(E)-O-Ethyl N-(4-nitro­phen­yl)thio­carbamate

The title compound, C₉H₁₀N₂O₃S, is effectively planar, adopts an E conformation about the central C—N bond and exists in the thione form. N—H...S and C—H...O hydrogen bonds link the mol­ecules into ribbons. Layers of ribbons are connected to adjacent layers via C—H...O inter­actions. The crystal is a non-merohedral twin, with the twin law describing a rotation of 180° around the [00] direction.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.052
• wR factor = 0.162
• Data-to-parameter ratio = 25.2

checkCIF/PLATON results

No syntax errors found



Alert level A
REFLT03_ALERT_3_A  Reflection count > 15% excess reflns - sys abs data present?
           From the CIF: _diffrn_reflns_theta_max           26.50
           From the CIF: _diffrn_reflns_theta_full          26.50
           From the CIF: _reflns_number_total               3481
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2096
           Completeness (_total/calc)            166.08%

Author Response: The problem with the overestimated completeness is due to the fact that the sample chosen for study was a twin. The twin law is explained in the "_publ_section_exptl_refinement". Since reflections from both twin components are used for refinement, the completeness should ideally be at least 190%. But due to incomplete overlap of some reflections (rejected) and to the fact that the data collection strategy may not provide 99% complete data for both components, we only get approximately 165% for this sample.

 Further response to a query about the number of reflections used in the cell
 refinement and the total number of reflections measured is also relevant and
 is reproduced here.

 TwinSolve integrated reflections out to a max theta of about 27.8deg.
 So the numbers from the tsarchive.cif include reflections that apparently were
 not used later, since the data collection section of the paper reports max
 theta of 26.5deg. Therefore I've recalculated the numbers using 26.5 as the
 cutoff. These numbers come from refining both components simultaneously so
 that reflections from both components are used:

 _cell_measurement_reflns_used               6050
 _cell_measurement_theta_min                  3.1
 _cell_measurement_theta_max                 26.5

 The total number of reflections measured is 14293, not 3641 as shown in the
 paper. The breakdown is this:
 5912 non-overlapped component 1
 5898 non-overlapped component 2
 2483 1+2 overlapped

 Once the equivalent reflections are averaged, keeping each group separate,
 there are 3481 unique reflections, and the breakdown is: 1451 non-overlapped
 component 1 1443 non-overlapped component 2  587 1+2 overlapped.  The actual
 hklf5 file contains 4068 reflections since the 587 overlaps are counted twice.

 Regarding the value of "Rint": It is impossible to calculate just one value
 for Rint. There is one for each set of reflections:

 non-overlapped component 1, Rint = 0.035
 non-overlapped component 2, Rint = 0.045

 SHELX won't report an Rint for an HKLF 5 twin refinement because merging is
 disabled (which is why the equivalent reflections within each component must
 be merged in advance by TwinSolve)."

 The 26.5 deg cut-off was applied so as to ensure data completeness.

PLAT707_ALERT_1_A D...A   Calc   47.932(9), Rep  3.4435(19), Dev..    4943.17 Sigma
              N1   -S1      1.555   2.333
PLAT707_ALERT_1_A D...A   Calc   28.262(6), Rep    3.481(3), Dev..    4130.17 Sigma
              C4   -O2      1.555   2.454
PLAT726_ALERT_1_A H...A   Calc    47.66000, Rep     2.70000 Dev...      44.96 Ang.
              H1#  -S1      1.555   2.333
PLAT726_ALERT_1_A H...A   Calc    27.42000, Rep     2.57000 Dev...      24.85 Ang.
              H4   -O2      1.555   2.454
PLAT728_ALERT_1_A D-H..A  Calc      108.00, Rep      142.00 Dev...      34.00 Deg.
              N1   -H1#  -S1      1.555   1.555   2.333
PLAT728_ALERT_1_A D-H..A  Calc      152.00, Rep      162.00 Dev...      10.00 Deg.
              C4   -H4   -O2      1.555   1.555   2.454

Alert level B
PLAT021_ALERT_1_B Ratio Unique / Expected Reflections too High ...       1.66
PLAT737_ALERT_1_B D...A   Calc   47.932(9), Rep  3.4435(19) ......       4.74 su-Ra
              N1   -S1      1.555   2.333

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.42
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

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

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Authors GAB, DJY and JLW were responsible for the synthesis of the compound. The crystallography, including the resolution of the twin, involved the UTSA (GAB & ERTT) and Rigaku groups (REB and LMD).

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: TwinSolve (Rigaku/MSC & Prekat, 2006); data reduction: TwinSolve; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

(E)—O-Ethyl N-(4-nitrophenyl)thiocarbamate

Crystal data

C9H10N2O3S	Z = 2
Mr = 226.25	F(000) = 236
Triclinic, P1	Dx = 1.485 Mg m^−3
Hall symbol: -P 1	Melting point = 451–452 K
a = 6.9247 (12) Å	Mo Kα radiation, λ = 0.71070 Å
b = 7.6430 (14) Å	Cell parameters from 6050 reflections
c = 10.4772 (19) Å	θ = 3.1–26.5°
α = 105.782 (8)°	µ = 0.31 mm^−1
β = 90.136 (8)°	T = 150 K
γ = 107.769 (7)°	Block, colorless
V = 505.94 (16) Å^3	0.22 × 0.13 × 0.13 mm

Data collection

Rigaku AFC12 κ/SATURN 724 diffractometer	3481 independent reflections
Radiation source: fine-focus sealed tube	3295 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 26.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.935, Tmax = 0.961	k = −9→9
14293 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.162	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0907P)^2 + 0.4757P] where P = (Fo^2 + 2Fc^2)/3
3481 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.75 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 1.48 (3H, t, J = 7.0 Hz, CH₃), 4.67 (2H, q, J = 7.0 Hz, CH₂), 7.57 (2H, br, aryl-H), 8.23 (2H, m, aryl-H), 8.42 (1H, br, NH); IR (crystals): ν(N—H) 3284 (br), ν(N—O₂) 1548 (s), ν(CN) 1494 (s), ν(N—O₂) 1376 (m), ν(CS) 1032 (s) cm^-1.

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
S1	0.92292 (7)	1.05291 (7)	1.20033 (5)	0.02160 (19)
O3	0.5460 (2)	−0.1845 (2)	0.77860 (15)	0.0238 (4)
O2	0.5533 (3)	−0.0994 (2)	0.59690 (15)	0.0287 (4)
O1	0.8260 (2)	0.7001 (2)	1.22545 (14)	0.0210 (3)
N2	0.5736 (3)	−0.0618 (2)	0.71902 (17)	0.0190 (4)
N1	0.8098 (3)	0.7171 (2)	1.01606 (17)	0.0190 (4)
H1N1	0.8223	0.7910	0.9631	0.023*
C5	0.6366 (3)	0.1400 (3)	0.7975 (2)	0.0177 (4)
C4	0.6548 (3)	0.2803 (3)	0.7333 (2)	0.0192 (4)
H4	0.6288	0.2472	0.6393	0.023*
C3	0.7117 (3)	0.4698 (3)	0.8100 (2)	0.0195 (4)
H3	0.7247	0.5679	0.7680	0.023*
C2	0.7506 (3)	0.5191 (3)	0.9491 (2)	0.0173 (4)
C7	0.7321 (3)	0.3748 (3)	1.0111 (2)	0.0200 (4)
H7	0.7589	0.4065	1.1050	0.024*
C6	0.6744 (3)	0.1847 (3)	0.9340 (2)	0.0193 (4)
H6	0.6608	0.0855	0.9750	0.023*
C1	0.8507 (3)	0.8134 (3)	1.1473 (2)	0.0183 (4)
C8	0.8656 (3)	0.7841 (3)	1.3696 (2)	0.0242 (5)
H8A	0.7767	0.8634	1.4025	0.029*
H8B	1.0094	0.8661	1.3937	0.029*
C9	0.8209 (4)	0.6200 (4)	1.4291 (2)	0.0332 (5)
H9A	0.8488	0.6697	1.5261	0.040*
H9B	0.9073	0.5408	1.3937	0.040*
H9C	0.6773	0.5420	1.4062	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0238 (3)	0.0154 (3)	0.0224 (3)	0.0047 (2)	0.0013 (2)	0.0020 (2)
O3	0.0298 (8)	0.0162 (7)	0.0255 (8)	0.0064 (6)	0.0032 (6)	0.0070 (6)
O2	0.0425 (9)	0.0220 (8)	0.0183 (7)	0.0092 (7)	0.0003 (7)	0.0017 (6)
O1	0.0262 (7)	0.0181 (7)	0.0159 (7)	0.0045 (6)	0.0007 (6)	0.0030 (5)
N2	0.0191 (8)	0.0172 (9)	0.0200 (8)	0.0060 (7)	0.0014 (6)	0.0042 (7)
N1	0.0221 (8)	0.0156 (8)	0.0185 (8)	0.0041 (7)	0.0013 (7)	0.0058 (7)
C5	0.0160 (9)	0.0153 (10)	0.0206 (10)	0.0051 (8)	0.0017 (7)	0.0031 (8)
C4	0.0218 (9)	0.0196 (10)	0.0159 (9)	0.0070 (8)	−0.0001 (7)	0.0041 (8)
C3	0.0210 (9)	0.0186 (10)	0.0206 (10)	0.0068 (8)	0.0016 (7)	0.0080 (8)
C2	0.0160 (8)	0.0149 (10)	0.0202 (10)	0.0051 (7)	0.0022 (7)	0.0035 (8)
C7	0.0225 (9)	0.0194 (10)	0.0171 (9)	0.0054 (8)	0.0008 (7)	0.0050 (8)
C6	0.0205 (9)	0.0172 (10)	0.0207 (10)	0.0050 (8)	0.0021 (7)	0.0074 (8)
C1	0.0149 (9)	0.0183 (10)	0.0210 (10)	0.0059 (8)	0.0017 (7)	0.0036 (8)
C8	0.0281 (10)	0.0230 (11)	0.0162 (10)	0.0048 (9)	−0.0015 (8)	0.0012 (8)
C9	0.0472 (14)	0.0303 (13)	0.0206 (11)	0.0112 (11)	−0.0002 (10)	0.0063 (9)

Geometric parameters (Å, º)

S1—C1	1.672 (2)	C3—C2	1.406 (3)
O3—N2	1.231 (2)	C3—H3	0.9500
O2—N2	1.230 (2)	C2—C7	1.400 (3)
O1—C1	1.322 (3)	C7—C6	1.389 (3)
O1—C8	1.460 (2)	C7—H7	0.9500
N2—C5	1.464 (2)	C6—H6	0.9500
N1—C1	1.354 (3)	C8—C9	1.499 (3)
N1—C2	1.412 (3)	C8—H8A	0.9900
N1—H1N1	0.8800	C8—H8B	0.9900
C5—C6	1.382 (3)	C9—H9A	0.9800
C5—C4	1.389 (3)	C9—H9B	0.9800
C4—C3	1.384 (3)	C9—H9C	0.9800
C4—H4	0.9500
C1—O1—C8	119.59 (16)	C6—C7—H7	120.3
O2—N2—O3	123.55 (17)	C2—C7—H7	120.3
O2—N2—C5	118.14 (17)	C5—C6—C7	119.92 (19)
O3—N2—C5	118.30 (16)	C5—C6—H6	120.0
C1—N1—C2	131.38 (18)	C7—C6—H6	120.0
C1—N1—H1N1	114.3	S1—C1—O1	124.93 (15)
C2—N1—H1N1	114.3	S1—C1—N1	121.58 (16)
C6—C5—C4	121.97 (19)	O1—C1—N1	113.49 (17)
C6—C5—N2	118.65 (18)	O1—C8—C9	106.55 (17)
C4—C5—N2	119.37 (17)	O1—C8—H8A	110.4
C3—C4—C5	118.20 (18)	C9—C8—H8A	110.4
C3—C4—H4	120.9	O1—C8—H8B	110.4
C5—C4—H4	120.9	C9—C8—H8B	110.4
C4—C3—C2	120.98 (19)	H8A—C8—H8B	108.6
C4—C3—H3	119.5	C8—C9—H9A	109.5
C2—C3—H3	119.5	C8—C9—H9B	109.5
C7—C2—C3	119.60 (19)	H9A—C9—H9B	109.5
C7—C2—N1	124.77 (18)	C8—C9—H9C	109.5
C3—C2—N1	115.63 (18)	H9A—C9—H9C	109.5
C6—C7—C2	119.32 (19)	H9B—C9—H9C	109.5
O2—N2—C5—C6	−175.30 (18)	C3—C2—C7—C6	−0.4 (3)
O3—N2—C5—C6	3.9 (3)	N1—C2—C7—C6	−179.38 (18)
C1—N1—C2—C3	177.19 (19)	C4—C5—C6—C7	0.1 (3)
O2—N2—C5—C4	5.3 (3)	N2—C5—C6—C7	−179.30 (18)
O3—N2—C5—C4	−175.49 (17)	C2—C7—C6—C5	0.3 (3)
C6—C5—C4—C3	−0.3 (3)	C8—O1—C1—N1	179.73 (17)
N2—C5—C4—C3	179.10 (17)	C8—O1—C1—S1	−0.9 (3)
C5—C4—C3—C2	0.1 (3)	C2—N1—C1—O1	−1.7 (3)
C4—C3—C2—C7	0.2 (3)	C2—N1—C1—S1	178.88 (16)
C4—C3—C2—N1	179.28 (17)	C1—O1—C8—C9	179.11 (18)
C1—N1—C2—C7	−3.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1^i	0.88	2.70	3.4435 (19)	142
C4—H4···O2^ii	0.95	2.57	3.481 (3)	162
C8—H8A···O2^iii	0.99	2.57	3.345 (3)	135
C3—H3···O3^iv	0.95	2.54	3.275 (3)	135

Symmetry codes: (i) −x−2, −y−2, −z−2; (ii) −x−1, −y, −z−1; (iii) x, y+1, z+1; (iv) x, y+1, z.