catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)cobalt(II)]-μ-malonato-κ⁴O¹,O^1′:O³,O^3′]

In the title compound, [Co(C₃H₂O₄)(C₁₄H₁₂N₂)]_n, the Co^II ion is in a distorted octa­hedral coordination being chelated by a 2,9-dimethyl-1,10-phenanthroline mol­ecule (dmphen) and two carboxyl­ate groups of two malonate ligands The malonate ligand acts in a bridging mode, forming coordination chains along [100]. π–π stacking inter­actions between dmphen ligands [inter­planar distances = 3.414 (4) and 3.447 (4) Å] organize the coordination polymers into supra­molecular double chains.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.048
• wR factor = 0.127
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Co1    --  O2      ..      10.19 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Co1    --  O4_a    ..      10.20 su
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C17

Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    --  O1      ..       8.47 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    --  O3_a    ..       6.05 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         26

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.17 Ratio

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Metal-phenanthroline complexes and their derivatives have attracted much attention because of their peculiar features. In turn dicarboxylate ligands play an important role in modern coordination chemistry and many complexes have been published with them as ligands (Rao et al., 2004; Zheng et al., 2004). The title complex, (I), was recently prepared and its crystal structure is reported here.

The crystal structure of the title compound consists of [Co(C₁₄H₁₂N₂)(C₃H₂O₄)]_n chains (Fig. 1). Each Co atom is surrounded by two nitrogen atoms of one 2,9-dimethyl-1,10-phenanthroline ligand and four oxygen atoms of two bis-chelating malonate anions to complete a seriously distorted octahedral coordination (Table 1). The malonate ligands bridge the Co atoms to form neutral one-dimensional chains [Co(C₁₄H₁₂N₂)(C₃H₂O₄)]_n along [100] with parallel orientated phen ligands at the same side. As shown in Fig. 2, through π-π stacking interactions the dmphen ligands of two adjacent coordination chains form supramolecular double chains. The interplanar distances between the neighbouring dmphen ligands are 3.414 (4) and 3.447 (4) Å.

Related literature

For coordination polymers with dicarboxylate ligands, see: Rao et al. (2004); Zheng et al. (2004).

S2. Experimental

Addition of 2.0 ml (1 M) NaOH to an aqueous solution of CoCl₂.6H₂O (0.238 g, 1.00 mmol) in 10.0 ml H₂O produced a pink precipitate, which was centrifugated and washed with doubly destilled water for several times until no Cl^- anions were detectable. The fresh precipitate was then added to a stirred solution of malonic acid (0.104 g, 1.00 mmol) and 2,9-dimethyl-1,10-phenanthroline hydrate (0.226 g, 1 mmol) in CH₃OH/H₂O (1:1 30 ml). The red mixture was allowed to stand at room temperature and after several days, red plate-like crystals suitable for X-ray analysis were formed. grown by slow evaporation.

S3. Refinement

All H atoms were placed in geometrically calculated position (C-H = 0.93-0.97 Å) and refined in a riding model approximation with U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: RAPID-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. ORTEP view of the title compound. The displacement ellipsoids are drawn at the 30% probability level [symmetry code: (i) x - 1, y, z; (ii) x + 1, y, z].
	Fig. 2. A double chain formed through π–π stacking interactions between dmphen ligands.

catena-Poly[[(2,9-dimethyl-1,10-phenanthroline- κ²N,N')cobalt(II)]-µ-malonato- κ⁴O¹,O^1':O³,O^3']

Crystal data

[Co(C3H2O4)(C14H12N2)]	Z = 2
Mr = 369.23	F(000) = 378
Triclinic, P1	Dx = 1.681 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8767 (14) Å	Cell parameters from 5667 reflections
b = 9.5293 (19) Å	θ = 3.5–27.5°
c = 11.149 (2) Å	µ = 1.20 mm^−1
α = 86.83 (3)°	T = 295 K
β = 89.53 (3)°	Plate, red
γ = 89.52 (3)°	0.33 × 0.11 × 0.07 mm
V = 729.4 (2) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	3309 independent reflections
Radiation source: fine-focus sealed tube	2590 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 0 pixels mm^-1	θmax = 27.5°, θmin = 3.5°
ω scans	h = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.653, Tmax = 0.782	l = −14→14
7245 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0568P)^2 + 0.8449P] where P = (Fo^2 + 2Fc^2)/3
3309 reflections	(Δ/σ)max = 0.015
222 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.40 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	0.23932 (7)	0.27775 (5)	0.73432 (4)	0.03063 (16)
N1	0.2539 (4)	0.0677 (3)	0.6805 (2)	0.0283 (6)
N2	0.2379 (4)	0.1661 (3)	0.9024 (2)	0.0264 (5)
C1	0.2526 (5)	0.0223 (4)	0.5691 (3)	0.0346 (7)
C2	0.2653 (5)	−0.1224 (4)	0.5494 (4)	0.0435 (9)
H2A	0.2659	−0.1521	0.4713	0.052*
C3	0.2765 (5)	−0.2181 (4)	0.6433 (4)	0.0439 (9)
H3A	0.2860	−0.3133	0.6297	0.053*
C4	0.2737 (5)	−0.1737 (3)	0.7614 (3)	0.0347 (7)
C5	0.2824 (5)	−0.2671 (4)	0.8659 (4)	0.0437 (9)
H5A	0.2923	−0.3633	0.8571	0.052*
C6	0.2766 (5)	−0.2182 (4)	0.9773 (4)	0.0413 (9)
H6A	0.2831	−0.2812	1.0439	0.050*
C7	0.2604 (5)	−0.0702 (3)	0.9941 (3)	0.0322 (7)
C8	0.2485 (5)	−0.0137 (4)	1.1072 (3)	0.0396 (8)
H8A	0.2515	−0.0724	1.1766	0.048*
C9	0.2326 (5)	0.1280 (4)	1.1146 (3)	0.0382 (8)
H9A	0.2249	0.1660	1.1896	0.046*
C10	0.2276 (5)	0.2173 (3)	1.0107 (3)	0.0312 (7)
C11	0.2530 (4)	0.0242 (3)	0.8937 (3)	0.0266 (6)
C12	0.2620 (4)	−0.0274 (3)	0.7747 (3)	0.0281 (7)
C13	0.2325 (6)	0.1281 (5)	0.4669 (3)	0.0461 (9)
H13A	0.1190	0.1850	0.4789	0.069*
H13B	0.2202	0.0809	0.3935	0.069*
H13C	0.3455	0.1867	0.4623	0.069*
C14	0.2121 (6)	0.3725 (4)	1.0190 (3)	0.0424 (9)
H14A	0.3391	0.4104	1.0304	0.064*
H14B	0.1298	0.3933	1.0858	0.064*
H14C	0.1574	0.4137	0.9462	0.064*
O1	0.4924 (4)	0.3945 (4)	0.7882 (3)	0.0622 (9)
O2	0.4560 (5)	0.3466 (4)	0.6052 (3)	0.0675 (9)
O3	0.9214 (4)	0.2696 (3)	0.6983 (3)	0.0646 (9)
O4	1.0687 (5)	0.4640 (4)	0.7095 (5)	0.0950 (15)
C15	0.5528 (5)	0.4017 (3)	0.6837 (3)	0.0331 (7)
C16	0.7380 (5)	0.4791 (4)	0.6502 (3)	0.0360 (8)
H16A	0.7421	0.4975	0.5638	0.043*
H16C	0.7359	0.5691	0.6869	0.043*
C17	0.9200 (5)	0.3999 (4)	0.6886 (3)	0.0343 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0319 (2)	0.0274 (2)	0.0321 (3)	−0.00231 (17)	−0.00176 (17)	0.00297 (17)
N1	0.0266 (13)	0.0290 (13)	0.0292 (14)	−0.0007 (11)	0.0004 (11)	−0.0026 (11)
N2	0.0265 (13)	0.0237 (12)	0.0289 (14)	−0.0015 (10)	−0.0022 (10)	−0.0008 (10)
C1	0.0240 (15)	0.045 (2)	0.0350 (18)	−0.0042 (14)	0.0005 (13)	−0.0083 (15)
C2	0.040 (2)	0.052 (2)	0.040 (2)	−0.0062 (17)	0.0002 (16)	−0.0192 (18)
C3	0.0363 (19)	0.0362 (19)	0.061 (3)	−0.0042 (16)	−0.0004 (17)	−0.0184 (18)
C4	0.0284 (16)	0.0271 (16)	0.049 (2)	−0.0028 (13)	0.0011 (15)	−0.0025 (15)
C5	0.0397 (19)	0.0227 (16)	0.068 (3)	−0.0011 (15)	−0.0021 (18)	0.0024 (16)
C6	0.0390 (19)	0.0301 (18)	0.053 (2)	−0.0029 (15)	−0.0025 (17)	0.0164 (16)
C7	0.0245 (15)	0.0318 (17)	0.0393 (19)	−0.0044 (13)	−0.0043 (13)	0.0089 (14)
C8	0.0374 (18)	0.047 (2)	0.0331 (19)	−0.0060 (16)	−0.0018 (15)	0.0127 (16)
C9	0.0413 (19)	0.050 (2)	0.0238 (17)	−0.0036 (16)	−0.0022 (14)	−0.0013 (15)
C10	0.0293 (16)	0.0340 (17)	0.0303 (17)	−0.0014 (14)	−0.0010 (13)	−0.0011 (13)
C11	0.0210 (14)	0.0272 (15)	0.0314 (17)	−0.0034 (12)	−0.0024 (12)	0.0022 (12)
C12	0.0223 (14)	0.0261 (15)	0.0360 (18)	−0.0014 (12)	0.0002 (12)	−0.0006 (13)
C13	0.046 (2)	0.064 (3)	0.0282 (19)	−0.0095 (19)	−0.0032 (16)	−0.0023 (17)
C14	0.052 (2)	0.0385 (19)	0.037 (2)	0.0000 (17)	0.0006 (17)	−0.0080 (16)
O1	0.0481 (16)	0.097 (3)	0.0412 (17)	−0.0195 (17)	0.0000 (13)	0.0045 (16)
O2	0.063 (2)	0.083 (2)	0.059 (2)	−0.0335 (18)	0.0073 (16)	−0.0249 (18)
O3	0.0481 (17)	0.0449 (17)	0.101 (3)	0.0117 (14)	−0.0200 (17)	−0.0033 (17)
O4	0.0404 (17)	0.059 (2)	0.183 (5)	−0.0152 (16)	−0.040 (2)	0.027 (2)
C15	0.0266 (15)	0.0300 (16)	0.042 (2)	0.0048 (13)	−0.0038 (14)	0.0032 (14)
C16	0.0349 (17)	0.0307 (17)	0.042 (2)	−0.0006 (14)	−0.0031 (15)	0.0068 (14)
C17	0.0327 (17)	0.0369 (18)	0.0327 (18)	0.0018 (15)	−0.0001 (14)	0.0021 (14)

Geometric parameters (Å, º)

Co1—O1	2.180 (3)	C7—C8	1.400 (5)
Co1—O2	2.145 (3)	C8—C9	1.361 (5)
Co1—O3^i	2.229 (3)	C8—H8A	0.9300
Co1—O4^i	2.126 (4)	C9—C10	1.399 (5)
Co1—N1	2.122 (3)	C9—H9A	0.9300
Co1—N2	2.103 (3)	C10—C14	1.489 (5)
Co1—C15	2.512 (4)	C11—C12	1.440 (5)
Co1—C17^i	2.519 (3)	C13—H13A	0.9600
N1—C1	1.338 (4)	C13—H13B	0.9600
N1—C12	1.350 (4)	C13—H13C	0.9600
N2—C10	1.328 (4)	C14—H14A	0.9600
N2—C11	1.364 (4)	C14—H14B	0.9600
C1—C2	1.410 (5)	C14—H14C	0.9600
C1—C13	1.485 (5)	O1—C15	1.233 (4)
C2—C3	1.352 (6)	O2—C15	1.246 (5)
C2—H2A	0.9300	O3—C17	1.240 (4)
C3—C4	1.405 (5)	O3—Co1^ii	2.229 (3)
C3—H3A	0.9300	O4—C17	1.226 (5)
C4—C12	1.411 (4)	O4—Co1^ii	2.126 (4)
C4—C5	1.428 (5)	C15—C16	1.511 (5)
C5—C6	1.350 (6)	C16—C17	1.509 (5)
C5—H5A	0.9300	C16—H16A	0.9700
C6—C7	1.436 (5)	C16—H16C	0.9700
C6—H6A	0.9300	C17—Co1^ii	2.519 (3)
C7—C11	1.398 (4)
N2—Co1—N1	79.24 (10)	C9—C8—H8A	120.3
N2—Co1—O4^i	119.53 (16)	C7—C8—H8A	120.3
N1—Co1—O4^i	140.97 (13)	C8—C9—C10	120.8 (3)
N2—Co1—O2	136.06 (13)	C8—C9—H9A	119.6
N1—Co1—O2	92.45 (12)	C10—C9—H9A	119.6
O4^i—Co1—O2	93.90 (16)	N2—C10—C9	120.9 (3)
N2—Co1—O1	89.80 (11)	N2—C10—C14	118.4 (3)
N1—Co1—O1	123.50 (12)	C9—C10—C14	120.7 (3)
O4^i—Co1—O1	92.30 (13)	N2—C11—C7	122.8 (3)
O2—Co1—O1	59.10 (12)	N2—C11—C12	117.3 (3)
N2—Co1—O3^i	97.95 (12)	C7—C11—C12	119.9 (3)
N1—Co1—O3^i	86.71 (11)	N1—C12—C4	123.0 (3)
O4^i—Co1—O3^i	58.47 (12)	N1—C12—C11	117.8 (3)
O2—Co1—O3^i	124.82 (14)	C4—C12—C11	119.2 (3)
O1—Co1—O3^i	149.76 (13)	C1—C13—H13A	109.5
C1—N1—C12	119.0 (3)	C1—C13—H13B	109.5
C1—N1—Co1	128.3 (2)	H13A—C13—H13B	109.5
C12—N1—Co1	112.6 (2)	C1—C13—H13C	109.5
C10—N2—C11	118.9 (3)	H13A—C13—H13C	109.5
C10—N2—Co1	128.1 (2)	H13B—C13—H13C	109.5
C11—N2—Co1	113.0 (2)	C10—C14—H14A	109.5
N1—C1—C2	120.9 (3)	C10—C14—H14B	109.5
N1—C1—C13	118.2 (3)	H14A—C14—H14B	109.5
C2—C1—C13	120.9 (3)	C10—C14—H14C	109.5
C3—C2—C1	120.4 (3)	H14A—C14—H14C	109.5
C3—C2—H2A	119.8	H14B—C14—H14C	109.5
C1—C2—H2A	119.8	C15—O1—Co1	90.4 (2)
C2—C3—C4	120.0 (3)	C15—O2—Co1	91.7 (2)
C2—C3—H3A	120.0	O1—C15—O2	118.8 (3)
C4—C3—H3A	120.0	O1—C15—C16	120.9 (3)
C3—C4—C12	116.7 (3)	O2—C15—C16	120.3 (3)
C3—C4—C5	123.9 (3)	O1—C15—Co1	60.2 (2)
C12—C4—C5	119.4 (3)	O2—C15—Co1	58.6 (2)
C6—C5—C4	121.2 (3)	C16—C15—Co1	178.2 (2)
C6—C5—H5A	119.4	C17—C16—C15	113.5 (3)
C4—C5—H5A	119.4	C17—C16—H16A	108.9
C5—C6—C7	120.8 (3)	C15—C16—H16A	108.9
C5—C6—H6A	119.6	C17—C16—H16C	108.9
C7—C6—H6A	119.6	C15—C16—H16C	108.9
C11—C7—C8	117.2 (3)	H16A—C16—H16C	107.7
C11—C7—C6	119.4 (3)	O4—C17—O3	119.4 (4)
C8—C7—C6	123.4 (3)	O4—C17—C16	120.1 (3)
C9—C8—C7	119.4 (3)	O3—C17—C16	120.5 (3)

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