	S1—C14—H141	109.5
C11—C6—C7	118.44 (10)	S1—C14—H142	109.5
C11—C6—C5	115.77 (9)	H141—C14—H142	109.5
C7—C6—C5	125.79 (10)	S1—C14—H143	109.5
C8—C7—C6	118.69 (10)	H141—C14—H143	109.5
C8—C7—S1	120.94 (8)	H142—C14—H143	109.5
C5—N3—C1—C4	−173.63 (10)	C13—N2—C4—C1	−178.11 (9)
C5—N3—C1—C2	6.25 (17)	N3—C1—C4—N4	−1.25 (14)
C3—N1—C2—O1	−179.44 (9)	C2—C1—C4—N4	178.85 (9)
C12—N1—C2—O1	−1.49 (14)	N3—C1—C4—N2	178.43 (9)
C3—N1—C2—C1	0.49 (15)	C2—C1—C4—N2	−1.47 (15)
C12—N1—C2—C1	178.43 (9)	C1—N3—C5—C6	179.53 (9)
N3—C1—C2—O1	0.43 (17)	N3—C5—C6—C11	−177.63 (10)
C4—C1—C2—O1	−179.68 (10)	N3—C5—C6—C7	2.35 (17)
N3—C1—C2—N1	−179.49 (9)	C11—C6—C7—C8	−1.72 (15)
C4—C1—C2—N1	0.40 (14)	C5—C6—C7—C8	178.31 (10)
C2—N1—C3—O2	179.92 (9)	C11—C6—C7—S1	176.75 (8)
C12—N1—C3—O2	1.93 (15)	C5—C6—C7—S1	−3.23 (15)
C2—N1—C3—N2	−0.31 (15)	C14—S1—C7—C8	−5.40 (10)
C12—N1—C3—N2	−178.30 (9)	C14—S1—C7—C6	176.17 (9)
C4—N2—C3—O2	178.97 (10)	C6—C7—C8—C9	0.86 (16)
C13—N2—C3—O2	−1.22 (15)	S1—C7—C8—C9	−177.60 (9)
C4—N2—C3—N1	−0.80 (14)	C7—C8—C9—C10	0.49 (17)
C13—N2—C3—N1	179.01 (9)	C8—C9—C10—C11	−0.93 (17)
C3—N2—C4—N4	−178.61 (9)	C9—C10—C11—C6	0.01 (17)
C13—N2—C4—N4	1.58 (14)	C7—C6—C11—C10	1.31 (16)
C3—N2—C4—C1	1.70 (15)	C5—C6—C11—C10	−178.71 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H741···S1	0.83 (2)	2.675 (17)	3.5060 (10)	176 (1)
N4—H742···O1i	0.86 (2)	2.058 (16)	2.8797 (12)	160 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H741⋯S1	0.83 (2)	2.675 (17)	3.5060 (10)	176 (1)
N4—H742⋯O1i	0.86 (2)	2.058 (16)	2.8797 (12)	160 (1)

Symmetry code: (i) .