Bis(μ-3,5-dinitro-2-oxidobenzoato)-κO,O:O;κO:O,O-bis[aqua-(2-phenyl-1,3,7,8-tetra-azacyclo-penta-[l]phenanthrene-κN,N)cobalt(II)].

In the title compound, [Co(2)(C(7)H(2)N(2)O(7))(2)(C(19)H(12)N(4))(2)(H(2)O)(2)], the Co(II) atom is six-coordinated by two N atoms from a 2-phenyl-1H-1,3,7,8,-tetraaza-cyclo-penta-[l]phenanthrene (L) ligand, three O atoms from two 3,5-dinitro-2-oxidobenzoate (3,5-dinitro-salicylate or DNSA) ligands and one O atom from a water mol-ecule in a distorted octa-hedral geometry. The Co(II) atoms are bridged by two carboxyl-ate O atoms from two DNSA ligands, forming a centrosymmetric dinuclear structure. Neighbouring dinuclear units inter-act with each other through two types of π-π inter-actions between the L ligands [shortest centroid-centroid distance = 3.646 (3) Å] and between the L and DNSA ligands [shortest atom-to-centroid distance = 3.794 (3) Å]. N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds are observed, which lead to a three-dimensional structure.

Related literature

For general background to metal–organic coordination polymers, see: Che et al. (2008 ▶). For a related structure, see: Liu et al. (2009 ▶). For the ligand synthesis, see: Steck & Day (1943 ▶).

Experimental

Crystal data

[Co2(C7H2N2O7)2(C19H12N4)2(H2O)2]

M = 1198.76

Triclinic,

a = 8.2943 (4) Å

b = 11.0232 (5) Å

c = 13.6139 (7) Å

α = 102.690 (4)°

β = 107.282 (4)°

γ = 90.459 (4)°

V = 1155.9 (1) Å3

Z = 1

Mo Kα radiation

μ = 0.81 mm−1

T = 292 K

0.32 × 0.27 × 0.23 mm

Data collection

Oxford Diffraction Gemini R Ultra CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.771, T max = 0.829

7153 measured reflections

4041 independent reflections

2933 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.111

S = 1.00

4041 reflections

378 parameters

168 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.97 e Å−3

Δρmin = −1.00 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017629/hy2303sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017629/hy2303Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co2(C7H2N2O7)2(C19H12N4)2(H2O)2]	Z = 1
Mr = 1198.76	F(000) = 610
Triclinic, P1	Dx = 1.722 Mg m−3Dm = 1.722 Mg m−3Dm measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2943 (4) Å	Cell parameters from 3653 reflections
b = 11.0232 (5) Å	θ = 4.4–25°
c = 13.6139 (7) Å	µ = 0.81 mm−1
α = 102.690 (4)°	T = 292 K
β = 107.282 (4)°	Block, yellow
γ = 90.459 (4)°	0.32 × 0.27 × 0.23 mm
V = 1155.9 (1) Å3

Oxford Diffraction Gemini R Ultra CCD diffractometer	4041 independent reflections
Radiation source: fine-focus sealed tube	2933 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω scans	θmax = 25.0°, θmin = 4.4°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −9→9
Tmin = 0.771, Tmax = 0.829	k = −13→11
7153 measured reflections	l = −14→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0638P)2] where P = (Fo2 + 2Fc2)/3
4041 reflections	(Δ/σ)max = 0.002
378 parameters	Δρmax = 0.97 e Å−3
168 restraints	Δρmin = −1.00 e Å−3

	x	y	z	Uiso*/Ueq
C1	−0.0231 (5)	0.3815 (4)	0.6428 (3)	0.0304 (9)
H1	0.0452	0.3635	0.7049	0.037*
C2	−0.1233 (6)	0.4828 (4)	0.6499 (3)	0.0346 (10)
H2	−0.1214	0.5307	0.7157	0.041*
C3	−0.2237 (5)	0.5105 (4)	0.5595 (3)	0.0336 (9)
H3	−0.2911	0.5774	0.5631	0.040*
C4	−0.2245 (5)	0.4375 (4)	0.4614 (3)	0.0286 (8)
C5	−0.3250 (5)	0.4543 (4)	0.3592 (3)	0.0299 (8)
C6	−0.3182 (5)	0.3757 (4)	0.2679 (3)	0.0311 (9)
C7	−0.2138 (5)	0.2745 (4)	0.2631 (3)	0.0277 (8)
C8	−0.1991 (5)	0.1923 (4)	0.1726 (3)	0.0344 (9)
H8	−0.2600	0.2020	0.1058	0.041*
C9	−0.0946 (6)	0.0974 (4)	0.1829 (3)	0.0369 (10)
H9	−0.0838	0.0422	0.1233	0.044*
C10	−0.0049 (5)	0.0841 (4)	0.2834 (3)	0.0325 (9)
H10	0.0650	0.0189	0.2895	0.039*
C11	−0.1165 (5)	0.2559 (4)	0.3627 (3)	0.0247 (8)
C12	−0.1215 (5)	0.3373 (3)	0.4607 (3)	0.0249 (8)
C13	−0.4998 (5)	0.5157 (4)	0.2329 (3)	0.0322 (9)
C14	−0.6334 (5)	0.5801 (4)	0.1703 (3)	0.0356 (9)
C15	−0.6963 (6)	0.6831 (4)	0.2208 (4)	0.0438 (11)
H15	−0.6518	0.7137	0.2935	0.053*
C16	−0.8264 (7)	0.7403 (5)	0.1618 (4)	0.0546 (13)
H16	−0.8696	0.8091	0.1957	0.066*
C17	−0.8916 (7)	0.6973 (5)	0.0553 (4)	0.0606 (14)
H17	−0.9787	0.7365	0.0167	0.073*
C18	−0.8286 (7)	0.5960 (6)	0.0052 (4)	0.0619 (15)
H18	−0.8723	0.5671	−0.0677	0.074*
C19	−0.7008 (7)	0.5364 (5)	0.0621 (4)	0.0511 (13)
H19	−0.6599	0.4668	0.0276	0.061*
C20	0.3815 (5)	−0.0284 (4)	0.6442 (3)	0.0269 (8)
C21	0.5087 (5)	−0.0973 (4)	0.6896 (3)	0.0328 (9)
H21	0.5419	−0.1637	0.6466	0.039*
C22	0.5884 (5)	−0.0697 (4)	0.7980 (3)	0.0368 (9)
C23	0.5475 (5)	0.0299 (4)	0.8637 (3)	0.0360 (9)
H23	0.6050	0.0499	0.9358	0.043*
C24	0.4202 (5)	0.0997 (4)	0.8213 (3)	0.0323 (9)
C25	0.3257 (5)	0.0739 (4)	0.7106 (3)	0.0265 (8)
C26	0.2996 (5)	−0.0712 (4)	0.5268 (3)	0.0271 (8)
N1	−0.0218 (4)	0.3109 (3)	0.5517 (2)	0.0254 (7)
N2	−0.0149 (4)	0.1606 (3)	0.3706 (2)	0.0250 (6)
N3	−0.4378 (4)	0.5429 (3)	0.3369 (3)	0.0324 (8)
N4	−0.4312 (4)	0.4167 (3)	0.1875 (3)	0.0321 (8)
H4	−0.4538	0.3850	0.1209	0.039*
N5	0.7161 (5)	−0.1487 (4)	0.8424 (3)	0.0484 (9)
N6	0.3854 (5)	0.2056 (4)	0.8942 (3)	0.0446 (9)
O1	0.1485 (3)	−0.0397 (2)	0.4865 (2)	0.0305 (5)
O2	0.3743 (4)	−0.1379 (3)	0.4735 (2)	0.0459 (8)
O3	0.2036 (4)	0.1369 (3)	0.6762 (2)	0.0339 (5)
O4	0.7338 (5)	−0.2469 (4)	0.7867 (3)	0.0650 (9)
O5	0.8033 (5)	−0.1117 (4)	0.9352 (3)	0.0691 (10)
O6	0.4661 (6)	0.2254 (4)	0.9869 (3)	0.0813 (11)
O7	0.2851 (6)	0.2779 (4)	0.8644 (3)	0.0857 (10)
OW1	0.3241 (4)	0.2215 (3)	0.5222 (3)	0.0345 (5)
Co	0.09090 (7)	0.14151 (5)	0.52610 (4)	0.0264 (2)
H1WA	0.362 (7)	0.285 (6)	0.566 (5)	0.064 (18)*
H1WB	0.407 (7)	0.184 (5)	0.523 (4)	0.058 (16)*

	U11	U22	U33	U12	U13	U23
C1	0.034 (2)	0.031 (2)	0.0251 (15)	0.0072 (17)	0.0071 (17)	0.0072 (14)
C2	0.041 (3)	0.031 (2)	0.0312 (16)	0.0091 (18)	0.0129 (18)	0.0042 (17)
C3	0.032 (2)	0.031 (2)	0.0381 (15)	0.0114 (19)	0.0118 (18)	0.0079 (15)
C4	0.027 (2)	0.0249 (19)	0.0326 (12)	0.0062 (16)	0.0055 (16)	0.0089 (14)
C5	0.026 (2)	0.027 (2)	0.0351 (13)	0.0054 (16)	0.0042 (16)	0.0115 (14)
C6	0.027 (2)	0.035 (2)	0.0308 (14)	0.0071 (17)	0.0025 (16)	0.0133 (14)
C7	0.024 (2)	0.0286 (19)	0.0279 (13)	0.0026 (15)	0.0021 (15)	0.0094 (14)
C8	0.036 (3)	0.040 (2)	0.0254 (16)	0.0039 (18)	0.0045 (18)	0.0088 (15)
C9	0.040 (3)	0.041 (2)	0.0267 (14)	0.0078 (19)	0.0101 (18)	0.0022 (17)
C10	0.029 (2)	0.037 (2)	0.0295 (13)	0.0080 (19)	0.0082 (17)	0.0038 (15)
C11	0.020 (2)	0.0269 (19)	0.0264 (12)	0.0036 (15)	0.0042 (15)	0.0091 (13)
C12	0.021 (2)	0.0230 (18)	0.0279 (12)	0.0032 (15)	0.0026 (15)	0.0069 (13)
C13	0.031 (2)	0.030 (2)	0.0349 (14)	0.0058 (16)	0.0057 (16)	0.0121 (16)
C14	0.030 (2)	0.036 (2)	0.0398 (16)	0.0072 (17)	0.0048 (16)	0.0158 (16)
C15	0.044 (3)	0.036 (2)	0.049 (2)	0.011 (2)	0.008 (2)	0.0137 (18)
C16	0.048 (3)	0.047 (3)	0.072 (2)	0.021 (2)	0.014 (2)	0.025 (2)
C17	0.046 (3)	0.070 (3)	0.069 (2)	0.023 (3)	0.005 (2)	0.041 (2)
C18	0.058 (4)	0.074 (4)	0.045 (2)	0.015 (3)	−0.005 (2)	0.024 (2)
C19	0.050 (3)	0.059 (3)	0.0401 (16)	0.018 (2)	0.005 (2)	0.0139 (19)
C20	0.019 (2)	0.029 (2)	0.0318 (13)	0.0034 (15)	0.0040 (13)	0.0095 (14)
C21	0.025 (2)	0.035 (2)	0.0384 (15)	0.0094 (17)	0.0063 (16)	0.0134 (16)
C22	0.024 (2)	0.047 (2)	0.0400 (16)	0.0079 (18)	0.0040 (16)	0.0203 (16)
C23	0.027 (2)	0.051 (2)	0.0278 (19)	0.0026 (18)	−0.0005 (17)	0.0160 (16)
C24	0.025 (2)	0.042 (2)	0.0263 (13)	0.0014 (17)	0.0010 (14)	0.0089 (14)
C25	0.022 (2)	0.031 (2)	0.0252 (13)	0.0047 (15)	0.0029 (14)	0.0104 (13)
C26	0.0219 (17)	0.0223 (19)	0.0328 (14)	0.0051 (15)	0.0040 (12)	0.0035 (14)
N1	0.0257 (17)	0.0237 (14)	0.0258 (11)	0.0052 (13)	0.0052 (13)	0.0070 (11)
N2	0.0223 (16)	0.0260 (15)	0.0258 (10)	0.0044 (12)	0.0052 (12)	0.0071 (11)
N3	0.032 (2)	0.0288 (17)	0.0350 (13)	0.0090 (15)	0.0051 (15)	0.0109 (13)
N4	0.033 (2)	0.0336 (18)	0.0272 (14)	0.0092 (15)	0.0014 (14)	0.0112 (13)
N5	0.034 (2)	0.062 (2)	0.0523 (18)	0.0166 (19)	0.0058 (15)	0.0300 (15)
N6	0.041 (2)	0.057 (2)	0.0267 (13)	0.0099 (17)	0.0015 (15)	0.0037 (14)
O1	0.0280 (10)	0.0323 (9)	0.0278 (9)	0.0142 (9)	0.0037 (8)	0.0059 (8)
O2	0.0315 (15)	0.0534 (16)	0.0404 (14)	0.0173 (13)	0.0048 (12)	−0.0062 (12)
O3	0.0321 (11)	0.0361 (11)	0.0274 (8)	0.0156 (9)	0.0014 (8)	0.0050 (8)
O4	0.055 (2)	0.0667 (19)	0.0686 (19)	0.0307 (17)	0.0039 (16)	0.0270 (15)
O5	0.059 (2)	0.084 (2)	0.0569 (17)	0.0309 (18)	−0.0046 (14)	0.0289 (16)
O6	0.092 (2)	0.092 (2)	0.0308 (12)	0.0423 (19)	−0.0108 (15)	−0.0076 (15)
O7	0.0906 (19)	0.0901 (18)	0.0420 (14)	0.0503 (15)	−0.0127 (14)	−0.0113 (14)
OW1	0.0268 (11)	0.0354 (13)	0.0367 (13)	0.0091 (10)	0.0058 (10)	0.0039 (11)
Co	0.0251 (3)	0.0267 (3)	0.0236 (3)	0.0104 (2)	0.0015 (2)	0.0059 (2)

C1—N1	1.314 (5)	C17—C18	1.369 (8)
C1—C2	1.401 (5)	C17—H17	0.9300
C1—H1	0.9300	C18—C19	1.379 (6)
C2—C3	1.365 (6)	C18—H18	0.9300
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.398 (6)	C20—C21	1.379 (5)
C3—H3	0.9300	C20—C25	1.453 (5)
C4—C12	1.402 (5)	C20—C26	1.503 (6)
C4—C5	1.446 (5)	C21—C22	1.389 (6)
C5—C6	1.366 (6)	C21—H21	0.9300
C5—N3	1.377 (5)	C22—C23	1.368 (6)
C6—N4	1.376 (5)	C22—N5	1.454 (5)
C6—C7	1.420 (5)	C23—C24	1.373 (5)
C7—C8	1.398 (6)	C23—H23	0.9300
C7—C11	1.416 (5)	C24—C25	1.440 (5)
C8—C9	1.368 (6)	C24—N6	1.448 (5)
C8—H8	0.9300	C25—O3	1.265 (4)
C9—C10	1.389 (6)	C26—O2	1.220 (5)
C9—H9	0.9300	C26—O1	1.294 (4)
C10—N2	1.322 (5)	N4—H4	0.8600
C10—H10	0.9300	N5—O4	1.215 (5)
C11—N2	1.356 (5)	N5—O5	1.229 (5)
C11—C12	1.447 (5)	N6—O7	1.202 (5)
C12—N1	1.363 (5)	N6—O6	1.209 (5)
C13—N3	1.319 (5)	OW1—H1WA	0.81 (6)
C13—N4	1.349 (5)	OW1—H1WB	0.80 (5)
C13—C14	1.475 (5)	Co—N1	2.102 (3)
C14—C19	1.383 (6)	Co—N2	2.095 (3)
C14—C15	1.383 (6)	Co—O1	2.050 (2)
C15—C16	1.388 (6)	Co—O1i	2.216 (3)
C15—H15	0.9300	Co—O3	1.991 (3)
C16—C17	1.359 (8)	Co—OW1	2.139 (3)
C16—H16	0.9300
N1—C1—C2	122.5 (4)	C21—C20—C26	116.4 (3)
N1—C1—H1	118.8	C25—C20—C26	123.5 (3)
C2—C1—H1	118.8	C20—C21—C22	121.5 (4)
C3—C2—C1	119.4 (4)	C20—C21—H21	119.3
C3—C2—H2	120.3	C22—C21—H21	119.3
C1—C2—H2	120.3	C23—C22—C21	121.1 (4)
C2—C3—C4	119.4 (4)	C23—C22—N5	119.6 (4)
C2—C3—H3	120.3	C21—C22—N5	119.3 (4)
C4—C3—H3	120.3	C22—C23—C24	118.9 (4)
C3—C4—C12	117.8 (3)	C22—C23—H23	120.6
C3—C4—C5	125.9 (3)	C24—C23—H23	120.6
C12—C4—C5	116.3 (3)	C23—C24—C25	123.5 (4)
C6—C5—N3	110.5 (3)	C23—C24—N6	116.4 (4)
C6—C5—C4	121.0 (3)	C25—C24—N6	120.0 (3)
N3—C5—C4	128.5 (4)	O3—C25—C24	121.1 (3)
C5—C6—N4	105.3 (3)	O3—C25—C20	124.0 (3)
C5—C6—C7	124.8 (3)	C24—C25—C20	114.9 (3)
N4—C6—C7	129.9 (4)	O2—C26—O1	122.3 (4)
C8—C7—C11	117.7 (3)	O2—C26—C20	119.4 (3)
C8—C7—C6	127.5 (4)	O1—C26—C20	118.2 (3)
C11—C7—C6	114.8 (3)	C1—N1—C12	118.8 (3)
C9—C8—C7	119.6 (4)	C1—N1—Co	127.4 (2)
C9—C8—H8	120.2	C12—N1—Co	113.2 (2)
C7—C8—H8	120.2	C10—N2—C11	119.2 (3)
C8—C9—C10	119.4 (4)	C10—N2—Co	127.0 (2)
C8—C9—H9	120.3	C11—N2—Co	113.5 (2)
C10—C9—H9	120.3	C13—N3—C5	104.8 (3)
N2—C10—C9	122.7 (4)	C13—N4—C6	107.2 (3)
N2—C10—H10	118.7	C13—N4—H4	126.4
C9—C10—H10	118.7	C6—N4—H4	126.4
N2—C11—C7	121.5 (3)	O4—N5—O5	123.0 (4)
N2—C11—C12	116.9 (3)	O4—N5—C22	119.2 (4)
C7—C11—C12	121.7 (3)	O5—N5—C22	117.9 (4)
N1—C12—C4	122.0 (3)	O7—N6—O6	119.1 (4)
N1—C12—C11	116.5 (3)	O7—N6—C24	121.8 (4)
C4—C12—C11	121.5 (3)	O6—N6—C24	118.9 (3)
N3—C13—N4	112.1 (3)	C26—O1—Co	120.4 (3)
N3—C13—C14	125.6 (4)	C26—O1—Coi	125.8 (2)
N4—C13—C14	122.2 (4)	Co—O1—Coi	100.87 (10)
C19—C14—C15	119.4 (4)	C25—O3—Co	127.0 (2)
C19—C14—C13	120.8 (4)	Co—OW1—H1WA	116 (4)
C15—C14—C13	119.8 (4)	Co—OW1—H1WB	124 (4)
C14—C15—C16	119.4 (5)	H1WA—OW1—H1WB	102 (5)
C14—C15—H15	120.3	O3—Co—O1	87.05 (10)
C16—C15—H15	120.3	O3—Co—N2	175.08 (14)
C17—C16—C15	120.9 (5)	O1—Co—N2	96.09 (11)
C17—C16—H16	119.5	O3—Co—N1	98.70 (11)
C15—C16—H16	119.5	O1—Co—N1	167.77 (12)
C16—C17—C18	119.7 (4)	N2—Co—N1	78.95 (12)
C16—C17—H17	120.1	O3—Co—OW1	88.76 (12)
C18—C17—H17	120.1	O1—Co—OW1	95.00 (13)
C17—C18—C19	120.5 (5)	N2—Co—OW1	87.20 (12)
C17—C18—H18	119.7	N1—Co—OW1	95.91 (13)
C19—C18—H18	119.7	O3—Co—O1i	95.02 (11)
C18—C19—C14	120.0 (5)	O1—Co—O1i	79.13 (10)
C18—C19—H19	120.0	N2—Co—O1i	89.30 (11)
C14—C19—H19	120.0	N1—Co—O1i	89.56 (11)
C21—C20—C25	119.9 (4)	OW1—Co—O1i	172.82 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O6ii	0.86	2.17	2.948 (5)	150
OW1—H1WA···N3iii	0.81 (6)	2.03 (6)	2.831 (5)	172 (5)
OW1—H1WB···O2iv	0.80 (5)	1.88 (5)	2.662 (4)	165 (5)

Table 1

Selected bond lengths (Å)

Co—N1	2.102 (3)
Co—N2	2.095 (3)
Co—O1	2.050 (2)
Co—O1i	2.216 (3)
Co—O3	1.991 (3)
Co—OW1	2.139 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O6ii	0.86	2.17	2.948 (5)	150
OW1—H1WA⋯N3iii	0.81 (6)	2.03 (6)	2.831 (5)	172 (5)
OW1—H1WB⋯O2iv	0.80 (5)	1.88 (5)	2.662 (4)	165 (5)

Symmetry codes: (ii) ; (iii) ; (iv) .