3,4,7-Trimethyl-2-(4-methyl-phen-yl)-2H-pyrazolo-[3,4-d]pyridazin-5-ium thio-cyanate.

1,1'-[5-Methyl-1-(4-methyl-phen-yl)-1H-pyrazole-3,4-di-yl)di-ethan-one condenses with thio-semicarbazide in the presence of acetic acid to form the title salt, C(15)H(17)N(4) (+)·NCS(-). The fused-ring system of the cation is almost planar (r.m.s. deviation = 0.020 Å) and the aromatic substituent is aligned at an angle of 48.2 (1)° with respect to the mean plane of the fused-ring system. The N atom at the 5-position is protonated and forms a N-H⋯N hydrogen bond to the thio-cyanate cointer-ion.

Related literature

For reviews on pyrazolo-pyridazines, see: Akbas & Berber (2006 ▶); Matiichuk et al. (2009 ▶). For a related structure, see: Dinçer et al. (2004 ▶).

Experimental

Crystal data

C15H17N4 +·NCS−

M = 311.41

Monoclinic,

a = 18.2445 (5) Å

b = 7.3341 (2) Å

c = 24.2396 (8) Å

β = 106.121 (3)°

V = 3115.89 (16) Å3

Z = 8

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.30 × 0.10 × 0.05 mm

Data collection

Agilent SuperNova diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010 ▶) T min = 0.939, T max = 0.990

7809 measured reflections

3491 independent reflections

2968 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.096

S = 1.00

3491 reflections

207 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Agilent Technologies, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681004883X/bt5414sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004883X/bt5414Isup2.hkl

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

C15H17N4+·NCS−	F(000) = 1312
Mr = 311.41	Dx = 1.328 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4295 reflections
a = 18.2445 (5) Å	θ = 2.2–29.3°
b = 7.3341 (2) Å	µ = 0.21 mm−1
c = 24.2396 (8) Å	T = 100 K
β = 106.121 (3)°	Prism, yellow
V = 3115.89 (16) Å3	0.30 × 0.10 × 0.05 mm
Z = 8

Agilent SuperNova diffractometer	3491 independent reflections
Radiation source: fine-focus sealed tube	2968 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.3°
ω scans	h = −16→23
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010)	k = −9→9
Tmin = 0.939, Tmax = 0.990	l = −31→23
7809 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0472P)2 + 3.0958P] where P = (Fo2 + 2Fc2)/3
3491 reflections	(Δ/σ)max = 0.001
207 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

	x	y	z	Uiso*/Ueq
S1	0.41884 (2)	1.03962 (5)	0.678227 (15)	0.01918 (11)
N1	0.30697 (7)	0.87179 (17)	0.44978 (5)	0.0175 (3)
N2	0.37098 (7)	0.79621 (17)	0.43977 (5)	0.0182 (3)
N3	0.28626 (6)	0.74548 (16)	0.28642 (5)	0.0148 (2)
N4	0.21174 (6)	0.79970 (16)	0.26392 (5)	0.0142 (2)
N5	0.33646 (8)	0.96211 (19)	0.56469 (6)	0.0255 (3)
C1	0.43819 (8)	0.6806 (2)	0.37464 (6)	0.0195 (3)
H1A	0.4780	0.6633	0.4109	0.029*
H1B	0.4564	0.7659	0.3502	0.029*
H1C	0.4262	0.5632	0.3549	0.029*
C2	0.36843 (8)	0.75572 (19)	0.38665 (6)	0.0156 (3)
C3	0.29986 (8)	0.78638 (18)	0.34177 (6)	0.0146 (3)
C4	0.23596 (8)	0.86541 (18)	0.35465 (6)	0.0146 (3)
C5	0.24134 (8)	0.91093 (19)	0.41184 (6)	0.0164 (3)
C6	0.18028 (9)	0.9977 (2)	0.43299 (7)	0.0221 (3)
H6A	0.1980	1.0103	0.4749	0.033*
H6B	0.1344	0.9214	0.4226	0.033*
H6C	0.1684	1.1185	0.4155	0.033*
C7	0.17924 (8)	0.87516 (19)	0.30233 (6)	0.0147 (3)
C8	0.10123 (8)	0.9549 (2)	0.28774 (6)	0.0193 (3)
H8A	0.0845	0.9835	0.2466	0.029*
H8B	0.1019	1.0668	0.3100	0.029*
H8C	0.0659	0.8671	0.2970	0.029*
C9	0.17735 (8)	0.77377 (19)	0.20373 (6)	0.0144 (3)
C10	0.10569 (8)	0.69513 (19)	0.18460 (6)	0.0165 (3)
H10	0.0803	0.6507	0.2112	0.020*
C11	0.07151 (8)	0.68226 (19)	0.12579 (6)	0.0170 (3)
H11	0.0222	0.6295	0.1123	0.020*
C12	0.10849 (8)	0.74559 (19)	0.08639 (6)	0.0165 (3)
C13	0.18234 (8)	0.81476 (19)	0.10713 (6)	0.0158 (3)
H13	0.2092	0.8524	0.0807	0.019*
C14	0.21737 (8)	0.82962 (19)	0.16553 (6)	0.0152 (3)
H14	0.2676	0.8769	0.1792	0.018*
C15	0.06899 (9)	0.7449 (2)	0.02308 (6)	0.0218 (3)
H15A	0.0200	0.6814	0.0161	0.033*
H15B	0.1011	0.6822	0.0026	0.033*
H15C	0.0602	0.8708	0.0092	0.033*
C16	0.37098 (8)	0.9940 (2)	0.61179 (6)	0.0176 (3)
H1	0.3146 (11)	0.898 (3)	0.4877 (9)	0.037 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.01806 (18)	0.0235 (2)	0.01600 (19)	−0.00002 (14)	0.00481 (14)	−0.00172 (14)
N1	0.0221 (6)	0.0185 (6)	0.0116 (6)	−0.0013 (5)	0.0040 (5)	−0.0010 (5)
N2	0.0195 (6)	0.0184 (6)	0.0159 (6)	−0.0008 (5)	0.0035 (5)	−0.0004 (5)
N3	0.0133 (5)	0.0157 (6)	0.0141 (6)	−0.0002 (5)	0.0015 (4)	0.0008 (5)
N4	0.0144 (5)	0.0142 (5)	0.0134 (6)	−0.0009 (5)	0.0030 (4)	−0.0001 (5)
N5	0.0310 (7)	0.0304 (7)	0.0158 (7)	−0.0012 (6)	0.0078 (5)	−0.0009 (6)
C1	0.0170 (7)	0.0225 (7)	0.0172 (7)	0.0005 (6)	0.0018 (5)	−0.0019 (6)
C2	0.0171 (7)	0.0142 (7)	0.0143 (7)	−0.0026 (6)	0.0026 (5)	0.0002 (5)
C3	0.0175 (7)	0.0124 (6)	0.0142 (7)	−0.0024 (5)	0.0045 (5)	0.0002 (5)
C4	0.0171 (6)	0.0125 (6)	0.0141 (7)	−0.0016 (5)	0.0040 (5)	−0.0001 (5)
C5	0.0201 (7)	0.0141 (6)	0.0150 (7)	−0.0019 (6)	0.0050 (5)	0.0010 (5)
C6	0.0261 (8)	0.0248 (8)	0.0175 (7)	0.0029 (6)	0.0094 (6)	−0.0016 (6)
C7	0.0184 (7)	0.0125 (6)	0.0136 (7)	−0.0016 (5)	0.0053 (5)	−0.0005 (5)
C8	0.0184 (7)	0.0221 (8)	0.0169 (7)	0.0027 (6)	0.0040 (6)	−0.0007 (6)
C9	0.0173 (6)	0.0138 (6)	0.0112 (6)	0.0015 (5)	0.0024 (5)	0.0003 (5)
C10	0.0182 (7)	0.0166 (7)	0.0152 (7)	−0.0011 (6)	0.0054 (5)	0.0012 (5)
C11	0.0156 (6)	0.0165 (7)	0.0174 (7)	−0.0026 (6)	0.0020 (5)	−0.0013 (6)
C12	0.0189 (7)	0.0153 (7)	0.0146 (7)	0.0025 (6)	0.0036 (5)	−0.0003 (5)
C13	0.0178 (7)	0.0169 (7)	0.0141 (7)	0.0021 (6)	0.0065 (5)	0.0009 (5)
C14	0.0137 (6)	0.0144 (7)	0.0173 (7)	0.0001 (5)	0.0042 (5)	−0.0007 (5)
C15	0.0223 (7)	0.0269 (8)	0.0143 (7)	0.0006 (6)	0.0018 (6)	0.0006 (6)
C16	0.0198 (7)	0.0170 (7)	0.0189 (7)	0.0010 (6)	0.0105 (6)	0.0020 (6)

S1—C16	1.6390 (15)	C6—H6B	0.9800
N1—C5	1.3229 (18)	C6—H6C	0.9800
N1—N2	1.3738 (17)	C7—C8	1.4877 (19)
N1—H1	0.91 (2)	C8—H8A	0.9800
N2—C2	1.3097 (18)	C8—H8B	0.9800
N3—C3	1.3293 (18)	C8—H8C	0.9800
N3—N4	1.3755 (16)	C9—C10	1.386 (2)
N4—C7	1.3533 (17)	C9—C14	1.3905 (19)
N4—C9	1.4320 (17)	C10—C11	1.3915 (19)
N5—C16	1.164 (2)	C10—H10	0.9500
C1—C2	1.4879 (19)	C11—C12	1.393 (2)
C1—H1A	0.9800	C11—H11	0.9500
C1—H1B	0.9800	C12—C13	1.396 (2)
C1—H1C	0.9800	C12—C15	1.5034 (19)
C2—C3	1.4294 (19)	C13—C14	1.3863 (19)
C3—C4	1.4124 (19)	C13—H13	0.9500
C4—C7	1.3984 (19)	C14—H14	0.9500
C4—C5	1.4025 (19)	C15—H15A	0.9800
C5—C6	1.492 (2)	C15—H15B	0.9800
C6—H6A	0.9800	C15—H15C	0.9800
C5—N1—N2	127.91 (12)	N4—C7—C8	124.77 (12)
C5—N1—H1	120.8 (12)	C4—C7—C8	130.84 (13)
N2—N1—H1	111.3 (12)	C7—C8—H8A	109.5
C2—N2—N1	117.73 (12)	C7—C8—H8B	109.5
C3—N3—N4	102.82 (11)	H8A—C8—H8B	109.5
C7—N4—N3	114.78 (11)	C7—C8—H8C	109.5
C7—N4—C9	127.13 (12)	H8A—C8—H8C	109.5
N3—N4—C9	118.08 (11)	H8B—C8—H8C	109.5
C2—C1—H1A	109.5	C10—C9—C14	121.39 (13)
C2—C1—H1B	109.5	C10—C9—N4	120.13 (12)
H1A—C1—H1B	109.5	C14—C9—N4	118.48 (12)
C2—C1—H1C	109.5	C9—C10—C11	118.94 (13)
H1A—C1—H1C	109.5	C9—C10—H10	120.5
H1B—C1—H1C	109.5	C11—C10—H10	120.5
N2—C2—C3	119.82 (13)	C12—C11—C10	121.00 (13)
N2—C2—C1	118.53 (12)	C12—C11—H11	119.5
C3—C2—C1	121.65 (13)	C10—C11—H11	119.5
N3—C3—C4	112.43 (12)	C11—C12—C13	118.48 (13)
N3—C3—C2	127.69 (13)	C11—C12—C15	120.84 (13)
C4—C3—C2	119.87 (13)	C13—C12—C15	120.65 (13)
C7—C4—C5	135.66 (13)	C14—C13—C12	121.43 (13)
C7—C4—C3	105.60 (12)	C14—C13—H13	119.3
C5—C4—C3	118.72 (12)	C12—C13—H13	119.3
N1—C5—C4	115.91 (13)	C13—C14—C9	118.58 (13)
N1—C5—C6	118.14 (13)	C13—C14—H14	120.7
C4—C5—C6	125.95 (13)	C9—C14—H14	120.7
C5—C6—H6A	109.5	C12—C15—H15A	109.5
C5—C6—H6B	109.5	C12—C15—H15B	109.5
H6A—C6—H6B	109.5	H15A—C15—H15B	109.5
C5—C6—H6C	109.5	C12—C15—H15C	109.5
H6A—C6—H6C	109.5	H15A—C15—H15C	109.5
H6B—C6—H6C	109.5	H15B—C15—H15C	109.5
N4—C7—C4	104.34 (12)	N5—C16—S1	179.46 (14)
C5—N1—N2—C2	−0.3 (2)	C9—N4—C7—C4	179.09 (12)
C3—N3—N4—C7	1.25 (15)	N3—N4—C7—C8	175.84 (12)
C3—N3—N4—C9	−179.52 (11)	C9—N4—C7—C8	−3.3 (2)
N1—N2—C2—C3	−1.58 (19)	C5—C4—C7—N4	−177.34 (15)
N1—N2—C2—C1	177.60 (12)	C3—C4—C7—N4	1.48 (15)
N4—N3—C3—C4	−0.19 (15)	C5—C4—C7—C8	5.3 (3)
N4—N3—C3—C2	178.40 (13)	C3—C4—C7—C8	−175.91 (14)
N2—C2—C3—N3	−176.53 (13)	C7—N4—C9—C10	−48.7 (2)
C1—C2—C3—N3	4.3 (2)	N3—N4—C9—C10	132.23 (13)
N2—C2—C3—C4	2.0 (2)	C7—N4—C9—C14	131.16 (15)
C1—C2—C3—C4	−177.20 (13)	N3—N4—C9—C14	−47.96 (17)
N3—C3—C4—C7	−0.83 (16)	C14—C9—C10—C11	−3.9 (2)
C2—C3—C4—C7	−179.55 (12)	N4—C9—C10—C11	175.90 (12)
N3—C3—C4—C5	178.22 (12)	C9—C10—C11—C12	0.5 (2)
C2—C3—C4—C5	−0.5 (2)	C10—C11—C12—C13	3.0 (2)
N2—N1—C5—C4	1.7 (2)	C10—C11—C12—C15	−175.17 (13)
N2—N1—C5—C6	−178.41 (13)	C11—C12—C13—C14	−3.3 (2)
C7—C4—C5—N1	177.48 (15)	C15—C12—C13—C14	174.88 (13)
C3—C4—C5—N1	−1.22 (19)	C12—C13—C14—C9	0.0 (2)
C7—C4—C5—C6	−2.4 (3)	C10—C9—C14—C13	3.6 (2)
C3—C4—C5—C6	178.94 (13)	N4—C9—C14—C13	−176.18 (12)
N3—N4—C7—C4	−1.76 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5	0.91 (2)	1.86 (2)	2.7668 (18)	175.6 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N5	0.91 (2)	1.86 (2)	2.7668 (18)	175.6 (19)