Synchrotron charge-density studies in materials chemistry: 16 K X-ray charge density of a new magnetic metal-organic framework material, [Mn₂(C₈H₄O₄)₂(C₃H₇NO)₂]

A new magnetic metal-organic framework material, [Mn₂(C₈OH₄₄)₂(C₃H₇NO)₂], has been synthesized. The structure consists of chains of carboxylate-bridged Mn atoms interconnected with acid linkers, giving much larger interchain than intrachain Mn...Mn distances. Magnetic susceptibility data fitted to a Curie–Weiss law give Θ = −5.7 K and a total magnetic moment of 5.96 µ_B. The heat capacity provides no evidence of magnetic ordering down to 2 K. The X-ray charge density was determined from multipole modeling of 16 (1) K single-crystal synchrotron-radiation data. The structural surroundings of the two unique Mn centers are different, but orbital population analysis reveals close to single electron occupation in all 3d orbitals of both Mn sites, in agreement with the magnetic susceptibility measurements. Bader topological analysis shows the presence of direct chemical Mn...Mn interactions only in two out of three intrachain contacts, which suggests a `broken' chain. The topological measures and approximate energy densities at the metal–ligand bond critical points (ρ, ∇²ρ, G, V and H) indicate ionic interactions. Formal electron counting suggests mixed-valence Mn sites, but this hypothesis is not supported by the Bader atomic charges [q(Mn) = +2.035 and +2.031].

S1. Refinement

The Mangese framwork crystallized in the monoclinic system: spacegroup P2₁/c from systematic absences. The position of the hydrogren atoms were placed at a fixed distanced based on neutron diffraction experiments, 1.101 Å for sp3 hybridized carbon atoms and 1.084 Å for sp2 hybridized carbon atoms. The isotropic displacement parameters were fixed at 120% of the U_eq values of the bonding carbon atom.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART and SAINT (Bruker,1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: Koritsanszky et al., (2003); molecular graphics: Koritsanszky et al., (2003); software used to prepare material for publication: Koritsanszky et al., (2003).

Figures

(I)

Crystal data

C22H22Mn2N2O10	Z = 4
Mr = 584.30	Dx = 1.607 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.4200 Å
Hall symbol: -P 2ybc	Cell parameters from 11589 reflections
a = 13.3957 Å	θ = 4.3–57.4°
b = 10.1716 Å	µ = 0.22 mm^−1
c = 17.7250 Å	T = 15 K
β = 90.090°	Trapez shape, colourless
V = 2415.13 Å^3	0.04 × 0.03 × 0.02 mm

Data collection

APS,ChemMat Cars, Huber type diffractometer	12180 reflections with I > 2u(I)
ϕscan	Rint = 0.047
Absorption correction: multi-scan (Blessing, R., SORTAV, 1980)	θmax = 60.0°
Tmin = 0.992, Tmax = 0.997	h = −30→30
99809 measured reflections	k = 0→23
18127 independent reflections	l = 0→31

Refinement

Refinement on F^2	888 parameters
Least-squares matrix: full	3 restraints
R[F^2 > 2σ(F^2)] = 0.022	H parameters constrained
wR(F^2) = 0.045	w2 = q/[s^2(Fo^2) + (0.00 P)^2 + 0.00 P + 0.00 + 0.00 sin(th)] where P = (0.3333 Fo^2 + 0.6667 Fc^2) q = 1.0
S = 0.71	(Δ/σ)max = 0.001
12180 reflections

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
MN(1)	0.11157 (1)	0.58200 (2)	0.53151 (2)	0.003
MN(2)	0.346075 (8)	0.422982 (13)	0.514599 (12)	0.003
O(1)	0.10790 (5)	0.44123 (7)	0.61832 (6)	0.007
O(2)	0.23920 (5)	0.31575 (7)	0.58531 (6)	0.006
O(8)	0.04688 (5)	0.40134 (7)	0.45250 (6)	0.006
O(9)	0.20079 (5)	0.47663 (7)	0.44529 (6)	0.005
O(11)	0.18082 (5)	0.71125 (7)	0.60932 (6)	0.007
O(12)	0.31862 (6)	0.60033 (7)	0.57821 (7)	0.007
O(18)	0.45359 (5)	0.34893 (7)	0.59312 (6)	0.007
O(19)	0.41687 (5)	0.51357 (8)	0.42224 (6)	0.007
O(21)	0.09789 (5)	0.73933 (7)	0.44926 (6)	0.007
O(31)	0.35921 (6)	0.23426 (7)	0.45372 (6)	0.007
N(21)	0.02645 (5)	0.92170 (7)	0.39741 (5)	0.007
N(31)	0.37204 (5)	0.01035 (7)	0.45539 (6)	0.008
C(1)	0.16975 (5)	0.34947 (6)	0.62919 (5)	0.005
C(2)	0.15764 (5)	0.27510 (6)	0.70201 (5)	0.005
C(3)	0.06421 (5)	0.26948 (6)	0.73736 (5)	0.006
C(4)	0.05452 (5)	0.29480 (6)	0.30633 (5)	0.005
C(5)	0.13933 (4)	0.34778 (6)	0.34197 (5)	0.005
C(6)	0.23294 (5)	0.34258 (6)	0.30659 (5)	0.006
C(7)	0.24108 (5)	0.21635 (6)	0.73574 (5)	0.006
C(8)	0.12870 (4)	0.41096 (6)	0.41744 (5)	0.004
C(11)	0.27059 (5)	0.67624 (6)	0.62114 (5)	0.005
C(12)	0.32135 (5)	0.73132 (6)	0.69018 (5)	0.005
C(13)	0.42527 (5)	0.72340 (6)	0.69845 (5)	0.006
C(14)	0.47051 (5)	0.72304 (6)	0.26281 (5)	0.006
C(15)	0.41319 (4)	0.66269 (6)	0.31915 (5)	0.005
C(16)	0.30910 (5)	0.65710 (6)	0.31115 (5)	0.006
C(17)	0.26377 (5)	0.79080 (6)	0.74675 (5)	0.006
C(18)	0.46253 (4)	0.60458 (6)	0.38848 (5)	0.004
C(21)	0.02517 (5)	0.81442 (7)	0.44054 (5)	0.007
C(22)	0.11533 (6)	0.95737 (8)	0.35428 (7)	0.011
C(23)	−0.06256 (6)	1.00266 (8)	0.38775 (6)	0.010
C(31)	0.35203 (5)	0.12665 (7)	0.48696 (5)	0.007
C(32)	0.36005 (6)	−0.11238 (7)	0.49710 (6)	0.011
C(33)	0.40616 (8)	0.00148 (8)	0.37752 (7)	0.014
H(3)	−0.00017	0.31526	0.71116	0.007
H(4)	−0.01818	0.30377	0.33260	0.007
H(6)	0.29817	0.38399	0.33397	0.007
H(7)	0.31224	0.21674	0.70671	0.008
H(13)	0.47039	0.67629	0.65553	0.008
H(14)	0.55092	0.72839	0.26900	0.008
H(16)	0.26398	0.61242	0.35491	0.007
H(17)	0.18336	0.79641	0.74057	0.008
H(21)	−0.04342	0.79048	0.46985	0.008
H(22A)	0.17446	0.88421	0.36428	0.017
H(22B)	0.14148	1.05522	0.37205	0.017
H(22C)	0.09654	0.95951	0.29380	0.017
H(23A)	−0.12285	0.96498	0.42394	0.015
H(23B)	−0.08679	0.99931	0.32840	0.015
H(23C)	−0.04574	1.10494	0.40363	0.015
H(31)	0.32780	0.12758	0.54528	0.009
H(32A)	0.33931	−0.09045	0.55585	0.017
H(32B)	0.43073	−0.16760	0.49640	0.017
H(32C)	0.30089	−0.17189	0.47070	0.017
H(33A)	0.41420	0.10087	0.35368	0.020
H(33B)	0.35163	−0.05439	0.34381	0.020
H(33C)	0.47888	−0.04886	0.37570	0.020
DUM0	0.14720	0.62760	0.51980	0.000	0.0000
DUM1	0.13900	0.53170	0.52200	0.000	0.0000
DUM2	0.38840	0.38650	0.50600	0.000	0.0000
DUM3	0.37970	0.46730	0.50230	0.000	0.0000

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
MN(1)	0.00375 (4)	0.00363 (4)	0.00242 (9)	−0.00010 (3)	−0.00060 (3)	−0.00020 (4)
MN(2)	0.00364 (3)	0.00348 (3)	0.00243 (9)	0.00004 (2)	−0.00043 (3)	0.00017 (4)
O(1)	0.0081 (2)	0.0070 (2)	0.0052 (4)	0.0020 (2)	0.0002 (2)	0.0027 (2)
O(2)	0.0069 (2)	0.0075 (2)	0.0048 (4)	0.0004 (2)	0.0024 (2)	0.0016 (2)
O(8)	0.0044 (2)	0.0096 (2)	0.0046 (4)	0.0002 (2)	0.0006 (2)	−0.0010 (2)
O(9)	0.0056 (2)	0.0062 (2)	0.0034 (4)	−0.0010 (1)	−0.0012 (2)	−0.0014 (2)
O(11)	0.0058 (2)	0.0075 (2)	0.0073 (4)	0.0001 (2)	−0.0033 (2)	−0.0018 (2)
O(12)	0.0097 (2)	0.0072 (2)	0.0052 (4)	0.0008 (2)	0.0001 (2)	−0.0031 (2)
O(18)	0.0064 (2)	0.0081 (2)	0.0062 (4)	−0.0015 (2)	−0.0036 (2)	0.0025 (2)
O(19)	0.0066 (2)	0.0084 (2)	0.0049 (4)	−0.0010 (2)	0.0001 (2)	0.0034 (2)
O(21)	0.0077 (2)	0.0067 (2)	0.0071 (4)	0.0011 (2)	−0.0007 (2)	0.0024 (2)
O(31)	0.0111 (2)	0.0046 (2)	0.0057 (4)	0.0001 (2)	0.0002 (2)	0.0000 (2)
N(21)	0.0076 (2)	0.0058 (2)	0.0087 (4)	0.0011 (2)	−0.0001 (2)	0.0024 (2)
N(31)	0.0117 (2)	0.0046 (2)	0.0071 (4)	−0.0002 (2)	0.0030 (2)	−0.0006 (2)
C(1)	0.0057 (2)	0.0058 (2)	0.0032 (4)	−0.0003 (1)	0.0001 (2)	0.0009 (2)
C(2)	0.0052 (2)	0.0064 (2)	0.0032 (4)	0.0003 (1)	0.0002 (2)	0.0012 (2)
C(3)	0.0052 (2)	0.0076 (2)	0.0044 (4)	0.0009 (1)	−0.0001 (2)	0.0019 (2)
C(4)	0.0047 (2)	0.0078 (2)	0.0038 (4)	−0.0008 (1)	0.0004 (2)	−0.0022 (2)
C(5)	0.0048 (2)	0.0066 (2)	0.0030 (4)	−0.0004 (1)	−0.0002 (2)	−0.0011 (2)
C(6)	0.0050 (2)	0.0080 (2)	0.0037 (4)	−0.0006 (1)	−0.0006 (2)	−0.0017 (2)
C(7)	0.0048 (2)	0.0088 (2)	0.0050 (4)	0.0002 (1)	0.0002 (2)	0.0022 (2)
C(8)	0.0046 (2)	0.0057 (2)	0.0028 (4)	−0.0001 (1)	−0.0004 (2)	−0.0006 (2)
C(11)	0.0060 (2)	0.0053 (2)	0.0038 (4)	−0.0004 (1)	−0.0009 (2)	−0.0012 (2)
C(12)	0.0048 (2)	0.0065 (2)	0.0033 (4)	0.0000 (1)	−0.0010 (2)	−0.0014 (2)
C(13)	0.0054 (2)	0.0089 (2)	0.0042 (4)	0.0005 (1)	−0.0007 (2)	−0.0030 (2)
C(14)	0.0045 (2)	0.0093 (2)	0.0049 (4)	−0.0007 (1)	−0.0007 (2)	0.0024 (2)
C(15)	0.0044 (2)	0.0061 (2)	0.0031 (4)	−0.0001 (1)	−0.0011 (2)	0.0014 (2)
C(16)	0.0049 (2)	0.0077 (2)	0.0044 (4)	−0.0004 (1)	−0.0008 (2)	0.0023 (2)
C(17)	0.0045 (2)	0.0085 (2)	0.0049 (4)	0.0002 (1)	−0.0007 (2)	−0.0023 (2)
C(18)	0.0049 (2)	0.0054 (2)	0.0030 (4)	−0.0002 (1)	−0.0013 (2)	0.0008 (2)
C(21)	0.0073 (2)	0.0063 (2)	0.0068 (4)	0.0006 (2)	−0.0008 (2)	0.0012 (2)
C(22)	0.0105 (2)	0.0095 (2)	0.0135 (5)	0.0009 (2)	0.0023 (2)	0.0045 (3)
C(23)	0.0099 (2)	0.0086 (2)	0.0125 (5)	0.0029 (2)	−0.0011 (2)	0.0015 (3)
C(31)	0.0095 (2)	0.0051 (2)	0.0061 (4)	0.0005 (1)	0.0005 (2)	0.0000 (2)
C(32)	0.0147 (3)	0.0063 (2)	0.0117 (5)	−0.0001 (2)	0.0008 (3)	0.0013 (3)
C(33)	0.0213 (4)	0.0084 (3)	0.0119 (5)	−0.0024 (2)	0.0066 (3)	−0.0025 (3)

Geometric parameters (Å, º)

MN(1)—MN(1)^i	3.5992 (4)	C(3)—C(4)^iii	1.3925 (11)
MN(1)—MN(2)	3.5465 (2)	C(3)—H(3)	1.0840 (7)
MN(2)—MN(2)^ii	4.4425 (2)	C(4)—C(5)	1.4064 (9)
MN(1)—O(1)	2.1026 (10)	C(4)—H(4)	1.0840 (7)
MN(1)—O(8)	2.4668 (9)	C(5)—C(6)	1.4040 (9)
MN(1)—O(8)^i	2.1484 (7)	C(5)—C(8)	1.4910 (11)
MN(1)—O(9)	2.2178 (9)	C(6)—C(7)^iv	1.3958 (12)
MN(1)—O(11)	2.1183 (9)	C(6)—H(6)	1.0840 (7)
MN(1)—O(21)	2.1723 (10)	C(7)—H(7)	1.0840 (7)
MN(1)—C(8)	2.6776 (8)	C(11)—C(12)	1.5070 (11)
MN(2)—O(2)	2.1945 (8)	C(12)—C(13)	1.4019 (9)
MN(2)—O(9)	2.3637 (8)	C(12)—C(17)	1.4032 (10)
MN(2)—O(12)	2.1592 (8)	C(13)—C(14)^v	1.4011 (11)
MN(2)—O(18)	2.1383 (9)	C(13)—H(13)	1.0840 (8)
MN(2)—O(19)	2.1056 (9)	C(14)—C(15)	1.4021 (10)
MN(2)—O(31)	2.2092 (8)	C(14)—H(14)	1.0840 (6)
O(1)—C(1)	1.2627 (9)	C(15)—C(16)	1.4024 (8)
O(2)—C(1)	1.2611 (10)	C(15)—C(18)	1.5145 (11)
O(8)—C(8)	1.2647 (10)	C(16)—C(17)^vi	1.3966 (11)
O(9)—C(8)	1.2732 (10)	C(16)—H(16)	1.0840 (8)
O(11)—C(11)	1.2713 (9)	C(17)—H(17)	1.0840 (6)
O(12)—C(11)	1.2612 (11)	C(21)—H(21)	1.0840 (7)
O(18)—C(18)^ii	1.2615 (9)	C(22)—H(22A)	1.1010 (8)
O(19)—C(18)	1.2610 (10)	C(22)—H(22B)	1.1010 (9)
O(21)—C(21)	1.2473 (9)	C(22)—H(22C)	1.1010 (12)
O(31)—C(31)	1.2469 (11)	C(23)—H(23A)	1.1010 (9)
N(21)—C(21)	1.3324 (11)	C(23)—H(23B)	1.1010 (11)
N(21)—C(22)	1.4617 (11)	C(23)—H(23C)	1.1010 (8)
N(21)—C(23)	1.4589 (9)	C(31)—H(31)	1.0840 (9)
N(31)—C(31)	1.3360 (10)	C(32)—H(32A)	1.1010 (11)
N(31)—C(32)	1.4599 (11)	C(32)—H(32B)	1.1010 (8)
N(31)—C(33)	1.4575 (14)	C(32)—H(32C)	1.1010 (9)
C(1)—C(2)	1.5050 (11)	C(33)—H(33A)	1.1010 (9)
C(2)—C(3)	1.4017 (9)	C(33)—H(33B)	1.1010 (11)
C(2)—C(7)	1.4006 (10)	C(33)—H(33C)	1.1010 (10)
O(1)—MN(1)—O(8)	84.24 (4)	C(5)—C(4)—H(4)	120.03 (8)
O(1)—MN(1)—O(8)^i	86.15 (3)	C(4)—C(5)—C(6)	120.42 (8)
O(1)—MN(1)—O(9)	100.86 (3)	C(4)—C(5)—C(8)	119.33 (6)
O(1)—MN(1)—O(11)	87.52 (4)	C(6)—C(5)—C(8)	120.24 (6)
O(1)—MN(1)—O(21)	172.22 (3)	C(5)—C(6)—C(7)^iv	119.28 (7)
O(1)—MN(1)—C(8)	96.45 (3)	C(5)—C(6)—H(6)	120.34 (8)
O(8)—MN(1)—O(8)^i	77.72 (3)	C(7)^iv—C(6)—H(6)	120.38 (6)
O(8)—MN(1)—O(9)	55.81 (2)	C(2)—C(7)—C(6)^iii	120.26 (6)
O(8)—MN(1)—O(11)	170.08 (3)	C(2)—C(7)—H(7)	119.84 (8)
O(8)—MN(1)—O(21)	97.97 (4)	C(6)^iii—C(7)—H(7)	119.90 (7)
O(8)—MN(1)—C(8)	28.08 (2)	O(8)—C(8)—O(9)	120.49 (9)
O(8)^i—MN(1)—O(9)	131.50 (4)	O(8)—C(8)—C(5)	119.45 (7)
O(8)^i—MN(1)—O(11)	107.27 (3)	O(9)—C(8)—C(5)	120.04 (7)
O(8)^i—MN(1)—O(21)	87.03 (3)	O(11)—C(11)—O(12)	123.74 (9)
O(8)^i—MN(1)—C(8)	103.69 (3)	O(11)—C(11)—C(12)	117.07 (7)
O(9)—MN(1)—O(11)	120.84 (3)	O(12)—C(11)—C(12)	119.18 (7)
O(9)—MN(1)—O(21)	86.48 (3)	C(11)—C(12)—C(13)	120.68 (7)
O(9)—MN(1)—C(8)	28.20 (2)	C(11)—C(12)—C(17)	119.52 (6)
O(11)—MN(1)—O(21)	90.93 (4)	C(13)—C(12)—C(17)	119.80 (7)
O(11)—MN(1)—C(8)	148.98 (3)	C(12)—C(13)—C(14)^v	119.40 (7)
O(21)—MN(1)—C(8)	88.80 (3)	C(12)—C(13)—H(13)	120.44 (8)
O(2)—MN(2)—O(9)	82.77 (3)	C(14)^v—C(13)—H(13)	120.16 (6)
O(2)—MN(2)—O(12)	90.30 (3)	C(13)^vi—C(14)—C(15)	120.89 (6)
O(2)—MN(2)—O(18)	83.83 (3)	C(13)^vi—C(14)—H(14)	119.43 (7)
O(2)—MN(2)—O(19)	163.06 (4)	C(15)—C(14)—H(14)	119.68 (8)
O(2)—MN(2)—O(31)	84.24 (3)	C(14)—C(15)—C(16)	119.42 (7)
O(9)—MN(2)—O(12)	86.43 (3)	C(14)—C(15)—C(18)	120.66 (6)
O(9)—MN(2)—O(18)	166.60 (3)	C(16)—C(15)—C(18)	119.91 (7)
O(9)—MN(2)—O(19)	82.32 (3)	C(15)—C(16)—C(17)^vi	119.88 (7)
O(9)—MN(2)—O(31)	90.74 (3)	C(15)—C(16)—H(16)	120.01 (8)
O(12)—MN(2)—O(18)	93.99 (4)	C(17)^vi—C(16)—H(16)	120.12 (6)
O(12)—MN(2)—O(19)	96.76 (4)	C(12)—C(17)—C(16)^v	120.59 (6)
O(12)—MN(2)—O(31)	174.13 (3)	C(12)—C(17)—H(17)	119.85 (8)
O(18)—MN(2)—O(19)	110.88 (3)	C(16)^v—C(17)—H(17)	119.56 (7)
O(18)—MN(2)—O(31)	87.58 (4)	O(18)^ii—C(18)—O(19)	125.80 (9)
O(19)—MN(2)—O(31)	87.95 (4)	O(18)^ii—C(18)—C(15)	116.80 (7)
MN(1)—O(1)—C(1)	126.80 (7)	O(19)—C(18)—C(15)	117.40 (7)
MN(2)—O(2)—C(1)	134.40 (6)	O(21)—C(21)—N(21)	124.19 (8)
MN(1)—O(8)—MN(1)^i	102.28 (3)	O(21)—C(21)—H(21)	117.75 (8)
MN(1)—O(8)—C(8)	85.26 (5)	N(21)—C(21)—H(21)	118.07 (6)
MN(1)^i—O(8)—C(8)	156.33 (8)	N(21)—C(22)—H(22A)	109.54 (7)
MN(1)—O(9)—MN(2)	101.40 (4)	N(21)—C(22)—H(22B)	109.51 (8)
MN(1)—O(9)—C(8)	96.40 (5)	N(21)—C(22)—H(22C)	109.21 (8)
MN(2)—O(9)—C(8)	134.73 (6)	H(22A)—C(22)—H(22B)	109.65 (8)
MN(1)—O(11)—C(11)	110.28 (6)	H(22A)—C(22)—H(22C)	109.47 (9)
MN(2)—O(12)—C(12)	153.73 (5)	H(22B)—C(22)—H(22C)	109.44 (8)
MN(2)—O(18)—C(18)^ii	129.42 (6)	N(21)—C(23)—H(23A)	109.59 (7)
MN(2)—O(19)—C(18)	155.44 (8)	N(21)—C(23)—H(23B)	109.54 (8)
MN(1)—O(21)—C(21)	126.82 (7)	N(21)—C(23)—H(23C)	109.67 (7)
MN(2)—O(31)—C(31)	121.71 (8)	H(23A)—C(23)—H(23B)	109.29 (7)
C(21)—N(21)—C(22)	120.97 (7)	H(23A)—C(23)—H(23C)	109.27 (8)
C(21)—N(21)—C(23)	121.23 (7)	H(23B)—C(23)—H(23C)	109.48 (8)
C(22)—N(21)—C(23)	117.69 (7)	O(31)—C(31)—N(31)	124.31 (10)
C(31)—N(31)—C(32)	121.52 (9)	O(31)—C(31)—H(31)	117.81 (8)
C(31)—N(31)—C(33)	120.99 (8)	N(31)—C(31)—H(31)	117.89 (7)
C(32)—N(31)—C(33)	117.49 (7)	N(31)—C(32)—H(32A)	109.51 (7)
O(1)—C(1)—O(2)	126.26 (9)	N(31)—C(32)—H(32B)	109.59 (7)
O(1)—C(1)—C(2)	115.52 (7)	N(31)—C(32)—H(32C)	109.55 (9)
O(2)—C(1)—C(2)	118.22 (7)	H(32A)—C(32)—H(32B)	109.40 (9)
C(1)—C(2)—C(3)	120.09 (6)	H(32A)—C(32)—H(32C)	109.31 (7)
C(1)—C(2)—C(7)	119.57 (6)	H(32B)—C(32)—H(32C)	109.47 (7)
C(3)—C(2)—C(7)	120.28 (7)	N(31)—C(33)—H(33A)	109.73 (7)
C(2)—C(3)—C(4)^iii	119.74 (6)	N(31)—C(33)—H(33B)	109.69 (7)
C(2)—C(3)—H(3)	120.09 (8)	N(31)—C(33)—H(33C)	109.59 (10)
C(4)^iii—C(3)—H(3)	120.17 (6)	H(33A)—C(33)—H(33B)	109.32 (11)
C(3)^iv—C(4)—C(5)	119.86 (6)	H(33A)—C(33)—H(33C)	109.20 (8)
C(3)^iv—C(4)—H(4)	120.11 (7)	H(33B)—C(33)—H(33C)	109.29 (8)
C(22)—N(21)—C(21)—O(21)	1.9 (1)	C(6)^iii—C(7)—C(2)—C(1)	174.1 (2)
C(23)—N(21)—C(21)—O(21)	177.9 (2)	C(6)^iii—C(7)—C(2)—C(3)	−3.2 (1)
C(32)—N(31)—C(31)—O(31)	−178.7 (2)	O(11)—C(11)—C(12)—C(13)	−165.1 (2)
C(33)—N(31)—C(31)—O(31)	0.9 (1)	O(11)—C(11)—C(12)—C(17)	15.0 (1)
O(1)—C(1)—C(2)—C(3)	25.7 (1)	O(12)—C(11)—C(12)—C(13)	14.1 (1)
O(1)—C(1)—C(2)—C(7)	−151.7 (2)	O(12)—C(11)—C(12)—C(17)	−165.8 (2)
O(2)—C(1)—C(2)—C(3)	−154.4 (2)	C(14)^v—C(13)—C(12)—C(11)	179.2 (2)
O(2)—C(1)—C(2)—C(7)	28.2 (1)	C(14)^v—C(13)—C(12)—C(17)	−1.0 (1)
C(4)^iii—C(3)—C(2)—C(1)	−177.3 (2)	C(13)^vi—C(14)—C(15)—C(16)	−0.6 (1)
C(4)^iii—C(3)—C(2)—C(7)	0.0 (1)	C(13)^vi—C(14)—C(15)—C(18)	179.8 (2)
C(3)^iv—C(4)—C(5)—C(6)	3.5 (1)	C(14)—C(15)—C(18)—O(19)	−154.8 (2)
C(3)^iv—C(4)—C(5)—C(8)	−177.2 (2)	C(16)—C(15)—C(18)—O(19)	25.6 (1)
C(4)—C(5)—C(8)—O(8)	9.0 (1)	C(17)^vi—C(16)—C(15)—C(14)	1.2 (1)
C(4)—C(5)—C(8)—O(9)	−169.3 (2)	C(17)^vi—C(16)—C(15)—C(18)	−179.2 (2)
C(6)—C(5)—C(8)—O(8)	−171.7 (2)	C(16)^v—C(17)—C(12)—C(11)	−179.8 (2)
C(6)—C(5)—C(8)—O(9)	10.0 (1)	C(16)^v—C(17)—C(12)—C(13)	0.3 (1)
C(7)^iv—C(6)—C(5)—C(4)	−0.3 (1)	O(18)^ii—C(18)—C(15)—C(14)	24.5 (1)
C(7)^iv—C(6)—C(5)—C(8)	−179.6 (2)	O(18)^ii—C(18)—C(15)—C(16)	−155.1 (2)

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