Structural investigation of N-[2-(4-fluoro-3-phen­oxy­benzo­yl)hydrazinecarbo­thio­yl]benzamide and N-[2-(4-fluoro-3-phen­oxy­benzo­yl)hydrazinecarbo­thio­yl]-4-meth­oxy­benzamide

Crystal structure analysis of N-[2-(4-fluoro-3-phen­oxy­benzo­yl)hydrazinecarbo­thio­yl]benzamide and its 4-meth­oxy derivative highlights the significance of strong and weak hydrogen bonds. The difference in the contributions of atom–atom contacts obtained from Hirshfeld surface analysis and fingerprint plots helps in distinguishing the variations in the crystal packing of the two compounds.

Key indicators

Structure: A1

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.119
• Data-to-parameter ratio = 17.0

Structure: A2

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.046
• wR factor = 0.122
• Data-to-parameter ratio = 7.8

checkCIF/PLATON results

No syntax errors found



Datablock: A1


Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    F1       --C8       .        5.1 s.u.
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O1 Check
PLAT480_ALERT_4_C Long H...A H-Bond Reported H19      ..S1       .       2.98 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H20      ..O1       .       2.77 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      8.421 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         53 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

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

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: A2


Alert level A
THETM01_ALERT_3_A  The value of sine(theta_max)/wavelength is less than 0.550
            Calculated sin(theta_max)/wavelength =    0.5026

Author Response: The value of sine(theta_max)/wavelength is less due to weakly diffracting nature of the crystal.

PLAT023_ALERT_3_A Resolution (too) Low [sin(theta)/Lambda < 0.6]..      20.93 Ang-1

Author Response: This is on account of the weakly diffracting nature of the crystal.

Alert level B
PLAT088_ALERT_3_B Poor Data / Parameter Ratio ....................       7.79 Note

Alert level C
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O1 Check
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         C3 Check
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C1 Check
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C8 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............      0.007 Ang.
PLAT414_ALERT_2_C Short Intra D-H..H-X       H3N      ..H17              1.98 Ang.
                                                      x,y,z  =      1_555 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.492 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.503          4 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large       7.46 Why ?
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        61% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note

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

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

---

Computing details

For both structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020), WinGX (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

N-[2-(4-Fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide (A1)

Crystal data

C21H16FN3O3S	F(000) = 848
Mr = 409.43	Dx = 1.401 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.3849 (13) Å	Cell parameters from 10485 reflections
b = 7.7063 (6) Å	θ = 2.2–28.6°
c = 13.9216 (10) Å	µ = 0.20 mm^−1
β = 100.136 (5)°	T = 298 K
V = 1941.6 (2) Å^3	Plates, colorless
Z = 4	0.27 × 0.20 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer	2753 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.043
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 27.7°, θmin = 2.3°
	h = −23→21
31160 measured reflections	k = −10→10
4460 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 0.1773P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4460 reflections	Δρmax = 0.15 e Å^−3
262 parameters	Δρmin = −0.17 e Å^−3
0 restraints

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
N2	0.35731 (8)	0.0786 (2)	0.88306 (10)	0.0603 (4)
H2N	0.398146	0.108884	0.865793	0.072*
O2	0.35727 (7)	0.08997 (19)	0.69344 (9)	0.0715 (4)
N1	0.30299 (8)	0.0015 (2)	0.81656 (10)	0.0635 (4)
H1	0.267495	−0.053998	0.835584	0.076*
C15	0.47522 (9)	0.2198 (2)	1.01326 (12)	0.0544 (4)
N3	0.40609 (7)	0.18548 (18)	1.03435 (9)	0.0538 (4)
H3N	0.398570	0.216229	1.091172	0.065*
C19	0.63953 (10)	0.4486 (3)	1.22873 (13)	0.0637 (5)
H19	0.675815	0.500499	1.274731	0.076*
C13	0.30627 (10)	0.0143 (2)	0.72070 (12)	0.0546 (4)
C11	0.24397 (10)	−0.0680 (2)	0.65341 (12)	0.0548 (4)
O3	0.48982 (7)	0.18773 (19)	0.93243 (8)	0.0737 (4)
C12	0.23455 (10)	−0.0202 (2)	0.55602 (12)	0.0587 (5)
H12	0.267655	0.056422	0.535242	0.070*
C18	0.58177 (10)	0.3634 (3)	1.25799 (13)	0.0651 (5)
H18	0.579476	0.355776	1.324057	0.078*
C16	0.53052 (9)	0.2979 (2)	1.09115 (11)	0.0509 (4)
C7	0.17640 (11)	−0.0857 (3)	0.48974 (13)	0.0650 (5)
C17	0.52695 (10)	0.2888 (2)	1.19000 (12)	0.0589 (5)
H17	0.487572	0.232436	1.210329	0.071*
O1	0.16903 (8)	−0.0470 (2)	0.39147 (9)	0.0815 (4)
C20	0.64377 (11)	0.4571 (3)	1.13081 (13)	0.0683 (5)
H20	0.683089	0.514503	1.110943	0.082*
C14	0.34729 (9)	0.1066 (2)	0.97367 (11)	0.0524 (4)
C1	0.13186 (10)	0.1053 (3)	0.35731 (13)	0.0658 (5)
C10	0.19555 (10)	−0.1858 (3)	0.68345 (14)	0.0678 (5)
H10	0.202440	−0.221053	0.748315	0.081*
C21	0.59024 (10)	0.3814 (3)	1.06281 (12)	0.0610 (5)
H21	0.593940	0.385998	0.997084	0.073*
C8	0.12811 (11)	−0.1982 (3)	0.52212 (15)	0.0755 (6)
F1	0.07018 (8)	−0.2577 (2)	0.45739 (10)	0.1157 (5)
C9	0.13740 (12)	−0.2507 (3)	0.61757 (16)	0.0828 (6)
H9	0.104704	−0.329362	0.637526	0.099*
C6	0.09068 (11)	0.2008 (3)	0.41052 (15)	0.0756 (6)
H6	0.086151	0.166959	0.473327	0.091*
C4	0.06114 (16)	0.3971 (4)	0.2770 (2)	0.1119 (9)
H4	0.036467	0.495305	0.249363	0.134*
C2	0.13978 (13)	0.1537 (3)	0.26449 (15)	0.0849 (7)
H2	0.169036	0.089353	0.229477	0.102*
C3	0.10316 (18)	0.3001 (4)	0.2249 (2)	0.1101 (9)
H3	0.107028	0.333605	0.161870	0.132*
C5	0.05585 (13)	0.3485 (4)	0.3694 (2)	0.0958 (7)
H5	0.028365	0.415792	0.405426	0.115*
S1	0.26986 (3)	0.05350 (8)	1.01272 (3)	0.07183 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0605 (9)	0.0788 (10)	0.0420 (8)	−0.0123 (8)	0.0097 (7)	−0.0069 (7)
O2	0.0662 (8)	0.0981 (10)	0.0499 (7)	−0.0220 (7)	0.0097 (6)	0.0030 (7)
N1	0.0659 (10)	0.0808 (11)	0.0435 (8)	−0.0197 (8)	0.0090 (7)	−0.0051 (8)
C15	0.0558 (10)	0.0637 (11)	0.0457 (9)	0.0021 (8)	0.0147 (8)	−0.0033 (8)
N3	0.0539 (8)	0.0702 (10)	0.0381 (7)	−0.0016 (7)	0.0100 (6)	−0.0055 (7)
C19	0.0562 (11)	0.0809 (13)	0.0525 (10)	−0.0022 (10)	0.0053 (8)	−0.0055 (10)
C13	0.0590 (11)	0.0618 (11)	0.0425 (9)	−0.0026 (9)	0.0076 (8)	0.0010 (8)
C11	0.0566 (10)	0.0612 (11)	0.0457 (9)	−0.0014 (9)	0.0070 (8)	−0.0016 (8)
O3	0.0684 (8)	0.1078 (11)	0.0495 (7)	−0.0126 (7)	0.0229 (6)	−0.0201 (7)
C12	0.0637 (11)	0.0683 (12)	0.0444 (9)	−0.0035 (9)	0.0107 (8)	−0.0032 (8)
C18	0.0610 (11)	0.0937 (14)	0.0408 (9)	0.0028 (10)	0.0095 (8)	−0.0040 (9)
C16	0.0512 (10)	0.0590 (10)	0.0433 (8)	0.0056 (8)	0.0104 (7)	−0.0012 (8)
C7	0.0693 (12)	0.0775 (13)	0.0450 (10)	0.0071 (10)	0.0012 (9)	−0.0073 (9)
C17	0.0540 (10)	0.0781 (12)	0.0467 (9)	−0.0011 (9)	0.0149 (8)	−0.0006 (9)
O1	0.0998 (11)	0.0991 (11)	0.0421 (7)	0.0170 (9)	0.0026 (7)	−0.0105 (7)
C20	0.0595 (11)	0.0891 (14)	0.0576 (11)	−0.0121 (10)	0.0136 (9)	0.0041 (10)
C14	0.0585 (11)	0.0573 (10)	0.0409 (8)	0.0019 (8)	0.0076 (8)	0.0015 (8)
C1	0.0568 (11)	0.0850 (14)	0.0496 (10)	−0.0092 (10)	−0.0068 (9)	−0.0020 (10)
C10	0.0663 (12)	0.0775 (13)	0.0573 (11)	−0.0110 (10)	0.0048 (9)	0.0084 (10)
C21	0.0609 (11)	0.0792 (13)	0.0443 (9)	−0.0033 (10)	0.0134 (8)	0.0014 (9)
C8	0.0648 (13)	0.0863 (15)	0.0666 (13)	−0.0101 (11)	−0.0126 (10)	−0.0100 (11)
F1	0.0972 (10)	0.1390 (12)	0.0957 (9)	−0.0334 (9)	−0.0246 (8)	−0.0135 (9)
C9	0.0714 (13)	0.0906 (15)	0.0824 (15)	−0.0234 (12)	0.0023 (11)	0.0080 (13)
C6	0.0658 (13)	0.0965 (17)	0.0625 (12)	0.0016 (11)	0.0058 (10)	−0.0011 (12)
C4	0.101 (2)	0.112 (2)	0.116 (2)	0.0046 (17)	0.0013 (18)	0.034 (2)
C2	0.0881 (16)	0.1073 (18)	0.0569 (12)	−0.0178 (14)	0.0063 (11)	−0.0009 (13)
C3	0.128 (2)	0.122 (2)	0.0745 (16)	−0.0238 (19)	0.0032 (16)	0.0288 (17)
C5	0.0718 (15)	0.1026 (19)	0.111 (2)	0.0045 (14)	0.0110 (14)	0.0038 (16)
S1	0.0630 (3)	0.1025 (4)	0.0515 (3)	−0.0143 (3)	0.0141 (2)	−0.0031 (3)

Geometric parameters (Å, º)

N2—C14	1.3242 (19)	C7—O1	1.383 (2)
N2—N1	1.3718 (19)	C17—H17	0.9300
N2—H2N	0.8600	O1—C1	1.399 (2)
O2—C13	1.220 (2)	C20—C21	1.370 (3)
N1—C13	1.350 (2)	C20—H20	0.9300
N1—H1	0.8600	C14—S1	1.6617 (17)
C15—O3	1.2272 (18)	C1—C6	1.364 (3)
C15—N3	1.379 (2)	C1—C2	1.377 (3)
C15—C16	1.478 (2)	C10—C9	1.374 (3)
N3—C14	1.389 (2)	C10—H10	0.9300
N3—H3N	0.8600	C21—H21	0.9300
C19—C18	1.370 (3)	C8—F1	1.349 (2)
C19—C20	1.381 (2)	C8—C9	1.371 (3)
C19—H19	0.9300	C9—H9	0.9300
C13—C11	1.488 (2)	C6—C5	1.380 (3)
C11—C12	1.386 (2)	C6—H6	0.9300
C11—C10	1.387 (2)	C4—C5	1.360 (4)
C12—C7	1.379 (3)	C4—C3	1.370 (4)
C12—H12	0.9300	C4—H4	0.9300
C18—C17	1.381 (2)	C2—C3	1.378 (4)
C18—H18	0.9300	C2—H2	0.9300
C16—C21	1.389 (2)	C3—H3	0.9300
C16—C17	1.391 (2)	C5—H5	0.9300
C7—C8	1.372 (3)
C14—N2—N1	120.44 (14)	C21—C20—C19	120.23 (17)
C14—N2—H2N	119.8	C21—C20—H20	119.9
N1—N2—H2N	119.8	C19—C20—H20	119.9
C13—N1—N2	118.79 (14)	N2—C14—N3	115.25 (14)
C13—N1—H1	120.6	N2—C14—S1	122.85 (13)
N2—N1—H1	120.6	N3—C14—S1	121.90 (12)
O3—C15—N3	120.99 (16)	C6—C1—C2	121.6 (2)
O3—C15—C16	121.44 (15)	C6—C1—O1	123.55 (18)
N3—C15—C16	117.57 (13)	C2—C1—O1	114.8 (2)
C15—N3—C14	127.02 (13)	C9—C10—C11	120.14 (18)
C15—N3—H3N	116.5	C9—C10—H10	119.9
C14—N3—H3N	116.5	C11—C10—H10	119.9
C18—C19—C20	119.86 (17)	C20—C21—C16	120.58 (16)
C18—C19—H19	120.1	C20—C21—H21	119.7
C20—C19—H19	120.1	C16—C21—H21	119.7
O2—C13—N1	120.86 (16)	F1—C8—C9	119.7 (2)
O2—C13—C11	123.81 (15)	F1—C8—C7	118.42 (19)
N1—C13—C11	115.33 (15)	C9—C8—C7	121.84 (18)
C12—C11—C10	119.51 (17)	C8—C9—C10	119.28 (19)
C12—C11—C13	116.91 (16)	C8—C9—H9	120.4
C10—C11—C13	123.57 (16)	C10—C9—H9	120.4
C7—C12—C11	120.40 (18)	C1—C6—C5	118.7 (2)
C7—C12—H12	119.8	C1—C6—H6	120.6
C11—C12—H12	119.8	C5—C6—H6	120.6
C19—C18—C17	120.41 (16)	C5—C4—C3	119.4 (3)
C19—C18—H18	119.8	C5—C4—H4	120.3
C17—C18—H18	119.8	C3—C4—H4	120.3
C21—C16—C17	118.81 (16)	C1—C2—C3	118.1 (2)
C21—C16—C15	117.16 (14)	C1—C2—H2	120.9
C17—C16—C15	124.01 (15)	C3—C2—H2	120.9
C8—C7—C12	118.78 (17)	C4—C3—C2	121.1 (2)
C8—C7—O1	120.31 (18)	C4—C3—H3	119.4
C12—C7—O1	120.81 (18)	C2—C3—H3	119.4
C18—C17—C16	120.09 (16)	C4—C5—C6	121.0 (3)
C18—C17—H17	120.0	C4—C5—H5	119.5
C16—C17—H17	120.0	C6—C5—H5	119.5
C7—O1—C1	118.30 (15)
C14—N2—N1—C13	163.27 (16)	N1—N2—C14—S1	−0.5 (2)
O3—C15—N3—C14	3.4 (3)	C15—N3—C14—N2	−7.4 (2)
C16—C15—N3—C14	−177.17 (15)	C15—N3—C14—S1	173.17 (14)
N2—N1—C13—O2	1.4 (3)	C7—O1—C1—C6	−12.8 (3)
N2—N1—C13—C11	−178.11 (15)	C7—O1—C1—C2	167.18 (18)
O2—C13—C11—C12	−15.9 (3)	C12—C11—C10—C9	−1.9 (3)
N1—C13—C11—C12	163.59 (16)	C13—C11—C10—C9	177.23 (19)
O2—C13—C11—C10	164.89 (19)	C19—C20—C21—C16	1.1 (3)
N1—C13—C11—C10	−15.6 (3)	C17—C16—C21—C20	−1.5 (3)
C10—C11—C12—C7	1.7 (3)	C15—C16—C21—C20	179.92 (17)
C13—C11—C12—C7	−177.53 (17)	C12—C7—C8—F1	178.13 (18)
C20—C19—C18—C17	−1.2 (3)	O1—C7—C8—F1	−5.5 (3)
O3—C15—C16—C21	19.2 (3)	C12—C7—C8—C9	−1.9 (3)
N3—C15—C16—C21	−160.26 (15)	O1—C7—C8—C9	174.4 (2)
O3—C15—C16—C17	−159.26 (18)	F1—C8—C9—C10	−178.4 (2)
N3—C15—C16—C17	21.3 (3)	C7—C8—C9—C10	1.7 (4)
C11—C12—C7—C8	0.2 (3)	C11—C10—C9—C8	0.3 (3)
C11—C12—C7—O1	−176.13 (16)	C2—C1—C6—C5	0.5 (3)
C19—C18—C17—C16	0.8 (3)	O1—C1—C6—C5	−179.55 (18)
C21—C16—C17—C18	0.6 (3)	C6—C1—C2—C3	−1.7 (3)
C15—C16—C17—C18	179.02 (17)	O1—C1—C2—C3	178.36 (19)
C8—C7—O1—C1	97.3 (2)	C5—C4—C3—C2	0.4 (4)
C12—C7—O1—C1	−86.4 (2)	C1—C2—C3—C4	1.3 (4)
C18—C19—C20—C21	0.3 (3)	C3—C4—C5—C6	−1.6 (4)
N1—N2—C14—N3	−179.95 (15)	C1—C6—C5—C4	1.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.86	1.88	2.555 (2)	135
C18—H18···O3^i	0.93	2.45	3.218 (2)	141
N3—H3N···O2^i	0.86	2.28	3.067 (2)	152
C19—H19···S1^ii	0.93	2.98	3.778 (2)	145
C20—H20···O1^iii	0.93	2.77	3.510 (3)	138

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+5/2; (iii) −x+1, y+1/2, −z+3/2.

N-[2-(4-Fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide (A2)

Crystal data

C22H18FN3O4S	F(000) = 1824
Mr = 439.45	Dx = 1.412 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 47.298 (3) Å	Cell parameters from 9864 reflections
b = 4.8054 (3) Å	θ = 2.3–21.0°
c = 18.4939 (10) Å	µ = 0.20 mm^−1
β = 100.429 (6)°	T = 298 K
V = 4134.0 (4) Å^3	Plates, colorless
Z = 8	0.25 × 0.17 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	1751 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.062
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 20.9°, θmin = 2.3°
	h = −46→38
9841 measured reflections	k = −4→4
2188 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.122	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 7.4575P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2188 reflections	Δρmax = 0.20 e Å^−3
281 parameters	Δρmin = −0.16 e Å^−3
0 restraints

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
S1	0.46155 (2)	0.5067 (2)	0.20257 (5)	0.0570 (4)
O3	0.48485 (5)	−0.1767 (5)	0.05581 (13)	0.0564 (7)
O2	0.40193 (5)	−0.2064 (6)	0.06269 (16)	0.0693 (8)
N3	0.49466 (6)	0.1596 (6)	0.14319 (15)	0.0476 (8)
H3N	0.508458	0.244009	0.171425	0.057*
O4	0.61871 (6)	−0.3864 (7)	0.15455 (17)	0.0846 (9)
N2	0.44651 (6)	0.1428 (6)	0.09635 (17)	0.0548 (8)
H2N	0.450510	0.022383	0.065314	0.066*
F1	0.28801 (5)	0.3872 (7)	0.11032 (16)	0.1091 (10)
C16	0.53329 (7)	−0.1387 (7)	0.11626 (18)	0.0431 (9)
N1	0.41856 (7)	0.2174 (7)	0.09631 (18)	0.0636 (9)
H1	0.414588	0.386840	0.105555	0.076*
C13	0.39757 (8)	0.0319 (9)	0.0822 (2)	0.0514 (10)
C11	0.36866 (8)	0.1329 (8)	0.0915 (2)	0.0516 (10)
C14	0.46729 (8)	0.2578 (7)	0.14456 (18)	0.0438 (9)
O1	0.29250 (6)	0.0013 (8)	0.01236 (19)	0.1023 (12)
C21	0.54221 (8)	−0.3385 (8)	0.0720 (2)	0.0547 (10)
H21	0.528867	−0.416711	0.034349	0.066*
C15	0.50265 (8)	−0.0588 (7)	0.10183 (19)	0.0441 (9)
C19	0.59029 (8)	−0.3153 (9)	0.1383 (2)	0.0576 (10)
C20	0.57034 (9)	−0.4253 (8)	0.0820 (2)	0.0603 (11)
H20	0.575894	−0.558120	0.050737	0.072*
C17	0.55367 (9)	−0.0281 (8)	0.1725 (2)	0.0601 (11)
H17	0.548250	0.107588	0.203190	0.072*
C12	0.34481 (8)	0.0178 (9)	0.0473 (2)	0.0638 (11)
H12	0.347192	−0.119851	0.013548	0.077*
C18	0.58180 (9)	−0.1171 (10)	0.1835 (2)	0.0678 (12)
H18	0.595147	−0.042543	0.221674	0.081*
C10	0.36521 (9)	0.3291 (9)	0.1432 (2)	0.0663 (11)
H10	0.381175	0.405703	0.173417	0.080*
C7	0.31751 (9)	0.1059 (10)	0.0528 (2)	0.0710 (12)
C8	0.31463 (9)	0.3024 (10)	0.1041 (3)	0.0714 (12)
C9	0.33763 (11)	0.4125 (10)	0.1500 (3)	0.0804 (14)
H9	0.334955	0.542017	0.185500	0.096*
C1	0.29108 (10)	−0.0900 (12)	−0.0591 (3)	0.0824 (15)
C22	0.62909 (10)	−0.5808 (11)	0.1078 (3)	0.0994 (17)
H22A	0.619623	−0.756318	0.110327	0.149*
H22B	0.649439	−0.604267	0.123394	0.149*
H22C	0.625228	−0.513264	0.058166	0.149*
C2	0.27240 (11)	−0.3041 (13)	−0.0798 (3)	0.1014 (17)
H2	0.262932	−0.386389	−0.045353	0.122*
C5	0.30114 (16)	−0.0664 (17)	−0.1801 (4)	0.120 (2)
H5	0.310776	0.012404	−0.214659	0.144*
C4	0.28168 (18)	−0.2822 (19)	−0.1998 (4)	0.128 (3)
H4	0.278282	−0.348577	−0.247824	0.153*
C6	0.30602 (11)	0.0306 (13)	−0.1075 (3)	0.1001 (17)
H6	0.319071	0.173145	−0.092598	0.120*
C3	0.26762 (14)	−0.3964 (17)	−0.1492 (5)	0.131 (2)
H3	0.254553	−0.539896	−0.162868	0.157*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0682 (7)	0.0481 (6)	0.0553 (6)	0.0142 (5)	0.0124 (5)	−0.0014 (5)
O3	0.0554 (16)	0.0545 (17)	0.0589 (16)	0.0012 (14)	0.0092 (13)	−0.0131 (14)
O2	0.0576 (17)	0.0393 (18)	0.109 (2)	0.0029 (14)	0.0092 (15)	−0.0124 (16)
N3	0.0473 (19)	0.0409 (18)	0.0556 (18)	−0.0008 (16)	0.0119 (14)	−0.0034 (16)
O4	0.0587 (19)	0.094 (2)	0.098 (2)	0.0215 (18)	0.0072 (16)	−0.0099 (19)
N2	0.047 (2)	0.0453 (19)	0.074 (2)	0.0059 (17)	0.0161 (17)	−0.0125 (17)
F1	0.0701 (18)	0.141 (3)	0.127 (2)	0.0232 (18)	0.0454 (15)	−0.0117 (19)
C16	0.051 (2)	0.036 (2)	0.045 (2)	0.0000 (19)	0.0154 (19)	0.0032 (18)
N1	0.050 (2)	0.036 (2)	0.107 (3)	0.0023 (18)	0.0183 (18)	−0.0086 (18)
C13	0.052 (3)	0.039 (3)	0.062 (2)	0.003 (2)	0.0088 (19)	0.003 (2)
C11	0.047 (2)	0.044 (2)	0.065 (2)	0.001 (2)	0.013 (2)	0.002 (2)
C14	0.050 (2)	0.036 (2)	0.047 (2)	0.000 (2)	0.0138 (19)	0.0088 (18)
O1	0.0447 (18)	0.159 (3)	0.104 (3)	−0.010 (2)	0.0170 (17)	−0.039 (2)
C21	0.055 (3)	0.053 (3)	0.058 (2)	0.001 (2)	0.0142 (19)	−0.006 (2)
C15	0.052 (2)	0.039 (2)	0.045 (2)	0.000 (2)	0.018 (2)	0.0040 (19)
C19	0.053 (3)	0.057 (3)	0.063 (3)	0.008 (2)	0.010 (2)	0.005 (2)
C20	0.065 (3)	0.052 (3)	0.068 (3)	0.007 (2)	0.022 (2)	−0.011 (2)
C17	0.063 (3)	0.060 (3)	0.059 (2)	0.005 (2)	0.015 (2)	−0.011 (2)
C12	0.051 (3)	0.064 (3)	0.079 (3)	0.003 (2)	0.020 (2)	−0.014 (2)
C18	0.056 (3)	0.080 (3)	0.064 (3)	0.008 (2)	0.002 (2)	−0.013 (2)
C10	0.060 (3)	0.066 (3)	0.075 (3)	−0.004 (2)	0.017 (2)	−0.010 (3)
C7	0.059 (3)	0.082 (3)	0.074 (3)	0.001 (3)	0.017 (2)	−0.003 (3)
C8	0.053 (3)	0.084 (3)	0.084 (3)	0.012 (3)	0.031 (3)	−0.001 (3)
C9	0.089 (4)	0.073 (3)	0.088 (3)	0.003 (3)	0.039 (3)	−0.017 (3)
C1	0.050 (3)	0.104 (4)	0.088 (4)	0.017 (3)	0.000 (3)	−0.024 (3)
C22	0.077 (3)	0.097 (4)	0.129 (4)	0.028 (3)	0.031 (3)	−0.010 (4)
C2	0.073 (3)	0.121 (5)	0.106 (4)	0.014 (4)	0.005 (3)	−0.023 (4)
C5	0.118 (5)	0.142 (6)	0.099 (5)	0.046 (5)	0.015 (4)	0.027 (5)
C4	0.128 (6)	0.151 (7)	0.091 (5)	0.056 (5)	−0.015 (5)	−0.018 (5)
C6	0.082 (4)	0.117 (5)	0.101 (4)	0.013 (3)	0.015 (3)	0.001 (4)
C3	0.100 (5)	0.158 (7)	0.125 (6)	0.022 (5)	−0.006 (5)	−0.039 (6)

Geometric parameters (Å, º)

S1—C14	1.661 (4)	C20—H20	0.9300
O3—C15	1.223 (4)	C17—C18	1.377 (5)
O2—C13	1.229 (4)	C17—H17	0.9300
N3—C14	1.383 (4)	C12—C7	1.380 (5)
N3—C15	1.391 (4)	C12—H12	0.9300
N3—H3N	0.8600	C18—H18	0.9300
O4—C19	1.367 (4)	C10—C9	1.392 (6)
O4—C22	1.419 (5)	C10—H10	0.9300
N2—C14	1.322 (4)	C7—C8	1.362 (6)
N2—N1	1.369 (4)	C8—C9	1.360 (6)
N2—H2N	0.8600	C9—H9	0.9300
F1—C8	1.348 (4)	C1—C2	1.365 (7)
C16—C21	1.377 (5)	C1—C6	1.365 (7)
C16—C17	1.390 (5)	C22—H22A	0.9600
C16—C15	1.476 (5)	C22—H22B	0.9600
N1—C13	1.325 (5)	C22—H22C	0.9600
N1—H1	0.8600	C2—C3	1.338 (8)
C13—C11	1.490 (5)	C2—H2	0.9300
C11—C10	1.373 (5)	C5—C4	1.390 (9)
C11—C12	1.383 (5)	C5—C6	1.401 (8)
O1—C7	1.375 (5)	C5—H5	0.9300
O1—C1	1.383 (5)	C4—C3	1.359 (9)
C21—C20	1.374 (5)	C4—H4	0.9300
C21—H21	0.9300	C6—H6	0.9300
C19—C18	1.374 (5)	C3—H3	0.9300
C19—C20	1.378 (5)
C14—N3—C15	128.0 (3)	C11—C12—H12	119.8
C14—N3—H3N	116.0	C19—C18—C17	120.5 (4)
C15—N3—H3N	116.0	C19—C18—H18	119.8
C19—O4—C22	117.7 (3)	C17—C18—H18	119.8
C14—N2—N1	119.4 (3)	C11—C10—C9	119.4 (4)
C14—N2—H2N	120.3	C11—C10—H10	120.3
N1—N2—H2N	120.3	C9—C10—H10	120.3
C21—C16—C17	117.8 (3)	C8—C7—O1	116.6 (4)
C21—C16—C15	118.1 (3)	C8—C7—C12	118.5 (4)
C17—C16—C15	124.1 (3)	O1—C7—C12	124.9 (4)
C13—N1—N2	120.9 (3)	F1—C8—C9	118.9 (4)
C13—N1—H1	119.6	F1—C8—C7	118.8 (4)
N2—N1—H1	119.6	C9—C8—C7	122.3 (4)
O2—C13—N1	121.7 (3)	C8—C9—C10	119.3 (4)
O2—C13—C11	122.9 (4)	C8—C9—H9	120.4
N1—C13—C11	115.4 (4)	C10—C9—H9	120.4
C10—C11—C12	120.0 (4)	C2—C1—C6	121.5 (5)
C10—C11—C13	122.1 (4)	C2—C1—O1	115.1 (5)
C12—C11—C13	117.9 (4)	C6—C1—O1	123.4 (5)
N2—C14—N3	115.4 (3)	O4—C22—H22A	109.5
N2—C14—S1	123.2 (3)	O4—C22—H22B	109.5
N3—C14—S1	121.4 (3)	H22A—C22—H22B	109.5
C7—O1—C1	121.6 (4)	O4—C22—H22C	109.5
C20—C21—C16	121.7 (4)	H22A—C22—H22C	109.5
C20—C21—H21	119.2	H22B—C22—H22C	109.5
C16—C21—H21	119.2	C3—C2—C1	120.4 (7)
O3—C15—N3	120.7 (3)	C3—C2—H2	119.8
O3—C15—C16	122.3 (3)	C1—C2—H2	119.8
N3—C15—C16	116.9 (3)	C4—C5—C6	119.0 (7)
O4—C19—C18	115.0 (4)	C4—C5—H5	120.5
O4—C19—C20	125.6 (4)	C6—C5—H5	120.5
C18—C19—C20	119.3 (4)	C3—C4—C5	120.3 (7)
C21—C20—C19	119.9 (4)	C3—C4—H4	119.9
C21—C20—H20	120.0	C5—C4—H4	119.9
C19—C20—H20	120.0	C1—C6—C5	118.2 (6)
C18—C17—C16	120.8 (4)	C1—C6—H6	120.9
C18—C17—H17	119.6	C5—C6—H6	120.9
C16—C17—H17	119.6	C2—C3—C4	120.6 (7)
C7—C12—C11	120.5 (4)	C2—C3—H3	119.7
C7—C12—H12	119.8	C4—C3—H3	119.7
C14—N2—N1—C13	−143.5 (4)	C13—C11—C12—C7	−179.2 (4)
N2—N1—C13—O2	−6.2 (6)	O4—C19—C18—C17	180.0 (4)
N2—N1—C13—C11	173.9 (3)	C20—C19—C18—C17	−0.2 (6)
O2—C13—C11—C10	147.9 (4)	C16—C17—C18—C19	0.7 (6)
N1—C13—C11—C10	−32.2 (5)	C12—C11—C10—C9	−0.6 (6)
O2—C13—C11—C12	−30.6 (5)	C13—C11—C10—C9	−179.1 (4)
N1—C13—C11—C12	149.3 (4)	C1—O1—C7—C8	149.6 (5)
N1—N2—C14—N3	176.7 (3)	C1—O1—C7—C12	−33.4 (7)
N1—N2—C14—S1	−4.1 (5)	C11—C12—C7—C8	−1.8 (6)
C15—N3—C14—N2	−5.7 (5)	C11—C12—C7—O1	−178.8 (4)
C15—N3—C14—S1	175.2 (3)	O1—C7—C8—F1	−2.0 (6)
C17—C16—C21—C20	−0.7 (5)	C12—C7—C8—F1	−179.3 (4)
C15—C16—C21—C20	−179.7 (3)	O1—C7—C8—C9	176.8 (4)
C14—N3—C15—O3	5.9 (5)	C12—C7—C8—C9	−0.4 (7)
C14—N3—C15—C16	−174.1 (3)	F1—C8—C9—C10	−179.1 (4)
C21—C16—C15—O3	5.2 (5)	C7—C8—C9—C10	2.1 (7)
C17—C16—C15—O3	−173.8 (3)	C11—C10—C9—C8	−1.5 (7)
C21—C16—C15—N3	−174.7 (3)	C7—O1—C1—C2	148.1 (4)
C17—C16—C15—N3	6.3 (5)	C7—O1—C1—C6	−34.9 (7)
C22—O4—C19—C18	−177.2 (4)	C6—C1—C2—C3	−2.0 (8)
C22—O4—C19—C20	3.0 (6)	O1—C1—C2—C3	175.1 (5)
C16—C21—C20—C19	1.2 (6)	C6—C5—C4—C3	0.1 (9)
O4—C19—C20—C21	179.1 (4)	C2—C1—C6—C5	1.7 (8)
C18—C19—C20—C21	−0.7 (6)	O1—C1—C6—C5	−175.1 (4)
C21—C16—C17—C18	−0.2 (6)	C4—C5—C6—C1	−0.7 (8)
C15—C16—C17—C18	178.8 (3)	C1—C2—C3—C4	1.3 (9)
C10—C11—C12—C7	2.3 (6)	C5—C4—C3—C2	−0.4 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.86	1.92	2.589 (4)	134
N3—H3N···S1^i	0.86	2.80	3.615 (3)	159
C17—H17···S1^i	0.93	2.69	3.614 (4)	174
N1—H1···O2^ii	0.86	2.15	2.915 (4)	148
C21—H21···O3^iii	0.93	2.57	3.399 (4)	148

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