Crystal structure of ethyl 2-phenyl-4-(prop-2-yn-1-yl-oxy)-5,6,7,8-tetra-hydro-pyrido[4',3':4,5]thieno[2,3-d]pyrimidine-7-carboxyl-ate.

In the title compound, C21H19N3O3S, the 5,6,7,8-tetra-hydro-pyridine ring adopts a half-chair conformation. The fused-thieno[2,3-d]pyrimidine ring system is essentially planar (r.m.s. deviation = 0.001 Å) and forms a dihedral angle of 2.66 (6)° with the attached phenyl ring. The three-dimensional crystal packing is stabilized by C-H⋯O and C-H⋯N hydrogen bonds and C-H⋯π inter-actions.

Related literature

For general chemistry background to heterocyclic thieno[2,3-d]pyrimidines, see: Litvinov (2004 ▸). For the diversity of biological activities of thieno-pyrimidine derivatives, see: Nasr & Gineinah (2002 ▸); Bhuiyan et al. (2005 ▸); Chambhare et al. (2003 ▸); Alagarsamy et al. (2006 ▸). Kapustina et al. (1992 ▸). For related structures, see: Liu et al. (2005 ▸); Ren et al. (2006 ▸).

Experimental

Crystal data

C21H19N3O3S

M = 393.45

Monoclinic,

a = 13.143 (2) Å

b = 8.013 (2) Å

c = 17.880 (2) Å

β = 96.129 (14)°

V = 1872.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 296 K

0.28 × 0.14 × 0.08 mm

Data collection

Agilent Xcalibur, Eos, Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▸) T min = 0.834, T max = 1.000

14345 measured reflections

6319 independent reflections

4721 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.117

S = 1.04

6319 reflections

254 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015018447/tk5390sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018447/tk5390Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018447/tk5390Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015018447/tk5390fig1.tif

View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989015018447/tk5390fig2.tif

The mol­ecular packing viewed down a axis. H atoms not involved in H bonding are omitted for clarity.

CCDC reference: 1429186

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H19N3O3S	F(000) = 824
Mr = 393.45	Dx = 1.396 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2782 reflections
a = 13.143 (2) Å	θ = 3.7–32.7°
b = 8.013 (2) Å	µ = 0.20 mm−1
c = 17.880 (2) Å	T = 296 K
β = 96.129 (14)°	Prism, colourless
V = 1872.3 (6) Å3	0.28 × 0.14 × 0.08 mm
Z = 4

Agilent Xcalibur, Eos, Gemini diffractometer	6319 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4721 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 16.0416 pixels mm-1	θmax = 33.1°, θmin = 3.1°
ω scans	h = −16→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −11→5
Tmin = 0.834, Tmax = 1.000	l = −25→26
14345 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0488P)2 + 0.4469P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
6319 reflections	Δρmax = 0.35 e Å−3
254 parameters	Δρmin = −0.31 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	−0.00878 (3)	0.26271 (5)	1.21398 (2)	0.0319 (1)
O1	−0.08120 (7)	0.17676 (13)	0.94088 (4)	0.0274 (3)
O2	−0.38389 (8)	0.19716 (14)	1.25060 (6)	0.0369 (3)
O3	−0.45126 (7)	0.06635 (13)	1.14545 (5)	0.0325 (3)
N1	0.06668 (8)	0.31874 (14)	0.98114 (5)	0.0249 (3)
N2	0.11346 (8)	0.37095 (15)	1.11181 (6)	0.0276 (3)
N3	−0.28451 (9)	0.03958 (16)	1.18227 (6)	0.0314 (3)
C1	0.24352 (11)	0.48532 (17)	0.94671 (7)	0.0307 (4)
C2	0.33262 (12)	0.5631 (2)	0.93051 (8)	0.0366 (4)
C3	0.40123 (11)	0.6245 (2)	0.98760 (9)	0.0371 (4)
C4	0.38043 (11)	0.6085 (2)	1.06113 (8)	0.0371 (4)
C5	0.29176 (10)	0.5315 (2)	1.07789 (8)	0.0335 (4)
C6	0.22226 (10)	0.46768 (16)	1.02092 (7)	0.0263 (3)
C7	0.12892 (9)	0.38147 (16)	1.03956 (7)	0.0250 (3)
C8	−0.01623 (9)	0.23971 (16)	0.99661 (6)	0.0235 (3)
C9	−0.04163 (9)	0.21700 (16)	1.07030 (6)	0.0232 (3)
C10	0.02839 (10)	0.28884 (17)	1.12482 (7)	0.0262 (3)
C11	−0.12525 (9)	0.13753 (16)	1.10142 (6)	0.0242 (3)
C12	−0.21248 (10)	0.04461 (17)	1.06005 (7)	0.0258 (3)
C13	−0.26836 (11)	−0.05731 (18)	1.11502 (7)	0.0313 (4)
C14	−0.19118 (10)	0.0880 (2)	1.22777 (7)	0.0316 (4)
C15	−0.11712 (10)	0.15527 (17)	1.17729 (7)	0.0266 (3)
C16	−0.37375 (10)	0.10798 (17)	1.19685 (7)	0.0283 (3)
C17	−0.54903 (11)	0.1367 (2)	1.15901 (9)	0.0382 (4)
C18	−0.62591 (13)	0.0838 (2)	1.09628 (10)	0.0491 (6)
C19	−0.05720 (10)	0.20882 (18)	0.86513 (6)	0.0279 (3)
C20	−0.14696 (11)	0.1659 (2)	0.81452 (7)	0.0336 (4)
C21	−0.21842 (12)	0.1381 (3)	0.77141 (9)	0.0533 (6)
H1	0.19760	0.44460	0.90780	0.0370*
H2	0.34630	0.57400	0.88080	0.0440*
H3	0.46110	0.67630	0.97650	0.0450*
H4	0.42650	0.64990	1.09980	0.0440*
H5	0.27830	0.52210	1.12770	0.0400*
H12A	−0.18690	−0.02910	1.02330	0.0310*
H12B	−0.25960	0.12300	1.03350	0.0310*
H13A	−0.33400	−0.09310	1.09030	0.0380*
H13B	−0.22870	−0.15630	1.12980	0.0380*
H14A	−0.16170	−0.00790	1.25530	0.0380*
H14B	−0.20610	0.17250	1.26390	0.0380*
H17A	−0.54460	0.25750	1.16090	0.0460*
H17B	−0.56870	0.09700	1.20660	0.0460*
H18A	−0.69180	0.12800	1.10420	0.0740*
H18B	−0.62930	−0.03590	1.09460	0.0740*
H18C	−0.60620	0.12500	1.04950	0.0740*
H19A	0.00070	0.14160	0.85410	0.0330*
H19B	−0.04000	0.32550	0.85940	0.0330*
H21	−0.27520	0.11590	0.73720	0.0640*

	U11	U22	U33	U12	U13	U23
S1	0.0328 (2)	0.0447 (2)	0.0173 (1)	−0.0006 (2)	−0.0014 (1)	−0.0032 (1)
O1	0.0298 (4)	0.0363 (5)	0.0155 (4)	−0.0005 (4)	−0.0002 (3)	−0.0024 (3)
O2	0.0381 (5)	0.0412 (6)	0.0326 (5)	−0.0020 (4)	0.0090 (4)	−0.0131 (4)
O3	0.0330 (5)	0.0359 (5)	0.0287 (4)	−0.0009 (4)	0.0033 (4)	−0.0053 (4)
N1	0.0258 (5)	0.0280 (5)	0.0201 (4)	0.0051 (4)	−0.0008 (4)	−0.0011 (4)
N2	0.0279 (5)	0.0330 (6)	0.0211 (5)	0.0039 (4)	−0.0013 (4)	−0.0016 (4)
N3	0.0328 (6)	0.0374 (6)	0.0243 (5)	0.0000 (5)	0.0051 (4)	−0.0073 (5)
C1	0.0387 (7)	0.0254 (6)	0.0279 (6)	0.0036 (5)	0.0028 (5)	−0.0028 (5)
C2	0.0459 (8)	0.0332 (7)	0.0326 (7)	0.0015 (6)	0.0125 (6)	−0.0016 (6)
C3	0.0333 (7)	0.0321 (7)	0.0469 (8)	0.0025 (6)	0.0090 (6)	0.0037 (6)
C4	0.0317 (7)	0.0403 (8)	0.0375 (7)	−0.0004 (6)	−0.0039 (6)	0.0015 (6)
C5	0.0310 (6)	0.0402 (8)	0.0283 (6)	0.0006 (6)	−0.0017 (5)	0.0014 (6)
C6	0.0280 (6)	0.0240 (6)	0.0264 (6)	0.0073 (5)	0.0002 (5)	−0.0005 (5)
C7	0.0260 (6)	0.0258 (6)	0.0225 (5)	0.0078 (5)	−0.0012 (4)	−0.0015 (4)
C8	0.0267 (6)	0.0248 (6)	0.0179 (5)	0.0075 (5)	−0.0023 (4)	−0.0019 (4)
C9	0.0251 (6)	0.0250 (6)	0.0186 (5)	0.0072 (4)	−0.0012 (4)	−0.0010 (4)
C10	0.0277 (6)	0.0317 (7)	0.0184 (5)	0.0063 (5)	−0.0018 (4)	−0.0008 (4)
C11	0.0272 (6)	0.0244 (6)	0.0203 (5)	0.0072 (5)	−0.0006 (4)	−0.0018 (4)
C12	0.0284 (6)	0.0275 (6)	0.0211 (5)	0.0052 (5)	0.0006 (4)	−0.0049 (4)
C13	0.0381 (7)	0.0292 (7)	0.0272 (6)	−0.0001 (6)	0.0064 (5)	−0.0071 (5)
C14	0.0351 (7)	0.0395 (8)	0.0204 (5)	0.0013 (6)	0.0035 (5)	−0.0010 (5)
C15	0.0287 (6)	0.0302 (6)	0.0200 (5)	0.0051 (5)	−0.0009 (4)	−0.0012 (5)
C16	0.0351 (7)	0.0268 (6)	0.0237 (5)	−0.0031 (5)	0.0066 (5)	−0.0002 (5)
C17	0.0355 (7)	0.0382 (8)	0.0408 (7)	0.0040 (6)	0.0034 (6)	−0.0029 (6)
C18	0.0413 (9)	0.0483 (10)	0.0556 (10)	−0.0036 (8)	−0.0050 (7)	−0.0020 (8)
C19	0.0304 (6)	0.0355 (7)	0.0173 (5)	0.0013 (5)	0.0006 (4)	−0.0012 (5)
C20	0.0339 (7)	0.0465 (8)	0.0203 (5)	0.0003 (6)	0.0028 (5)	−0.0047 (5)
C21	0.0351 (8)	0.0966 (16)	0.0278 (7)	−0.0078 (9)	0.0016 (6)	−0.0129 (8)

S1—C10	1.7292 (14)	C11—C15	1.3568 (17)
S1—C15	1.7319 (14)	C12—C13	1.5253 (19)
O1—C8	1.3397 (15)	C14—C15	1.4968 (19)
O1—C19	1.4461 (14)	C17—C18	1.489 (2)
O2—C16	1.2163 (17)	C19—C20	1.4495 (19)
O3—C16	1.3393 (16)	C20—C21	1.171 (2)
O3—C17	1.4472 (18)	C1—H1	0.9300
N1—C7	1.3529 (16)	C2—H2	0.9300
N1—C8	1.3150 (16)	C3—H3	0.9300
N2—C7	1.3316 (17)	C4—H4	0.9300
N2—C10	1.3389 (18)	C5—H5	0.9300
N3—C13	1.4657 (18)	C12—H12A	0.9700
N3—C14	1.4505 (18)	C12—H12B	0.9700
N3—C16	1.3451 (18)	C13—H13A	0.9700
C1—C2	1.384 (2)	C13—H13B	0.9700
C1—C6	1.3921 (18)	C14—H14A	0.9700
C2—C3	1.379 (2)	C14—H14B	0.9700
C3—C4	1.377 (2)	C17—H17A	0.9700
C4—C5	1.380 (2)	C17—H17B	0.9700
C5—C6	1.3910 (19)	C18—H18A	0.9600
C6—C7	1.4767 (18)	C18—H18B	0.9600
C8—C9	1.4052 (16)	C18—H18C	0.9600
C9—C10	1.3918 (18)	C19—H19A	0.9700
C9—C11	1.4330 (17)	C19—H19B	0.9700
C11—C12	1.4949 (18)	C21—H21	0.9300
C10—S1—C15	90.73 (6)	C2—C1—H1	120.00
C8—O1—C19	116.38 (10)	C6—C1—H1	120.00
C16—O3—C17	114.33 (11)	C1—C2—H2	120.00
C7—N1—C8	117.57 (10)	C3—C2—H2	120.00
C7—N2—C10	114.61 (11)	C2—C3—H3	120.00
C13—N3—C14	114.45 (11)	C4—C3—H3	120.00
C13—N3—C16	125.49 (11)	C3—C4—H4	120.00
C14—N3—C16	119.01 (11)	C5—C4—H4	120.00
C2—C1—C6	120.37 (13)	C4—C5—H5	120.00
C1—C2—C3	120.45 (13)	C6—C5—H5	120.00
C2—C3—C4	119.53 (14)	C11—C12—H12A	110.00
C3—C4—C5	120.49 (14)	C11—C12—H12B	110.00
C4—C5—C6	120.62 (13)	C13—C12—H12A	110.00
C1—C6—C5	118.54 (12)	C13—C12—H12B	110.00
C1—C6—C7	121.25 (12)	H12A—C12—H12B	108.00
C5—C6—C7	120.21 (12)	N3—C13—H13A	109.00
N1—C7—N2	125.67 (11)	N3—C13—H13B	109.00
N1—C7—C6	116.61 (11)	C12—C13—H13A	109.00
N2—C7—C6	117.71 (11)	C12—C13—H13B	109.00
O1—C8—N1	120.10 (10)	H13A—C13—H13B	108.00
O1—C8—C9	116.89 (11)	N3—C14—H14A	110.00
N1—C8—C9	123.01 (11)	N3—C14—H14B	110.00
C8—C9—C10	113.43 (11)	C15—C14—H14A	110.00
C8—C9—C11	133.67 (11)	C15—C14—H14B	110.00
C10—C9—C11	112.89 (10)	H14A—C14—H14B	108.00
S1—C10—N2	122.89 (10)	O3—C17—H17A	110.00
S1—C10—C9	111.40 (10)	O3—C17—H17B	110.00
N2—C10—C9	125.70 (11)	C18—C17—H17A	110.00
C9—C11—C12	127.49 (10)	C18—C17—H17B	110.00
C9—C11—C15	111.09 (11)	H17A—C17—H17B	109.00
C12—C11—C15	121.42 (11)	C17—C18—H18A	110.00
C11—C12—C13	110.15 (10)	C17—C18—H18B	109.00
N3—C13—C12	111.52 (12)	C17—C18—H18C	110.00
N3—C14—C15	108.88 (10)	H18A—C18—H18B	109.00
S1—C15—C11	113.87 (10)	H18A—C18—H18C	109.00
S1—C15—C14	120.79 (9)	H18B—C18—H18C	109.00
C11—C15—C14	125.33 (12)	O1—C19—H19A	110.00
O2—C16—O3	123.30 (12)	O1—C19—H19B	110.00
O2—C16—N3	124.33 (12)	C20—C19—H19A	110.00
O3—C16—N3	112.37 (11)	C20—C19—H19B	110.00
O3—C17—C18	107.83 (13)	H19A—C19—H19B	108.00
O1—C19—C20	107.35 (11)	C20—C21—H21	180.00
C19—C20—C21	176.57 (18)
C10—S1—C15—C11	0.63 (11)	C2—C3—C4—C5	0.1 (2)
C15—S1—C10—N2	179.24 (12)	C3—C4—C5—C6	0.5 (2)
C15—S1—C10—C9	0.26 (11)	C4—C5—C6—C7	178.35 (13)
C10—S1—C15—C14	179.45 (12)	C4—C5—C6—C1	−0.9 (2)
C19—O1—C8—N1	−3.14 (17)	C1—C6—C7—N2	−179.40 (12)
C8—O1—C19—C20	−166.90 (12)	C5—C6—C7—N1	−178.14 (13)
C19—O1—C8—C9	176.72 (11)	C1—C6—C7—N1	1.06 (18)
C17—O3—C16—N3	179.78 (12)	C5—C6—C7—N2	1.40 (19)
C16—O3—C17—C18	178.23 (12)	O1—C8—C9—C11	0.2 (2)
C17—O3—C16—O2	0.06 (19)	N1—C8—C9—C10	1.12 (19)
C8—N1—C7—C6	179.19 (11)	O1—C8—C9—C10	−178.73 (11)
C7—N1—C8—C9	−0.62 (19)	N1—C8—C9—C11	−179.97 (14)
C8—N1—C7—N2	−0.3 (2)	C8—C9—C10—N2	−0.8 (2)
C7—N1—C8—O1	179.22 (11)	C8—C9—C10—S1	178.11 (9)
C10—N2—C7—C6	−178.91 (12)	C8—C9—C11—C15	−177.42 (14)
C10—N2—C7—N1	0.58 (19)	C10—C9—C11—C12	−178.29 (13)
C7—N2—C10—S1	−178.78 (10)	C10—C9—C11—C15	1.50 (16)
C7—N2—C10—C9	0.1 (2)	C8—C9—C11—C12	2.8 (2)
C14—N3—C16—O2	−7.3 (2)	C11—C9—C10—N2	−180.00 (13)
C13—N3—C16—O2	−174.90 (13)	C11—C9—C10—S1	−1.04 (15)
C14—N3—C16—O3	172.98 (12)	C9—C11—C15—C14	179.93 (12)
C13—N3—C14—C15	46.00 (16)	C12—C11—C15—S1	178.50 (10)
C13—N3—C16—O3	5.37 (19)	C15—C11—C12—C13	−14.47 (17)
C14—N3—C13—C12	−64.08 (15)	C9—C11—C15—S1	−1.31 (15)
C16—N3—C13—C12	104.02 (15)	C9—C11—C12—C13	165.30 (13)
C16—N3—C14—C15	−122.93 (13)	C12—C11—C15—C14	−0.3 (2)
C6—C1—C2—C3	−0.2 (2)	C11—C12—C13—N3	44.25 (15)
C2—C1—C6—C7	−178.48 (13)	N3—C14—C15—S1	166.88 (10)
C2—C1—C6—C5	0.7 (2)	N3—C14—C15—C11	−14.4 (2)
C1—C2—C3—C4	−0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1	0.93	2.49	2.8050 (19)	100
C5—H5···N2	0.93	2.47	2.7961 (19)	101
C13—H13A···O3	0.97	2.30	2.7085 (19)	104
C14—H14A···O2i	0.97	2.44	3.294 (2)	146
C14—H14B···O2	0.97	2.33	2.7509 (19)	105
C21—H21···N2ii	0.93	2.55	3.418 (2)	156
C12—H12B···Cg4iii	0.97	2.80	3.6643 (17)	149
C19—H19A···Cg1iv	0.97	2.92	3.6736 (18)	136

Table 1

Hydrogen-bond geometry (, )

Cg1 and Cg4 are the centroids of the S1,C9C11/C15 and C1C6 rings, respectively.

DHA	DH	HA	D A	DHA
C14H14AO2i	0.97	2.44	3.294(2)	146
C21H21N2ii	0.93	2.55	3.418(2)	156
C12H12B Cg4iii	0.97	2.80	3.6643(17)	149
C19H19A Cg1iv	0.97	2.92	3.6736(18)	136

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .