The molecular and crystalline structure of ethyl 1′,2′,3′,4′,4a′,5′,6′,7′-octahydrodispiro[cyclohexane-1,2′-quinazoline-4′,1′′-cyclohexane]-8′-carbodithioate (I) was solved and refined from powder synchrotron X-ray diffraction data. The initial model for the structural solution in direct space using the simulated annealing algorithm implemented in
DASH [David
et al. (2006).
J. Appl. Cryst. 39, 910–915] was obtained performing a conformational study on the fused six-membered rings of the octahydroquinazoline system and the two spiran cyclohexane rings of (I). The best model was chosen using experimental evidence from
1H and
13C NMR [Contreras
et al. (2001).
J. Heterocycl. Chem. 38, 1223–1225] in combination with semi-empirical AM1 calculations. In the refined structure the two spiran rings have the chair conformation, while both of the fused rings in the octahydroquinazoline system have half-chair conformations compared with in-vacuum density-functional theory (DFT) B3LYP/6-311G*, DFTB (density-functional tight-binding) theoretical calculations in the solid state and other related structures from X-ray diffraction data. Compound (I) presents weak intramolecular hydrogen bonds of the type N—H

S and C—H

S, which produce delocalization of the electron density in the generated rings described by graph symbols
S(6) and
S(5). Packing of the molecules is dominated by van der Waals interactions.
Supporting information
CCDC reference: 760200
(type here to add preparation details)
(type here to add refinement details)
Molecular graphics: PLATON (Spek, 2003) and DIAMOND 2.1e (Brandenburg, 2001); software used to prepare material for publication: GSAS2CIF (Toby et al., 2003), PLATON (Spek, 2003), and publCIF (Westrip, 2009).
ethyl 1',2',3',4',4a',5',6',7'-octahydrodispiro[cyclohexane-1,2'-
quinazoline-4',1''-cyclohexane]-8'-carbodithioate
top
Crystal data top
C21H34N2S2 | F(000) = 824 |
Mr = 378.64 | Dx = 1.236 Mg m−3 |
Monoclinic, P21/n | Synchrotron radiation, λ = 0.80098 Å |
Hall symbol: -P 2yn | µ = 0.00 mm−1 |
a = 21.7356 (4) Å | T = 298 K |
b = 10.0565 (2) Å | Particle morphology: thin powder |
c = 9.45108 (18) Å | yellow |
β = 99.9602 (8)° | cylinder, 40 × 10 mm |
V = 2034.72 (7) Å3 | Specimen preparation: Prepared at 298 K |
Z = 4 | |
Data collection top
High Resolution Diffractometer ID31, ESRF, Grenoble, France. | Specimen mounting: borosilicate glass capillary |
Radiation source: synchrotron, Beamline ID31 | Data collection mode: transmission |
Double crystal Si 111 monochromator | Scan method: step |
Refinement top
Refinement on Inet | Profile function: CW Profile function number 4 with 21 terms
Pseudovoigt profile coefficients as parameterized in
P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83.
Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994).
J. Appl. Cryst.,27,892-900.
Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289.
#1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000
#4(GP) = 0.000 #5(LX) = 2.373 #6(ptec) = 0.00
#7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00
#10(S/L) = 0.0030 #11(H/L) = 0.0016 #12(eta) = 0.0000
#13(S400 ) = 6.4E-04 #14(S040 ) = 3.8E-03 #15(S004 ) = 5.5E-03
#16(S220 ) = 6.7E-03 #17(S202 ) = 1.3E-03 #18(S022 ) = 1.2E-02
#19(S301 ) = 0.0E+00 #20(S103 ) = 3.1E-04 #21(S121 ) = 2.7E-03
Peak tails are ignored where the intensity is below 0.0015 times the peak
Aniso. broadening axis 0.0 0.0 1.0 |
Least-squares matrix: full | 127 parameters |
Rp = 0.044 | 186 restraints |
Rwp = 0.054 | 1 constraint |
Rexp = 0.024 | H-atom parameters constrained |
R(F2) = 0.12634 | (Δ/σ)max = 0.05 |
χ2 = 5.290 | Background function: GSAS Background function number 1 with 20 terms.
Shifted Chebyshev function of 1st kind
1: 1003.18 2: -242.455 3: 44.5847 4: 55.6979
5: -29.4706 6: -81.1134 7: 127.180 8: -98.3496
9: 20.8256 10: 37.3447 11: -40.7733 12: 13.3524
13: 13.5172 14: -16.2420 15: 32.6866 16: 8.33642
17: -35.1107 18: 7.23691 19: 5.42771 20: 5.20341 |
15665 data points | Preferred orientation correction: Spherical Harmonic |
Excluded region(s): none | |
Crystal data top
C21H34N2S2 | V = 2034.72 (7) Å3 |
Mr = 378.64 | Z = 4 |
Monoclinic, P21/n | Synchrotron radiation, λ = 0.80098 Å |
a = 21.7356 (4) Å | µ = 0.00 mm−1 |
b = 10.0565 (2) Å | T = 298 K |
c = 9.45108 (18) Å | cylinder, 40 × 10 mm |
β = 99.9602 (8)° | |
Data collection top
High Resolution Diffractometer ID31, ESRF, Grenoble, France. | Data collection mode: transmission |
Specimen mounting: borosilicate glass capillary | Scan method: step |
Refinement top
Rp = 0.044 | 15665 data points |
Rwp = 0.054 | 127 parameters |
Rexp = 0.024 | 186 restraints |
R(F2) = 0.12634 | H-atom parameters constrained |
χ2 = 5.290 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.32712 (15) | 0.7025 (3) | 0.0351 (4) | 0.0556 (7)* | |
S2 | 0.45772 (16) | 0.6464 (4) | 0.1717 (4) | 0.0556 (7)* | |
N1 | 0.25389 (18) | 0.6346 (8) | 0.2538 (4) | 0.0556 (7)* | |
N2 | 0.18148 (16) | 0.5883 (5) | 0.4136 (4) | 0.0556 (7)* | |
C1 | 0.18865 (19) | 0.6238 (4) | 0.2697 (4) | 0.0556 (7)* | |
C2 | 0.22928 (19) | 0.6328 (4) | 0.5320 (4) | 0.0556 (7)* | |
C3 | 0.34955 (17) | 0.6326 (3) | 0.6171 (3) | 0.0556 (7)* | |
C4 | 0.40475 (15) | 0.5606 (3) | 0.5778 (4) | 0.0556 (7)* | |
C5 | 0.41936 (15) | 0.6178 (3) | 0.4421 (4) | 0.0556 (7)* | |
C6 | 0.36432 (19) | 0.6389 (9) | 0.3248 (5) | 0.0556 (7)* | |
C7 | 0.3035 (2) | 0.6267 (9) | 0.3579 (5) | 0.0556 (7)* | |
C8 | 0.29393 (18) | 0.5908 (3) | 0.5055 (4) | 0.0556 (7)* | |
C9 | 0.15551 (17) | 0.7531 (3) | 0.2148 (3) | 0.0556 (7)* | |
C10 | 0.08500 (16) | 0.7428 (3) | 0.2039 (3) | 0.0556 (7)* | |
C11 | 0.06036 (13) | 0.6345 (4) | 0.0975 (3) | 0.0556 (7)* | |
C12 | 0.09052 (16) | 0.5051 (3) | 0.1495 (3) | 0.0556 (7)* | |
C13 | 0.16133 (16) | 0.5092 (3) | 0.1698 (3) | 0.0556 (7)* | |
C14 | 0.22770 (15) | 0.7821 (3) | 0.5579 (3) | 0.0556 (7)* | |
C15 | 0.16609 (15) | 0.8265 (3) | 0.5969 (3) | 0.0556 (7)* | |
C16 | 0.15206 (13) | 0.7511 (3) | 0.7253 (3) | 0.0556 (7)* | |
C17 | 0.15536 (15) | 0.6020 (3) | 0.7110 (3) | 0.0556 (7)* | |
C18 | 0.21347 (15) | 0.5534 (3) | 0.6592 (4) | 0.0556 (7)* | |
C19 | 0.3798 (2) | 0.6567 (11) | 0.1841 (5) | 0.0556 (7)* | |
C20 | 0.46088 (13) | 0.6879 (3) | −0.0107 (4) | 0.0556 (7)* | |
C21 | 0.47095 (13) | 0.8327 (3) | −0.0297 (3) | 0.0556 (7)* | |
H1 | 0.2617 | 0.6594 | 0.1599 | 0.0681 (9)* | |
H2 | 0.142 | 0.6301 | 0.4306 | 0.0681 (9)* | |
H31 | 0.3556 | 0.7303 | 0.6124 | 0.0681 (9)* | |
H32 | 0.3433 | 0.6063 | 0.7154 | 0.0681 (9)* | |
H41 | 0.4414 | 0.571 | 0.6558 | 0.0681 (9)* | |
H42 | 0.3945 | 0.4634 | 0.5633 | 0.0681 (9)* | |
H51 | 0.4389 | 0.7062 | 0.4642 | 0.0681 (9)* | |
H52 | 0.449 | 0.5567 | 0.4049 | 0.0681 (9)* | |
H81 | 0.2931 | 0.4908 | 0.5099 | 0.0681 (9)* | |
H91 | 0.171 | 0.8282 | 0.2819 | 0.0681 (9)* | |
H92 | 0.1647 | 0.774 | 0.1172 | 0.0681 (9)* | |
H101 | 0.0653 | 0.8302 | 0.1716 | 0.0681 (9)* | |
H102 | 0.0753 | 0.7209 | 0.3013 | 0.0681 (9)* | |
H111 | 0.0714 | 0.6576 | 0.0026 | 0.0681 (9)* | |
H112 | 0.0145 | 0.6285 | 0.0909 | 0.0681 (9)* | |
H121 | 0.0781 | 0.4814 | 0.244 | 0.0681 (9)* | |
H122 | 0.0754 | 0.4345 | 0.0776 | 0.0681 (9)* | |
H131 | 0.174 | 0.5226 | 0.075 | 0.0681 (9)* | |
H132 | 0.1785 | 0.424 | 0.2137 | 0.0681 (9)* | |
H141 | 0.2619 | 0.8073 | 0.6393 | 0.0681 (9)* | |
H142 | 0.2337 | 0.8297 | 0.4693 | 0.0681 (9)* | |
H151 | 0.1683 | 0.924 | 0.6203 | 0.0681 (9)* | |
H152 | 0.132 | 0.8103 | 0.5139 | 0.0681 (9)* | |
H161 | 0.1832 | 0.7786 | 0.812 | 0.0681 (9)* | |
H162 | 0.1091 | 0.7755 | 0.7411 | 0.0681 (9)* | |
H171 | 0.1539 | 0.5612 | 0.8074 | 0.0681 (9)* | |
H172 | 0.1181 | 0.5721 | 0.641 | 0.0681 (9)* | |
H181 | 0.2493 | 0.5593 | 0.7419 | 0.0681 (9)* | |
H182 | 0.207 | 0.4583 | 0.6297 | 0.0681 (9)* | |
H201 | 0.4961 | 0.6377 | −0.0365 | 0.0681 (9)* | |
H202 | 0.4207 | 0.6613 | −0.072 | 0.0681 (9)* | |
H211 | 0.4736 | 0.8515 | −0.1317 | 0.0681 (9)* | |
H212 | 0.5107 | 0.8617 | 0.0336 | 0.0681 (9)* | |
H213 | 0.4353 | 0.8853 | −0.0018 | 0.0681 (9)* | |
Geometric parameters (Å, º) top
S1—C19 | 1.717 (6) | C3—H32 | 1.0000 |
S2—C19 | 1.721 (6) | C4—H41 | 0.9900 |
S2—C20 | 1.787 (5) | C4—H42 | 1.0100 |
N1—C1 | 1.456 (6) | C5—H51 | 0.9900 |
N1—C7 | 1.330 (6) | C5—H52 | 1.0000 |
N2—C1 | 1.440 (5) | C8—H81 | 1.0100 |
N2—C2 | 1.459 (5) | C9—H91 | 1.0100 |
N1—H1 | 0.9600 | C9—H92 | 1.0000 |
N2—H2 | 0.9900 | C10—H101 | 1.0000 |
C1—C13 | 1.542 (5) | C10—H102 | 1.0000 |
C1—C9 | 1.533 (5) | C11—H111 | 1.0000 |
C2—C8 | 1.529 (6) | C11—H112 | 0.9900 |
C2—C14 | 1.523 (5) | C12—H121 | 1.0100 |
C2—C18 | 1.531 (5) | C12—H122 | 1.0000 |
C3—C4 | 1.502 (5) | C13—H131 | 0.9900 |
C3—C8 | 1.520 (5) | C13—H132 | 1.0000 |
C4—C5 | 1.489 (5) | C14—H141 | 1.0100 |
C5—C6 | 1.499 (6) | C14—H142 | 0.9900 |
C6—C19 | 1.438 (7) | C15—H151 | 1.0000 |
C6—C7 | 1.416 (6) | C15—H152 | 0.9900 |
C7—C8 | 1.490 (6) | C16—H161 | 1.0100 |
C9—C10 | 1.522 (5) | C16—H162 | 1.0000 |
C10—C11 | 1.516 (4) | C17—H171 | 1.0000 |
C11—C12 | 1.501 (4) | C17—H172 | 1.0000 |
C12—C13 | 1.518 (5) | C18—H181 | 1.0100 |
C14—C15 | 1.516 (5) | C18—H182 | 1.0000 |
C15—C16 | 1.506 (4) | C20—H201 | 0.9800 |
C16—C17 | 1.508 (4) | C20—H202 | 1.0000 |
C17—C18 | 1.513 (5) | C21—H211 | 0.9900 |
C20—C21 | 1.488 (4) | C21—H212 | 1.0100 |
C3—H31 | 0.9900 | C21—H213 | 1.0100 |
| | | |
C19—S2—C20 | 104.7 (3) | C7—C8—H81 | 107.00 |
C1—N1—C7 | 126.8 (4) | C1—C9—H91 | 110.00 |
C1—N2—C2 | 118.0 (4) | C1—C9—H92 | 109.00 |
C1—N1—H1 | 116.00 | C10—C9—H91 | 108.00 |
C7—N1—H1 | 117.00 | C10—C9—H92 | 108.00 |
C1—N2—H2 | 107.00 | H91—C9—H92 | 109.00 |
C2—N2—H2 | 105.00 | C9—C10—H101 | 109.00 |
N2—C1—C13 | 107.4 (3) | C9—C10—H102 | 109.00 |
C9—C1—C13 | 108.6 (3) | C11—C10—H101 | 110.00 |
N1—C1—C13 | 105.8 (4) | C11—C10—H102 | 110.00 |
N1—C1—N2 | 112.5 (3) | H101—C10—H102 | 109.00 |
N1—C1—C9 | 108.1 (4) | C10—C11—H111 | 109.00 |
N2—C1—C9 | 114.1 (3) | C10—C11—H112 | 109.00 |
N2—C2—C8 | 110.0 (3) | C12—C11—H111 | 110.00 |
C14—C2—C18 | 111.9 (3) | C12—C11—H112 | 110.00 |
C8—C2—C18 | 108.8 (3) | H111—C11—H112 | 111.00 |
N2—C2—C14 | 113.1 (3) | C11—C12—H121 | 109.00 |
N2—C2—C18 | 102.4 (3) | C11—C12—H122 | 109.00 |
C8—C2—C14 | 110.2 (3) | C13—C12—H121 | 108.00 |
C4—C3—C8 | 105.6 (3) | C13—C12—H122 | 108.00 |
C3—C4—C5 | 109.0 (3) | H121—C12—H122 | 109.00 |
C4—C5—C6 | 115.5 (3) | C1—C13—H131 | 108.00 |
C5—C6—C7 | 118.7 (4) | C1—C13—H132 | 108.00 |
C5—C6—C19 | 114.7 (4) | C12—C13—H131 | 109.00 |
C7—C6—C19 | 126.3 (4) | C12—C13—H132 | 109.00 |
N1—C7—C6 | 120.0 (4) | H131—C13—H132 | 111.00 |
C6—C7—C8 | 121.0 (4) | C2—C14—H141 | 110.00 |
N1—C7—C8 | 118.7 (4) | C2—C14—H142 | 109.00 |
C2—C8—C3 | 117.0 (3) | C15—C14—H141 | 108.00 |
C2—C8—C7 | 111.6 (3) | C15—C14—H142 | 108.00 |
C3—C8—C7 | 111.1 (3) | H141—C14—H142 | 110.00 |
C1—C9—C10 | 112.0 (3) | C14—C15—H151 | 109.00 |
C9—C10—C11 | 109.3 (2) | C14—C15—H152 | 109.00 |
C10—C11—C12 | 108.8 (2) | C16—C15—H151 | 109.00 |
C11—C12—C13 | 113.2 (3) | C16—C15—H152 | 109.00 |
C1—C13—C12 | 111.9 (3) | H151—C15—H152 | 110.00 |
C2—C14—C15 | 112.0 (3) | C15—C16—H161 | 108.00 |
C14—C15—C16 | 111.0 (2) | C15—C16—H162 | 109.00 |
C15—C16—C17 | 114.1 (2) | C17—C16—H161 | 108.00 |
C16—C17—C18 | 113.9 (3) | C17—C16—H162 | 108.00 |
C2—C18—C17 | 113.5 (3) | H161—C16—H162 | 109.00 |
S1—C19—C6 | 124.2 (4) | C16—C17—H171 | 108.00 |
S2—C19—C6 | 116.5 (4) | C16—C17—H172 | 108.00 |
S1—C19—S2 | 119.0 (3) | C18—C17—H171 | 109.00 |
S2—C20—C21 | 112.1 (3) | C18—C17—H172 | 108.00 |
C4—C3—H31 | 110.00 | H171—C17—H172 | 109.00 |
C4—C3—H32 | 110.00 | C2—C18—H181 | 109.00 |
C8—C3—H31 | 110.00 | C2—C18—H182 | 109.00 |
C8—C3—H32 | 111.00 | C17—C18—H181 | 108.00 |
H31—C3—H32 | 110.00 | C17—C18—H182 | 108.00 |
C3—C4—H41 | 110.00 | H181—C18—H182 | 109.00 |
C3—C4—H42 | 110.00 | S2—C20—H201 | 106.00 |
C5—C4—H41 | 110.00 | S2—C20—H202 | 109.00 |
C5—C4—H42 | 109.00 | C21—C20—H201 | 110.00 |
H41—C4—H42 | 109.00 | C21—C20—H202 | 109.00 |
C4—C5—H51 | 108.00 | H201—C20—H202 | 111.00 |
C4—C5—H52 | 108.00 | C20—C21—H211 | 110.00 |
C6—C5—H51 | 107.00 | C20—C21—H212 | 110.00 |
C6—C5—H52 | 108.00 | C20—C21—H213 | 110.00 |
H51—C5—H52 | 110.00 | H211—C21—H212 | 110.00 |
C2—C8—H81 | 104.00 | H211—C21—H213 | 109.00 |
C3—C8—H81 | 105.00 | H212—C21—H213 | 108.00 |
| | | |
C7—C6—C19—S1 | 14.9 (15) | C20—S2—C19—C6 | −174.8 (7) |
C20—S2—C19—S1 | −1.0 (8) | C19—S2—C20—C21 | 91.3 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1 | 0.96 | 2.040 | 2.900 (5) | 147 |
C5—H52···S2 | 1.00 | 2.420 | 2.837 (5) | 104 |
C20—H202···S1 | 1.00 | 2.460 | 3.016 (4) | 115 |
Experimental details
Crystal data |
Chemical formula | C21H34N2S2 |
Mr | 378.64 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 21.7356 (4), 10.0565 (2), 9.45108 (18) |
β (°) | 99.9602 (8) |
V (Å3) | 2034.72 (7) |
Z | 4 |
Radiation type | Synchrotron, λ = 0.80098 Å |
µ (mm−1) | 0.00 |
Specimen shape, size (mm) | Cylinder, 40 × 10 |
|
Data collection |
Diffractometer | High Resolution Diffractometer ID31, ESRF, Grenoble, France. |
Specimen mounting | Borosilicate glass capillary |
Data collection mode | Transmission |
Scan method | Step |
2θ values (°) | 2θmin = ? 2θmax = ? 2θstep = ? |
|
Refinement |
R factors and goodness of fit | Rp = 0.044, Rwp = 0.054, Rexp = 0.024, R(F2) = 0.12634, χ2 = 5.290 |
No. of data points | 15665 |
No. of parameters | 127 |
No. of restraints | 186 |
H-atom treatment | H-atom parameters constrained |
Selected geometric parameters (Å, º) topS1—C19 | 1.717 (6) | N1—C7 | 1.330 (6) |
S2—C19 | 1.721 (6) | N2—C1 | 1.440 (5) |
S2—C20 | 1.787 (5) | N2—C2 | 1.459 (5) |
N1—C1 | 1.456 (6) | | |
| | | |
C19—S2—C20 | 104.7 (3) | N2—C2—C14 | 113.1 (3) |
C1—N1—C7 | 126.8 (4) | N2—C2—C18 | 102.4 (3) |
C1—N2—C2 | 118.0 (4) | N1—C7—C6 | 120.0 (4) |
N2—C1—C13 | 107.4 (3) | N1—C7—C8 | 118.7 (4) |
N1—C1—C13 | 105.8 (4) | S1—C19—C6 | 124.2 (4) |
N1—C1—N2 | 112.5 (3) | S2—C19—C6 | 116.5 (4) |
N1—C1—C9 | 108.1 (4) | S1—C19—S2 | 119.0 (3) |
N2—C1—C9 | 114.1 (3) | S2—C20—C21 | 112.1 (3) |
N2—C2—C8 | 110.0 (3) | | |
| | | |
C7—C6—C19—S1 | 14.9 (15) | C20—S2—C19—C6 | −174.8 (7) |
C20—S2—C19—S1 | −1.0 (8) | C19—S2—C20—C21 | 91.3 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1 | 0.96 | 2.040 | 2.900 (5) | 147 |
C5—H52···S2 | 1.00 | 2.420 | 2.837 (5) | 104 |
C20—H202···S1 | 1.00 | 2.460 | 3.016 (4) | 115 |