A new monoclinic polymorph of 3-diethyl-amino-4-(4-meth-oxy-phen-yl)-1,1-dioxo-4H-1λ,2-thia-zete-4-carbonitrile.

A new monoclinic form of the title compound, C(14)H(17)N(3)O(3)S, has been found upon slow crystallization from water. Another monoclinic form of the compound was obtained previously from a mixture of dichloro-methane and diethyl ether [Clerici et al. (2002 ▶). Tetra-hedron, 58, 5173-5178]. Both phases crystallize in space group P2(1)/n with one mol-ecule in the asymmetric unit. The formally single exocyclic C-N bond that connects the -NEt(2) unit with the thia-zete ring is considerably shorter than the adjacent, formally double, endocyclic C=N bond. This is likely to be due to the extended conjugated system between the electron-donor diethyl-ammine fragment and the electron-withdrawing sulfonyl group. In the newly discovered polymorph, the meth-oxy group is rotated by almost 180° around the phen-yl-OCH(3) bond, resulting in a different mol-ecular conformation.

Related literature

For the synthesis of the title compound and the crystal structure of the other polymorph, see: Clerici et al. (2002 ▶). For a related structure, see: Clerici et al. (1996 ▶). For the biological activity of β-sultam derivatives, see: Barwick et al. (2008 ▶) and references therein.

Experimental

Crystal data

C14H17N3O3S

M = 307.37

Monoclinic,

a = 8.3853 (17) Å

b = 17.554 (4) Å

c = 10.458 (2) Å

β = 95.07 (3)°

V = 1533.4 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 293 K

0.18 × 0.16 × 0.16 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.855, T max = 0.947

16661 measured reflections

2814 independent reflections

1949 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.01

2814 reflections

258 parameters

All H-atom parameters refined

Δρmax = 0.16 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810027558/nk2045sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027558/nk2045Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H17N3O3S	F(000) = 648
Mr = 307.37	Dx = 1.331 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2885 reflections
a = 8.3853 (17) Å	θ = 2.3–21.6°
b = 17.554 (4) Å	µ = 0.22 mm−1
c = 10.458 (2) Å	T = 293 K
β = 95.07 (3)°	Prism, colourless
V = 1533.4 (5) Å3	0.18 × 0.16 × 0.16 mm
Z = 4

Bruker APEX CCD area-detector diffractometer	2814 independent reflections
Radiation source: fine-focus sealed tube	1949 reflections with I > 2σ(I)
graphite	Rint = 0.043
ω scans	θmax = 25.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.855, Tmax = 0.947	k = −21→21
16661 measured reflections	l = −12→12

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: difference Fourier map
wR(F2) = 0.102	All H-atom parameters refined
S = 1.01	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.4078P] where P = (Fo2 + 2Fc2)/3
2814 reflections	(Δ/σ)max < 0.001
258 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.46791 (6)	0.19850 (4)	0.39836 (6)	0.0569 (2)
O1	0.1824 (2)	0.00687 (9)	−0.10877 (14)	0.0636 (5)
O2	0.57694 (19)	0.19314 (11)	0.51054 (16)	0.0758 (5)
O3	0.53410 (19)	0.20903 (10)	0.27881 (16)	0.0724 (5)
N1	0.0608 (2)	0.20205 (10)	0.44220 (16)	0.0472 (4)
N2	0.3156 (2)	0.25469 (11)	0.41859 (19)	0.0611 (5)
N3	0.3384 (3)	0.02616 (14)	0.5764 (2)	0.0739 (6)
C1	0.2489 (4)	−0.06433 (17)	−0.1428 (3)	0.0698 (8)
C2	0.2106 (2)	0.03021 (12)	0.01541 (19)	0.0458 (5)
C3	0.2867 (3)	−0.01266 (14)	0.1123 (2)	0.0521 (6)
C4	0.3129 (3)	0.01743 (13)	0.2346 (2)	0.0491 (5)
C5	0.1573 (3)	0.10253 (13)	0.0415 (2)	0.0497 (5)
C6	0.1842 (3)	0.13239 (13)	0.1623 (2)	0.0474 (5)
C7	0.2636 (2)	0.09019 (11)	0.26096 (18)	0.0395 (5)
C8	0.3043 (2)	0.12520 (12)	0.39177 (19)	0.0425 (5)
C9	0.2122 (2)	0.19738 (12)	0.42216 (19)	0.0448 (5)
C10	0.3242 (2)	0.06955 (14)	0.4954 (2)	0.0496 (5)
C11	−0.0148 (3)	0.27758 (15)	0.4525 (3)	0.0599 (7)
C12	−0.0724 (4)	0.3089 (2)	0.3236 (3)	0.0769 (8)
C13	−0.0377 (3)	0.13436 (15)	0.4614 (2)	0.0553 (6)
C14	−0.0494 (4)	0.1173 (2)	0.6015 (3)	0.0780 (9)
H1A	0.226 (3)	−0.0650 (17)	−0.234 (3)	0.105 (10)*
H1B	0.201 (3)	−0.1077 (16)	−0.096 (3)	0.085 (9)*
H1C	0.364 (3)	−0.0633 (15)	−0.122 (2)	0.081 (9)*
H3	0.317 (3)	−0.0621 (14)	0.100 (2)	0.066 (7)*
H4	0.367 (2)	−0.0118 (12)	0.299 (2)	0.055 (6)*
H5	0.100 (2)	0.1321 (12)	−0.027 (2)	0.055 (6)*
H6	0.153 (3)	0.1815 (13)	0.176 (2)	0.056 (7)*
H11A	−0.101 (3)	0.2705 (13)	0.502 (2)	0.068 (7)*
H11B	0.064 (3)	0.3094 (15)	0.495 (2)	0.078 (9)*
H12A	−0.122 (3)	0.3602 (18)	0.334 (3)	0.095 (9)*
H12B	−0.152 (4)	0.2716 (19)	0.279 (3)	0.114 (12)*
H12C	0.016 (4)	0.3143 (15)	0.271 (3)	0.088 (9)*
H13A	−0.139 (3)	0.1458 (12)	0.4177 (19)	0.053 (6)*
H13B	0.008 (2)	0.0906 (13)	0.4177 (19)	0.052 (6)*
H14A	−0.113 (4)	0.073 (2)	0.613 (3)	0.126 (12)*
H14B	−0.094 (3)	0.1583 (18)	0.642 (3)	0.095 (10)*
H14C	0.062 (4)	0.1065 (18)	0.653 (3)	0.116 (12)*

	U11	U22	U33	U12	U13	U23
S1	0.0428 (3)	0.0691 (4)	0.0599 (4)	−0.0149 (3)	0.0108 (3)	−0.0137 (3)
O1	0.0840 (12)	0.0642 (11)	0.0414 (9)	0.0047 (9)	−0.0024 (8)	−0.0079 (8)
O2	0.0492 (9)	0.1081 (15)	0.0690 (11)	−0.0171 (9)	−0.0014 (8)	−0.0233 (10)
O3	0.0624 (10)	0.0883 (13)	0.0705 (11)	−0.0220 (9)	0.0270 (9)	−0.0068 (10)
N1	0.0434 (10)	0.0506 (11)	0.0489 (10)	−0.0011 (8)	0.0116 (8)	−0.0073 (8)
N2	0.0559 (12)	0.0537 (12)	0.0755 (14)	−0.0126 (9)	0.0162 (10)	−0.0154 (10)
N3	0.0798 (15)	0.0884 (17)	0.0534 (13)	0.0113 (13)	0.0047 (11)	0.0129 (12)
C1	0.092 (2)	0.0672 (19)	0.0505 (17)	−0.0020 (17)	0.0059 (15)	−0.0149 (14)
C2	0.0466 (12)	0.0514 (13)	0.0392 (12)	−0.0049 (10)	0.0033 (9)	−0.0013 (10)
C3	0.0619 (14)	0.0448 (14)	0.0492 (13)	0.0077 (11)	0.0032 (10)	−0.0051 (11)
C4	0.0510 (13)	0.0524 (14)	0.0428 (13)	0.0089 (11)	−0.0011 (10)	0.0024 (11)
C5	0.0563 (13)	0.0506 (14)	0.0417 (12)	0.0046 (11)	0.0010 (10)	0.0066 (11)
C6	0.0517 (13)	0.0415 (13)	0.0495 (14)	0.0046 (10)	0.0072 (10)	0.0021 (11)
C7	0.0355 (10)	0.0430 (12)	0.0405 (11)	−0.0034 (9)	0.0066 (8)	−0.0013 (9)
C8	0.0371 (11)	0.0492 (13)	0.0415 (12)	−0.0022 (9)	0.0054 (9)	−0.0042 (10)
C9	0.0437 (11)	0.0491 (13)	0.0422 (12)	−0.0050 (10)	0.0064 (9)	−0.0074 (10)
C10	0.0447 (12)	0.0619 (15)	0.0421 (13)	0.0007 (11)	0.0040 (10)	−0.0062 (12)
C11	0.0602 (16)	0.0581 (16)	0.0635 (17)	0.0092 (13)	0.0169 (13)	−0.0099 (13)
C12	0.083 (2)	0.073 (2)	0.077 (2)	0.0205 (18)	0.0162 (17)	0.0058 (17)
C13	0.0408 (13)	0.0619 (16)	0.0640 (16)	−0.0094 (11)	0.0095 (11)	−0.0148 (13)
C14	0.085 (2)	0.078 (2)	0.077 (2)	−0.0188 (19)	0.0353 (18)	−0.0019 (17)

S1—O3	1.4241 (17)	C5—C6	1.369 (3)
S1—O2	1.4252 (18)	C5—H5	0.98 (2)
S1—N2	1.642 (2)	C6—C7	1.391 (3)
S1—C8	1.878 (2)	C6—H6	0.92 (2)
O1—C2	1.362 (2)	C7—C8	1.511 (3)
O1—C1	1.426 (3)	C8—C10	1.457 (3)
N1—C9	1.307 (3)	C8—C9	1.532 (3)
N1—C13	1.471 (3)	C11—C12	1.496 (4)
N1—C11	1.478 (3)	C11—H11A	0.94 (2)
N2—C9	1.331 (3)	C11—H11B	0.95 (3)
N3—C10	1.138 (3)	C12—H12A	1.00 (3)
C1—H1A	0.96 (3)	C12—H12B	1.02 (3)
C1—H1B	1.01 (3)	C12—H12C	0.97 (3)
C1—H1C	0.97 (3)	C13—C14	1.508 (4)
C2—C3	1.373 (3)	C13—H13A	0.95 (2)
C2—C5	1.381 (3)	C13—H13B	0.99 (2)
C3—C4	1.384 (3)	C14—H14A	0.95 (4)
C3—H3	0.92 (2)	C14—H14B	0.93 (3)
C4—C7	1.377 (3)	C14—H14C	1.06 (3)
C4—H4	0.94 (2)
O3—S1—O2	117.38 (11)	C10—C8—C7	113.72 (18)
O3—S1—N2	113.77 (11)	C10—C8—C9	115.25 (17)
O2—S1—N2	112.54 (11)	C7—C8—C9	116.52 (17)
O3—S1—C8	113.38 (10)	C10—C8—S1	113.39 (14)
O2—S1—C8	113.47 (10)	C7—C8—S1	114.70 (13)
N2—S1—C8	80.92 (9)	C9—C8—S1	78.81 (12)
C2—O1—C1	117.5 (2)	N1—C9—N2	127.0 (2)
C9—N1—C13	122.43 (19)	N1—C9—C8	126.87 (18)
C9—N1—C11	119.8 (2)	N2—C9—C8	106.11 (17)
C13—N1—C11	117.72 (19)	N3—C10—C8	179.4 (2)
C9—N2—S1	93.77 (15)	N1—C11—C12	111.7 (2)
O1—C1—H1A	102.2 (18)	N1—C11—H11A	106.2 (15)
O1—C1—H1B	111.1 (15)	C12—C11—H11A	110.1 (15)
H1A—C1—H1B	115 (2)	N1—C11—H11B	106.1 (16)
O1—C1—H1C	109.3 (16)	C12—C11—H11B	111.2 (16)
H1A—C1—H1C	109 (2)	H11A—C11—H11B	111 (2)
H1B—C1—H1C	110 (2)	C11—C12—H12A	109.8 (16)
O1—C2—C3	124.6 (2)	C11—C12—H12B	108.9 (18)
O1—C2—C5	115.63 (19)	H12A—C12—H12B	111 (2)
C3—C2—C5	119.7 (2)	C11—C12—H12C	110.2 (17)
C2—C3—C4	119.9 (2)	H12A—C12—H12C	109 (2)
C2—C3—H3	122.2 (15)	H12B—C12—H12C	108 (2)
C4—C3—H3	117.9 (15)	N1—C13—C14	112.2 (2)
C7—C4—C3	120.9 (2)	N1—C13—H13A	104.7 (13)
C7—C4—H4	120.0 (13)	C14—C13—H13A	112.1 (13)
C3—C4—H4	119.1 (13)	N1—C13—H13B	108.5 (12)
C6—C5—C2	120.3 (2)	C14—C13—H13B	110.8 (12)
C6—C5—H5	120.4 (12)	H13A—C13—H13B	108.2 (17)
C2—C5—H5	119.3 (12)	C13—C14—H14A	111 (2)
C5—C6—C7	120.7 (2)	C13—C14—H14B	110.7 (19)
C5—C6—H6	118.4 (14)	H14A—C14—H14B	109 (3)
C7—C6—H6	120.8 (14)	C13—C14—H14C	113.6 (17)
C4—C7—C6	118.55 (19)	H14A—C14—H14C	106 (3)
C4—C7—C8	120.69 (18)	H14B—C14—H14C	106 (3)
C6—C7—C8	120.64 (19)
O3—S1—N2—C9	116.10 (15)	N2—S1—C8—C10	−116.78 (16)
O2—S1—N2—C9	−107.28 (15)	O3—S1—C8—C7	−1.80 (19)
C8—S1—N2—C9	4.46 (13)	O2—S1—C8—C7	−139.02 (15)
C1—O1—C2—C3	−5.7 (3)	N2—S1—C8—C7	110.27 (16)
C1—O1—C2—C5	174.0 (2)	O3—S1—C8—C9	−116.00 (13)
O1—C2—C3—C4	178.3 (2)	O2—S1—C8—C9	106.78 (13)
C5—C2—C3—C4	−1.5 (3)	N2—S1—C8—C9	−3.94 (12)
C2—C3—C4—C7	−0.1 (3)	C13—N1—C9—N2	−171.6 (2)
O1—C2—C5—C6	−177.87 (19)	C11—N1—C9—N2	5.4 (3)
C3—C2—C5—C6	1.9 (3)	C13—N1—C9—C8	11.5 (3)
C2—C5—C6—C7	−0.8 (3)	C11—N1—C9—C8	−171.5 (2)
C3—C4—C7—C6	1.2 (3)	S1—N2—C9—N1	176.98 (19)
C3—C4—C7—C8	−174.95 (19)	S1—N2—C9—C8	−5.62 (17)
C5—C6—C7—C4	−0.7 (3)	C10—C8—C9—N1	−66.9 (3)
C5—C6—C7—C8	175.38 (19)	C7—C8—C9—N1	70.2 (3)
C4—C7—C8—C10	−28.1 (3)	S1—C8—C9—N1	−177.6 (2)
C6—C7—C8—C10	155.89 (18)	C10—C8—C9—N2	115.7 (2)
C4—C7—C8—C9	−165.80 (18)	C7—C8—C9—N2	−107.2 (2)
C6—C7—C8—C9	18.2 (3)	S1—C8—C9—N2	5.00 (15)
C4—C7—C8—S1	104.7 (2)	C9—N1—C11—C12	85.4 (3)
C6—C7—C8—S1	−71.3 (2)	C13—N1—C11—C12	−97.4 (3)
O3—S1—C8—C10	131.15 (16)	C9—N1—C13—C14	96.4 (3)
O2—S1—C8—C10	−6.06 (19)	C11—N1—C13—C14	−80.6 (3)