Chloro­[5,6-di­phenyl-1,2,4-triazine-3(2H)-thionato]­di­methyl­tin(IV)

The reaction between di­chloro­di­methyl­tin(IV) and 5-meth­oxy-5,6-di­phenyl-4,5-di­hydro-2H-1,2,4-triazine-3-thione yields the title complex, [SnClMe₂(C₁₅H₁₀N₃S)]. The coordination sphere of the Sn atom is formed by the S, amine N and Cl atoms and two methyl groups, giving a pentacoordinate geometry. The distances Sn-N = 2.525 (2) Å, Sn-S = 2.4671 (7) Å, Sn-C = 2.109 (3) and 2.111 (4) Å, and Sn-Cl = 2.4220 (7) Å are in the ranges expected for this type of complex. The coordination mode of the triazine­thione ligand results in a four-membered chelate ring.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.028
• wR factor = 0.071
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .....       0.94

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           70.44
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               3309
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3537
           Completeness (_total/calc)             93.55%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ..       0.94
PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) ...         10 Ang.
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) ...         10 Ang.
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ..          Sn1

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

---

S1. Comment

In the title molecule, (I), the geometry is intermediate between a square-base pyramid and a trigonal bipyramid (t = 0.41). The thione bond distance of 1.738 (3) Å is longer than in the uncoordinated precursor molecule [1.628 (2) Å; Arquero et al., 1998] andis intermediate between the theoretical C—S single and double bond lengths (Sutton, 1965), as occurs with N—N bonds. The X-ray analysis confirms the structure proposed from spectroscopy measurements.

S2. Experimental

The complex was synthesized as described by López-Torres et al. (2003). Recrystallization from chloroform afforded colourless crystal suitable for X-ray analysis.

S3. Refinement

The H atoms were placed in the idealized positions with C—H distances of 0.93 Å (0.96 Å for methyl) and included in the refinement in the riding-model approximation with U_iso values equal to 1.2U_eq (1.5U_eq for methyl) of the carrier atom.

Computing details

Data collection: SMART (Bruker, 1997-2001); cell refinement: SMART; data reduction: SAINT-Plus-NT (Bruker, 1997-2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

(I)

Crystal data

[SnCl(CH3)2(C15H10N3S)]	V = 923.89 (2) Å^3
Mr = 448.53	Z = 2
Triclinic, P1	F(000) = 444
Hall symbol: -P 1	Dx = 1.612 Mg m^−3
a = 7.5737 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.6393 (1) Å	µ = 13.39 mm^−1
c = 12.4602 (1) Å	T = 296 K
α = 79.524 (1)°	Prism, yellow
β = 74.738 (1)°	0.30 × 0.20 × 0.20 mm
γ = 73.828 (1)°

Data collection

Bruker SMART CCD diffractometer	3309 independent reflections
Radiation source: rotating anode	3256 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 70.4°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997–2001)	h = −9→9
Tmin = 0.062, Tmax = 0.069	k = −12→12
10236 measured reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.3651P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3309 reflections	Δρmax = 0.91 e Å^−3
211 parameters	Δρmin = −0.73 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3818 (5)	−0.4604 (4)	0.3716 (4)	0.0704 (10)
H1A	0.4567	−0.4151	0.3943	0.106*
H1B	0.4470	−0.4918	0.3007	0.106*
H1C	0.3607	−0.5338	0.4266	0.106*
C2	−0.0820 (6)	−0.2083 (4)	0.4703 (3)	0.0669 (9)
H2A	−0.1422	−0.2619	0.5317	0.100*
H2B	−0.1750	−0.1502	0.4327	0.100*
H2C	−0.0210	−0.1572	0.4981	0.100*
C3	0.2216 (4)	−0.1131 (2)	0.1870 (2)	0.0382 (5)
C4	0.3311 (3)	0.0721 (2)	0.1373 (2)	0.0316 (5)
C5	0.4223 (3)	0.0308 (2)	0.2295 (2)	0.0347 (5)
C6	0.3196 (3)	0.2008 (2)	0.0677 (2)	0.0335 (5)
C7	0.3019 (4)	0.2109 (3)	−0.0421 (2)	0.0406 (6)
H7	0.3035	0.1360	−0.0713	0.049*
C8	0.2823 (5)	0.3303 (3)	−0.1077 (3)	0.0581 (8)
H8	0.2739	0.3356	−0.1816	0.070*
C9	0.2748 (6)	0.4421 (3)	−0.0643 (4)	0.0689 (10)
H9	0.2618	0.5229	−0.1089	0.083*
C10	0.2868 (6)	0.4343 (3)	0.0457 (4)	0.0680 (10)
H10	0.2792	0.5103	0.0754	0.082*
C11	0.3100 (4)	0.3145 (3)	0.1114 (3)	0.0488 (6)
H11	0.3191	0.3096	0.1851	0.059*
C12	0.5605 (3)	0.0936 (2)	0.2493 (2)	0.0349 (5)
C13	0.6977 (4)	0.1320 (3)	0.1603 (2)	0.0408 (5)
H13	0.7027	0.1180	0.0879	0.049*
C14	0.8264 (4)	0.1911 (3)	0.1791 (3)	0.0500 (7)
H14	0.9172	0.2171	0.1194	0.060*
C15	0.8203 (5)	0.2112 (3)	0.2861 (3)	0.0611 (8)
H15	0.9055	0.2523	0.2984	0.073*
C16	0.6874 (5)	0.1706 (4)	0.3755 (3)	0.0604 (8)
H16	0.6847	0.1834	0.4478	0.073*
C17	0.5589 (4)	0.1111 (3)	0.3577 (2)	0.0459 (6)
H17	0.4712	0.0826	0.4181	0.055*
N1	0.2771 (4)	−0.1411 (2)	0.2841 (2)	0.0446 (5)
N2	0.3856 (3)	−0.0714 (2)	0.30284 (19)	0.0431 (5)
N3	0.2409 (3)	−0.0065 (2)	0.11380 (18)	0.0358 (4)
S1	0.10706 (11)	−0.22346 (7)	0.16482 (6)	0.04904 (18)
Sn1	0.12042 (2)	−0.330147 (15)	0.356620 (13)	0.04039 (10)
Cl1	−0.05400 (14)	−0.48659 (8)	0.34937 (7)	0.0644 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0493 (18)	0.070 (2)	0.081 (2)	−0.0088 (15)	−0.0230 (17)	0.0223 (19)
C2	0.070 (2)	0.056 (2)	0.064 (2)	−0.0071 (16)	−0.0076 (17)	−0.0038 (15)
C3	0.0432 (13)	0.0308 (12)	0.0443 (13)	−0.0151 (10)	−0.0165 (11)	0.0057 (10)
C4	0.0310 (11)	0.0278 (11)	0.0361 (12)	−0.0092 (8)	−0.0095 (9)	0.0018 (9)
C5	0.0354 (12)	0.0334 (12)	0.0368 (12)	−0.0114 (9)	−0.0118 (10)	0.0026 (9)
C6	0.0296 (11)	0.0269 (11)	0.0437 (13)	−0.0080 (8)	−0.0127 (10)	0.0055 (9)
C7	0.0381 (13)	0.0379 (13)	0.0474 (14)	−0.0118 (10)	−0.0171 (11)	0.0062 (11)
C8	0.0588 (18)	0.0543 (19)	0.0588 (18)	−0.0181 (14)	−0.0253 (15)	0.0239 (14)
C9	0.074 (2)	0.0357 (16)	0.091 (3)	−0.0163 (15)	−0.031 (2)	0.0292 (16)
C10	0.077 (2)	0.0261 (14)	0.103 (3)	−0.0124 (13)	−0.029 (2)	−0.0006 (16)
C11	0.0555 (16)	0.0313 (13)	0.0619 (17)	−0.0104 (11)	−0.0194 (14)	−0.0026 (12)
C12	0.0358 (12)	0.0298 (12)	0.0415 (12)	−0.0081 (9)	−0.0158 (10)	0.0001 (9)
C13	0.0390 (13)	0.0405 (14)	0.0448 (13)	−0.0142 (10)	−0.0114 (11)	0.0003 (11)
C14	0.0390 (14)	0.0423 (15)	0.0724 (19)	−0.0165 (11)	−0.0190 (13)	0.0037 (13)
C15	0.0596 (19)	0.0548 (18)	0.087 (2)	−0.0246 (15)	−0.0387 (18)	−0.0044 (16)
C16	0.072 (2)	0.063 (2)	0.0619 (19)	−0.0190 (16)	−0.0358 (17)	−0.0119 (16)
C17	0.0504 (15)	0.0478 (15)	0.0440 (14)	−0.0151 (12)	−0.0178 (12)	−0.0015 (12)
N1	0.0541 (14)	0.0405 (12)	0.0457 (12)	−0.0253 (10)	−0.0185 (11)	0.0112 (10)
N2	0.0510 (13)	0.0424 (12)	0.0425 (11)	−0.0221 (10)	−0.0202 (10)	0.0095 (9)
N3	0.0409 (11)	0.0283 (10)	0.0423 (11)	−0.0120 (8)	−0.0179 (9)	0.0038 (8)
S1	0.0701 (5)	0.0394 (4)	0.0525 (4)	−0.0318 (3)	−0.0311 (3)	0.0117 (3)
Sn1	0.04355 (14)	0.03489 (13)	0.04653 (14)	−0.01537 (8)	−0.01881 (9)	0.00762 (8)
Cl1	0.0899 (6)	0.0561 (4)	0.0678 (5)	−0.0478 (4)	−0.0396 (4)	0.0201 (4)

Geometric parameters (Å, º)

C1—Sn1	2.109 (3)	C8—H8	0.9300
C1—H1A	0.9600	C9—C10	1.383 (6)
C1—H1B	0.9600	C9—H9	0.9300
C1—H1C	0.9600	C10—C11	1.378 (5)
C2—Sn1	2.111 (4)	C10—H10	0.9300
C2—H2A	0.9600	C11—H11	0.9300
C2—H2B	0.9600	C12—C13	1.393 (4)
C2—H2C	0.9600	C12—C17	1.394 (4)
C3—N3	1.337 (3)	C13—C14	1.385 (4)
C3—N1	1.340 (3)	C13—H13	0.9300
C3—S1	1.738 (3)	C14—C15	1.375 (5)
C4—N3	1.328 (3)	C14—H14	0.9300
C4—C5	1.434 (3)	C15—C16	1.385 (6)
C4—C6	1.475 (3)	C15—H15	0.9300
C5—N2	1.330 (3)	C16—C17	1.380 (5)
C5—C12	1.478 (3)	C16—H16	0.9300
C6—C11	1.390 (4)	C17—H17	0.9300
C6—C7	1.391 (4)	N1—N2	1.336 (3)
C7—C8	1.373 (4)	N1—Sn1	2.525 (2)
C7—H7	0.9300	S1—Sn1	2.4671 (7)
C8—C9	1.376 (6)	Sn1—Cl1	2.4220 (7)
Sn1—C1—H1A	109.5	C10—C11—H11	120.0
Sn1—C1—H1B	109.5	C6—C11—H11	120.0
H1A—C1—H1B	109.5	C13—C12—C17	119.2 (2)
Sn1—C1—H1C	109.5	C13—C12—C5	120.5 (2)
H1A—C1—H1C	109.5	C17—C12—C5	120.3 (2)
H1B—C1—H1C	109.5	C14—C13—C12	120.3 (3)
Sn1—C2—H2A	109.5	C14—C13—H13	119.9
Sn1—C2—H2B	109.5	C12—C13—H13	119.9
H2A—C2—H2B	109.5	C15—C14—C13	120.1 (3)
Sn1—C2—H2C	109.5	C15—C14—H14	120.0
H2A—C2—H2C	109.5	C13—C14—H14	120.0
H2B—C2—H2C	109.5	C14—C15—C16	120.2 (3)
N3—C3—N1	124.5 (2)	C14—C15—H15	119.9
N3—C3—S1	120.9 (2)	C16—C15—H15	119.9
N1—C3—S1	114.48 (19)	C17—C16—C15	120.3 (3)
N3—C4—C5	119.2 (2)	C17—C16—H16	119.9
N3—C4—C6	115.7 (2)	C15—C16—H16	119.9
C5—C4—C6	124.9 (2)	C16—C17—C12	120.0 (3)
N2—C5—C4	119.6 (2)	C16—C17—H17	120.0
N2—C5—C12	116.1 (2)	C12—C17—H17	120.0
C4—C5—C12	124.3 (2)	N2—N1—C3	118.9 (2)
C11—C6—C7	118.9 (2)	N2—N1—Sn1	146.18 (17)
C11—C6—C4	121.9 (2)	C3—N1—Sn1	94.88 (16)
C7—C6—C4	119.0 (2)	C5—N2—N1	119.3 (2)
C8—C7—C6	120.6 (3)	C4—N3—C3	116.8 (2)
C8—C7—H7	119.7	C3—S1—Sn1	87.58 (9)
C6—C7—H7	119.7	C1—Sn1—C2	130.86 (17)
C7—C8—C9	120.1 (3)	C1—Sn1—Cl1	99.90 (12)
C7—C8—H8	120.0	C2—Sn1—Cl1	100.51 (12)
C9—C8—H8	120.0	C1—Sn1—S1	114.59 (12)
C8—C9—C10	119.9 (3)	C2—Sn1—S1	108.16 (11)
C8—C9—H9	120.0	Cl1—Sn1—S1	93.57 (2)
C10—C9—H9	120.0	C1—Sn1—N1	90.80 (13)
C11—C10—C9	120.3 (3)	C2—Sn1—N1	87.95 (13)
C11—C10—H10	119.9	Cl1—Sn1—N1	156.25 (6)
C9—C10—H10	119.9	S1—Sn1—N1	62.68 (5)
C10—C11—C6	120.1 (3)
N3—C4—C5—N2	−13.0 (4)	C5—C12—C17—C16	−179.5 (3)
C6—C4—C5—N2	163.5 (2)	N3—C3—N1—N2	−11.4 (4)
N3—C4—C5—C12	166.0 (2)	S1—C3—N1—N2	172.1 (2)
C6—C4—C5—C12	−17.5 (4)	N3—C3—N1—Sn1	170.7 (2)
N3—C4—C6—C11	144.4 (3)	S1—C3—N1—Sn1	−5.8 (2)
C5—C4—C6—C11	−32.2 (4)	C4—C5—N2—N1	5.7 (4)
N3—C4—C6—C7	−30.0 (3)	C12—C5—N2—N1	−173.3 (2)
C5—C4—C6—C7	153.4 (2)	C3—N1—N2—C5	5.8 (4)
C11—C6—C7—C8	2.4 (4)	Sn1—N1—N2—C5	−177.9 (2)
C4—C6—C7—C8	177.0 (2)	C5—C4—N3—C3	7.9 (3)
C6—C7—C8—C9	−1.7 (5)	C6—C4—N3—C3	−168.9 (2)
C7—C8—C9—C10	−0.1 (6)	N1—C3—N3—C4	4.0 (4)
C8—C9—C10—C11	1.3 (6)	S1—C3—N3—C4	−179.72 (19)
C9—C10—C11—C6	−0.6 (6)	N3—C3—S1—Sn1	−170.7 (2)
C7—C6—C11—C10	−1.2 (4)	N1—C3—S1—Sn1	5.9 (2)
C4—C6—C11—C10	−175.7 (3)	C3—S1—Sn1—C1	−80.55 (17)
N2—C5—C12—C13	137.7 (3)	C3—S1—Sn1—C2	74.57 (16)
C4—C5—C12—C13	−41.2 (4)	C3—S1—Sn1—Cl1	176.86 (10)
N2—C5—C12—C17	−40.2 (3)	C3—S1—Sn1—N1	−3.20 (11)
C4—C5—C12—C17	140.8 (3)	N2—N1—Sn1—C1	−55.1 (4)
C17—C12—C13—C14	−2.2 (4)	C3—N1—Sn1—C1	121.6 (2)
C5—C12—C13—C14	179.8 (2)	N2—N1—Sn1—C2	75.8 (4)
C12—C13—C14—C15	0.4 (4)	C3—N1—Sn1—C2	−107.5 (2)
C13—C14—C15—C16	1.1 (5)	N2—N1—Sn1—Cl1	−172.4 (3)
C14—C15—C16—C17	−0.8 (5)	C3—N1—Sn1—Cl1	4.3 (3)
C15—C16—C17—C12	−1.0 (5)	N2—N1—Sn1—S1	−172.6 (4)
C13—C12—C17—C16	2.5 (4)	C3—N1—Sn1—S1	4.16 (15)