Methyl 4-tert-butoxy­carbonyl-N-cyano­piperazine-1-carboximidothio­ate

The title compound, C₁₂H₂₀N₄O₂S, 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.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](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

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Computing details

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

Crystal data

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) Å^3	Spicula, yellow
Z = 4	0.20 × 0.15 × 0.10 mm
F(000) = 608

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 0.11P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O2^i	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.