Secondary bonding in di­methyl­bis­(morpholine-4-carbodi­thio­ato-κ²S,S′)tin(IV): crystal structure and Hirshfeld surface analysis

In (CH₃)₂Sn[S₂CN(CH₂CH₂)₂O]₂, a skew-trapezoidal bipyramidal coordination geometry based on a C₂S₄ donor set is found. Secondary Sn...S inter­actions lead to centrosymmetric dimeric aggregates in the crystal.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.024
• wR factor = 0.065
• Data-to-parameter ratio = 20.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT977_ALERT_2_C Check the Negative Difference Density on    H11C      -0.32 eA-3

Alert level G
PLAT142_ALERT_4_G s.u. on b - Axis Small or Missing ..............    0.00010 Ang.
PLAT143_ALERT_4_G s.u. on c - Axis Small or Missing ..............    0.00010 Ang.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Sn     --  S2      ..        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Sn     --  S4      ..        8.7 s.u.
PLAT398_ALERT_2_G Deviating  C-O-C  Angle from 120 Deg for O1           109.5 Degree
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         35 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Note

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Dimethylbis(morpholine-4-carbodithioato-κ²S,S')tin(IV)

Crystal data

[Sn(CH3)2(C5H8NOS2)2]	F(000) = 952
Mr = 473.24	Dx = 1.699 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.1472 (1) Å	Cell parameters from 14936 reflections
b = 13.6653 (1) Å	θ = 3.2–76.6°
c = 13.8122 (1) Å	µ = 15.25 mm^−1
β = 104.959 (1)°	T = 100 K
V = 1850.36 (3) Å^3	Prism, colourless
Z = 4	0.24 × 0.09 × 0.06 mm

Data collection

Agilent SuperNova, Dual, Cu at zero, AtlasS2 diffractometer	3865 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	3809 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.031
ω scans	θmax = 76.8°, θmin = 4.6°
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −12→12
Tmin = 0.242, Tmax = 0.759	k = −13→17
19588 measured reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0322P)^2 + 2.5554P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3865 reflections	Δρmax = 0.45 e Å^−3
192 parameters	Δρmin = −0.50 e Å^−3

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
Sn	0.54609 (2)	0.47196 (2)	0.20083 (2)	0.01811 (6)
S1	0.60114 (7)	0.47340 (5)	0.39117 (5)	0.02266 (14)
S2	0.76105 (7)	0.60660 (4)	0.29478 (4)	0.02164 (13)
S3	0.36959 (7)	0.34005 (5)	0.20926 (4)	0.02368 (13)
S4	0.38512 (7)	0.40224 (5)	0.00694 (4)	0.02491 (14)
O1	0.9722 (2)	0.62761 (17)	0.68544 (15)	0.0315 (4)
O2	−0.1073 (2)	0.28893 (17)	−0.02186 (16)	0.0334 (5)
N1	0.7980 (2)	0.59004 (16)	0.49256 (16)	0.0216 (4)
N2	0.1802 (2)	0.29886 (17)	0.04134 (16)	0.0235 (5)
C1	0.7294 (3)	0.56096 (18)	0.40120 (18)	0.0188 (5)
C2	0.8983 (3)	0.6702 (2)	0.5084 (2)	0.0245 (5)
H2A	0.8543	0.7321	0.5205	0.029*
H2B	0.9318	0.6786	0.4477	0.029*
C3	1.0169 (3)	0.6474 (2)	0.5975 (2)	0.0294 (6)
H3A	1.0670	0.5899	0.5817	0.035*
H3B	1.0805	0.7036	0.6103	0.035*
C4	0.8853 (3)	0.5444 (2)	0.6688 (2)	0.0285 (6)
H4A	0.8579	0.5290	0.7309	0.034*
H4B	0.9355	0.4874	0.6522	0.034*
C5	0.7594 (3)	0.5622 (2)	0.58459 (19)	0.0253 (5)
H5A	0.7031	0.5021	0.5722	0.030*
H5B	0.7044	0.6151	0.6037	0.030*
C6	0.2990 (3)	0.34278 (18)	0.07953 (18)	0.0202 (5)
C7	0.1020 (3)	0.2459 (2)	0.1005 (2)	0.0267 (6)
H7A	0.1494	0.2502	0.1726	0.032*
H7B	0.0943	0.1760	0.0810	0.032*
C8	−0.0379 (3)	0.2905 (2)	0.0819 (2)	0.0310 (6)
H8A	−0.0919	0.2539	0.1201	0.037*
H8B	−0.0296	0.3590	0.1061	0.037*
C9	−0.0330 (3)	0.3430 (2)	−0.0777 (2)	0.0303 (6)
H9A	−0.0261	0.4120	−0.0551	0.036*
H9B	−0.0829	0.3418	−0.1495	0.036*
C10	0.1087 (3)	0.3021 (2)	−0.06570 (19)	0.0249 (5)
H10A	0.1028	0.2354	−0.0945	0.030*
H10B	0.1599	0.3439	−0.1020	0.030*
C11	0.4147 (3)	0.5961 (2)	0.1692 (2)	0.0260 (5)
H11A	0.4573	0.6513	0.2110	0.039*
H11B	0.3275	0.5803	0.1837	0.039*
H11C	0.3987	0.6137	0.0983	0.039*
C12	0.7041 (3)	0.38945 (19)	0.1667 (2)	0.0242 (5)
H12A	0.7154	0.4095	0.1012	0.036*
H12B	0.6809	0.3197	0.1650	0.036*
H12C	0.7894	0.4008	0.2181	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn	0.02190 (10)	0.01935 (10)	0.01260 (9)	0.00090 (6)	0.00357 (6)	−0.00052 (5)
S1	0.0275 (3)	0.0258 (3)	0.0140 (3)	−0.0074 (2)	0.0041 (2)	−0.0009 (2)
S2	0.0290 (3)	0.0213 (3)	0.0154 (3)	−0.0032 (2)	0.0069 (2)	−0.0006 (2)
S3	0.0290 (3)	0.0286 (3)	0.0117 (3)	−0.0060 (2)	0.0022 (2)	0.0025 (2)
S4	0.0282 (3)	0.0332 (3)	0.0131 (3)	−0.0068 (3)	0.0051 (2)	0.0014 (2)
O1	0.0294 (10)	0.0400 (11)	0.0208 (9)	−0.0022 (9)	−0.0013 (8)	−0.0006 (8)
O2	0.0246 (10)	0.0416 (12)	0.0313 (11)	−0.0046 (9)	0.0025 (8)	−0.0013 (9)
N1	0.0257 (11)	0.0236 (10)	0.0149 (10)	−0.0024 (9)	0.0041 (8)	−0.0016 (8)
N2	0.0258 (11)	0.0271 (11)	0.0163 (10)	−0.0043 (9)	0.0033 (9)	0.0012 (9)
C1	0.0234 (12)	0.0153 (11)	0.0168 (11)	0.0006 (9)	0.0036 (9)	−0.0018 (9)
C2	0.0249 (13)	0.0256 (13)	0.0201 (12)	−0.0042 (10)	0.0007 (10)	−0.0027 (10)
C3	0.0248 (13)	0.0337 (15)	0.0273 (14)	0.0014 (11)	0.0023 (11)	0.0002 (12)
C4	0.0323 (15)	0.0301 (14)	0.0208 (13)	0.0020 (12)	0.0029 (11)	0.0029 (11)
C5	0.0291 (14)	0.0320 (14)	0.0140 (11)	−0.0044 (11)	0.0040 (10)	−0.0019 (10)
C6	0.0233 (12)	0.0204 (11)	0.0160 (11)	0.0013 (9)	0.0037 (9)	−0.0002 (9)
C7	0.0293 (14)	0.0290 (13)	0.0212 (12)	−0.0091 (11)	0.0053 (11)	0.0022 (11)
C8	0.0284 (14)	0.0373 (15)	0.0278 (14)	−0.0074 (12)	0.0083 (11)	−0.0038 (12)
C9	0.0300 (14)	0.0314 (15)	0.0253 (13)	−0.0019 (12)	−0.0002 (11)	−0.0020 (11)
C10	0.0265 (13)	0.0295 (13)	0.0161 (12)	−0.0074 (11)	0.0010 (10)	−0.0027 (10)
C11	0.0279 (13)	0.0244 (13)	0.0260 (13)	0.0111 (11)	0.0074 (11)	0.0042 (10)
C12	0.0264 (13)	0.0222 (12)	0.0228 (12)	0.0052 (10)	0.0043 (10)	−0.0042 (10)

Geometric parameters (Å, º)

Sn—S1	2.5429 (6)	C3—H3A	0.9900
Sn—S2	2.8923 (6)	C3—H3B	0.9900
Sn—S3	2.5649 (7)	C4—C5	1.509 (4)
Sn—S4	2.9137 (6)	C4—H4A	0.9900
Sn—C11	2.132 (3)	C4—H4B	0.9900
Sn—C12	2.111 (3)	C5—H5A	0.9900
C1—S1	1.747 (3)	C5—H5B	0.9900
C1—S2	1.702 (3)	C7—C8	1.505 (4)
C6—S3	1.750 (3)	C7—H7A	0.9900
C6—S4	1.697 (3)	C7—H7B	0.9900
O1—C4	1.421 (4)	C8—H8A	0.9900
O1—C3	1.428 (4)	C8—H8B	0.9900
O2—C9	1.418 (4)	C9—C10	1.512 (4)
O2—C8	1.424 (4)	C9—H9A	0.9900
N1—C1	1.335 (3)	C9—H9B	0.9900
N1—C2	1.472 (3)	C10—H10A	0.9900
N1—C5	1.473 (3)	C10—H10B	0.9900
N2—C6	1.328 (4)	C11—H11A	0.9800
N2—C7	1.468 (3)	C11—H11B	0.9800
N2—C10	1.470 (3)	C11—H11C	0.9800
C2—C3	1.515 (4)	C12—H12A	0.9800
C2—H2A	0.9900	C12—H12B	0.9800
C2—H2B	0.9900	C12—H12C	0.9800
S1—Sn—S2	65.935 (19)	H4A—C4—H4B	108.0
S1—Sn—S3	85.878 (19)	N1—C5—C4	110.3 (2)
S1—Sn—S4	150.95 (2)	N1—C5—H5A	109.6
S1—Sn—C11	99.49 (8)	C4—C5—H5A	109.6
S1—Sn—C12	104.96 (8)	N1—C5—H5B	109.6
S2—Sn—S3	151.798 (18)	C4—C5—H5B	109.6
S2—Sn—S4	143.066 (18)	H5A—C5—H5B	108.1
S2—Sn—C11	86.87 (8)	N2—C6—S4	122.32 (19)
S2—Sn—C12	84.93 (8)	N2—C6—S3	119.1 (2)
S3—Sn—S4	65.137 (18)	S4—C6—S3	118.56 (15)
S3—Sn—C12	102.37 (8)	N2—C7—C8	109.1 (2)
S3—Sn—C11	99.28 (8)	N2—C7—H7A	109.9
S4—Sn—C11	84.20 (8)	C8—C7—H7A	109.9
S4—Sn—C12	84.15 (7)	N2—C7—H7B	109.9
C11—Sn—C12	148.24 (11)	C8—C7—H7B	109.9
C1—S1—Sn	92.73 (8)	H7A—C7—H7B	108.3
C1—S2—Sn	82.29 (9)	O2—C8—C7	111.4 (2)
C6—S3—Sn	92.55 (9)	O2—C8—H8A	109.3
C6—S4—Sn	82.27 (9)	C7—C8—H8A	109.3
C4—O1—C3	109.5 (2)	O2—C8—H8B	109.3
C9—O2—C8	110.2 (2)	C7—C8—H8B	109.3
C1—N1—C2	122.2 (2)	H8A—C8—H8B	108.0
C1—N1—C5	123.3 (2)	O2—C9—C10	111.8 (2)
C2—N1—C5	113.0 (2)	O2—C9—H9A	109.2
C6—N2—C7	124.6 (2)	C10—C9—H9A	109.2
C6—N2—C10	123.2 (2)	O2—C9—H9B	109.2
C7—N2—C10	112.2 (2)	C10—C9—H9B	109.2
N1—C1—S2	122.6 (2)	H9A—C9—H9B	107.9
N1—C1—S1	118.35 (19)	N2—C10—C9	109.3 (2)
S2—C1—S1	119.04 (14)	N2—C10—H10A	109.8
N1—C2—C3	110.0 (2)	C9—C10—H10A	109.8
N1—C2—H2A	109.7	N2—C10—H10B	109.8
C3—C2—H2A	109.7	C9—C10—H10B	109.8
N1—C2—H2B	109.7	H10A—C10—H10B	108.3
C3—C2—H2B	109.7	Sn—C11—H11A	109.5
H2A—C2—H2B	108.2	Sn—C11—H11B	109.5
O1—C3—C2	111.7 (2)	H11A—C11—H11B	109.5
O1—C3—H3A	109.3	Sn—C11—H11C	109.5
C2—C3—H3A	109.3	H11A—C11—H11C	109.5
O1—C3—H3B	109.3	H11B—C11—H11C	109.5
C2—C3—H3B	109.3	Sn—C12—H12A	109.5
H3A—C3—H3B	107.9	Sn—C12—H12B	109.5
O1—C4—C5	111.3 (2)	H12A—C12—H12B	109.5
O1—C4—H4A	109.4	Sn—C12—H12C	109.5
C5—C4—H4A	109.4	H12A—C12—H12C	109.5
O1—C4—H4B	109.4	H12B—C12—H12C	109.5
C5—C4—H4B	109.4
C2—N1—C1—S2	5.5 (4)	C7—N2—C6—S4	179.6 (2)
C5—N1—C1—S2	171.0 (2)	C10—N2—C6—S4	−3.5 (4)
C2—N1—C1—S1	−173.9 (2)	C7—N2—C6—S3	−0.7 (4)
C5—N1—C1—S1	−8.4 (3)	C10—N2—C6—S3	176.2 (2)
Sn—S2—C1—N1	179.7 (2)	Sn—S4—C6—N2	168.6 (2)
Sn—S2—C1—S1	−0.98 (13)	Sn—S4—C6—S3	−11.13 (13)
Sn—S1—C1—N1	−179.5 (2)	Sn—S3—C6—N2	−167.2 (2)
Sn—S1—C1—S2	1.11 (15)	Sn—S3—C6—S4	12.56 (15)
C1—N1—C2—C3	−143.1 (3)	C6—N2—C7—C8	122.6 (3)
C5—N1—C2—C3	50.1 (3)	C10—N2—C7—C8	−54.6 (3)
C4—O1—C3—C2	61.3 (3)	C9—O2—C8—C7	−60.3 (3)
N1—C2—C3—O1	−55.1 (3)	N2—C7—C8—O2	57.4 (3)
C3—O1—C4—C5	−61.7 (3)	C8—O2—C9—C10	59.5 (3)
C1—N1—C5—C4	142.5 (3)	C6—N2—C10—C9	−123.5 (3)
C2—N1—C5—C4	−50.8 (3)	C7—N2—C10—C9	53.7 (3)
O1—C4—C5—N1	56.3 (3)	O2—C9—C10—N2	−55.8 (3)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the (C8–C13) ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···S1^i	0.99	2.86	3.809 (3)	161
C12—H12C···O1^ii	0.98	2.47	3.399 (4)	158

Symmetry codes: (i) x−3/2, −y−1/2, z−3/2; (ii) −x+2, −y+1, −z+1.