Preliminary observations of the interplay of radiation damage with spin crossover

Intense synchrotron radiation makes time-resolved structural experiments with increasingly finer time sampling possible. On the other hand, radiation heating, radiation-induced volume change and structural disorder become more frequent. Temperature, volume change and disorder are known to be coupled with equilibrium in molecular spin complexes, balancing between two or more spin state configurations. Combining single-crystal diffraction and synchrotron radiation it is illustrated how the radiation damage and associated effects can affect the spin crossover process and may serve as yet another tool to further manipulate the spin crossover properties.

Computing details

For all structures, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014).

(1st_257K)

Crystal data

C8.25H25.50Br1.50Fe0.75N4.50O0.75	Dx = 1.612 Mg m^−3
Mr = 361.58	Synchrotron radiation, λ = 0.78405 Å
Trigonal, R3m:H	Cell parameters from 1661 reflections
a = 7.3806 (2) Å	θ = 2.1–32.1°
c = 31.5783 (16) Å	µ = 6.11 mm^−1
V = 1489.71 (11) Å^3	T = 257 K
Z = 4	Hexagonal flat prism, colourless
F(000) = 738	0.24 × 0.22 × 0.16 mm

Data collection

Abstract diffractometer	393 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.007
ω scans	θmax = 29.3°, θmin = 2.1°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→9
Tmin = 0.873, Tmax = 1.000	k = −9→9
2292 measured reflections	l = −37→37
397 independent reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0806P)^2 + 2.6123P] where P = (Fo^2 + 2Fc^2)/3
S = 1.23	(Δ/σ)max = 0.009
397 reflections	Δρmax = 0.60 e Å^−3
33 parameters	Δρmin = −0.66 e Å^−3

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)
C1	0.0000	0.0000	0.15095 (16)	0.0580 (16)
H1A	−0.1487	−0.0744	0.1613	0.087*
C2	0.0000	0.0000	0.10217 (14)	0.0379 (11)
C3	−0.1146 (3)	0.1146 (3)	0.08746 (9)	0.0517 (7)
H3A	−0.2479	0.0604	0.1037	0.062*	0.5
H3B	−0.0253	0.2696	0.0949	0.062*	0.5
C4	0.1671 (7)	0.5835 (3)	0.13760 (16)	0.079 (7)*	0.1667
H4A	0.2217	0.5910	0.1090	0.118*	0.0833
H4B	0.0947	0.6643	0.1387	0.118*	0.0833
H4C	0.0688	0.4373	0.1448	0.118*	0.0833
O1	0.3333	0.6667	0.1667	0.164 (6)
H1	0.3665	0.5729	0.1728	0.246*	0.0833
Fe1	0.0000	0.0000	0.0000	0.02883 (19)
Br1	0.3333	0.6667	0.03711 (2)	0.04913 (15)
N1	−0.1589 (4)	0.1059 (4)	0.04252 (7)	0.0374 (6)	0.5
H1B	−0.1336	0.2373	0.0339	0.045*	0.5
H1C	−0.3022	0.0129	0.0397	0.045*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.073 (2)	0.073 (2)	0.028 (2)	0.0366 (12)	0.000	0.000
C2	0.0450 (15)	0.0450 (15)	0.0236 (18)	0.0225 (8)	0.000	0.000
C3	0.0711 (7)	0.0711 (7)	0.0323 (11)	0.0500 (9)	0.0033 (6)	−0.0033 (6)
O1	0.183 (9)	0.183 (9)	0.126 (9)	0.091 (4)	0.000	0.000
Fe1	0.0327 (2)	0.0327 (2)	0.0210 (3)	0.01637 (12)	0.000	0.000
Br1	0.04825 (19)	0.04825 (19)	0.0509 (3)	0.02413 (10)	0.000	0.000
N1	0.0399 (11)	0.0402 (11)	0.0351 (11)	0.0224 (7)	0.0029 (10)	0.0032 (9)

Geometric parameters (Å, º)

C1—C2	1.540 (7)	Fe1—N1^ix	2.169 (3)
C2—C3^i	1.536 (3)	Fe1—N1^ii	2.169 (3)
C2—C3^ii	1.536 (3)	Fe1—N1^x	2.169 (3)
C2—C3	1.536 (3)	Fe1—N1^xi	2.169 (3)
C3—N1	1.451 (4)	Fe1—N1^iii	2.169 (3)
C3—N1^iii	1.451 (4)	Fe1—N1^xii	2.169 (3)
C4—O1	1.404 (3)	Fe1—N1^xiii	2.169 (3)
C4—C4^iv	1.841 (8)	Fe1—N1^xiv	2.169 (3)
C4—C4^v	1.841 (8)	Fe1—N1^xv	2.169 (3)
O1—C4^vi	1.404 (3)	Fe1—N1^xvi	2.169 (3)
O1—C4^vii	1.404 (3)	Fe1—N1^i	2.169 (3)
O1—C4^iv	1.404 (3)	Fe1—N1	2.169 (3)
O1—C4^v	1.404 (3)	N1—N1^iii	0.391 (5)
O1—C4^viii	1.405 (3)
C3^i—C2—C3^ii	111.27 (18)	N1^ix—Fe1—N1^xiv	87.76 (13)
C3^i—C2—C3	111.27 (18)	N1^ii—Fe1—N1^xiv	92.24 (13)
C3^ii—C2—C3	111.27 (18)	N1^x—Fe1—N1^xiv	85.72 (10)
C3^i—C2—C1	107.60 (19)	N1^xi—Fe1—N1^xiv	94.28 (10)
C3^ii—C2—C1	107.60 (19)	N1^iii—Fe1—N1^xiv	85.72 (10)
C3—C2—C1	107.61 (19)	N1^xii—Fe1—N1^xiv	94.28 (10)
N1—C3—N1^iii	15.5 (2)	N1^xiii—Fe1—N1^xiv	101.81 (14)
N1—C3—C2	116.5 (3)	N1^ix—Fe1—N1^xv	92.24 (13)
N1^iii—C3—C2	116.5 (3)	N1^ii—Fe1—N1^xv	87.76 (13)
O1—C4—C4^iv	49.06 (18)	N1^x—Fe1—N1^xv	94.28 (10)
O1—C4—C4^v	49.06 (18)	N1^xi—Fe1—N1^xv	85.72 (10)
C4^iv—C4—C4^v	60.001 (1)	N1^iii—Fe1—N1^xv	94.28 (10)
C4—O1—C4^vi	180.0	N1^xii—Fe1—N1^xv	85.72 (10)
C4—O1—C4^vii	98.1 (4)	N1^xiii—Fe1—N1^xv	78.19 (14)
C4^vi—O1—C4^vii	81.9 (4)	N1^xiv—Fe1—N1^xv	180.00 (17)
C4—O1—C4^iv	81.9 (4)	N1^ix—Fe1—N1^xvi	85.72 (10)
C4^vi—O1—C4^iv	98.1 (4)	N1^ii—Fe1—N1^xvi	94.28 (10)
C4^vii—O1—C4^iv	180.0	N1^x—Fe1—N1^xvi	101.81 (14)
C4—O1—C4^v	81.9 (4)	N1^xi—Fe1—N1^xvi	78.19 (14)
C4^vi—O1—C4^v	98.1 (4)	N1^iii—Fe1—N1^xvi	87.76 (13)
C4^vii—O1—C4^v	98.1 (4)	N1^xii—Fe1—N1^xvi	92.24 (13)
C4^iv—O1—C4^v	81.9 (4)	N1^xiii—Fe1—N1^xvi	85.72 (10)
C4—O1—C4^viii	98.1 (4)	N1^xiv—Fe1—N1^xvi	169.65 (13)
C4^vi—O1—C4^viii	81.9 (4)	N1^xv—Fe1—N1^xvi	10.35 (13)
C4^vii—O1—C4^viii	81.9 (4)	N1^ix—Fe1—N1^i	94.28 (10)
C4^iv—O1—C4^viii	98.1 (4)	N1^ii—Fe1—N1^i	85.72 (10)
C4^v—O1—C4^viii	180.0	N1^x—Fe1—N1^i	78.19 (14)
N1^ix—Fe1—N1^ii	180.00 (17)	N1^xi—Fe1—N1^i	101.81 (14)
N1^ix—Fe1—N1^x	169.65 (13)	N1^iii—Fe1—N1^i	92.24 (13)
N1^ii—Fe1—N1^x	10.35 (13)	N1^xii—Fe1—N1^i	87.76 (13)
N1^ix—Fe1—N1^xi	10.35 (13)	N1^xiii—Fe1—N1^i	94.28 (10)
N1^ii—Fe1—N1^xi	169.65 (13)	N1^xiv—Fe1—N1^i	10.35 (13)
N1^x—Fe1—N1^xi	180.00 (19)	N1^xv—Fe1—N1^i	169.65 (13)
N1^ix—Fe1—N1^iii	101.81 (14)	N1^xvi—Fe1—N1^i	180.00 (16)
N1^ii—Fe1—N1^iii	78.19 (14)	N1^ix—Fe1—N1	94.28 (10)
N1^x—Fe1—N1^iii	85.72 (10)	N1^ii—Fe1—N1	85.72 (10)
N1^xi—Fe1—N1^iii	94.28 (10)	N1^x—Fe1—N1	92.24 (13)
N1^ix—Fe1—N1^xii	78.19 (14)	N1^xi—Fe1—N1	87.76 (13)
N1^ii—Fe1—N1^xii	101.81 (14)	N1^iii—Fe1—N1	10.35 (13)
N1^x—Fe1—N1^xii	94.28 (10)	N1^xii—Fe1—N1	169.65 (13)
N1^xi—Fe1—N1^xii	85.72 (10)	N1^xiii—Fe1—N1	180.0
N1^iii—Fe1—N1^xii	180.00 (16)	N1^xiv—Fe1—N1	78.19 (14)
N1^ix—Fe1—N1^xiii	85.72 (10)	N1^xv—Fe1—N1	101.81 (14)
N1^ii—Fe1—N1^xiii	94.28 (10)	N1^xvi—Fe1—N1	94.28 (10)
N1^x—Fe1—N1^xiii	87.76 (13)	N1^i—Fe1—N1	85.72 (10)
N1^xi—Fe1—N1^xiii	92.24 (13)	N1^iii—N1—C3	82.26 (10)
N1^iii—Fe1—N1^xiii	169.65 (13)	N1^iii—N1—Fe1	84.82 (7)
N1^xii—Fe1—N1^xiii	10.35 (13)	C3—N1—Fe1	118.1 (2)
C3^i—C2—C3—N1	−53.7 (3)	C4^v—C4—O1—C4^iv	82.9 (3)
C3^ii—C2—C3—N1	71.0 (2)	C4^iv—C4—O1—C4^v	−82.9 (3)
C1—C2—C3—N1	−171.34 (11)	C4^iv—C4—O1—C4^viii	97.1 (3)
C3^i—C2—C3—N1^iii	−71.0 (2)	C4^v—C4—O1—C4^viii	180.001 (1)
C3^ii—C2—C3—N1^iii	53.7 (3)	C2—C3—N1—N1^iii	−93.88 (7)
C1—C2—C3—N1^iii	171.34 (11)	N1^iii—C3—N1—Fe1	79.88 (14)
C4^iv—C4—O1—C4^vii	179.995 (1)	C2—C3—N1—Fe1	−14.01 (18)
C4^v—C4—O1—C4^vii	−97.1 (3)

Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) −y, −x, z; (iv) −x+y, −x+1, z; (v) −y+1, x−y+1, z; (vi) −x+2/3, −y+4/3, −z+1/3; (vii) x−y+2/3, x+1/3, −z+1/3; (viii) y−1/3, −x+y+1/3, −z+1/3; (ix) x−y, x, −z; (x) −x+y, y, z; (xi) x−y, −y, −z; (xii) y, x, −z; (xiii) −x, −y, −z; (xiv) x, x−y, z; (xv) −x, −x+y, −z; (xvi) y, −x+y, −z.

(1st_152K)

Crystal data

C8.25H25.50Br1.50Fe0.75N4.50O0.75	Dx = 1.628 Mg m^−3
Mr = 361.58	Synchrotron radiation, λ = 0.78405 Å
Trigonal, R3m:H	Cell parameters from 1210 reflections
a = 7.3869 (3) Å	θ = 3.6–32.5°
c = 31.2243 (14) Å	µ = 6.17 mm^−1
V = 1475.53 (14) Å^3	T = 152 K
Z = 4	Hexagonal flat prism, colourless
F(000) = 738	0.24 × 0.22 × 0.16 mm

Data collection

Abstract diffractometer	361 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.007
ω scans	θmax = 29.3°, θmin = 2.2°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.833, Tmax = 1.000	k = −9→9
2246 measured reflections	l = −37→37
391 independent reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.0871P)^2 + 5.7826P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.032
391 reflections	Δρmax = 0.76 e Å^−3
33 parameters	Δρmin = −0.51 e Å^−3

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)
C1	0.0000	0.0000	0.1505 (3)	0.085 (3)
H1A	−0.1487	−0.0744	0.1609	0.128*
C2	0.0000	0.0000	0.1010 (2)	0.0627 (19)
C3	−0.1135 (4)	0.1135 (4)	0.08615 (13)	0.0733 (11)
H3A	−0.2468	0.0604	0.1024	0.088*	0.5
H3B	−0.0242	0.2696	0.0935	0.088*	0.5
C4	0.1621 (7)	0.5811 (3)	0.13848 (17)	0.116 (13)*	0.1667
H4A	0.2074	0.5612	0.1102	0.174*	0.0833
H4B	0.1064	0.6763	0.1360	0.174*	0.0833
H4C	0.0532	0.4459	0.1496	0.174*	0.0833
O1	0.3333	0.6667	0.1667	0.199 (9)
H1	0.3665	0.5729	0.1728	0.299*	0.0833
Fe1	0.0000	0.0000	0.0000	0.0432 (3)
Br1	0.3333	0.6667	0.03682 (3)	0.0686 (2)
N1	−0.1539 (6)	0.1033 (6)	0.04134 (10)	0.0595 (10)	0.5
H1B	−0.1287	0.2346	0.0327	0.071*	0.5
H1C	−0.2973	0.0103	0.0385	0.071*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.101 (4)	0.101 (4)	0.053 (4)	0.051 (2)	0.000	0.000
C2	0.073 (3)	0.073 (3)	0.043 (3)	0.0363 (13)	0.000	0.000
C3	0.0899 (13)	0.0899 (13)	0.055 (2)	0.0560 (15)	0.0045 (10)	−0.0045 (10)
O1	0.227 (13)	0.227 (13)	0.144 (13)	0.113 (6)	0.000	0.000
Fe1	0.0469 (4)	0.0469 (4)	0.0357 (5)	0.02344 (18)	0.000	0.000
Br1	0.0680 (3)	0.0680 (3)	0.0697 (5)	0.03399 (14)	0.000	0.000
N1	0.0616 (18)	0.0672 (19)	0.0546 (18)	0.0359 (11)	0.0017 (16)	0.0050 (16)

Geometric parameters (Å, º)

C1—C2	1.548 (11)	Fe1—N1^ix	2.100 (4)
C2—C3	1.523 (5)	Fe1—N1^ii	2.100 (4)
C2—C3^i	1.523 (5)	Fe1—N1^x	2.100 (4)
C2—C3^ii	1.523 (5)	Fe1—N1^xi	2.100 (4)
C3—N1	1.425 (5)	Fe1—N1^iii	2.100 (4)
C3—N1^iii	1.425 (5)	Fe1—N1^xii	2.100 (4)
C4—O1	1.405 (3)	Fe1—N1^xiii	2.100 (4)
C4—C4^iv	1.897 (8)	Fe1—N1^xiv	2.100 (4)
C4—C4^v	1.897 (8)	Fe1—N1^xv	2.100 (4)
O1—C4^v	1.405 (3)	Fe1—N1^xvi	2.100 (4)
O1—C4^iv	1.405 (3)	Fe1—N1^i	2.100 (4)
O1—C4^vi	1.405 (3)	Fe1—N1	2.100 (4)
O1—C4^vii	1.405 (3)	N1—N1^iii	0.374 (8)
O1—C4^viii	1.405 (3)
C3—C2—C3^i	111.2 (3)	N1^ix—Fe1—N1^xiv	87.4 (2)
C3—C2—C3^ii	111.2 (3)	N1^ii—Fe1—N1^xiv	92.6 (2)
C3^i—C2—C3^ii	111.2 (3)	N1^x—Fe1—N1^xiv	86.17 (15)
C3—C2—C1	107.7 (3)	N1^xi—Fe1—N1^xiv	93.83 (15)
C3^i—C2—C1	107.7 (3)	N1^iii—Fe1—N1^xiv	86.17 (15)
C3^ii—C2—C1	107.7 (3)	N1^xii—Fe1—N1^xiv	93.83 (15)
N1—C3—N1^iii	15.1 (3)	N1^xiii—Fe1—N1^xiv	101.3 (2)
N1—C3—C2	115.3 (4)	N1^ix—Fe1—N1^xv	92.6 (2)
N1^iii—C3—C2	115.3 (4)	N1^ii—Fe1—N1^xv	87.4 (2)
O1—C4—C4^iv	47.54 (18)	N1^x—Fe1—N1^xv	93.83 (15)
O1—C4—C4^v	47.54 (18)	N1^xi—Fe1—N1^xv	86.17 (15)
C4^iv—C4—C4^v	60.000 (1)	N1^iii—Fe1—N1^xv	93.83 (15)
C4—O1—C4^v	84.9 (4)	N1^xii—Fe1—N1^xv	86.17 (15)
C4—O1—C4^iv	84.9 (4)	N1^xiii—Fe1—N1^xv	78.7 (2)
C4^v—O1—C4^iv	84.9 (4)	N1^xiv—Fe1—N1^xv	180.0 (3)
C4—O1—C4^vi	180.0	N1^ix—Fe1—N1^xvi	86.17 (15)
C4^v—O1—C4^vi	95.1 (4)	N1^ii—Fe1—N1^xvi	93.83 (15)
C4^iv—O1—C4^vi	95.1 (4)	N1^x—Fe1—N1^xvi	101.3 (2)
C4—O1—C4^vii	95.1 (4)	N1^xi—Fe1—N1^xvi	78.7 (2)
C4^v—O1—C4^vii	180.0	N1^iii—Fe1—N1^xvi	87.4 (2)
C4^iv—O1—C4^vii	95.1 (4)	N1^xii—Fe1—N1^xvi	92.6 (2)
C4^vi—O1—C4^vii	84.9 (4)	N1^xiii—Fe1—N1^xvi	86.17 (15)
C4—O1—C4^viii	95.1 (4)	N1^xiv—Fe1—N1^xvi	169.8 (2)
C4^v—O1—C4^viii	95.1 (4)	N1^xv—Fe1—N1^xvi	10.2 (2)
C4^iv—O1—C4^viii	180.0	N1^ix—Fe1—N1^i	93.83 (15)
C4^vi—O1—C4^viii	84.9 (4)	N1^ii—Fe1—N1^i	86.17 (15)
C4^vii—O1—C4^viii	84.9 (4)	N1^x—Fe1—N1^i	78.7 (2)
N1^ix—Fe1—N1^ii	180.0 (3)	N1^xi—Fe1—N1^i	101.3 (2)
N1^ix—Fe1—N1^x	169.8 (2)	N1^iii—Fe1—N1^i	92.6 (2)
N1^ii—Fe1—N1^x	10.2 (2)	N1^xii—Fe1—N1^i	87.4 (2)
N1^ix—Fe1—N1^xi	10.2 (2)	N1^xiii—Fe1—N1^i	93.83 (15)
N1^ii—Fe1—N1^xi	169.8 (2)	N1^xiv—Fe1—N1^i	10.2 (2)
N1^x—Fe1—N1^xi	180.00 (13)	N1^xv—Fe1—N1^i	169.8 (2)
N1^ix—Fe1—N1^iii	101.3 (2)	N1^xvi—Fe1—N1^i	180.0 (2)
N1^ii—Fe1—N1^iii	78.7 (2)	N1^ix—Fe1—N1	93.83 (15)
N1^x—Fe1—N1^iii	86.17 (15)	N1^ii—Fe1—N1	86.17 (15)
N1^xi—Fe1—N1^iii	93.83 (15)	N1^x—Fe1—N1	92.6 (2)
N1^ix—Fe1—N1^xii	78.7 (2)	N1^xi—Fe1—N1	87.4 (2)
N1^ii—Fe1—N1^xii	101.3 (2)	N1^iii—Fe1—N1	10.2 (2)
N1^x—Fe1—N1^xii	93.83 (15)	N1^xii—Fe1—N1	169.8 (2)
N1^xi—Fe1—N1^xii	86.17 (15)	N1^xiii—Fe1—N1	180.0
N1^iii—Fe1—N1^xii	180.0 (2)	N1^xiv—Fe1—N1	78.7 (2)
N1^ix—Fe1—N1^xiii	86.17 (15)	N1^xv—Fe1—N1	101.3 (2)
N1^ii—Fe1—N1^xiii	93.83 (15)	N1^xvi—Fe1—N1	93.83 (15)
N1^x—Fe1—N1^xiii	87.4 (2)	N1^i—Fe1—N1	86.17 (15)
N1^xi—Fe1—N1^xiii	92.6 (2)	N1^iii—N1—C3	82.47 (16)
N1^iii—Fe1—N1^xiii	169.8 (2)	N1^iii—N1—Fe1	84.88 (10)
N1^xii—Fe1—N1^xiii	10.2 (2)	C3—N1—Fe1	119.0 (3)
C3^i—C2—C3—N1	−53.9 (4)	C4^iv—C4—O1—C4^vii	−94.7 (3)
C3^ii—C2—C3—N1	70.6 (4)	C4^v—C4—O1—C4^vii	179.997 (1)
C1—C2—C3—N1	−171.65 (17)	C4^iv—C4—O1—C4^viii	180.001 (1)
C3^i—C2—C3—N1^iii	−70.6 (4)	C4^v—C4—O1—C4^viii	94.7 (3)
C3^ii—C2—C3—N1^iii	53.9 (4)	C2—C3—N1—N1^iii	−93.59 (10)
C1—C2—C3—N1^iii	171.65 (17)	N1^iii—C3—N1—Fe1	79.8 (2)
C4^iv—C4—O1—C4^v	85.3 (3)	C2—C3—N1—Fe1	−13.7 (3)
C4^v—C4—O1—C4^iv	−85.3 (3)

Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) −y, −x, z; (iv) −y+1, x−y+1, z; (v) −x+y, −x+1, z; (vi) −x+2/3, −y+4/3, −z+1/3; (vii) x−y+2/3, x+1/3, −z+1/3; (viii) y−1/3, −x+y+1/3, −z+1/3; (ix) x−y, x, −z; (x) −x+y, y, z; (xi) x−y, −y, −z; (xii) y, x, −z; (xiii) −x, −y, −z; (xiv) x, x−y, z; (xv) −x, −x+y, −z; (xvi) y, −x+y, −z.

(1st_083K)

Crystal data

C8.25H25.50Br1.50Fe0.75N4.50O0.75	Dx = 1.618 Mg m^−3
Mr = 361.58	Synchrotron radiation, λ = 0.78405 Å
Trigonal, R3m	Cell parameters from 860 reflections
a = 7.4091 (4) Å	θ = 2.2–27.7°
c = 31.216 (2) Å	µ = 6.13 mm^−1
V = 1484.02 (19) Å^3	T = 83 K
Z = 4	Hexagonal flat prism, colourless
F(000) = 738	0.24 × 0.22 × 0.16 mm

Data collection

Abstract diffractometer	335 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.008
ω scans	θmax = 29.3°, θmin = 2.2°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→9
Tmin = 0.789, Tmax = 1.000	k = −9→9
2197 measured reflections	l = −37→37
396 independent reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.086	H-atom parameters constrained
wR(F^2) = 0.243	w = 1/[σ^2(Fo^2) + (0.1376P)^2 + 10.4317P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.403
396 reflections	Δρmax = 1.20 e Å^−3
33 parameters	Δρmin = −0.42 e Å^−3

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)
C1	0.0000	0.0000	0.1511 (5)	0.118 (6)
H1A	−0.1487	−0.0744	0.1615	0.177*
C2	0.0000	0.0000	0.0997 (4)	0.090 (4)
C3	−0.1129 (7)	0.1129 (7)	0.0847 (2)	0.096 (2)
H3A	−0.2462	0.0604	0.1010	0.115*	0.5
H3B	−0.0236	0.2696	0.0921	0.115*	0.5
C4	0.1624 (7)	0.5812 (3)	0.13854 (17)	0.13 (2)*	0.1667
H4A	0.1539	0.4600	0.1240	0.199*	0.0833
H4B	0.1801	0.6860	0.1172	0.199*	0.0833
H4C	0.0340	0.5380	0.1548	0.199*	0.0833
O1	0.3333	0.6667	0.1667	0.254 (18)
H1	0.3665	0.5729	0.1728	0.381*	0.0833
Fe1	0.0000	0.0000	0.0000	0.0589 (5)
Br1	0.3333	0.6667	0.03649 (5)	0.0923 (5)
N1	−0.1449 (11)	0.1060 (13)	0.04029 (18)	0.0917 (19)	0.5
H1B	−0.1197	0.2373	0.0317	0.110*	0.5
H1C	−0.2883	0.0130	0.0374	0.110*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.132 (8)	0.132 (8)	0.090 (9)	0.066 (4)	0.000	0.000
C2	0.107 (6)	0.107 (6)	0.058 (6)	0.053 (3)	0.000	0.000
C3	0.114 (2)	0.114 (2)	0.077 (4)	0.069 (3)	0.0081 (19)	−0.0081 (19)
O1	0.28 (3)	0.28 (3)	0.20 (3)	0.141 (13)	0.000	0.000
Fe1	0.0618 (6)	0.0618 (6)	0.0529 (9)	0.0309 (3)	0.000	0.000
Br1	0.0895 (6)	0.0895 (6)	0.0979 (10)	0.0447 (3)	0.000	0.000
N1	0.086 (3)	0.130 (4)	0.080 (4)	0.070 (2)	0.008 (3)	0.010 (4)

Geometric parameters (Å, º)

C1—C2	1.60 (2)	Fe1—N1	2.048 (7)
C2—C3^i	1.522 (10)	Fe1—N1^ix	2.048 (7)
C2—C3^ii	1.522 (10)	Fe1—N1^x	2.048 (7)
C2—C3	1.522 (10)	Fe1—N1^i	2.048 (7)
C3—N1^iii	1.404 (9)	Fe1—N1^xi	2.048 (7)
C3—N1	1.404 (9)	Fe1—N1^ii	2.048 (7)
C4—O1	1.405 (3)	Fe1—N1^xii	2.048 (7)
C4—C4^iv	1.900 (8)	Fe1—N1^xiii	2.048 (7)
C4—C4^v	1.900 (8)	Fe1—N1^xiv	2.048 (7)
O1—C4^iv	1.405 (3)	Fe1—N1^iii	2.048 (7)
O1—C4^v	1.405 (3)	Fe1—N1^xv	2.048 (7)
O1—C4^vi	1.405 (3)	Fe1—N1^xvi	2.048 (7)
O1—C4^vii	1.405 (3)	N1—N1^iii	0.289 (15)
O1—C4^viii	1.405 (3)
C3^i—C2—C3^ii	111.0 (5)	N1—Fe1—N1^xiii	80.4 (4)
C3^i—C2—C3	111.0 (5)	N1^ix—Fe1—N1^xiii	86.2 (3)
C3^ii—C2—C3	111.0 (5)	N1^x—Fe1—N1^xiii	93.8 (3)
C3^i—C2—C1	107.9 (5)	N1^i—Fe1—N1^xiii	8.1 (4)
C3^ii—C2—C1	107.9 (5)	N1^xi—Fe1—N1^xiii	171.9 (4)
C3—C2—C1	107.9 (5)	N1^ii—Fe1—N1^xiii	91.4 (4)
N1^iii—C3—N1	11.8 (6)	N1^xii—Fe1—N1^xiii	88.6 (4)
N1^iii—C3—C2	114.4 (8)	N1—Fe1—N1^xiv	99.6 (4)
N1—C3—C2	114.4 (8)	N1^ix—Fe1—N1^xiv	93.8 (3)
O1—C4—C4^iv	47.46 (18)	N1^x—Fe1—N1^xiv	86.2 (3)
O1—C4—C4^v	47.46 (18)	N1^i—Fe1—N1^xiv	171.9 (4)
C4^iv—C4—C4^v	60.0	N1^xi—Fe1—N1^xiv	8.1 (4)
C4^iv—O1—C4^v	85.1 (4)	N1^ii—Fe1—N1^xiv	88.6 (4)
C4^iv—O1—C4^vi	94.9 (4)	N1^xii—Fe1—N1^xiv	91.4 (4)
C4^v—O1—C4^vi	94.9 (4)	N1^xiii—Fe1—N1^xiv	180.0 (5)
C4^iv—O1—C4^vii	180.0	N1—Fe1—N1^iii	8.1 (4)
C4^v—O1—C4^vii	94.9 (4)	N1^ix—Fe1—N1^iii	86.2 (3)
C4^vi—O1—C4^vii	85.1 (4)	N1^x—Fe1—N1^iii	93.8 (3)
C4^iv—O1—C4	85.1 (4)	N1^i—Fe1—N1^iii	91.4 (4)
C4^v—O1—C4	85.1 (4)	N1^xi—Fe1—N1^iii	88.6 (4)
C4^vi—O1—C4	180.0 (3)	N1^ii—Fe1—N1^iii	80.4 (4)
C4^vii—O1—C4	94.9 (4)	N1^xii—Fe1—N1^iii	99.6 (4)
C4^iv—O1—C4^viii	94.9 (4)	N1^xiii—Fe1—N1^iii	86.2 (3)
C4^v—O1—C4^viii	180.0	N1^xiv—Fe1—N1^iii	93.8 (3)
C4^vi—O1—C4^viii	85.1 (4)	N1—Fe1—N1^xv	171.9 (4)
C4^vii—O1—C4^viii	85.1 (4)	N1^ix—Fe1—N1^xv	93.8 (3)
C4—O1—C4^viii	94.9 (4)	N1^x—Fe1—N1^xv	86.2 (3)
N1—Fe1—N1^ix	91.4 (4)	N1^i—Fe1—N1^xv	88.6 (4)
N1—Fe1—N1^x	88.6 (4)	N1^xi—Fe1—N1^xv	91.4 (4)
N1^ix—Fe1—N1^x	180.0 (2)	N1^ii—Fe1—N1^xv	99.6 (4)
N1—Fe1—N1^i	86.2 (3)	N1^xii—Fe1—N1^xv	80.4 (4)
N1^ix—Fe1—N1^i	80.4 (4)	N1^xiii—Fe1—N1^xv	93.8 (3)
N1^x—Fe1—N1^i	99.6 (4)	N1^xiv—Fe1—N1^xv	86.2 (3)
N1—Fe1—N1^xi	93.8 (3)	N1^iii—Fe1—N1^xv	180.0 (5)
N1^ix—Fe1—N1^xi	99.6 (4)	N1—Fe1—N1^xvi	180.0
N1^x—Fe1—N1^xi	80.4 (4)	N1^ix—Fe1—N1^xvi	88.6 (4)
N1^i—Fe1—N1^xi	180.0 (4)	N1^x—Fe1—N1^xvi	91.4 (4)
N1—Fe1—N1^ii	86.2 (3)	N1^i—Fe1—N1^xvi	93.8 (3)
N1^ix—Fe1—N1^ii	8.1 (4)	N1^xi—Fe1—N1^xvi	86.2 (3)
N1^x—Fe1—N1^ii	171.9 (4)	N1^ii—Fe1—N1^xvi	93.8 (3)
N1^i—Fe1—N1^ii	86.2 (3)	N1^xii—Fe1—N1^xvi	86.2 (3)
N1^xi—Fe1—N1^ii	93.8 (3)	N1^xiii—Fe1—N1^xvi	99.6 (4)
N1—Fe1—N1^xii	93.8 (3)	N1^xiv—Fe1—N1^xvi	80.4 (4)
N1^ix—Fe1—N1^xii	171.9 (4)	N1^iii—Fe1—N1^xvi	171.9 (4)
N1^x—Fe1—N1^xii	8.1 (4)	N1^xv—Fe1—N1^xvi	8.1 (4)
N1^i—Fe1—N1^xii	93.8 (3)	N1^iii—N1—C3	84.1 (3)
N1^xi—Fe1—N1^xii	86.2 (3)	N1^iii—N1—Fe1	86.0 (2)
N1^ii—Fe1—N1^xii	180.0 (2)	C3—N1—Fe1	120.6 (6)
C3^i—C2—C3—N1^iii	−68.5 (7)	C4^iv—C4—O1—C4^vii	179.997 (1)
C3^ii—C2—C3—N1^iii	55.5 (8)	C4^v—C4—O1—C4^vii	−94.5 (3)
C1—C2—C3—N1^iii	173.5 (3)	C4^iv—C4—O1—C4^viii	94.5 (3)
C3^i—C2—C3—N1	−55.5 (8)	C4^v—C4—O1—C4^viii	180.001 (1)
C3^ii—C2—C3—N1	68.5 (7)	C2—C3—N1—N1^iii	−92.70 (17)
C1—C2—C3—N1	−173.5 (3)	N1^iii—C3—N1—Fe1	81.7 (4)
C4^v—C4—O1—C4^iv	85.5 (3)	C2—C3—N1—Fe1	−10.9 (6)
C4^iv—C4—O1—C4^v	−85.5 (3)

Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) −y, −x, z; (iv) −x+y, −x+1, z; (v) −y+1, x−y+1, z; (vi) −x+2/3, −y+4/3, −z+1/3; (vii) x−y+2/3, x+1/3, −z+1/3; (viii) y−1/3, −x+y+1/3, −z+1/3; (ix) −x+y, y, z; (x) x−y, −y, −z; (xi) y, −x+y, −z; (xii) x−y, x, −z; (xiii) x, x−y, z; (xiv) −x, −x+y, −z; (xv) y, x, −z; (xvi) −x, −y, −z.