An unexpected tautomer: synthesis and crystal structure of N-[6-amino-4-(methyl­sulfan­yl)-1,2-di­hydro-1,3,5-triazin-2-yl­idene]benzenesulfonamide

The title compound, C₁₀H₁₁N₅O₂S₂, consists of an unexpected imino-di­hydro-triazine tautomer. Mol­ecules are linked by hydrogen bonds and by O_{sulf­on­amide}...(C—NH—C)_triazine contacts.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.085
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1       ..C6       .       2.89 Ang.
                                                    1+x,y,z  =      1_655 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1       ..C2       .       2.97 Ang.
                                                    1+x,y,z  =      1_655 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H7C      ..O2       .       2.63 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
              H01     H04A    H04B
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         19 Note
PLAT969_ALERT_5_G The 'Henn et al.' R-Factor-gap value ...........       6.13 Note
              Predicted wR2: Based on SigI   2  1.39 or SHELX Weight  8.40       
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

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

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

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Computing details

N-[6-Amino-4-(methylsulfanyl)-1,2-dihydro-1,3,5-triazin-2-ylidene]benzenesulfonamide

Crystal data

C10H11N5O2S2	F(000) = 616
Mr = 297.36	Dx = 1.538 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 5.44832 (9) Å	Cell parameters from 32085 reflections
b = 9.03714 (14) Å	θ = 3.4–79.7°
c = 26.1141 (4) Å	µ = 3.84 mm^−1
β = 92.9914 (14)°	T = 100 K
V = 1284.03 (4) Å^3	Plate, colourless
Z = 4	0.15 × 0.12 × 0.02 mm

Data collection

XtaLAB Synergy diffractometer	2789 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2713 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.038
Detector resolution: 10.0000 pixels mm^-1	θmax = 80.3°, θmin = 3.4°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −11→11
Tmin = 0.625, Tmax = 1.000	l = −33→33
49520 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 0.9076P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2789 reflections	Δρmax = 0.41 e Å^−3
185 parameters	Δρmin = −0.38 e Å^−3
0 restraints

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
N1	0.3855 (2)	0.19499 (14)	0.48875 (5)	0.0195 (3)
H01	0.372 (4)	0.118 (3)	0.5077 (8)	0.032 (5)*
C2	0.5437 (3)	0.19268 (16)	0.44955 (5)	0.0192 (3)
N3	0.5680 (2)	0.31253 (13)	0.41996 (5)	0.0191 (2)
C4	0.4203 (3)	0.42490 (16)	0.42942 (5)	0.0192 (3)
N5	0.2456 (2)	0.43104 (13)	0.46351 (5)	0.0201 (3)
C6	0.2256 (3)	0.31003 (16)	0.49263 (5)	0.0196 (3)
N2	0.6629 (2)	0.06574 (14)	0.44327 (5)	0.0214 (3)
N4	0.0509 (2)	0.30223 (15)	0.52541 (5)	0.0237 (3)
H04A	−0.033 (4)	0.382 (3)	0.5295 (8)	0.032 (5)*
H04B	0.050 (4)	0.231 (2)	0.5456 (8)	0.030 (5)*
S1	0.44381 (7)	0.58924 (4)	0.39493 (2)	0.02499 (11)
C7	0.7117 (3)	0.55651 (19)	0.35892 (7)	0.0323 (4)
H7A	0.663476	0.504404	0.327051	0.048*
H7B	0.829641	0.496006	0.379343	0.048*
H7C	0.787821	0.651309	0.350761	0.048*
S2	0.84801 (6)	0.05740 (4)	0.39640 (2)	0.02013 (11)
O1	1.04319 (19)	0.16344 (13)	0.40001 (4)	0.0258 (2)
O2	0.9209 (2)	−0.09690 (12)	0.39465 (4)	0.0290 (3)
C8	0.6737 (3)	0.09070 (17)	0.33828 (6)	0.0226 (3)
C9	0.4618 (3)	0.0090 (2)	0.32667 (7)	0.0312 (4)
H9	0.404045	−0.061191	0.350305	0.037*
C10	0.3369 (3)	0.0325 (2)	0.27967 (8)	0.0396 (4)
H10	0.192098	−0.022469	0.270891	0.047*
C11	0.4215 (4)	0.1354 (3)	0.24549 (7)	0.0416 (5)
H11	0.334422	0.150368	0.213437	0.050*
C12	0.6317 (4)	0.2166 (2)	0.25758 (7)	0.0361 (4)
H12	0.688191	0.287312	0.233994	0.043*
C13	0.7600 (3)	0.19439 (19)	0.30433 (6)	0.0272 (3)
H13	0.904891	0.249408	0.312962	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0203 (6)	0.0178 (6)	0.0208 (6)	0.0047 (5)	0.0039 (5)	0.0021 (5)
C2	0.0166 (6)	0.0197 (7)	0.0211 (6)	0.0013 (5)	0.0003 (5)	−0.0005 (5)
N3	0.0187 (6)	0.0170 (6)	0.0218 (6)	0.0018 (4)	0.0018 (4)	−0.0003 (5)
C4	0.0188 (7)	0.0181 (7)	0.0204 (7)	−0.0002 (5)	−0.0008 (5)	−0.0014 (5)
N5	0.0206 (6)	0.0167 (6)	0.0231 (6)	0.0031 (4)	0.0028 (5)	0.0001 (5)
C6	0.0196 (7)	0.0182 (7)	0.0210 (6)	0.0029 (5)	0.0001 (5)	−0.0008 (5)
N2	0.0220 (6)	0.0191 (6)	0.0235 (6)	0.0047 (5)	0.0058 (5)	0.0019 (5)
N4	0.0247 (7)	0.0193 (6)	0.0278 (6)	0.0077 (5)	0.0081 (5)	0.0049 (5)
S1	0.0290 (2)	0.01943 (19)	0.0270 (2)	0.00336 (14)	0.00611 (15)	0.00326 (13)
C7	0.0398 (10)	0.0247 (8)	0.0337 (9)	−0.0005 (7)	0.0147 (7)	0.0017 (7)
S2	0.01881 (19)	0.01887 (18)	0.02305 (18)	0.00429 (12)	0.00438 (13)	0.00141 (13)
O1	0.0183 (5)	0.0310 (6)	0.0280 (5)	−0.0006 (4)	0.0017 (4)	−0.0004 (4)
O2	0.0339 (6)	0.0215 (6)	0.0327 (6)	0.0113 (5)	0.0126 (5)	0.0041 (4)
C8	0.0204 (7)	0.0241 (7)	0.0235 (7)	0.0046 (6)	0.0023 (5)	−0.0051 (6)
C9	0.0252 (8)	0.0308 (8)	0.0379 (9)	0.0001 (7)	0.0046 (6)	−0.0084 (7)
C10	0.0253 (8)	0.0486 (11)	0.0444 (10)	0.0002 (8)	−0.0028 (7)	−0.0176 (9)
C11	0.0375 (10)	0.0596 (13)	0.0271 (8)	0.0123 (9)	−0.0045 (7)	−0.0106 (8)
C12	0.0401 (10)	0.0437 (10)	0.0248 (8)	0.0089 (8)	0.0044 (7)	−0.0003 (7)
C13	0.0282 (8)	0.0290 (8)	0.0246 (7)	0.0035 (6)	0.0042 (6)	−0.0018 (6)

Geometric parameters (Å, º)

N1—C6	1.3637 (18)	C9—C10	1.389 (3)
N1—C2	1.3725 (18)	C10—C11	1.385 (3)
C2—N2	1.3326 (18)	C11—C12	1.382 (3)
C2—N3	1.3410 (19)	C12—C13	1.389 (2)
N3—C4	1.3270 (18)	N1—H01	0.86 (2)
C4—N5	1.3379 (19)	N4—H04A	0.87 (2)
C4—S1	1.7451 (15)	N4—H04B	0.83 (2)
N5—C6	1.3398 (19)	C7—H7A	0.9800
C6—N4	1.3144 (19)	C7—H7B	0.9800
N2—S2	1.6279 (13)	C7—H7C	0.9800
S1—C7	1.8017 (17)	C9—H9	0.9500
S2—O1	1.4309 (12)	C10—H10	0.9500
S2—O2	1.4512 (11)	C11—H11	0.9500
S2—C8	1.7737 (16)	C12—H12	0.9500
C8—C13	1.389 (2)	C13—H13	0.9500
C8—C9	1.390 (2)
C6—N1—C2	119.71 (13)	C12—C11—C10	120.59 (17)
N2—C2—N3	124.13 (13)	C11—C12—C13	119.80 (18)
N2—C2—N1	115.72 (13)	C8—C13—C12	119.11 (16)
N3—C2—N1	120.15 (13)	C6—N1—H01	119.8 (14)
C4—N3—C2	115.57 (12)	C2—N1—H01	119.8 (14)
N3—C4—N5	127.97 (13)	C6—N4—H04A	116.2 (14)
N3—C4—S1	119.57 (11)	C6—N4—H04B	118.6 (14)
N5—C4—S1	112.46 (10)	H04A—N4—H04B	123 (2)
C4—N5—C6	115.19 (12)	S1—C7—H7A	109.5
N4—C6—N5	119.77 (13)	S1—C7—H7B	109.5
N4—C6—N1	119.64 (13)	H7A—C7—H7B	109.5
N5—C6—N1	120.59 (13)	S1—C7—H7C	109.5
C2—N2—S2	117.22 (10)	H7A—C7—H7C	109.5
C4—S1—C7	102.30 (8)	H7B—C7—H7C	109.5
O1—S2—O2	116.23 (7)	C10—C9—H9	120.8
O1—S2—N2	114.00 (7)	C8—C9—H9	120.8
O2—S2—N2	104.44 (6)	C11—C10—H10	119.7
O1—S2—C8	107.80 (7)	C9—C10—H10	119.7
O2—S2—C8	105.75 (7)	C12—C11—H11	119.7
N2—S2—C8	108.09 (7)	C10—C11—H11	119.7
C13—C8—C9	121.62 (15)	C11—C12—H12	120.1
C13—C8—S2	118.46 (12)	C13—C12—H12	120.1
C9—C8—S2	119.86 (13)	C8—C13—H13	120.4
C10—C9—C8	118.34 (17)	C12—C13—H13	120.4
C11—C10—C9	120.54 (17)
C6—N1—C2—N2	−168.87 (13)	C2—N2—S2—O2	−172.04 (11)
C6—N1—C2—N3	10.2 (2)	C2—N2—S2—C8	−59.77 (13)
N2—C2—N3—C4	174.90 (14)	O1—S2—C8—C13	7.00 (14)
N1—C2—N3—C4	−4.1 (2)	O2—S2—C8—C13	−117.95 (13)
C2—N3—C4—N5	−2.5 (2)	N2—S2—C8—C13	130.67 (12)
C2—N3—C4—S1	177.57 (10)	O1—S2—C8—C9	−175.82 (12)
N3—C4—N5—C6	2.6 (2)	O2—S2—C8—C9	59.23 (14)
S1—C4—N5—C6	−177.41 (11)	N2—S2—C8—C9	−52.15 (14)
C4—N5—C6—N4	−176.47 (13)	C13—C8—C9—C10	0.4 (2)
C4—N5—C6—N1	3.8 (2)	S2—C8—C9—C10	−176.69 (13)
C2—N1—C6—N4	170.22 (14)	C8—C9—C10—C11	−0.3 (3)
C2—N1—C6—N5	−10.1 (2)	C9—C10—C11—C12	−0.1 (3)
N3—C2—N2—S2	−0.3 (2)	C10—C11—C12—C13	0.3 (3)
N1—C2—N2—S2	178.74 (10)	C9—C8—C13—C12	−0.2 (2)
N3—C4—S1—C7	−6.77 (14)	S2—C8—C13—C12	176.96 (13)
N5—C4—S1—C7	173.26 (12)	C11—C12—C13—C8	−0.2 (3)
C2—N2—S2—O1	60.06 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···N2^i	0.86 (2)	2.11 (2)	2.9701 (18)	178 (2)
N4—H04A···N5^ii	0.87 (2)	2.06 (2)	2.9245 (18)	177 (2)
N4—H04B···O2^i	0.83 (2)	1.97 (2)	2.7912 (18)	166 (2)
C7—H7C···O2^iii	0.98	2.63	3.445 (2)	140

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