Diaqua­(2,9-dimethyl-1,10-phenanthroline-κ2N,N′)(4-hydroxy­benzoato-κ2O,O′)cobalt(II) nitrate dihydrate

Zhai, C.; Yan, F.; Zhao, P.

doi:10.1107/S1600536808038117

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Pages m1591-m1592

doi:10.1107/S1600536808038117

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Diaqua(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)(4-hydroxybenzoato-κ²O,O′)cobalt(II) nitrate dihydrate

Cuiping Zhai,^a Fengmei Yan ^b and Peizheng Zhao ^c ^*

^aCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, People's Republic of China, ^bDepartment of Chemistry and Chemical Engineering, Huanghuai University, Zhumadian 463000, People's Republic of China, and ^cCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: pz_zhao@hotmail.com

(Received 28 October 2008; accepted 16 November 2008; online 22 November 2008)

In the title compound, [Co(C₇H₅O₃)(C₁₄H₁₂N₂)(H₂O)₂]NO₃·2H₂O, the Co^II ion is six-coordinated by two N atoms of a 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand, two carboxylate O atoms of one 4-hydroxybenzoate anion and two O atoms of two water molecules, in a distorted octahedral environment; the two water molecules occupy the apical positions. In the crystal structure, the ionic units and water molecules are linked through O—H⋯O hydrogen bonds, leading to the formation of a three-dimensional network. In addition, π–π interactions between a pyridine ring of the dmphen ligand and the benzene ring of the hydroxybenzoate anion [centroid–centroid separation = 3.6861 (3) Å] are observed.

Related literature

For related structures, see: Xuan et al. (2007 ); Xuan & Zhao (2007a ,b ).

Experimental

Crystal data

[Co(C₇H₅O₃)(C₁₄H₁₂N₂)(H₂O)₂]NO₃·2H₂O
M_r = 538.37
Monoclinic, P 2₁ /c
a = 9.8001 (8) Å
b = 22.2638 (19) Å
c = 10.8676 (9) Å
β = 94.602 (1)°
V = 2363.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 291 (2) K
0.35 × 0.25 × 0.14 mm

Data collection

Buker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.771, T_max = 0.899
17391 measured reflections
4385 independent reflections
3689 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.081
S = 1.01
4385 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O5	2.0685 (14)
Co1—O4	2.1187 (14)
Co1—N1	2.1213 (15)
Co1—N2	2.1357 (15)
Co1—O1	2.1425 (13)
Co1—O2	2.2311 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H8W⋯O6	0.83	2.26	2.960 (3)	142
O9—H5W⋯O6	0.83	2.09	2.904 (3)	169
O9—H6W⋯O7ⁱ	0.83	2.09	2.888 (3)	161
O10—H7W⋯O8ⁱⁱ	0.83	2.01	2.829 (3)	169
O5—H4W⋯O10	0.81	1.93	2.720 (2)	167
O4—H2W⋯O2ⁱⁱⁱ	0.83	2.01	2.846 (2)	180
O5—H3W⋯O1^iv	0.82	2.05	2.826 (2)	157
O4—H1W⋯O9^v	0.82	1.96	2.758 (2)	164
O3—H3⋯O8^vi	0.82	2.57	3.133 (3)	127
O3—H3⋯O7^vi	0.82	2.07	2.861 (3)	164
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1; (iii) -x+1, -y+1, -z+2; (iv) -x, -y+1, -z+2; (v) x, y, z+1; (vi) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038117/ci2703sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038117/ci2703Isup2.hkl

checkCIF report

Comment top

We have recently reported the syntheses and crystal structures of [Ni(dmphen)(3-OH-benzoate)(H₂O)NO₃] (Xuan & Zhao, 2007a), [Ni(dmphen)(benzoate)(H₂O)NO₃] (Xuan et al., 2007) and [Co(dmphen)(3-OH-benzoate)(H₂O)NO₃](Xuan & Zhao, 2007b) complexes. Now, we report here the crystal structure of the title compound.

Each Co^II ion is six-coordinated by two N atoms from a dmphen ligand, and two O atoms from two water molecules and two O atoms from carboxylate group of one 4-hydroxy-benzoate anion (Fig.1). The CoO₄N₂ unit forms a distorted octahedral geometry, with two O atoms of two water molecules occupying the axial positions at 2.0685 (14) or 2.1187 (14) Å (Table 1). The equatorial plane is defined by the N atoms of dmphen and carboxy O atoms of the 3-hydroxybenzoate anion.

In the crystal structure, an extensive series of O—H···O hydrogen bonds, involving the coordinated and solvent water molecules, 4-hydroxybenzoate and nitrate anions, lead to a supramolecular network structure (Table 2 and Fig. 2). In addition, inversion related molecules are linked via π-π interactions involving the pyridine ring of the dmphen (N1/C1-C4/C12; centroid Cg1) ligand and the benzene ring of the hydroxybenzoate (C15—C20; centroid Cg2) anion (Fig.3); the Cg1—Cg2ⁱⁱⁱ distance is 3.6861 (11) Å (symmetry code is given in Table 2). This combination of hydrogen bonds and stacking interactions build a three-dimensional network.

Related literature top

For related structures, see: Xuan et al. (2007); Xuan & Zhao (2007a,b).

Experimental top

To a solution of 2,9-dimethyl-1,10-phenanthroline (0.1095 g, 0.5 mmol), 4-hydroxy-benzoate (0.1382 g, 1 mmol) and sodium hydroxide (0.03740 g, 1 mmol) in ethanol-water (v:v 1:1, 15 ml) was added a solution of Ni(NO₃)₂.6H₂O (0.1457 g, 0.5 mmol) in distilled water (10 ml). The resulting solution was stirred for 5 h at 323 K and then the precipitate obtained was filtered. Pink single crystals of the title compound were obtained by slow evaporation of the filtrate over 80 d.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: publCIF (Westrip, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. The crystal structure of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines.

Diaqua(2,9-dimethyl-1,10-phenanthroline-κ²N,N')(4- hydroxybenzoato-κ²O,O')cobalt(II) nitrate dihydrate top

Crystal data top

[Co(C₇H₅O₃)(C₁₄H₁₂N₂)(H₂O)₂]NO₃·2H₂O	F(000) = 1116
M_r = 538.37	D_x = 1.513 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6780 reflections
a = 9.8001 (8) Å	θ = 2.3–27.4°
b = 22.2638 (19) Å	µ = 0.79 mm⁻¹
c = 10.8676 (9) Å	T = 291 K
β = 94.602 (1)°	Block, pink
V = 2363.5 (3) Å³	0.35 × 0.25 × 0.14 mm
Z = 4

Data collection top

Buker SMART CCD area-detector diffractometer	4385 independent reflections
Radiation source: fine-focus sealed tube	3689 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −11→11
T_min = 0.771, T_max = 0.899	k = −26→26
17391 measured reflections	l = −12→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0425P)² + 0.9518P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
4385 reflections	Δρ_max = 0.36 e Å⁻³
319 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (4)

Crystal data top

[Co(C₇H₅O₃)(C₁₄H₁₂N₂)(H₂O)₂]NO₃·2H₂O	V = 2363.5 (3) Å³
M_r = 538.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8001 (8) Å	µ = 0.79 mm⁻¹
b = 22.2638 (19) Å	T = 291 K
c = 10.8676 (9) Å	0.35 × 0.25 × 0.14 mm
β = 94.602 (1)°

Data collection top

Buker SMART CCD area-detector diffractometer	4385 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	3689 reflections with I > 2σ(I)
T_min = 0.771, T_max = 0.899	R_int = 0.024
17391 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.01	Δρ_max = 0.36 e Å⁻³
4385 reflections	Δρ_min = −0.24 e Å⁻³
319 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.24510 (2)	0.564923 (11)	0.97828 (2)	0.02979 (10)
O1	0.17733 (13)	0.49074 (6)	1.08320 (12)	0.0366 (3)
O2	0.33021 (13)	0.47337 (6)	0.95100 (12)	0.0374 (3)
O3	0.2669 (2)	0.21307 (7)	1.18959 (16)	0.0605 (5)
H3	0.2922	0.1902	1.1368	0.091*
O4	0.41725 (13)	0.57880 (6)	1.10585 (13)	0.0393 (3)
H1W	0.3985	0.5685	1.1749	0.059*
H2W	0.4911	0.5635	1.0890	0.059*
O5	0.08164 (14)	0.54783 (7)	0.85063 (13)	0.0463 (4)
H3W	0.0120	0.5431	0.8866	0.070*
H4W	0.0724	0.5513	0.7766	0.070*
O6	0.2587 (2)	0.46630 (9)	0.4839 (2)	0.0894 (7)
O7	0.3605 (2)	0.38408 (10)	0.5460 (2)	0.0809 (6)
O8	0.1450 (2)	0.38603 (9)	0.5079 (2)	0.0793 (6)
N1	0.32511 (15)	0.62761 (7)	0.85585 (14)	0.0318 (3)
N2	0.15796 (15)	0.64623 (7)	1.04080 (15)	0.0335 (4)
N3	0.2548 (2)	0.41299 (10)	0.51267 (18)	0.0539 (5)
C1	0.40177 (19)	0.61783 (9)	0.76179 (18)	0.0365 (4)
C2	0.4510 (2)	0.66576 (10)	0.6932 (2)	0.0453 (5)
H2	0.5028	0.6578	0.6270	0.054*
C3	0.4234 (2)	0.72318 (10)	0.7231 (2)	0.0488 (5)
H3A	0.4580	0.7547	0.6788	0.059*
C4	0.3424 (2)	0.73521 (9)	0.8210 (2)	0.0411 (5)
C5	0.3063 (2)	0.79459 (9)	0.8560 (2)	0.0508 (6)
H5A	0.3428	0.8274	0.8170	0.061*
C6	0.2207 (3)	0.80379 (9)	0.9444 (2)	0.0522 (6)
H6A	0.1975	0.8428	0.9649	0.063*
C7	0.1645 (2)	0.75432 (9)	1.0074 (2)	0.0425 (5)
C8	0.0722 (2)	0.76153 (10)	1.0991 (2)	0.0523 (6)
H8A	0.0427	0.7997	1.1195	0.063*
C9	0.0264 (2)	0.71247 (10)	1.1575 (2)	0.0495 (6)
H9	−0.0353	0.7172	1.2176	0.059*
C10	0.07125 (19)	0.65450 (9)	1.12827 (19)	0.0393 (5)
C11	0.20282 (19)	0.69525 (8)	0.98025 (18)	0.0343 (4)
C12	0.29325 (18)	0.68556 (8)	0.88414 (18)	0.0334 (4)
C13	0.4357 (2)	0.55479 (10)	0.7305 (2)	0.0475 (5)
H13A	0.5202	0.5434	0.7752	0.071*
H13B	0.4450	0.5517	0.6435	0.071*
H13C	0.3638	0.5286	0.7527	0.071*
C14	0.0247 (2)	0.60129 (10)	1.1968 (2)	0.0500 (6)
H14A	−0.0272	0.5751	1.1406	0.075*
H14B	−0.0317	0.6144	1.2599	0.075*
H14C	0.1028	0.5802	1.2340	0.075*
C15	0.25751 (18)	0.38985 (8)	1.06962 (18)	0.0315 (4)
C16	0.21346 (19)	0.37361 (8)	1.18382 (18)	0.0350 (4)
H16	0.1813	0.4030	1.2350	0.042*
C17	0.2169 (2)	0.31459 (9)	1.22188 (19)	0.0398 (5)
H17	0.1887	0.3044	1.2989	0.048*
C18	0.2626 (2)	0.27028 (9)	1.1450 (2)	0.0401 (5)
C19	0.3045 (2)	0.28577 (9)	1.03029 (19)	0.0408 (5)
H19	0.3334	0.2561	0.9781	0.049*
C20	0.3033 (2)	0.34506 (9)	0.99351 (19)	0.0374 (4)
H20	0.3333	0.3552	0.9172	0.045*
C21	0.25521 (18)	0.45407 (9)	1.03250 (17)	0.0326 (4)
O9	0.38611 (19)	0.56246 (7)	0.35357 (16)	0.0590 (4)
H5W	0.3520	0.5320	0.3824	0.089*
H6W	0.4632	0.5696	0.3884	0.089*
O10	0.0934 (2)	0.55782 (10)	0.60222 (17)	0.0801 (6)
H7W	0.0195	0.5697	0.5695	0.120*
H8W	0.1089	0.5228	0.5809	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02697 (15)	0.02584 (15)	0.03723 (16)	0.00085 (9)	0.00663 (10)	0.00142 (10)
O1	0.0339 (7)	0.0294 (7)	0.0479 (8)	0.0028 (5)	0.0117 (6)	0.0027 (6)
O2	0.0354 (7)	0.0328 (7)	0.0457 (8)	−0.0002 (6)	0.0131 (6)	0.0061 (6)
O3	0.0890 (13)	0.0308 (8)	0.0644 (11)	0.0015 (8)	0.0237 (10)	0.0087 (7)
O4	0.0313 (7)	0.0439 (8)	0.0428 (8)	0.0022 (6)	0.0042 (6)	0.0025 (6)
O5	0.0323 (7)	0.0644 (10)	0.0423 (8)	−0.0086 (7)	0.0028 (6)	0.0030 (7)
O6	0.123 (2)	0.0482 (12)	0.1012 (16)	−0.0095 (11)	0.0364 (15)	0.0098 (10)
O7	0.0641 (12)	0.0851 (14)	0.0940 (16)	0.0112 (11)	0.0088 (11)	−0.0044 (12)
O8	0.0701 (13)	0.0730 (13)	0.0944 (15)	−0.0149 (11)	0.0030 (11)	0.0118 (11)
N1	0.0275 (8)	0.0300 (8)	0.0381 (9)	0.0009 (6)	0.0030 (6)	0.0036 (7)
N2	0.0275 (8)	0.0311 (8)	0.0421 (9)	0.0027 (6)	0.0030 (7)	−0.0035 (7)
N3	0.0643 (14)	0.0494 (12)	0.0491 (12)	−0.0014 (10)	0.0115 (10)	−0.0038 (9)
C1	0.0293 (10)	0.0426 (11)	0.0375 (11)	0.0018 (8)	0.0022 (8)	0.0050 (9)
C2	0.0391 (11)	0.0553 (14)	0.0422 (12)	−0.0014 (10)	0.0080 (9)	0.0113 (10)
C3	0.0433 (12)	0.0488 (13)	0.0542 (14)	−0.0077 (10)	0.0030 (10)	0.0193 (11)
C4	0.0393 (11)	0.0342 (11)	0.0484 (12)	−0.0040 (8)	−0.0049 (9)	0.0097 (9)
C5	0.0586 (14)	0.0299 (11)	0.0622 (15)	−0.0052 (10)	−0.0047 (12)	0.0104 (10)
C6	0.0642 (15)	0.0247 (10)	0.0656 (16)	0.0058 (10)	−0.0087 (12)	0.0015 (10)
C7	0.0411 (12)	0.0333 (11)	0.0516 (13)	0.0077 (9)	−0.0055 (9)	−0.0022 (9)
C8	0.0513 (13)	0.0366 (12)	0.0684 (16)	0.0153 (10)	0.0008 (11)	−0.0092 (11)
C9	0.0425 (12)	0.0484 (13)	0.0589 (14)	0.0131 (10)	0.0111 (10)	−0.0110 (11)
C10	0.0298 (10)	0.0410 (11)	0.0472 (12)	0.0036 (8)	0.0041 (8)	−0.0066 (9)
C11	0.0306 (9)	0.0285 (10)	0.0426 (11)	0.0013 (8)	−0.0044 (8)	0.0010 (8)
C12	0.0277 (9)	0.0306 (10)	0.0411 (11)	0.0005 (7)	−0.0028 (8)	0.0034 (8)
C13	0.0509 (13)	0.0468 (12)	0.0471 (13)	0.0047 (10)	0.0180 (10)	0.0009 (10)
C14	0.0475 (13)	0.0481 (13)	0.0576 (14)	0.0002 (10)	0.0235 (11)	−0.0060 (11)
C15	0.0272 (9)	0.0291 (9)	0.0385 (10)	−0.0024 (7)	0.0041 (8)	0.0015 (8)
C16	0.0323 (10)	0.0337 (10)	0.0396 (11)	0.0005 (8)	0.0071 (8)	−0.0011 (8)
C17	0.0419 (11)	0.0371 (11)	0.0416 (11)	−0.0036 (9)	0.0109 (9)	0.0064 (9)
C18	0.0424 (11)	0.0292 (10)	0.0489 (12)	−0.0045 (8)	0.0041 (9)	0.0052 (9)
C19	0.0455 (11)	0.0324 (10)	0.0453 (12)	−0.0011 (9)	0.0082 (9)	−0.0059 (9)
C20	0.0389 (11)	0.0373 (11)	0.0369 (11)	−0.0017 (9)	0.0090 (8)	0.0007 (9)
C21	0.0283 (9)	0.0324 (10)	0.0373 (11)	−0.0018 (8)	0.0028 (8)	0.0009 (8)
O9	0.0772 (12)	0.0438 (9)	0.0572 (10)	0.0025 (8)	0.0119 (9)	0.0023 (7)
O10	0.0746 (13)	0.1064 (17)	0.0584 (12)	0.0092 (11)	0.0001 (10)	−0.0031 (11)

Geometric parameters (Å, º) top

Co1—O5	2.0685 (14)	C6—C7	1.430 (3)
Co1—O4	2.1187 (14)	C6—H6A	0.93
Co1—N1	2.1213 (15)	C7—C11	1.406 (3)
Co1—N2	2.1357 (15)	C7—C8	1.407 (3)
Co1—O1	2.1425 (13)	C8—C9	1.358 (3)
Co1—O2	2.2311 (13)	C8—H8A	0.93
O1—C21	1.273 (2)	C9—C10	1.408 (3)
O2—C21	1.270 (2)	C9—H9	0.93
O3—C18	1.362 (2)	C10—C14	1.490 (3)
O3—H3	0.82	C11—C12	1.439 (3)
O4—H1W	0.82	C13—H13A	0.96
O4—H2W	0.83	C13—H13B	0.96
O5—H3W	0.82	C13—H13C	0.96
O5—H4W	0.81	C14—H14A	0.96
O6—N3	1.229 (3)	C14—H14B	0.96
O7—N3	1.249 (3)	C14—H14C	0.96
O8—N3	1.229 (3)	C15—C20	1.392 (3)
N1—C1	1.334 (2)	C15—C16	1.394 (3)
N1—C12	1.368 (2)	C15—C21	1.485 (3)
N2—C10	1.338 (2)	C16—C17	1.377 (3)
N2—C11	1.365 (2)	C16—H16	0.93
C1—C2	1.409 (3)	C17—C18	1.390 (3)
C1—C13	1.488 (3)	C17—H17	0.93
C2—C3	1.352 (3)	C18—C19	1.386 (3)
C2—H2	0.93	C19—C20	1.379 (3)
C3—C4	1.403 (3)	C19—H19	0.93
C3—H3A	0.93	C20—H20	0.93
C4—C12	1.407 (3)	O9—H5W	0.83
C4—C5	1.428 (3)	O9—H6W	0.83
C5—C6	1.341 (3)	O10—H7W	0.82
C5—H5A	0.93	O10—H8W	0.83

O5—Co1—O4	177.28 (6)	C11—C7—C6	120.0 (2)
O5—Co1—N1	90.33 (6)	C8—C7—C6	123.0 (2)
O4—Co1—N1	89.97 (6)	C9—C8—C7	119.7 (2)
O5—Co1—N2	93.52 (6)	C9—C8—H8A	120.2
O4—Co1—N2	89.19 (6)	C7—C8—H8A	120.2
N1—Co1—N2	79.59 (6)	C8—C9—C10	120.7 (2)
O5—Co1—O1	87.63 (6)	C8—C9—H9	119.7
O4—Co1—O1	91.65 (5)	C10—C9—H9	119.7
N1—Co1—O1	170.71 (6)	N2—C10—C9	120.96 (19)
N2—Co1—O1	109.58 (6)	N2—C10—C14	118.91 (17)
O5—Co1—O2	91.17 (6)	C9—C10—C14	120.12 (19)
O4—Co1—O2	86.19 (5)	N2—C11—C7	123.02 (19)
N1—Co1—O2	110.90 (5)	N2—C11—C12	118.08 (16)
N2—Co1—O2	168.50 (6)	C7—C11—C12	118.90 (18)
O1—Co1—O2	60.11 (5)	N1—C12—C4	122.56 (18)
C21—O1—Co1	92.40 (11)	N1—C12—C11	118.00 (16)
C21—O2—Co1	88.46 (11)	C4—C12—C11	119.42 (18)
C18—O3—H3	109.5	C1—C13—H13A	109.5
Co1—O4—H1W	109.5	C1—C13—H13B	109.5
Co1—O4—H2W	117.1	H13A—C13—H13B	109.5
H1W—O4—H2W	110.5	C1—C13—H13C	109.5
Co1—O5—H3W	109.5	H13A—C13—H13C	109.5
Co1—O5—H4W	132.1	H13B—C13—H13C	109.5
H3W—O5—H4W	117.1	C10—C14—H14A	109.5
C1—N1—C12	118.60 (16)	C10—C14—H14B	109.5
C1—N1—Co1	129.23 (13)	H14A—C14—H14B	109.5
C12—N1—Co1	112.14 (12)	C10—C14—H14C	109.5
C10—N2—C11	118.69 (16)	H14A—C14—H14C	109.5
C10—N2—Co1	129.48 (13)	H14B—C14—H14C	109.5
C11—N2—Co1	111.83 (12)	C20—C15—C16	118.73 (17)
O6—N3—O8	120.4 (2)	C20—C15—C21	121.77 (17)
O6—N3—O7	122.0 (2)	C16—C15—C21	119.49 (17)
O8—N3—O7	117.6 (2)	C17—C16—C15	120.86 (18)
N1—C1—C2	121.30 (19)	C17—C16—H16	119.6
N1—C1—C13	118.61 (17)	C15—C16—H16	119.6
C2—C1—C13	120.09 (19)	C16—C17—C18	119.85 (18)
C3—C2—C1	120.4 (2)	C16—C17—H17	120.1
C3—C2—H2	119.8	C18—C17—H17	120.1
C1—C2—H2	119.8	O3—C18—C19	123.33 (19)
C2—C3—C4	119.94 (19)	O3—C18—C17	116.85 (18)
C2—C3—H3A	120.0	C19—C18—C17	119.79 (18)
C4—C3—H3A	120.0	C20—C19—C18	120.15 (19)
C3—C4—C12	117.17 (19)	C20—C19—H19	119.9
C3—C4—C5	123.1 (2)	C18—C19—H19	119.9
C12—C4—C5	119.7 (2)	C19—C20—C15	120.59 (19)
C6—C5—C4	121.0 (2)	C19—C20—H20	119.7
C6—C5—H5A	119.5	C15—C20—H20	119.7
C4—C5—H5A	119.5	O2—C21—O1	119.03 (18)
C5—C6—C7	120.8 (2)	O2—C21—C15	121.20 (17)
C5—C6—H6A	119.6	O1—C21—C15	119.77 (16)
C7—C6—H6A	119.6	H5W—O9—H6W	111.3
C11—C7—C8	116.9 (2)	H7W—O10—H8W	110.8

O5—Co1—O1—C21	93.01 (11)	C11—N2—C10—C9	0.2 (3)
O4—Co1—O1—C21	−84.36 (11)	Co1—N2—C10—C9	179.14 (15)
N2—Co1—O1—C21	−174.09 (11)	C11—N2—C10—C14	−178.51 (18)
O2—Co1—O1—C21	0.29 (10)	Co1—N2—C10—C14	0.4 (3)
O5—Co1—O2—C21	−86.88 (11)	C8—C9—C10—N2	−1.2 (3)
O4—Co1—O2—C21	93.81 (11)	C8—C9—C10—C14	177.5 (2)
N1—Co1—O2—C21	−177.68 (10)	C10—N2—C11—C7	1.4 (3)
N2—Co1—O2—C21	27.2 (3)	Co1—N2—C11—C7	−177.69 (15)
O1—Co1—O2—C21	−0.29 (10)	C10—N2—C11—C12	−178.40 (17)
O5—Co1—N1—C1	−83.02 (16)	Co1—N2—C11—C12	2.5 (2)
O4—Co1—N1—C1	94.28 (16)	C8—C7—C11—N2	−2.0 (3)
N2—Co1—N1—C1	−176.54 (17)	C6—C7—C11—N2	176.94 (19)
O2—Co1—N1—C1	8.36 (18)	C8—C7—C11—C12	177.86 (18)
O5—Co1—N1—C12	98.92 (13)	C6—C7—C11—C12	−3.2 (3)
O4—Co1—N1—C12	−83.79 (12)	C1—N1—C12—C4	−2.5 (3)
N2—Co1—N1—C12	5.40 (12)	Co1—N1—C12—C4	175.82 (14)
O2—Co1—N1—C12	−169.70 (11)	C1—N1—C12—C11	175.81 (17)
O5—Co1—N2—C10	87.09 (17)	Co1—N1—C12—C11	−5.9 (2)
O4—Co1—N2—C10	−93.10 (17)	C3—C4—C12—N1	2.1 (3)
N1—Co1—N2—C10	176.78 (18)	C5—C4—C12—N1	−179.36 (18)
O1—Co1—N2—C10	−1.64 (18)	C3—C4—C12—C11	−176.18 (18)
O2—Co1—N2—C10	−26.8 (4)	C5—C4—C12—C11	2.4 (3)
O5—Co1—N2—C11	−93.90 (13)	N2—C11—C12—N1	2.4 (3)
O4—Co1—N2—C11	85.91 (13)	C7—C11—C12—N1	−177.50 (17)
N1—Co1—N2—C11	−4.21 (12)	N2—C11—C12—C4	−179.31 (17)
O1—Co1—N2—C11	177.37 (12)	C7—C11—C12—C4	0.8 (3)
O2—Co1—N2—C11	152.2 (2)	C20—C15—C16—C17	1.0 (3)
C12—N1—C1—C2	0.8 (3)	C21—C15—C16—C17	−178.71 (17)
Co1—N1—C1—C2	−177.17 (14)	C15—C16—C17—C18	−1.1 (3)
C12—N1—C1—C13	−179.64 (17)	C16—C17—C18—O3	178.27 (19)
Co1—N1—C1—C13	2.4 (3)	C16—C17—C18—C19	0.0 (3)
N1—C1—C2—C3	1.2 (3)	O3—C18—C19—C20	−176.9 (2)
C13—C1—C2—C3	−178.3 (2)	C17—C18—C19—C20	1.2 (3)
C1—C2—C3—C4	−1.6 (3)	C18—C19—C20—C15	−1.4 (3)
C2—C3—C4—C12	0.0 (3)	C16—C15—C20—C19	0.2 (3)
C2—C3—C4—C5	−178.5 (2)	C21—C15—C20—C19	179.93 (18)
C3—C4—C5—C6	175.1 (2)	Co1—O2—C21—O1	0.49 (17)
C12—C4—C5—C6	−3.3 (3)	Co1—O2—C21—C15	−179.24 (16)
C4—C5—C6—C7	0.9 (4)	Co1—O1—C21—O2	−0.51 (17)
C5—C6—C7—C11	2.4 (3)	Co1—O1—C21—C15	179.23 (15)
C5—C6—C7—C8	−178.8 (2)	C20—C15—C21—O2	−21.5 (3)
C11—C7—C8—C9	0.9 (3)	C16—C15—C21—O2	158.19 (18)
C6—C7—C8—C9	−178.0 (2)	C20—C15—C21—O1	158.77 (18)
C7—C8—C9—C10	0.6 (3)	C16—C15—C21—O1	−21.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H8W···O6	0.83	2.26	2.960 (3)	142
O9—H5W···O6	0.83	2.09	2.904 (3)	169
O9—H6W···O7ⁱ	0.83	2.09	2.888 (3)	161
O10—H7W···O8ⁱⁱ	0.83	2.01	2.829 (3)	169
O5—H4W···O10	0.81	1.93	2.720 (2)	167
O4—H2W···O2ⁱⁱⁱ	0.83	2.01	2.846 (2)	180
O5—H3W···O1^iv	0.82	2.05	2.826 (2)	157
O4—H1W···O9^v	0.82	1.96	2.758 (2)	164
O3—H3···O8^vi	0.82	2.57	3.133 (3)	127
O3—H3···O7^vi	0.82	2.07	2.861 (3)	164

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

Experimental details

Crystal data
Chemical formula	[Co(C₇H₅O₃)(C₁₄H₁₂N₂)(H₂O)₂]NO₃·2H₂O
M_r	538.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	9.8001 (8), 22.2638 (19), 10.8676 (9)
β (°)	94.602 (1)
V (Å³)	2363.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.35 × 0.25 × 0.14

Data collection
Diffractometer	Buker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.771, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	17391, 4385, 3689
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.081, 1.01
No. of reflections	4385
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.24

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2008).

Selected bond lengths (Å) top

Co1—O5	2.0685 (14)	Co1—N2	2.1357 (15)
Co1—O4	2.1187 (14)	Co1—O1	2.1425 (13)
Co1—N1	2.1213 (15)	Co1—O2	2.2311 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H8W···O6	0.83	2.26	2.960 (3)	142
O9—H5W···O6	0.83	2.09	2.904 (3)	169
O9—H6W···O7ⁱ	0.83	2.09	2.888 (3)	161
O10—H7W···O8ⁱⁱ	0.83	2.01	2.829 (3)	169
O5—H4W···O10	0.81	1.93	2.720 (2)	167
O4—H2W···O2ⁱⁱⁱ	0.83	2.01	2.846 (2)	180
O5—H3W···O1^iv	0.82	2.05	2.826 (2)	157
O4—H1W···O9^v	0.82	1.96	2.758 (2)	164
O3—H3···O8^vi	0.82	2.57	3.133 (3)	127
O3—H3···O7^vi	0.82	2.07	2.861 (3)	164

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

Acknowledgements

Financial support from the Science Fund of Henan Province for Distinguished Young Scholars (grant No. 07410051005) is gratefully acknowledged.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
Xuan, X. & Zhao, P. (2007a). Acta Cryst. E63, m2856. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xuan, X. & Zhao, P. (2007b). Acta Cryst. E63, m3009. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xuan, X.-P., Zhao, P.-Z. & Tang, Q.-H. (2007). Acta Cryst. E63, m2405. Web of Science CSD CrossRef IUCr Journals Google Scholar

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