A cyano-bridged trimeric complex [Mn(CH₃OH)₂(H₂O)₂][Fe(bpb)(CN)₂]₂·2H₂O [bpb²⁻ is 1,2-bis­(pyridine-2-carbox­amido)­benzenate]

The structure of the title complex, di­aqua­di-μ-cyano-di­cyano­di­methano­lbis­[N,N′-o-phenyl­enebis­(pyridine-2-carboxamidato)]­diiron(III)­manganese(II), [MnFe₂(C₁₈H₁₂N₄O₂)₂(CN)₄(CH₄O)₂(H₂O)₂]·2H₂O, consists of neutral centrosymmetric [Mn(CH₃OH)₂(H₂O)₂][Fe(bpb)(CN)₂]₂ heterotrinuclear units [bpb²⁻ = 1,2-bis­(pyridine-2-carbox­amido)­benzene(2−)] and water mol­ecules of crystallization. Each [Fe(bpb)(CN)₂]⁻ unit acts as a monodentate ligand through one of its two cyanide groups toward the central Mn^II ion (site symmetry ) in a bent fashion [C—N—Mn = 159.7 (2)°].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.112
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Fe     -   C1      ..       8.19 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Fe     -   C2      ..       7.37 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Mn
PLAT417_ALERT_2_C Short Inter D-H..H-D       H101   ..  H200    ..       2.12 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

diaquadi-µ-cyano-dicyanodimethanolbis[N,N'-o-phenylenebis(pyridine-2- carboxamidato)]diiron(III)manganese(II)

Crystal data

[MnFe2(C18H12N4O2)2(CN)4(CH4O)2(H2O)2]·2H2O	F(000) = 1066
Mr = 1039.50	Dx = 1.530 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1748 reflections
a = 14.011 (3) Å	θ = 2.4–22.5°
b = 13.247 (2) Å	µ = 0.98 mm^−1
c = 12.701 (2) Å	T = 293 K
β = 106.834 (15)°	Block, black
V = 2256.5 (7) Å^3	0.25 × 0.18 × 0.14 mm
Z = 2

Data collection

Bruker P4 diffractometer	3403 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scans	h = −16→15
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.820, Tmax = 0.873	l = 0→15
4141 measured reflections	3 standard reflections every 97 reflections
3946 independent reflections	intensity decay: none

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0744P)^2 + 0.0733P] where P = (Fo^2 + 2Fc^2)/3
3946 reflections	(Δ/σ)max = 0.001
309 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.21 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
Fe	0.28637 (2)	−0.03256 (2)	−0.18282 (2)	0.03453 (14)
Mn	0.0000	0.0000	0.0000	0.03942 (16)
N4	0.24410 (13)	−0.14078 (14)	−0.28319 (14)	0.0370 (4)
O3	0.04077 (13)	−0.12894 (13)	0.11344 (15)	0.0558 (4)
N6	0.31078 (14)	0.10163 (15)	−0.10736 (15)	0.0419 (4)
O1	0.23597 (13)	−0.31516 (13)	−0.29967 (15)	0.0542 (4)
N3	0.34675 (13)	−0.14619 (14)	−0.08076 (15)	0.0393 (4)
C8	0.26397 (16)	−0.23527 (17)	−0.24722 (18)	0.0406 (5)
N5	0.21793 (13)	0.04772 (14)	−0.30355 (15)	0.0404 (4)
C2	0.41410 (17)	−0.01955 (17)	−0.21723 (19)	0.0427 (5)
O1W	−0.12003 (13)	−0.08808 (13)	−0.11021 (16)	0.0617 (5)
C1	0.17174 (17)	−0.04431 (16)	−0.12377 (19)	0.0405 (5)
C7	0.32593 (16)	−0.23769 (18)	−0.13023 (18)	0.0419 (5)
O2	0.16867 (17)	0.21100 (15)	−0.35871 (17)	0.0715 (6)
C16	0.26837 (18)	0.17846 (18)	−0.1753 (2)	0.0463 (5)
N1	0.10732 (16)	−0.04800 (16)	−0.08617 (18)	0.0512 (5)
C3	0.39999 (18)	−0.1450 (2)	0.02581 (18)	0.0513 (6)
H3A	0.4150	−0.0829	0.0610	0.062*
C6	0.35820 (19)	−0.32586 (19)	−0.0741 (2)	0.0550 (6)
H6A	0.3427	−0.3877	−0.1095	0.066*
C14	0.17629 (17)	−0.00602 (19)	−0.40213 (18)	0.0421 (5)
C9	0.19032 (16)	−0.11122 (18)	−0.39099 (17)	0.0406 (5)
C17	0.2753 (2)	0.2773 (2)	−0.1394 (2)	0.0600 (7)
H17A	0.2468	0.3289	−0.1880	0.072*
C13	0.1261 (2)	0.0351 (2)	−0.5047 (2)	0.0581 (7)
H13A	0.1156	0.1044	−0.5127	0.070*
C15	0.21260 (18)	0.14841 (19)	−0.2900 (2)	0.0480 (6)
C10	0.15531 (19)	−0.1732 (2)	−0.4820 (2)	0.0515 (6)
H10A	0.1647	−0.2427	−0.4755	0.062*
N2	0.48738 (16)	−0.0140 (2)	−0.2388 (2)	0.0630 (6)
C5	0.4136 (2)	−0.3223 (2)	0.0350 (2)	0.0606 (7)
H5A	0.4369	−0.3813	0.0735	0.073*
C12	0.0923 (2)	−0.0282 (3)	−0.5935 (2)	0.0691 (8)
H12A	0.0596	−0.0012	−0.6621	0.083*
C20	0.3586 (2)	0.1243 (2)	−0.0026 (2)	0.0547 (6)
H20A	0.3881	0.0723	0.0449	0.066*
C18	0.3248 (2)	0.2991 (2)	−0.0311 (3)	0.0664 (8)
H18A	0.3298	0.3653	−0.0057	0.080*
C4	0.4333 (2)	−0.2311 (2)	0.0850 (2)	0.0609 (7)
H4A	0.4691	−0.2270	0.1590	0.073*
C19	0.3659 (2)	0.2223 (2)	0.0378 (2)	0.0646 (7)
H19A	0.3987	0.2351	0.1114	0.077*
C11	0.1062 (2)	−0.1305 (3)	−0.5827 (2)	0.0653 (7)
H11A	0.0823	−0.1719	−0.6439	0.078*
C22	−0.0238 (2)	−0.2051 (2)	0.1295 (2)	0.0690 (8)
H22A	0.0132	−0.2526	0.1830	0.104*
H22B	−0.0532	−0.2394	0.0611	0.104*
H22C	−0.0754	−0.1754	0.1552	0.104*
H100	−0.1267	−0.1512	−0.1187	0.088 (11)*
H101	−0.1771	−0.0603	−0.1422	0.098 (12)*
H50	0.1018	−0.1459	0.1392	0.063 (8)*
O2W	0.69774 (14)	−0.01065 (15)	−0.21753 (19)	0.0696 (6)
H200	0.7123	0.0511	−0.2032	0.095 (12)*
H201	0.6350	−0.0145	−0.2289	0.113 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.0318 (2)	0.0366 (2)	0.0344 (2)	0.00083 (11)	0.00840 (14)	−0.00054 (11)
Mn	0.0320 (3)	0.0413 (3)	0.0454 (3)	0.00085 (19)	0.0119 (2)	−0.0038 (2)
N4	0.0358 (9)	0.0368 (10)	0.0368 (9)	−0.0011 (7)	0.0077 (7)	−0.0016 (8)
O3	0.0413 (9)	0.0517 (10)	0.0719 (11)	0.0017 (8)	0.0123 (8)	0.0112 (9)
N6	0.0404 (10)	0.0417 (10)	0.0455 (10)	−0.0023 (8)	0.0150 (8)	−0.0039 (8)
O1	0.0505 (9)	0.0409 (9)	0.0610 (10)	0.0011 (8)	−0.0001 (8)	−0.0078 (8)
N3	0.0353 (9)	0.0425 (10)	0.0397 (9)	0.0022 (8)	0.0104 (8)	0.0001 (8)
C8	0.0362 (11)	0.0405 (12)	0.0440 (12)	−0.0011 (9)	0.0101 (9)	−0.0025 (10)
N5	0.0390 (10)	0.0380 (10)	0.0425 (10)	0.0010 (7)	0.0092 (8)	0.0047 (8)
C2	0.0386 (13)	0.0472 (13)	0.0395 (12)	−0.0036 (9)	0.0070 (10)	−0.0062 (9)
O1W	0.0458 (10)	0.0435 (10)	0.0803 (13)	−0.0014 (8)	−0.0065 (9)	−0.0101 (9)
C1	0.0404 (12)	0.0364 (11)	0.0435 (12)	0.0033 (9)	0.0104 (10)	−0.0014 (9)
C7	0.0360 (11)	0.0426 (12)	0.0462 (12)	0.0021 (9)	0.0106 (9)	0.0026 (10)
O2	0.0897 (15)	0.0434 (10)	0.0690 (12)	0.0072 (10)	0.0035 (11)	0.0112 (9)
C16	0.0444 (12)	0.0404 (13)	0.0551 (14)	−0.0017 (10)	0.0163 (11)	0.0013 (10)
N1	0.0461 (11)	0.0516 (12)	0.0619 (13)	0.0041 (9)	0.0252 (11)	−0.0001 (10)
C3	0.0534 (14)	0.0560 (14)	0.0390 (12)	0.0082 (12)	0.0044 (10)	−0.0014 (11)
C6	0.0575 (15)	0.0424 (13)	0.0611 (15)	0.0020 (11)	0.0108 (12)	0.0059 (12)
C14	0.0359 (11)	0.0512 (13)	0.0378 (12)	0.0000 (10)	0.0083 (9)	0.0056 (10)
C9	0.0348 (11)	0.0486 (13)	0.0379 (11)	−0.0013 (9)	0.0095 (9)	0.0004 (9)
C17	0.0653 (17)	0.0420 (14)	0.0705 (17)	0.0002 (12)	0.0164 (14)	−0.0037 (12)
C13	0.0584 (16)	0.0645 (17)	0.0443 (14)	0.0019 (13)	0.0036 (12)	0.0121 (12)
C15	0.0472 (13)	0.0421 (13)	0.0523 (13)	0.0029 (10)	0.0106 (10)	0.0060 (11)
C10	0.0525 (14)	0.0551 (15)	0.0451 (13)	−0.0068 (11)	0.0112 (11)	−0.0048 (11)
N2	0.0415 (12)	0.0893 (17)	0.0595 (14)	−0.0129 (11)	0.0168 (10)	−0.0182 (12)
C5	0.0618 (16)	0.0586 (16)	0.0575 (16)	0.0115 (13)	0.0112 (13)	0.0206 (13)
C12	0.0666 (19)	0.090 (2)	0.0414 (15)	−0.0009 (16)	0.0004 (13)	0.0119 (14)
C20	0.0628 (16)	0.0527 (15)	0.0453 (13)	−0.0005 (12)	0.0102 (11)	−0.0055 (11)
C18	0.0717 (18)	0.0463 (15)	0.084 (2)	−0.0046 (14)	0.0268 (16)	−0.0179 (14)
C4	0.0580 (16)	0.0775 (19)	0.0418 (13)	0.0096 (14)	0.0060 (11)	0.0081 (13)
C19	0.0733 (19)	0.0619 (18)	0.0567 (16)	−0.0057 (14)	0.0160 (14)	−0.0201 (14)
C11	0.0617 (16)	0.086 (2)	0.0418 (13)	−0.0080 (15)	0.0042 (12)	−0.0078 (14)
C22	0.0666 (18)	0.0684 (18)	0.0667 (17)	−0.0152 (15)	0.0109 (14)	0.0095 (15)
O2W	0.0439 (11)	0.0496 (11)	0.1084 (17)	−0.0009 (8)	0.0111 (10)	0.0064 (11)

Geometric parameters (Å, º)

Fe—N5	1.8842 (19)	C16—C15	1.495 (3)
Fe—N4	1.8958 (18)	C3—C4	1.372 (4)
Fe—C1	1.966 (2)	C3—H3A	0.9300
Fe—C2	1.969 (2)	C6—C5	1.378 (4)
Fe—N6	2.0014 (19)	C6—H6A	0.9300
Fe—N3	2.0067 (19)	C14—C13	1.400 (3)
Mn—O1W	2.1876 (17)	C14—C9	1.409 (3)
Mn—O1W^i	2.1876 (17)	C9—C10	1.387 (3)
Mn—N1	2.195 (2)	C17—C18	1.381 (4)
Mn—N1^i	2.195 (2)	C17—H17A	0.9300
Mn—O3^i	2.2007 (17)	C13—C12	1.375 (4)
Mn—O3	2.2007 (17)	C13—H13A	0.9300
N4—C8	1.334 (3)	C10—C11	1.386 (4)
N4—C9	1.414 (3)	C10—H10A	0.9300
O3—C22	1.409 (3)	C5—C4	1.356 (4)
O3—H50	0.8520	C5—H5A	0.9300
N6—C20	1.339 (3)	C12—C11	1.370 (4)
N6—C16	1.355 (3)	C12—H12A	0.9300
O1—C8	1.252 (3)	C20—C19	1.389 (4)
N3—C3	1.343 (3)	C20—H20A	0.9300
N3—C7	1.358 (3)	C18—C19	1.357 (4)
C8—C7	1.488 (3)	C18—H18A	0.9300
N5—C15	1.350 (3)	C4—H4A	0.9300
N5—C14	1.411 (3)	C19—H19A	0.9300
C2—N2	1.139 (3)	C11—H11A	0.9300
O1W—H100	0.8449	C22—H22A	0.9600
O1W—H101	0.8672	C22—H22B	0.9600
C1—N1	1.138 (3)	C22—H22C	0.9600
C7—C6	1.375 (3)	O2W—H200	0.8499
O2—C15	1.231 (3)	O2W—H201	0.8499
C16—C17	1.381 (4)
N5—Fe—N4	83.87 (8)	N6—C16—C17	121.8 (2)
N5—Fe—C1	94.35 (9)	N6—C16—C15	115.5 (2)
N4—Fe—C1	93.79 (8)	C17—C16—C15	122.8 (2)
N5—Fe—C2	92.93 (9)	C1—N1—Mn	159.75 (19)
N4—Fe—C2	92.52 (8)	N3—C3—C4	122.9 (2)
C1—Fe—C2	170.84 (9)	N3—C3—H3A	118.5
N5—Fe—N6	82.22 (8)	C4—C3—H3A	118.5
N4—Fe—N6	166.05 (8)	C7—C6—C5	119.8 (2)
C1—Fe—N6	86.15 (8)	C7—C6—H6A	120.1
C2—Fe—N6	89.33 (8)	C5—C6—H6A	120.1
N5—Fe—N3	165.72 (8)	C13—C14—C9	119.8 (2)
N4—Fe—N3	81.85 (8)	C13—C14—N5	126.6 (2)
C1—Fe—N3	86.12 (8)	C9—C14—N5	113.58 (19)
C2—Fe—N3	88.21 (9)	C10—C9—C14	119.8 (2)
N6—Fe—N3	112.04 (8)	C10—C9—N4	127.1 (2)
O1W—Mn—O1W^i	180.00 (15)	C14—C9—N4	113.02 (19)
O1W—Mn—N1	92.13 (8)	C16—C17—C18	119.6 (3)
O1W^i—Mn—N1	87.87 (8)	C16—C17—H17A	120.2
O1W—Mn—N1^i	87.87 (8)	C18—C17—H17A	120.2
O1W^i—Mn—N1^i	92.13 (8)	C12—C13—C14	119.1 (3)
N1—Mn—N1^i	180.00 (13)	C12—C13—H13A	120.4
O1W—Mn—O3^i	89.39 (7)	C14—C13—H13A	120.4
O1W^i—Mn—O3^i	90.61 (7)	O2—C15—N5	127.6 (2)
N1—Mn—O3^i	89.07 (7)	O2—C15—C16	121.6 (2)
N1^i—Mn—O3^i	90.93 (7)	N5—C15—C16	110.8 (2)
O1W—Mn—O3	90.61 (7)	C11—C10—C9	119.3 (3)
O1W^i—Mn—O3	89.39 (7)	C11—C10—H10A	120.4
N1—Mn—O3	90.93 (7)	C9—C10—H10A	120.4
N1^i—Mn—O3	89.07 (7)	C4—C5—C6	118.7 (2)
O3^i—Mn—O3	180.00 (10)	C4—C5—H5A	120.6
C8—N4—C9	126.27 (19)	C6—C5—H5A	120.6
C8—N4—Fe	119.06 (15)	C11—C12—C13	121.1 (3)
C9—N4—Fe	114.64 (15)	C11—C12—H12A	119.5
C22—O3—Mn	126.50 (16)	C13—C12—H12A	119.5
C22—O3—H50	111.7	N6—C20—C19	122.6 (3)
Mn—O3—H50	119.9	N6—C20—H20A	118.7
C20—N6—C16	117.7 (2)	C19—C20—H20A	118.7
C20—N6—Fe	129.92 (18)	C19—C18—C17	118.9 (3)
C16—N6—Fe	112.30 (15)	C19—C18—H18A	120.6
C3—N3—C7	117.3 (2)	C17—C18—H18A	120.6
C3—N3—Fe	130.47 (17)	C5—C4—C3	119.5 (2)
C7—N3—Fe	112.14 (14)	C5—C4—H4A	120.2
O1—C8—N4	127.5 (2)	C3—C4—H4A	120.2
O1—C8—C7	121.0 (2)	C18—C19—C20	119.4 (3)
N4—C8—C7	111.46 (18)	C18—C19—H19A	120.3
C15—N5—C14	126.0 (2)	C20—C19—H19A	120.3
C15—N5—Fe	119.23 (16)	C12—C11—C10	121.0 (3)
C14—N5—Fe	114.81 (15)	C12—C11—H11A	119.5
N2—C2—Fe	178.3 (2)	C10—C11—H11A	119.5
Mn—O1W—H100	130.3	O3—C22—H22A	109.5
Mn—O1W—H101	120.4	O3—C22—H22B	109.5
H100—O1W—H101	107.9	H22A—C22—H22B	109.5
N1—C1—Fe	177.0 (2)	O3—C22—H22C	109.5
N3—C7—C6	121.6 (2)	H22A—C22—H22C	109.5
N3—C7—C8	115.33 (19)	H22B—C22—H22C	109.5
C6—C7—C8	123.0 (2)	H200—O2W—H201	105.5

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H100···O2^ii	0.85	1.91	2.747 (4)	169
O1W—H101···O2W^iii	0.87	1.86	2.723 (4)	175
O3—H50···O1^iv	0.85	1.89	2.738 (4)	178
O2W—H200···O1^v	0.85	1.91	2.738 (4)	164
O2W—H201···N2	0.85	2.04	2.881 (4)	173

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