Methyl 4-(1′-carboxy­ferrocen-1-yl)­butyrate

The title compound, [Fe(C₆H₅O₂)(C₁₀H₁₃O₂)], contains a heteroannularly substituted ferrocene unit, with the two substituents, viz. 3-(methoxy­carbon­yl)propyl and carboxyl, both capable of forming O—H...O hydrogen bonds. The keto ester group is stereochemically hindered by the trimethyl­ene spacer and does not participate in intra­molecular hydrogen-bond formation. Instead, the carb­oxy groups form self-complementary inter­molecular hydrogen bonds [O...O = 2.650 (2) Å], which join the mol­ecules into centrosymmetric dimers with a graph-set descriptor R²₂(8).

S1. Comment

In previous reports, we described the synthesis and structural properties of 1'-aminoferrocene-1-carboxylic acid (Fca; H₂NCpFeCpCOOH; Pavlović et al., 2002, 2003; Barišić et al., 2002). Fca was successfully coupled with natural amino acids and peptides giving oligopeptides with antiparallel peptide strands (Barišić et al., 2004, 2006). Unlike all previous metallocene turn structures, these compounds are the first truly organometallic turn mimetics. It was shown that intramolecular hydrogen bond(s) between podand peptide chains introduced helical conformations of the metallocene. We planned to research the influence of a trimethylene spacer between a carboxylic acid or amine group and a ferrocene unit on the formation of intramolecular hydrogen bonds. For that purpose, N-protected derivatives of 1'-(3-aminopropyl)ferrocene-1-carboxylic acid [H₂N(CH₃)₃CpFeCpCOOH] and 1'-amino-1-ferrocenebutyric acid [H₂NCpFeCp(CH₃)₃COOH] were synthesized (Barišić et al., 2003). The crystal structure analysis of both compounds confirmed only intermolecular hydrogen bonds. In this context, the crystal structure of the intermediate `ester–acid' (I) is presented.

Within the ferrocenyl moieties in (I) (Fig.1), the Fe—C bond distance range for the unsubstituted C atoms is 2.038 (2)–2.063 (2) Å, and the bonds to the substituted C atoms have values that do not deviate significantly from that range. The Cp rings are almost eclipsed. The dihedral angle between the planes C1/Cg1/Fe1/Cg2 and C7/Cg2/Fe1/Cg1 is 2.34 (16)° (Cg1 and Cg2 are the planes of the C1–C5 and C7–C11 rings, respectively). The Fe-to-centroid distances are 1.6487 (10) (Cg1) and 1.6561 (10) Å (Cg2), and the Cg1—Fe1—Cg2 angle is 179.46 (2)°. The exocyclic C1—C6 bond distance, 1.458 (3) Å, is slightly shortened owing to the coupling of the Cp ring π-electrons and the carboxyl moiety. While this distance is in agreement with the theoretical C_ring—C_carboxyl bond distance of 1.460 Å (Lin et al., 1998), indicating π-electron delocalization between the carboxy group and the Cp ring, the C7—C12 bond, 1.496 (3) Å, is slightly longer, but still shorter than C12—C13, 1.525 (3) Å, and C13—C14, 1.523 (3) Å, of the trimethylene spacer, which are predominantly σ in character. The double-bond character of the C15═O3 bond is reflected in its length (Table 1), as is the single-bond character of C15—O4. In contrast, the carboxyl group geometry for the C6—O1 and C6—O2 bonds is consistent with disorder between the single and double C—O bonds (see below), with the C6—O1 bond being slightly longer (Allen et al., 1987). The deviation of the carboxy group from coplanarity with the C1–C5 Cp ring is not significant [the dihedral angle is 3.03 (3)°].

Neighboring molecules are joined into discrete centrosymmetric dimers (Fig. 2) via O—H···O intermolecular hydrogen bonding (Table 2) [R²₂ (8) according to graph-set analysis], which is the most frequent supramolecular synthon in molecular fragments containing carboxy groups. The same synthon is found in the structure of 1,1'-ferrocenedicarboxylic acid (at 78 K; Takusagawa & Koetzle, 1979) with O···O distances of 2.5997 (1)–2.6597 (1) Å; in the structure of ferrocenecarboxylic acid (Cotton & Reid, 1985), with O···O distances of 2.714 (14) Å; and in the structure of 1'-(tert-butoxycarbonylamino)-ferrocene-1-carboxylic acid [2.656 (3) and 2.663 (3) Å for two independent molecules; Pavlović et al., 2002]. There are no important contacts between the dimers, other than van der Waals.

S2. Experimental

Compound (I) was prepared by partial esterification of 1'-carboxy-1-ferrocenebutyric acid (which was obtained in five steps starting from N,N-diphenylferrocenecarboxyamide; Barišić et al., 2003). Work-up of the reaction mixture gave orange crystals (m.p. 342–348 K) in 94% yield.

S3. Refinement

C-bound H atoms were positioned geometrically and refined as riding with U_iso(H) set to 1.2 or 1.5 times U_eq of the carrier C atom. Two possible positions of the H atom of the carboxylate group at C6 were found in a difference Fourier map at the final stages of the refinement, with O1—H1 and O2—H2A bond distances of 1.00 and 0.85 Å, respectively [please clarify; these values have s.u. values in CIF but not Table 2]. This result is consistent with the apparent C6—O1 and C6—O2 bond distances being disordered with each other. The occupancy factors were estimated only from the electron densities found in the difference map and were fixed, thus yielding 65:35 H-atom positional disorder with the major component attached to O1 and the minor component attached to O2. The coordinates of the partially occupied H-atom sites were fixed in the final refinement, yielding the hydrogen-bond geometry reflected in Table 2. The U_iso values of these H atoms were set to 1.2U_eq of their respective carrier O atoms.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON98 (Spek, 1998); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Only the major component (65%) of the disordered H atom of the carboxyl group is shown.
	Fig. 2. PLATON view of the crystal structure of (I). Dimerization occurs with eight-membered ring formation via intermolecular hydrogen bonds (dashed lines). Only the major component (65%) of the disordered H atom of the carboxyl group is shown; other H atoms have been omitted for clarity.

Methyl 4-(1'-carboxyferrocen-1-yl)butyrate

Crystal data

[Fe(C6H5O2)(C10H13O2)]	F(000) = 688
Mr = 330.15	Dx = 1.502 Mg m^−3
Monoclinic, P21/n	Melting point = 342–348 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.4324 (8) Å	Cell parameters from 6878 reflections
b = 7.5565 (5) Å	θ = 15–20°
c = 18.9837 (15) Å	µ = 1.05 mm^−1
β = 102.641 (7)°	T = 296 K
V = 1460.26 (19) Å^3	Plate, orange
Z = 4	0.56 × 0.50 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur2 diffractometer with Sapphire-3 CCD detector	3174 independent reflections
Radiation source: fine-focus sealed tube	3120 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ϕ and ω scans	θmax = 27.0°, θmin = 4.3°
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2004)	h = −13→13
Tmin = 0.461, Tmax = 0.881	k = −9→9
30324 measured reflections	l = −24→24

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)] = 0.041	Hydrogen site location: geom & dmap
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.948P] where P = (Fo^2 + 2Fc^2)/3
3174 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.98567 (3)	0.22897 (4)	0.224098 (16)	0.03727 (11)
O1	1.03891 (18)	0.5675 (2)	0.08958 (9)	0.0586 (4)
H1A	1.0688	0.5777	0.0431	0.071*	0.65
O2	0.87685 (17)	0.3936 (2)	0.03145 (9)	0.0576 (4)
H2A	0.9038	0.4061	−0.0074	0.069*	0.35
O3	1.4412 (2)	0.2020 (4)	0.05340 (12)	0.0959 (8)
O4	1.3248 (2)	0.2218 (3)	−0.05933 (10)	0.0653 (5)
C1	0.9052 (2)	0.4284 (3)	0.15713 (12)	0.0425 (5)
C2	0.9701 (2)	0.4979 (3)	0.22564 (12)	0.0447 (5)
H2	1.0399	0.5773	0.2340	0.054*
C3	0.9090 (2)	0.4245 (3)	0.27859 (13)	0.0479 (5)
H3	0.9311	0.4483	0.3278	0.057*
C4	0.8081 (2)	0.3082 (3)	0.24355 (13)	0.0479 (5)
H4	0.7531	0.2427	0.2661	0.057*
C5	0.8051 (2)	0.3087 (3)	0.16863 (13)	0.0458 (5)
H5	0.7487	0.2435	0.1334	0.055*
C6	0.9413 (2)	0.4638 (3)	0.08847 (13)	0.0454 (5)
C7	1.1144 (2)	0.0945 (3)	0.17540 (12)	0.0436 (5)
C8	1.1807 (2)	0.1686 (3)	0.24217 (13)	0.0462 (5)
H8	1.2489	0.2504	0.2484	0.055*
C9	1.1256 (2)	0.0969 (3)	0.29782 (13)	0.0469 (5)
H9	1.1518	0.1225	0.3468	0.056*
C10	1.0237 (2)	−0.0204 (3)	0.26604 (12)	0.0453 (5)
H10	0.9708	−0.0850	0.2902	0.054*
C11	1.0167 (2)	−0.0218 (3)	0.19047 (13)	0.0446 (5)
H11	0.9581	−0.0877	0.1565	0.054*
C12	1.1464 (3)	0.1238 (3)	0.10321 (13)	0.0524 (6)
H12A	1.1899	0.2372	0.1030	0.063*
H12B	1.0659	0.1265	0.0663	0.063*
C13	1.2354 (3)	−0.0229 (3)	0.08621 (13)	0.0522 (6)
H13A	1.3169	−0.0223	0.1225	0.063*
H13B	1.1931	−0.1362	0.0889	0.063*
C14	1.2667 (3)	−0.0034 (4)	0.01189 (14)	0.0617 (7)
H14A	1.3087	−0.1110	0.0005	0.074*
H14B	1.1851	0.0103	−0.0238	0.074*
C15	1.3537 (3)	0.1498 (4)	0.00641 (13)	0.0556 (6)
C16	1.4047 (3)	0.3681 (5)	−0.07103 (17)	0.0773 (9)
H16A	1.3885	0.4670	−0.0425	0.116*
H16B	1.3836	0.4001	−0.1212	0.116*
H16C	1.4957	0.3354	−0.0573	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.03356 (17)	0.03265 (17)	0.04725 (19)	0.00004 (11)	0.01242 (12)	−0.00088 (12)
O1	0.0645 (11)	0.0540 (10)	0.0600 (10)	−0.0192 (8)	0.0197 (8)	0.0023 (8)
O2	0.0599 (10)	0.0610 (11)	0.0516 (9)	−0.0129 (8)	0.0117 (8)	0.0000 (8)
O3	0.0827 (15)	0.141 (2)	0.0582 (12)	−0.0436 (15)	0.0030 (11)	0.0139 (14)
O4	0.0756 (13)	0.0709 (12)	0.0486 (10)	−0.0080 (10)	0.0116 (9)	0.0020 (9)
C1	0.0400 (11)	0.0362 (10)	0.0530 (12)	0.0032 (8)	0.0139 (9)	0.0036 (9)
C2	0.0443 (11)	0.0314 (10)	0.0590 (13)	0.0008 (8)	0.0127 (10)	−0.0029 (9)
C3	0.0482 (12)	0.0429 (12)	0.0547 (13)	0.0101 (10)	0.0159 (10)	−0.0025 (10)
C4	0.0364 (11)	0.0502 (13)	0.0608 (14)	0.0067 (9)	0.0187 (10)	0.0069 (11)
C5	0.0337 (10)	0.0454 (12)	0.0578 (13)	0.0013 (9)	0.0087 (9)	0.0033 (10)
C6	0.0461 (12)	0.0369 (11)	0.0546 (13)	0.0011 (9)	0.0136 (10)	0.0053 (10)
C7	0.0421 (11)	0.0383 (11)	0.0544 (12)	0.0068 (9)	0.0192 (9)	0.0011 (9)
C8	0.0324 (10)	0.0394 (11)	0.0677 (14)	0.0020 (8)	0.0126 (10)	−0.0022 (10)
C9	0.0457 (12)	0.0438 (12)	0.0496 (12)	0.0070 (10)	0.0070 (9)	−0.0014 (10)
C10	0.0510 (12)	0.0324 (10)	0.0555 (13)	0.0033 (9)	0.0182 (10)	0.0049 (9)
C11	0.0468 (12)	0.0337 (10)	0.0541 (13)	0.0009 (9)	0.0128 (10)	−0.0048 (9)
C12	0.0559 (14)	0.0486 (13)	0.0581 (14)	0.0101 (11)	0.0241 (11)	0.0078 (11)
C13	0.0589 (14)	0.0465 (13)	0.0558 (14)	0.0041 (11)	0.0225 (11)	−0.0005 (11)
C14	0.0679 (17)	0.0667 (17)	0.0564 (15)	−0.0021 (13)	0.0262 (13)	−0.0097 (13)
C15	0.0524 (14)	0.0699 (17)	0.0488 (13)	0.0009 (12)	0.0208 (11)	−0.0047 (12)
C16	0.090 (2)	0.077 (2)	0.0663 (18)	−0.0092 (17)	0.0206 (16)	0.0097 (15)

Geometric parameters (Å, º)

Fe1—C1	2.031 (2)	C4—H4	0.9300
Fe1—C5	2.038 (2)	C5—H5	0.9300
Fe1—C2	2.040 (2)	C7—C8	1.419 (3)
Fe1—C8	2.040 (2)	C7—C11	1.422 (3)
Fe1—C9	2.047 (2)	C7—C12	1.496 (3)
Fe1—C11	2.048 (2)	C8—C9	1.417 (3)
Fe1—C10	2.050 (2)	C8—H8	0.9300
Fe1—C4	2.056 (2)	C9—C10	1.413 (3)
Fe1—C7	2.058 (2)	C9—H9	0.9300
Fe1—C3	2.063 (2)	C10—C11	1.420 (3)
O1—C6	1.282 (3)	C10—H10	0.9300
O1—H1A	1.00	C11—H11	0.9300
O2—C6	1.260 (3)	C12—C13	1.525 (3)
O2—H2A	0.85	C12—H12A	0.9700
O3—C15	1.195 (3)	C12—H12B	0.9700
O4—C15	1.334 (3)	C13—C14	1.523 (3)
O4—C16	1.431 (4)	C13—H13A	0.9700
C1—C2	1.428 (3)	C13—H13B	0.9700
C1—C5	1.434 (3)	C14—C15	1.489 (4)
C1—C6	1.458 (3)	C14—H14A	0.9700
C2—C3	1.416 (3)	C14—H14B	0.9700
C2—H2	0.9300	C16—H16A	0.9600
C3—C4	1.420 (3)	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600
C4—C5	1.416 (3)
C1—Fe1—C5	41.27 (9)	C5—C4—H4	125.7
C1—Fe1—C2	41.09 (9)	C3—C4—H4	125.7
C5—Fe1—C2	69.21 (9)	Fe1—C4—H4	126.7
C1—Fe1—C8	122.12 (9)	C4—C5—C1	107.3 (2)
C5—Fe1—C8	158.19 (10)	C4—C5—Fe1	70.46 (13)
C2—Fe1—C8	107.47 (9)	C1—C5—Fe1	69.12 (12)
C1—Fe1—C9	157.65 (9)	C4—C5—H5	126.3
C5—Fe1—C9	159.65 (10)	C1—C5—H5	126.3
C2—Fe1—C9	121.55 (9)	Fe1—C5—H5	125.7
C8—Fe1—C9	40.56 (9)	O2—C6—O1	123.0 (2)
C1—Fe1—C11	124.29 (9)	O2—C6—C1	119.8 (2)
C5—Fe1—C11	107.70 (10)	O1—C6—C1	117.2 (2)
C2—Fe1—C11	160.92 (9)	C8—C7—C11	107.14 (19)
C8—Fe1—C11	68.00 (9)	C8—C7—C12	126.6 (2)
C9—Fe1—C11	67.92 (9)	C11—C7—C12	126.1 (2)
C1—Fe1—C10	160.63 (9)	C8—C7—Fe1	69.05 (12)
C5—Fe1—C10	123.44 (9)	C11—C7—Fe1	69.36 (12)
C2—Fe1—C10	156.85 (10)	C12—C7—Fe1	129.55 (16)
C8—Fe1—C10	68.15 (9)	C9—C8—C7	108.5 (2)
C9—Fe1—C10	40.35 (9)	C9—C8—Fe1	70.00 (12)
C11—Fe1—C10	40.56 (9)	C7—C8—Fe1	70.42 (12)
C1—Fe1—C4	68.35 (9)	C9—C8—H8	125.8
C5—Fe1—C4	40.47 (9)	C7—C8—H8	125.8
C2—Fe1—C4	68.24 (9)	Fe1—C8—H8	125.4
C8—Fe1—C4	160.04 (10)	C10—C9—C8	108.2 (2)
C9—Fe1—C4	123.70 (10)	C10—C9—Fe1	69.94 (13)
C11—Fe1—C4	122.40 (10)	C8—C9—Fe1	69.44 (13)
C10—Fe1—C4	107.67 (9)	C10—C9—H9	125.9
C1—Fe1—C7	107.82 (9)	C8—C9—H9	125.9
C5—Fe1—C7	122.30 (10)	Fe1—C9—H9	126.3
C2—Fe1—C7	124.08 (9)	C9—C10—C11	107.7 (2)
C8—Fe1—C7	40.53 (9)	C9—C10—Fe1	69.71 (13)
C9—Fe1—C7	68.19 (9)	C11—C10—Fe1	69.63 (12)
C11—Fe1—C7	40.51 (9)	C9—C10—H10	126.2
C10—Fe1—C7	68.32 (9)	C11—C10—H10	126.2
C4—Fe1—C7	157.97 (10)	Fe1—C10—H10	126.1
C1—Fe1—C3	68.28 (9)	C10—C11—C7	108.5 (2)
C5—Fe1—C3	68.36 (10)	C10—C11—Fe1	69.82 (12)
C2—Fe1—C3	40.38 (9)	C7—C11—Fe1	70.13 (12)
C8—Fe1—C3	123.92 (10)	C10—C11—H11	125.7
C9—Fe1—C3	107.65 (10)	C7—C11—H11	125.7
C11—Fe1—C3	157.55 (9)	Fe1—C11—H11	125.9
C10—Fe1—C3	121.80 (9)	C7—C12—C13	110.76 (19)
C4—Fe1—C3	40.33 (10)	C7—C12—H12A	109.5
C7—Fe1—C3	160.36 (9)	C13—C12—H12A	109.5
C6—O1—H1A	116	C7—C12—H12B	109.5
C6—O2—H2A	119	C13—C12—H12B	109.5
C15—O4—C16	116.1 (2)	H12A—C12—H12B	108.1
C2—C1—C5	108.0 (2)	C14—C13—C12	112.9 (2)
C2—C1—C6	125.7 (2)	C14—C13—H13A	109.0
C5—C1—C6	126.2 (2)	C12—C13—H13A	109.0
C2—C1—Fe1	69.78 (12)	C14—C13—H13B	109.0
C5—C1—Fe1	69.61 (12)	C12—C13—H13B	109.0
C6—C1—Fe1	122.92 (15)	H13A—C13—H13B	107.8
C3—C2—C1	107.8 (2)	C15—C14—C13	113.4 (2)
C3—C2—Fe1	70.68 (13)	C15—C14—H14A	108.9
C1—C2—Fe1	69.13 (12)	C13—C14—H14A	108.9
C3—C2—H2	126.1	C15—C14—H14B	108.9
C1—C2—H2	126.1	C13—C14—H14B	108.9
Fe1—C2—H2	125.6	H14A—C14—H14B	107.7
C2—C3—C4	108.2 (2)	O3—C15—O4	122.9 (3)
C2—C3—Fe1	68.94 (12)	O3—C15—C14	125.6 (3)
C4—C3—Fe1	69.58 (13)	O4—C15—C14	111.5 (2)
C2—C3—H3	125.9	O4—C16—H16A	109.5
C4—C3—H3	125.9	O4—C16—H16B	109.5
Fe1—C3—H3	127.2	H16A—C16—H16B	109.5
C5—C4—C3	108.7 (2)	O4—C16—H16C	109.5
C5—C4—Fe1	69.07 (12)	H16A—C16—H16C	109.5
C3—C4—Fe1	70.10 (12)	H16B—C16—H16C	109.5
C5—Fe1—C1—C2	119.22 (19)	C2—Fe1—C7—C8	76.49 (16)
C8—Fe1—C1—C2	−79.60 (15)	C9—Fe1—C7—C8	−37.69 (14)
C9—Fe1—C1—C2	−45.9 (3)	C11—Fe1—C7—C8	−118.78 (19)
C11—Fe1—C1—C2	−163.43 (13)	C10—Fe1—C7—C8	−81.28 (14)
C10—Fe1—C1—C2	163.0 (2)	C4—Fe1—C7—C8	−164.9 (2)
C4—Fe1—C1—C2	81.28 (14)	C3—Fe1—C7—C8	43.7 (3)
C7—Fe1—C1—C2	−121.80 (13)	C1—Fe1—C7—C11	−122.32 (14)
C3—Fe1—C1—C2	37.73 (13)	C5—Fe1—C7—C11	−79.27 (16)
C2—Fe1—C1—C5	−119.22 (19)	C2—Fe1—C7—C11	−164.73 (13)
C8—Fe1—C1—C5	161.18 (14)	C8—Fe1—C7—C11	118.78 (19)
C9—Fe1—C1—C5	−165.1 (2)	C9—Fe1—C7—C11	81.09 (14)
C11—Fe1—C1—C5	77.35 (16)	C10—Fe1—C7—C11	37.49 (14)
C10—Fe1—C1—C5	43.8 (3)	C4—Fe1—C7—C11	−46.1 (3)
C4—Fe1—C1—C5	−37.94 (14)	C3—Fe1—C7—C11	162.5 (3)
C7—Fe1—C1—C5	118.99 (14)	C1—Fe1—C7—C12	−1.9 (2)
C3—Fe1—C1—C5	−81.48 (15)	C5—Fe1—C7—C12	41.1 (3)
C5—Fe1—C1—C6	−120.7 (2)	C2—Fe1—C7—C12	−44.4 (3)
C2—Fe1—C1—C6	120.1 (2)	C8—Fe1—C7—C12	−120.8 (3)
C8—Fe1—C1—C6	40.5 (2)	C9—Fe1—C7—C12	−158.5 (2)
C9—Fe1—C1—C6	74.2 (3)	C11—Fe1—C7—C12	120.4 (3)
C11—Fe1—C1—C6	−43.3 (2)	C10—Fe1—C7—C12	157.9 (2)
C10—Fe1—C1—C6	−76.9 (3)	C4—Fe1—C7—C12	74.3 (3)
C4—Fe1—C1—C6	−158.6 (2)	C3—Fe1—C7—C12	−77.2 (4)
C7—Fe1—C1—C6	−1.7 (2)	C11—C7—C8—C9	0.8 (2)
C3—Fe1—C1—C6	157.8 (2)	C12—C7—C8—C9	−175.7 (2)
C5—C1—C2—C3	−1.1 (2)	Fe1—C7—C8—C9	59.89 (15)
C6—C1—C2—C3	−177.1 (2)	C11—C7—C8—Fe1	−59.13 (15)
Fe1—C1—C2—C3	−60.41 (15)	C12—C7—C8—Fe1	124.4 (2)
C5—C1—C2—Fe1	59.34 (15)	C1—Fe1—C8—C9	161.07 (13)
C6—C1—C2—Fe1	−116.7 (2)	C5—Fe1—C8—C9	−164.0 (2)
C1—Fe1—C2—C3	118.65 (18)	C2—Fe1—C8—C9	118.41 (14)
C5—Fe1—C2—C3	80.64 (15)	C11—Fe1—C8—C9	−81.30 (14)
C8—Fe1—C2—C3	−122.20 (14)	C10—Fe1—C8—C9	−37.42 (13)
C9—Fe1—C2—C3	−80.05 (16)	C4—Fe1—C8—C9	44.2 (3)
C11—Fe1—C2—C3	164.8 (3)	C7—Fe1—C8—C9	−119.18 (19)
C10—Fe1—C2—C3	−47.1 (3)	C3—Fe1—C8—C9	77.06 (16)
C4—Fe1—C2—C3	37.08 (14)	C1—Fe1—C8—C7	−79.74 (15)
C7—Fe1—C2—C3	−163.68 (14)	C5—Fe1—C8—C7	−44.8 (3)
C5—Fe1—C2—C1	−38.01 (13)	C2—Fe1—C8—C7	−122.40 (14)
C8—Fe1—C2—C1	119.15 (13)	C9—Fe1—C8—C7	119.18 (19)
C9—Fe1—C2—C1	161.30 (13)	C11—Fe1—C8—C7	37.89 (13)
C11—Fe1—C2—C1	46.1 (3)	C10—Fe1—C8—C7	81.76 (14)
C10—Fe1—C2—C1	−165.7 (2)	C4—Fe1—C8—C7	163.4 (2)
C4—Fe1—C2—C1	−81.57 (14)	C3—Fe1—C8—C7	−163.75 (13)
C7—Fe1—C2—C1	77.67 (15)	C7—C8—C9—C10	−0.7 (2)
C3—Fe1—C2—C1	−118.65 (18)	Fe1—C8—C9—C10	59.44 (15)
C1—C2—C3—C4	0.8 (2)	C7—C8—C9—Fe1	−60.15 (15)
Fe1—C2—C3—C4	−58.63 (15)	C1—Fe1—C9—C10	−165.7 (2)
C1—C2—C3—Fe1	59.43 (15)	C5—Fe1—C9—C10	43.5 (3)
C1—Fe1—C3—C2	−38.37 (13)	C2—Fe1—C9—C10	160.70 (13)
C5—Fe1—C3—C2	−82.95 (14)	C8—Fe1—C9—C10	−119.41 (19)
C8—Fe1—C3—C2	76.57 (16)	C11—Fe1—C9—C10	−37.92 (13)
C9—Fe1—C3—C2	118.26 (14)	C4—Fe1—C9—C10	77.20 (16)
C11—Fe1—C3—C2	−167.0 (2)	C7—Fe1—C9—C10	−81.75 (14)
C10—Fe1—C3—C2	160.21 (13)	C3—Fe1—C9—C10	118.66 (14)
C4—Fe1—C3—C2	−120.1 (2)	C1—Fe1—C9—C8	−46.2 (3)
C7—Fe1—C3—C2	43.8 (3)	C5—Fe1—C9—C8	162.9 (3)
C1—Fe1—C3—C4	81.70 (15)	C2—Fe1—C9—C8	−79.89 (16)
C5—Fe1—C3—C4	37.12 (14)	C11—Fe1—C9—C8	81.50 (14)
C2—Fe1—C3—C4	120.1 (2)	C10—Fe1—C9—C8	119.41 (19)
C8—Fe1—C3—C4	−163.35 (14)	C4—Fe1—C9—C8	−163.38 (14)
C9—Fe1—C3—C4	−121.67 (14)	C7—Fe1—C9—C8	37.66 (13)
C11—Fe1—C3—C4	−46.9 (3)	C3—Fe1—C9—C8	−121.93 (14)
C10—Fe1—C3—C4	−79.72 (16)	C8—C9—C10—C11	0.4 (2)
C7—Fe1—C3—C4	163.9 (2)	Fe1—C9—C10—C11	59.51 (15)
C2—C3—C4—C5	−0.2 (3)	C8—C9—C10—Fe1	−59.13 (15)
Fe1—C3—C4—C5	−58.45 (16)	C1—Fe1—C10—C9	163.5 (2)
C2—C3—C4—Fe1	58.24 (15)	C5—Fe1—C10—C9	−163.34 (14)
C1—Fe1—C4—C5	38.67 (14)	C2—Fe1—C10—C9	−45.8 (3)
C2—Fe1—C4—C5	83.05 (15)	C8—Fe1—C10—C9	37.61 (14)
C8—Fe1—C4—C5	164.3 (2)	C11—Fe1—C10—C9	118.85 (19)
C9—Fe1—C4—C5	−162.68 (14)	C4—Fe1—C10—C9	−121.63 (14)
C11—Fe1—C4—C5	−79.10 (16)	C7—Fe1—C10—C9	81.40 (14)
C10—Fe1—C4—C5	−121.18 (14)	C3—Fe1—C10—C9	−79.70 (16)
C7—Fe1—C4—C5	−45.4 (3)	C1—Fe1—C10—C11	44.6 (3)
C3—Fe1—C4—C5	120.2 (2)	C5—Fe1—C10—C11	77.80 (16)
C1—Fe1—C4—C3	−81.51 (15)	C2—Fe1—C10—C11	−164.6 (2)
C5—Fe1—C4—C3	−120.2 (2)	C8—Fe1—C10—C11	−81.25 (14)
C2—Fe1—C4—C3	−37.13 (14)	C9—Fe1—C10—C11	−118.85 (19)
C8—Fe1—C4—C3	44.1 (3)	C4—Fe1—C10—C11	119.52 (14)
C9—Fe1—C4—C3	77.13 (17)	C7—Fe1—C10—C11	−37.45 (13)
C11—Fe1—C4—C3	160.71 (14)	C3—Fe1—C10—C11	161.45 (13)
C10—Fe1—C4—C3	118.63 (14)	C9—C10—C11—C7	0.1 (2)
C7—Fe1—C4—C3	−165.6 (2)	Fe1—C10—C11—C7	59.65 (15)
C3—C4—C5—C1	−0.5 (3)	C9—C10—C11—Fe1	−59.56 (15)
Fe1—C4—C5—C1	−59.53 (15)	C8—C7—C11—C10	−0.5 (2)
C3—C4—C5—Fe1	59.08 (15)	C12—C7—C11—C10	176.0 (2)
C2—C1—C5—C4	0.9 (2)	Fe1—C7—C11—C10	−59.46 (15)
C6—C1—C5—C4	176.9 (2)	C8—C7—C11—Fe1	58.93 (15)
Fe1—C1—C5—C4	60.38 (15)	C12—C7—C11—Fe1	−124.6 (2)
C2—C1—C5—Fe1	−59.45 (15)	C1—Fe1—C11—C10	−163.62 (13)
C6—C1—C5—Fe1	116.5 (2)	C5—Fe1—C11—C10	−121.11 (14)
C1—Fe1—C5—C4	−118.3 (2)	C2—Fe1—C11—C10	161.4 (2)
C2—Fe1—C5—C4	−80.45 (15)	C8—Fe1—C11—C10	81.65 (14)
C8—Fe1—C5—C4	−165.6 (2)	C9—Fe1—C11—C10	37.73 (13)
C9—Fe1—C5—C4	45.4 (3)	C4—Fe1—C11—C10	−79.13 (16)
C11—Fe1—C5—C4	119.51 (15)	C7—Fe1—C11—C10	119.55 (19)
C10—Fe1—C5—C4	77.66 (17)	C3—Fe1—C11—C10	−45.1 (3)
C7—Fe1—C5—C4	161.57 (14)	C1—Fe1—C11—C7	76.84 (16)
C3—Fe1—C5—C4	−37.00 (14)	C5—Fe1—C11—C7	119.34 (14)
C2—Fe1—C5—C1	37.84 (13)	C2—Fe1—C11—C7	41.9 (3)
C8—Fe1—C5—C1	−47.3 (3)	C8—Fe1—C11—C7	−37.90 (14)
C9—Fe1—C5—C1	163.7 (2)	C9—Fe1—C11—C7	−81.82 (15)
C11—Fe1—C5—C1	−122.20 (14)	C10—Fe1—C11—C7	−119.55 (19)
C10—Fe1—C5—C1	−164.04 (13)	C4—Fe1—C11—C7	161.33 (14)
C4—Fe1—C5—C1	118.3 (2)	C3—Fe1—C11—C7	−164.6 (2)
C7—Fe1—C5—C1	−80.13 (16)	C8—C7—C12—C13	94.9 (3)
C3—Fe1—C5—C1	81.30 (14)	C11—C7—C12—C13	−80.9 (3)
C2—C1—C6—O2	179.5 (2)	Fe1—C7—C12—C13	−173.03 (17)
C5—C1—C6—O2	4.2 (3)	C7—C12—C13—C14	177.7 (2)
Fe1—C1—C6—O2	91.9 (2)	C12—C13—C14—C15	69.5 (3)
C2—C1—C6—O1	−0.7 (3)	C16—O4—C15—O3	−0.3 (4)
C5—C1—C6—O1	−175.9 (2)	C16—O4—C15—C14	−178.7 (2)
Fe1—C1—C6—O1	−88.2 (2)	C13—C14—C15—O3	35.4 (4)
C1—Fe1—C7—C8	118.90 (14)	C13—C14—C15—O4	−146.3 (2)
C5—Fe1—C7—C8	161.95 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2^i	1.0014	1.6501	2.650 (3)	176
O2—H2A···O1^i	0.8501	1.7997	2.650 (3)	180

Symmetry code: (i) −x+2, −y+1, −z.