Structures and phase transitions in a new ferroelectric – pyridinium chlorochromate – studied by X-ray diffraction, DSC and dielectric methods

Pyridinium chlorochromate, [C₅H₅NH]⁺[ClCrO₃]⁻ (hereafter referred to as PyClCrO₃), was studied by X-ray diffraction, differential scanning calorimetry (DSC) and dielectric methods. Studies reveal three reversible phase transitions at 346, 316 and 170 K with the following phase sequence: (I) → R3m (II) → Cm (III) → Cc (IV), c′ = 2c. PyClCrO₃ is the first pyridinium salt in which all four phases have been successfully characterized by a single-crystal X-ray diffraction method. Structural results together with dielectric and calorimetric studies allow the classification of the two intermediate phases (II) and (III) as ferroelectric with the Curie point at 346 K, and the lowest phase (IV) as most probably ferroelectric. The ferroelectric hysteresis loop was observed only in phase (III). The high ionic conductivity hindered its observation in phase (II).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction,2009) for r-3m, r3m; CrysAlis PRO, Oxford Diffraction Ltd., 2010 for exp_181, 120_enan. Cell refinement: CrysAlis CCD (Oxford Diffraction,2009) for r-3m, r3m; CrysAlis PRO, Oxford Diffraction Ltd., 2010 for exp_181, 120_enan. Data reduction: CrysAlis RED (Oxford Diffraction,2009) for r-3m, r3m; CrysAlis PRO, Oxford Diffraction Ltd., 2010 for exp_181, 120_enan. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008).

Figures

(r-3m) pyridinium chlorochromate

Crystal data

[C5H5NH]^+[ClCrO3]^−	Dx = 1.626 Mg m^−3
Mr = 215.56	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3m	Cell parameters from 175 reflections
a = 9.021 (2) Å	θ = 3.4–32.8°
c = 9.369 (4) Å	µ = 1.56 mm^−1
V = 660.2 (4) Å^3	T = 355 K
Z = 3	Prism, orange
F(000) = 324	0.5 × 0.3 × 0.3 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	44 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.055
Graphite monochromator	θmax = 32.8°, θmin = 3.4°
Detector resolution: 10.3200 pixels mm^-1	h = −13→13
ω scan	k = −13→13
1606 measured reflections	l = −13→8
305 independent reflections

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.268	H-atom parameters constrained
S = 0.75	w = 1/[σ^2(Fo^2) + (0.121P)^2] where P = (Fo^2 + 2Fc^2)/3
305 reflections	(Δ/σ)max = 0.897
18 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.10 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)
Cr1	0.0000	0.0000	0.046 (2)	0.247 (15)	0.50
O	−0.0908 (11)	−0.182 (2)	0.103 (2)	0.291 (7)	0.50
Cl	0.0000	0.0000	0.157 (4)	0.58 (6)	0.50
C	0.0000	0.1477 (7)	0.5000	0.213 (4)	0.83
N	0.0000	0.1477 (7)	0.5000	0.213 (4)	0.17
H0A	0.0000	0.2508	0.5000	0.255*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.184 (3)	0.184 (3)	0.37 (5)	0.0922 (16)	0.000	0.000
O	0.334 (15)	0.201 (15)	0.295 (19)	0.101 (8)	0.011 (5)	0.022 (10)
Cl	0.75 (8)	0.75 (8)	0.25 (2)	0.38 (4)	0.000	0.000
C	0.259 (8)	0.205 (5)	0.193 (6)	0.129 (4)	−0.002 (4)	−0.0012 (19)
N	0.259 (8)	0.205 (5)	0.193 (6)	0.129 (4)	−0.002 (4)	−0.0012 (19)

Geometric parameters (Å, º)

Cr1—Cr1^i	0.87 (4)	O—Cl	1.511 (18)
Cr1—Cl	1.04 (3)	O—Cr1^i	1.99 (2)
Cr1—O^ii	1.52 (2)	Cl—O^ii	1.511 (18)
Cr1—O	1.52 (2)	Cl—O^iii	1.511 (18)
Cr1—O^iii	1.52 (2)	Cl—Cr1^i	1.91 (5)
Cr1—Cl^i	1.91 (5)	C—N^vi	1.332 (6)
Cr1—O^iv	1.99 (2)	C—C^vi	1.332 (6)
Cr1—O^v	1.99 (2)	C—C^vii	1.332 (6)
Cr1—O^i	1.99 (2)	C—N^vii	1.332 (6)
Cr1^i—Cr1—Cl	180.000 (1)	Cr1^i—Cr1—O^i	45.5 (5)
Cr1^i—Cr1—O^ii	110.5 (11)	Cl—Cr1—O^i	134.5 (5)
Cl—Cr1—O^ii	69.5 (11)	O^ii—Cr1—O^i	84.9 (10)
Cr1^i—Cr1—O	110.5 (11)	O—Cr1—O^i	156.0 (12)
Cl—Cr1—O	69.5 (11)	O^iii—Cr1—O^i	84.9 (10)
O^ii—Cr1—O	108.5 (12)	Cl^i—Cr1—O^i	45.5 (5)
Cr1^i—Cr1—O^iii	110.5 (11)	O^iv—Cr1—O^i	76.3 (8)
Cl—Cr1—O^iii	69.5 (11)	O^v—Cr1—O^i	76.3 (8)
O^ii—Cr1—O^iii	108.5 (12)	Cl—O—Cr1	40.2 (14)
O—Cr1—O^iii	108.5 (12)	Cl—O—Cr1^i	64 (2)
Cr1^i—Cr1—Cl^i	0.000 (1)	Cr1—O—Cr1^i	24.0 (12)
Cl—Cr1—Cl^i	180.000 (1)	Cr1—Cl—O	70.3 (19)
O^ii—Cr1—Cl^i	110.5 (11)	Cr1—Cl—O^ii	70.3 (19)
O—Cr1—Cl^i	110.5 (11)	O—Cl—O^ii	109.2 (19)
O^iii—Cr1—Cl^i	110.5 (11)	Cr1—Cl—O^iii	70.3 (19)
Cr1^i—Cr1—O^iv	45.5 (5)	O—Cl—O^iii	109.2 (19)
Cl—Cr1—O^iv	134.5 (5)	O^ii—Cl—O^iii	109.2 (19)
O^ii—Cr1—O^iv	84.9 (10)	Cr1—Cl—Cr1^i	0.000 (1)
O—Cr1—O^iv	84.9 (10)	O—Cl—Cr1^i	70.3 (19)
O^iii—Cr1—O^iv	156.0 (12)	O^ii—Cl—Cr1^i	70.3 (19)
Cl^i—Cr1—O^iv	45.5 (5)	O^iii—Cl—Cr1^i	70.3 (19)
Cr1^i—Cr1—O^v	45.5 (5)	N^vi—C—C^vi	0.0 (4)
Cl—Cr1—O^v	134.5 (5)	N^vi—C—C^vii	120.000 (2)
O^ii—Cr1—O^v	156.0 (12)	C^vi—C—C^vii	120.000 (2)
O—Cr1—O^v	84.9 (10)	N^vi—C—N^vii	120.000 (2)
O^iii—Cr1—O^v	84.9 (10)	C^vi—C—N^vii	120.000 (2)
Cl^i—Cr1—O^v	45.5 (5)	C^vii—C—N^vii	0.0 (4)
O^iv—Cr1—O^v	76.3 (8)

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

(r3m) pyridinium chlorochromate

Crystal data

[C5H5NH]^+[ClCrO3]^−	Dx = 1.691 Mg m^−3
Mr = 215.56	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3m	Cell parameters from 835 reflections
a = 8.8349 (12) Å	θ = 3.4–28.9°
c = 9.3960 (16) Å	µ = 1.62 mm^−1
V = 635.15 (16) Å^3	T = 320 K
Z = 3	Prism, orange
F(000) = 324	0.70 × 0.25 × 0.15 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	401 independent reflections
Radiation source: Enhance (Mo) X-ray Source	194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 10.3200 pixels mm^-1	θmax = 28.9°, θmin = 3.4°
ω scan	h = −8→12
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.64 (release 22-03-2010 CrysAlis171 .NET) (compiled Mar 22 2010,13:57:49) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −11→10
Tmin = 0.667, Tmax = 1.000	l = −11→11
1845 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0992P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.016
401 reflections	Δρmax = 0.91 e Å^−3
22 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (7)

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)
Cr1	0.0000	0.0000	0.2007	0.1002 (7)
Cl	0.0000	0.0000	−0.0245 (4)	0.1506 (16)
O1	−0.0980 (4)	0.0980 (4)	0.2533 (6)	0.152 (2)
C	0.0003 (7)	−0.1504 (6)	0.6195 (5)	0.1068 (14)	0.83
N	0.0003 (7)	−0.1504 (6)	0.6195 (5)	0.1068 (14)	0.17
H0A	0.0003	−0.2589	0.6195	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.0924 (8)	0.0924 (8)	0.1158 (14)	0.0462 (4)	0.000	0.000
Cl	0.176 (2)	0.176 (2)	0.101 (2)	0.0878 (12)	0.000	0.000
O1	0.162 (4)	0.162 (4)	0.167 (6)	0.108 (4)	0.0233 (19)	−0.0233 (19)
C	0.142 (3)	0.098 (3)	0.096 (2)	0.071 (2)	−0.007 (2)	−0.008 (2)
N	0.142 (3)	0.098 (3)	0.096 (2)	0.071 (2)	−0.007 (2)	−0.008 (2)

Geometric parameters (Å, º)

Cr1—O1^i	1.578 (5)	C—N^iii	1.334 (10)
Cr1—O1^ii	1.578 (5)	C—C^iii	1.334 (10)
Cr1—O1	1.578 (5)	C—C^iv	1.326 (11)
Cr1—Cl	2.116 (4)	C—N^iv	1.326 (11)
O1^i—Cr1—O1^ii	110.7 (2)	N^iii—C—C^iii	0.000 (1)
O1^i—Cr1—O1	110.7 (2)	N^iii—C—C^iv	120.000 (3)
O1^ii—Cr1—O1	110.7 (2)	C^iii—C—C^iv	120.000 (3)
O1^i—Cr1—Cl	108.2 (2)	N^iii—C—N^iv	120.000 (3)
O1^ii—Cr1—Cl	108.2 (2)	C^iii—C—N^iv	120.000 (3)
O1—Cr1—Cl	108.2 (2)	C^iv—C—N^iv	0.0 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C—H0A···O1^v	0.96	2.40	3.277 (5)	153

Symmetry code: (v) −x+y−1/3, −x−2/3, z+1/3.

(exp_181) pyridinium chlorochromate

Crystal data

[C5H5NH]^+[ClCrO3]^−	F(000) = 216
Mr = 215.56	Dx = 1.701 Mg m^−3
Monoclinic, Cm	Mo Kα radiation, λ = 0.71073 Å
a = 7.7193 (7) Å	Cell parameters from 993 reflections
b = 8.6842 (7) Å	θ = 3.2–29.1°
c = 6.3139 (5) Å	µ = 1.63 mm^−1
β = 96.250 (9)°	T = 298 K
V = 420.74 (6) Å^3	Prism, orange
Z = 2	0.70 × 0.25 × 0.15 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	884 independent reflections
Radiation source: Enhance (Mo) X-ray Source	571 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 10.3200 pixels mm^-1	θmax = 29.0°, θmin = 3.3°
ω scan	h = −10→10
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.64 (release 22-03-2010 CrysAlis171 .NET) (compiled Mar 22 2010,13:57:49) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −11→10
Tmin = 0.819, Tmax = 1.000	l = −8→8
2023 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0626P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.82	(Δ/σ)max = 0.071
884 reflections	Δρmax = 0.58 e Å^−3
55 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (4)

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)
Cr	0.67097 (4)	0.0000	0.23471 (4)	0.0721 (3)
Cl	0.8777 (4)	0.0000	0.4897 (4)	0.1267 (8)
C1	1.2529 (7)	0.1547 (4)	0.8200 (8)	0.0819 (13)
H1A	1.2548	0.2617	0.8216	0.098*
C2	1.3249 (6)	0.0769 (5)	0.6695 (8)	0.0845 (13)
H2A	1.3750	0.1305	0.5641	0.101*
O1	0.5586 (5)	0.1521 (4)	0.2549 (7)	0.1198 (13)
C3	1.1794 (6)	0.0796 (6)	0.9676 (7)	0.0939 (13)	0.50
N	1.1794 (6)	0.0796 (6)	0.9676 (7)	0.0939 (13)	0.50
H3A	1.1274	0.1331	1.0715	0.113*
O2	0.7535 (9)	0.0000	0.0184 (8)	0.1201 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr	0.0762 (6)	0.0721 (5)	0.0701 (6)	0.000	0.0179 (4)	0.000
Cl	0.1425 (19)	0.1009 (13)	0.1220 (16)	0.000	−0.0522 (14)	0.000
C1	0.081 (3)	0.059 (2)	0.104 (4)	−0.009 (2)	0.000 (3)	−0.005 (2)
C2	0.082 (3)	0.087 (2)	0.086 (3)	−0.006 (2)	0.018 (3)	0.016 (2)
O1	0.109 (3)	0.115 (3)	0.137 (3)	0.051 (2)	0.018 (2)	0.003 (2)
C3	0.078 (3)	0.116 (3)	0.086 (3)	0.008 (2)	0.001 (2)	−0.033 (2)
N	0.078 (3)	0.116 (3)	0.086 (3)	0.008 (2)	0.001 (2)	−0.033 (2)
O2	0.159 (5)	0.126 (4)	0.084 (3)	0.000	0.050 (4)	0.000

Geometric parameters (Å, º)

Cr—O2	1.568 (5)	C1—C2	1.335 (6)
Cr—O1^i	1.593 (3)	C2—C2^i	1.336 (10)
Cr—O1	1.593 (3)	C3—N^i	1.383 (11)
Cr—Cl	2.140 (2)	C3—C3^i	1.383 (11)
C1—C3	1.316 (6)
O2—Cr—O1^i	110.23 (19)	C3—C1—C2	119.9 (4)
O2—Cr—O1	110.23 (19)	C2^i—C2—C1	120.4 (3)
O1^i—Cr—O1	112.1 (3)	C1—C3—N^i	119.7 (3)
O2—Cr—Cl	108.3 (3)	C1—C3—C3^i	119.7 (3)
O1^i—Cr—Cl	107.92 (17)	N^i—C3—C3^i	0.0 (6)
O1—Cr—Cl	107.92 (17)

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H3A···O1^ii	0.93	2.29	3.155 (6)	155
C1—H1A···O2^iii	0.93	2.41	3.250 (4)	150
C2—H2A···O1^iv	0.93	2.54	3.400 (6)	154

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

(120_enan) pyridinium chlorochromate

Crystal data

[C5H5NH]^+[ClCrO3]^−	F(000) = 432
Mr = 215.56	Dx = 1.774 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 7.3539 (3) Å	Cell parameters from 2913 reflections
b = 8.4985 (3) Å	θ = 2.4–28.2°
c = 12.9706 (6) Å	µ = 1.70 mm^−1
β = 95.481 (3)°	T = 120 K
V = 806.91 (6) Å^3	Prism, orange
Z = 4	0.2 × 0.1 × 0.08 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	1845 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1718 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 10.3200 pixels mm^-1	θmax = 28.2°, θmin = 3.2°
ω scan	h = −9→9
Absorption correction: multi-scan ?	k = −11→11
Tmin = 0.862, Tmax = 1.000	l = −17→16
5194 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	All H-atom parameters refined
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0356P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.025
1845 reflections	Δρmax = 0.37 e Å^−3
125 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.831 (17)

Special details

Experimental. CrysAlis PRO, Agilent Technologies, Version 1.171.35.15 (release 03–08-2011 CrysAlis171. NET) (compiled Aug 3 2011,13:03:54) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cr	0.90619 (3)	−0.01049 (3)	−0.03123 (3)	0.02014 (10)
Cl	1.09727 (11)	−0.00537 (5)	0.10759 (6)	0.0426 (2)
O1	0.7719 (2)	0.1368 (2)	−0.02724 (14)	0.0352 (4)
O2	0.7943 (2)	−0.1749 (2)	−0.03186 (13)	0.0325 (4)
O3	1.0213 (3)	0.00009 (14)	−0.12942 (17)	0.0354 (4)
N	1.4193 (2)	−0.0944 (2)	0.33317 (16)	0.0283 (4)
C1	1.4162 (3)	0.0630 (3)	0.3408 (2)	0.0307 (5)
C2	1.4879 (3)	0.1526 (3)	0.2671 (2)	0.0329 (6)
C3	1.5624 (3)	0.0789 (3)	0.1861 (2)	0.0310 (5)
C4	1.5657 (3)	−0.0820 (3)	0.1807 (2)	0.0293 (5)
C5	1.4930 (3)	−0.1681 (3)	0.25574 (19)	0.0289 (5)
H	1.372 (4)	−0.155 (3)	0.388 (2)	0.065 (10)*
H1	1.363 (4)	0.099 (3)	0.395 (2)	0.036 (7)*
H2	1.468 (4)	0.265 (3)	0.278 (2)	0.050 (8)*
H3	1.587 (5)	0.135 (5)	0.133 (3)	0.066 (11)*
H4	1.591 (5)	−0.130 (5)	0.130 (3)	0.063 (11)*
H5	1.471 (4)	−0.283 (3)	0.263 (2)	0.052 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr	0.02070 (16)	0.02180 (17)	0.01824 (16)	0.0001 (4)	0.00359 (12)	−0.0007 (4)
Cl	0.0538 (4)	0.0269 (4)	0.0415 (4)	0.0014 (3)	−0.0246 (4)	−0.0015 (3)
O1	0.0327 (10)	0.0347 (9)	0.0381 (10)	0.0122 (9)	0.0027 (8)	−0.0010 (10)
O2	0.0329 (10)	0.0342 (9)	0.0314 (9)	−0.0120 (8)	0.0080 (8)	−0.0044 (9)
O3	0.0462 (11)	0.0317 (10)	0.0314 (10)	−0.0024 (6)	0.0202 (9)	0.0016 (5)
N	0.0218 (8)	0.0361 (11)	0.0268 (10)	0.0003 (9)	0.0020 (8)	0.0041 (10)
C1	0.0204 (10)	0.0381 (13)	0.0327 (15)	0.0026 (11)	−0.0020 (10)	−0.0143 (13)
C2	0.0265 (11)	0.0228 (10)	0.0478 (17)	−0.0007 (9)	−0.0039 (12)	−0.0049 (11)
C3	0.0277 (11)	0.0271 (12)	0.0380 (14)	−0.0031 (9)	0.0022 (10)	0.0054 (10)
C4	0.0286 (11)	0.0278 (12)	0.0327 (13)	0.0018 (9)	0.0087 (10)	−0.0020 (10)
C5	0.0256 (10)	0.0230 (11)	0.0380 (13)	0.0048 (9)	0.0025 (10)	0.0036 (9)

Geometric parameters (Å, º)

Cr—O3	1.598 (2)	N—C1	1.342 (4)
Cr—O1	1.5984 (16)	C1—C2	1.367 (4)
Cr—O2	1.6209 (16)	C2—C3	1.380 (4)
Cr—Cl	2.1761 (7)	C3—C4	1.369 (4)
N—C5	1.341 (3)	C4—C5	1.367 (3)
O3—Cr—O1	110.96 (9)	C5—N—C1	122.11 (19)
O3—Cr—O2	110.60 (9)	N—C1—C2	119.6 (2)
O1—Cr—O2	111.11 (12)	C1—C2—C3	119.2 (2)
O3—Cr—Cl	108.00 (9)	C4—C3—C2	120.1 (2)
O1—Cr—Cl	108.04 (7)	C5—C4—C3	119.2 (2)
O2—Cr—Cl	107.99 (7)	N—C5—C4	119.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H···O2^i	0.97 (3)	1.90 (3)	2.839 (3)	162 (3)
C1—H1···O3^ii	0.90 (3)	2.64 (3)	3.014 (3)	106 (2)
C1—H1···O1^iii	0.90 (3)	2.57 (3)	3.303 (3)	139 (2)
C2—H2···O3^iii	0.98 (3)	2.34 (3)	3.242 (3)	152 (2)
C3—H3···O1^iv	0.87 (4)	2.59 (4)	3.330 (3)	143 (3)
C4—H4···O2^iv	0.81 (4)	2.71 (4)	3.455 (3)	152 (3)
C5—H5···O3^i	1.00 (3)	2.32 (3)	3.188 (3)	145 (2)

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