The title compound, C
12H
20N
4O
2S, has been synthesized for use as an intermediate for antihypertensive agents, potential antimalarials and molecular rectification materials. The intermolecular S
N non-bonded separation within a column in the crystal structure is 3.308 (2) Å, indicating a strong intermolecular interaction between the cyano groups and the S atoms. Attractive C—H
O hydrogen bonds are responsible for zigzag molecular chains propagating in the
a-axis direction; these types of intermolecular interactions combine to form an extended three-dimensional network in the lattice.
Supporting information
CCDC reference: 283745
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.097
- Data-to-parameter ratio = 16.6
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ... 0.30
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - C5 .. 5.32 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su .. 0.30
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 26.01
From the CIF: _reflns_number_total 2875
Count of symmetry unique reflns 1696
Completeness (_total/calc) 169.52%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1179
Fraction of Friedel pairs measured 0.695
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 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
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
Methyl
4-
tert-butoxycarbonyl-
N-cyanopiperazine-1-carboximidothioate
top
Crystal data top
C12H20N4O2S | Dx = 1.285 Mg m−3 |
Mr = 284.38 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 2619 reflections |
a = 6.358 (2) Å | θ = 2.3–22.1° |
b = 9.382 (3) Å | µ = 0.23 mm−1 |
c = 24.646 (8) Å | T = 273 K |
V = 1470.1 (8) Å3 | Spicula, yellow |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
F(000) = 608 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2875 independent reflections |
Radiation source: fine-focus sealed tube | 2436 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.956, Tmax = 0.978 | k = −11→10 |
7193 measured reflections | l = −30→29 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0538P)2 + 0.11P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2875 reflections | Δρmax = 0.21 e Å−3 |
173 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.0 (3) |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.7178 (6) | 1.0313 (4) | −0.12784 (10) | 0.0842 (10) | |
H1A | 0.6366 | 0.9463 | −0.1336 | 0.126* | |
H1B | 0.8587 | 1.0058 | −0.1178 | 0.126* | |
H1C | 0.7207 | 1.0865 | −0.1606 | 0.126* | |
C2 | 0.7366 (6) | 1.2548 (3) | −0.07259 (13) | 0.0842 (10) | |
H2A | 0.6676 | 1.3075 | −0.0443 | 0.126* | |
H2B | 0.7393 | 1.3107 | −0.1052 | 0.126* | |
H2C | 0.8779 | 1.2331 | −0.0617 | 0.126* | |
C3 | 0.3898 (5) | 1.1485 (4) | −0.09437 (12) | 0.0884 (10) | |
H3A | 0.3176 | 1.0605 | −0.1014 | 0.133* | |
H3B | 0.3785 | 1.2095 | −0.1255 | 0.133* | |
H3C | 0.3275 | 1.1947 | −0.0635 | 0.133* | |
C4 | 0.6188 (4) | 1.1184 (2) | −0.08287 (8) | 0.0524 (6) | |
C5 | 0.7804 (4) | 0.9823 (3) | −0.00919 (8) | 0.0440 (5) | |
C6 | 0.5205 (4) | 0.8779 (3) | 0.05560 (8) | 0.0498 (6) | |
H6A | 0.4861 | 0.7779 | 0.0511 | 0.060* | |
H6B | 0.4199 | 0.9336 | 0.0350 | 0.060* | |
C7 | 0.5062 (4) | 0.9173 (3) | 0.11470 (7) | 0.0467 (6) | |
H7A | 0.5218 | 1.0196 | 0.1187 | 0.056* | |
H7B | 0.3692 | 0.8907 | 0.1287 | 0.056* | |
C8 | 0.8945 (4) | 0.8364 (3) | 0.06705 (9) | 0.0543 (6) | |
H8A | 1.0310 | 0.8641 | 0.0530 | 0.065* | |
H8B | 0.8819 | 0.7338 | 0.0635 | 0.065* | |
C9 | 0.8809 (4) | 0.8761 (3) | 0.12584 (9) | 0.0457 (5) | |
H9A | 0.9838 | 0.8224 | 0.1465 | 0.055* | |
H9B | 0.9111 | 0.9768 | 0.1303 | 0.055* | |
C10 | 0.6246 (3) | 0.7694 (2) | 0.19003 (7) | 0.0356 (4) | |
C11 | 0.7863 (5) | 0.5420 (3) | 0.24881 (14) | 0.0761 (9) | |
H11A | 0.8966 | 0.5059 | 0.2716 | 0.114* | |
H11B | 0.7778 | 0.4856 | 0.2164 | 0.114* | |
H11C | 0.6548 | 0.5371 | 0.2679 | 0.114* | |
C12 | 0.3697 (4) | 0.6860 (3) | 0.24741 (9) | 0.0486 (5) | |
N1 | 0.7311 (3) | 0.9047 (2) | 0.03538 (7) | 0.0525 (5) | |
N2 | 0.6699 (3) | 0.84499 (18) | 0.14580 (6) | 0.0388 (4) | |
N3 | 0.4286 (3) | 0.7408 (2) | 0.20055 (7) | 0.0456 (5) | |
N4 | 0.2989 (4) | 0.6391 (3) | 0.28653 (9) | 0.0707 (7) | |
O1 | 0.6075 (3) | 1.03331 (18) | −0.03269 (6) | 0.0531 (4) | |
O2 | 0.9594 (3) | 0.9996 (2) | −0.02443 (7) | 0.0627 (5) | |
S1 | 0.84118 (9) | 0.72301 (7) | 0.23127 (2) | 0.05208 (18) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.128 (3) | 0.083 (2) | 0.0420 (12) | 0.007 (2) | 0.0034 (16) | −0.0009 (13) |
C2 | 0.110 (3) | 0.0516 (17) | 0.091 (2) | −0.0136 (16) | −0.0077 (18) | 0.0149 (14) |
C3 | 0.080 (2) | 0.114 (3) | 0.0715 (18) | 0.0011 (19) | −0.0130 (17) | 0.0448 (19) |
C4 | 0.0684 (17) | 0.0500 (14) | 0.0388 (11) | −0.0047 (12) | −0.0002 (11) | 0.0133 (10) |
C5 | 0.0505 (14) | 0.0451 (12) | 0.0365 (11) | −0.0025 (11) | 0.0061 (10) | −0.0010 (9) |
C6 | 0.0431 (13) | 0.0681 (16) | 0.0381 (11) | −0.0053 (12) | −0.0029 (10) | 0.0109 (10) |
C7 | 0.0401 (13) | 0.0607 (14) | 0.0392 (11) | 0.0086 (11) | 0.0018 (9) | 0.0124 (10) |
C8 | 0.0441 (14) | 0.0738 (17) | 0.0449 (12) | 0.0148 (12) | 0.0081 (10) | 0.0119 (11) |
C9 | 0.0378 (12) | 0.0527 (13) | 0.0466 (11) | −0.0038 (11) | −0.0011 (9) | 0.0105 (10) |
C10 | 0.0408 (11) | 0.0345 (10) | 0.0316 (9) | 0.0015 (9) | −0.0014 (8) | −0.0021 (8) |
C11 | 0.0656 (17) | 0.0612 (16) | 0.101 (2) | 0.0162 (14) | 0.0079 (16) | 0.0339 (16) |
C12 | 0.0400 (12) | 0.0608 (14) | 0.0449 (11) | 0.0055 (11) | 0.0011 (10) | 0.0113 (10) |
N1 | 0.0446 (11) | 0.0767 (14) | 0.0362 (9) | 0.0058 (10) | 0.0052 (8) | 0.0149 (9) |
N2 | 0.0350 (9) | 0.0483 (10) | 0.0331 (8) | 0.0026 (8) | −0.0002 (7) | 0.0065 (7) |
N3 | 0.0419 (10) | 0.0573 (12) | 0.0376 (9) | −0.0026 (9) | −0.0010 (7) | 0.0091 (8) |
N4 | 0.0582 (13) | 0.0947 (18) | 0.0592 (12) | 0.0091 (12) | 0.0116 (11) | 0.0321 (12) |
O1 | 0.0485 (10) | 0.0661 (10) | 0.0449 (8) | −0.0011 (8) | 0.0019 (7) | 0.0216 (7) |
O2 | 0.0532 (10) | 0.0767 (12) | 0.0582 (10) | −0.0014 (9) | 0.0129 (9) | 0.0180 (9) |
S1 | 0.0477 (3) | 0.0596 (4) | 0.0489 (3) | −0.0031 (3) | −0.0119 (3) | 0.0159 (3) |
Geometric parameters (Å, º) top
C1—C4 | 1.514 (4) | C7—N2 | 1.460 (3) |
C1—H1A | 0.9600 | C7—H7A | 0.9700 |
C1—H1B | 0.9600 | C7—H7B | 0.9700 |
C1—H1C | 0.9600 | C8—N1 | 1.449 (3) |
C2—C4 | 1.504 (4) | C8—C9 | 1.499 (3) |
C2—H2A | 0.9600 | C8—H8A | 0.9700 |
C2—H2B | 0.9600 | C8—H8B | 0.9700 |
C2—H2C | 0.9600 | C9—N2 | 1.458 (3) |
C3—C4 | 1.510 (4) | C9—H9A | 0.9700 |
C3—H3A | 0.9600 | C9—H9B | 0.9700 |
C3—H3B | 0.9600 | C10—N3 | 1.301 (3) |
C3—H3C | 0.9600 | C10—N2 | 1.332 (2) |
C4—O1 | 1.474 (3) | C10—S1 | 1.766 (2) |
C5—O2 | 1.209 (3) | C11—S1 | 1.787 (3) |
C5—O1 | 1.332 (3) | C11—H11A | 0.9600 |
C5—N1 | 1.355 (3) | C11—H11B | 0.9600 |
C6—N1 | 1.451 (3) | C11—H11C | 0.9600 |
C6—C7 | 1.506 (3) | C12—N4 | 1.152 (3) |
C6—H6A | 0.9700 | C12—N3 | 1.319 (3) |
C6—H6B | 0.9700 | | |
| | | |
C4—C1—H1A | 109.5 | C6—C7—H7A | 109.5 |
C4—C1—H1B | 109.5 | N2—C7—H7B | 109.5 |
H1A—C1—H1B | 109.5 | C6—C7—H7B | 109.5 |
C4—C1—H1C | 109.5 | H7A—C7—H7B | 108.1 |
H1A—C1—H1C | 109.5 | N1—C8—C9 | 111.7 (2) |
H1B—C1—H1C | 109.5 | N1—C8—H8A | 109.3 |
C4—C2—H2A | 109.5 | C9—C8—H8A | 109.3 |
C4—C2—H2B | 109.5 | N1—C8—H8B | 109.3 |
H2A—C2—H2B | 109.5 | C9—C8—H8B | 109.3 |
C4—C2—H2C | 109.5 | H8A—C8—H8B | 107.9 |
H2A—C2—H2C | 109.5 | N2—C9—C8 | 109.24 (19) |
H2B—C2—H2C | 109.5 | N2—C9—H9A | 109.8 |
C4—C3—H3A | 109.5 | C8—C9—H9A | 109.8 |
C4—C3—H3B | 109.5 | N2—C9—H9B | 109.8 |
H3A—C3—H3B | 109.5 | C8—C9—H9B | 109.8 |
C4—C3—H3C | 109.5 | H9A—C9—H9B | 108.3 |
H3A—C3—H3C | 109.5 | N3—C10—N2 | 118.68 (18) |
H3B—C3—H3C | 109.5 | N3—C10—S1 | 125.54 (15) |
O1—C4—C2 | 110.09 (19) | N2—C10—S1 | 115.72 (15) |
O1—C4—C3 | 102.24 (19) | S1—C11—H11A | 109.5 |
C2—C4—C3 | 110.6 (2) | S1—C11—H11B | 109.5 |
O1—C4—C1 | 110.0 (2) | H11A—C11—H11B | 109.5 |
C2—C4—C1 | 112.0 (2) | S1—C11—H11C | 109.5 |
C3—C4—C1 | 111.4 (2) | H11A—C11—H11C | 109.5 |
O2—C5—O1 | 126.4 (2) | H11B—C11—H11C | 109.5 |
O2—C5—N1 | 122.8 (2) | N4—C12—N3 | 173.5 (3) |
O1—C5—N1 | 110.78 (19) | C5—N1—C8 | 120.57 (19) |
N1—C6—C7 | 110.21 (19) | C5—N1—C6 | 125.81 (19) |
N1—C6—H6A | 109.6 | C8—N1—C6 | 113.61 (17) |
C7—C6—H6A | 109.6 | C10—N2—C9 | 125.56 (17) |
N1—C6—H6B | 109.6 | C10—N2—C7 | 121.54 (17) |
C7—C6—H6B | 109.6 | C9—N2—C7 | 112.68 (16) |
H6A—C6—H6B | 108.1 | C10—N3—C12 | 121.83 (18) |
N2—C7—C6 | 110.54 (19) | C5—O1—C4 | 121.29 (18) |
N2—C7—H7A | 109.5 | C10—S1—C11 | 102.78 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O2 | 0.96 | 2.39 | 2.991 (2) | 120 |
C2—H2C···O2 | 0.96 | 2.43 | 3.025 (2) | 120 |
C6—H6A···O2i | 0.97 | 2.69 | 3.645 (3) | 168 |
C9—H9A···S1 | 0.97 | 2.46 | 2.980 (2) | 113 |
C11—H11C···N4 | 0.96 | 2.50 | 3.361 (2) | 149 |
C11—H11C···C12 | 0.96 | 2.34 | 2.974 (2) | 123 |
Symmetry code: (i) x−1/2, −y+3/2, −z. |