3-(Dimethyl­hydrazino)-2-(methyl­sulfonyl)propenenitrile

In the title compound, C₆H₁₁N₃O₂S, which is an example of a push–pull olefin, a network of N—H...O, C—H...O and C—H...N inter­actions help to establish the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.057
• wR factor = 0.152
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.42 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5C    ..  N1      ..       2.68 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4B    ..  O1      ..       2.62 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A    ..  O1      ..       2.73 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A    ..  O1      ..       2.65 Ang.

   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

3-N,N-dimethylhydrazino-2-methylsulfonyl propenenitrile (Fig. 1) belongs to the so-called push-pull olefins. Push-pull alkenes are substituted ethylenes containing electron- donor groups (D) at one end and electron-acceptor groups (A) at the other end of the general formula D¹D²C=CA¹A². These compounds very often contain alkoxy, amino, alkylamino, dialkylamino or (hetero)aryl groups as electron-donor groups and cyano, acetyl, alkylester, methylsulfonyl or NO₂ groups as electron-acceptor groups. They are useful as starting reactants or intermediates for a lot of pharmaceutical, polymer and other syntheses (Cook, 1969, Dyke, 1973).

Due to the opposite character of the substituents, the olefinic C=C double bond order is reduced and accompanied by the increased bond orders of the bonds between the olefinic carbon atoms and their electron donor and electron acceptor groups, respectively. This leads to the substantial decrease of the rotational barrier about the C=C double bond and to the increase of an analogues barrier about the adjecent bonds. These changes are connected with the separation of the possitive and negative charges and electron delocalization within the π-electron system. Such compounds belong to the most developed structures in the search for new compounds with non-linear optics responses (Nalwa et al., 1997, Chemla & Zyss, 1987).

Related literature

For background literature, see: Cook (1969); Dyke (1973); Chemla & Zyss (1987); Nalwa et al. (1997).

S2. Experimental

2.5 mmol (150 mg) of 1,1-dimethylhydrazine was added at room temperature to 2.5 mmol (438 mg) of 3-ethoxy-2-methylsulfonylpropenenitrile (acrylonitrile) without any solvent. The reaction mixture became hot and after 10 min. of stirring ethanol (formed by the reaction) was removed and the crude product was recrystallized from ethyl acetate-hexane (1:4 v/v), to yield a light yellow powder (86%). Recrystallization from chloroform gave pink blocks of (I).

S3. Refinement

The H atoms were geometrically placed (C—H = 0.93–0.96 Å, N—H = 0.86 Å) and refined as riding with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXS97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level (arbitrary spheres for the H atoms).
	Fig. 2. Packing diagram of (I). Hydrogen-bond interactions are indicated by dashed lines.

3-N,N-dimethylhydrazino-2-methylsulfonyl propenenitrile

Crystal data

C6H11N3O2S	F(000) = 400
Mr = 189.24	Dx = 1.425 Mg m^−3
Monoclinic, P21/c	Melting point: 421 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.526 (2) Å	Cell parameters from 5328 reflections
b = 6.881 (1) Å	θ = 3.5–27.9°
c = 11.577 (2) Å	µ = 0.33 mm^−1
β = 106.06 (3)°	T = 100 K
V = 882.4 (3) Å^3	Slab, pink
Z = 4	0.28 × 0.24 × 0.04 mm

Data collection

Oxford Diffraction GEMINI R diffractometer	1606 independent reflections
Radiation source: fine-focus sealed tube	1310 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Rotation method data acquisition using ω and phi scans	θmax = 25.3°, θmin = 4.2°
Absorption correction: analytical (Clark & Reid, 1995)	h = −13→13
Tmin = 0.935, Tmax = 0.987	k = −8→8
14473 measured reflections	l = −13→13

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.152	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.082P)^2 + 1.0681P] where P = (Fo^2 + 2Fc^2)/3
1606 reflections	(Δ/σ)max = 0.003
113 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006)

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
S1	0.90922 (6)	0.76365 (10)	0.88325 (6)	0.0210 (3)
N1	0.6238 (2)	0.8154 (4)	0.6634 (2)	0.0294 (6)
N3	0.6663 (2)	0.3452 (3)	0.6091 (2)	0.0226 (6)
N2	0.7653 (2)	0.2899 (4)	0.7060 (2)	0.0239 (6)
H2A	0.7844	0.1691	0.7171	0.029*
C2	0.8065 (2)	0.6173 (4)	0.7816 (2)	0.0221 (6)
C1	0.7039 (3)	0.7189 (4)	0.7119 (2)	0.0213 (6)
C6	0.5527 (3)	0.3072 (5)	0.6390 (3)	0.0280 (7)
H6C	0.4860	0.3464	0.5731	0.034*
H6B	0.5514	0.3794	0.7096	0.034*
H6A	0.5464	0.1709	0.6539	0.034*
C3	0.8286 (3)	0.4217 (4)	0.7794 (2)	0.0223 (6)
H3A	0.8966	0.3766	0.8369	0.027*
C5	0.6735 (3)	0.2423 (4)	0.5005 (3)	0.0256 (7)
H5C	0.6078	0.2823	0.4338	0.031*
H5B	0.6685	0.1048	0.5124	0.031*
H5A	0.7487	0.2724	0.4842	0.031*
O1	1.02390 (17)	0.6673 (3)	0.91967 (17)	0.0247 (5)
O2	0.90420 (19)	0.9546 (3)	0.82968 (18)	0.0287 (5)
C4	0.8543 (3)	0.7845 (4)	1.0102 (3)	0.0248 (7)
H4C	0.9053	0.8710	1.0673	0.030*
H4B	0.8542	0.6588	1.0462	0.030*
H4A	0.7736	0.8350	0.9864	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0198 (4)	0.0233 (4)	0.0185 (4)	−0.0014 (3)	0.0031 (3)	0.0009 (3)
N1	0.0256 (14)	0.0259 (13)	0.0308 (14)	0.0016 (12)	−0.0021 (11)	−0.0010 (11)
N3	0.0220 (12)	0.0246 (13)	0.0186 (12)	0.0045 (10)	0.0011 (10)	−0.0013 (10)
N2	0.0258 (13)	0.0223 (12)	0.0215 (13)	0.0062 (10)	0.0029 (10)	0.0018 (10)
C2	0.0199 (14)	0.0256 (15)	0.0186 (14)	0.0013 (12)	0.0020 (11)	0.0018 (12)
C1	0.0206 (15)	0.0246 (14)	0.0175 (14)	−0.0047 (12)	0.0030 (11)	−0.0033 (11)
C6	0.0265 (16)	0.0295 (16)	0.0277 (16)	−0.0008 (13)	0.0071 (13)	0.0000 (13)
C3	0.0212 (14)	0.0273 (15)	0.0177 (13)	0.0003 (12)	0.0041 (11)	0.0014 (12)
C5	0.0255 (16)	0.0286 (16)	0.0204 (15)	0.0016 (12)	0.0026 (12)	−0.0047 (12)
O1	0.0213 (11)	0.0276 (11)	0.0234 (10)	0.0002 (9)	0.0030 (8)	0.0022 (9)
O2	0.0302 (12)	0.0242 (11)	0.0275 (11)	−0.0044 (9)	0.0011 (9)	0.0041 (9)
C4	0.0241 (15)	0.0287 (15)	0.0201 (15)	−0.0011 (12)	0.0036 (12)	−0.0052 (12)

Geometric parameters (Å, º)

S1—O1	1.434 (2)	C2—C1	1.418 (4)
S1—O2	1.447 (2)	C6—H6C	0.9600
S1—C2	1.740 (3)	C6—H6B	0.9600
S1—C4	1.759 (3)	C6—H6A	0.9600
N1—C1	1.150 (4)	C3—H3A	0.9300
N3—N2	1.413 (3)	C5—H5C	0.9600
N3—C5	1.465 (4)	C5—H5B	0.9600
N3—C6	1.468 (4)	C5—H5A	0.9600
N2—C3	1.317 (4)	C4—H4C	0.9600
N2—H2A	0.8600	C4—H4B	0.9600
C2—C3	1.371 (4)	C4—H4A	0.9600
O1—S1—O2	118.04 (13)	N3—C6—H6A	109.5
O1—S1—C2	109.30 (13)	H6C—C6—H6A	109.5
O2—S1—C2	107.24 (13)	H6B—C6—H6A	109.5
O1—S1—C4	107.89 (13)	N2—C3—C2	128.0 (3)
O2—S1—C4	107.64 (14)	N2—C3—H3A	116.0
C2—S1—C4	106.12 (14)	C2—C3—H3A	116.0
N2—N3—C5	109.0 (2)	N3—C5—H5C	109.5
N2—N3—C6	110.0 (2)	N3—C5—H5B	109.5
C5—N3—C6	112.5 (2)	H5C—C5—H5B	109.5
C3—N2—N3	120.5 (2)	N3—C5—H5A	109.5
C3—N2—H2A	119.7	H5C—C5—H5A	109.5
N3—N2—H2A	119.7	H5B—C5—H5A	109.5
C3—C2—C1	127.1 (3)	S1—C4—H4C	109.5
C3—C2—S1	119.0 (2)	S1—C4—H4B	109.5
C1—C2—S1	113.8 (2)	H4C—C4—H4B	109.5
N1—C1—C2	173.4 (3)	S1—C4—H4A	109.5
N3—C6—H6C	109.5	H4C—C4—H4A	109.5
N3—C6—H6B	109.5	H4B—C4—H4A	109.5
H6C—C6—H6B	109.5
C5—N3—N2—C3	134.3 (3)	O2—S1—C2—C1	−32.2 (2)
C6—N3—N2—C3	−101.9 (3)	C4—S1—C2—C1	82.6 (2)
O1—S1—C2—C3	21.2 (3)	N3—N2—C3—C2	5.4 (4)
O2—S1—C2—C3	150.3 (2)	C1—C2—C3—N2	6.4 (5)
C4—S1—C2—C3	−94.9 (3)	S1—C2—C3—N2	−176.5 (2)
O1—S1—C2—C1	−161.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1	0.93	2.51	2.922 (4)	107
C5—H5C···N1^i	0.96	2.68	3.449 (5)	138
C6—H6A···N1^ii	0.96	2.60	3.475 (2)	152
C4—H4B···O1^iii	0.96	2.62	3.415 (4)	141
C3—H3A···O1^iii	0.93	2.73	3.482 (5)	139
C5—H5A···O1^iv	0.96	2.65	3.392 (3)	135
N2—H2A···O2^ii	0.86	2.19	2.944 (2)	147
C4—H4C···O2^v	0.96	2.50	3.399 (4)	156

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