N-Methyl-4-(4-pivalamido-phenyl-sulfan-yl)picolinamide hemihydrate.

In the title compound, C(18)H(21)N(3)O(2)S·0.5H(2)O, the benzene ring makes dihedral angles of 88.59 (6) and 40.74 (8)° with the pyridine ring and the amide group, respectively. The water O atom lies on a twofold axis. In the crystal, the organic mol-ecules and the water mol-ecules are linked via O-H⋯O hydrogen bonds, while the organic mol-ecules are connected to each other via N-H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For related compounds and their biological activity, see: Khire et al. (2004 ▶); Dominguez et al. (2007 ▶).

Experimental

Crystal data

C18H21N3O2S·0.5H2O

M = 352.46

Monoclinic,

a = 12.7413 (4) Å

b = 17.5056 (8) Å

c = 17.1978 (6) Å

β = 108.632 (4)°

V = 3634.8 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.20 mm−1

T = 293 K

0.24 × 0.22 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.966, T max = 1.000

3714 measured reflections

3714 independent reflections

2498 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.111

S = 0.96

3714 reflections

238 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012268/zq2092sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012268/zq2092Isup2.hkl

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

C18H21N3O2S·0.5H2O	F(000) = 1496
Mr = 352.46	Dx = 1.288 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -C 2yc	Cell parameters from 4009 reflections
a = 12.7413 (4) Å	θ = 3.2–28.9°
b = 17.5056 (8) Å	µ = 0.20 mm−1
c = 17.1978 (6) Å	T = 293 K
β = 108.632 (4)°	Block, colourless
V = 3634.8 (2) Å3	0.24 × 0.22 × 0.18 mm
Z = 8

Oxford Diffraction Xcalibur Eos diffractometer	3714 independent reflections
Radiation source: fine-focus sealed tube	2498 reflections with I > 2σ(I)
graphite	Rint = 0.000
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 3.4°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = 0→21
Tmin = 0.966, Tmax = 1.000	l = 0→21
3714 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ2(Fo2) + (0.0661P)2] where P = (Fo2 + 2Fc2)/3
3714 reflections	(Δ/σ)max = 0.001
238 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd. (version 1.171.33.66). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.61494 (4)	0.59213 (4)	0.36246 (3)	0.0608 (2)
O1	1.13699 (9)	0.68403 (8)	0.59009 (7)	0.0587 (4)
O2	0.18072 (9)	0.62917 (8)	0.30133 (7)	0.0501 (3)
N1	1.04402 (11)	0.59473 (9)	0.63584 (9)	0.0426 (4)
N2	0.36966 (11)	0.62678 (10)	0.50293 (8)	0.0467 (4)
N3	0.15906 (11)	0.66751 (9)	0.42051 (9)	0.0437 (4)
C1	1.33721 (15)	0.64847 (17)	0.70547 (13)	0.0802 (8)
H1B	1.3331	0.6977	0.6800	0.120*
H1A	1.3476	0.6098	0.6690	0.120*
H1C	1.3984	0.6476	0.7556	0.120*
C2	1.23823 (17)	0.55645 (13)	0.76612 (13)	0.0702 (7)
H2C	1.3062	0.5537	0.8111	0.105*
H2A	1.2368	0.5165	0.7276	0.105*
H2B	1.1767	0.5505	0.7864	0.105*
C3	1.2132 (2)	0.69544 (16)	0.78024 (13)	0.0901 (8)
H3C	1.2060	0.7439	0.7528	0.135*
H3D	1.2756	0.6969	0.8296	0.135*
H3B	1.1471	0.6850	0.7938	0.135*
C4	1.23043 (13)	0.63306 (10)	0.72414 (10)	0.0412 (4)
C5	1.13433 (13)	0.63957 (11)	0.64372 (10)	0.0397 (4)
C6	0.94575 (12)	0.59550 (10)	0.56813 (10)	0.0382 (4)
C7	0.89869 (14)	0.66307 (11)	0.53038 (11)	0.0458 (4)
H7	0.9337	0.7095	0.5478	0.055*
C8	0.79980 (14)	0.66091 (12)	0.46693 (10)	0.0481 (5)
H8	0.7689	0.7062	0.4415	0.058*
C9	0.74604 (13)	0.59274 (12)	0.44062 (10)	0.0446 (5)
C10	0.79331 (13)	0.52514 (12)	0.47770 (10)	0.0479 (5)
H10	0.7582	0.4787	0.4601	0.058*
C11	0.89264 (13)	0.52707 (11)	0.54086 (10)	0.0444 (4)
H11	0.9243	0.4816	0.5654	0.053*
C12	0.52341 (13)	0.60419 (10)	0.41985 (10)	0.0399 (4)
C13	0.41182 (12)	0.61603 (10)	0.37742 (9)	0.0381 (4)
H13	0.3863	0.6161	0.3204	0.046*
C14	0.34005 (12)	0.62763 (10)	0.42101 (9)	0.0366 (4)
C15	0.47617 (14)	0.61313 (12)	0.54174 (11)	0.0559 (5)
H15	0.4987	0.6107	0.5987	0.067*
C16	0.55535 (14)	0.60244 (12)	0.50456 (10)	0.0507 (5)
H16	0.6289	0.5942	0.5356	0.061*
C17	0.21897 (12)	0.64171 (10)	0.37579 (10)	0.0382 (4)
C18	0.04265 (13)	0.68624 (11)	0.38587 (11)	0.0509 (5)
H18B	0.0278	0.7041	0.3306	0.076*
H18C	0.0240	0.7254	0.4183	0.076*
H18A	−0.0010	0.6415	0.3858	0.076*
H3A	0.1891 (14)	0.6747 (11)	0.4720 (11)	0.051 (5)*
H1	1.0476 (15)	0.5594 (11)	0.6705 (11)	0.056 (6)*
H3	0.9464 (16)	0.4381 (12)	0.7371 (14)	0.072 (7)*
O3	1.0000	0.47126 (12)	0.7500	0.0502 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0340 (2)	0.1137 (5)	0.0331 (2)	0.0111 (3)	0.00870 (18)	0.0027 (3)
O1	0.0487 (7)	0.0767 (10)	0.0474 (7)	−0.0134 (7)	0.0109 (6)	0.0197 (7)
O2	0.0346 (6)	0.0727 (9)	0.0386 (7)	−0.0011 (6)	0.0059 (5)	−0.0086 (6)
N1	0.0340 (7)	0.0498 (10)	0.0401 (8)	−0.0034 (7)	0.0061 (6)	0.0113 (8)
N2	0.0369 (7)	0.0677 (11)	0.0349 (8)	−0.0007 (7)	0.0106 (6)	−0.0011 (7)
N3	0.0350 (7)	0.0564 (10)	0.0389 (8)	0.0019 (7)	0.0107 (7)	−0.0019 (7)
C1	0.0398 (10)	0.134 (2)	0.0608 (13)	−0.0199 (12)	0.0076 (10)	0.0188 (14)
C2	0.0557 (11)	0.0722 (16)	0.0628 (13)	−0.0126 (11)	−0.0090 (10)	0.0177 (12)
C3	0.105 (2)	0.100 (2)	0.0551 (14)	0.0152 (16)	0.0122 (14)	−0.0235 (13)
C4	0.0380 (9)	0.0493 (11)	0.0338 (9)	−0.0092 (8)	0.0082 (7)	−0.0009 (8)
C5	0.0370 (9)	0.0459 (11)	0.0375 (9)	−0.0023 (8)	0.0139 (7)	0.0013 (8)
C6	0.0308 (8)	0.0478 (11)	0.0370 (9)	0.0005 (8)	0.0121 (7)	0.0052 (8)
C7	0.0409 (9)	0.0453 (11)	0.0507 (10)	0.0015 (8)	0.0138 (8)	0.0057 (9)
C8	0.0416 (9)	0.0563 (12)	0.0475 (10)	0.0138 (9)	0.0159 (8)	0.0157 (9)
C9	0.0300 (8)	0.0690 (13)	0.0352 (9)	0.0052 (9)	0.0108 (7)	0.0052 (9)
C10	0.0386 (9)	0.0567 (13)	0.0458 (10)	−0.0040 (9)	0.0098 (8)	−0.0017 (9)
C11	0.0368 (9)	0.0451 (11)	0.0471 (10)	0.0023 (8)	0.0073 (8)	0.0090 (8)
C12	0.0323 (8)	0.0511 (11)	0.0347 (9)	0.0008 (7)	0.0083 (7)	−0.0002 (8)
C13	0.0326 (8)	0.0485 (11)	0.0295 (8)	−0.0005 (7)	0.0048 (7)	−0.0007 (7)
C14	0.0323 (8)	0.0392 (10)	0.0351 (9)	−0.0035 (7)	0.0065 (7)	−0.0043 (8)
C15	0.0404 (9)	0.0945 (17)	0.0300 (9)	0.0005 (10)	0.0071 (7)	0.0001 (9)
C16	0.0340 (8)	0.0802 (15)	0.0331 (9)	0.0042 (9)	0.0042 (7)	0.0015 (9)
C17	0.0315 (8)	0.0397 (10)	0.0422 (10)	−0.0042 (7)	0.0102 (7)	−0.0014 (8)
C18	0.0380 (9)	0.0586 (13)	0.0585 (12)	0.0060 (9)	0.0189 (8)	0.0009 (10)
O3	0.0371 (10)	0.0505 (12)	0.0565 (11)	0.000	0.0056 (9)	0.000

S1—C9	1.7783 (16)	C4—C5	1.531 (2)
S1—C12	1.7646 (17)	C6—C7	1.390 (2)
O1—C5	1.215 (2)	C6—C11	1.382 (2)
O2—C17	1.2355 (18)	C7—H7	0.9300
N1—C5	1.364 (2)	C7—C8	1.379 (2)
N1—C6	1.412 (2)	C8—H8	0.9300
N1—H1	0.850 (19)	C8—C9	1.378 (3)
N2—C14	1.337 (2)	C9—C10	1.387 (3)
N2—C15	1.329 (2)	C10—H10	0.9300
N3—C17	1.324 (2)	C10—C11	1.380 (2)
N3—C18	1.448 (2)	C11—H11	0.9300
N3—H3A	0.854 (18)	C12—C13	1.391 (2)
C1—H1B	0.9600	C12—C16	1.382 (2)
C1—H1A	0.9600	C13—H13	0.9300
C1—H1C	0.9600	C13—C14	1.370 (2)
C1—C4	1.519 (2)	C14—C17	1.510 (2)
C2—H2C	0.9600	C15—H15	0.9300
C2—H2A	0.9600	C15—C16	1.369 (2)
C2—H2B	0.9600	C16—H16	0.9300
C2—C4	1.511 (3)	C18—H18B	0.9600
C3—H3C	0.9600	C18—H18C	0.9600
C3—H3D	0.9600	C18—H18A	0.9600
C3—H3B	0.9600	O3—H3	0.87 (2)
C3—C4	1.519 (3)
O1—C5—N1	121.37 (15)	C6—N1—H1	114.8 (13)
O1—C5—C4	121.67 (15)	C6—C7—H7	120.2
O2—C17—N3	123.57 (14)	C6—C11—H11	119.5
O2—C17—C14	120.31 (14)	C7—C6—N1	122.01 (16)
N1—C5—C4	116.93 (14)	C7—C8—H8	119.5
N2—C14—C13	124.18 (14)	C8—C7—C6	119.68 (17)
N2—C14—C17	116.27 (14)	C8—C7—H7	120.2
N2—C15—H15	117.4	C8—C9—S1	120.11 (14)
N2—C15—C16	125.22 (16)	C8—C9—C10	119.37 (15)
N3—C17—C14	116.12 (14)	C9—C8—C7	121.07 (16)
N3—C18—H18B	109.5	C9—C8—H8	119.5
N3—C18—H18C	109.5	C9—C10—H10	120.2
N3—C18—H18A	109.5	C10—C9—S1	120.48 (15)
C1—C4—C3	109.12 (19)	C10—C11—C6	120.98 (16)
C1—C4—C5	107.93 (13)	C10—C11—H11	119.5
H1B—C1—H1A	109.5	C11—C6—N1	118.74 (15)
H1B—C1—H1C	109.5	C11—C6—C7	119.20 (15)
H1A—C1—H1C	109.5	C11—C10—C9	119.68 (17)
C2—C4—C1	109.39 (17)	C11—C10—H10	120.2
C2—C4—C3	109.59 (18)	C12—S1—C9	101.86 (7)
C2—C4—C5	114.16 (14)	C12—C13—H13	120.5
H2C—C2—H2A	109.5	C12—C16—H16	120.8
H2C—C2—H2B	109.5	C13—C12—S1	118.16 (12)
H2A—C2—H2B	109.5	C13—C14—C17	119.55 (14)
C3—C4—C5	106.51 (15)	C14—C13—C12	118.96 (14)
H3C—C3—H3D	109.5	C14—C13—H13	120.5
H3C—C3—H3B	109.5	C15—N2—C14	115.50 (14)
H3D—C3—H3B	109.5	C15—C16—C12	118.47 (15)
C4—C1—H1B	109.5	C15—C16—H16	120.8
C4—C1—H1A	109.5	C16—C12—S1	124.21 (12)
C4—C1—H1C	109.5	C16—C12—C13	117.62 (15)
C4—C2—H2C	109.5	C16—C15—H15	117.4
C4—C2—H2A	109.5	C17—N3—C18	122.88 (15)
C4—C2—H2B	109.5	C17—N3—H3A	120.1 (12)
C4—C3—H3C	109.5	C18—N3—H3A	117.0 (12)
C4—C3—H3D	109.5	H18B—C18—H18C	109.5
C4—C3—H3B	109.5	H18B—C18—H18A	109.5
C5—N1—C6	125.06 (15)	H18C—C18—H18A	109.5
C5—N1—H1	119.7 (13)
S1—C9—C10—C11	−176.99 (13)	C7—C8—C9—S1	176.56 (13)
S1—C12—C13—C14	−178.20 (13)	C7—C8—C9—C10	−1.1 (3)
S1—C12—C16—C15	179.54 (16)	C8—C9—C10—C11	0.7 (3)
N1—C6—C7—C8	−176.92 (15)	C9—S1—C12—C13	172.12 (14)
N1—C6—C11—C10	176.57 (15)	C9—S1—C12—C16	−8.07 (19)
N2—C14—C17—O2	−166.19 (16)	C9—C10—C11—C6	0.3 (3)
N2—C14—C17—N3	13.7 (2)	C11—C6—C7—C8	0.4 (3)
N2—C15—C16—C12	−1.4 (3)	C12—S1—C9—C8	−87.13 (15)
C1—C4—C5—O1	−32.9 (2)	C12—S1—C9—C10	90.55 (15)
C1—C4—C5—N1	148.93 (18)	C12—C13—C14—N2	−1.5 (3)
C2—C4—C5—O1	−154.74 (18)	C12—C13—C14—C17	179.11 (15)
C2—C4—C5—N1	27.1 (2)	C13—C12—C16—C15	−0.6 (3)
C3—C4—C5—O1	84.2 (2)	C13—C14—C17—O2	13.2 (2)
C3—C4—C5—N1	−94.0 (2)	C13—C14—C17—N3	−166.83 (16)
C5—N1—C6—C7	−41.0 (2)	C14—N2—C15—C16	1.9 (3)
C5—N1—C6—C11	141.63 (17)	C15—N2—C14—C13	−0.4 (3)
C6—N1—C5—O1	−1.4 (3)	C15—N2—C14—C17	178.99 (17)
C6—N1—C5—C4	176.82 (15)	C16—C12—C13—C14	2.0 (2)
C6—C7—C8—C9	0.6 (3)	C18—N3—C17—O2	−2.2 (3)
C7—C6—C11—C10	−0.9 (3)	C18—N3—C17—C14	177.90 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1i	0.854 (18)	2.335 (18)	3.0317 (19)	139.0 (15)
O3—H3···O2ii	0.87 (2)	1.94 (2)	2.8059 (18)	174.2
N1—H1···O3	0.850 (19)	2.269 (19)	3.089 (2)	162.3 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1i	0.854 (18)	2.335 (18)	3.0317 (19)	139.0 (15)
O3—H3⋯O2ii	0.87 (2)	1.94 (2)	2.8059 (18)	174.2
N1—H1⋯O3	0.850 (19)	2.269 (19)	3.089 (2)	162.3 (18)

Symmetry codes: (i) ; (ii) .