4-{[3,5-Bis(methoxy­carbon­yl)-4,5-dihydro-1H-pyrazol-5-yl]methyl­amino}pyridine 1-oxide monohydrate

The title compound, C₁₃H₁₆N₄O₅·H₂O, was isolated following the cyclo­addition reaction of 4-azido­pyridine 1-oxide with an excess of methyl acrylate. The compound arises from a reaction sequence whereby the expected triazoline product undergoes rearrangement and a second cyclo­addition reaction to yield the title pyrazoline product without the presence of a strong base which is usually required for such transformations.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.046
• wR factor = 0.131
• Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSMU01_ALERT_1_B  The ratio of given/expected absorption coefficient lies
               outside the range 0.95 <> 1.05
            Calculated value of mu =     0.117
            Value of mu given      =     0.109

Alert level C
REFNR01_ALERT_3_C  Ratio of reflections to parameters is < 10 for a
            centrosymmetric structure
            sine(theta)/lambda                0.6569
            Proportion of unique data used    0.7925
            Ratio reflections to parameters   9.1393
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.14
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.90 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C12    -   C121    ..       5.68 su
PLAT320_ALERT_2_C Check Hybridisation of  C13    in Main Residue .          ?
PLAT353_ALERT_3_C Long    N-H Bond (0.87A)   N10    -   H10    ...       1.01 Ang.
PLAT390_ALERT_3_C Deviating Methyl C123    X-C-H Bond Angle ......     100.00 Deg.
PLAT391_ALERT_3_C Deviating Methyl C93     H-C-H Bond Angle ......     101.20 Deg.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C13 H16 N4 O5

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  10 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003); software used to prepare material for publication: Please supply.

4-{[3,5-Bis(methoxycarbonyl)-4,5-dihydro-1H-pyrazol-5-yl)]methylamino}pyridine 1-oxide monohydrate

Crystal data

C13H16N4O5·H2O	Z = 2
Mr = 326.31	F(000) = 344
Triclinic, P1	Dx = 1.459 Mg m^−3
Hall symbol: -P 1	Mo - Kα radiation, λ = 0.71073 Å
a = 6.0678 (7) Å	Cell parameters from 8766 reflections
b = 8.7476 (9) Å	θ = 2–27°
c = 15.0449 (18) Å	µ = 0.11 mm^−1
α = 104.435 (6)°	T = 150 K
β = 94.885 (6)°	Chunk, colourless
γ = 103.676 (6)°	0.40 × 0.35 × 0.29 mm
V = 742.57 (15) Å^3

Data collection

Nonius KappaCCD diffractometer	1906 reflections with I > 2.0σ(I)
Graphite 002 monochromator	Rint = 0.029
ω scans	θmax = 27.8°, θmin = 2.5°
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	h = 0→7
Tmin = 0.936, Tmax = 0.969	k = −11→11
8766 measured reflections	l = −19→19
2559 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.0806P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.131	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.47 e Å^−3
2559 reflections	Δρmin = −0.24 e Å^−3
280 parameters

Special details

Experimental. ¹H NMR (d₆-DMSO, 400 MHz): δ 8.88 (s, 1H), 7.81 (d, 2H, J = 7.7 Hz), 6.73 (t, 1H, J = 8.4 Hz), 6.60 (d, 2H, J = 7.3 Hz), 3.69 (s, 3H), 3.64 (s, 3H), 3.49 (d, 2H, J = 6.6 Hz), 3.37 (s, 2H), 3.21 (d, 1H, J = 17.6 Hz), 3.00 (d, 1H, J = 17.6 Hz); ¹³C NMR (d₆-DMSO, 100 MHz): δ 172.2, 163.1, 147.5, 139.0, 138.5, 109.9, 73.8, 53.5, 52.2, 47.8, 38.1; IR (KBr, ν cm^-1): 1735; ESMS C₁₃H₁₆N₄O₅Na⁺ requires m/z = 331.264, found m/z = 331.101.

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R_factor_obs 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
O(1)	0.3739 (3)	0.92493 (17)	0.61361 (10)	0.0353 (4)
O(1W)	0.6188 (3)	0.8263 (2)	0.47558 (13)	0.0358 (4)
O(91)	−0.3029 (3)	−0.0054 (2)	0.83549 (11)	0.0396 (4)
O(92)	0.0516 (2)	0.05867 (17)	0.79991 (10)	0.0297 (4)
O(121)	−0.1487 (3)	0.69967 (18)	0.96714 (10)	0.0353 (4)
O(122)	−0.5292 (3)	0.62268 (18)	0.91620 (11)	0.0365 (4)
N(1)	0.2422 (3)	0.7822 (2)	0.62159 (12)	0.0274 (4)
N(7)	−0.1541 (3)	0.3372 (2)	0.63695 (13)	0.0301 (4)
N(10)	−0.4357 (3)	0.2115 (2)	0.75419 (14)	0.0358 (5)
N(11)	−0.4930 (3)	0.3438 (2)	0.80260 (12)	0.0300 (5)
C(2)	0.3380 (4)	0.6909 (3)	0.66583 (15)	0.0283 (5)
C(3)	0.2142 (4)	0.5445 (3)	0.67368 (15)	0.0273 (5)
C(4)	−0.0204 (3)	0.4838 (2)	0.63575 (13)	0.0244 (5)
C(5)	−0.1150 (4)	0.5846 (3)	0.59284 (14)	0.0272 (5)
C(6)	0.0174 (4)	0.7298 (3)	0.58598 (14)	0.0279 (5)
C(8)	−0.0880 (4)	0.2203 (3)	0.67996 (15)	0.0262 (5)
C(9)	−0.1877 (3)	0.2231 (2)	0.77078 (14)	0.0265 (5)
C(12)	−0.3076 (3)	0.4467 (2)	0.85505 (14)	0.0249 (5)
C(13)	−0.0975 (4)	0.3877 (3)	0.84731 (17)	0.0326 (6)
C(91)	−0.1571 (3)	0.0796 (3)	0.80603 (14)	0.0266 (5)
C(93)	0.1021 (4)	−0.0683 (3)	0.83872 (18)	0.0336 (6)
C(121)	−0.3188 (4)	0.6015 (3)	0.91833 (15)	0.0286 (5)
C(123)	−0.5433 (5)	0.7740 (3)	0.97963 (18)	0.0351 (6)
H(2)	0.490 (4)	0.738 (3)	0.6911 (15)	0.031 (6)*
H(3)	0.296 (4)	0.487 (2)	0.7035 (14)	0.026 (5)*
H(5)	−0.284 (4)	0.552 (3)	0.5656 (16)	0.036 (6)*
H(6)	−0.026 (3)	0.803 (2)	0.5573 (14)	0.020 (5)*
H(7)	−0.296 (5)	0.312 (3)	0.6130 (17)	0.041 (7)*
H(10)	−0.560 (5)	0.111 (4)	0.717 (2)	0.078 (10)*
H(81)	−0.157 (4)	0.112 (3)	0.6336 (16)	0.037 (6)*
H(82)	0.066 (4)	0.244 (3)	0.6918 (15)	0.025 (6)*
H(131)	0.045 (4)	0.437 (3)	0.8300 (15)	0.029 (6)*
H(132)	−0.042 (4)	0.372 (3)	0.9028 (18)	0.036 (6)*
H(1W1)	0.550 (5)	0.863 (4)	0.520 (2)	0.061 (10)*
H(1W2)	0.670 (6)	0.902 (4)	0.458 (2)	0.067 (11)*
H(231)	−0.472 (4)	0.786 (3)	1.0431 (18)	0.038 (6)*
H(232)	−0.461 (4)	0.867 (3)	0.9631 (15)	0.033 (6)*
H(233)	−0.703 (5)	0.756 (3)	0.9738 (19)	0.057 (8)*
H(931)	0.095 (4)	−0.049 (3)	0.9083 (16)	0.037 (6)*
H(932)	0.260 (4)	−0.062 (3)	0.8374 (15)	0.029 (6)*
H(933)	−0.004 (4)	−0.175 (3)	0.8020 (16)	0.033 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O(1)	0.0459 (10)	0.0199 (7)	0.0359 (9)	−0.0021 (7)	0.0073 (7)	0.0100 (6)
O(1W)	0.0330 (10)	0.0362 (10)	0.0379 (10)	0.0074 (8)	0.0010 (8)	0.0134 (8)
O(91)	0.0267 (9)	0.0483 (10)	0.0497 (10)	0.0055 (8)	0.0119 (8)	0.0267 (8)
O(92)	0.0251 (8)	0.0311 (8)	0.0388 (9)	0.0077 (7)	0.0093 (7)	0.0185 (7)
O(121)	0.0335 (9)	0.0320 (8)	0.0362 (9)	0.0044 (7)	−0.0008 (7)	0.0078 (7)
O(122)	0.0285 (9)	0.0330 (9)	0.0450 (10)	0.0083 (7)	0.0035 (7)	0.0060 (7)
N(1)	0.0342 (11)	0.0215 (9)	0.0255 (9)	0.0033 (8)	0.0055 (8)	0.0085 (7)
N(7)	0.0233 (10)	0.0290 (10)	0.0357 (11)	−0.0007 (8)	−0.0030 (9)	0.0144 (8)
N(10)	0.0256 (11)	0.0353 (11)	0.0426 (11)	0.0108 (9)	0.0028 (9)	0.0026 (9)
N(11)	0.0303 (10)	0.0269 (9)	0.0328 (10)	0.0052 (8)	0.0017 (8)	0.0115 (8)
C(2)	0.0255 (12)	0.0266 (11)	0.0310 (12)	0.0037 (10)	0.0007 (10)	0.0090 (9)
C(3)	0.0277 (12)	0.0241 (11)	0.0299 (12)	0.0067 (10)	0.0003 (9)	0.0088 (9)
C(4)	0.0265 (11)	0.0226 (10)	0.0221 (11)	0.0042 (9)	0.0022 (9)	0.0052 (8)
C(5)	0.0284 (12)	0.0278 (11)	0.0241 (11)	0.0071 (10)	0.0000 (9)	0.0066 (9)
C(6)	0.0347 (13)	0.0256 (11)	0.0240 (11)	0.0098 (10)	0.0013 (9)	0.0076 (9)
C(8)	0.0247 (13)	0.0225 (11)	0.0299 (12)	0.0015 (9)	0.0019 (10)	0.0096 (9)
C(9)	0.0243 (11)	0.0265 (11)	0.0274 (11)	0.0058 (9)	0.0028 (9)	0.0061 (9)
C(12)	0.0261 (11)	0.0245 (11)	0.0257 (11)	0.0062 (9)	0.0038 (9)	0.0106 (9)
C(13)	0.0297 (13)	0.0347 (13)	0.0298 (13)	0.0057 (11)	−0.0002 (11)	0.0066 (10)
C(91)	0.0241 (12)	0.0304 (11)	0.0231 (11)	0.0047 (10)	0.0026 (9)	0.0063 (9)
C(93)	0.0328 (14)	0.0346 (14)	0.0409 (15)	0.0130 (12)	0.0068 (11)	0.0199 (11)
C(121)	0.0291 (12)	0.0299 (12)	0.0313 (12)	0.0068 (10)	0.0053 (10)	0.0171 (10)
C(123)	0.0398 (15)	0.0270 (13)	0.0412 (15)	0.0128 (12)	0.0143 (12)	0.0082 (11)

Geometric parameters (Å, º)

O(1)—N(1)	1.353 (2)	C(3)—H(3)	0.94 (2)
O(1W)—H(1W1)	0.85 (3)	C(4)—C(5)	1.409 (3)
O(1W)—H(1W2)	0.78 (4)	C(5)—C(6)	1.366 (3)
O(91)—C(91)	1.205 (3)	C(5)—H(5)	1.02 (2)
O(92)—C(91)	1.329 (2)	C(6)—H(6)	0.93 (2)
O(92)—C(93)	1.457 (3)	C(8)—C(9)	1.538 (3)
O(121)—C(121)	1.217 (3)	C(8)—H(81)	1.00 (2)
O(122)—C(121)	1.331 (3)	C(8)—H(82)	0.90 (2)
O(122)—C(123)	1.452 (3)	C(9)—C(91)	1.522 (3)
N(1)—C(6)	1.347 (3)	C(9)—C(13)	1.547 (3)
N(1)—C(2)	1.356 (3)	C(12)—C(121)	1.468 (3)
N(7)—C(4)	1.351 (3)	C(12)—C(13)	1.487 (3)
N(7)—C(8)	1.451 (3)	C(13)—H(131)	0.96 (2)
N(7)—H(7)	0.86 (3)	C(13)—H(132)	0.93 (3)
N(10)—N(11)	1.343 (3)	C(93)—H(931)	1.02 (2)
N(10)—C(9)	1.479 (3)	C(93)—H(932)	0.95 (2)
N(10)—H(10)	1.02 (3)	C(93)—H(933)	0.99 (3)
N(11)—C(12)	1.309 (3)	C(123)—H(231)	0.99 (3)
C(2)—C(3)	1.362 (3)	C(123)—H(232)	0.95 (3)
C(2)—H(2)	0.92 (2)	C(123)—H(233)	0.94 (3)
C(3)—C(4)	1.410 (3)
H(1W1)—O(1W)—H(1W2)	105 (3)	N(10)—C(9)—C(91)	108.65 (17)
C(91)—O(92)—C(93)	115.16 (17)	N(10)—C(9)—C(8)	109.51 (17)
C(121)—O(122)—C(123)	114.36 (18)	C(91)—C(9)—C(8)	110.79 (16)
C(6)—N(1)—O(1)	120.82 (17)	N(10)—C(9)—C(13)	101.45 (15)
C(6)—N(1)—C(2)	119.67 (19)	C(91)—C(9)—C(13)	111.65 (17)
O(1)—N(1)—C(2)	119.50 (18)	C(8)—C(9)—C(13)	114.28 (18)
C(4)—N(7)—C(8)	126.94 (19)	N(11)—C(12)—C(121)	120.68 (18)
C(4)—N(7)—H(7)	117.5 (17)	N(11)—C(12)—C(13)	114.16 (17)
C(8)—N(7)—H(7)	115.4 (17)	C(121)—C(12)—C(13)	125.09 (19)
N(11)—N(10)—C(9)	113.87 (18)	C(12)—C(13)—C(9)	101.95 (17)
N(11)—N(10)—H(10)	119.9 (17)	C(12)—C(13)—H(131)	129.1 (13)
C(9)—N(10)—H(10)	125.9 (17)	C(9)—C(13)—H(131)	103.4 (13)
C(12)—N(11)—N(10)	108.36 (17)	C(12)—C(13)—H(132)	111.2 (14)
N(1)—C(2)—C(3)	121.8 (2)	C(9)—C(13)—H(132)	111.3 (14)
N(1)—C(2)—H(2)	114.2 (14)	H(131)—C(13)—H(132)	99 (2)
C(3)—C(2)—H(2)	124.0 (14)	O(91)—C(91)—O(92)	123.88 (19)
C(2)—C(3)—C(4)	120.3 (2)	O(91)—C(91)—C(9)	124.69 (18)
C(2)—C(3)—H(3)	116.3 (13)	O(92)—C(91)—C(9)	111.43 (17)
C(4)—C(3)—H(3)	123.4 (13)	O(92)—C(93)—H(931)	114.9 (12)
N(7)—C(4)—C(5)	119.44 (19)	O(92)—C(93)—H(932)	107.1 (13)
N(7)—C(4)—C(3)	124.39 (19)	H(931)—C(93)—H(932)	101.3 (18)
C(5)—C(4)—C(3)	116.17 (19)	O(92)—C(93)—H(933)	107.9 (13)
C(6)—C(5)—C(4)	121.2 (2)	H(931)—C(93)—H(933)	111.1 (19)
C(6)—C(5)—H(5)	117.4 (13)	H(932)—C(93)—H(933)	114.6 (18)
C(4)—C(5)—H(5)	121.4 (13)	O(121)—C(121)—O(122)	124.30 (19)
N(1)—C(6)—C(5)	120.9 (2)	O(121)—C(121)—C(12)	121.89 (19)
N(1)—C(6)—H(6)	111.2 (13)	O(122)—C(121)—C(12)	113.81 (19)
C(5)—C(6)—H(6)	128.0 (13)	O(122)—C(123)—H(231)	110.7 (13)
N(7)—C(8)—C(9)	110.97 (17)	O(122)—C(123)—H(232)	111.6 (13)
N(7)—C(8)—H(81)	104.6 (13)	H(231)—C(123)—H(232)	106 (2)
C(9)—C(8)—H(81)	109.6 (14)	O(122)—C(123)—H(233)	100.0 (17)
N(7)—C(8)—H(82)	109.5 (14)	H(231)—C(123)—H(233)	113 (2)
C(9)—C(8)—H(82)	109.6 (14)	H(232)—C(123)—H(233)	116 (2)
H(81)—C(8)—H(82)	112.5 (18)
C(9)—N(10)—N(11)—C(12)	−2.3 (2)	N(10)—N(11)—C(12)—C(13)	−1.1 (3)
C(6)—N(1)—C(2)—C(3)	1.5 (3)	N(11)—C(12)—C(13)—C(9)	3.7 (3)
O(1)—N(1)—C(2)—C(3)	−178.33 (18)	C(121)—C(12)—C(13)—C(9)	−179.45 (19)
N(1)—C(2)—C(3)—C(4)	−0.3 (3)	N(10)—C(9)—C(13)—C(12)	−4.4 (2)
C(8)—N(7)—C(4)—C(5)	−178.14 (18)	C(91)—C(9)—C(13)—C(12)	−119.95 (19)
C(8)—N(7)—C(4)—C(3)	3.1 (3)	C(8)—C(9)—C(13)—C(12)	113.3 (2)
C(2)—C(3)—C(4)—N(7)	177.26 (19)	C(93)—O(92)—C(91)—O(91)	−4.8 (3)
C(2)—C(3)—C(4)—C(5)	−1.6 (3)	C(93)—O(92)—C(91)—C(9)	175.53 (17)
N(7)—C(4)—C(5)—C(6)	−176.60 (18)	N(10)—C(9)—C(91)—O(91)	−15.6 (3)
C(3)—C(4)—C(5)—C(6)	2.3 (3)	C(8)—C(9)—C(91)—O(91)	−135.9 (2)
O(1)—N(1)—C(6)—C(5)	179.05 (17)	C(13)—C(9)—C(91)—O(91)	95.5 (2)
C(2)—N(1)—C(6)—C(5)	−0.8 (3)	N(10)—C(9)—C(91)—O(92)	164.09 (16)
C(4)—C(5)—C(6)—N(1)	−1.1 (3)	C(8)—C(9)—C(91)—O(92)	43.8 (2)
C(4)—N(7)—C(8)—C(9)	104.6 (2)	C(13)—C(9)—C(91)—O(92)	−84.9 (2)
N(11)—N(10)—C(9)—C(91)	122.11 (18)	C(123)—O(122)—C(121)—O(121)	−1.4 (3)
N(11)—N(10)—C(9)—C(8)	−116.76 (19)	C(123)—O(122)—C(121)—C(12)	179.01 (18)
N(11)—N(10)—C(9)—C(13)	4.4 (2)	N(11)—C(12)—C(121)—O(121)	−179.3 (2)
N(7)—C(8)—C(9)—N(10)	49.4 (2)	C(13)—C(12)—C(121)—O(121)	4.0 (3)
N(7)—C(8)—C(9)—C(91)	169.25 (17)	N(11)—C(12)—C(121)—O(122)	0.3 (3)
N(7)—C(8)—C(9)—C(13)	−63.6 (2)	C(13)—C(12)—C(121)—O(122)	−176.4 (2)
N(10)—N(11)—C(12)—C(121)	−178.12 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N(7)—H(7)···O(1W)^i	0.86 (3)	2.17 (2)	2.989 (4)	159 (2)
N(10)—H(10)···O(1)^ii	1.01 (3)	1.88 (3)	2.768 (3)	144 (3)
O(1W)—H(1W1)···O(1)	0.85 (3)	1.89 (3)	2.739 (3)	174 (3)
O(1W)—H(1W2)···O(1)^iii	0.78 (4)	2.12 (4)	2.821 (3)	150 (3)

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