A new heterometallic complex: [Mn(H₂O)₆][Co(dmg)₂(N₃)₂]₂·2H₂O, where dmg is di­methyl­glyoximate

The title heterometallic complex, hexa­aqua­manganese(II) bis­[di­azido­bis­(di­methyl­glyoximato)­cobaltate(III)] dihydrate, [Mn(H₂O)₆][Co(dmg)₂(N₃)₂]₂·2H₂O (dmg = di­methyl­glyoximate, C₄H₇N₂O₂), has been synthesized. Each Co atom is surrounded by two dmg ligands and two N₃ groups in an octahedral geometry. The Mn atom is hexacoordinated by six water mol­ecules. Each metal atom lies on a center of symmetry. The Mn-centered cation is linked to four neighboring Co1-centered anions, two Co2-centered anions and two uncoordinated water mol­ecules through extensive intermol­ecular O—H...N and O—H...O hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.031
• wR factor = 0.077
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       2.52 Ratio
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         N9
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Mn1
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O4     -   H4D      =       1.06 Ang.
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ......         C4
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ......         C5
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ......         C8
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H12 Mn O6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

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

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

---

Computing details

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

hexaaquamanganese bis[diazidobis(dimethylglyoximato)cobaltate] dihydrate

Crystal data

[Mn(H2O)6][Co(C4H7N2O2)2(N3)2]2·2H2O	Z = 1
Mr = 945.51	F(000) = 487
Triclinic, P1	Dx = 1.641 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7345 (14) Å	Cell parameters from 34 reflections
b = 9.7893 (16) Å	θ = 5.0–12.5°
c = 11.4276 (15) Å	µ = 1.27 mm^−1
α = 87.225 (10)°	T = 293 K
β = 67.328 (9)°	Prism, dark red
γ = 72.767 (11)°	0.4 × 0.2 × 0.2 mm
V = 957.0 (3) Å^3

Data collection

Bruker P4 diffractometer	2918 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
ω scans	h = −1→11
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.601, Tmax = 0.774	l = −12→13
4022 measured reflections	3 standard reflections every 100 reflections
3369 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.001P)^2 + 1.2P] where P = (Fo^2 + 2Fc^2)/3
3369 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.24 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
Co1	0.0000	0.0000	0.0000	0.03262 (13)
Co2	0.5000	0.5000	0.5000	0.03373 (13)
Mn1	0.5000	−0.5000	0.0000	0.03979 (15)
O1	0.0212 (2)	0.0508 (2)	−0.25296 (18)	0.0460 (5)
O2	0.2399 (2)	−0.0560 (2)	0.09544 (18)	0.0432 (5)
H2A	0.1149	−0.0499	0.1782	0.087 (13)*
O3	0.5202 (2)	0.7108 (2)	0.31861 (18)	0.0440 (5)
O4	0.2248 (2)	0.4759 (2)	0.70815 (19)	0.0509 (5)
H4D	0.3223	0.3927	0.7098	0.087 (13)*
O5	0.3790 (2)	−0.3781 (2)	−0.11430 (19)	0.0507 (5)
H5D	0.4302	−0.3804	−0.1939	0.061*
H5E	0.2797	−0.3482	−0.0827	0.061*
O6	0.2876 (3)	−0.5507 (3)	0.1183 (2)	0.0640 (6)
H6A	0.2050	−0.4950	0.1733	0.077*
H6B	0.2510	−0.5926	0.0791	0.077*
O7	0.4370 (3)	−0.3119 (2)	0.1197 (2)	0.0589 (6)
H7A	0.3742	−0.2305	0.1191	0.071*
H7B	0.4442	−0.3015	0.1903	0.071*
N1	0.1000 (3)	0.0180 (2)	−0.1755 (2)	0.0367 (5)
N2	0.2053 (3)	−0.0316 (2)	−0.0087 (2)	0.0357 (5)
N3	0.4264 (3)	0.6664 (2)	0.4222 (2)	0.0378 (5)
N4	0.2866 (3)	0.5523 (2)	0.6089 (2)	0.0379 (5)
N5	0.0547 (3)	−0.2088 (2)	−0.0339 (2)	0.0435 (6)
N6	−0.0495 (3)	−0.2631 (3)	−0.0032 (2)	0.0475 (6)
N7	−0.1454 (4)	−0.3181 (3)	0.0246 (4)	0.0762 (9)
N8	0.4697 (3)	0.3832 (3)	0.3823 (2)	0.0444 (6)
N9	0.3591 (3)	0.3399 (3)	0.4198 (2)	0.0513 (6)
N10	0.2578 (5)	0.2916 (5)	0.4504 (4)	0.0951 (13)
C1	0.3445 (4)	0.0129 (4)	−0.3534 (3)	0.0514 (8)
H1A	0.2799	0.0343	−0.4017	0.077*
H1B	0.4257	−0.0759	−0.3875	0.077*
H1C	0.3902	0.0886	−0.3581	0.077*
C2	0.2481 (3)	0.0004 (3)	−0.2188 (3)	0.0388 (6)
C3	0.3118 (3)	−0.0313 (3)	−0.1194 (3)	0.0382 (6)
C4	0.4801 (3)	−0.0593 (4)	−0.1460 (3)	0.0538 (8)
H4A	0.4967	−0.0777	−0.0684	0.081*
H4B	0.5117	0.0229	−0.1808	0.081*
H4C	0.5407	−0.1412	−0.2059	0.081*
C5	0.2000 (4)	0.8662 (3)	0.4278 (3)	0.0572 (8)
H5A	0.2759	0.8922	0.3549	0.086*
H5B	0.1528	0.9426	0.4937	0.086*
H5C	0.1211	0.8495	0.4047	0.086*
C6	0.2783 (3)	0.7329 (3)	0.4748 (3)	0.0401 (6)
C7	0.1949 (3)	0.6645 (3)	0.5853 (3)	0.0407 (6)
C8	0.0230 (3)	0.7175 (4)	0.6601 (3)	0.0554 (8)
H8A	−0.0058	0.6563	0.7277	0.083*
H8B	−0.0309	0.7166	0.6055	0.083*
H8C	−0.0048	0.8136	0.6953	0.083*
O1W	0.0429 (4)	−0.3590 (3)	0.2909 (4)	0.1217 (15)
H1D	−0.0425	−0.3781	0.3099	0.146*
H1E	0.0232	−0.2695	0.2819	0.146*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0325 (3)	0.0341 (3)	0.0324 (3)	−0.0089 (2)	−0.0147 (2)	0.0032 (2)
Co2	0.0323 (3)	0.0372 (3)	0.0328 (3)	−0.0091 (2)	−0.0151 (2)	0.0039 (2)
Mn1	0.0383 (3)	0.0423 (3)	0.0384 (3)	−0.0096 (3)	−0.0161 (3)	0.0003 (3)
O1	0.0479 (12)	0.0580 (12)	0.0377 (11)	−0.0149 (10)	−0.0238 (9)	0.0086 (9)
O2	0.0415 (11)	0.0514 (12)	0.0423 (11)	−0.0097 (9)	−0.0253 (9)	0.0045 (9)
O3	0.0478 (11)	0.0472 (11)	0.0394 (11)	−0.0168 (9)	−0.0186 (9)	0.0116 (9)
O4	0.0432 (12)	0.0599 (13)	0.0458 (12)	−0.0190 (10)	−0.0119 (10)	0.0154 (10)
O5	0.0414 (11)	0.0617 (13)	0.0411 (11)	−0.0027 (10)	−0.0170 (9)	0.0029 (10)
O6	0.0496 (13)	0.0761 (16)	0.0624 (15)	−0.0276 (12)	−0.0101 (11)	−0.0037 (12)
O7	0.0784 (16)	0.0438 (12)	0.0568 (13)	0.0036 (11)	−0.0435 (13)	−0.0083 (10)
N1	0.0404 (13)	0.0375 (12)	0.0351 (12)	−0.0116 (10)	−0.0177 (10)	0.0025 (9)
N2	0.0378 (12)	0.0347 (11)	0.0386 (12)	−0.0101 (10)	−0.0197 (10)	0.0034 (9)
N3	0.0420 (13)	0.0408 (12)	0.0348 (12)	−0.0135 (10)	−0.0188 (10)	0.0045 (10)
N4	0.0367 (12)	0.0433 (13)	0.0350 (12)	−0.0131 (10)	−0.0145 (10)	0.0032 (10)
N5	0.0409 (13)	0.0383 (13)	0.0517 (14)	−0.0116 (11)	−0.0182 (11)	0.0007 (11)
N6	0.0515 (15)	0.0386 (13)	0.0533 (15)	−0.0117 (12)	−0.0226 (13)	0.0017 (11)
N7	0.068 (2)	0.065 (2)	0.103 (3)	−0.0372 (17)	−0.0288 (19)	0.0075 (18)
N8	0.0463 (14)	0.0524 (15)	0.0392 (13)	−0.0177 (12)	−0.0189 (11)	0.0003 (11)
N9	0.0541 (16)	0.0640 (17)	0.0438 (14)	−0.0224 (14)	−0.0236 (13)	0.0002 (12)
N10	0.093 (3)	0.145 (4)	0.076 (2)	−0.078 (3)	−0.031 (2)	0.003 (2)
C1	0.0483 (18)	0.062 (2)	0.0415 (16)	−0.0210 (15)	−0.0116 (14)	0.0048 (14)
C2	0.0410 (15)	0.0366 (14)	0.0374 (14)	−0.0122 (12)	−0.0133 (12)	0.0015 (11)
C3	0.0356 (14)	0.0365 (14)	0.0422 (15)	−0.0119 (11)	−0.0137 (12)	0.0006 (11)
C4	0.0380 (16)	0.070 (2)	0.0542 (19)	−0.0195 (15)	−0.0162 (14)	0.0007 (16)
C5	0.058 (2)	0.0514 (19)	0.058 (2)	0.0007 (15)	−0.0305 (17)	0.0050 (15)
C6	0.0412 (15)	0.0410 (15)	0.0401 (15)	−0.0056 (12)	−0.0227 (13)	−0.0001 (12)
C7	0.0375 (15)	0.0457 (16)	0.0409 (15)	−0.0082 (12)	−0.0197 (12)	−0.0035 (12)
C8	0.0385 (16)	0.059 (2)	0.061 (2)	−0.0044 (14)	−0.0175 (15)	−0.0030 (16)
O1W	0.075 (2)	0.0678 (19)	0.157 (3)	−0.0170 (16)	0.021 (2)	0.002 (2)

Geometric parameters (Å, º)

Co1—N1	1.887 (2)	O7—H7B	0.8500
Co1—N1^i	1.887 (2)	N1—C2	1.291 (4)
Co1—N2^i	1.893 (2)	N2—C3	1.291 (3)
Co1—N2	1.893 (2)	N3—C6	1.296 (4)
Co1—N5	1.971 (2)	N4—C7	1.285 (4)
Co1—N5^i	1.971 (2)	N5—N6	1.209 (3)
Co2—N4	1.888 (2)	N6—N7	1.147 (4)
Co2—N4^ii	1.888 (2)	N8—N9	1.191 (4)
Co2—N3	1.902 (2)	N9—N10	1.145 (4)
Co2—N3^ii	1.902 (2)	C1—C2	1.483 (4)
Co2—N8	1.964 (2)	C1—H1A	0.9600
Co2—N8^ii	1.964 (2)	C1—H1B	0.9600
Mn1—O7^iii	2.136 (2)	C1—H1C	0.9600
Mn1—O7	2.136 (2)	C2—C3	1.471 (4)
Mn1—O5^iii	2.173 (2)	C3—C4	1.486 (4)
Mn1—O5	2.173 (2)	C4—H4A	0.9600
Mn1—O6^iii	2.177 (2)	C4—H4B	0.9600
Mn1—O6	2.177 (2)	C4—H4C	0.9600
O1—N1	1.351 (3)	C5—C6	1.492 (4)
O2—N2	1.349 (3)	C5—H5A	0.9600
O2—H2A	1.2059	C5—H5B	0.9600
O3—N3	1.332 (3)	C5—H5C	0.9600
O4—N4	1.367 (3)	C6—C7	1.468 (4)
O4—H4D	1.0572	C7—C8	1.491 (4)
O5—H5D	0.8500	C8—H8A	0.9600
O5—H5E	0.8501	C8—H8B	0.9600
O6—H6A	0.8500	C8—H8C	0.9600
O6—H6B	0.8500	O1W—H1D	0.8499
O7—H7A	0.8500	O1W—H1E	0.8501
N1—Co1—N1^i	180.0	H7A—O7—H7B	100.2
N1—Co1—N2^i	98.89 (9)	C2—N1—O1	120.8 (2)
N1^i—Co1—N2^i	81.11 (9)	C2—N1—Co1	116.94 (19)
N1—Co1—N2	81.11 (9)	O1—N1—Co1	122.24 (17)
N1^i—Co1—N2	98.89 (9)	C3—N2—O2	121.2 (2)
N2^i—Co1—N2	180.00 (13)	C3—N2—Co1	116.98 (18)
N1—Co1—N5	89.82 (10)	O2—N2—Co1	121.76 (17)
N1^i—Co1—N5	90.18 (10)	C6—N3—O3	121.8 (2)
N2^i—Co1—N5	92.65 (10)	C6—N3—Co2	115.82 (19)
N2—Co1—N5	87.35 (10)	O3—N3—Co2	122.39 (17)
N1—Co1—N5^i	90.18 (10)	C7—N4—O4	118.8 (2)
N1^i—Co1—N5^i	89.82 (10)	C7—N4—Co2	117.5 (2)
N2^i—Co1—N5^i	87.35 (10)	O4—N4—Co2	123.75 (17)
N2—Co1—N5^i	92.65 (10)	N6—N5—Co1	118.6 (2)
N5—Co1—N5^i	180.0	N7—N6—N5	178.2 (3)
N4—Co2—N4^ii	180.000 (1)	N9—N8—Co2	119.2 (2)
N4—Co2—N3	81.20 (10)	N10—N9—N8	175.9 (4)
N4^ii—Co2—N3	98.80 (10)	C2—C1—H1A	109.5
N4—Co2—N3^ii	98.80 (10)	C2—C1—H1B	109.5
N4^ii—Co2—N3^ii	81.20 (10)	H1A—C1—H1B	109.5
N3—Co2—N3^ii	180.000 (1)	C2—C1—H1C	109.5
N4—Co2—N8	92.38 (10)	H1A—C1—H1C	109.5
N4^ii—Co2—N8	87.62 (10)	H1B—C1—H1C	109.5
N3—Co2—N8	89.07 (10)	N1—C2—C3	112.7 (2)
N3^ii—Co2—N8	90.93 (10)	N1—C2—C1	124.1 (3)
N4—Co2—N8^ii	87.62 (10)	C3—C2—C1	123.2 (3)
N4^ii—Co2—N8^ii	92.38 (10)	N2—C3—C2	112.2 (2)
N3—Co2—N8^ii	90.93 (10)	N2—C3—C4	124.8 (3)
N3^ii—Co2—N8^ii	89.07 (10)	C2—C3—C4	122.9 (3)
N8—Co2—N8^ii	180.00 (10)	C3—C4—H4A	109.5
O7^iii—Mn1—O7	180.00 (10)	C3—C4—H4B	109.5
O7^iii—Mn1—O5^iii	90.93 (8)	H4A—C4—H4B	109.5
O7—Mn1—O5^iii	89.07 (8)	C3—C4—H4C	109.5
O7^iii—Mn1—O5	89.07 (8)	H4A—C4—H4C	109.5
O7—Mn1—O5	90.93 (8)	H4B—C4—H4C	109.5
O5^iii—Mn1—O5	180.00 (11)	C6—C5—H5A	109.5
O7^iii—Mn1—O6^iii	91.93 (9)	C6—C5—H5B	109.5
O7—Mn1—O6^iii	88.07 (9)	H5A—C5—H5B	109.5
O5^iii—Mn1—O6^iii	89.31 (9)	C6—C5—H5C	109.5
O5—Mn1—O6^iii	90.69 (9)	H5A—C5—H5C	109.5
O7^iii—Mn1—O6	88.07 (9)	H5B—C5—H5C	109.5
O7—Mn1—O6	91.93 (9)	N3—C6—C7	113.3 (2)
O5^iii—Mn1—O6	90.69 (9)	N3—C6—C5	123.4 (3)
O5—Mn1—O6	89.31 (9)	C7—C6—C5	123.3 (3)
O6^iii—Mn1—O6	180.0	N4—C7—C6	112.2 (2)
N2—O2—H2A	102.4	N4—C7—C8	124.0 (3)
N4—O4—H4D	104.4	C6—C7—C8	123.9 (3)
Mn1—O5—H5D	118.0	C7—C8—H8A	109.5
Mn1—O5—H5E	119.0	C7—C8—H8B	109.5
H5D—O5—H5E	121.1	H8A—C8—H8B	109.5
Mn1—O6—H6A	127.5	C7—C8—H8C	109.5
Mn1—O6—H6B	115.4	H8A—C8—H8C	109.5
H6A—O6—H6B	102.0	H8B—C8—H8C	109.5
Mn1—O7—H7A	126.7	H1D—O1W—H1E	106.4
Mn1—O7—H7B	131.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5D···N8^iv	0.85	1.99	2.836 (3)	174
O5—H5E···N5	0.85	2.08	2.892 (3)	159
O6—H6A···O1W	0.85	1.83	2.678 (4)	172
O6—H6B···N7^v	0.85	2.19	3.038 (4)	175
O7—H7A···O2	0.85	1.90	2.744 (3)	173
O7—H7B···O3^vi	0.85	1.90	2.729 (3)	164
O1W—H1D···O4^vii	0.85	2.33	3.138 (4)	160
O1W—H1E···O1^i	0.85	2.09	2.940 (4)	178

Symmetry codes: (i) −x, −y, −z; (iv) −x+1, −y, −z; (v) −x, −y−1, −z; (vi) x, y−1, z; (vii) −x, −y, −z+1.