Methyl 12-bromo-13,14-(thio­dinitrilo)deisopropyl­dehydro­abietate

The structure of the title compound, C₁₈H₂₁BrN₂O₂S, features a five-membered 2,1,3-thia­diazole ring in which the N atoms are two-coordinate [N-S-N = 101.6 (2)°].

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.040
• wR factor = 0.101
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact  H4A    ..  H4A     ..       1.93 Ang.

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.66 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.32 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   C15     ..       6.18 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7

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           25.30
           From the CIF: _reflns_number_total               3068
           Count of symmetry unique reflns         1706
           Completeness (_total/calc)            179.84%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1362
           Fraction of Friedel pairs measured     0.798
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11    = .          S

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Methyl 12-bromo-13,14-(thiodiimino)deisopropyldehydroabietate

Crystal data

C18H21BrN2O2S	F(000) = 840
Mr = 409.34	Dx = 1.536 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 1738 reflections
a = 20.847 (2) Å	θ = 2.9–21.2°
b = 12.180 (1) Å	µ = 2.45 mm^−1
c = 7.1222 (7) Å	T = 295 K
β = 101.738 (2)°	Block, yellow
V = 1770.5 (3) Å^3	0.26 × 0.25 × 0.24 mm
Z = 4

Data collection

Bruker SMART 1000 area-detector diffractometer	2244 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 25.3°, θmin = 2.0°
φ and ω scans	h = −24→21
4679 measured reflections	k = −14→14
3068 independent reflections	l = −7→8

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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0522P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max = 0.001
3068 reflections	Δρmax = 0.34 e Å^−3
221 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1368 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (1)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.11216 (3)	0.50000 (5)	0.27189 (8)	0.0915 (2)
S1	−0.09285 (7)	0.6869 (2)	0.2480 (2)	0.0927 (6)
O1	0.1121 (2)	1.2758 (4)	−0.0386 (6)	0.113 (1)
O2	0.1200 (3)	1.1426 (5)	−0.2391 (7)	0.132 (2)
N1	−0.0302 (2)	0.6076 (4)	0.2528 (5)	0.084 (1)
N2	−0.0606 (2)	0.8048 (5)	0.2514 (5)	0.077 (1)
C1	0.0208 (2)	0.6765 (4)	0.2580 (5)	0.062 (1)
C2	0.0038 (2)	0.7899 (5)	0.2569 (6)	0.062 (1)
C3	0.0513 (2)	0.8731 (4)	0.2615 (6)	0.056 (1)
C4	0.0287 (2)	0.9895 (6)	0.2601 (7)	0.083 (2)
C5	0.0786 (2)	1.0757 (5)	0.2380 (7)	0.069 (1)
C6	0.1337 (2)	1.0297 (3)	0.1483 (6)	0.048 (1)
C7	0.1784 (2)	1.1217 (4)	0.0905 (6)	0.063 (1)
C8	0.2335 (2)	1.0691 (4)	0.0114 (7)	0.065 (1)
C9	0.2700 (2)	0.9805 (4)	0.1382 (7)	0.067 (1)
C10	0.2226 (2)	0.8901 (4)	0.1721 (7)	0.062 (1)
C11	0.1672 (2)	0.9317 (4)	0.2654 (5)	0.050 (1)
C12	0.1144 (2)	0.8440 (4)	0.2631 (5)	0.048 (1)
C13	0.1322 (2)	0.7293 (4)	0.2694 (5)	0.055 (1)
C14	0.0872 (3)	0.6489 (4)	0.2675 (6)	0.061 (1)
C15	0.1324 (3)	1.1809 (4)	−0.0851 (9)	0.077 (1)
C16	0.0658 (4)	1.3277 (7)	−0.206 (1)	0.126 (3)
C17	0.2069 (3)	1.2041 (5)	0.2474 (9)	0.094 (2)
C18	0.1952 (2)	0.9578 (4)	0.4796 (6)	0.075 (2)
H4a	0.0141	1.0034	0.3789	0.100*
H4b	−0.0090	0.9981	0.1561	0.100*
H5a	0.0973	1.1061	0.3630	0.083*
H5b	0.0568	1.1347	0.1582	0.083*
H6	0.1113	0.9976	0.0263	0.057*
H8a	0.2153	1.0377	−0.1132	0.078*
H8b	0.2643	1.1257	−0.0070	0.078*
H9a	0.2913	1.0120	0.2600	0.080*
H9b	0.3036	0.9494	0.0777	0.080*
H10a	0.2036	0.8561	0.0503	0.074*
H10b	0.2470	0.8341	0.2536	0.074*
H13	0.1758	0.7102	0.2749	0.066*
H16a	0.0906	1.3676	−0.2833	0.189*
H16b	0.0368	1.3770	−0.1590	0.189*
H16c	0.0407	1.2714	−0.2820	0.189*
H17a	0.2336	1.1660	0.3531	0.141*
H17b	0.1718	1.2410	0.2905	0.141*
H17c	0.2331	1.2570	0.1971	0.141*
H18a	0.2123	0.8918	0.5448	0.113*
H18b	0.1610	0.9866	0.5375	0.113*
H18c	0.2297	1.0110	0.4889	0.113*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.1103 (5)	0.0589 (3)	0.1084 (4)	−0.0120 (4)	0.0292 (3)	−0.0038 (4)
S1	0.0609 (8)	0.149 (2)	0.0645 (7)	−0.029 (1)	0.0041 (6)	0.0166 (9)
O1	0.127 (4)	0.080 (3)	0.127 (4)	0.023 (3)	0.018 (3)	0.014 (3)
O2	0.191 (6)	0.105 (4)	0.079 (3)	0.026 (3)	−0.022 (3)	0.001 (3)
N1	0.087 (3)	0.108 (4)	0.056 (2)	−0.039 (3)	0.009 (2)	−0.007 (2)
N2	0.042 (2)	0.133 (4)	0.056 (2)	0.002 (2)	0.0102 (17)	0.021 (2)
C1	0.060 (3)	0.087 (4)	0.037 (2)	−0.021 (3)	0.0041 (17)	0.003 (2)
C2	0.060 (3)	0.087 (4)	0.039 (2)	0.000 (3)	0.0127 (19)	0.007 (2)
C3	0.048 (3)	0.077 (3)	0.044 (2)	0.001 (2)	0.0142 (18)	0.010 (2)
C4	0.075 (3)	0.094 (4)	0.091 (3)	0.027 (4)	0.043 (3)	0.032 (4)
C5	0.064 (3)	0.074 (3)	0.070 (3)	0.019 (3)	0.013 (2)	−0.007 (3)
C6	0.049 (2)	0.042 (3)	0.049 (2)	−0.001 (2)	0.0050 (17)	−0.0075 (16)
C7	0.065 (3)	0.049 (2)	0.071 (3)	−0.004 (2)	0.002 (2)	−0.014 (2)
C8	0.061 (3)	0.061 (3)	0.073 (3)	−0.015 (2)	0.014 (2)	0.003 (2)
C9	0.054 (3)	0.059 (3)	0.093 (3)	−0.004 (2)	0.027 (2)	0.002 (3)
C10	0.064 (3)	0.054 (3)	0.072 (3)	0.008 (2)	0.025 (2)	0.008 (2)
C11	0.052 (3)	0.053 (2)	0.044 (2)	0.001 (2)	0.0083 (18)	−0.0033 (19)
C12	0.050 (3)	0.056 (3)	0.037 (2)	0.002 (2)	0.0078 (17)	0.0060 (19)
C13	0.061 (3)	0.063 (3)	0.043 (2)	−0.002 (2)	0.0141 (18)	−0.0002 (19)
C14	0.076 (3)	0.057 (3)	0.051 (2)	−0.007 (2)	0.016 (2)	0.000 (2)
C15	0.107 (4)	0.037 (2)	0.091 (4)	0.003 (3)	0.030 (3)	0.013 (3)
C16	0.121 (6)	0.104 (5)	0.133 (6)	0.022 (5)	−0.021 (5)	0.033 (4)
C17	0.095 (4)	0.069 (4)	0.113 (4)	−0.012 (3)	0.010 (3)	−0.030 (3)
C18	0.069 (3)	0.102 (4)	0.048 (2)	−0.005 (2)	−0.003 (2)	0.007 (2)

Geometric parameters (Å, º)

Br1—C14	1.885 (5)	C11—C18	1.551 (6)
S1—N2	1.584 (6)	C12—C13	1.443 (6)
S1—N1	1.619 (6)	C13—C14	1.355 (7)
O1—C15	1.298 (7)	C4—H4a	0.97
O1—C16	1.510 (7)	C4—H4b	0.97
O2—C15	1.171 (6)	C5—H5a	0.97
N1—C1	1.348 (6)	C5—H5b	0.97
N2—C2	1.346 (6)	C6—H6	0.98
C1—C14	1.414 (7)	C8—H8a	0.97
C1—C2	1.426 (7)	C8—H8b	0.97
C2—C3	1.412 (7)	C9—H9a	0.97
C3—C12	1.360 (6)	C9—H9b	0.97
C3—C4	1.494 (8)	C10—H10a	0.97
C4—C5	1.508 (8)	C10—H10b	0.97
C5—C6	1.530 (6)	C13—H13	0.93
C6—C11	1.539 (5)	C16—H16a	0.96
C6—C7	1.565 (6)	C16—H16b	0.96
C7—C8	1.520 (7)	C16—H16c	0.96
C7—C17	1.529 (7)	C17—H17a	0.96
C7—C15	1.586 (7)	C17—H17b	0.96
C8—C9	1.509 (7)	C17—H17c	0.96
C9—C10	1.532 (6)	C18—H18a	0.96
C10—C11	1.530 (6)	C18—H18b	0.96
C11—C12	1.531 (6)	C18—H18c	0.96
N2—S1—N1	101.6 (2)	C5—C4—H4b	108.3
C15—O1—C16	111.1 (5)	H4a—C4—H4b	107.4
C1—N1—S1	105.0 (4)	C4—C5—H5a	109.1
C2—N2—S1	107.2 (4)	C6—C5—H5a	109.1
N1—C1—C14	127.8 (5)	C4—C5—H5b	109.1
N1—C1—C2	114.1 (5)	C6—C5—H5b	109.1
C14—C1—C2	118.1 (4)	H5a—C5—H5b	107.9
N2—C2—C3	126.5 (5)	C5—C6—H6	104.7
N2—C2—C1	112.1 (5)	C11—C6—H6	104.7
C3—C2—C1	121.5 (4)	C7—C6—H6	104.7
C12—C3—C2	119.1 (5)	C9—C8—H8a	108.7
C12—C3—C4	123.4 (4)	C7—C8—H8a	108.7
C2—C3—C4	117.5 (4)	C9—C8—H8b	108.7
C3—C4—C5	116.0 (4)	C7—C8—H8b	108.7
C4—C5—C6	112.4 (4)	H8a—C8—H8b	107.6
C5—C6—C11	110.8 (3)	C8—C9—H9a	109.6
C5—C6—C7	112.7 (4)	C10—C9—H9a	109.6
C11—C6—C7	118.0 (3)	C8—C9—H9b	109.6
C8—C7—C17	109.7 (4)	C10—C9—H9b	109.6
C8—C7—C6	109.3 (3)	H9a—C9—H9b	108.1
C17—C7—C6	116.2 (4)	C11—C10—H10a	108.9
C8—C7—C15	106.2 (4)	C9—C10—H10a	108.9
C17—C7—C15	111.2 (4)	C11—C10—H10b	108.9
C6—C7—C15	103.7 (4)	C9—C10—H10b	108.9
C9—C8—C7	114.0 (4)	H10a—C10—H10b	107.7
C8—C9—C10	110.2 (4)	C14—C13—H13	119.1
C11—C10—C9	113.5 (4)	C12—C13—H13	119.1
C10—C11—C12	111.6 (4)	O1—C16—H16a	109.5
C10—C11—C6	108.7 (3)	O1—C16—H16b	109.5
C12—C11—C6	106.8 (3)	H16a—C16—H16b	109.5
C10—C11—C18	109.1 (4)	O1—C16—H16c	109.5
C12—C11—C18	106.2 (3)	H16a—C16—H16c	109.5
C6—C11—C18	114.4 (4)	H16b—C16—H16c	109.5
C3—C12—C13	119.6 (4)	C7—C17—H17a	109.5
C3—C12—C11	120.7 (4)	C7—C17—H17b	109.5
C13—C12—C11	119.7 (4)	H17a—C17—H17b	109.5
C14—C13—C12	121.8 (4)	C7—C17—H17c	109.5
C13—C14—C1	119.9 (5)	H17a—C17—H17c	109.5
C13—C14—Br1	120.5 (4)	H17b—C17—H17c	109.5
C1—C14—Br1	119.6 (4)	C11—C18—H18a	109.5
O2—C15—O1	124.9 (5)	C11—C18—H18b	109.5
O2—C15—C7	122.8 (5)	H18a—C18—H18b	109.5
O1—C15—C7	112.3 (5)	C11—C18—H18c	109.5
C3—C4—H4a	108.3	H18a—C18—H18c	109.5
C5—C4—H4a	108.3	H18b—C18—H18c	109.5
C3—C4—H4b	108.3
N2—S1—N1—C1	0.1 (3)	C5—C6—C11—C10	−179.0 (4)
N1—S1—N2—C2	0.0 (3)	C7—C6—C11—C10	−47.1 (5)
S1—N1—C1—C14	178.6 (3)	C5—C6—C11—C12	60.4 (4)
S1—N1—C1—C2	−0.2 (4)	C7—C6—C11—C12	−167.7 (3)
S1—N2—C2—C3	−180.0 (3)	C5—C6—C11—C18	−56.8 (5)
S1—N2—C2—C1	−0.1 (4)	C7—C6—C11—C18	75.1 (5)
N1—C1—C2—N2	0.2 (5)	C2—C3—C12—C13	−3.0 (5)
C14—C1—C2—N2	−178.8 (3)	C4—C3—C12—C13	178.4 (4)
N1—C1—C2—C3	−179.9 (4)	C2—C3—C12—C11	179.2 (4)
C14—C1—C2—C3	1.2 (6)	C4—C3—C12—C11	0.6 (6)
N2—C2—C3—C12	−178.7 (4)	C10—C11—C12—C3	−152.4 (4)
C1—C2—C3—C12	1.3 (6)	C6—C11—C12—C3	−33.7 (5)
N2—C2—C3—C4	0.0 (6)	C18—C11—C12—C3	88.8 (4)
C1—C2—C3—C4	−179.9 (4)	C10—C11—C12—C13	29.8 (5)
C12—C3—C4—C5	6.6 (6)	C6—C11—C12—C13	148.5 (3)
C2—C3—C4—C5	−172.0 (4)	C18—C11—C12—C13	−89.0 (4)
C3—C4—C5—C6	21.3 (6)	C3—C12—C13—C14	2.2 (6)
C4—C5—C6—C11	−55.9 (5)	C11—C12—C13—C14	−180.0 (4)
C4—C5—C6—C7	169.5 (4)	C12—C13—C14—C1	0.4 (6)
C5—C6—C7—C8	177.4 (4)	C12—C13—C14—Br1	179.0 (3)
C11—C6—C7—C8	46.4 (5)	N1—C1—C14—C13	179.2 (4)
C5—C6—C7—C17	52.7 (6)	C2—C1—C14—C13	−2.0 (6)
C11—C6—C7—C17	−78.4 (5)	N1—C1—C14—Br1	0.6 (6)
C5—C6—C7—C15	−69.6 (4)	C2—C1—C14—Br1	179.4 (3)
C11—C6—C7—C15	159.4 (4)	C16—O1—C15—O2	4.2 (9)
C17—C7—C8—C9	78.0 (5)	C16—O1—C15—C7	−177.2 (5)
C6—C7—C8—C9	−50.5 (5)	C8—C7—C15—O2	39.2 (7)
C15—C7—C8—C9	−161.8 (4)	C17—C7—C15—O2	158.5 (6)
C7—C8—C9—C10	57.9 (5)	C6—C7—C15—O2	−76.0 (7)
C8—C9—C10—C11	−58.6 (5)	C8—C7—C15—O1	−139.5 (5)
C9—C10—C11—C12	169.6 (4)	C17—C7—C15—O1	−20.2 (6)
C9—C10—C11—C6	52.0 (5)	C6—C7—C15—O1	105.3 (5)
C9—C10—C11—C18	−73.3 (5)