2-(4-Chloro­phenyl)-4,4-bis­(methyl­sulfanyl)-1,3-buta­diene-1,1-dicarbo­nitrile

The title complex, C₁₄H₁₁ClN₂S₂, is an example of a push–pull buta­diene. Typical π-electron delocalization along the buta­diene moiety, influenced by the donor and acceptor groups, is observed.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.102
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT703_ALERT_1_A Torsion Calc    179.3(2), Rep    0.72(18), Dev..     892.90 Sigma
              CL1 -C1  -C2  -C3     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc     -2.8(4), Rep      2.7(3), Dev..      13.75 Sigma
              C2  -C3  -C4  -C5     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc    177.1(2), Rep      2.9(2), Dev..     871.00 Sigma
              C2  -C3  -C4  -C7     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -178.9(2), Rep      1.1(2), Dev..     900.00 Sigma
              C7  -C4  -C5  -C6     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc     -2.1(4), Rep      2.1(4), Dev..      10.50 Sigma
              C2  -C1  -C6  -C5     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc    179.0(2), Rep    1.03(18), Dev..     889.85 Sigma
              CL1 -C1  -C6  -C5     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -111.2(3), Rep     68.8(2), Dev..     600.00 Sigma
              C5  -C4  -C7  -C8     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -111.3(3), Rep     68.7(3), Dev..     600.00 Sigma
              C3  -C4  -C7  -C9     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -176.9(2), Rep      3.1(2), Dev..     900.00 Sigma
              C4  -C7  -C8  -C11    1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -175.8(2), Rep      4.2(2), Dev..     900.00 Sigma
              C9  -C7  -C8  -C10    1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -166.9(3), Rep     13.0(2), Dev..     599.67 Sigma
              C8  -C7  -C9  -C12    1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc    179.3(2), Rep    0.65(19), Dev..     893.25 Sigma
              C7  -C9  -C12 -S2     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc    173.9(2), Rep      6.1(2), Dev..     839.00 Sigma
              C13 -S1  -C12 -C9     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc   -5.90(19), Rep    5.88(17), Dev..      62.00 Sigma
              C13 -S1  -C12 -S2     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc    -11.5(3), Rep     11.5(2), Dev..      76.67 Sigma
              C14 -S2  -C12 -C9     1.555   1.555   1.555   1.555
PLAT703_ALERT_1_A Torsion Calc  168.31(15), Rep   11.69(14), Dev..    1044.13 Sigma
              C14 -S2  -C12 -S1     1.555   1.555   1.555   1.555

Alert level B
PLAT703_ALERT_1_B Torsion Calc     -0.5(4), Rep      0.4(4), Dev..       2.25 Sigma
              C7  -C9  -C12 -S1     1.555   1.555   1.555   1.555

Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C10    ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C11    ...       1.43 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            C7  -C8  -C10 -N1     53.00  9.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         22
            C7  -C8  -C11 -N2     13.00  7.00   1.555   1.555   1.555   1.555

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

  17 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
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: P3/P4-PC (Siemens, 1989); cell refinement: P3/P4-PC; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

2-(4-Chlorophenyl)-4,4-bis(methylsulfanyl)-1,3-butadiene-1,1-dicarbonitrile

Crystal data

C14H11ClN2S2	F(000) = 632
Mr = 306.82	Dx = 1.365 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 40 reflections
a = 9.1633 (18) Å	θ = 5.0–15.0°
b = 11.836 (2) Å	µ = 0.52 mm^−1
c = 13.911 (3) Å	T = 296 K
β = 98.40 (3)°	Block, yellow
V = 1492.6 (5) Å^3	0.55 × 0.40 × 0.40 mm
Z = 4

Data collection

Siemens P3 diffractometer	Rint = 0.024
Radiation source: normal-focus sealed tube	θmax = 27.6°, θmin = 2.3°
Graphite monochromator	h = 0→11
θ–2θ scans	k = 0→15
3649 measured reflections	l = −18→17
3442 independent reflections	3 standard reflections every 300 reflections
2345 reflections with I > 2σ(I)	intensity decay: <2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 0.6836P] where P = (Fo^2 + 2Fc^2)/3
3442 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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
Cl1	0.26745 (10)	0.97560 (7)	0.49461 (5)	0.0814 (3)
S1	0.12018 (8)	0.87710 (6)	0.10780 (5)	0.05283 (18)
S2	0.14420 (9)	0.84396 (6)	−0.09845 (5)	0.0594 (2)
N1	0.5335 (3)	1.3189 (2)	0.19990 (17)	0.0707 (7)
N2	0.4318 (3)	1.2400 (2)	−0.10914 (17)	0.0644 (6)
C1	0.2917 (3)	1.0080 (2)	0.37617 (16)	0.0487 (6)
C2	0.2142 (3)	1.0966 (2)	0.33022 (18)	0.0512 (6)
H2	0.1490	1.1380	0.3617	0.061*
C3	0.2345 (3)	1.12338 (19)	0.23643 (17)	0.0456 (5)
H3	0.1849	1.1849	0.2054	0.055*
C4	0.3274 (2)	1.05992 (17)	0.18836 (15)	0.0379 (5)
C5	0.4049 (3)	0.97193 (19)	0.23698 (17)	0.0459 (5)
H5	0.4690	0.9293	0.2055	0.055*
C6	0.3886 (3)	0.9464 (2)	0.33146 (17)	0.0501 (6)
H6	0.4428	0.8880	0.3643	0.060*
C7	0.3433 (2)	1.08571 (18)	0.08595 (15)	0.0393 (5)
C8	0.4130 (3)	1.18447 (18)	0.06690 (16)	0.0424 (5)
C9	0.2899 (3)	1.01202 (19)	0.00832 (15)	0.0432 (5)
H9	0.3235	1.0272	−0.0503	0.052*
C10	0.4782 (3)	1.2594 (2)	0.14157 (18)	0.0496 (6)
C11	0.4253 (3)	1.2169 (2)	−0.03036 (19)	0.0483 (6)
C12	0.1962 (3)	0.92205 (19)	0.00705 (16)	0.0424 (5)
C13	−0.0076 (3)	0.7681 (2)	0.06349 (19)	0.0587 (7)
H13A	−0.0539	0.7393	0.1161	0.088*
H13B	0.0440	0.7081	0.0365	0.088*
H13C	−0.0814	0.7985	0.0142	0.088*
C14	0.2045 (3)	0.9234 (2)	−0.19412 (17)	0.0651 (8)
H14A	0.1785	0.8840	−0.2545	0.098*
H14B	0.3096	0.9327	−0.1812	0.098*
H14C	0.1579	0.9962	−0.1982	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1117 (7)	0.0860 (6)	0.0491 (4)	−0.0068 (5)	0.0209 (4)	0.0102 (4)
S1	0.0604 (4)	0.0474 (4)	0.0501 (3)	−0.0151 (3)	0.0060 (3)	−0.0019 (3)
S2	0.0747 (5)	0.0505 (4)	0.0509 (4)	−0.0133 (3)	0.0018 (3)	−0.0121 (3)
N1	0.0828 (18)	0.0620 (15)	0.0673 (15)	−0.0199 (13)	0.0108 (13)	−0.0181 (12)
N2	0.0828 (17)	0.0560 (14)	0.0575 (13)	−0.0052 (12)	0.0202 (12)	0.0066 (11)
C1	0.0574 (15)	0.0473 (14)	0.0407 (12)	−0.0113 (12)	0.0045 (11)	0.0020 (10)
C2	0.0516 (15)	0.0512 (15)	0.0528 (14)	0.0030 (12)	0.0141 (12)	−0.0058 (12)
C3	0.0476 (13)	0.0373 (12)	0.0512 (13)	0.0050 (11)	0.0053 (11)	0.0015 (10)
C4	0.0391 (12)	0.0317 (11)	0.0416 (11)	−0.0026 (9)	0.0017 (9)	−0.0015 (9)
C5	0.0488 (14)	0.0404 (13)	0.0475 (12)	0.0066 (11)	0.0041 (10)	−0.0022 (10)
C6	0.0587 (15)	0.0387 (13)	0.0497 (13)	0.0044 (12)	−0.0030 (11)	0.0049 (11)
C7	0.0402 (12)	0.0352 (11)	0.0418 (11)	0.0003 (10)	0.0040 (9)	0.0001 (9)
C8	0.0459 (13)	0.0372 (12)	0.0442 (12)	−0.0004 (10)	0.0070 (10)	−0.0010 (10)
C9	0.0510 (14)	0.0407 (12)	0.0382 (11)	−0.0012 (11)	0.0071 (10)	−0.0014 (9)
C10	0.0532 (15)	0.0423 (13)	0.0547 (14)	−0.0057 (11)	0.0125 (12)	−0.0023 (11)
C11	0.0530 (15)	0.0375 (12)	0.0555 (14)	−0.0041 (11)	0.0124 (12)	−0.0011 (11)
C12	0.0450 (13)	0.0366 (12)	0.0438 (12)	0.0031 (10)	0.0004 (10)	−0.0012 (10)
C13	0.0550 (16)	0.0508 (15)	0.0674 (16)	−0.0145 (13)	−0.0013 (13)	0.0024 (13)
C14	0.081 (2)	0.0671 (18)	0.0444 (14)	−0.0038 (16)	0.0010 (13)	−0.0087 (13)

Geometric parameters (Å, º)

Cl1—C1	1.737 (2)	C5—C6	1.378 (3)
S1—C12	1.737 (2)	C5—H5	0.9300
S1—C13	1.790 (3)	C6—H6	0.9300
S2—C12	1.741 (2)	C7—C8	1.376 (3)
S2—C14	1.782 (3)	C7—C9	1.419 (3)
N1—C10	1.136 (3)	C8—C11	1.427 (3)
N2—C11	1.140 (3)	C8—C10	1.429 (3)
C1—C6	1.368 (3)	C9—C12	1.366 (3)
C1—C2	1.371 (3)	C9—H9	0.9300
C2—C3	1.381 (3)	C13—H13A	0.9600
C2—H2	0.9300	C13—H13B	0.9600
C3—C4	1.380 (3)	C13—H13C	0.9600
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.381 (3)	C14—H14B	0.9600
C4—C7	1.485 (3)	C14—H14C	0.9600
C12—S1—C13	105.20 (12)	C7—C8—C11	121.0 (2)
C12—S2—C14	105.84 (12)	C7—C8—C10	122.9 (2)
C6—C1—C2	121.5 (2)	C11—C8—C10	116.1 (2)
C6—C1—Cl1	119.65 (19)	C12—C9—C7	129.5 (2)
C2—C1—Cl1	118.8 (2)	C12—C9—H9	115.3
C1—C2—C3	118.9 (2)	C7—C9—H9	115.3
C1—C2—H2	120.5	N1—C10—C8	178.1 (3)
C3—C2—H2	120.5	N2—C11—C8	177.7 (3)
C4—C3—C2	120.7 (2)	C9—C12—S1	123.60 (18)
C4—C3—H3	119.6	C9—C12—S2	121.26 (18)
C2—C3—H3	119.6	S1—C12—S2	115.13 (13)
C3—C4—C5	118.9 (2)	S1—C13—H13A	109.5
C3—C4—C7	120.5 (2)	S1—C13—H13B	109.5
C5—C4—C7	120.6 (2)	H13A—C13—H13B	109.5
C6—C5—C4	120.9 (2)	S1—C13—H13C	109.5
C6—C5—H5	119.6	H13A—C13—H13C	109.5
C4—C5—H5	119.6	H13B—C13—H13C	109.5
C1—C6—C5	119.0 (2)	S2—C14—H14A	109.5
C1—C6—H6	120.5	S2—C14—H14B	109.5
C5—C6—H6	120.5	H14A—C14—H14B	109.5
C8—C7—C9	119.6 (2)	S2—C14—H14C	109.5
C8—C7—C4	118.21 (19)	H14A—C14—H14C	109.5
C9—C7—C4	122.19 (19)	H14B—C14—H14C	109.5
C6—C1—C2—C3	0.3 (4)	C9—C7—C8—C11	3.4 (3)
Cl1—C1—C2—C3	0.72 (18)	C4—C7—C8—C11	3.1 (2)
C1—C2—C3—C4	2.1 (4)	C9—C7—C8—C10	4.2 (2)
C2—C3—C4—C5	2.7 (3)	C4—C7—C8—C10	3.9 (3)
C2—C3—C4—C7	2.9 (2)	C8—C7—C9—C12	13.0 (2)
C3—C4—C5—C6	0.9 (3)	C4—C7—C9—C12	13.3 (4)
C7—C4—C5—C6	1.1 (2)	C7—C8—C10—N1	53 (9)
C2—C1—C6—C5	2.1 (4)	C7—C8—C11—N2	13 (7)
Cl1—C1—C6—C5	1.03 (18)	C7—C9—C12—S1	0.4 (4)
C4—C5—C6—C1	1.4 (4)	C7—C9—C12—S2	0.65 (19)
C3—C4—C7—C8	69.0 (3)	C13—S1—C12—C9	6.1 (2)
C5—C4—C7—C8	68.8 (2)	C13—S1—C12—S2	5.88 (17)
C3—C4—C7—C9	68.7 (3)	C14—S2—C12—C9	11.5 (2)
C5—C4—C7—C9	68.5 (3)	C14—S2—C12—S1	11.69 (14)