Syntheses, crystal structures and Hirshfeld surface analysis of 4-(4-nitro­phen­yl)piperazin-1-ium tri­fluoro­acetate and 4-(4-nitro­phen­yl)piperazin-1-ium tri­chloro­acetate

The supra­molecular assemblies of the two title structures are one-dimensional: the chain-of-rings motifs are supported by aromatic π–π inter­actions.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.041
• wR factor = 0.106
• Data-to-parameter ratio = 10.5

Structure: II

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.036
• wR factor = 0.104
• Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        C11 Check
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        3.0 Note
PLAT410_ALERT_2_C Short Intra H...H Contact  H2       ..H10A     .       1.98 Ang.
                                                      x,y,z  =      1_555 Check
PLAT410_ALERT_2_C Short Intra H...H Contact  H6       ..H7B      .       1.96 Ang.
                                                      x,y,z  =      1_555 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.412 Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          9 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          6 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          1 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          2 Report
PLAT177_ALERT_4_G The CIF-Embedded .res File Contains DELU Records          1 Report
PLAT178_ALERT_4_G The CIF-Embedded .res File Contains SIMU Records          1 Report
PLAT186_ALERT_4_G The CIF-Embedded .res File Contains ISOR Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT231_ALERT_4_G Hirshfeld Test (Solvent)   C11      --C12B     .        7.0 s.u.
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  2  )        57% Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         84 Note
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        57% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        1.9 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 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
  17 ALERT level G = General information/check it is not something unexpected

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




Datablock: II


Alert level C
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        C12 Check
PLAT410_ALERT_2_C Short Intra H...H Contact  H2       ..H10A     .       1.93 Ang.
                                                      x,y,z  =      1_555 Check
PLAT410_ALERT_2_C Short Intra H...H Contact  H6       ..H7B      .       1.95 Ang.
                                                      x,y,z  =      1_555 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.232 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          3 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          1 Report
PLAT177_ALERT_4_G The CIF-Embedded .res File Contains DELU Records          1 Report
PLAT178_ALERT_4_G The CIF-Embedded .res File Contains SIMU Records          1 Report
PLAT186_ALERT_4_G The CIF-Embedded .res File Contains ISOR Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  2  )        43% Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         35 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        1.8 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 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
  14 ALERT level G = General information/check it is not something unexpected

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

---

Computing details

For both structures, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

4-(4-Nitrophenyl)piperazin-1-ium trifluoroacetate (I)

Crystal data

C10H14N3O2^+·C2F3O2^−	F(000) = 664
Mr = 321.26	Dx = 1.542 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.6889 (4) Å	Cell parameters from 2766 reflections
b = 18.376 (1) Å	θ = 2.9–27.8°
c = 11.2600 (7) Å	µ = 0.14 mm^−1
β = 91.131 (6)°	T = 293 K
V = 1383.76 (14) Å^3	Prism, yellow
Z = 4	0.50 × 0.44 × 0.44 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	1908 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.020
Rotation method data acquisition using ω scans.	θmax = 25.3°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction (2009)	h = −8→7
Tmin = 0.784, Tmax = 1.000	k = −17→22
4855 measured reflections	l = −11→13
2515 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.041	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.5034P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.106	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.28 e Å^−3
2515 reflections	Δρmin = −0.28 e Å^−3
239 parameters	Extinction correction: SHELXL2019/2 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
84 restraints	Extinction coefficient: 0.053 (3)
Primary atom site location: structure-invariant direct methods

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)
O1	0.6694 (3)	0.05792 (11)	−0.27331 (14)	0.0805 (6)
O2	0.6790 (2)	−0.05336 (10)	−0.21928 (14)	0.0636 (5)
N1	0.8545 (2)	0.10090 (8)	0.26900 (12)	0.0356 (4)
N2	0.6570 (2)	0.12077 (8)	0.48752 (13)	0.0312 (4)
N3	0.6925 (2)	0.01145 (11)	−0.19696 (15)	0.0476 (5)
C1	0.8114 (2)	0.07873 (10)	0.15542 (15)	0.0312 (4)
C2	0.8000 (3)	0.12928 (11)	0.06160 (16)	0.0419 (5)
H2	0.818859	0.178501	0.077433	0.050*
C3	0.7615 (3)	0.10711 (12)	−0.05228 (17)	0.0447 (5)
H3	0.753987	0.141171	−0.113294	0.054*
C4	0.7339 (3)	0.03448 (11)	−0.07686 (15)	0.0365 (4)
C5	0.7466 (2)	−0.01673 (11)	0.01221 (16)	0.0377 (4)
H5	0.729993	−0.065848	−0.005234	0.045*
C6	0.7840 (3)	0.00528 (10)	0.12678 (16)	0.0355 (4)
H6	0.791371	−0.029400	0.186860	0.043*
C7	0.8875 (3)	0.05084 (10)	0.36718 (15)	0.0341 (4)
H7A	1.001562	0.066979	0.414794	0.041*
H7B	0.917467	0.002845	0.336392	0.041*
C8	0.7060 (3)	0.04672 (9)	0.44371 (15)	0.0320 (4)
H8A	0.593779	0.027324	0.397946	0.038*
H8B	0.732201	0.014504	0.510461	0.038*
C9	0.6318 (3)	0.17363 (10)	0.38863 (16)	0.0373 (4)
H9A	0.610217	0.221963	0.420550	0.045*
H9B	0.515721	0.160535	0.340249	0.045*
C10	0.8162 (3)	0.17372 (10)	0.31302 (16)	0.0401 (5)
H10A	0.796762	0.206785	0.246641	0.048*
H10B	0.930352	0.190504	0.359862	0.048*
C11	0.1577 (3)	0.17011 (10)	0.61221 (17)	0.0386 (5)
C12A	0.2811 (6)	0.2193 (2)	0.6965 (3)	0.0574 (11)	0.779 (4)
C12B	0.295 (2)	0.2305 (8)	0.6565 (13)	0.0574 (11)	0.221 (4)
O3	0.2518 (2)	0.12351 (8)	0.55930 (14)	0.0522 (4)
O4	−0.0240 (2)	0.18168 (9)	0.61548 (14)	0.0593 (5)
F1A	0.4768 (4)	0.22180 (19)	0.6652 (3)	0.0873 (11)	0.779 (4)
F2A	0.2265 (4)	0.28753 (13)	0.6917 (4)	0.0974 (13)	0.779 (4)
F3A	0.2611 (5)	0.2012 (2)	0.8079 (2)	0.1261 (13)	0.779 (4)
F1B	0.2251 (14)	0.2549 (8)	0.7591 (12)	0.089 (3)	0.221 (4)
F2B	0.4517 (17)	0.1991 (8)	0.7164 (11)	0.090 (3)	0.221 (4)
F3B	0.2926 (17)	0.2875 (5)	0.5852 (13)	0.129 (3)	0.221 (4)
H21	0.541 (3)	0.1200 (11)	0.5272 (17)	0.047 (6)*
H22	0.752 (2)	0.1340 (10)	0.5372 (15)	0.038 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1184 (16)	0.0917 (14)	0.0310 (8)	−0.0055 (11)	−0.0098 (9)	0.0050 (9)
O2	0.0640 (10)	0.0726 (12)	0.0539 (10)	0.0033 (8)	−0.0089 (8)	−0.0253 (8)
N1	0.0441 (9)	0.0359 (8)	0.0268 (8)	0.0041 (7)	0.0012 (6)	0.0023 (7)
N2	0.0272 (8)	0.0362 (8)	0.0301 (8)	0.0006 (7)	−0.0020 (6)	−0.0032 (7)
N3	0.0359 (9)	0.0719 (13)	0.0349 (9)	0.0018 (9)	−0.0004 (7)	−0.0080 (9)
C1	0.0234 (8)	0.0406 (10)	0.0298 (9)	0.0020 (7)	0.0030 (7)	0.0014 (8)
C2	0.0518 (12)	0.0397 (11)	0.0341 (10)	0.0012 (9)	0.0002 (8)	0.0025 (9)
C3	0.0508 (12)	0.0527 (13)	0.0306 (10)	0.0033 (10)	−0.0012 (8)	0.0079 (9)
C4	0.0277 (9)	0.0528 (12)	0.0289 (9)	0.0020 (8)	−0.0003 (7)	−0.0037 (9)
C5	0.0269 (9)	0.0433 (11)	0.0429 (11)	−0.0001 (8)	0.0005 (8)	−0.0064 (9)
C6	0.0317 (9)	0.0404 (11)	0.0344 (10)	0.0005 (8)	0.0001 (7)	0.0038 (8)
C7	0.0342 (9)	0.0388 (10)	0.0291 (9)	0.0075 (8)	−0.0028 (7)	0.0002 (8)
C8	0.0358 (9)	0.0312 (9)	0.0288 (9)	0.0000 (8)	−0.0048 (7)	0.0006 (7)
C9	0.0438 (11)	0.0314 (10)	0.0363 (10)	0.0062 (8)	−0.0056 (8)	0.0005 (8)
C10	0.0523 (11)	0.0346 (10)	0.0335 (10)	−0.0058 (9)	−0.0005 (8)	0.0011 (8)
C11	0.0313 (10)	0.0398 (11)	0.0446 (11)	−0.0015 (8)	−0.0029 (8)	−0.0100 (9)
C12A	0.0369 (14)	0.068 (2)	0.067 (3)	0.0037 (13)	0.0025 (19)	−0.036 (2)
C12B	0.0369 (14)	0.068 (2)	0.067 (3)	0.0037 (13)	0.0025 (19)	−0.036 (2)
O3	0.0386 (8)	0.0484 (8)	0.0695 (10)	0.0011 (7)	−0.0020 (7)	−0.0248 (8)
O4	0.0308 (8)	0.0745 (11)	0.0724 (11)	−0.0014 (7)	−0.0055 (7)	−0.0315 (8)
F1A	0.0316 (11)	0.103 (2)	0.128 (3)	−0.0196 (12)	0.0112 (14)	−0.0703 (18)
F2A	0.0739 (15)	0.0495 (14)	0.168 (4)	0.0015 (12)	−0.012 (2)	−0.0513 (17)
F3A	0.146 (3)	0.168 (3)	0.0625 (16)	−0.035 (2)	−0.0317 (15)	−0.0260 (18)
F1B	0.055 (4)	0.112 (6)	0.100 (5)	−0.010 (5)	0.006 (4)	−0.068 (4)
F2B	0.036 (4)	0.120 (5)	0.111 (5)	0.015 (4)	−0.032 (4)	−0.057 (4)
F3B	0.126 (5)	0.083 (5)	0.178 (6)	−0.035 (4)	0.003 (5)	−0.029 (5)

Geometric parameters (Å, º)

O1—N3	1.219 (2)	C7—C8	1.505 (2)
O2—N3	1.220 (2)	C7—H7A	0.9700
N1—C1	1.368 (2)	C7—H7B	0.9700
N1—C10	1.452 (2)	C8—H8A	0.9700
N1—C7	1.452 (2)	C8—H8B	0.9700
N2—C9	1.485 (2)	C9—C10	1.512 (3)
N2—C8	1.486 (2)	C9—H9A	0.9700
N2—H21	0.901 (15)	C9—H9B	0.9700
N2—H22	0.873 (15)	C10—H10A	0.9700
N3—C4	1.439 (2)	C10—H10B	0.9700
C1—C6	1.399 (3)	C11—O3	1.224 (2)
C1—C2	1.408 (2)	C11—O4	1.235 (2)
C2—C3	1.365 (3)	C11—C12B	1.518 (15)
C2—H2	0.9300	C11—C12A	1.539 (4)
C3—C4	1.375 (3)	C12A—F2A	1.306 (5)
C3—H3	0.9300	C12A—F3A	1.307 (5)
C4—C5	1.377 (3)	C12A—F1A	1.364 (5)
C5—C6	1.370 (3)	C12B—F3B	1.319 (13)
C5—H5	0.9300	C12B—F1B	1.332 (14)
C6—H6	0.9300	C12B—F2B	1.365 (14)
C1—N1—C10	123.95 (15)	N2—C8—C7	109.25 (14)
C1—N1—C7	123.34 (15)	N2—C8—H8A	109.8
C10—N1—C7	110.45 (13)	C7—C8—H8A	109.8
C9—N2—C8	111.88 (13)	N2—C8—H8B	109.8
C9—N2—H21	107.2 (13)	C7—C8—H8B	109.8
C8—N2—H21	110.4 (13)	H8A—C8—H8B	108.3
C9—N2—H22	111.7 (13)	N2—C9—C10	109.95 (15)
C8—N2—H22	107.8 (12)	N2—C9—H9A	109.7
H21—N2—H22	107.9 (18)	C10—C9—H9A	109.7
O1—N3—O2	122.05 (18)	N2—C9—H9B	109.7
O1—N3—C4	118.42 (19)	C10—C9—H9B	109.7
O2—N3—C4	119.53 (19)	H9A—C9—H9B	108.2
N1—C1—C6	121.82 (16)	N1—C10—C9	110.05 (15)
N1—C1—C2	120.84 (17)	N1—C10—H10A	109.7
C6—C1—C2	117.31 (16)	C9—C10—H10A	109.7
C3—C2—C1	120.96 (18)	N1—C10—H10B	109.7
C3—C2—H2	119.5	C9—C10—H10B	109.7
C1—C2—H2	119.5	H10A—C10—H10B	108.2
C2—C3—C4	120.06 (18)	O3—C11—O4	130.58 (17)
C2—C3—H3	120.0	O3—C11—C12B	111.0 (6)
C4—C3—H3	120.0	O4—C11—C12B	116.9 (6)
C3—C4—C5	120.72 (17)	O3—C11—C12A	115.9 (2)
C3—C4—N3	119.83 (18)	O4—C11—C12A	113.3 (2)
C5—C4—N3	119.45 (18)	F2A—C12A—F3A	104.5 (4)
C6—C5—C4	119.45 (18)	F2A—C12A—F1A	103.1 (4)
C6—C5—H5	120.3	F3A—C12A—F1A	112.0 (4)
C4—C5—H5	120.3	F2A—C12A—C11	113.1 (3)
C5—C6—C1	121.49 (17)	F3A—C12A—C11	112.2 (3)
C5—C6—H6	119.3	F1A—C12A—C11	111.5 (3)
C1—C6—H6	119.3	F3B—C12B—F1B	105.1 (13)
N1—C7—C8	110.83 (14)	F3B—C12B—F2B	129.5 (15)
N1—C7—H7A	109.5	F1B—C12B—F2B	89.6 (11)
C8—C7—H7A	109.5	F3B—C12B—C11	112.5 (10)
N1—C7—H7B	109.5	F1B—C12B—C11	108.2 (11)
C8—C7—H7B	109.5	F2B—C12B—C11	107.8 (11)
H7A—C7—H7B	108.1
C10—N1—C1—C6	−157.34 (17)	C10—N1—C7—C8	61.08 (19)
C7—N1—C1—C6	3.9 (3)	C9—N2—C8—C7	54.85 (18)
C10—N1—C1—C2	24.9 (2)	N1—C7—C8—N2	−57.36 (18)
C7—N1—C1—C2	−173.79 (16)	C8—N2—C9—C10	−54.97 (19)
N1—C1—C2—C3	178.48 (17)	C1—N1—C10—C9	103.02 (19)
C6—C1—C2—C3	0.7 (3)	C7—N1—C10—C9	−60.34 (19)
C1—C2—C3—C4	−0.2 (3)	N2—C9—C10—N1	56.90 (19)
C2—C3—C4—C5	−0.7 (3)	O3—C11—C12A—F2A	139.1 (3)
C2—C3—C4—N3	179.71 (17)	O4—C11—C12A—F2A	−45.3 (4)
O1—N3—C4—C3	−4.9 (3)	O3—C11—C12A—F3A	−103.0 (3)
O2—N3—C4—C3	175.97 (18)	O4—C11—C12A—F3A	72.6 (4)
O1—N3—C4—C5	175.49 (18)	O3—C11—C12A—F1A	23.5 (5)
O2—N3—C4—C5	−3.6 (3)	O4—C11—C12A—F1A	−160.9 (3)
C3—C4—C5—C6	1.1 (3)	O3—C11—C12B—F3B	98.1 (11)
N3—C4—C5—C6	−179.33 (15)	O4—C11—C12B—F3B	−69.4 (12)
C4—C5—C6—C1	−0.6 (3)	O3—C11—C12B—F1B	−146.3 (10)
N1—C1—C6—C5	−178.08 (16)	O4—C11—C12B—F1B	46.2 (12)
C2—C1—C6—C5	−0.3 (3)	O3—C11—C12B—F2B	−50.7 (12)
C1—N1—C7—C8	−102.40 (18)	O4—C11—C12B—F2B	141.8 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3	0.90 (2)	1.98 (2)	2.844 (2)	161 (2)
N2—H22···O4^i	0.87 (2)	1.93 (2)	2.786 (2)	165 (2)
C7—H7A···O3^i	0.97	2.53	3.492 (2)	169

Symmetry code: (i) x+1, y, z.

4-(4-Nitrophenyl)piperazin-1-ium trichloroacetate (II)

Crystal data

C10H14N3O2^+·C2Cl3O2^−	F(000) = 760
Mr = 370.61	Dx = 1.603 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7825 (5) Å	Cell parameters from 2813 reflections
b = 6.6142 (3) Å	θ = 3.0–27.8°
c = 20.3271 (9) Å	µ = 0.62 mm^−1
β = 104.173 (4)°	T = 293 K
V = 1535.91 (12) Å^3	Prism, brown
Z = 4	0.48 × 0.44 × 0.40 mm

Data collection

Oxford Diffraction Xcalibu with Sapphire CCD diffractometer	2068 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.013
Rotation method data acquisition using ω scans.	θmax = 25.4°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction (2009)	h = −14→13
Tmin = 0.840, Tmax = 1.000	k = −7→6
5078 measured reflections	l = −24→14
2802 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 0.1937P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.104	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.25 e Å^−3
2802 reflections	Δρmin = −0.28 e Å^−3
236 parameters	Extinction correction: SHELXL2019/2 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
35 restraints	Extinction coefficient: 0.0084 (12)
Primary atom site location: structure-invariant direct methods

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)
O1	1.25261 (14)	0.5140 (3)	0.20561 (10)	0.0741 (5)
O2	1.24364 (14)	0.5039 (2)	0.30936 (10)	0.0669 (5)
N1	0.70718 (14)	0.5089 (3)	0.16441 (8)	0.0449 (4)
N2	0.47368 (15)	0.3654 (3)	0.13414 (9)	0.0428 (4)
N3	1.19635 (15)	0.5092 (2)	0.24883 (10)	0.0477 (5)
C1	0.82694 (16)	0.5103 (2)	0.18508 (9)	0.0332 (4)
C2	0.89695 (17)	0.5088 (3)	0.13812 (10)	0.0410 (5)
H2	0.861345	0.508580	0.091922	0.049*
C3	1.01632 (18)	0.5077 (3)	0.15913 (11)	0.0432 (5)
H3	1.061159	0.506564	0.127313	0.052*
C4	1.07033 (16)	0.5084 (3)	0.22736 (10)	0.0369 (4)
C5	1.00483 (17)	0.5083 (3)	0.27476 (10)	0.0379 (5)
H5	1.041717	0.507704	0.320778	0.046*
C6	0.88472 (17)	0.5091 (3)	0.25404 (9)	0.0370 (4)
H6	0.840985	0.508872	0.286420	0.044*
C7	0.63004 (17)	0.5611 (3)	0.20782 (11)	0.0452 (5)
H7A	0.590860	0.688009	0.192889	0.054*
H7B	0.675741	0.578246	0.254138	0.054*
C8	0.54056 (16)	0.3977 (3)	0.20527 (10)	0.0425 (5)
H8A	0.579293	0.273110	0.223440	0.051*
H8B	0.487520	0.436125	0.232840	0.051*
C9	0.55236 (18)	0.3230 (3)	0.08906 (10)	0.0466 (5)
H9A	0.506515	0.312758	0.042528	0.056*
H9B	0.591456	0.194556	0.101561	0.056*
C10	0.64214 (18)	0.4869 (3)	0.09421 (10)	0.0489 (5)
H10A	0.695324	0.453110	0.066221	0.059*
H10B	0.603791	0.613458	0.077935	0.059*
O3	0.39831 (14)	−0.0360 (2)	0.13071 (8)	0.0613 (5)
O4	0.35547 (15)	−0.3109 (2)	0.06595 (8)	0.0619 (5)
C11	0.33900 (17)	−0.1382 (3)	0.08446 (10)	0.0412 (5)
C12	0.22438 (17)	−0.0367 (3)	0.04153 (9)	0.0394 (5)
Cl1A	0.1882 (4)	0.1717 (9)	0.0837 (2)	0.0708 (9)	0.494 (15)
Cl2A	0.2502 (7)	0.0289 (11)	−0.0355 (3)	0.0911 (17)	0.494 (15)
Cl3A	0.1076 (4)	−0.2089 (7)	0.0240 (3)	0.0746 (11)	0.494 (15)
Cl1B	0.2023 (4)	0.2189 (9)	0.0640 (4)	0.0790 (16)	0.506 (15)
Cl2B	0.2284 (6)	−0.0136 (10)	−0.0438 (2)	0.0839 (13)	0.506 (15)
Cl3B	0.1049 (4)	−0.1756 (13)	0.0517 (5)	0.100 (2)	0.506 (15)
H21	0.4277 (18)	0.263 (3)	0.1340 (11)	0.047 (6)*
H22	0.4300 (19)	0.468 (3)	0.1176 (11)	0.061 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0405 (9)	0.0979 (15)	0.0875 (13)	0.0003 (9)	0.0227 (9)	−0.0052 (10)
O2	0.0443 (9)	0.0759 (12)	0.0697 (11)	−0.0015 (8)	−0.0068 (8)	−0.0106 (9)
N1	0.0330 (9)	0.0664 (12)	0.0364 (9)	−0.0058 (8)	0.0106 (7)	−0.0123 (8)
N2	0.0334 (9)	0.0375 (10)	0.0536 (11)	−0.0019 (8)	0.0033 (8)	0.0032 (8)
N3	0.0357 (9)	0.0363 (10)	0.0689 (13)	0.0012 (7)	0.0087 (9)	−0.0069 (8)
C1	0.0344 (10)	0.0273 (9)	0.0388 (10)	−0.0020 (8)	0.0106 (8)	−0.0025 (8)
C2	0.0406 (11)	0.0483 (12)	0.0350 (10)	0.0030 (9)	0.0108 (8)	0.0016 (9)
C3	0.0405 (11)	0.0439 (12)	0.0491 (12)	0.0042 (9)	0.0181 (9)	0.0022 (9)
C4	0.0333 (10)	0.0252 (9)	0.0506 (12)	−0.0004 (8)	0.0076 (8)	−0.0017 (8)
C5	0.0429 (11)	0.0286 (10)	0.0395 (10)	−0.0014 (8)	0.0046 (9)	−0.0032 (8)
C6	0.0423 (11)	0.0349 (10)	0.0359 (10)	−0.0026 (8)	0.0136 (8)	−0.0024 (8)
C7	0.0348 (10)	0.0567 (12)	0.0464 (12)	−0.0050 (9)	0.0144 (9)	−0.0130 (10)
C8	0.0368 (10)	0.0466 (12)	0.0442 (11)	0.0020 (9)	0.0104 (8)	0.0017 (9)
C9	0.0449 (12)	0.0509 (12)	0.0388 (11)	0.0026 (10)	0.0001 (9)	−0.0060 (9)
C10	0.0391 (11)	0.0675 (15)	0.0386 (11)	−0.0004 (10)	0.0066 (8)	−0.0006 (10)
O3	0.0579 (10)	0.0507 (9)	0.0598 (10)	−0.0039 (8)	−0.0152 (8)	0.0023 (7)
O4	0.0640 (10)	0.0505 (9)	0.0616 (10)	0.0210 (8)	−0.0030 (8)	−0.0044 (8)
C11	0.0383 (11)	0.0456 (12)	0.0375 (11)	0.0031 (9)	0.0054 (8)	0.0057 (9)
C12	0.0386 (11)	0.0401 (10)	0.0378 (11)	0.0010 (9)	0.0062 (8)	−0.0024 (8)
Cl1A	0.0801 (15)	0.0735 (19)	0.0577 (13)	0.0376 (13)	0.0150 (12)	−0.0120 (11)
Cl2A	0.121 (3)	0.099 (3)	0.067 (3)	0.040 (2)	0.050 (2)	0.053 (2)
Cl3A	0.0501 (11)	0.0651 (12)	0.095 (2)	−0.0146 (8)	−0.0082 (13)	0.0026 (15)
Cl1B	0.0603 (14)	0.0597 (17)	0.095 (3)	0.0272 (12)	−0.0224 (15)	−0.0358 (18)
Cl2B	0.100 (2)	0.107 (3)	0.0388 (11)	0.060 (2)	0.0071 (13)	0.0062 (15)
Cl3B	0.0427 (9)	0.115 (3)	0.137 (4)	−0.0141 (15)	0.0102 (19)	0.063 (3)

Geometric parameters (Å, º)

O1—N3	1.224 (3)	C7—C8	1.502 (3)
O2—N3	1.221 (2)	C7—H7A	0.9700
N1—C1	1.370 (2)	C7—H7B	0.9700
N1—C10	1.452 (2)	C8—H8A	0.9700
N1—C7	1.455 (2)	C8—H8B	0.9700
N2—C9	1.481 (3)	C9—C10	1.501 (3)
N2—C8	1.483 (2)	C9—H9A	0.9700
N2—H21	0.867 (16)	C9—H9B	0.9700
N2—H22	0.870 (16)	C10—H10A	0.9700
N3—C4	1.442 (2)	C10—H10B	0.9700
C1—C6	1.400 (3)	O3—C11	1.228 (2)
C1—C2	1.406 (3)	O4—C11	1.233 (2)
C2—C3	1.366 (3)	C11—C12	1.568 (3)
C2—H2	0.9300	C12—Cl2A	1.722 (4)
C3—C4	1.377 (3)	C12—Cl1A	1.730 (5)
C3—H3	0.9300	C12—Cl3B	1.736 (4)
C4—C5	1.374 (3)	C12—Cl2B	1.753 (5)
C5—C6	1.374 (3)	C12—Cl3A	1.754 (5)
C5—H5	0.9300	C12—Cl1B	1.787 (4)
C6—H6	0.9300
C1—N1—C10	123.91 (16)	H7A—C7—H7B	108.1
C1—N1—C7	124.18 (17)	N2—C8—C7	109.76 (16)
C10—N1—C7	111.23 (17)	N2—C8—H8A	109.7
C9—N2—C8	111.52 (15)	C7—C8—H8A	109.7
C9—N2—H21	109.6 (14)	N2—C8—H8B	109.7
C8—N2—H21	107.4 (14)	C7—C8—H8B	109.7
C9—N2—H22	108.0 (16)	H8A—C8—H8B	108.2
C8—N2—H22	112.8 (16)	N2—C9—C10	110.93 (16)
H21—N2—H22	107 (2)	N2—C9—H9A	109.5
O2—N3—O1	122.05 (19)	C10—C9—H9A	109.5
O2—N3—C4	119.16 (19)	N2—C9—H9B	109.5
O1—N3—C4	118.79 (19)	C10—C9—H9B	109.5
N1—C1—C6	121.24 (17)	H9A—C9—H9B	108.0
N1—C1—C2	121.54 (17)	N1—C10—C9	109.53 (17)
C6—C1—C2	117.21 (18)	N1—C10—H10A	109.8
C3—C2—C1	121.20 (18)	C9—C10—H10A	109.8
C3—C2—H2	119.4	N1—C10—H10B	109.8
C1—C2—H2	119.4	C9—C10—H10B	109.8
C2—C3—C4	120.09 (19)	H10A—C10—H10B	108.2
C2—C3—H3	120.0	O3—C11—O4	129.89 (19)
C4—C3—H3	120.0	O3—C11—C12	116.20 (18)
C5—C4—C3	120.39 (18)	O4—C11—C12	113.91 (17)
C5—C4—N3	120.10 (18)	C11—C12—Cl2A	107.1 (3)
C3—C4—N3	119.52 (18)	C11—C12—Cl1A	110.38 (19)
C4—C5—C6	119.88 (18)	Cl2A—C12—Cl1A	111.7 (2)
C4—C5—H5	120.1	C11—C12—Cl3B	108.7 (2)
C6—C5—H5	120.1	C11—C12—Cl2B	111.1 (2)
C5—C6—C1	121.24 (18)	Cl3B—C12—Cl2B	112.5 (3)
C5—C6—H6	119.4	C11—C12—Cl3A	111.2 (2)
C1—C6—H6	119.4	Cl2A—C12—Cl3A	106.4 (3)
N1—C7—C8	110.22 (17)	Cl1A—C12—Cl3A	110.0 (2)
N1—C7—H7A	109.6	C11—C12—Cl1B	114.97 (18)
C8—C7—H7A	109.6	Cl3B—C12—Cl1B	107.3 (2)
N1—C7—H7B	109.6	Cl2B—C12—Cl1B	102.2 (3)
C8—C7—H7B	109.6
C10—N1—C1—C6	−172.70 (18)	C10—N1—C7—C8	60.7 (2)
C7—N1—C1—C6	17.6 (3)	C9—N2—C8—C7	54.7 (2)
C10—N1—C1—C2	6.0 (3)	N1—C7—C8—N2	−57.0 (2)
C7—N1—C1—C2	−163.77 (18)	C8—N2—C9—C10	−54.9 (2)
N1—C1—C2—C3	−179.19 (18)	C1—N1—C10—C9	129.3 (2)
C6—C1—C2—C3	−0.5 (3)	C7—N1—C10—C9	−59.8 (2)
C1—C2—C3—C4	−0.1 (3)	N2—C9—C10—N1	56.4 (2)
C2—C3—C4—C5	0.6 (3)	O3—C11—C12—Cl2A	105.8 (4)
C2—C3—C4—N3	−179.41 (18)	O4—C11—C12—Cl2A	−74.1 (4)
O2—N3—C4—C5	2.1 (3)	O3—C11—C12—Cl1A	−16.0 (3)
O1—N3—C4—C5	−178.32 (17)	O4—C11—C12—Cl1A	164.1 (3)
O2—N3—C4—C3	−177.92 (18)	O3—C11—C12—Cl3B	−117.0 (5)
O1—N3—C4—C3	1.7 (3)	O4—C11—C12—Cl3B	63.2 (5)
C3—C4—C5—C6	−0.5 (3)	O3—C11—C12—Cl2B	118.7 (3)
N3—C4—C5—C6	179.50 (16)	O4—C11—C12—Cl2B	−61.1 (3)
C4—C5—C6—C1	−0.1 (3)	O3—C11—C12—Cl3A	−138.3 (3)
N1—C1—C6—C5	179.29 (17)	O4—C11—C12—Cl3A	41.8 (3)
C2—C1—C6—C5	0.6 (3)	O3—C11—C12—Cl1B	3.3 (5)
C1—N1—C7—C8	−128.4 (2)	O4—C11—C12—Cl1B	−176.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3	0.87 (2)	2.01 (2)	2.795 (2)	151 (2)
N2—H21···Cl1A	0.87 (2)	2.82 (2)	3.510 (5)	138 (2)
N2—H22···O4^i	0.87 (2)	1.89 (2)	2.738 (2)	167 (2)

Symmetry code: (i) x, y+1, z.