Reversible phase transition of 2-carb­oxy­pyridinium perchlorate-pyridinium-2-carboxyl­ate (1/1)

The title salt, C₆H₆NO₂⁺·ClO₄^-·C₆H₅NO₂, was crystallized from an aqueous solution of equimolar quantities of per­chloric acid and pyridine-2-carboxylic acid. Differential scanning calorimetry (DSC) measurements show that the compound undergoes a reversible phase transition at about 261.7 K, with a wide heat hysteresis of 21.9 K. The lower-temperature polymorph (denoted LT; T = 223 K) crystallizes in the space group C2/c, while the higher-temperature polymorph (denoted RT; T = 296 K) crystallizes in the space group P2/c. The relationship between these two phases can be described as: 2a_RT = a_LT; 2b_RT = b_LT; c_RT = c_LT. The crystal structure contains an infinite zigzag hydrogen-bonded chain network of 2-carb­oxy­pyridinium cations. The most distinct difference between the higher (RT) and lower (LT) temperature phases is the change in dihedral angle between the planes of the carb­oxy­lic acid group and the pyridinium ring, which leads to the formation of different ten-membered hydrogen-bonded rings. In the RT phase, both the perchlorate anions and the hydrogen-bonded H atom within the carb­oxy­lic acid group are disordered. The disordered H atom is located on a twofold rotation axis. In the LT phase, the asymmetric unit is composed of two 2-carb­oxy­pyridinium cations, half an ordered perchlorate anion with ideal tetra­hedral geometry and a disordered perchlorate anion. The phase transition is attributable to the order-disorder transition of half of the perchlorate anions.

Computing details

For both compounds, data collection: RAPID-AUTO (Rigaku, 2000); cell refinement: RAPID-AUTO (Rigaku, 2000); data reduction: RAPID-AUTO (Rigaku, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008). Molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), Marvinsketch (ChemAxon, 2010) for 296K; SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005) for 223K. For both compounds, software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(296K) 2-Carboxypyridinium perchlorate–pyridinium-2-carboxylate (1/1)

Crystal data

C6H6NO2^+·ClO4^−·C6H5NO2	F(000) = 356
Mr = 346.68	Dx = 1.584 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 5941 reflections
a = 10.252 (2) Å	θ = 3.0–27.5°
b = 5.8362 (12) Å	µ = 0.31 mm^−1
c = 12.656 (3) Å	T = 296 K
β = 106.29 (3)°	Block, colourless
V = 726.8 (3) Å^3	0.43 × 0.30 × 0.25 mm
Z = 2

Data collection

Rigaku RAPID diffractometer	1653 independent reflections
Radiation source: fine-focus sealed tube	1460 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 27.4°, θmin = 3.4°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2000)	h = −12→13
Tmin = 0.854, Tmax = 1.000	k = −5→7
6708 measured reflections	l = −16→16

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.258	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.1651P)^2 + 0.3529P] where P = (Fo^2 + 2Fc^2)/3
1653 reflections	(Δ/σ)max < 0.001
121 parameters	Δρmax = 0.86 e Å^−3
46 restraints	Δρmin = −0.51 e Å^−3

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.

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	Occ. (<1)
Cl1	0.0000	0.0825 (2)	0.2500	0.0659 (5)
O3	0.1473 (8)	0.0405 (17)	0.2797 (8)	0.125 (3)	0.50
O4	−0.073 (2)	−0.051 (3)	0.2792 (16)	0.287 (10)	0.50
O5	−0.0213 (10)	0.0573 (15)	0.1267 (5)	0.110 (3)	0.50
O6	0.0000	0.3270 (12)	0.2500	0.135 (2)
C1	0.2661 (4)	0.2338 (6)	0.6031 (3)	0.0585 (8)
H1B	0.2728	0.1233	0.6573	0.070*
C2	0.1825 (4)	0.4194 (7)	0.5974 (3)	0.0624 (9)
H2A	0.1314	0.4357	0.6471	0.075*
C3	0.1753 (3)	0.5825 (6)	0.5162 (3)	0.0611 (9)
H3A	0.1200	0.7105	0.5120	0.073*
C4	0.2498 (3)	0.5556 (6)	0.4416 (3)	0.0541 (8)
H4A	0.2447	0.6639	0.3867	0.065*
C5	0.3322 (3)	0.3654 (5)	0.4498 (2)	0.0447 (7)
C6	0.4225 (3)	0.3163 (5)	0.3763 (2)	0.0467 (7)
O1	0.4247 (3)	0.4756 (4)	0.30881 (18)	0.0611 (7)
H1	0.5000	0.4570	0.2500	0.09 (2)*
O2	0.4862 (3)	0.1375 (5)	0.3883 (2)	0.0705 (8)
N1	0.3382 (2)	0.2126 (4)	0.5301 (2)	0.0496 (7)
H1A	0.3907	0.0957	0.5350	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0677 (8)	0.0555 (8)	0.0811 (9)	0.000	0.0315 (6)	0.000
O3	0.080 (5)	0.149 (8)	0.124 (6)	0.029 (5)	−0.006 (4)	−0.066 (6)
O4	0.26 (2)	0.273 (19)	0.31 (2)	−0.144 (15)	0.049 (16)	0.092 (16)
O5	0.144 (7)	0.114 (6)	0.068 (4)	0.005 (5)	0.023 (4)	−0.014 (4)
O6	0.153 (6)	0.104 (5)	0.153 (6)	0.000	0.050 (5)	0.000
C1	0.0616 (18)	0.067 (2)	0.0525 (16)	−0.0027 (15)	0.0255 (13)	0.0004 (14)
C2	0.0529 (17)	0.081 (2)	0.0589 (18)	−0.0016 (15)	0.0242 (14)	−0.0133 (16)
C3	0.0504 (16)	0.066 (2)	0.0653 (19)	0.0117 (13)	0.0143 (14)	−0.0109 (15)
C4	0.0512 (16)	0.0577 (18)	0.0498 (15)	0.0058 (12)	0.0085 (12)	−0.0016 (12)
C5	0.0422 (13)	0.0500 (15)	0.0412 (13)	−0.0001 (11)	0.0107 (10)	−0.0035 (10)
C6	0.0452 (14)	0.0541 (16)	0.0406 (13)	0.0026 (11)	0.0117 (10)	−0.0018 (11)
O1	0.0728 (16)	0.0613 (14)	0.0553 (13)	0.0102 (11)	0.0278 (11)	0.0078 (10)
O2	0.0848 (18)	0.0719 (16)	0.0652 (15)	0.0297 (14)	0.0383 (13)	0.0176 (12)
N1	0.0507 (13)	0.0500 (14)	0.0502 (13)	0.0024 (10)	0.0177 (10)	−0.0009 (10)

Geometric parameters (Å, º)

Cl1—O4^i	1.204 (11)	C1—H1B	0.9300
Cl1—O4	1.204 (11)	C2—C3	1.388 (5)
Cl1—O6	1.427 (7)	C2—H2A	0.9300
Cl1—O3^i	1.471 (7)	C3—C4	1.380 (5)
Cl1—O3	1.471 (7)	C3—H3A	0.9300
Cl1—O5	1.521 (7)	C4—C5	1.381 (4)
Cl1—O5^i	1.521 (7)	C4—H4A	0.9300
O3—O4^i	1.05 (2)	C5—N1	1.340 (4)
O4—O3^i	1.05 (2)	C5—C6	1.512 (4)
O4—O5^i	1.45 (2)	C6—O2	1.218 (4)
O5—O4^i	1.45 (2)	C6—O1	1.267 (4)
C1—N1	1.342 (4)	O1—H1	1.2185
C1—C2	1.370 (5)	N1—H1A	0.8600
O4^i—Cl1—O4	99 (2)	Cl1—O4—O5^i	69.2 (8)
O4^i—Cl1—O6	130.3 (11)	O4^i—O5—Cl1	47.8 (5)
O4—Cl1—O6	130.3 (11)	N1—C1—C2	119.6 (3)
O4^i—Cl1—O3^i	119.5 (11)	N1—C1—H1B	120.2
O4—Cl1—O3^i	44.9 (10)	C2—C1—H1B	120.2
O6—Cl1—O3^i	99.6 (4)	C1—C2—C3	118.9 (3)
O4^i—Cl1—O3	44.9 (10)	C1—C2—H2A	120.5
O4—Cl1—O3	119.5 (11)	C3—C2—H2A	120.5
O6—Cl1—O3	99.6 (4)	C4—C3—C2	120.3 (3)
O3^i—Cl1—O3	160.8 (8)	C4—C3—H3A	119.9
O4^i—Cl1—O5	63.0 (10)	C2—C3—H3A	119.9
O4—Cl1—O5	109.2 (10)	C3—C4—C5	119.0 (3)
O6—Cl1—O5	95.5 (3)	C3—C4—H4A	120.5
O3^i—Cl1—O5	83.1 (5)	C5—C4—H4A	120.5
O3—Cl1—O5	95.0 (5)	N1—C5—C4	119.3 (3)
O4^i—Cl1—O5^i	109.2 (10)	N1—C5—C6	115.7 (3)
O4—Cl1—O5^i	63.0 (10)	C4—C5—C6	125.0 (3)
O6—Cl1—O5^i	95.5 (3)	O2—C6—O1	127.0 (3)
O3^i—Cl1—O5^i	95.0 (5)	O2—C6—C5	119.0 (3)
O3—Cl1—O5^i	83.1 (5)	O1—C6—C5	113.9 (3)
O5—Cl1—O5^i	168.9 (7)	C6—O1—H1	118.7
O4^i—O3—Cl1	54.0 (7)	C5—N1—C1	122.9 (3)
O3^i—O4—Cl1	81.1 (10)	C5—N1—H1A	118.5
O3^i—O4—O5^i	123.0 (19)	C1—N1—H1A	118.5
O4—Cl1—O3—O4^i	73 (3)	O6—Cl1—O5—O4^i	132.8 (13)
O6—Cl1—O3—O4^i	−139.4 (17)	O3^i—Cl1—O5—O4^i	−128.2 (13)
O3^i—Cl1—O3—O4^i	40.6 (17)	O3—Cl1—O5—O4^i	32.6 (14)
O5—Cl1—O3—O4^i	−42.9 (18)	O5^i—Cl1—O5—O4^i	−47.2 (13)
O5^i—Cl1—O3—O4^i	126.1 (18)	N1—C1—C2—C3	−0.5 (5)
O4^i—Cl1—O4—O3^i	−122.7 (19)	C1—C2—C3—C4	1.0 (5)
O6—Cl1—O4—O3^i	57.3 (19)	C2—C3—C4—C5	−0.5 (5)
O3—Cl1—O4—O3^i	−165.8 (9)	C3—C4—C5—N1	−0.4 (5)
O5—Cl1—O4—O3^i	−58.1 (17)	C3—C4—C5—C6	−178.1 (3)
O5^i—Cl1—O4—O3^i	130 (2)	N1—C5—C6—O2	5.4 (4)
O4^i—Cl1—O4—O5^i	106.8 (12)	C4—C5—C6—O2	−176.8 (3)
O6—Cl1—O4—O5^i	−73.2 (12)	N1—C5—C6—O1	−173.1 (2)
O3^i—Cl1—O4—O5^i	−130 (2)	C4—C5—C6—O1	4.7 (4)
O3—Cl1—O4—O5^i	63.8 (13)	C4—C5—N1—C1	0.9 (4)
O5—Cl1—O4—O5^i	171.4 (6)	C6—C5—N1—C1	178.9 (3)
O4—Cl1—O5—O4^i	−91 (2)	C2—C1—N1—C5	−0.4 (5)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1^ii	1.22	1.22	2.427 (5)	170
N1—H1A···O2^iii	0.86	1.92	2.727 (4)	155

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

(223K) 2-Carboxypyridinium perchlorate–pyridinium-2-carboxylate (1/1)

Crystal data

C6H6NO2^+·ClO4^−·C6H5NO2	F(000) = 1424
Mr = 346.68	Dx = 1.614 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9700 reflections
a = 20.904 (4) Å	θ = 3.1–27.4°
b = 11.953 (2) Å	µ = 0.32 mm^−1
c = 12.018 (2) Å	T = 223 K
β = 108.18 (3)°	Block, colourless
V = 2852.8 (10) Å^3	0.43 × 0.30 × 0.25 mm
Z = 8

Data collection

Rigaku RAPID diffractometer	3245 independent reflections
Radiation source: fine-focus sealed tube	2854 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.4°, θmin = 3.5°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2000)	h = −26→27
Tmin = 0.652, Tmax = 1.000	k = −12→15
13514 measured reflections	l = −15→15

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.165	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1057P)^2 + 2.190P] where P = (Fo^2 + 2Fc^2)/3
3245 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

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.

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	Occ. (<1)
Cl1	0.5000	0.44877 (5)	0.7500	0.0351 (2)
O4	0.70447 (7)	0.74680 (14)	0.33260 (13)	0.0420 (4)
H4B	0.7313	0.7326	0.2962	0.063*	0.50
N2	0.65780 (8)	0.60176 (14)	0.55031 (14)	0.0357 (4)
H2A	0.6856	0.5463	0.5565	0.043*
O3	0.73367 (10)	0.57781 (16)	0.40846 (16)	0.0589 (5)
C12	0.70224 (10)	0.66473 (18)	0.39856 (16)	0.0359 (4)
C10	0.61344 (10)	0.77205 (18)	0.46109 (17)	0.0375 (4)
H10A	0.6118	0.8292	0.4065	0.045*
C9	0.57293 (10)	0.77693 (19)	0.53425 (19)	0.0420 (5)
H9A	0.5441	0.8383	0.5299	0.050*
C11	0.65560 (9)	0.68213 (17)	0.47070 (15)	0.0325 (4)
C8	0.57523 (10)	0.6918 (2)	0.61269 (18)	0.0411 (5)
H8A	0.5472	0.6938	0.6605	0.049*
C7	0.61898 (10)	0.60360 (18)	0.62039 (18)	0.0394 (4)
H7A	0.6215	0.5454	0.6742	0.047*
Cl2	0.5000	0.96787 (7)	0.7500	0.0520 (2)
O1	0.77749 (7)	0.73989 (13)	0.20873 (12)	0.0400 (3)
H1C	0.7499	0.7277	0.2442	0.060*	0.50
O2	0.74865 (9)	0.56814 (14)	0.13636 (14)	0.0485 (4)
N1	0.82078 (8)	0.59328 (14)	−0.01206 (15)	0.0368 (4)
H1A	0.7960	0.5348	−0.0124	0.044*
C5	0.82236 (9)	0.67533 (16)	0.06529 (15)	0.0317 (4)
C6	0.77878 (9)	0.65715 (16)	0.14345 (15)	0.0333 (4)
C2	0.89779 (10)	0.77548 (19)	−0.01224 (18)	0.0395 (5)
H2B	0.9244	0.8389	−0.0123	0.047*
C4	0.85552 (11)	0.59724 (19)	−0.08847 (19)	0.0421 (5)
H4A	0.8528	0.5379	−0.1411	0.051*
C3	0.89544 (10)	0.68894 (19)	−0.08961 (18)	0.0407 (5)
H3A	0.9206	0.6924	−0.1421	0.049*
C1	0.86075 (9)	0.76884 (18)	0.06592 (16)	0.0362 (4)
H1B	0.8620	0.8277	0.1185	0.043*
O10	0.53517 (13)	0.3813 (2)	0.6925 (2)	0.0849 (7)
O9	0.45293 (12)	0.5178 (2)	0.6689 (2)	0.0809 (7)
O5	0.5000	0.8505 (3)	0.7500	0.0840 (10)
O7	0.4720 (5)	1.0047 (10)	0.6389 (9)	0.173 (6)	0.50
O6	0.5756 (2)	0.9917 (4)	0.7706 (5)	0.0813 (14)	0.50
O8	0.4912 (7)	1.0098 (9)	0.8470 (12)	0.197 (7)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0387 (4)	0.0338 (4)	0.0379 (4)	0.000	0.0192 (3)	0.000
O4	0.0480 (8)	0.0461 (8)	0.0408 (8)	0.0041 (6)	0.0266 (6)	0.0053 (6)
N2	0.0423 (8)	0.0358 (9)	0.0343 (8)	0.0005 (6)	0.0198 (7)	−0.0017 (6)
O3	0.0820 (12)	0.0582 (10)	0.0545 (10)	0.0303 (9)	0.0474 (9)	0.0184 (8)
C12	0.0380 (9)	0.0433 (11)	0.0296 (8)	0.0021 (8)	0.0153 (7)	−0.0003 (7)
C10	0.0353 (9)	0.0446 (11)	0.0343 (9)	0.0028 (7)	0.0131 (7)	0.0021 (8)
C9	0.0339 (10)	0.0532 (12)	0.0404 (10)	0.0068 (8)	0.0140 (8)	−0.0027 (9)
C11	0.0325 (9)	0.0389 (10)	0.0286 (8)	−0.0017 (7)	0.0131 (7)	−0.0026 (7)
C8	0.0350 (9)	0.0579 (13)	0.0356 (10)	−0.0019 (8)	0.0185 (8)	−0.0056 (9)
C7	0.0451 (10)	0.0438 (11)	0.0358 (9)	−0.0058 (8)	0.0218 (8)	−0.0014 (8)
Cl2	0.0690 (5)	0.0377 (4)	0.0522 (5)	0.000	0.0230 (4)	0.000
O1	0.0441 (8)	0.0462 (8)	0.0376 (7)	−0.0087 (6)	0.0242 (6)	−0.0061 (6)
O2	0.0648 (10)	0.0456 (9)	0.0469 (8)	−0.0170 (7)	0.0345 (7)	−0.0065 (7)
N1	0.0417 (9)	0.0361 (9)	0.0391 (9)	−0.0011 (6)	0.0220 (7)	0.0015 (6)
C5	0.0303 (8)	0.0394 (10)	0.0271 (8)	0.0004 (7)	0.0116 (7)	0.0031 (7)
C6	0.0333 (9)	0.0401 (10)	0.0291 (8)	−0.0025 (7)	0.0136 (7)	0.0034 (7)
C2	0.0337 (9)	0.0518 (12)	0.0350 (9)	−0.0072 (8)	0.0135 (8)	0.0053 (8)
C4	0.0493 (11)	0.0432 (11)	0.0418 (10)	0.0043 (8)	0.0258 (9)	−0.0003 (8)
C3	0.0371 (10)	0.0549 (12)	0.0363 (10)	0.0024 (8)	0.0205 (8)	0.0062 (8)
C1	0.0344 (9)	0.0461 (11)	0.0293 (9)	−0.0051 (8)	0.0117 (7)	0.0001 (7)
O10	0.1020 (17)	0.0758 (15)	0.1047 (18)	0.0087 (12)	0.0725 (15)	−0.0230 (13)
O9	0.0765 (14)	0.0827 (16)	0.0699 (14)	0.0166 (11)	0.0033 (11)	0.0222 (11)
O5	0.109 (3)	0.0494 (17)	0.111 (3)	0.000	0.059 (2)	0.000
O7	0.132 (7)	0.162 (8)	0.148 (8)	−0.027 (6)	−0.070 (7)	0.097 (7)
O6	0.058 (2)	0.094 (3)	0.093 (3)	−0.022 (2)	0.025 (2)	0.021 (3)
O8	0.313 (15)	0.127 (8)	0.267 (14)	−0.086 (10)	0.258 (14)	−0.114 (9)

Geometric parameters (Å, º)

Cl1—O10^i	1.4087 (19)	Cl2—O6	1.548 (4)
Cl1—O10	1.4087 (19)	Cl2—O6^i	1.548 (4)
Cl1—O9	1.414 (2)	O1—C6	1.268 (2)
Cl1—O9^i	1.414 (2)	O1—H1C	0.8300
O4—C12	1.271 (3)	O2—C6	1.226 (2)
O4—H4B	0.8300	N1—C4	1.338 (3)
N2—C7	1.340 (3)	N1—C5	1.345 (3)
N2—C11	1.346 (3)	N1—H1A	0.8700
N2—H2A	0.8700	C5—C1	1.375 (3)
O3—C12	1.215 (3)	C5—C6	1.514 (2)
C12—C11	1.508 (3)	C2—C3	1.381 (3)
C10—C11	1.372 (3)	C2—C1	1.394 (3)
C10—C9	1.399 (3)	C2—H2B	0.9400
C10—H10A	0.9400	C4—C3	1.380 (3)
C9—C8	1.378 (3)	C4—H4A	0.9400
C9—H9A	0.9400	C3—H3A	0.9400
C8—C7	1.380 (3)	C1—H1B	0.9400
C8—H8A	0.9400	O7—O8^i	0.735 (15)
C7—H7A	0.9400	O7—O6^i	1.696 (13)
Cl2—O8	1.333 (7)	O6—O8^i	1.663 (15)
Cl2—O8^i	1.333 (7)	O6—O7^i	1.696 (13)
Cl2—O7^i	1.353 (7)	O8—O7^i	0.735 (15)
Cl2—O7	1.353 (7)	O8—O6^i	1.663 (15)
Cl2—O5	1.403 (3)
O10^i—Cl1—O10	110.2 (2)	O7^i—Cl2—O6	71.2 (5)
O10^i—Cl1—O9	108.32 (15)	O7—Cl2—O6	101.7 (5)
O10—Cl1—O9	110.68 (16)	O5—Cl2—O6	100.6 (2)
O10^i—Cl1—O9^i	110.68 (16)	O8—Cl2—O6^i	70.0 (6)
O10—Cl1—O9^i	108.32 (15)	O8^i—Cl2—O6^i	101.7 (6)
O9—Cl1—O9^i	108.6 (2)	O7^i—Cl2—O6^i	101.7 (5)
C12—O4—H4B	109.5	O7—Cl2—O6^i	71.2 (5)
C7—N2—C11	122.81 (18)	O5—Cl2—O6^i	100.6 (2)
C7—N2—H2A	118.6	O6—Cl2—O6^i	158.8 (4)
C11—N2—H2A	118.6	C6—O1—H1C	109.5
O3—C12—O4	126.65 (19)	C4—N1—C5	123.18 (18)
O3—C12—C11	119.25 (18)	C4—N1—H1A	118.4
O4—C12—C11	114.10 (18)	C5—N1—H1A	118.4
C11—C10—C9	118.59 (19)	N1—C5—C1	119.03 (17)
C11—C10—H10A	120.7	N1—C5—C6	115.74 (17)
C9—C10—H10A	120.7	C1—C5—C6	125.20 (18)
C8—C9—C10	120.0 (2)	O2—C6—O1	127.62 (18)
C8—C9—H9A	120.0	O2—C6—C5	118.49 (17)
C10—C9—H9A	120.0	O1—C6—C5	113.88 (16)
N2—C11—C10	119.83 (18)	C3—C2—C1	120.03 (19)
N2—C11—C12	115.17 (17)	C3—C2—H2B	120.0
C10—C11—C12	124.99 (18)	C1—C2—H2B	120.0
C9—C8—C7	119.41 (19)	N1—C4—C3	119.6 (2)
C9—C8—H8A	120.3	N1—C4—H4A	120.2
C7—C8—H8A	120.3	C3—C4—H4A	120.2
N2—C7—C8	119.29 (19)	C4—C3—C2	118.85 (19)
N2—C7—H7A	120.4	C4—C3—H3A	120.6
C8—C7—H7A	120.4	C2—C3—H3A	120.6
O8—Cl2—O8^i	135.8 (11)	C5—C1—C2	119.26 (19)
O8—Cl2—O7^i	31.7 (7)	C5—C1—H1B	120.4
O8^i—Cl2—O7^i	127.3 (7)	C2—C1—H1B	120.4
O8—Cl2—O7	127.3 (7)	O8^i—O7—Cl2	72.6 (10)
O8^i—Cl2—O7	31.7 (7)	O8^i—O7—O6^i	129.8 (16)
O7^i—Cl2—O7	142.0 (12)	Cl2—O7—O6^i	59.8 (5)
O8—Cl2—O5	112.1 (5)	Cl2—O6—O8^i	48.9 (3)
O8^i—Cl2—O5	112.1 (5)	Cl2—O6—O7^i	49.0 (2)
O7^i—Cl2—O5	109.0 (6)	O8^i—O6—O7^i	91.5 (4)
O7—Cl2—O5	109.0 (6)	O7^i—O8—Cl2	75.7 (10)
O8—Cl2—O6	101.7 (6)	O7^i—O8—O6^i	136.5 (14)
O8^i—Cl2—O6	70.0 (6)	Cl2—O8—O6^i	61.1 (5)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^ii	0.87	1.93	2.752 (2)	156
N1—H1A···O3^iii	0.87	1.91	2.706 (2)	152
O4—H4B···O1	0.83	1.64	2.444 (2)	164
O1—H1C···O4	0.83	1.65	2.444 (2)	160

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