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Molecules of the title compound, C12H8N2S2, which are effectively planar, have all four heteroatoms on the same side but do not have twofold symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102016037/gg1137sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102016037/gg1137Isup2.hkl
Contains datablock I

CCDC reference: 199421

Comment top

3,6-Bis(substituted)pyridazines can act as bis(bidentate) chelating ligands to generate dinuclear complexes with M···M ~3.6 Å. Many dicopper systems have been prepared with N4 donor ligands containing 2-aminopyridine or 1-pyrazole as substituents (Hubberstey & Russell, 1995; Thompson et al., 1985). To extend and diversify this chemistry, we have synthesized a number of N2S2 donor ligands, including 3,6-bis(thiophen-2-yl)pyridazine, (I). This molecule, first prepared by the cross coupling of 3,6-dichloropyridazine with the Grignard reagent obtained by treatment of 2-bromothiophene with Mg (Montheard & Dubois, 1985), and subsequently by thermal decomposition of either 2,7-dihydro-1,4,5-thiadiazepine, obtained by condensation of 1,5-di(thiophen-2-yl)-3-thiapentane-1,5-dione with hydrazine (Nakayama et al., 1989), or 4,5-dihydropyridazine, obtained by condensation of 1,4-di(thiophen-2-yl)-1,4-dione with hydrazine (Kossmehl et al., 1993), has been little studied. Our attempts to prepare coordination complexes of (I) with CuII, CuI and PdII have been unsuccessful. \sch

Although the two thiophene rings of (I) are crystallographically independent (Fig. 1), their conformation is such that all four heteroatoms are located on the same side of the molecule. The adopted conformation is such that the molecules do not possess twofold symmetry, but do have approximate non-crystallographic Cs symmetry. This arrangement differs from that in previously structurally characterized bis(substituted) pyridazines, where the heteroatoms of the substituent rings are trans with respect to the N atoms of the pyridazine ring (Blake et al., 2002). An explanation is not immediately obvious in view of, firstly, the steric interactions between atoms H4 and H35 (2.40 Å), and H5 and H65 (2.36 Å), which results in the three aromatic rings not being coplanar [the dihedral angles between the central and terminal rings are 11.18 (14)° (pyridazine N1/N2/C3—C6 and thiophene C31/S32/C33—C35) and 14.91 (14)° (pyridazine N1/N2/C3—C6 and thiophene C61/S62/C63—C65), and that between the terminal rings is 7.9 (2)°] and, secondly, the absence of the hydrogen-bonding interactions [C35—H35···N2 and C65—H65···N1], however weak, that would result from the alternative conformation.

An analysis of the extended structure reveals the only intermolecular forces to be weak S···S contacts [S32···S62i 3.980 (2) Å; symmetry code: (i) 1 - x, 1/2 + y, 1/2 - z]. As a result of these interactions, the molecules of (I) form chains which lie along the b axis (Fig. 2) and which interdigitate to form a planar arrangement parallel to the (100) plane (Fig. 3).

Although there is the potential for a C33—H33···N1i hydrogen bond with an acceptable C—H···N angle of 160°, the long C33···N1i and H33···N1 distances of 3.503 and 2.615 Å, respectively, and the unfavourable H···N—N and H···N—C angles of 91 and 141°, indicate that this is, at most, a rather weak interaction.

Experimental top

2-Bromothiophene (6.33 ml, 10.76 g, 33 mmol) in pre-dried diethyl ether (30 ml) was slowly added to dry Mg turnings (1.60 g, 66 mmol) in pre-dried diethyl ether (20 ml) and stirred until the Mg dissolved completely. After cooling to 273 K, dichloro[bis(diphenylphosphino)propane]nickel(II) (0.067 g, 0.12 mmol) and 3,6-dichloropyridazine (5.0 g, 33 mmol) in pre-dried diethyl ether (30 ml) were added consecutively. After stirring for 48 h, the solid product was filtered, washed with HCl (2 M, 50 ml), dissolved in hot acetone (250 ml), filtered, and precipitated by addition of water. Recrystallization from an acetone-water (ratio?) mixture gave tiny golden needles of (I) (1.6 g, 0.70 mmol, 20% yield). Analysis found (calculated for C12H8N2S2): C 58.85 (59.00), H 3.20 (3.25), N 11.50% (11.45%); m.p. 447–449 K (literature value 448–449 K; Montheard & Dubois, 1985). Larger yellow tabular crystals of (I), used for the present X-ray analysis Is this OK?, were recovered from a failed attempt to prepare a dinuclear palladium(II) chloride complex, in which (I) was expected to act as a bis(bidentate) ligand bridging two PdII centres.

Refinement top

A total of 822 Friedel pairs were employed in the estimation of the Flack (1983) parameter. Aromatic H atoms, after location from difference Fourier syntheses, were placed geometrically and refined with a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: STADI4 (Stoe & Cie, 1995); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Figures top
[Figure 1] Fig. 1. A view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A projection of the structure of (I) onto the (001) plane, showing the weak intermolecular S···S contacts and the resultant chain architecture.
[Figure 3] Fig. 3. A projection of the structure of (I) onto the (100) plane, showing the interdigitation of the chain architecture.
3,6-Bis(thiophen-2-yl)pyridazine top
Crystal data top
C12H8N2S2F(000) = 504
Mr = 244.32Dx = 1.408 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2abCell parameters from 29 reflections
a = 5.6862 (4) Åθ = 26.3–35.0°
b = 13.0264 (8) ŵ = 0.43 mm1
c = 15.563 (2) ÅT = 298 K
V = 1152.76 (18) Å3Tablet, yellow
Z = 40.68 × 0.51 × 0.39 mm
Data collection top
Stoe STADI4 four-circle
diffractometer
Rint = 0.012
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.6°
Graphite monochromatorh = 66
ω/θ scansk = 1515
3064 measured reflectionsl = 018
2031 independent reflections3 standard reflections every 60 min
1878 reflections with I > 2σ(I) intensity decay: 6%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032 w = 1/[σ2(Fo2) + (0.025P)2 + 0.351P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.074(Δ/σ)max < 0.001
S = 1.11Δρmax = 0.16 e Å3
2031 reflectionsΔρmin = 0.21 e Å3
145 parametersAbsolute structure: Flack (1983)
0 restraintsAbsolute structure parameter: 0.01 (10)
Primary atom site location: structure-invariant direct methods
Crystal data top
C12H8N2S2V = 1152.76 (18) Å3
Mr = 244.32Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.6862 (4) ŵ = 0.43 mm1
b = 13.0264 (8) ÅT = 298 K
c = 15.563 (2) Å0.68 × 0.51 × 0.39 mm
Data collection top
Stoe STADI4 four-circle
diffractometer
Rint = 0.012
3064 measured reflections3 standard reflections every 60 min
2031 independent reflections intensity decay: 6%
1878 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.16 e Å3
S = 1.11Δρmin = 0.21 e Å3
2031 reflectionsAbsolute structure: Flack (1983)
145 parametersAbsolute structure parameter: 0.01 (10)
0 restraints
Special details top

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

1.6924 (0.0047) x + 6.3728 (0.0097) y - 12.7586 (0.0078) z = 3.2761 (0.0070)

* -0.0062 (0.0014) N1 * -0.0027 (0.0014) N2 * 0.0074 (0.0015) C3 * -0.0034 (0.0015) C4 * -0.0051 (0.0015) C5 * 0.0100 (0.0015) C6

Rms deviation of fitted atoms = 0.0063

2.6794 (0.0051) x + 5.3371 (0.0136) y - 12.1561 (0.0123) z = 2.6824 (0.0147)

Angle to previous plane (with approximate e.s.d.) = 11.18 (0.14)

* -0.0029 (0.0014) C31 * 0.0037 (0.0012) S32 * -0.0043 (0.0016) C33 * 0.0029 (0.0018) C34 * 0.0007 (0.0016) C35

Rms deviation of fitted atoms = 0.0031

2.9722 (0.0052) x + 6.5023 (0.0156) y - 10.7556 (0.0131) z = 3.5421 (0.0060)

Angle to previous plane (with approximate e.s.d.) = 7.85 (0.17)

* -0.0001 (0.0015) C61 * 0.0007 (0.0013) S62 * -0.0012 (0.0018) C63 * 0.0012 (0.0020) C64 * -0.0006 (0.0017) C65

Rms deviation of fitted atoms = 0.0009

1.6924 (0.0047) x + 6.3728 (0.0097) y - 12.7586 (0.0078) z = 3.2761 (0.0070)

Angle to previous plane (with approximate e.s.d.) = 14.91 (0.14)

* -0.0062 (0.0014) N1 * -0.0027 (0.0014) N2 * 0.0074 (0.0015) C3 * -0.0034 (0.0015) C4 * -0.0051 (0.0015) C5 * 0.0100 (0.0015) C6

Rms deviation of fitted atoms = 0.0063

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
xyzUiso*/Ueq
N10.3116 (3)0.60713 (16)0.08830 (13)0.0553 (5)
N20.3118 (3)0.69565 (16)0.13227 (13)0.0543 (5)
C30.1187 (4)0.75376 (16)0.13489 (13)0.0471 (5)
C40.0883 (4)0.72428 (18)0.09355 (15)0.0521 (6)
H40.22250.76490.09650.063*
C50.0889 (4)0.63475 (19)0.04888 (15)0.0524 (6)
H50.22370.61240.02070.063*
C60.1176 (4)0.57715 (17)0.04632 (13)0.0483 (5)
C310.1391 (4)0.84939 (18)0.18317 (13)0.0498 (5)
S320.38234 (13)0.87200 (5)0.24615 (4)0.0671 (2)
C330.2787 (5)0.9894 (2)0.27552 (18)0.0725 (8)
H330.35691.03350.31280.087*
C340.0705 (5)1.0111 (2)0.23855 (17)0.0694 (8)
H340.01071.07220.24700.083*
C350.0102 (4)0.9311 (2)0.18584 (16)0.0599 (7)
H350.15140.93370.15580.072*
C610.1365 (4)0.48103 (18)0.00077 (15)0.0531 (5)
S620.37223 (14)0.40039 (6)0.01553 (5)0.0761 (2)
C630.2746 (6)0.3178 (2)0.0612 (2)0.0821 (9)
H630.35120.25730.07640.099*
C640.0717 (6)0.3505 (2)0.0977 (2)0.0773 (8)
H640.00680.31520.14100.093*
C650.0064 (5)0.4436 (2)0.06284 (18)0.0628 (7)
H650.14320.47650.08060.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0393 (10)0.0613 (12)0.0652 (12)0.0015 (9)0.0072 (9)0.0050 (11)
N20.0376 (11)0.0620 (13)0.0633 (12)0.0000 (9)0.0064 (9)0.0055 (10)
C30.0363 (11)0.0588 (13)0.0463 (11)0.0000 (12)0.0017 (11)0.0133 (10)
C40.0354 (12)0.0625 (14)0.0584 (13)0.0044 (11)0.0013 (12)0.0107 (12)
C50.0341 (12)0.0659 (15)0.0574 (13)0.0060 (12)0.0064 (10)0.0119 (12)
C60.0381 (11)0.0582 (13)0.0485 (11)0.0057 (12)0.0016 (11)0.0138 (10)
C310.0387 (11)0.0658 (14)0.0449 (11)0.0013 (12)0.0013 (11)0.0073 (10)
S320.0530 (3)0.0789 (4)0.0693 (4)0.0011 (4)0.0175 (4)0.0022 (3)
C330.0720 (18)0.086 (2)0.0594 (16)0.0028 (16)0.0042 (14)0.0115 (15)
C340.0666 (18)0.0801 (18)0.0615 (16)0.0107 (14)0.0080 (14)0.0154 (14)
C350.0453 (13)0.0809 (18)0.0535 (14)0.0086 (13)0.0002 (11)0.0036 (13)
C610.0447 (12)0.0572 (13)0.0573 (13)0.0053 (12)0.0004 (13)0.0122 (11)
S620.0662 (4)0.0741 (4)0.0880 (5)0.0164 (4)0.0144 (4)0.0033 (4)
C630.089 (2)0.0629 (17)0.095 (2)0.0041 (16)0.0030 (19)0.0075 (16)
C640.084 (2)0.0679 (17)0.0804 (19)0.0096 (16)0.0086 (17)0.0042 (16)
C650.0559 (15)0.0618 (16)0.0708 (17)0.0062 (13)0.0068 (13)0.0071 (13)
Geometric parameters (Å, º) top
N1—C61.340 (3)C61—C651.353 (3)
N1—N21.341 (3)C61—S621.722 (2)
N2—C31.334 (3)S62—C631.701 (3)
C3—C41.395 (3)C63—C641.354 (4)
C3—C311.459 (3)C64—C651.401 (4)
C4—C51.358 (3)C4—H40.93
C5—C61.394 (3)C5—H50.93
C6—C611.455 (3)C33—H330.93
C31—C351.362 (3)C34—H340.93
C31—S321.721 (2)C35—H350.93
S32—C331.702 (3)C63—H630.93
C33—C341.346 (4)C64—H640.93
C34—C351.403 (4)C65—H650.93
C6—N1—N2120.02 (19)C63—S62—C6191.63 (14)
C3—N2—N1120.18 (19)C64—C63—S62111.9 (3)
N2—C3—C4121.6 (2)C63—C64—C65112.4 (3)
N2—C3—C31115.8 (2)C61—C65—C64113.4 (3)
C4—C3—C31122.6 (2)C3—C4—H4120.86
C5—C4—C3118.3 (2)C5—C4—H4120.80
C4—C5—C6118.4 (2)C4—C5—H5120.83
N1—C6—C5121.5 (2)C6—C5—H5120.82
N1—C6—C61115.8 (2)S32—C33—H33123.87
C5—C6—C61122.7 (2)C34—C33—H33123.89
C35—C31—C3129.3 (2)C33—C34—H34123.79
C35—C31—S32110.47 (18)C35—C34—H34123.79
C3—C31—S32120.22 (18)C31—C35—H35123.46
C33—S32—C3191.64 (13)C34—C35—H35123.32
C34—C33—S32112.2 (2)S62—C63—H63124.14
C33—C34—C35112.5 (3)C64—C63—H63123.92
C31—C35—C34113.2 (2)C63—C64—H64123.86
C65—C61—C6128.7 (2)C65—C64—H64123.82
C65—C61—S62110.68 (19)C61—C65—H65123.25
C6—C61—S62120.57 (18)C64—C65—H65123.29
C6—N1—N2—C30.5 (3)C31—S32—C33—C340.7 (2)
N1—N2—C3—C40.9 (3)S32—C33—C34—C350.6 (3)
N1—N2—C3—C31178.91 (18)C3—C31—C35—C34178.7 (2)
N2—C3—C4—C50.9 (3)S32—C31—C35—C340.3 (3)
C31—C3—C4—C5178.82 (19)C33—C34—C35—C310.2 (4)
C3—C4—C5—C60.3 (3)N1—C6—C61—C65163.9 (2)
N2—N1—C6—C51.7 (3)C5—C6—C61—C6516.7 (4)
N2—N1—C6—C61178.87 (19)N1—C6—C61—S6212.7 (3)
C4—C5—C6—N11.6 (3)C5—C6—C61—S62166.70 (17)
C4—C5—C6—C61179.0 (2)C65—C61—S62—C630.1 (2)
N2—C3—C31—C35168.0 (2)C6—C61—S62—C63177.2 (2)
C4—C3—C31—C3511.7 (4)C61—S62—C63—C640.2 (3)
N2—C3—C31—S3210.3 (3)S62—C63—C64—C650.2 (4)
C4—C3—C31—S32169.93 (18)C6—C61—C65—C64176.8 (2)
C35—C31—S32—C330.5 (2)S62—C61—C65—C640.1 (3)
C3—C31—S32—C33179.16 (19)C63—C64—C65—C610.2 (4)

Experimental details

Crystal data
Chemical formulaC12H8N2S2
Mr244.32
Crystal system, space groupOrthorhombic, P212121
Temperature (K)298
a, b, c (Å)5.6862 (4), 13.0264 (8), 15.563 (2)
V3)1152.76 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.68 × 0.51 × 0.39
Data collection
DiffractometerStoe STADI4 four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3064, 2031, 1878
Rint0.012
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.074, 1.11
No. of reflections2031
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.21
Absolute structureFlack (1983)
Absolute structure parameter0.01 (10)

Computer programs: STADI4 (Stoe & Cie, 1995), STADI4, X-RED (Stoe & Cie, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998) and CAMERON (Watkin et al., 1996), SHELXL97 and PLATON (Spek, 2002).

 

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