Concomitant dimorphism in poly[di-μ-azido-(5,5′-dimethyl-2,2′-bi­pyridine)­iron(II)]

Setifi, Z.; Bernès, S.; Geiger, D.K.; Setifi, F.; Reedijk, J.

doi:10.1107/S2053229622006908

Concomitant dimorphism in poly[di-μ-azido-(5,5′-dimethyl-2,2′-bipyridine)iron(II)]

Z. Setifi, S. Bernès, D. K. Geiger, F. Setifi and J. Reedijk

The title metal–organic polymer, catena-poly[[(5,5′-dimethyl-2,2′-bipyridine-κ²N,N′)iron(II)]-di-μ-azido-κ²N¹:N³-[(5,5′-dimethyl-2,2′-bipyridine-κ²N,N′)iron(II)]-di-μ-azido-κ²N¹:N¹], [Fe(N₃)₂(C₁₂H₁₂N₂)]_n, features alternating μ-1,1 (end-on mode of coordination) and μ-1,3 (end-to-end mode of coordination) double azide bridges, forming chains running in the [100] direction. The octahedral coordination geometry around the Fe^II centre is completed by a bidentate 5,5′-dimethyl-2,2′-bipyridine ligand. Two polymorphs for this compound were obtained from the crude reaction product, the first in the space group P $\overline{1}$ and the other in P2₁/c. The molecular and crystal structures are very similar for both forms, the main difference being that the eight-membered Fe(μ-1,3-N₃)₂Fe metallacycle formed with end-to-end azide ligands has a nearly flat conformation in the triclinic form and a chair conformation in the monoclinic form. In spite of this geometric difference, both forms have the same density, the same packing index and similar arrangements of the one-dimensional chains in the crystal. As a consequence, they also share very similar Hirshfeld surfaces and fingerprint plots. However, a density functional theory (DFT) computational study showed that the monoclinic form is more stable than the triclinic form by ca 30.5 kJ mol⁻¹.

Keywords: concomitant polymorphs; inorganic polymer; azide bridge; concomitant crystallization; crystal structure; DFT.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229622006908/dg3032sup1.cif Contains datablocks I, II, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622006908/dg3032Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622006908/dg3032IIsup3.hkl Contains datablock II

CCDC references: 2184384; 2184383

Computing details top

For both structures, data collection: APEX2 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

catena-Poly[[(5,5'-dimethyl-2,2'-bipyridine-κ²N,N')iron(II)]-di-µ-azido-κ²N¹:N³-[(5,5'-dimethyl-2,2'-bipyridine-κ²N,N')iron(II)]-di-µ-azido-κ²N¹:N¹] (I) top

Crystal data top

[Fe(N₃)₂(C₁₂H₁₂N₂)]	Z = 2
M_r = 324.15	F(000) = 332
Triclinic, P1	D_x = 1.573 Mg m⁻³
a = 7.7235 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4051 (7) Å	Cell parameters from 9616 reflections
c = 10.5846 (9) Å	θ = 2.4–32.7°
α = 112.585 (3)°	µ = 1.11 mm⁻¹
β = 102.828 (4)°	T = 298 K
γ = 92.852 (3)°	Prism, red
V = 684.36 (10) Å³	0.39 × 0.21 × 0.13 mm

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	5184 independent reflections
Radiation source: sealed tube	3821 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.063
ω and φ scans	θ_max = 33.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −11→11
T_min = 0.847, T_max = 0.909	k = −14→14
54520 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0368P)² + 0.6298P] where P = (F_o² + 2F_c²)/3
5184 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 1.12 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.31470 (4)	0.39201 (4)	0.49060 (4)	0.03489 (10)
C1	0.0681 (3)	0.0841 (3)	0.2645 (3)	0.0426 (5)
H1	0.036695	0.146193	0.215216	0.051*
C2	−0.0163 (3)	−0.0688 (3)	0.2040 (3)	0.0455 (5)
C3	0.0307 (4)	−0.1575 (3)	0.2817 (3)	0.0498 (6)
H3	−0.023499	−0.260461	0.246505	0.060*
C4	0.1573 (4)	−0.0938 (3)	0.4105 (3)	0.0451 (5)
H4	0.188731	−0.153397	0.462327	0.054*
C5	0.2378 (3)	0.0602 (2)	0.4625 (2)	0.0346 (4)
C6	0.3736 (3)	0.1392 (2)	0.6000 (2)	0.0341 (4)
C7	0.4279 (4)	0.0690 (3)	0.6934 (3)	0.0439 (5)
H7	0.381975	−0.034011	0.669038	0.053*
C8	0.5500 (4)	0.1528 (3)	0.8220 (3)	0.0459 (5)
H8	0.585076	0.106822	0.885449	0.055*
C9	0.6205 (3)	0.3055 (3)	0.8572 (3)	0.0411 (5)
C10	0.5618 (3)	0.3660 (3)	0.7570 (2)	0.0378 (4)
H10	0.609093	0.467815	0.777970	0.045*
C11	−0.1515 (4)	−0.1316 (4)	0.0621 (3)	0.0621 (8)
H11A	−0.096083	−0.191935	−0.009813	0.093*
H11B	−0.194391	−0.046578	0.041765	0.093*
H11C	−0.250433	−0.196310	0.063597	0.093*
C12	0.7525 (5)	0.4028 (4)	0.9964 (3)	0.0614 (7)
H12A	0.689529	0.463788	1.062202	0.092*
H12B	0.836432	0.470794	0.982755	0.092*
H12C	0.815996	0.336070	1.033418	0.092*
N1	0.1920 (2)	0.1485 (2)	0.3892 (2)	0.0356 (4)
N2	0.4419 (2)	0.2876 (2)	0.6327 (2)	0.0342 (4)
N3	0.1346 (3)	0.4453 (3)	0.3358 (2)	0.0483 (5)
N4	0.0055 (2)	0.5004 (2)	0.35759 (19)	0.0323 (3)
N5	−0.1213 (3)	0.5572 (3)	0.3744 (3)	0.0517 (6)
N6	0.4691 (3)	0.6197 (2)	0.6137 (2)	0.0401 (4)
N7	0.4462 (3)	0.7108 (2)	0.7213 (2)	0.0415 (4)
N8	0.4226 (5)	0.7980 (3)	0.8239 (3)	0.0795 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.03320 (16)	0.03699 (16)	0.04092 (18)	0.00862 (11)	0.01261 (12)	0.02063 (13)
C1	0.0423 (12)	0.0474 (12)	0.0398 (12)	0.0055 (10)	0.0105 (10)	0.0198 (10)
C2	0.0417 (12)	0.0511 (13)	0.0401 (12)	0.0001 (10)	0.0141 (10)	0.0136 (10)
C3	0.0554 (15)	0.0424 (12)	0.0475 (14)	−0.0063 (11)	0.0169 (12)	0.0138 (11)
C4	0.0534 (14)	0.0398 (11)	0.0473 (13)	0.0019 (10)	0.0175 (11)	0.0215 (10)
C5	0.0349 (10)	0.0365 (10)	0.0389 (11)	0.0068 (8)	0.0165 (8)	0.0184 (9)
C6	0.0342 (9)	0.0358 (10)	0.0401 (11)	0.0097 (8)	0.0164 (8)	0.0197 (9)
C7	0.0511 (13)	0.0421 (12)	0.0474 (13)	0.0063 (10)	0.0145 (11)	0.0267 (11)
C8	0.0509 (13)	0.0535 (14)	0.0448 (13)	0.0112 (11)	0.0134 (11)	0.0310 (12)
C9	0.0377 (11)	0.0506 (13)	0.0393 (11)	0.0094 (9)	0.0118 (9)	0.0217 (10)
C10	0.0364 (10)	0.0388 (10)	0.0409 (11)	0.0061 (8)	0.0101 (9)	0.0189 (9)
C11	0.0598 (17)	0.0673 (18)	0.0447 (15)	−0.0069 (14)	0.0055 (13)	0.0140 (14)
C12	0.0635 (18)	0.0697 (19)	0.0460 (15)	0.0009 (15)	0.0016 (13)	0.0264 (14)
N1	0.0343 (8)	0.0379 (9)	0.0378 (9)	0.0045 (7)	0.0119 (7)	0.0175 (8)
N2	0.0328 (8)	0.0369 (9)	0.0382 (9)	0.0093 (7)	0.0119 (7)	0.0189 (7)
N3	0.0450 (11)	0.0686 (14)	0.0501 (12)	0.0272 (10)	0.0212 (10)	0.0369 (11)
N4	0.0334 (8)	0.0370 (8)	0.0315 (8)	0.0041 (7)	0.0091 (7)	0.0192 (7)
N5	0.0440 (11)	0.0795 (16)	0.0560 (13)	0.0290 (11)	0.0266 (10)	0.0436 (13)
N6	0.0406 (10)	0.0359 (9)	0.0481 (11)	0.0065 (7)	0.0231 (9)	0.0154 (8)
N7	0.0560 (12)	0.0329 (9)	0.0431 (11)	0.0089 (8)	0.0196 (9)	0.0196 (8)
N8	0.136 (3)	0.0480 (14)	0.0575 (16)	0.0098 (16)	0.0505 (19)	0.0119 (12)

Geometric parameters (Å, º) top

Fe1—N3	2.135 (2)	C7—C8	1.377 (4)
Fe1—N6	2.149 (2)	C7—H7	0.9300
Fe1—N1	2.1770 (19)	C8—C9	1.385 (4)
Fe1—N6ⁱ	2.1825 (19)	C8—H8	0.9300
Fe1—N2	2.1832 (18)	C9—C10	1.390 (3)
Fe1—N5ⁱⁱ	2.235 (2)	C9—C12	1.501 (4)
C1—N1	1.338 (3)	C10—N2	1.333 (3)
C1—C2	1.384 (4)	C10—H10	0.9300
C1—H1	0.9300	C11—H11A	0.9600
C2—C3	1.389 (4)	C11—H11B	0.9600
C2—C11	1.502 (4)	C11—H11C	0.9600
C3—C4	1.377 (4)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.391 (3)	C12—H12C	0.9600
C4—H4	0.9300	N3—N4	1.174 (3)
C5—N1	1.349 (3)	N4—N5	1.154 (3)
C5—C6	1.478 (3)	N6—N7	1.190 (3)
C6—N2	1.350 (3)	N7—N8	1.142 (3)
C6—C7	1.390 (3)

N3—Fe1—N6	98.41 (9)	C6—C7—H7	120.2
N3—Fe1—N1	91.43 (9)	C7—C8—C9	120.1 (2)
N6—Fe1—N1	170.10 (8)	C7—C8—H8	119.9
N3—Fe1—N6ⁱ	92.55 (8)	C9—C8—H8	119.9
N6—Fe1—N6ⁱ	78.72 (8)	C8—C9—C10	116.6 (2)
N1—Fe1—N6ⁱ	99.84 (7)	C8—C9—C12	122.4 (2)
N3—Fe1—N2	164.94 (8)	C10—C9—C12	121.0 (2)
N6—Fe1—N2	95.43 (8)	N2—C10—C9	124.2 (2)
N1—Fe1—N2	74.91 (7)	N2—C10—H10	117.9
N6ⁱ—Fe1—N2	95.97 (7)	C9—C10—H10	117.9
N3—Fe1—N5ⁱⁱ	90.37 (8)	C2—C11—H11A	109.5
N6—Fe1—N5ⁱⁱ	91.51 (9)	C2—C11—H11B	109.5
N1—Fe1—N5ⁱⁱ	89.53 (9)	H11A—C11—H11B	109.5
N6ⁱ—Fe1—N5ⁱⁱ	170.11 (9)	C2—C11—H11C	109.5
N2—Fe1—N5ⁱⁱ	83.33 (7)	H11A—C11—H11C	109.5
N1—C1—C2	124.4 (2)	H11B—C11—H11C	109.5
N1—C1—H1	117.8	C9—C12—H12A	109.5
C2—C1—H1	117.8	C9—C12—H12B	109.5
C1—C2—C3	116.4 (2)	H12A—C12—H12B	109.5
C1—C2—C11	120.6 (3)	C9—C12—H12C	109.5
C3—C2—C11	123.0 (3)	H12A—C12—H12C	109.5
C4—C3—C2	120.3 (2)	H12B—C12—H12C	109.5
C4—C3—H3	119.8	C1—N1—C5	118.4 (2)
C2—C3—H3	119.8	C1—N1—Fe1	124.67 (16)
C3—C4—C5	119.6 (2)	C5—N1—Fe1	116.77 (15)
C3—C4—H4	120.2	C10—N2—C6	118.59 (19)
C5—C4—H4	120.2	C10—N2—Fe1	124.46 (15)
N1—C5—C4	120.8 (2)	C6—N2—Fe1	116.22 (15)
N1—C5—C6	115.63 (19)	N4—N3—Fe1	121.79 (17)
C4—C5—C6	123.5 (2)	N5—N4—N3	176.9 (2)
N2—C6—C7	120.8 (2)	N4—N5—Fe1ⁱⁱ	143.68 (18)
N2—C6—C5	115.89 (18)	N7—N6—Fe1	124.80 (16)
C7—C6—C5	123.3 (2)	N7—N6—Fe1ⁱ	133.05 (17)
C8—C7—C6	119.7 (2)	Fe1—N6—Fe1ⁱ	101.28 (8)
C8—C7—H7	120.2	N8—N7—N6	179.4 (3)

N1—C1—C2—C3	1.3 (4)	C7—C8—C9—C12	179.4 (3)
N1—C1—C2—C11	−178.9 (2)	C8—C9—C10—N2	1.0 (4)
C1—C2—C3—C4	−1.0 (4)	C12—C9—C10—N2	−178.4 (2)
C11—C2—C3—C4	179.2 (3)	C2—C1—N1—C5	−0.6 (4)
C2—C3—C4—C5	0.1 (4)	C2—C1—N1—Fe1	−176.49 (18)
C3—C4—C5—N1	0.8 (4)	C4—C5—N1—C1	−0.5 (3)
C3—C4—C5—C6	179.4 (2)	C6—C5—N1—C1	−179.29 (19)
N1—C5—C6—N2	−3.1 (3)	C4—C5—N1—Fe1	175.71 (17)
C4—C5—C6—N2	178.2 (2)	C6—C5—N1—Fe1	−3.1 (2)
N1—C5—C6—C7	175.7 (2)	C9—C10—N2—C6	−0.8 (3)
C4—C5—C6—C7	−3.0 (3)	C9—C10—N2—Fe1	169.09 (17)
N2—C6—C7—C8	1.4 (4)	C7—C6—N2—C10	−0.5 (3)
C5—C6—C7—C8	−177.4 (2)	C5—C6—N2—C10	178.38 (19)
C6—C7—C8—C9	−1.1 (4)	C7—C6—N2—Fe1	−171.17 (17)
C7—C8—C9—C10	−0.1 (4)	C5—C6—N2—Fe1	7.7 (2)

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

catena-Poly[[(5,5'-dimethyl-2,2'-bipyridine-κ²N,N')iron(II)]-di-µ-azido-κ²N¹:N³-[(5,5'-dimethyl-2,2'-bipyridine-κ²N,N')iron(II)]-di-µ-azido-κ²N¹:N¹] (II) top

Crystal data top

[Fe(N₃)₂(C₁₂H₁₂N₂)]	F(000) = 664
M_r = 324.15	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4901 (2) Å	Cell parameters from 9954 reflections
b = 18.3242 (5) Å	θ = 2.3–32.0°
c = 10.6219 (3) Å	µ = 1.11 mm⁻¹
β = 110.017 (1)°	T = 298 K
V = 1369.79 (7) Å³	Needle, red
Z = 4	0.48 × 0.25 × 0.11 mm

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	5235 independent reflections
Radiation source: sealed tube	3944 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.051
ω and φ scans	θ_max = 33.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −11→11
T_min = 0.768, T_max = 0.946	k = −28→28
59826 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0352P)² + 0.4096P] where P = (F_o² + 2F_c²)/3
5235 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.72559 (3)	0.98811 (2)	0.10470 (2)	0.03060 (6)
C1	0.9324 (2)	0.85425 (8)	0.27457 (15)	0.0365 (3)
H1	0.950823	0.840841	0.195475	0.044*
C2	1.0006 (2)	0.80795 (9)	0.38451 (16)	0.0416 (3)
C3	0.9682 (2)	0.82909 (10)	0.49945 (16)	0.0468 (4)
H3	1.007877	0.799138	0.574648	0.056*
C4	0.8777 (2)	0.89406 (10)	0.50440 (15)	0.0423 (4)
H4	0.858581	0.908477	0.582771	0.051*
C5	0.81549 (19)	0.93765 (9)	0.39050 (13)	0.0323 (3)
C6	0.7200 (2)	1.00889 (8)	0.38550 (13)	0.0324 (3)
C7	0.6869 (2)	1.04041 (10)	0.49472 (15)	0.0395 (3)
H7	0.728727	1.017411	0.577785	0.047*
C8	0.5921 (2)	1.10573 (10)	0.47870 (17)	0.0438 (4)
H8	0.568329	1.126733	0.551090	0.053*
C9	0.5316 (2)	1.14062 (10)	0.35559 (17)	0.0413 (3)
C10	0.5745 (2)	1.10657 (9)	0.25239 (15)	0.0380 (3)
H10	0.538119	1.129619	0.169423	0.046*
C11	1.1088 (3)	0.73995 (11)	0.3770 (2)	0.0599 (5)
H11A	1.174306	0.722134	0.465895	0.090*
H11B	1.199238	0.750901	0.333903	0.090*
H11C	1.021839	0.703398	0.326463	0.090*
C12	0.4240 (3)	1.21139 (11)	0.3304 (2)	0.0612 (5)
H12A	0.300820	1.204140	0.263878	0.092*
H12B	0.492598	1.247195	0.299201	0.092*
H12C	0.409648	1.228076	0.412123	0.092*
N1	0.84183 (16)	0.91686 (7)	0.27619 (11)	0.0321 (2)
N2	0.66459 (16)	1.04288 (7)	0.26560 (11)	0.0326 (2)
N3	0.8213 (2)	0.92024 (8)	−0.02225 (14)	0.0436 (3)
N4	0.91373 (16)	0.93544 (7)	−0.08793 (12)	0.0316 (2)
N5	1.0032 (2)	0.94771 (8)	−0.15657 (14)	0.0453 (3)
N6	0.56138 (18)	1.06440 (7)	−0.04290 (12)	0.0362 (3)
N7	0.61896 (18)	1.09552 (7)	−0.12009 (12)	0.0363 (3)
N8	0.6717 (3)	1.12661 (12)	−0.19359 (18)	0.0690 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.03131 (10)	0.03888 (12)	0.02221 (9)	0.00153 (8)	0.00992 (7)	0.00392 (7)
C1	0.0388 (7)	0.0382 (8)	0.0291 (6)	−0.0016 (6)	0.0073 (6)	0.0018 (5)
C2	0.0408 (8)	0.0375 (8)	0.0384 (8)	−0.0052 (6)	0.0032 (6)	0.0063 (6)
C3	0.0480 (9)	0.0526 (10)	0.0339 (8)	−0.0045 (8)	0.0064 (7)	0.0160 (7)
C4	0.0418 (8)	0.0572 (10)	0.0271 (7)	−0.0052 (7)	0.0110 (6)	0.0088 (6)
C5	0.0290 (6)	0.0436 (8)	0.0235 (6)	−0.0076 (5)	0.0080 (5)	0.0027 (5)
C6	0.0279 (6)	0.0439 (8)	0.0256 (6)	−0.0085 (5)	0.0098 (5)	−0.0007 (5)
C7	0.0402 (7)	0.0534 (9)	0.0280 (7)	−0.0116 (7)	0.0156 (6)	−0.0046 (6)
C8	0.0418 (8)	0.0559 (10)	0.0395 (8)	−0.0116 (7)	0.0213 (7)	−0.0134 (7)
C9	0.0342 (7)	0.0462 (9)	0.0450 (9)	−0.0059 (6)	0.0152 (6)	−0.0100 (7)
C10	0.0355 (7)	0.0436 (8)	0.0333 (7)	−0.0012 (6)	0.0099 (6)	−0.0005 (6)
C11	0.0698 (13)	0.0429 (10)	0.0528 (11)	0.0092 (9)	0.0029 (9)	0.0057 (8)
C12	0.0604 (12)	0.0546 (12)	0.0715 (14)	0.0070 (9)	0.0264 (10)	−0.0089 (10)
N1	0.0320 (5)	0.0385 (6)	0.0243 (5)	−0.0023 (5)	0.0076 (4)	0.0029 (4)
N2	0.0307 (5)	0.0417 (7)	0.0252 (5)	−0.0022 (5)	0.0091 (4)	0.0000 (5)
N3	0.0457 (7)	0.0531 (8)	0.0376 (7)	−0.0048 (6)	0.0215 (6)	−0.0067 (6)
N4	0.0309 (5)	0.0334 (6)	0.0290 (5)	−0.0015 (4)	0.0083 (4)	−0.0056 (4)
N5	0.0475 (7)	0.0525 (9)	0.0418 (7)	−0.0108 (6)	0.0231 (6)	−0.0071 (6)
N6	0.0354 (6)	0.0448 (7)	0.0277 (5)	−0.0012 (5)	0.0097 (5)	0.0081 (5)
N7	0.0365 (6)	0.0429 (7)	0.0291 (6)	0.0003 (5)	0.0107 (5)	0.0050 (5)
N8	0.0703 (11)	0.0911 (14)	0.0542 (10)	−0.0058 (10)	0.0323 (9)	0.0258 (10)

Geometric parameters (Å, º) top

Fe1—N3	2.1308 (14)	C7—C8	1.372 (3)
Fe1—N6	2.1459 (12)	C7—H7	0.9300
Fe1—N2	2.1614 (12)	C8—C9	1.385 (3)
Fe1—N1	2.1668 (12)	C8—H8	0.9300
Fe1—N6ⁱ	2.2385 (13)	C9—C10	1.391 (2)
Fe1—N5ⁱⁱ	2.2465 (14)	C9—C12	1.502 (3)
C1—N1	1.336 (2)	C10—N2	1.331 (2)
C1—C2	1.391 (2)	C10—H10	0.9300
C1—H1	0.9300	C11—H11A	0.9600
C2—C3	1.379 (2)	C11—H11B	0.9600
C2—C11	1.503 (3)	C11—H11C	0.9600
C3—C4	1.380 (3)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.390 (2)	C12—H12C	0.9600
C4—H4	0.9300	N3—N4	1.1723 (17)
C5—N1	1.3498 (18)	N4—N5	1.1687 (17)
C5—C6	1.481 (2)	N6—N7	1.1939 (17)
C6—N2	1.3493 (18)	N7—N8	1.1406 (19)
C6—C7	1.392 (2)

N3—Fe1—N6	98.67 (5)	C6—C7—H7	120.3
N3—Fe1—N2	168.34 (5)	C7—C8—C9	120.53 (15)
N6—Fe1—N2	92.97 (5)	C7—C8—H8	119.7
N3—Fe1—N1	93.15 (5)	C9—C8—H8	119.7
N6—Fe1—N1	166.31 (5)	C8—C9—C10	116.59 (16)
N2—Fe1—N1	75.40 (5)	C8—C9—C12	123.29 (16)
N3—Fe1—N6ⁱ	93.49 (5)	C10—C9—C12	120.11 (17)
N6—Fe1—N6ⁱ	79.23 (5)	N2—C10—C9	123.75 (15)
N2—Fe1—N6ⁱ	89.42 (5)	N2—C10—H10	118.1
N1—Fe1—N6ⁱ	93.25 (4)	C9—C10—H10	118.1
N3—Fe1—N5ⁱⁱ	89.36 (5)	C2—C11—H11A	109.5
N6—Fe1—N5ⁱⁱ	94.71 (5)	C2—C11—H11B	109.5
N2—Fe1—N5ⁱⁱ	88.92 (5)	H11A—C11—H11B	109.5
N1—Fe1—N5ⁱⁱ	92.28 (5)	C2—C11—H11C	109.5
N6ⁱ—Fe1—N5ⁱⁱ	173.62 (5)	H11A—C11—H11C	109.5
N1—C1—C2	123.72 (15)	H11B—C11—H11C	109.5
N1—C1—H1	118.1	C9—C12—H12A	109.5
C2—C1—H1	118.1	C9—C12—H12B	109.5
C3—C2—C1	116.51 (16)	H12A—C12—H12B	109.5
C3—C2—C11	122.75 (16)	C9—C12—H12C	109.5
C1—C2—C11	120.72 (16)	H12A—C12—H12C	109.5
C2—C3—C4	120.90 (15)	H12B—C12—H12C	109.5
C2—C3—H3	119.6	C1—N1—C5	119.02 (12)
C4—C3—H3	119.6	C1—N1—Fe1	124.50 (10)
C3—C4—C5	119.03 (15)	C5—N1—Fe1	116.47 (10)
C3—C4—H4	120.5	C10—N2—C6	119.03 (13)
C5—C4—H4	120.5	C10—N2—Fe1	124.09 (10)
N1—C5—C4	120.79 (15)	C6—N2—Fe1	116.87 (10)
N1—C5—C6	115.73 (12)	N4—N3—Fe1	129.28 (12)
C4—C5—C6	123.47 (14)	N5—N4—N3	176.96 (16)
N2—C6—C7	120.68 (15)	N4—N5—Fe1ⁱⁱ	127.68 (11)
N2—C6—C5	115.44 (12)	N7—N6—Fe1	124.15 (10)
C7—C6—C5	123.89 (13)	N7—N6—Fe1ⁱ	122.70 (10)
C8—C7—C6	119.39 (15)	Fe1—N6—Fe1ⁱ	100.77 (5)
C8—C7—H7	120.3	N8—N7—N6	178.44 (19)

N1—C1—C2—C3	0.9 (2)	C7—C8—C9—C12	178.80 (16)
N1—C1—C2—C11	−177.29 (15)	C8—C9—C10—N2	1.6 (2)
C1—C2—C3—C4	−1.9 (2)	C12—C9—C10—N2	−178.08 (15)
C11—C2—C3—C4	176.25 (17)	C2—C1—N1—C5	0.7 (2)
C2—C3—C4—C5	1.3 (2)	C2—C1—N1—Fe1	−177.78 (11)
C3—C4—C5—N1	0.4 (2)	C4—C5—N1—C1	−1.4 (2)
C3—C4—C5—C6	−178.88 (14)	C6—C5—N1—C1	177.94 (12)
N1—C5—C6—N2	2.45 (18)	C4—C5—N1—Fe1	177.26 (11)
C4—C5—C6—N2	−178.27 (13)	C6—C5—N1—Fe1	−3.44 (15)
N1—C5—C6—C7	−177.60 (13)	C9—C10—N2—C6	−0.6 (2)
C4—C5—C6—C7	1.7 (2)	C9—C10—N2—Fe1	178.34 (11)
N2—C6—C7—C8	1.9 (2)	C7—C6—N2—C10	−1.2 (2)
C5—C6—C7—C8	−178.07 (14)	C5—C6—N2—C10	178.74 (12)
C6—C7—C8—C9	−0.8 (2)	C7—C6—N2—Fe1	179.78 (10)
C7—C8—C9—C10	−0.9 (2)	C5—C6—N2—Fe1	−0.26 (15)

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

Calculated ground-state energies (Hartrees) for the dianion [M₂(N₃)₆(dmbpy)₂]^2-, with M = Fe^II, Co^II and Mn^II, considering high-spin (HS) and low-spin (LS) metal configurations, and space groups P1 and P2₁/c for the crystal structures. top

Compound^a	Fe^II/HS	Fe^II/LS	Co^II/HS	Co^II/LS	Mn^II/HS	Mn^II/LS
Unpaired electrons^b	8	0	6	2	10	2
E(P1)	-4659.709754	-4659.557172	-4897.742353	-4897.635987	-4434.408852	-4434.184707
E(P2₁/c)	-4659.721369	-4659.569654	-4897.747558	-4897.653790	-4434.414746	-4434.196997
Δ (Hartrees)^c	0.011615	0.012482	0.005205	0.017803	0.005894	0.012290
Δ (kJ mol^-1)^c	30.50	32.77	13.67	46.74	15.47	32.27

Notes: (a) HS = high-spin electronic ground state for M and LS = low-spin electronic ground state for M. (b) The number of unpaired electrons is given for a couple of metals in the dianion. (c) Δ = E(P1) - E(P2₁/c).

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Concomitant dimorphism in poly[di-μ-azido-(5,5′-dimethyl-2,2′-bi­pyridine)­iron(II)]

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Concomitant dimorphism in poly[di-μ-azido-(5,5′-dimethyl-2,2′-bipyridine)iron(II)]