Crystal structure of a new phen­yl(morpholino)methane­thione derivative: 4-[(morpholin-4-yl)carbothioyl]benzoic acid

The first mol­ecular compound synthesized and crystallized in Benin is reported. This work was carried out during the first crystallographic training session at the X-TechLab in Sèmè City, organized within the IUCr–UNESCO OpenLab framework.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.048
• wR factor = 0.131
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3       ..O3       .       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6       ..S1       .       3.00 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.831 Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT012_ALERT_1_G N.O.K.   _shelx_res_checksum Found in CIF ......     Please Check
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 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.

   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

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Computing details

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019), PLATON (Spek, 2020); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: enCIFer (Allen et al., 2004) and WinGX (Farrugia, 2012).

4-[(Morpholin-4-yl)carbothioyl]benzoic acid

Crystal data

C12H13NO3S	F(000) = 528
Mr = 251.29	Dx = 1.394 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3252 (1) Å	Cell parameters from 22827 reflections
b = 17.1485 (3) Å	θ = 2.4–30.5°
c = 9.3505 (1) Å	µ = 0.27 mm^−1
β = 116.249 (1)°	T = 293 K
V = 1197.26 (3) Å^3	Prism, brown
Z = 4	0.15 × 0.15 × 0.08 mm

Data collection

Bruker D8 Quest diffractometer	Rint = 0.024
Radiation source: micro-focus sealed X-ray tube	θmax = 30.5°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2019)	k = −24→24
Tmin = 0.959, Tmax = 0.981	l = −13→13
22827 measured reflections	60 standard reflections every 120 min
3664 independent reflections	intensity decay: none
3317 reflections with I > 2σ(I)

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	All H-atom parameters refined
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0661P)^2 + 0.4174P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3664 reflections	Δρmax = 0.55 e Å^−3
211 parameters	Δρmin = −0.47 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.44570 (18)	0.31569 (7)	0.41547 (15)	0.0357 (3)
C9	0.4178 (2)	0.39766 (8)	0.36720 (19)	0.0375 (3)
C10	0.5884 (2)	0.43113 (10)	0.3757 (2)	0.0453 (4)
C11	0.6791 (3)	0.30807 (11)	0.3284 (3)	0.0539 (4)
C12	0.5096 (3)	0.27137 (10)	0.3165 (2)	0.0470 (4)
O3	0.65390 (19)	0.38815 (8)	0.28269 (17)	0.0541 (3)
H7	−0.016 (3)	0.4221 (12)	0.575 (2)	0.050 (5)*
H6	0.112 (3)	0.3489 (12)	0.444 (2)	0.046 (5)*
H4	0.573 (3)	0.3397 (12)	0.835 (2)	0.047 (5)*
H9A	0.378 (3)	0.4270 (12)	0.438 (2)	0.051 (5)*
H3	0.452 (3)	0.4107 (13)	0.975 (3)	0.052 (5)*
H9B	0.324 (3)	0.4011 (12)	0.258 (3)	0.050 (5)*
H12B	0.532 (3)	0.2169 (15)	0.355 (3)	0.061 (6)*
H10A	0.679 (3)	0.4269 (14)	0.494 (3)	0.062 (6)*
H12A	0.412 (4)	0.2743 (15)	0.199 (3)	0.074 (7)*
H11A	0.716 (3)	0.2808 (14)	0.256 (3)	0.062 (6)*
H11B	0.783 (3)	0.3030 (14)	0.449 (3)	0.062 (6)*
H10B	0.569 (3)	0.4855 (13)	0.333 (3)	0.053 (6)*
H1B	−0.099 (6)	0.496 (3)	0.869 (5)	0.074 (19)*	0.54 (6)
H1A	0.147 (5)	0.509 (2)	1.062 (5)	0.045 (16)*	0.46 (6)
S1	0.47641 (7)	0.19242 (2)	0.59878 (5)	0.04786 (14)
C2	0.20398 (17)	0.42178 (8)	0.78784 (14)	0.0292 (2)
C5	0.35519 (17)	0.33605 (7)	0.62500 (15)	0.0283 (2)
O1	0.21386 (16)	0.48436 (8)	1.01739 (13)	0.0468 (3)
C1	0.11742 (19)	0.46256 (8)	0.87542 (16)	0.0333 (3)
O2	−0.05100 (16)	0.47194 (9)	0.80599 (14)	0.0517 (3)
C4	0.45678 (18)	0.35472 (8)	0.78541 (16)	0.0330 (3)
C6	0.17845 (18)	0.36164 (9)	0.54576 (16)	0.0343 (3)
C8	0.43045 (17)	0.28503 (8)	0.53941 (15)	0.0296 (2)
C3	0.38209 (18)	0.39791 (8)	0.86649 (15)	0.0331 (3)
C7	0.10388 (18)	0.40414 (9)	0.62725 (16)	0.0343 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0492 (7)	0.0297 (5)	0.0396 (6)	0.0039 (5)	0.0299 (5)	−0.0014 (4)
C9	0.0458 (7)	0.0344 (7)	0.0408 (7)	0.0079 (5)	0.0269 (6)	0.0062 (5)
C10	0.0557 (9)	0.0376 (7)	0.0566 (10)	−0.0006 (6)	0.0375 (8)	−0.0012 (7)
C11	0.0636 (11)	0.0508 (9)	0.0685 (12)	0.0107 (8)	0.0486 (10)	−0.0014 (8)
C12	0.0703 (11)	0.0390 (8)	0.0488 (9)	0.0014 (7)	0.0420 (9)	−0.0097 (7)
O3	0.0700 (8)	0.0506 (7)	0.0682 (8)	0.0016 (6)	0.0547 (7)	0.0014 (6)
S1	0.0679 (3)	0.0341 (2)	0.0500 (2)	0.01608 (17)	0.0337 (2)	0.01035 (15)
C2	0.0329 (6)	0.0322 (6)	0.0277 (5)	0.0021 (4)	0.0182 (5)	−0.0003 (4)
C5	0.0311 (6)	0.0297 (6)	0.0292 (5)	0.0014 (4)	0.0181 (5)	0.0000 (4)
O1	0.0478 (6)	0.0604 (7)	0.0327 (5)	0.0117 (5)	0.0184 (5)	−0.0096 (5)
C1	0.0378 (6)	0.0367 (6)	0.0308 (6)	0.0059 (5)	0.0201 (5)	0.0003 (5)
O2	0.0395 (6)	0.0794 (9)	0.0390 (6)	0.0177 (6)	0.0200 (5)	−0.0067 (6)
C4	0.0291 (6)	0.0400 (7)	0.0301 (6)	0.0050 (5)	0.0132 (5)	−0.0006 (5)
C6	0.0309 (6)	0.0474 (7)	0.0255 (5)	0.0028 (5)	0.0134 (5)	−0.0043 (5)
C8	0.0306 (6)	0.0302 (6)	0.0312 (6)	0.0023 (4)	0.0167 (5)	−0.0016 (5)
C3	0.0332 (6)	0.0400 (7)	0.0257 (5)	0.0024 (5)	0.0128 (5)	−0.0028 (5)
C7	0.0281 (6)	0.0466 (7)	0.0299 (6)	0.0056 (5)	0.0145 (5)	−0.0019 (5)

Geometric parameters (Å, º)

N1—C8	1.3288 (17)	C2—C7	1.3906 (18)
N1—C9	1.4631 (18)	C2—C3	1.3938 (18)
N1—C12	1.4674 (17)	C2—C1	1.4836 (17)
C9—C10	1.501 (2)	C5—C6	1.3937 (18)
C9—H9A	1.00 (2)	C5—C4	1.3948 (18)
C9—H9B	0.98 (2)	C5—C8	1.4973 (17)
C10—O3	1.4202 (19)	O1—C1	1.2664 (17)
C10—H10A	1.03 (2)	O1—H1A	0.926 (19)
C10—H10B	1.00 (2)	C1—O2	1.2681 (18)
C11—O3	1.426 (2)	O2—H1B	0.93 (2)
C11—C12	1.503 (3)	C4—C3	1.3881 (18)
C11—H11A	0.98 (2)	C4—H4	0.91 (2)
C11—H11B	1.08 (2)	C6—C7	1.3841 (18)
C12—H12B	0.99 (3)	C6—H6	0.89 (2)
C12—H12A	1.04 (3)	C3—H3	0.94 (2)
S1—C8	1.6700 (13)	C7—H7	0.95 (2)
C8—N1—C9	125.87 (11)	C10—O3—C11	111.19 (13)
C8—N1—C12	123.12 (12)	C7—C2—C3	119.70 (11)
C9—N1—C12	110.80 (12)	C7—C2—C1	119.55 (11)
N1—C9—C10	109.51 (12)	C3—C2—C1	120.68 (11)
N1—C9—H9A	109.5 (12)	C6—C5—C4	119.66 (11)
C10—C9—H9A	110.8 (12)	C6—C5—C8	119.52 (11)
N1—C9—H9B	109.0 (13)	C4—C5—C8	120.72 (11)
C10—C9—H9B	109.6 (12)	C1—O1—H1A	112 (3)
H9A—C9—H9B	108.4 (17)	O1—C1—O2	122.96 (12)
O3—C10—C9	112.31 (14)	O1—C1—C2	118.70 (12)
O3—C10—H10A	109.0 (13)	O2—C1—C2	118.31 (12)
C9—C10—H10A	104.7 (13)	C1—O2—H1B	115 (3)
O3—C10—H10B	105.9 (13)	C3—C4—C5	120.32 (12)
C9—C10—H10B	111.0 (13)	C3—C4—H4	120.4 (13)
H10A—C10—H10B	114.1 (18)	C5—C4—H4	119.3 (13)
O3—C11—C12	111.86 (15)	C7—C6—C5	119.89 (12)
O3—C11—H11A	107.6 (14)	C7—C6—H6	120.1 (13)
C12—C11—H11A	108.8 (14)	C5—C6—H6	119.9 (13)
O3—C11—H11B	109.5 (13)	N1—C8—C5	117.32 (11)
C12—C11—H11B	109.6 (13)	N1—C8—S1	124.75 (10)
H11A—C11—H11B	109.5 (18)	C5—C8—S1	117.81 (9)
N1—C12—C11	109.05 (14)	C4—C3—C2	119.84 (12)
N1—C12—H12B	108.6 (14)	C4—C3—H3	119.8 (13)
C11—C12—H12B	110.5 (13)	C2—C3—H3	120.4 (13)
N1—C12—H12A	108.2 (15)	C6—C7—C2	120.56 (12)
C11—C12—H12A	109.0 (15)	C6—C7—H7	121.0 (13)
H12B—C12—H12A	111.5 (19)	C2—C7—H7	118.5 (13)
C8—N1—C9—C10	118.33 (16)	C8—C5—C6—C7	175.39 (13)
C12—N1—C9—C10	−56.57 (18)	C9—N1—C8—C5	8.5 (2)
N1—C9—C10—O3	55.99 (19)	C12—N1—C8—C5	−177.18 (14)
C8—N1—C12—C11	−117.94 (17)	C9—N1—C8—S1	−175.68 (12)
C9—N1—C12—C11	57.12 (19)	C12—N1—C8—S1	−1.4 (2)
O3—C11—C12—N1	−57.0 (2)	C6—C5—C8—N1	64.84 (17)
C9—C10—O3—C11	−56.2 (2)	C4—C5—C8—N1	−118.65 (15)
C12—C11—O3—C10	56.8 (2)	C6—C5—C8—S1	−111.26 (13)
C7—C2—C1—O1	−173.78 (14)	C4—C5—C8—S1	65.25 (15)
C3—C2—C1—O1	9.1 (2)	C5—C4—C3—C2	0.9 (2)
C7—C2—C1—O2	8.3 (2)	C7—C2—C3—C4	−1.9 (2)
C3—C2—C1—O2	−168.82 (14)	C1—C2—C3—C4	175.16 (13)
C6—C5—C4—C3	0.6 (2)	C5—C6—C7—C2	0.1 (2)
C8—C5—C4—C3	−175.88 (13)	C3—C2—C7—C6	1.4 (2)
C4—C5—C6—C7	−1.2 (2)	C1—C2—C7—C6	−175.72 (14)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O1^i	0.98 (2)	2.47 (2)	3.2985 (19)	142.1 (16)
C12—H12B···S1	0.99 (3)	2.55 (2)	3.0860 (18)	113.8 (17)
O2—H1B···O1^ii	0.93 (2)	1.75 (2)	2.6661 (15)	165 (5)
O1—H1A···O2^ii	0.93 (2)	1.78 (2)	2.6661 (15)	160 (4)
C3—H3···O3^iii	0.94 (2)	2.64 (2)	3.536 (2)	158 (2)
C6—H6···S1^iv	0.89 (2)	2.996 (2)	3.8650 (14)	166 (2)
C10—H10B···Cg^v	1.00 (2)	2.74 (2)	3.6180 (18)	147 (2)

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