The tetra­chloro­di­phenyl­stannate(IV) salt of protonated di-2-pyridyl ketone N⁴-ethyl­thio­semicarbazone

Reaction of di-2-pyridyl ketone N⁴-ethyl­thio­semicarbazone with SnPh₂Cl₂ resulted in the formation of the title complex salt, namely 2-[(ethyl­amino­thio­yl­hydrazono)(2-pyridyl)­methyl]­pyridinium tetra­chloro­di­phenyl­stannate(IV), (C₁₄H₁₆N₅S)₂[SnCl₄(C₆H₅)₂]. The Sn atom is not coordin­ated directly by the nitro­gen base, but one of the pyridines of dipyridylketone is protonated, forming the cation. The Sn atom of the anion lies on an inversion center; thus, the two phenyl groups are trans to each other, with an Sn—C distance of 2.1424 (14) Å. The Sn—Cl distances are 2.5541 (4) and 2.6066 (4) Å. The N—H groups form hydrogen bonds to Cl atoms of the anion and the cation contains an intramolecular N—H...N hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 102 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.029
• wR factor = 0.066
• Data-to-parameter ratio = 31.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.50 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Sn1    -   C1      ..       5.26 su

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

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

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL SCALEPACK and DENZO (Otwinowski & Minor 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

2-[(ethylaminothioylhydrazono)(2-pyridyl)methyl]pyridinium tetrachlorodiphenylstannate(IV)

Crystal data

2C14H16N5S^+·C12H10Cl4Sn^2^−	Z = 1
Mr = 987.45	F(000) = 502
Triclinic, P1	Dx = 1.537 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4878 (10) Å	Cell parameters from 7524 reflections
b = 12.009 (2) Å	θ = 2.5–33.7°
c = 13.585 (2) Å	µ = 0.99 mm^−1
α = 110.872 (9)°	T = 102 K
β = 102.803 (7)°	Fragment, yellow
γ = 100.404 (7)°	0.35 × 0.30 × 0.20 mm
V = 1066.9 (3) Å^3

Data collection

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	8420 independent reflections
Radiation source: fine-focus sealed tube	7364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans with κ offsets	θmax = 33.7°, θmin = 2.8°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	h = −11→11
Tmin = 0.696, Tmax = 0.820	k = −18→18
34148 measured reflections	l = −21→20

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0222P)^2 + 0.6943P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
8420 reflections	Δρmax = 0.87 e Å^−3
270 parameters	Δρmin = −0.82 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: 0.0072 (7)

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
Sn1	0.0000	0.5000	0.0000	0.01112 (4)
Cl1	0.25764 (5)	0.42032 (3)	0.08791 (3)	0.01529 (6)
Cl2	0.23999 (5)	0.60871 (3)	−0.07324 (3)	0.01528 (6)
S1	0.52760 (5)	0.16520 (3)	0.35629 (3)	0.01867 (7)
N1	0.66877 (17)	0.63291 (11)	0.23120 (10)	0.0135 (2)
H1N	0.689 (3)	0.5640 (18)	0.2019 (16)	0.016*
N2	0.7484 (2)	0.58289 (12)	0.57396 (10)	0.0186 (2)
N3	0.64295 (17)	0.47978 (11)	0.33260 (10)	0.0136 (2)
N4	0.64409 (18)	0.39372 (11)	0.37465 (10)	0.0150 (2)
H4N	0.660 (3)	0.4163 (18)	0.4447 (17)	0.018*
N5	0.5342 (2)	0.24590 (12)	0.19616 (11)	0.0203 (2)
H5N	0.556 (3)	0.310 (2)	0.1784 (17)	0.024*
C1	0.08042 (19)	0.66536 (13)	0.14971 (11)	0.0143 (2)
C2	0.1180 (2)	0.65826 (15)	0.25217 (11)	0.0180 (3)
H2	0.1158	0.5805	0.2557	0.022*
C3	0.1587 (2)	0.76431 (17)	0.34945 (13)	0.0246 (3)
H3	0.1858	0.7588	0.4190	0.030*
C4	0.1598 (2)	0.87768 (17)	0.34480 (14)	0.0290 (4)
H4	0.1840	0.9495	0.4109	0.035*
C5	0.1254 (2)	0.88641 (15)	0.24325 (15)	0.0263 (3)
H5	0.1288	0.9646	0.2402	0.032*
C6	0.0860 (2)	0.78074 (14)	0.14605 (13)	0.0190 (3)
H6	0.0627	0.7871	0.0769	0.023*
C7	0.70636 (19)	0.59739 (13)	0.39836 (11)	0.0132 (2)
C8	0.67596 (19)	0.67788 (12)	0.33909 (11)	0.0124 (2)
C9	0.6409 (2)	0.79181 (13)	0.38432 (12)	0.0164 (2)
H9	0.6449	0.8260	0.4598	0.020*
C10	0.6000 (2)	0.85575 (14)	0.31859 (13)	0.0193 (3)
H10	0.5767	0.9342	0.3493	0.023*
C11	0.5930 (2)	0.80512 (15)	0.20838 (13)	0.0198 (3)
H11	0.5646	0.8481	0.1629	0.024*
C12	0.6278 (2)	0.69140 (14)	0.16563 (12)	0.0170 (3)
H12	0.6227	0.6549	0.0901	0.020*
C13	0.7985 (2)	0.65333 (13)	0.52051 (11)	0.0142 (2)
C14	0.9350 (2)	0.76891 (14)	0.57500 (12)	0.0172 (3)
H14	0.9678	0.8162	0.5352	0.021*
C15	1.0227 (2)	0.81401 (15)	0.68870 (12)	0.0210 (3)
H15	1.1176	0.8920	0.7276	0.025*
C16	0.9692 (2)	0.74321 (16)	0.74418 (12)	0.0239 (3)
H16	1.0254	0.7720	0.8219	0.029*
C17	0.8316 (3)	0.62918 (15)	0.68343 (12)	0.0228 (3)
H17	0.7945	0.5813	0.7219	0.027*
C18	0.5668 (2)	0.27008 (13)	0.30260 (12)	0.0150 (2)
C19	0.4663 (2)	0.12212 (15)	0.10593 (13)	0.0237 (3)
H19A	0.5029	0.0619	0.1349	0.028*
H19B	0.5296	0.1216	0.0491	0.028*
C20	0.2530 (3)	0.08137 (19)	0.05264 (18)	0.0375 (5)
H20A	0.1896	0.0774	0.1076	0.056*
H20B	0.2149	−0.0010	−0.0088	0.056*
H20C	0.2158	0.1411	0.0245	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.01193 (6)	0.01205 (6)	0.00996 (6)	0.00373 (4)	0.00358 (4)	0.00497 (4)
Cl1	0.01471 (14)	0.01932 (15)	0.01437 (13)	0.00740 (12)	0.00393 (11)	0.00890 (12)
Cl2	0.01641 (14)	0.01547 (15)	0.01631 (14)	0.00384 (11)	0.00793 (12)	0.00784 (12)
S1	0.02202 (17)	0.01413 (16)	0.02352 (17)	0.00539 (13)	0.00830 (14)	0.01101 (14)
N1	0.0148 (5)	0.0131 (5)	0.0128 (5)	0.0044 (4)	0.0042 (4)	0.0056 (4)
N2	0.0280 (6)	0.0169 (6)	0.0135 (5)	0.0088 (5)	0.0080 (5)	0.0072 (4)
N3	0.0165 (5)	0.0115 (5)	0.0144 (5)	0.0041 (4)	0.0064 (4)	0.0062 (4)
N4	0.0211 (6)	0.0115 (5)	0.0128 (5)	0.0037 (4)	0.0055 (4)	0.0058 (4)
N5	0.0306 (7)	0.0118 (5)	0.0158 (5)	0.0042 (5)	0.0060 (5)	0.0041 (4)
C1	0.0120 (5)	0.0150 (6)	0.0149 (6)	0.0038 (5)	0.0037 (5)	0.0052 (5)
C2	0.0158 (6)	0.0215 (7)	0.0128 (6)	0.0038 (5)	0.0033 (5)	0.0045 (5)
C3	0.0175 (7)	0.0329 (9)	0.0134 (6)	0.0034 (6)	0.0035 (5)	0.0009 (6)
C4	0.0199 (7)	0.0245 (8)	0.0242 (7)	0.0016 (6)	0.0049 (6)	−0.0071 (6)
C5	0.0206 (7)	0.0139 (7)	0.0350 (9)	0.0036 (6)	0.0060 (6)	0.0018 (6)
C6	0.0168 (6)	0.0148 (6)	0.0228 (7)	0.0035 (5)	0.0044 (5)	0.0063 (5)
C7	0.0155 (6)	0.0133 (6)	0.0122 (5)	0.0043 (5)	0.0053 (4)	0.0061 (5)
C8	0.0129 (5)	0.0119 (5)	0.0126 (5)	0.0036 (4)	0.0044 (4)	0.0052 (4)
C9	0.0180 (6)	0.0140 (6)	0.0175 (6)	0.0054 (5)	0.0062 (5)	0.0060 (5)
C10	0.0201 (7)	0.0142 (6)	0.0259 (7)	0.0068 (5)	0.0074 (6)	0.0099 (6)
C11	0.0203 (7)	0.0199 (7)	0.0230 (7)	0.0069 (6)	0.0052 (5)	0.0135 (6)
C12	0.0164 (6)	0.0198 (7)	0.0164 (6)	0.0047 (5)	0.0045 (5)	0.0098 (5)
C13	0.0164 (6)	0.0138 (6)	0.0127 (5)	0.0059 (5)	0.0048 (5)	0.0048 (5)
C14	0.0156 (6)	0.0181 (6)	0.0150 (6)	0.0044 (5)	0.0045 (5)	0.0041 (5)
C15	0.0172 (6)	0.0224 (7)	0.0159 (6)	0.0061 (6)	0.0013 (5)	0.0016 (5)
C16	0.0285 (8)	0.0287 (8)	0.0125 (6)	0.0160 (7)	0.0031 (6)	0.0044 (6)
C17	0.0362 (9)	0.0230 (7)	0.0146 (6)	0.0153 (7)	0.0096 (6)	0.0093 (6)
C18	0.0164 (6)	0.0128 (6)	0.0174 (6)	0.0052 (5)	0.0060 (5)	0.0070 (5)
C19	0.0288 (8)	0.0156 (7)	0.0198 (7)	0.0049 (6)	0.0060 (6)	0.0014 (5)
C20	0.0285 (9)	0.0270 (9)	0.0375 (10)	0.0065 (7)	0.0003 (8)	−0.0019 (8)

Geometric parameters (Å, º)

Sn1—C1^i	2.1424 (14)	C5—C6	1.393 (2)
Sn1—C1	2.1424 (14)	C5—H5	0.9500
Sn1—Cl1^i	2.5541 (4)	C6—H6	0.9500
Sn1—Cl1	2.5541 (4)	C7—C8	1.4789 (19)
Sn1—Cl2^i	2.6066 (4)	C7—C13	1.4872 (19)
Sn1—Cl2	2.6066 (4)	C8—C9	1.3857 (19)
S1—C18	1.6794 (15)	C9—C10	1.390 (2)
N1—C12	1.3356 (18)	C9—H9	0.9500
N1—C8	1.3541 (17)	C10—C11	1.385 (2)
N1—H1N	0.840 (19)	C10—H10	0.9500
N2—C17	1.3356 (19)	C11—C12	1.379 (2)
N2—C13	1.3518 (19)	C11—H11	0.9500
N3—C7	1.2996 (18)	C12—H12	0.9500
N3—N4	1.3476 (16)	C13—C14	1.393 (2)
N4—C18	1.3786 (18)	C14—C15	1.391 (2)
N4—H4N	0.86 (2)	C14—H14	0.9500
N5—C18	1.3243 (19)	C15—C16	1.385 (2)
N5—C19	1.457 (2)	C15—H15	0.9500
N5—H5N	0.88 (2)	C16—C17	1.388 (3)
C1—C2	1.394 (2)	C16—H16	0.9500
C1—C6	1.398 (2)	C17—H17	0.9500
C2—C3	1.394 (2)	C19—C20	1.506 (3)
C2—H2	0.9500	C19—H19A	0.9900
C3—C4	1.384 (3)	C19—H19B	0.9900
C3—H3	0.9500	C20—H20A	0.9800
C4—C5	1.391 (3)	C20—H20B	0.9800
C4—H4	0.9500	C20—H20C	0.9800
C1^i—Sn1—C1	180.0	C8—C7—C13	120.26 (12)
C1^i—Sn1—Cl1^i	90.82 (4)	N1—C8—C9	118.06 (12)
C1—Sn1—Cl1^i	89.18 (4)	N1—C8—C7	117.48 (11)
C1^i—Sn1—Cl1	89.18 (4)	C9—C8—C7	124.29 (12)
C1—Sn1—Cl1	90.82 (4)	C8—C9—C10	119.60 (13)
Cl1^i—Sn1—Cl1	180.0	C8—C9—H9	120.2
C1^i—Sn1—Cl2^i	90.56 (4)	C10—C9—H9	120.2
C1—Sn1—Cl2^i	89.44 (4)	C11—C10—C9	120.01 (14)
Cl1^i—Sn1—Cl2^i	90.515 (15)	C11—C10—H10	120.0
Cl1—Sn1—Cl2^i	89.484 (15)	C9—C10—H10	120.0
C1^i—Sn1—Cl2	89.44 (4)	C12—C11—C10	119.05 (14)
C1—Sn1—Cl2	90.56 (4)	C12—C11—H11	120.5
Cl1^i—Sn1—Cl2	89.486 (15)	C10—C11—H11	120.5
Cl1—Sn1—Cl2	90.516 (15)	N1—C12—C11	119.50 (13)
Cl2^i—Sn1—Cl2	179.999 (1)	N1—C12—H12	120.2
C12—N1—C8	123.76 (12)	C11—C12—H12	120.2
C12—N1—H1N	116.4 (13)	N2—C13—C14	122.40 (13)
C8—N1—H1N	119.8 (13)	N2—C13—C7	116.02 (12)
C17—N2—C13	117.60 (14)	C14—C13—C7	121.51 (13)
C7—N3—N4	120.13 (12)	C15—C14—C13	118.93 (14)
N3—N4—C18	118.33 (12)	C15—C14—H14	120.5
N3—N4—H4N	119.0 (13)	C13—C14—H14	120.5
C18—N4—H4N	120.0 (13)	C16—C15—C14	118.87 (15)
C18—N5—C19	125.27 (13)	C16—C15—H15	120.6
C18—N5—H5N	117.5 (14)	C14—C15—H15	120.6
C19—N5—H5N	117.2 (14)	C15—C16—C17	118.40 (14)
C2—C1—C6	118.97 (13)	C15—C16—H16	120.8
C2—C1—Sn1	120.23 (11)	C17—C16—H16	120.8
C6—C1—Sn1	120.70 (11)	N2—C17—C16	123.77 (15)
C3—C2—C1	120.59 (15)	N2—C17—H17	118.1
C3—C2—H2	119.7	C16—C17—H17	118.1
C1—C2—H2	119.7	N5—C18—N4	115.55 (13)
C4—C3—C2	120.03 (16)	N5—C18—S1	126.28 (11)
C4—C3—H3	120.0	N4—C18—S1	118.15 (11)
C2—C3—H3	120.0	N5—C19—C20	112.51 (14)
C3—C4—C5	119.95 (15)	N5—C19—H19A	109.1
C3—C4—H4	120.0	C20—C19—H19A	109.1
C5—C4—H4	120.0	N5—C19—H19B	109.1
C4—C5—C6	120.09 (16)	C20—C19—H19B	109.1
C4—C5—H5	120.0	H19A—C19—H19B	107.8
C6—C5—H5	120.0	C19—C20—H20A	109.5
C5—C6—C1	120.34 (15)	C19—C20—H20B	109.5
C5—C6—H6	119.8	H20A—C20—H20B	109.5
C1—C6—H6	119.8	C19—C20—H20C	109.5
N3—C7—C8	112.66 (12)	H20A—C20—H20C	109.5
N3—C7—C13	127.07 (12)	H20B—C20—H20C	109.5
C7—N3—N4—C18	176.81 (13)	C13—C7—C8—C9	−31.7 (2)
Cl1^i—Sn1—C1—C2	136.51 (11)	N1—C8—C9—C10	0.0 (2)
Cl1—Sn1—C1—C2	−43.49 (11)	C7—C8—C9—C10	−175.13 (14)
Cl2^i—Sn1—C1—C2	45.99 (11)	C8—C9—C10—C11	0.4 (2)
Cl2—Sn1—C1—C2	−134.01 (11)	C9—C10—C11—C12	−0.2 (2)
Cl1^i—Sn1—C1—C6	−40.00 (11)	C8—N1—C12—C11	1.0 (2)
Cl1—Sn1—C1—C6	140.00 (11)	C10—C11—C12—N1	−0.5 (2)
Cl2^i—Sn1—C1—C6	−130.52 (11)	C17—N2—C13—C14	1.6 (2)
Cl2—Sn1—C1—C6	49.48 (11)	C17—N2—C13—C7	178.59 (13)
C6—C1—C2—C3	0.6 (2)	N3—C7—C13—N2	−27.3 (2)
Sn1—C1—C2—C3	−175.98 (11)	C8—C7—C13—N2	151.78 (13)
C1—C2—C3—C4	0.8 (2)	N3—C7—C13—C14	149.66 (14)
C2—C3—C4—C5	−1.8 (2)	C8—C7—C13—C14	−31.21 (19)
C3—C4—C5—C6	1.4 (3)	N2—C13—C14—C15	−0.3 (2)
C4—C5—C6—C1	0.1 (2)	C7—C13—C14—C15	−177.11 (13)
C2—C1—C6—C5	−1.0 (2)	C13—C14—C15—C16	−0.9 (2)
Sn1—C1—C6—C5	175.52 (11)	C14—C15—C16—C17	0.8 (2)
N4—N3—C7—C8	−174.09 (12)	C13—N2—C17—C16	−1.8 (2)
N4—N3—C7—C13	5.1 (2)	C15—C16—C17—N2	0.6 (2)
C12—N1—C8—C9	−0.8 (2)	C19—N5—C18—N4	175.39 (14)
C12—N1—C8—C7	174.71 (13)	C19—N5—C18—S1	−3.2 (2)
N3—C7—C8—N1	−27.67 (17)	N3—N4—C18—N5	13.49 (19)
C13—C7—C8—N1	153.09 (12)	N3—N4—C18—S1	−167.80 (10)
N3—C7—C8—C9	147.51 (14)	C18—N5—C19—C20	95.9 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl2^ii	0.840 (19)	2.421 (19)	3.2279 (13)	161.4 (17)
N4—H4N···N2	0.86 (2)	2.01 (2)	2.6723 (18)	133.0 (17)
N5—H5N···Cl2^ii	0.88 (2)	2.60 (2)	3.3103 (15)	138.7 (17)

Symmetry code: (ii) −x+1, −y+1, −z.