Intermolecular interactions of proton transfer compounds: synthesis, crystal structure and Hirshfeld surface analysis

Three new proton transfer compounds, [2-ammonio-5-methylcarboxybenzene perchlorate (1), (C₈H₁₀NO₂⁺·ClO₄⁻), 4-(ammoniomethyl)carboxybenzene nitrate (2), (C₈H₁₀NO₂⁺·NO₃⁻), and 4-(ammoniomethyl)carboxybenzene perchlorate (3), (C₈H₁₀NO₂⁺·ClO₄⁻)], have been synthesized, their IR modes of vibrations have been assigned and their crystal structures studied by means of single-crystal X-ray diffraction. Their asymmetric units consist of one cation and one anion for both compounds (1) and (2). However, the crystal structure of compound (3) is based on a pair of cations and a pair of anions in its asymmetric unit. The three-dimensional Hirshfeld surface analysis and the two-dimensional fingerprint maps revealed that the three structures are dominated by H...O/O...H and H...H contacts. The strongest hydrogen-bonding interactions are associated with O—H...O and N—H...O constituting the highest fraction of approximately 50%, followed by those of the H...H type contributing 20%. Other close contacts are also present, including weak C...H/H...C contacts (with about 10%).

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

Computing details

Program(s) used to solve structure: SIR2014 (Burla et al., 2014) for (1). For all compounds, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: ORTEP for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

Figures

(1)

Crystal data

C8H10NO2·ClO4	F(000) = 520
Mr = 251.62	Dx = 1.539 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 0 reflections
a = 7.3914 (2) Å	θ = 0–0°
b = 11.6712 (10) Å	µ = 0.37 mm^−1
c = 12.5913 (9) Å	T = 298 K
β = 91.455 (4)°	Prism, yellow
V = 1085.86 (12) Å^3	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection

31541 measured reflections	θmax = 27.5°, θmin = 5.2°
2503 independent reflections	h = −9→9
1866 reflections with I > 2σ(I)	k = −15→15
Rint = 0.070	l = −16→16

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.0614P)^2 + 1.0043P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.148	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.34 e Å^−3
2503 reflections	Δρmin = −0.43 e Å^−3
149 parameters	Extinction correction: SHELXL2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.015 (3)
0 constraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.09327 (9)	0.35945 (6)	0.22732 (6)	0.0522 (3)
N1	0.5624 (3)	0.46532 (18)	0.17967 (17)	0.0426 (5)
H1A	0.5282	0.4871	0.1145	0.064*
H1B	0.4825	0.4156	0.2044	0.064*
H1C	0.6708	0.4323	0.1777	0.064*
O2	0.4669 (4)	0.62087 (19)	0.03279 (15)	0.0670 (7)
C2	0.5717 (3)	0.5656 (2)	0.24954 (18)	0.0351 (5)
O1	0.4553 (4)	0.80466 (18)	0.07413 (17)	0.0752 (8)
H1	0.4322	0.8109	0.0104	0.113*
C7	0.4841 (4)	0.6962 (2)	0.0975 (2)	0.0434 (6)
C6	0.5531 (3)	0.7682 (2)	0.28235 (19)	0.0392 (6)
H6	0.5319	0.8421	0.2575	0.047*
C5	0.6001 (3)	0.7516 (2)	0.3893 (2)	0.0419 (6)
C1	0.5373 (3)	0.6761 (2)	0.21164 (18)	0.0343 (5)
C4	0.6305 (4)	0.6403 (3)	0.4244 (2)	0.0484 (7)
H4	0.6606	0.6275	0.4956	0.058*
C3	0.6169 (4)	0.5477 (2)	0.3555 (2)	0.0460 (6)
H3	0.6381	0.4738	0.3805	0.055*
C8	0.6196 (5)	0.8523 (3)	0.4637 (2)	0.0614 (8)
H8A	0.6830	0.9130	0.4291	0.092*
H8B	0.6864	0.8293	0.5265	0.092*
H8C	0.5018	0.8787	0.4829	0.092*
O5	0.2178 (4)	0.4264 (2)	0.2889 (2)	0.0851 (9)
O3	0.1809 (4)	0.3235 (3)	0.1331 (2)	0.0972 (10)
O4	0.0487 (4)	0.2591 (2)	0.2851 (3)	0.0938 (9)
O6	−0.0633 (4)	0.4233 (3)	0.2059 (4)	0.1320 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0444 (4)	0.0448 (4)	0.0672 (5)	−0.0017 (3)	−0.0005 (3)	−0.0178 (3)
N1	0.0517 (13)	0.0348 (11)	0.0410 (12)	0.0029 (10)	−0.0047 (9)	−0.0015 (9)
O2	0.118 (2)	0.0474 (12)	0.0350 (10)	0.0157 (12)	−0.0183 (11)	−0.0073 (9)
C2	0.0358 (12)	0.0369 (12)	0.0324 (11)	0.0008 (10)	−0.0027 (9)	−0.0015 (10)
O1	0.144 (2)	0.0404 (12)	0.0400 (11)	0.0111 (13)	−0.0146 (13)	0.0063 (9)
C7	0.0566 (16)	0.0425 (14)	0.0310 (13)	0.0059 (12)	−0.0005 (11)	0.0010 (11)
C6	0.0443 (14)	0.0376 (13)	0.0358 (12)	−0.0004 (11)	0.0014 (10)	−0.0026 (10)
C5	0.0394 (13)	0.0524 (15)	0.0340 (12)	−0.0065 (12)	0.0017 (10)	−0.0093 (11)
C1	0.0363 (12)	0.0382 (12)	0.0282 (11)	0.0003 (10)	0.0005 (9)	0.0009 (10)
C4	0.0530 (15)	0.0638 (18)	0.0279 (12)	−0.0046 (14)	−0.0070 (11)	0.0020 (12)
C3	0.0540 (16)	0.0439 (14)	0.0398 (13)	0.0019 (12)	−0.0074 (12)	0.0077 (12)
C8	0.070 (2)	0.069 (2)	0.0450 (16)	−0.0112 (17)	0.0005 (14)	−0.0212 (15)
O5	0.0733 (16)	0.0820 (18)	0.1003 (19)	−0.0255 (14)	0.0040 (14)	−0.0424 (16)
O3	0.097 (2)	0.146 (3)	0.0484 (14)	0.0154 (19)	−0.0075 (13)	−0.0265 (16)
O4	0.115 (2)	0.0617 (16)	0.105 (2)	−0.0219 (16)	0.0145 (18)	−0.0035 (15)
O6	0.0556 (16)	0.082 (2)	0.257 (5)	0.0174 (15)	−0.020 (2)	0.001 (3)

Geometric parameters (Å, º)

Cl1—O6	1.397 (3)	C7—C1	1.499 (3)
Cl1—O5	1.422 (2)	C6—C5	1.396 (4)
Cl1—O4	1.422 (3)	C6—C1	1.398 (3)
Cl1—O3	1.429 (3)	C6—H6	0.9300
N1—C2	1.465 (3)	C5—C4	1.389 (4)
N1—H1A	0.8900	C5—C8	1.507 (4)
N1—H1B	0.8900	C4—C3	1.387 (4)
N1—H1C	0.8900	C4—H4	0.9300
O2—C7	1.203 (3)	C3—H3	0.9300
C2—C3	1.383 (3)	C8—H8A	0.9600
C2—C1	1.396 (3)	C8—H8B	0.9600
O1—C7	1.316 (3)	C8—H8C	0.9600
O1—H1	0.8200
O6—Cl1—O5	109.5 (2)	C5—C6—H6	119.2
O6—Cl1—O4	109.7 (2)	C1—C6—H6	119.2
O5—Cl1—O4	109.21 (19)	C4—C5—C6	118.0 (2)
O6—Cl1—O3	112.8 (3)	C4—C5—C8	121.3 (2)
O5—Cl1—O3	108.25 (18)	C6—C5—C8	120.6 (3)
O4—Cl1—O3	107.4 (2)	C2—C1—C6	118.7 (2)
C2—N1—H1A	109.5	C2—C1—C7	120.8 (2)
C2—N1—H1B	109.5	C6—C1—C7	120.4 (2)
H1A—N1—H1B	109.5	C3—C4—C5	121.4 (2)
C2—N1—H1C	109.5	C3—C4—H4	119.3
H1A—N1—H1C	109.5	C5—C4—H4	119.3
H1B—N1—H1C	109.5	C2—C3—C4	119.8 (3)
C3—C2—C1	120.4 (2)	C2—C3—H3	120.1
C3—C2—N1	117.7 (2)	C4—C3—H3	120.1
C1—C2—N1	121.8 (2)	C5—C8—H8A	109.5
C7—O1—H1	109.5	C5—C8—H8B	109.5
O2—C7—O1	122.5 (2)	H8A—C8—H8B	109.5
O2—C7—C1	123.8 (2)	C5—C8—H8C	109.5
O1—C7—C1	113.7 (2)	H8A—C8—H8C	109.5
C5—C6—C1	121.6 (2)	H8B—C8—H8C	109.5
C1—C6—C5—C4	−0.2 (4)	O1—C7—C1—C2	179.7 (3)
C1—C6—C5—C8	178.9 (2)	O2—C7—C1—C6	−179.5 (3)
C3—C2—C1—C6	1.3 (4)	O1—C7—C1—C6	−0.3 (4)
N1—C2—C1—C6	−178.4 (2)	C6—C5—C4—C3	0.7 (4)
C3—C2—C1—C7	−178.6 (2)	C8—C5—C4—C3	−178.4 (3)
N1—C2—C1—C7	1.7 (4)	C1—C2—C3—C4	−0.9 (4)
C5—C6—C1—C2	−0.8 (4)	N1—C2—C3—C4	178.9 (2)
C5—C6—C1—C7	179.1 (2)	C5—C4—C3—C2	−0.2 (4)
O2—C7—C1—C2	0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	1.92	2.674 (3)	142
N1—H1A···O2^i	0.89	2.24	2.861 (3)	126
N1—H1C···O6^ii	0.89	1.99	2.821 (4)	155
N1—H1B···O5	0.89	2.25	2.960 (4)	136
N1—H1B···O4^iii	0.89	2.32	2.939 (4)	126
O1—H1···O3^iv	0.82	1.98	2.781 (3)	167

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

(2)

Crystal data

C8H10NO2·NO3	F(000) = 896
Mr = 214.18	Dx = 1.509 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 0 reflections
a = 13.3114 (10) Å	θ = 0–0°
b = 6.0032 (4) Å	µ = 0.13 mm^−1
c = 24.1094 (15) Å	T = 298 K
β = 101.854 (5)°	Prism, colourless
V = 1885.5 (2) Å^3	0.35 × 0.3 × 0.1 mm
Z = 8

Data collection

10974 measured reflections	θmax = 27.5°, θmin = 5.1°
2146 independent reflections	h = −17→17
1379 reflections with I > 2σ(I)	k = −7→7
Rint = 0.073	l = −31→29

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0623P)^2 + 0.6027P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2146 reflections	Δρmax = 0.24 e Å^−3
138 parameters	Δρmin = −0.23 e Å^−3
0 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
O5	0.88315 (13)	0.0791 (2)	0.47340 (6)	0.0495 (4)
O4	0.88508 (13)	−0.2807 (3)	0.47615 (6)	0.0526 (4)
C1	0.87993 (14)	0.3437 (3)	0.77345 (8)	0.0336 (4)
O2	0.92232 (13)	0.1378 (3)	0.85910 (6)	0.0550 (4)
N2	0.88443 (13)	−0.0990 (3)	0.50077 (7)	0.0389 (4)
O3	0.88691 (14)	−0.0893 (3)	0.55249 (6)	0.0580 (5)
O1	0.87779 (14)	0.4931 (3)	0.86312 (6)	0.0555 (5)
H1	0.8844	0.4646	0.8969	0.083*
C3	0.82712 (16)	0.5651 (3)	0.68980 (8)	0.0398 (5)
H3	0.8027	0.6995	0.6731	0.048*
N1	0.91937 (13)	0.4039 (3)	0.56965 (7)	0.0418 (4)
H1A	0.9696	0.4763	0.5927	0.063*
H1B	0.9084	0.4664	0.5355	0.063*
H1C	0.9373	0.2621	0.5670	0.063*
C5	0.88235 (16)	0.1920 (3)	0.68162 (8)	0.0407 (5)
H5	0.8958	0.0733	0.6594	0.049*
C4	0.84524 (15)	0.3900 (3)	0.65592 (8)	0.0345 (4)
C6	0.89978 (15)	0.1682 (3)	0.73996 (8)	0.0378 (5)
H6	0.9248	0.0343	0.7567	0.045*
C7	0.89645 (15)	0.3133 (3)	0.83586 (8)	0.0378 (5)
C8	0.82403 (16)	0.4157 (4)	0.59254 (8)	0.0432 (5)
H8A	0.7774	0.2991	0.5754	0.052*
H8B	0.7907	0.5579	0.5823	0.052*
C2	0.84474 (16)	0.5435 (3)	0.74810 (8)	0.0382 (5)
H2	0.8329	0.6635	0.7703	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O5	0.0683 (11)	0.0415 (8)	0.0379 (7)	−0.0013 (7)	0.0094 (7)	0.0050 (6)
O4	0.0735 (11)	0.0415 (9)	0.0424 (8)	−0.0072 (8)	0.0113 (7)	−0.0107 (7)
C1	0.0288 (10)	0.0355 (10)	0.0370 (10)	0.0001 (8)	0.0081 (8)	0.0036 (8)
O2	0.0630 (11)	0.0540 (10)	0.0447 (8)	0.0119 (8)	0.0036 (7)	0.0148 (7)
N2	0.0421 (10)	0.0417 (10)	0.0326 (8)	−0.0034 (8)	0.0070 (7)	−0.0033 (8)
O3	0.0922 (13)	0.0508 (9)	0.0352 (8)	−0.0002 (9)	0.0227 (8)	−0.0022 (7)
O1	0.0829 (12)	0.0502 (9)	0.0333 (7)	0.0053 (9)	0.0117 (8)	−0.0010 (7)
C3	0.0458 (12)	0.0330 (10)	0.0409 (10)	0.0070 (9)	0.0094 (9)	0.0081 (9)
N1	0.0524 (11)	0.0412 (9)	0.0331 (8)	−0.0058 (8)	0.0117 (7)	−0.0074 (7)
C5	0.0466 (12)	0.0372 (11)	0.0395 (10)	0.0041 (9)	0.0117 (9)	−0.0029 (9)
C4	0.0309 (10)	0.0372 (10)	0.0359 (9)	−0.0012 (8)	0.0082 (7)	0.0021 (8)
C6	0.0412 (12)	0.0293 (10)	0.0434 (11)	0.0060 (8)	0.0094 (9)	0.0047 (8)
C7	0.0329 (10)	0.0438 (11)	0.0356 (10)	−0.0008 (9)	0.0045 (8)	0.0034 (9)
C8	0.0405 (11)	0.0520 (13)	0.0368 (10)	−0.0024 (10)	0.0074 (8)	0.0019 (9)
C2	0.0435 (11)	0.0338 (10)	0.0393 (10)	0.0053 (9)	0.0134 (8)	−0.0005 (8)

Geometric parameters (Å, º)

O5—N2	1.255 (2)	N1—C8	1.486 (3)
O4—N2	1.243 (2)	N1—H1A	0.8900
C1—C2	1.384 (3)	N1—H1B	0.8900
C1—C6	1.386 (3)	N1—H1C	0.8900
C1—C7	1.487 (3)	C5—C4	1.384 (3)
O2—C7	1.210 (2)	C5—C6	1.385 (3)
N2—O3	1.242 (2)	C5—H5	0.9300
O1—C7	1.314 (2)	C4—C8	1.504 (3)
O1—H1	0.8200	C6—H6	0.9300
C3—C4	1.383 (3)	C8—H8A	0.9700
C3—C2	1.383 (3)	C8—H8B	0.9700
C3—H3	0.9300	C2—H2	0.9300
C2—C1—C6	119.31 (17)	C3—C4—C5	118.57 (17)
C2—C1—C7	121.33 (17)	C3—C4—C8	120.20 (18)
C6—C1—C7	119.35 (17)	C5—C4—C8	121.23 (18)
O3—N2—O4	121.29 (17)	C5—C6—C1	120.09 (18)
O3—N2—O5	118.89 (16)	C5—C6—H6	120.0
O4—N2—O5	119.81 (15)	C1—C6—H6	120.0
C7—O1—H1	109.5	O2—C7—O1	123.30 (18)
C4—C3—C2	121.03 (18)	O2—C7—C1	123.01 (19)
C4—C3—H3	119.5	O1—C7—C1	113.67 (17)
C2—C3—H3	119.5	N1—C8—C4	112.09 (16)
C8—N1—H1A	109.5	N1—C8—H8A	109.2
C8—N1—H1B	109.5	C4—C8—H8A	109.2
H1A—N1—H1B	109.5	N1—C8—H8B	109.2
C8—N1—H1C	109.5	C4—C8—H8B	109.2
H1A—N1—H1C	109.5	H8A—C8—H8B	107.9
H1B—N1—H1C	109.5	C3—C2—C1	120.11 (18)
C4—C5—C6	120.87 (18)	C3—C2—H2	119.9
C4—C5—H5	119.6	C1—C2—H2	119.9
C6—C5—H5	119.6
C2—C3—C4—C5	−0.5 (3)	C6—C1—C7—O2	−3.5 (3)
C2—C3—C4—C8	179.05 (18)	C2—C1—C7—O1	−2.1 (3)
C6—C5—C4—C3	0.8 (3)	C6—C1—C7—O1	178.18 (18)
C6—C5—C4—C8	−178.72 (19)	C3—C4—C8—N1	114.5 (2)
C4—C5—C6—C1	0.1 (3)	C5—C4—C8—N1	−65.9 (3)
C2—C1—C6—C5	−1.4 (3)	C4—C3—C2—C1	−0.8 (3)
C7—C1—C6—C5	178.38 (18)	C6—C1—C2—C3	1.7 (3)
C2—C1—C7—O2	176.3 (2)	C7—C1—C2—C3	−178.06 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5^i	0.82	1.87	2.6803 (19)	172
O1—H1···N2^i	0.82	2.63	3.362 (2)	149
N1—H1A···O2^ii	0.89	1.92	2.806 (2)	178
N1—H1B···O4^iii	0.89	2.06	2.907 (2)	157
N1—H1C···O5	0.89	2.48	2.994 (2)	117
N1—H1C···O3	0.89	2.22	3.009 (2)	148
C8—H8A···O5^iv	0.97	2.58	3.524 (3)	164

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

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Crystal data

C8H10NO2·ClO4	Z = 4
Mr = 251.62	F(000) = 520
Triclinic, P1	Dx = 1.622 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9634 (4) Å	Cell parameters from 0 reflections
b = 12.9992 (11) Å	θ = 0–0°
c = 16.5405 (17) Å	µ = 0.39 mm^−1
α = 75.125 (8)°	T = 298 K
β = 88.907 (7)°	Prism, colourless
γ = 87.706 (6)°	0.25 × 0.13 × 0.05 mm
V = 1030.56 (16) Å^3

Data collection

30848 measured reflections	θmax = 27.5°, θmin = 5.1°
4751 independent reflections	h = −6→6
2918 reflections with I > 2σ(I)	k = −16→16
Rint = 0.131	l = −21→21

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.055	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 0.7374P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.118	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.32 e Å^−3
4751 reflections	Δρmin = −0.33 e Å^−3
290 parameters	Extinction correction: SHELXL2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0120 (16)
0 constraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cl1A	0.99712 (14)	0.10192 (6)	0.58213 (5)	0.0301 (2)
Cl1B	0.95503 (14)	0.40584 (6)	0.41075 (5)	0.0315 (2)
O2B	−0.2601 (4)	0.51342 (17)	0.06557 (15)	0.0419 (6)
O1B	−0.3445 (4)	0.36876 (18)	0.02148 (15)	0.0429 (6)
H1B	−0.4542	0.4102	−0.0076	0.064*
O2A	−0.2515 (4)	−0.01529 (17)	0.93540 (15)	0.0403 (6)
O1A	−0.3609 (5)	0.13082 (18)	0.97905 (15)	0.0449 (6)
H1A	−0.4690	0.0908	1.0080	0.067*
N1B	0.4350 (5)	0.1573 (2)	0.39003 (16)	0.0358 (6)
H1B1	0.5486	0.1186	0.4278	0.054*
H1B2	0.4114	0.2220	0.3985	0.054*
H1B3	0.2772	0.1260	0.3949	0.054*
C1B	−0.0069 (6)	0.3526 (2)	0.12364 (18)	0.0274 (6)
N1A	0.4226 (5)	0.3349 (2)	0.61052 (17)	0.0381 (7)
H1A1	0.5328	0.3733	0.5724	0.057*
H1A2	0.4135	0.2699	0.6026	0.057*
H1A3	0.2589	0.3663	0.6056	0.057*
C6B	0.0354 (6)	0.2445 (2)	0.12906 (19)	0.0313 (7)
H6B	−0.0579	0.2125	0.0944	0.038*
O3A	0.9194 (5)	0.00566 (19)	0.64015 (17)	0.0537 (7)
C1A	−0.0141 (6)	0.1429 (2)	0.87739 (19)	0.0281 (7)
O4A	0.8904 (5)	0.1087 (2)	0.50093 (16)	0.0495 (6)
C4A	0.3440 (6)	0.2618 (2)	0.76253 (19)	0.0289 (7)
C6A	0.0120 (6)	0.2499 (2)	0.8726 (2)	0.0347 (7)
H6A	−0.0898	0.2823	0.9076	0.042*
C8A	0.5282 (6)	0.3269 (3)	0.6963 (2)	0.0355 (7)
H8A1	0.5407	0.3977	0.7047	0.043*
H8A2	0.7077	0.2936	0.7015	0.043*
C8B	0.5487 (6)	0.1665 (2)	0.30411 (19)	0.0310 (7)
H8B1	0.5770	0.0959	0.2952	0.037*
H8B2	0.7220	0.1997	0.2991	0.037*
C4B	0.3603 (5)	0.2320 (2)	0.23820 (18)	0.0265 (6)
O3B	0.9994 (6)	0.5061 (2)	0.35287 (18)	0.0643 (8)
O5A	1.2861 (4)	0.1025 (2)	0.57574 (16)	0.0529 (7)
C3A	0.3263 (6)	0.1529 (2)	0.7704 (2)	0.0336 (7)
H3A	0.4352	0.1196	0.7376	0.040*
C3B	0.3250 (6)	0.3411 (2)	0.2293 (2)	0.0318 (7)
H3B	0.4255	0.3741	0.2616	0.038*
C7B	−0.2151 (6)	0.4180 (2)	0.06681 (19)	0.0301 (7)
C2A	0.1464 (6)	0.0945 (2)	0.8271 (2)	0.0340 (7)
H2A	0.1327	0.0221	0.8316	0.041*
C5B	0.2184 (6)	0.1849 (2)	0.1867 (2)	0.0326 (7)
H5B	0.2461	0.1126	0.1907	0.039*
C2B	0.1416 (6)	0.4005 (2)	0.1727 (2)	0.0336 (7)
H2B	0.1178	0.4732	0.1676	0.040*
O5B	1.2079 (5)	0.3556 (2)	0.43975 (18)	0.0575 (7)
C7A	−0.2203 (6)	0.0795 (2)	0.93370 (19)	0.0298 (7)
C5A	0.1918 (6)	0.3088 (2)	0.8150 (2)	0.0343 (7)
H5A	0.2095	0.3807	0.8117	0.041*
O6B	0.8154 (6)	0.3395 (2)	0.37080 (19)	0.0664 (8)
O4B	0.7983 (5)	0.4251 (2)	0.47970 (17)	0.0595 (8)
O6A	0.9002 (6)	0.1911 (2)	0.61098 (18)	0.0596 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1A	0.0270 (4)	0.0321 (4)	0.0294 (4)	0.0010 (3)	−0.0023 (3)	−0.0048 (3)
Cl1B	0.0287 (4)	0.0336 (4)	0.0308 (4)	−0.0048 (3)	0.0027 (3)	−0.0053 (3)
O2B	0.0449 (13)	0.0343 (13)	0.0445 (15)	0.0110 (10)	−0.0162 (11)	−0.0075 (11)
O1B	0.0443 (13)	0.0448 (14)	0.0425 (15)	0.0128 (10)	−0.0215 (11)	−0.0169 (11)
O2A	0.0462 (13)	0.0366 (13)	0.0389 (14)	−0.0141 (10)	0.0131 (10)	−0.0106 (11)
O1A	0.0465 (14)	0.0452 (14)	0.0452 (15)	−0.0140 (11)	0.0208 (11)	−0.0152 (12)
N1B	0.0338 (14)	0.0409 (15)	0.0275 (15)	−0.0007 (11)	−0.0086 (11)	0.0014 (12)
C1B	0.0264 (15)	0.0336 (16)	0.0203 (16)	0.0028 (12)	−0.0024 (12)	−0.0039 (12)
N1A	0.0390 (15)	0.0383 (15)	0.0315 (16)	−0.0037 (12)	0.0101 (12)	0.0008 (12)
C6B	0.0374 (17)	0.0319 (17)	0.0270 (17)	0.0005 (13)	−0.0095 (13)	−0.0116 (13)
O3A	0.0601 (16)	0.0427 (14)	0.0501 (17)	−0.0156 (12)	0.0025 (13)	0.0051 (12)
C1A	0.0301 (15)	0.0318 (16)	0.0211 (16)	−0.0031 (12)	0.0000 (12)	−0.0043 (12)
O4A	0.0467 (14)	0.0633 (16)	0.0386 (15)	0.0086 (12)	−0.0206 (11)	−0.0131 (12)
C4A	0.0271 (15)	0.0366 (17)	0.0229 (16)	−0.0053 (12)	0.0004 (12)	−0.0070 (13)
C6A	0.0393 (17)	0.0331 (17)	0.0318 (19)	−0.0028 (13)	0.0110 (14)	−0.0092 (14)
C8A	0.0341 (17)	0.0394 (18)	0.0341 (19)	−0.0106 (14)	0.0091 (14)	−0.0110 (15)
C8B	0.0293 (15)	0.0360 (17)	0.0259 (17)	0.0044 (12)	−0.0058 (13)	−0.0052 (13)
C4B	0.0245 (14)	0.0317 (16)	0.0213 (15)	0.0018 (11)	0.0009 (11)	−0.0037 (12)
O3B	0.084 (2)	0.0414 (15)	0.0540 (19)	−0.0007 (13)	0.0197 (15)	0.0106 (13)
O5A	0.0247 (12)	0.0839 (19)	0.0465 (16)	−0.0056 (11)	−0.0008 (11)	−0.0093 (14)
C3A	0.0346 (16)	0.0384 (18)	0.0304 (18)	−0.0025 (13)	0.0076 (13)	−0.0138 (14)
C3B	0.0330 (16)	0.0325 (17)	0.0319 (18)	−0.0011 (13)	−0.0086 (13)	−0.0112 (14)
C7B	0.0305 (16)	0.0356 (18)	0.0226 (16)	0.0031 (13)	−0.0027 (12)	−0.0052 (13)
C2A	0.0424 (18)	0.0300 (16)	0.0310 (18)	−0.0068 (13)	0.0059 (14)	−0.0097 (14)
C5B	0.0392 (17)	0.0239 (15)	0.0337 (18)	0.0031 (12)	−0.0068 (14)	−0.0055 (13)
C2B	0.0384 (17)	0.0284 (16)	0.0335 (19)	0.0063 (13)	−0.0083 (14)	−0.0076 (14)
O5B	0.0406 (14)	0.0689 (18)	0.0626 (19)	0.0146 (12)	−0.0161 (13)	−0.0174 (14)
C7A	0.0314 (16)	0.0367 (18)	0.0207 (16)	−0.0031 (13)	0.0004 (12)	−0.0059 (13)
C5A	0.0419 (18)	0.0271 (16)	0.0334 (19)	−0.0055 (13)	0.0047 (14)	−0.0070 (14)
O6B	0.0624 (18)	0.079 (2)	0.071 (2)	−0.0199 (15)	−0.0096 (15)	−0.0397 (17)
O4B	0.0611 (17)	0.0658 (18)	0.0572 (19)	−0.0222 (13)	0.0349 (14)	−0.0256 (15)
O6A	0.0776 (19)	0.0453 (15)	0.0605 (19)	0.0146 (13)	−0.0001 (15)	−0.0243 (13)

Geometric parameters (Å, º)

Cl1A—O6A	1.426 (3)	C6B—C5B	1.389 (4)
Cl1A—O3A	1.430 (2)	C6B—H6B	0.9300
Cl1A—O4A	1.433 (2)	C1A—C6A	1.384 (4)
Cl1A—O5A	1.436 (2)	C1A—C2A	1.388 (4)
Cl1B—O6B	1.421 (3)	C1A—C7A	1.494 (4)
Cl1B—O5B	1.424 (2)	C4A—C5A	1.380 (4)
Cl1B—O3B	1.427 (2)	C4A—C3A	1.395 (4)
Cl1B—O4B	1.437 (3)	C4A—C8A	1.516 (4)
O2B—C7B	1.246 (4)	C6A—C5A	1.392 (4)
O1B—C7B	1.297 (4)	C6A—H6A	0.9300
O1B—H1B	0.8200	C8A—H8A1	0.9700
O2A—C7A	1.241 (4)	C8A—H8A2	0.9700
O1A—C7A	1.302 (4)	C8B—C4B	1.513 (4)
O1A—H1A	0.8200	C8B—H8B1	0.9700
N1B—C8B	1.497 (4)	C8B—H8B2	0.9700
N1B—H1B1	0.8900	C4B—C5B	1.386 (4)
N1B—H1B2	0.8900	C4B—C3B	1.391 (4)
N1B—H1B3	0.8900	C3A—C2A	1.382 (4)
C1B—C2B	1.382 (4)	C3A—H3A	0.9300
C1B—C6B	1.392 (4)	C3B—C2B	1.381 (4)
C1B—C7B	1.494 (4)	C3B—H3B	0.9300
N1A—C8A	1.499 (4)	C2A—H2A	0.9300
N1A—H1A1	0.8900	C5B—H5B	0.9300
N1A—H1A2	0.8900	C2B—H2B	0.9300
N1A—H1A3	0.8900	C5A—H5A	0.9300
O6A—Cl1A—O3A	109.51 (17)	C5A—C6A—H6A	120.2
O6A—Cl1A—O4A	109.77 (16)	N1A—C8A—C4A	110.6 (2)
O3A—Cl1A—O4A	110.47 (16)	N1A—C8A—H8A1	109.5
O6A—Cl1A—O5A	109.44 (17)	C4A—C8A—H8A1	109.5
O3A—Cl1A—O5A	109.14 (15)	N1A—C8A—H8A2	109.5
O4A—Cl1A—O5A	108.48 (15)	C4A—C8A—H8A2	109.5
O6B—Cl1B—O5B	109.23 (18)	H8A1—C8A—H8A2	108.1
O6B—Cl1B—O3B	109.78 (19)	N1B—C8B—C4B	110.9 (2)
O5B—Cl1B—O3B	109 (11)	N1B—C8B—H8B1	109.5
O6B—Cl1B—O4B	110.38 (17)	C4B—C8B—H8B1	109.5
O5B—Cl1B—O4B	109.99 (18)	N1B—C8B—H8B2	109.5
O3B—Cl1B—O4B	108.07 (16)	C4B—C8B—H8B2	109.5
C7B—O1B—H1B	109.5	H8B1—C8B—H8B2	108.1
C7A—O1A—H1A	109.5	C5B—C4B—C3B	119.1 (3)
C8B—N1B—H1B1	109.5	C5B—C4B—C8B	121.0 (3)
C8B—N1B—H1B2	109.5	C3B—C4B—C8B	119.9 (3)
H1B1—N1B—H1B2	109.5	C2A—C3A—C4A	119.9 (3)
C8B—N1B—H1B3	109.5	C2A—C3A—H3A	120.1
H1B1—N1B—H1B3	109.5	C4A—C3A—H3A	120.1
H1B2—N1B—H1B3	109.5	C2B—C3B—C4B	120.4 (3)
C2B—C1B—C6B	119.9 (3)	C2B—C3B—H3B	119.8
C2B—C1B—C7B	118.9 (3)	C4B—C3B—H3B	119.8
C6B—C1B—C7B	121.3 (3)	O2B—C7B—O1B	123.5 (3)
C8A—N1A—H1A1	109.5	O2B—C7B—C1B	120.6 (3)
C8A—N1A—H1A2	109.5	O1B—C7B—C1B	115.8 (3)
H1A1—N1A—H1A2	109.5	C3A—C2A—C1A	120.6 (3)
C8A—N1A—H1A3	109.5	C3A—C2A—H2A	119.7
H1A1—N1A—H1A3	109.5	C1A—C2A—H2A	119.7
H1A2—N1A—H1A3	109.5	C4B—C5B—C6B	120.8 (3)
C5B—C6B—C1B	119.4 (3)	C4B—C5B—H5B	119.6
C5B—C6B—H6B	120.3	C6B—C5B—H5B	119.6
C1B—C6B—H6B	120.3	C3B—C2B—C1B	120.3 (3)
C6A—C1A—C2A	119.8 (3)	C3B—C2B—H2B	119.8
C6A—C1A—C7A	120.9 (3)	C1B—C2B—H2B	119.8
C2A—C1A—C7A	119.3 (3)	O2A—C7A—O1A	123.7 (3)
C5A—C4A—C3A	119.3 (3)	O2A—C7A—C1A	120.9 (3)
C5A—C4A—C8A	121.1 (3)	O1A—C7A—C1A	115.3 (3)
C3A—C4A—C8A	119.6 (3)	C4A—C5A—C6A	120.9 (3)
C1A—C6A—C5A	119.5 (3)	C4A—C5A—H5A	119.6
C1A—C6A—H6A	120.2	C6A—C5A—H5A	119.6
C2B—C1B—C6B—C5B	2.9 (5)	C4A—C3A—C2A—C1A	−1.0 (5)
C7B—C1B—C6B—C5B	−175.8 (3)	C6A—C1A—C2A—C3A	−2.0 (5)
C2A—C1A—C6A—C5A	2.5 (5)	C7A—C1A—C2A—C3A	175.7 (3)
C7A—C1A—C6A—C5A	−175.2 (3)	C3B—C4B—C5B—C6B	−2.5 (5)
C5A—C4A—C8A—N1A	−111.2 (3)	C8B—C4B—C5B—C6B	176.8 (3)
C3A—C4A—C8A—N1A	68.4 (4)	C1B—C6B—C5B—C4B	−0.5 (5)
N1B—C8B—C4B—C5B	−109.3 (3)	C4B—C3B—C2B—C1B	−0.7 (5)
N1B—C8B—C4B—C3B	69.9 (3)	C6B—C1B—C2B—C3B	−2.3 (5)
C5A—C4A—C3A—C2A	3.6 (5)	C7B—C1B—C2B—C3B	176.4 (3)
C8A—C4A—C3A—C2A	−176.0 (3)	C6A—C1A—C7A—O2A	176.9 (3)
C5B—C4B—C3B—C2B	3.1 (5)	C2A—C1A—C7A—O2A	−0.8 (4)
C8B—C4B—C3B—C2B	−176.2 (3)	C6A—C1A—C7A—O1A	−2.7 (4)
C2B—C1B—C7B—O2B	−2.2 (5)	C2A—C1A—C7A—O1A	179.6 (3)
C6B—C1B—C7B—O2B	176.5 (3)	C3A—C4A—C5A—C6A	−3.1 (5)
C2B—C1B—C7B—O1B	179.0 (3)	C8A—C4A—C5A—C6A	176.5 (3)
C6B—C1B—C7B—O1B	−2.3 (4)	C1A—C6A—C5A—C4A	0.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O4B	0.89	2.00	2.873 (4)	166
O1B—H1B···O2B^i	0.82	1.83	2.647 (3)	171
O1A—H1A···O2A^ii	0.82	1.83	2.644 (3)	172
N1B—H1B1···O4A	0.89	2.08	2.885 (3)	149
N1B—H1B2···O5B^iii	0.89	2.22	3.067 (4)	158
N1B—H1B2···O6B	0.89	2.53	3.037 (4)	117
N1B—H1B3···O3A^iv	0.89	2.21	2.950 (4)	140
N1B—H1B3···O4A^iii	0.89	2.55	3.228 (4)	133
N1A—H1A1···O4B	0.89	2.00	2.873 (4)	166
N1A—H1A2···O5A^iii	0.89	2.44	3.315 (4)	168
N1A—H1A3···O3B^v	0.89	2.29	3.045 (4)	142
C8A—H8A2···O6A	0.97	2.41	3.070 (4)	125
C8B—H8B2···O6B	0.97	2.47	3.097 (4)	122

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